JPH0334988A - Siloxane compound containing alkoxy group - Google Patents

Abstract

NEW MATERIAL:The compound of formula I {j is 1-2,000; R<5> is pentafluorophenyl, 3-(heptafluoroisopropoxy)propyl, etc.; X<1> is substituent of formula II or III [R<1> is alkoxy-containing substituent of formula IV (d and e are 0-3; R<0> is 1-6C hydrocarbon group); R<2> to R<4> are 1-4C alkyl or phenyl; X is 2-12C chain divalent hydrocarbon group or divalent substituent of formula V (R<6> and R<7> are 0-3C divalent hydrocarbon group); a is 0-2]}. EXAMPLE:1-(Tridecafluoro-1,1,2,2-tetrahydrooctyl)-9-{2-(dimethylethoxy silyl) ethyl}decamethylpentasiloxane. USE:A modifying agent effective in remarkably improving water-repellency, mold-releasability, etc., of synthetic resins. PREPARATION:A starting compound of formula VI (R<15> is 0-10C chain divalent hydrocarbon group, etc.; w is j) is made to react with a compound of formula VII. The starting compound of formula VI can be produced e.g. by reacting a lithium silanolate compound with a monochlorosilane compound having unsaturated double bond at the terminal.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an alkoxy group-containing siloxane compound, and more specifically, it relates to an alkoxy group-containing siloxane compound that can be suitably used, for example, in the modification of synthetic resins, as a raw material for coating compositions, etc. This invention relates to novel alkoxy group-containing siloxane compounds.

[Prior Art and Problems to be Solved by the Invention] Siloxane compounds are known to have excellent interfacial properties such as water repellency, mold releasability, and dye resistance, and various properties such as heat resistance.

Silicone resins made using this siloxane compound are widely used as resins that can be made into high-quality products having excellent properties as described above.

As the siloxane compound in this silicone resin, linear polysiloxane compounds are mainly used.
Those that do not have a group reactive with synthetic resins in their molecules are introduced into synthetic resins by friends, and those that have groups reactive with synthetic resins in their molecules are introduced into synthetic resins by chemical bonding.

However, in the past, attempts to improve the properties of synthetic resins relied solely on the actions and functions of polysiloxane in polysiloxane compounds, so the improvement in properties has reached a plateau. As the demand for superior functional properties increases, it has become difficult for conventional polysiloxane compounds to meet this demand.

Specifically, for example, if the proportion of the polysiloxane compound added is increased in order to obtain the desired properties, there is a problem in that the other physical properties of the synthetic resin are not adversely affected. In particular, in so-called double-end modified silicones that are composed of the same substituent at both ends, if the substituents at both ends are not reactive groups with the target synthetic resin, the amount added may be increased due to the fleet phenomenon. The disadvantage is that the desired characteristics cannot necessarily be obtained because the desired characteristics cannot be obtained, and even if the desired characteristics are obtained, the performance deteriorates so much over time that it is impossible to maintain the characteristics for a long period of time. Furthermore, even if a polysiloxane compound has reactive groups with the target synthetic resin at both ends, when it is used to modify the surface of the synthetic resin, the amount added must be increased in order to obtain the desired properties. Because of this, there is a problem that other physical properties are significantly deteriorated. Furthermore, even in single-end modified polysiloxane compounds, the end of the molecular chain that does not have a reactive group with synthetic resins is generally composed of a trimethylsiloxy group, and is used exclusively for improving the properties of synthetic resins. Because it relies on the action or function of siloxane compounds, it may not be possible to fully meet the demands for superior functional properties as mentioned above, or if the amount added is increased to obtain the desired properties, other There are some problems, such as having no adverse effect on physical properties. It has also been pointed out that in terms of oil repellency, a compound consisting only of dimethylsiloxane whose terminal chain is terminated with a trimethylsiloxy group shows almost no improvement in the property.

On the other hand, in the field of paints, fluorine compounds are being introduced for the purpose of imparting properties such as water resistance, weather resistance, chemical resistance, water repellency, and low abrasion.

However, in paints containing fluorine compounds, a major problem is whether the paint has good adhesion to the substrate on which it is coated.

Therefore, in order to improve the adhesion to the substrate to which it is applied, it is necessary to use two-component paints that cure at room temperature, which require additional curing components, or to use fluorocarbon paints, which are difficult to obtain because they always have the same properties. It may be necessary to use a copolymer of an olefin, vinyl needle, or olefinically unsaturated compound with a silicone compound having a hydrolyzable group.

However, even when using a two-component paint or using a J (polymer), it is difficult to fully satisfy the required properties in terms of adhesion to the substrate and deterioration of properties over time. The current situation is that we have not yet reached this point.

The present invention has been made based on the above circumstances.

The purpose of the present invention is, for example, to modify and coat synthetic resins,
When used in the raw material t1 of navy blue composition, it does not cause deterioration of other physical properties and has interfacial properties such as water repellency, mold releasability, stain resistance, and oil repellency, heat resistance, water resistance, weather resistance, and chemical resistance. The object of the present invention is to provide a novel alkoxy group-containing siloxane compound that can significantly improve target properties such as low abrasion properties.

[Means for Solving the Problems] In order to solve the above problems, as a result of intensive research by the present inventors, it was found that the present inventors have a substituent containing a fluorine atom at the α position and
A siloxane compound having an alkoxy group at the position, a fluorine atom-containing substituent at the α or α′ position, and ω
Siloxane compound with alkoxy group in position, α position, α
A siloxane compound having a fluorine atom-containing substituent at the ′ or α″ position and an alkoxy group at the ω position,
Has a fluorine atom-containing substituent at the α position and ω, ω′
A siloxane compound having an alkoxy group at the position and a fluorine atom-containing substituent at the α position and ω, ω′, ω
Any siloxane compound having an alkoxy group at the `` position, for example, when used for modifying synthetic resins or as a raw material for coating materials, can improve water repellency, water repellency, etc. without deteriorating other physical properties.
The present invention has been made based on the discovery that the desired properties such as interfacial properties such as mold releasability, fat dyeing properties, and water repellency, heat resistance, water resistance, weather resistance, chemical resistance, and low abrasion properties can be significantly improved. reached.

That is, the configuration of the first invention is based on the following general formula (Tatashi,
In formula (I), J is an integer of 1 to 2000, and R5 is a pentafluorophenyl group, 3(heptafluoroisopropoxy)propyl group, 1,1,2,2-tetrafluoroethyl group, or the following formula (II): ).

Cb H, F2. -0, (II) [Formula (II) In the formula, b is an integer from 3 to 18, and C represents an integer from 0 to 2b. ] represents a linear or branched fluoroalkyl group represented by the following formula (■): (In formula (III), R1 represents the following formula (XI);0-((:
82C11□0)d(CH2CIl(CH3)O)e-
R' (Xnl) [In the formula (XIl[), d and e each independently represent an integer of O to 3, and Ro represents a hydrocarbon group having 1 to 6 carbon atoms. ] represents an alkoxy group-containing substituent, R2, R3 and R4 each independently represent an alkyl group or phenyl group having 1 to 4 carbon atoms, and or a divalent hydrocarbon group of the following formula [wherein R6 and R7 are each independently a divalent hydrocarbon group having 0 to 3 carbon atoms. represents a divalent substituent, and a represents an integer of O to 2. ] or a substituent represented by the following formula (IV) [In formula (TJ), R', R' and a each have the same meaning as above. ] It is a substituent shown by these. ) The structure of the second invention is such that the substituent represented by R5 in the formula (1) is a 3,3,3-1-lifluoropropyl group, a tridecafluoropropyl group, -i,i.

2.2-tetrahydrooctyl group, 3-(heptafluoroisopropoxy)propyl group, l.

1.2.2-tetrafluoroethyl group or heptadecafluoro-1,1,2,2-tetrahydrodecyl group, and an alkoxy-containing substituent represented by R1 in the formula (III) or the formula (IV) is a methoxy group,
The alkoxy group-containing siloxane compound in the first invention is an ethoxy group, phenoxy group or 2-methoxyethoxy group, and the third invention has the following general formula (V> ), where k and the sentence each independently represent an integer of 1 to 2000, and R8 is a pentafluorophenyl group, 3-(heptafluoroisopropoxy)propyl group, 1, 1, 2.2-tetrafluoroethyl group, or the above-mentioned group. It is a linear or branched fluoroalkyl group represented by formula (II), and R9 has 1 to 6 carbon atoms.
Alkyl group, phenyl group, pentafluorophenyl group, 3-(hefrotafluoroisoproboxy)propyl group, l.

1.2.2-tetrafluoroethyl group or the above formula (n
), X2 is a linear or branched fluoroalkyl group represented by the following formula (■): [In formula (Vl), R2, R', X and a are each the same as in the above formula (III) and express the meaning. ] or the following formula (■) [Formula (■) Formula, R1 represents the same meaning as above. represents the substituent shown. ) is an alkoxy group-containing siloxane compound represented by the formula (V), in which R6 is a pentafluorophenyl group, a 3,3°3-trifluoropropyl group, or a tridecafluoro-1 , 1,2,2-tetrahydrooctyl group, 3-(heptafluoroisopropoxy)propyl group, l, l, 2,2-tetrafluoroethyl group or heptadecafluoro-1,1,2,2tetrahy1- is a rhodecyl group, and R9 has 1 to 1 carbon atoms.
6 alkyl group, phenyl group, pentafluorophenyl group, 3,3.3-)lifluorobyl group, tridecafluoro-1,l,2,2tel-rahi-1-looctyl group, 3-(heptafluoro isopropoxy)propyl group,
1,2゜2-tetrafluoroethyl group or heptadecafluoro-1,,1,2,2-tetrahydrodecyl group, and R1 in the formula (VI) or the formula (Vll) is - an alkoxy group-containing siloxane compound according to the third invention, which is an oxygen group, an ethoxy group, a phenoxy group, or a 2-methoxyethoxy group, and the structure of the fifth invention has the following general formula (VI[); and formula % formula % each independently represents an integer from 1 to 20 tl O, R'' is a pentafluorophenyl group, 3-(heptafluoroisopropoxy)propyl group, l, l, 2.2-tetrafluoroethyl group or a linear or branched fluoroalkyl group represented by the above formula (II), R'' and R'2 each independently represent an alkyl group having 1-6 carbon atoms, a phenyl group, a pentafluorophenyl group, 3-(heptafluoroisopropoxy)propyl group, l, 1,2.
2-tetrafluoroethyl group or a linear or branched fluoroalkyl group represented by the above formula (II), x3 is the following formula (■): [Formula (IX), where R' In formula (m), the meaning of `` and `` is not expressed. ] or the following formula (X) [In formula (X), R1 represents the same as the above. ] represents a substituent. ) The structure of the sixth invention is that in the formula (■), R'' is a pentafluorophenyl group (,3,3°3-trifluoropropyl group, tridecafluoropropyl group). -1,1,2,2-tetrahy-1herooctyl, !l(,3-(heptafluoroisopropoxy)propyl group, 1.l, 2.2-tetrafluoroethyl group or heptadecafluoro-1,l,
2.2 tetrahydrodecyl group, R” and R”
each independently represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, a pentafluorophenyl group, 3.3.3-1-lifluoropropyl group, tridecafluoro-1,1, 2.
2-tetrahydrodecyl group, 3-(heptafluoroisopropoxy)propyl group, 1. l,2,2-tetrafluoroethyl group or heptadecafluoro-1,l,2
゜2-tetrahydrodecyl group, and has the above formula (IX)
or an alkoxy group-containing siloxane compound according to the fifth invention, wherein the alkoxy group-containing substituent represented by R1 in the formula (X) is a methoxy group, an ethoxy group, a phenoxy group, or a 2-methoxyethoxy group; Or, the following general formula (XI) [Tap formula % formula % independently represents an integer from O to 2000, R'' is a pentafluorophenyl group, 3-(heptafluoroisopropoxy)propyl group, l , l, 2.2-tetrafluoroethyl group or a linear or branched fluoroalkyl group represented by the above formula (II), and R'' has 1 carbon atom.
~4 alkyls (or phenylnos, (representing X
4 and X5 each represent a substituent represented by the above formula (m). ] is an alkoxy group-containing siloxane compound, and the eighth aspect of the invention is such that the substituent represented by RlJ in the formula (sword) is a 3,3.3-1-lifluorofurovir group, a trideca Fluoro-1,1.

2.2-TeI~Rahai1~Looctyl group, 3-(heptafluoroisopropoxy)propyl group, 1゜1.2.2
-de1-rafluoroedyl group or heptadecafluoro-1,1,2,2-del-rahyyl group, and the alkoxy group represented by R1 in the formula (III) (where the combined substituent is methoxy )J(, 工１へきし、!
, (, is an alkoxy group 1 siloxane compound in the seventh invention which is a phenoxy group or a 2-methoxyethoxy group, and the structure of the ninth invention is the following general formula ([) [t, formula (X In [), s, t and U each independently represent an integer from 0 to 2000, and R'' is a pentafluorophenyl group, 3-(heptafluoroisopropoxy)propyl group, 1,1,2.2-tetra represents a fluoroethyl group or a linear or branched fluoroalkyl group represented by the above formula (II), and X6, X7 and xo
each represents a substituent represented by the above formula (III). ] is an alkoxy-based siloxane compound represented by
The substituent represented by 3 is a 3,3.3-trifluorofurovir group, tridecafluoro-1,l.

2.2-de1-lahytrooctyl group, 3-(heptafluoroisopropoxy)propyl group, 1゜1.2.2-
Tetrafluoroethyl group or hephtadecafluoro-1
, l, 2.2-de1 helahy 1 to lodecyl group, and the alkoxy group-containing substituent represented by R1 in the formula (m) is a mel-oxy group, an ethoxy group, a phenoxy group or a 2-methoxyethoxy group. It is an alkoxy group-containing siloxane compound in the ninth invention, which is a group.

The alkoxy group-containing siloxane compound of the present invention will be explained in detail below.

Alkoxy group-containing siloxane compound of the first or second invention The alkoxy group-containing siloxane compound of the first or second invention is a compound having a fluorine atom-containing substituent at the α position and an alkoxy group at the ω position. .

The alkoxy group-containing siloxane compound of the first invention is a compound represented by the above formula (■): - which simultaneously has a terminal alkoxy group part and a substituent part containing a fluorine atom at the terminal in the molecule. be.

That is, in the formula (I), R5 is a substituent containing a fluorine atom at the terminal, and specifically, R5 is a pentafluorophenyl group, 3-(heptafluoroisopropoxy)propyl, 1.1, 2.2-tetrafluoroethyl group or the above formula (II).

Cb HeF 2b-c-1 (II) [In formula (TI), b is an integer from 3 to 18, and C represents an integer from 0 to 2b. It is possible to cite straight-chain or branched fluoroalkyl groups as shown below.

Here, the linear or branched fluoroalkyl group represented by the formula (II) has the following properties: ease of raw material availability, ease of synthesis, fluoroalkyl), water repellency, antifouling properties, The above formula (
b in II) must be 3 to 8, preferably 3 to 1o, co or 2b, preferably 4 to 6,
Especially 3.3.3-trifluoropropyl2. (,1~ridecafluoro-1,1,2,2-terahyal~rooctyl group or heptadecafluoro-1,1,2゜2-
Preferably, it is a tetrahydrodecyl group. If R5 in the formula (I) is one of these groups, for example, when the alkoxy group-containing siloxane compound of the present invention is used for the purpose of introducing fluorine into paints or synthetic resins, water repellency, stain resistance, # It can be made into paints and resins with excellent surface properties such as moldability, non-adhesiveness, oil repellency, low friction, and snow and water adhesion resistance.

Further, in the formula (1), xl is a substituent having an alkoxy group at the terminal, and specifically, as Xl, the substituent represented by the formula (■): or the formula (■); The following substituents can be mentioned.

More specifically, in the formula (m), R1 is the formula (XI); 0-(C)12CI+20)d(CH2Cl(CH:+
)O)e-RO(Xll) It is necessary that it be an alkoxy group-containing substituent.

Here, the alkoxy group-containing substituent represented by the formula (Xli) is selected from d and e in
or 0 to 3, preferably 0 to 2, and Ro must be a hydrocarbon group having 1 to 6 carbon atoms.

In the formula (m), R2, R3 and R4 are each independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, and X is a linear or branched divalent carbonized group having 2 to 12 carbon atoms. A hydrogen group or [In formula (7), R6 and R7 each independently represent a divalent hydrocarbon group having 0 to 3 carbon atoms. ] is a divalent substituent represented by Furthermore, in the substituent represented by the formula (IV), the formula (
R', R' and a in IV) are each represented by the above formula (
R l , R4 and a in III) have the same meanings.

In the present invention, the formula (III) or the formula (I
The alkoxy group-containing substituent represented by R1 in V) is
Preferably, it is a methoxy group, an ethoxy group, a phenoxy group or a 2-methoxyethoxy group. Specifically, both d and e in the formula (XI) are O, and R
o is a methyl group, the formula (m) or the formula (
R1 in IV) is a methoxy group, and R1 in the above formula (Xllll
), when both d and e are 0, and the above formula (m) or the above formula (IV)
R is an ethoxy group, and when d and e in the above (XI) are both O and RO is a phenyl group, R1 in the above formula (III) or the above formula (IV) is a phenoxy group. be. Furthermore, when the above formula % formula % and Ro is an ethyl group, R1 in the above formula (m) or the above formula (1'V) is a 2-methoxyel hexyl group.

When the alkoxy group in the alkoxy group substituent represented by R' in formula (m) or formula (IV) is one of these groups, the synthetic resin can be easily incorporated and its properties will not deteriorate over time. It is possible to obtain synthetic resin with less
Furthermore, the paint can be one that has excellent adhesion to the base material and also has the characteristics of fluorine.

In the alkoxy group-containing siloxane compound of the present invention represented by the above formula (I), J in the above formula (I> represents the number of units in the polydimethylsiloxane linear chain portion, and the range thereof is within the range of the alkoxy group-containing siloxane compound of the present invention. In order to obtain a clear expression of the functional properties of polydimethylsiloxane when the compound is introduced into synthetic resins or paints, and from the viewpoint of ease of introduction into synthetic resins or paints, as well as ease of synthesis. 1 to 2,000, preferably 4 to 700. For example, when the alkoxy group-containing siloxane compound of the present invention is used for the purpose of introducing it into a synthetic resin or paint, the type of the intended synthetic resin or paint, Although it is not possible to define it unconditionally as it differs depending on the required functional characteristics, etc., it is usually particularly preferable to use polydimethylsiloxane having a linear chain unit number of 700 or less. Ru.

In any case, in the alkoxy group-containing siloxane compound of the present invention, even if j in the above formula (I) is a high molecular weight polymer, it contains a terminal alkoxy group portion in the molecule and a fluorine atom at the terminal. At the same time, it is possible to easily obtain a very well-controlled molecular weight distribution with a polymer dispersity of 1.1 to 1.2. It has the advantage of being able to

And, the alkoxy group-containing siloxane compound of the first invention or the second invention having such excellent features,
For example, it can be manufactured by the method detailed below.

Manufacturing method An example of manufacturing the alkoxy group-containing siloxane compound of the first or second invention will be described below with reference to the reaction formula.

First, using a lithium syralate compound (AI) or the compound (AI) as an initiator, hexamethylcyclotrisiloxane, octamethylsifurobutrasiloxane, or a mixture of these two, which does not have active hydrogen, is injected. Intermediate obtained by rebink polymerization in a polar solvent (A2
) is chain-terminated with a monochlorosilane compound (A3) having an unsaturated double bond at the end to obtain a raw material siloxane compound (A4).

(In the formula, R5 has the same meaning as above, and ■ is 3
or 4, and wo is an integer from 2 to Z000.

) (AI) (A3) (A4) [However, in the formula, R2 and R3 have the same meanings as above, and Rl5 is a linear or branched divalent hydrocarbon group having 0 to 10 carbon atoms. Or the following formula (where R6
represents a divalent substituent represented by (R" is a simple bond or a methylene group), and W represents an integer of 1 to 20 [10]. Specific examples of the silal-1-compound (A1) include lithium (tridecafluoro-1,1,2
,2-tetrahydrocdyl)dimethylsilate,
Lithium pentafluorophenyldimethylsilal-1-
, lithium-3,3,3-trifluorobrobylsimethylsilate, lithium (heptadecafluoro 1.1,
2.2-tetrahy1-lodecyl)dimethylsilal-1
~, lithium-3-(heptafluoroisofurboxy)
Propyldimethylsilal-1~, lithium-1,1,2
, 2-tetrofluoroethylsimethylsilate, and the like.

Specific examples of the chlorosilane compound (A3) include vinyldimethylchlorosilane, allyldimethylchlorosilane, 5-hexenyldimethylchlorosilane, 7-octynyldimethylchlorosilane, 13-tetradecenyldimethylchlorosilane, vinylmethylphenylchlorosilane, Allylmethylphenylchlorosilane, 5-hexenylmethylphenylchlorosilane, 7-octynylmethylphenylchlorosilane, 13-tetradecenylmethylphenylchlorosilane, (m-ethynylphenyl)dimethylchlorosilane, (0-ethynylphenyl)dimethylchlorosilane , (p-ethynylphenyl)dimethylchlorosilane, ((m-ethynylphenyl)methyl)dimethylchlorosilane, ((0-ethynylphenyl)methyl)dimethylchlorosilane, ((p-ethynylphenyl)methyl)dimethylchlorosilane, (β(m -ethynylphenyl)ethyl)dimethylchlorosilane, (β(0-ethynylphenyl)ethyl)dimethylchlorosilane, (β(p=
Ethynylphenyl)ethyl)dimethylchlorosilane, vinyldiphenylchlorosilane, allyldiphenylchlorosilane, 5-hexenyldiphenylchlorosilane, 7-
Examples include octynylsiphenylchlorosilane and 13-tetrathecenylsiphenylchlorosilane.

In addition, the raw material siloxane compound (A4) is prepared by using a lithium syralate compound (A2B) or the compound (A26) as an initiator, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, or a mixture of these two. The compound (A 27) obtained by Libbink polymerization in a polar solvent having no active hydrogen group was converted into a monochlorosilane compound (A 27) having a fluorine atom and chalcolithic substituent (
A28) It can also be obtained by stopping the chain.

(A26) (A27) (A28) (A4) Specific examples of the lithium syralate compound (A25) include lithium vinyldimethylsilal-1, lithium allyldimethylsilal, and lithium 5-hexenylsilate. Methylsilal-1-, lithium 7-ocdenylsimethylsilal-tritium 13-detradecenylsimethylsilal-to, lithium vinylmethylphenylsilal-to, lithium allylmethylphenylsilal-to, lithium 5-
hexenylmethylphenylsilalto, lithium 7-octynylmethylphenylsilalto, lithium 13-tetradecenylmethylphenylsilal-1~. lithium(
m-ethynylphenyl)dimethylsilalt, lithium (p-ethylphenyl)dimethylsilalt, lithium ((m-ethynylphenyl)methyl)dimethylsilalt
Lithium ((0-ethynylphenyl)methyl)dimethylsilal-1~, Lithium ((p-ethynylphenyl)methyl)dimethylsilal-1~, Lithium (β(m-ethynylphenyl)ethyl)dimethylsilal-1~, Lithium (β(0-ethynylphenyl)ethyl)dimethylsilal-1-, lithium (β(p-ethynylphenyl)ethyl)dimethylsilalto, lithium vinylcyphenylsilarate, lithium allyldiphenylsilalto, lithium Examples include 5-hexenyldiphenylsilate, lithium 7-ocdenyldiphenylsilate, and lithium 13tetradecenyldiphenylsilate.

Specific examples of the monochlorosilane compound (A28) include (tridecafluoro-1,1,2゜2-te1-lahytrooctyl)dimethylchlorosilane, pentafluorophenyldimethylchlorosilane, 3,3-tri Fluoropropyldimethylchlorosilane, (heptadecafluoro-1゜1.2.2-tetrahyl-lobucyl)dimethylchlorosilane, 3-(heptafluoroisopropoxy)probyldimethylchlorosilane, 1゜2.2-
Examples include tetrafluoroethyldimethylchlorosilane.

For example, the alkoxy group-containing siloxane compound (A7) of the present invention can be obtained by adding the raw material siloxane compound (A4) obtained as described above and the compound represented by the following formula (6) through a hydrosilylation reaction. I can do it.

(A4) + 4a i R'+: +-n+ (6) Here, as the compound (A6), for example, dimethylmethoxysilane, chetylmethoxysilane, diphenylmethoxysilane, methyldimethoxysilane, ethyljethoxy Silane, phenyldimethoxysilane, trimethoxysilane, dimethylethoxysilane, shetylethoxysilane, siphenylethoxysilane, methyljethoxysilane, ethyljethoxysilane, phenyldiethoxysilane, triethoxysilane, dimethylphenoxysilane, diethylphenoxy Examples include silane, diphenylphenoxysilane, methylsiphenoxysilane, ethylcyphenoxysilane, phenyldiphenoxysilane, and triphenoxysilane.

In addition, a raw material siloxane compound (A2) obtained by chain-terminating the intermediate compound Th (A2) with dialkylchlorosilane
The alkoxy group-containing siloxane compound (A9) of the present invention can also be obtained by adding 5) and the compound (8) represented by the following formula through a hydrosilylation reaction.

(H8) (A9) Here, as the compound Th (A8), for example, vinyldimethylmethoxysilane, vinyldiethylmethoxysilane, vinyldiphenylmethoxysilane, vinylmethyldimethoxysilane, vinylethyldimethoxysilane, vinylphenyl methoxysilane, xysilane, vinyltrimethoxysilane, vinyldiethylethoxysilane, vinyldiethylethoxysilane, vinylsiphenyl-1-ff disilane, vinylmethylsilane, vinylethyljethoxysilane, vinylphenyldiethoxysilane, vinyl tri-1-1 Xysilane, vinyldimethylphenoxysilane, vinyldiethylphenoxysilane, vinyldiphenylphenoxysilane, vinylmethylcyphenoxysilane, vinylethylcyphenoxysilane, vinyltriphenoxysilane, allyldimethylmethoxysilane, allylethyljethoxysilane, allyldiphenyl Methoxysilane, allylmethyldimethoxysilane, allylethyldimethoxysilane, allyl phenyldimethoxysilane,
Allyltrimethoxysilane, allyldimethylethoxysilane, allyldiethylethoxysilane, allyldiphenylethoxysilane, allylmethyljethoxysilane, allylethyljethoxysilane, allylphenyldiethoxysilane, allyltriethoxysilane, allyldimethylphenoxysilane, allyl ethylphenoxysilane allylcyphenylphenoxysilane, allylmethylcyphenoxysilane, allylethylcyphenoxysilane, allylphenylcyphenoxysilane, allyltriphenoxysilane, (II, p-)styrylethyldimethylmethoxysilane, ( rp, p-) styrylethyl diethylmethoxysilane, (m, p-) styrylethyl diphenylmethoxysilane, (m, p-) styrylethylmethyl dimethoxysilane, (nl, p-) styrylethyl diethyl methoxysilane, (m , p-) styrylethyl phenyldimethoxysilane, (Il,p-)styrylethyltrimethoxysilane, (wr, p-)styrylethyl ethyljethoxysilane, (Il,p-)styrylethyldiethyl ethoxysilane, (m , p-) styrylethyl diphenylethoxysilane, (11, p-) styrylethylmethyljethoxysilane, (m, p-)
Styrylethylethyljethoxysilane, (m, p-)
Styrylethyl phenyldiethoxysilane, (n, p-
) styrylethyltriethoxysilane, (m,p-)styrylethyldimethylphenoxysilane, (m,p-)
Styrylethyldiethylphenoxysilane, (lIl,
p-) styrylethyldiphenylphenoxysilane,
(Il,p-)styrylethylmethyldiphenoxysilane, (m,p-)styrylethyl ethylsiphenoxysilane, (+i,p-)styrylethyl phenyldiethoxysilane, (m,p-)styrylethyl trif Examples include enoxysilane.

Furthermore, the compound of the first or second invention having a substituent represented by the above formula (III), in which X is a substituent represented by the above formula (Xlil), can also be produced by the following reaction. It comes.

(A41) (A42) (A 4:1) (A44) (A45) (A41i) (A45) + C sentence.

(A47) (A46) +R111 (A48) Furthermore, the present invention can also be produced by reacting the lithium syralate compound (AI) or the intermediate compound (A2) with a chlorosilane (AID) represented by the following formula. It is possible to obtain an inventive alkoxy-based siloxane compound (A11).

Here, the chlorosilane (AID) includes, for example, dimethylmethoxychlorosilane, diethylmethoxychlorosilane, diphenylmethoxychlorosilane, methyldimethoxychlorosilane, ethyldimethoxychlorosilane, phenyldimethoxychlorosilane, trimethoxychlorosilane, dimethylethoxychlorosilane, diethyl ethoxychlorosilane, diphenyl Ethoxychlorosilane, methyldimethoxychlorosilane, ethyljethoxychlorosilane, phenyldiethoxychlorosilane, triethoxychlorosilane, dimethylphenoxychlorosilane, diethylphenoxychlorosilane, diphenylphenoxychlorosilane, methyldiphenoxychlorosilane, ethylsiphenoxychlorosilane, phenyldiphenoxychlorosilane, Examples include I-rifenoxychlorosilane.

In the living polymerization, the polar solvent used is not particularly limited as long as it does not have an active hydrogen group, such as tetrahydrofuran, 1,4-dioxane,
Ethylene tallicol dimethyl ether, diethylene glycol dimethyl ether, dimethyl formamide, diethyl sulfoxide and the like can all be suitably used.

These may be used alone or in combination of two or more.

Among these, particularly preferred is tetrahydrofuran.

Note that if the solvent used has active hydrogen, the reaction will be inhibited, and if it is a nonpolar solvent, the reaction will hardly proceed.

The reaction temperature of the living polymerization is usually 0 to 50°C.
Preferably it is 15-25°C. Reaction a! degrees or 0'
If it is lower than C, the polymerization rate will be slow, so it is not practical. On the other hand, if the temperature exceeds 50°C, compounds with the same substituents at both ends may be produced, or compounds with the same substituents at both ends may be produced that are difficult to purify and separate, resulting in an extremely poor purity of the target compound. or the molecular weight distribution may become broader.

The reaction time of the living polymerization varies depending on the type of reaction solvent used and the reaction temperature, but it is usually preferable to stop the reaction when about 95% of the raw material cyclic siloxane is consumed. reaction temperature is 1
In the case of 5 to 20°C, 10 to 20 hours is appropriate. If the reaction time is made longer than necessary, the resulting alkoxy group-containing siloxane compound will have a wide molecular weight distribution.

If the number of dimethylsiloxane units is 2,000 or less (number average molecular weight is approximately 150,000 or less), the molecular weight can be controlled by adjusting the amount of lithium syralate as an initiator and hexamethylcyclotrisiloxane and/or This is easily possible depending on the amount and ratio of octamethylsiloxane. Moreover, even those having a higher number average molecular weight can be easily obtained by changing the living polymerization conditions.

Lithium silal-1 to be used as a polymerization initiator can be easily obtained, for example, by reacting a desired trialkylsilanol having an alkyl group with a lithium-based catalyst.

Examples of the lithium-based catalyst include metallic lithium,
Methyllithium, lithium hydroxide, lithium bititerite or the following formula: [wherein y represents an integer from O to 3, RR" and R"
each represents an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 12 atoms, a phenyl group, a pentafluorophenyl group, or a linear or branched fluoroalkyl group represented by the above formula (II). ,R”,R”
and R18 may be rotated or may be different from each other. ] Examples include lithium trialkylsilates shown in the following.

In producing the alkoxy group-containing siloxane compound of the present invention, polymerization initiators other than the lithium syralate, such as other alkali metal compounds such as sodium catalysts and potassium catalysts, may be used.
If these are used, the yield of the alkoxy group-containing siloxane compound obtained will be low, so they cannot be used preferably.

In addition, the catalyst that can be used in the hydrosilylation reaction is generally a complex compound of a metal element of Group 1 of the periodic table, and in particular, a complex of chloroplatinic acid or a complex of platinum or rhodium with various olefins. Compounds etc. are preferred. For example, when using chloroplatinic acid, the amount added is a catalytic amount I
A range of 6 mol to 1 x 10-' mol is preferred. l
If the amount exceeds 10-3 moles of X, the siloxane button may be cut by the catalyst and the catalyst cost may be reduced.
~ Kasamu. On the other hand, if IX is less than 10-6 mol, it will be susceptible to trace amounts of moisture, interfering substances, etc., and the reaction may not proceed smoothly. The reaction temperature is usually 50 to 150°C, preferably 80 to 120°C.
It is C. If the temperature is less than 50°C, the reaction may not proceed smoothly or the reaction time may become significantly longer.

On the other hand, if the temperature exceeds 150°C, siloxane chains may be cut or side reactions may occur due to alkoxy group moieties.

For example, the compound obtained in the above manner is a siloxane compound having a fluorine atom at the α-position and an alkoxy group at the ω-position. When used for this purpose, it can improve interfacial properties such as water repellency, #-shape, fat dyeability, and oil repellency, heat resistance, water resistance, weather resistance, rigid chemical resistance, and low abrasion properties without causing deterioration of other physical properties. It is possible to significantly improve the target properties.

The alkoxy group-containing siloxane compound of the third or fourth invention The alkoxy group-containing siloxane compound of the third or fourth invention comprises a J-substituted group containing a fluorine atom at the α-position or α′-position (
It is a siloxane compound having an alkoxy group at the ω position.

The alkoxy group-containing siloxane compound of the third invention is a compound represented by the formula (V): - which simultaneously has a terminal alkoxy group part and a substituent part containing a fluorine atom at the terminal in the molecule. be.

That is, in the formula (V), at least R'' among R8 and R'' must be a substituent containing a fluorine atom at the terminal, and specifically, a pentafluorophenyl group, 3 -(heptafluoroisopropoxy)propyl group, ■.

1.2.2-de1herafluoroethyls (and a linear or branched fluoroalkyl group represented by the above formula (II)).

In the present invention, at least R of Ro and R9
If the substituent contains a fluorine atom at the o terminal, R9
does not have to be a substituent containing a fluorine atom at the terminal, but at least an alkyl group having 1 to 6 carbon atoms, a phenyl group, a pentafluorophenyl group, a 3-(heptafluoroisopropoxy)propyl group, 1, It must be either a 1,2,2-tetrafluoroethyl group or a linear or branched fluoroalkyl group represented by the above formula (II).

More specifically, in the formula (V), Ro is a pentafluorophenyl group, a 3,3.3-1 helifluoropropyl group, a tridecafluoro-1°1.2.2-tetrahydrooctyl group, 3(hebutafluoroisopropoxy)propyl group, 1,1,2,2-tetrafluoroethyl group or heptadecafluoro-1,1,2,2-tetrahydrodecyl group, R'' or carbon atom number 1 -6 alkyl group, phenyl group, pentafluorophenyl group,
3,3.3-trifluoropropyl group, tridecafluoro-1,l, 2.2-tetrahydrooctyl group, 3-
(heptafluoroisopropoxy)propyl group, 1. l
, 2,2-tetrafluoroethyl group or heptadecafluoro-1°1.2.2-tetrahydrodecyl group. R a in the formula (V),
When R9 is one of these groups, for example, when the alkoxy group-containing siloxane compound of the present invention is used for the purpose of introducing fluorine into paints or synthetic resins, water repellency, stain resistance, mold releasability, and non-adhesive properties are improved. It is possible to create paints with excellent surface properties such as oil repellency, low friction, and resistance to snow and icing.

In addition, in the formula (V), X2 is a substituent having an alkoxy group at the terminal, and specifically, as x2,
The above formula (VT) (In the formula (Vl), R', R2, R' and a each represent the same meaning as in the above formula (m), and X is a linear or branched chain having 2 to 12 carbon atoms. A divalent hydrocarbon group or a divalent substituent represented by the above formula (II) or the above formula (■): [In the formula (■), R1 has the same meaning as in the above formula (I) .

] represents the substituent shown. ) The ri substituent shown can also be mentioned.

More specifically, in the formula (Vl), R1 is the formula (Xlll); 0-(CH2Ct+20)d(c112cH(CI43
)O)e-R00! II) It is necessary that the substituent is an alkoxy group-containing substituent as shown in the following.

Here, the alkoxy group-containing substituent represented by the above formula (XI) is selected from d and e in the above formula (■) from the viewpoint of easy availability of raw materials, ease of synthesis, and manufacturing cost.
~3, preferably O~2, and Ro has 1 to 1 carbon atoms
6 hydrocarbon group is required.

In the present invention, the formula (Vl) or the formula (■)
The alkoxy group-containing substituent represented by R1 is preferably a methoxy group, an ethoxy group, a phenoxy group or a 2-methoxyethoxy group.

When the alkoxy group in the alkoxy group-containing substituent represented by R1 in the formula (VI) or the formula (■) is one of these groups, it is easy to incorporate into the synthetic resin, and it is easy to incorporate into the synthetic resin. It is possible to obtain a synthetic resin with less deterioration, and it is also possible to produce a coating material that has excellent adhesion to the substrate and has the characteristics of fluorine.

In the alkoxy group-containing siloxane compound of the present invention represented by the above formula (V), k and the letter in the above formula (V) each represent the number of units in the polydimethylsiloxane linear chain portion, and the range thereof is defined by the alkoxy group-containing siloxane compound of the present invention. In order to clearly express the functional properties of polydimethylsiloxane when a group-containing siloxane compound is introduced into a synthetic resin or paint, and from the viewpoint of ease of introduction into the synthetic resin or paint, as well as ease of synthesis. 1~2.000
, preferably 4-700. For example, when using the alkoxy-based siloxane compound of the present invention for the purpose of introducing it into synthetic resins or paints, it may vary depending on the type of synthetic resin or paint, the required functional characteristics, etc. Although it is not possible to specify the number of polydimethylsiloxane linear chain units, polydimethylsiloxane having 700 or less units can be particularly preferably used.

In any case, in the alkoxy group-containing siloxane compound of the present invention, even if k and the letter in the above formula (V) are high molecular weight polymers, there is a terminal alkoxy group portion in the molecule and a fluorine atom at the terminal. There is no difference in that the molecular weight distribution of the polymer is easily controlled, and the molecular weight distribution is 1.1 to 1.2. It has the feature of being able to say things.

And, the third or fourth product with such excellent features
The alkoxy group-containing siloxane compound of the invention can be produced, for example, by the method detailed below.

Manufacturing method An example of manufacturing the alkoxy-based siloxane compound of the third or fourth invention will be described below with reference to the reaction formula.

First, using one or two of the above lithium syralate compounds (Al) as an initiator, hexamethylcyclotrisiloxane, octamethylcyclotetrahexane, or a mixture of these two is injected into a polar compound without active hydrogen. The intermediate compound (A2) is produced by living polymerization in a solvent.
get.

Next, one or two of the lithium syralate compound (Al) and the intermediate compound (A2) and a dichlorosilane compound (A12) having an unsaturated double bond at the terminal are combined.
) by reacting with the raw material siloxane compound (
A13) is obtained.

(AI) (A2) (Tatashi, in the formula, R5, v and wo Each It has the same meaning as above.

(A12) [In the formula, R2, RI5 and W each represent the same meaning as above, and R5' is an alkyl group having 1 to 6 carbon atoms, a phenyl group, a pentafluorophenyl group, or a group of the above formula (n) represents a linear or branched fluoroalkyl group, and W' represents an integer of 1 to 2,000. ] Here, the dichlorosilane compound (A 12
), for example, vinylmethyldichlorosilane, allylmethyldichlorosilane, 5-hexenylmethyldichlorosilane, 7-octynylmethylcyclosilane, 13
-detradecenylmethylcyclosilane, vinylphenyldichlorosilane, (m-ethynylphenyl)methyldichlorosilane, (0-ethynylphenyl>methyldichlorosilane, (P-ethynylphenyl)methyldichlorosilane, (m-ethynylphenyl) ) methyl)dichlorosilane, ((〇methynylphenyl)methyl)methyldichlorosilane, ((p-ethynylphenyl)methyl)methyldichlorosilane, (β(m-ethynylphenyl)ethyl)methyldichlorosilane, (β(0 -ethynylphenyl)ethyl)methyldichlorosilane, (β(p-ethynylphenyl)ethyl)methyldichlorosilane, allyl phenyldichlorosilane, 5-hexenylphenyldichlorosilane, 7-octynylphenylcyclosilane, 13
-Tetradecenylphenyldichlorosilane and the like.

Further, when one or two of the lithium silalue-1 to compound (Al) and the intermediate compound (A2) are reacted with an alkyldichlorosilane, a raw material siloxane compound (A14) can be obtained.

(A14) The alkoxy group-containing siloxane compound (Al5) of the present invention is obtained by adding the thus obtained raw material compound (Al: ]) and the compound (A6) represented by the following formula through a hydrosilylation reaction. I can do it.

R1,.

(A6) Similarly, the alkoxy group-containing siloxane compound (AI6) of the present invention can be obtained by adding the raw material siloxane compound (A14) and the compound represented by the following formula (H8) through a hydrosilylation reaction. can.

4a R1<3 (A8) (A16) Furthermore, the compound (A50) of the third or fourth invention having a substituent represented by the formula (Vl) where X is a substituent represented by the above formula (yIj) is , the above compound (A41), (A
42) and (A4:l), in the process of producing (A48>), R'' instead of (A41)
It can also be produced by using SiCM z (A 49).

(A50) Furthermore, when one or two of the lithium syralate compound Th(Al) and the intermediate compound (A2) are reacted with a dichlorosilane compound (Al7) represented by the following formula, 1 gJ of an alkoxy-based siloxane compound (AI8) can be obtained.

(AI) andlor + (4zsi(R')2(A2) (A17) (A18) Here, the dichlorosilane compound (A17) includes, for example, dimethoxydichlorosilane, dimethoxydichlorosilane, diphenoxydichlorosilane, etc. Can be mentioned.

In addition, the nonpolar solvent used in the Ribbink polymerization, the reaction temperature, the reaction time, the control of the molecular weight of the obtained alkoxy group siloxane compound, the lithium syralate used as a polymerization initiator, and the control of the reaction temperature and reaction time, the lithium syralate used as a polymerization initiator, and the hydrosilylation reaction. The catalyst and the like are the same as those used in the production of the alkoxy group-containing siloxane compound of the first or second invention.

For example, the compound obtained as described above is a siloxane compound having a fluorine atom-containing substituent at the α-position or α'-position and an alkoxy group at the ω-position. When used as a material, it can improve interfacial properties such as water repellency, mold releasability, stain resistance, and oil repellency, heat resistance, water resistance, weather resistance, chemical resistance, and low abrasion without causing a decrease in other physical properties. It is possible to significantly improve desired characteristics such as gender.

Alkoxy group-containing siloxane compound of the fifth or sixth invention The alkoxy group-containing siloxane compound of the fifth or sixth invention has a fluorine atom-containing substituent at the α-position, α′-position or α″-position and at the ω-position. It is a siloxane compound with an alkoxy group.

The alkoxy group-containing siloxane compound of the fifth invention is a compound represented by the above formula (■), which simultaneously has a terminal alkoxy group part and a substituent part containing a fluorine atom at the terminal in the molecule. .

That is, in the above formula (V[), R10 must be a substituent containing a fluorine atom at the terminal, and specifically, a pentafluorophenyl group, a 3-(heptafluoroisopropoxy)propyl group, 1,1,2.2-
Examples include a tetrafluoroethyl group or a linear or branched fluoroalkyl group represented by the above formula (II).

In the present invention, among the substituents represented by R10, R'' and R12, if at least R10 has a substituent containing a fluorine atom at the terminal, R'' and R12 are the substituents containing a fluorine atom at the terminal. Although not necessary, at least an alkyl group having 1 to 6 carbon atoms, a phenyl group,
Is it a pentafluorophenyl group, 3-(heptafluoroisopropoxy)propyl group, 1, 1, 2,2-tetrafluoroethyl group, or a linear or branched fluoroalkyl group represented by the above formula (II)? is necessary.

More specifically, R l fl in the formula (■)
is a pentafluorophenyl group, 3,3.3-trifluoropropyl group, 1-ridecafluoro-1゜1.2.2
-tetrahytrooctyl group, 3(heptafluoroisopropoxy)propyl group, 1,1,2.2-tetrafluoroethyl group or heptadecafluoro-1,1,2.
2-de-l-rahi 1-mouth decylno, (where R'' and R+ 2 are an alkyl group having 1 to 6 carbon atoms, a phenyl group, a pentafluorophenyl group, a 3,3.3-trifluoropropyl group , tridecafluoro-1,1,2゜2
-tetrahy-1-looctyl group, 3-(heptafluoroisopropoxy)propyl (,1,1).

Preferably, it is a 2,2-tetrafluoroethyl group or a heptadecafluoro-1,1,2,2-tetrahydrodecyl group.

When Rlo, R'', and R12 in the formula (■) are these groups, for example, when the alkoxy group-containing siloxane compound of the present invention is used for the purpose of introducing fluorine into paints or synthetic resins, water repellency, It can be made into paints and synthetic resins with excellent surface properties such as stain resistance, mold releasability, non-adhesion, oil repellency, low friction, and resistance to snow and icing.

In addition, in the formula (■), X3 is a substituent having an alkoxy group at the terminal, and specifically, as x3, the formula (■): [In formula (IX), R' , R' , X and a have the same meaning as in the above formula (m). ] or the above formula (X) [In formula (X), R1 has the same meaning as above. ] The substituents shown can be listed.

More specifically, in the formula (IX), R1 is the formula (■) 0-(C11°C1120)a(Ct12CIl(Cl
13) O) e-R' (XIl[) It is necessary that the substituent is an alkoxy group-containing substituent.

Here, the alkoxy group-containing substituent represented by the above formula (■) is selected from d and e in the above formula (XI) from the viewpoint of easy availability of raw materials, ease of synthesis, and manufacturing cost.
~3, preferably O~2, and Ro must be a hydrocarbon group having 1 to 6 carbon atoms.

In the present invention, the formula (IX) or the formula (X)
The alkoxy group-containing substituent represented by R1 is preferably a methoxy group, an ethoxy group, a phenoxy group or a 2-methoxyethoxy group.

When the alkoxy group in the alkoxy group-containing substituent represented by R1 in the formula (IX) or the formula (X) is one of these groups, it can be easily incorporated into a synthetic resin.
Moreover, it is possible to obtain a synthetic resin whose properties are less likely to deteriorate over time, and it is also possible to obtain a coating material that has excellent adhesion to a substrate and has the characteristics of fluorine.

In the alkoxy group-containing siloxane compound of the present invention represented by the above formula (■), m, n and p in the above formula (■) each represent the number of units in the polydimethylsiloxane linear chain portion, and the range thereof is defined by the present invention. When the alkoxy group-containing siloxane compound is introduced into synthetic resins or paints, for example, in order to obtain clear expression of the functional properties possessed by polydimethylsiloxane, ease of introduction into synthetic resins or paints, and ease of synthesis. l~2.0 from the point of
00, preferably 4-700. For example, when using the alkoxy group-containing siloxane compound of the present invention for the purpose of introducing it into synthetic resins or paints, there are no general rules as it varies depending on the type of synthetic resin or paint, the required functional characteristics, etc. Although it is not possible to
The following can be particularly preferably used.

In any case, in the alkoxy group-containing siloxane compound of the present invention, m, n and p in the formula (■)
Even if the polymer has a large molecular weight, it still has a terminal alkoxy group and a substituent containing a fluorine atom at the end in the molecule, and the degree of dispersion of the polymer is It has the advantage that a very well-controlled molecular weight distribution of 1.1 to 1.2 can be easily obtained.

And, the fifth or sixth one has such excellent features.
The alkoxy group-containing siloxane compound of the invention can be produced, for example, by the method detailed below.

Manufacturing method An example of manufacturing the alkoxy group-containing siloxane compound of the fifth or sixth invention will be described below with reference to the reaction formula.

First, using one or more of the above lithium silate compounds (Al) as an initiator, hexamethylcyclotrisiloxane or octamethylcyclotrisiloxane or a mixture of these two is injected with active hydrogen. The intermediate compound (
A2) is obtained.

Next, one or more of the lithium silal-1 to compound (Al) and the intermediate compound (A2), and the 1-lichlorosilane compound (A19) having an unsaturated double bond at the terminal. By reacting with, a raw material siloxane compound (A20) is obtained.

(In the formula, R5, v and Wo each have the same meaning as above.) (A1) andlor + C13Si-R15C1l=C
II2(A2) (A19) (A20) [In the formula, R5, R15, and W each have the same meaning as above, and R'' and R'' each have 1 to 1 carbon atoms. 6 alkyl group, phenyl group, pentafluorophenyl group, 3-(heptafluoropropoxy)
represents a propyl group, a 1°1.2.2-tetrafluoroethyl group, or a linear or branched fluoroalkyl group represented by the above formula (H), and w' and w'' are each an integer of 1 to 2000. ] Here, as the trichlorosilane compound (A19), for example, vinyltrichlorosilane, allyl 1-helichlorosilane, 5-hexenyl 1-lichlorosilane, 7-
Octynyltrichlorosilane, 13-tetradecenyl
~licyclosilane, (methynylphenyl)trichlorosilane, (0-ethynylphenyl)1~lychlorosilane, (p-ethynylphenyl)trichlorosilane, ((
m-ethynylphenyl)methyl)trichlorosilane ((
0-ethynylphenyl)methyl)trichlorosilane, (
(p-ethynylphenyl)methyl)trichlorosilane,
Examples include (β(m-ethynylphenyl)ethyl)trichlorosilane, (β(0-ethynylphenyl)ethyl)trichlorosilane, and (β(p-ethynylphenyl)ethyl)1-lichlorosilane.

Further, by reacting one or more of the lithium syralate compound (Al) and the intermediate compound (A2) with trichlorosilane, a raw material siloxane compound (A21) can be obtained.

(A2],) The alkoxy group-containing siloxane compound of the present invention ¥5 (A22 ) can be obtained.

(A6) (A22) Similarly, by adding the raw material siloxane compound (A21) and the compound (H8) represented by the following formula through a hydrosilylation reaction, the alkoxy base compound of the present invention can be obtained.
A siloxane compound (A23) can be obtained.

4a 11'.

(A8) (A2:I) In addition, X is a substituent represented by the formula (W) above (I
The compound (A52) of the fifth or sixth invention having a substituent represented by X) is the aforementioned compound (A41), (A 4
2) and in the process of producing (A48) starting from (A43), 5iC1 instead of (A41)
:+ It can also be produced by using (A51).

(A52) Furthermore, when one or two of the lithium syralate compound (Al) and the intermediate compound (A2) are reacted with a trichlorosilane compound (A24) represented by the following formula, the present invention An alkoxy group-combined siloxane compound (A25) can be obtained.

(Al) andlor + C1zsi-R' (A2) (A24) (A25) Here, examples of the trichlorosilane compound (A24) include methoxytrichlorosilane, ethoxytrichlorosilane, and phenoxytrichlorosilane.

In addition, the nonpolar solvent used in the living polymerization, the reaction temperature, the reaction time, the control of the molecular weight of the alkoxy group-containing siloxane compound obtained, and the lithium silal-1 used as a polymerization initiator, used in the hydrosilylation reaction. The catalyst and the like are the same as those used in the production of the alkoxy group-containing siloxane compound of the first or second invention.

The analogy is as follows (↓1)
It is a siloxane compound that has a fluorine atom-containing substituent at the α', α', or α'' positions and an alkoxy group at the ω position. For example, when used to modify synthetic resins or as a raw material for coating compositions, it improves other physical properties. interface properties such as water repellency, mold releasability, stain resistance, oil repellency, heat resistance, water resistance,
Target properties such as weather resistance, chemical resistance, and low abrasion properties can be significantly improved.

The alkoxy group-containing siloxane compound of the '1st or 8th invention' The alkoxy group-containing siloxane compound of the 7th or 8th invention has a fluorine atom-containing substituent at the α position and at the ω and ω' positions. It is a siloxane compound containing an alkoxy group.

The alkoxy group-containing siloxane compound of the seventh invention is a compound represented by the above formula (XI), which simultaneously has a terminal alkoxy() and a substituent containing a fluorine atom at the terminal in the molecule. be.

That is, in the above formula (X[), the substituent represented by R13 must be a substituent containing a fluorine atom at the terminal, and specifically, pentafluorophenyl group, 3-(heptafluoropropoxy ) propyl group, 1
．． l, 2,2-tetrafluoroethyl group or the above formula (
The linear or branched fluoroalkyl group represented by II) can be mentioned.

Furthermore, in the formula (X[), the substituent represented by R'' must be an alkyl group having 1 to 4 carbon atoms or a phenyl group.

More specifically, R” in the above formula (deposit) is 3,
3.3-trifluoropropyl group, tridecafluoro-
1,1,2,2-tetrahydrooctyl group, 3-(heptafluoroisopropoxy)propyl group, 1,1,2
．． 2-tetrafluoroethyl group or heptadecafluoro-1,1.

2.2-tetrahydrodecyl group is preferred. If R13 in the formula (X[) is one of these groups, for example, when the alkoxy group-containing siloxane compound of the present invention is used for the purpose of introducing fluorine into paints or synthetic resins, water repellency, antifouling properties, Mold releasability, non-adhesion, oil repellency,
It is possible to create paints with excellent surface properties such as low friction and resistance to snow and icing.

Further, in the formula (XI), X 6 and X 7 are substituents having an alkoxy group at the end, and specifically, x6. As x', the above formula (■>: [Formula (m) Φ, R
', R2, R3, R', a and X each have the same meaning as above. represents the substituent shown. ) The substituents shown can be listed.

More specifically, in the formula (m), R1 is the formula (Xll); 0-(C11zC11□0)d(C112Cll(C1
h)0)e-80(X [[l ) It is necessary that the substituent is an alkoxy group-containing substituent.

Here, an alkoxy group represented by the above formula (Xllll).

(Resultant displacement fire is calculated from d and e in the above formula (XtO) or O to 31, preferably from 0 to 2, from the viewpoints of raw material acquisition, synthesis, and manufacturing cost. Yes, RO
is a hydrocarbon with 1 to 6 carbon atoms! , (it is necessary to be.

In the present invention, the alkoxy group-containing substituent represented by R' in the formula (m) is preferably a methoxy group, a 1-oxy group, a phenoxy group, or a 2-methoxy ethoxy group.

When the alkoxy group in the alkoxy group-containing substituent represented by R1 in the formula (m) is one of these groups, a synthetic resin can be easily incorporated and the properties of the synthetic resin are less deteriorated. In addition, it is possible to make a paint that has excellent adhesion to the base material and has the characteristics of fluorine.

In the alkoxy group-containing siloxane compound of the present invention represented by the formula (X When an alkoxy group-containing siloxane compound is introduced into a synthetic resin or paint, for example, the purpose is to clearly express the functional properties of polydimethylsiloxane, and to improve the ease of introduction into the synthetic resin or paint, as well as the ease of synthesis. 1-2 from the point, [
]On, preferably 4 to 700. For example, when the alkoxy group-containing siloxane compound of the present invention is used for the purpose of introducing it into synthetic resins or paints, it may vary depending on the type of the target synthetic resin or paint, the required functional characteristics, etc. Although it cannot be specified, usually
The number of units 1 to 7 in the polydimethylsiloxane linear chain part
00 or less can be particularly preferably used.

In any case, in the alkoxy group-containing siloxane compound of the present invention, even if q and r in the formula (XI) are high molecular weight polymers, There is no difference in the fact that the fluorine atom-containing substituent part and the fluorine atom-containing substituent moiety are simultaneously treated, and it is easy to easily control the molecular weight distribution such that the dispersity of the polymer is 1.1 to 1.2. It has the advantage of being able to be used in a variety of ways.

And the 7th or 8th point that shows these excellent features.
The alkoxy group-containing siloxane compound of the invention can be produced, for example, by the method detailed below.

Manufacturing method An example of manufacturing the alkoxy-based siloxane compound of the seventh or eighth invention will be described below with reference to the reaction formula.

First, using one or two of the lithium syralate compounds (A26) as an initiator, a polar solvent without active hydrogen such as hexamethylcyclotrisiloxane, octamethylcyclotetrahexane, or a mixture of these two types is used as an initiator. The intermediate compound (A 2
7) is obtained.

Next, one or two of the lithium syralate compound (A26) and intermediate compound (A27) and a dichlorosilane compound having a fluorine atom-containing substituent (A 2
9) to obtain a raw material siloxane compound (A 30).

(A26) (A26) RI4 andlor + C statement 2Si (A27) R declaration 3 (A29) (A30) (In the formula, R2, R3, a + 3, R'', RI5, Vw
, q and r each have the same meaning as above. ) Here, as the dichlorosilane compound (A29), for example, (tridecafluoro-1,1).

2.2-Tetrahydrooctyl)methyldichlorosilane, (tridecafluoro-1,1,2゜2-tetrahydrooctyl)phenylcyfucrosilane, pentafluorophenylmethyldichlorosilane, 3,3.3-1-
Lifluoropropylmethyldichlorosilane, (heptadecafluoro-1°1.1.2-tetrahydrodecyl)
Methyldichlorosilane, 3-(heptafluoroisopropoxy)propylmethyldichlorosilane, 1,1°2.
Examples include 2-te1helafluoroethylmethyldichlorosilane.

The raw material siloxane compound (A30
) and the compound Th(A6) represented by the following formula through a hydrosilylation reaction, the alkoxy group-containing siloxane compound <A31> of the present invention can be obtained.

R'a (A:lO) + 2 It-8i"'+1-
a) (F6) (A31) In addition, the nonpolar solvent 1 used in the living polymerization, the reaction temperature, the reaction waiting time, the control of the molecular weight of the alkoxy group-containing siloxane compound obtained, and the use as a polymerization initiator. The tium syralate, the catalyst that can be used in the hydrosilylation reaction, etc. are the same as in the production of the alkoxy group-containing siloxane compound of the first or second invention.

Furthermore, the compound (A 54) of the seventh or eighth invention having a substituent represented by X or the substituent (III) represented by the formula (W) is the compound (A 41) or (A 42) of the seventh or eighth invention.
) and (A4:I), it can also be produced by using the following siloxane compound (A5:I) in place of (A45).

(A54) For example, the compound obtained in the above manner is a siloxane compound having a fluorine atom and a substituent at the α position and an alkoxy group at the ω and ω′ positions. When used as raw materials for products, it improves interfacial properties such as water repellency, mold release, stain resistance, oil repellency, heat resistance, water resistance, weather resistance, chemical resistance, and low abrasion without causing a decrease in other physical properties. It can significantly improve desired characteristics such as sex.

Alkoxy group-containing siloxane compound of the ninth or tenth invention The alkoxy group-containing siloxane compound of the ninth or tenth invention has a fluorine atom-containing substituent at the α position and an alkoxy group at the ω, ω′, and ω″ positions. It is a siloxane compound having a group, (.

The alkoxy group-containing siloxane compound of the ninth invention is represented by the above formula (X[I); It is a compound that corresponds to

That is, in the above formula (Xll), the substituent represented by R'3 must be a substituent containing a fluorine atom at the terminal, and specifically, a pentafluorophenyl group, 3-(heptafluoro Examples include a (isopropoxy)propyl group, a l,1,2,2-tetrafluoroethyl group, and a linear or branched fluoroalkyl group represented by the above formula (II).

More specifically, R13 in the formula (X[) is
3,3.3-1-lifluoropropyl group, tridecafluoro-1,1,2,2-tetrahydrooctyl group, 3
-(heptafluoroisopropoxy)propyl group, l,
Preferably, it is a 1,122-tetrafluoroethyl group or a heptadecafluoro-1,1°2.2-te1-rahytrodecyl group. When R'' in the above formula (Kari) or these groups, for example, when the alkoxy group-containing siloxane compound of the present invention is used for the purpose of introducing fluorine into paints or synthetic resins, water repellency, stain resistance, It can be made into a paint with superior surface properties such as mold releasability, non-adhesiveness, oil repellency, low friction, and resistance to snow and icing.

In addition, in the above formula (double), XI'1. X9X1° is a substituent having an alkoxy group at the end, specifically xo, x9. x"0, the formula (m) [in formula (m), R', R2, R', R', a and
each has the same meaning as above. ] The substituents shown can be listed.

More specifically, in the formula (m), R1 is the formula (Xll); 0-(CI+zCII□0)d(CI+2CH(CH:
+)O)e-R' (X1ll) It is necessary that the substituent is an alkoxy group-containing substituent.

Here, the alkoxy fund I1 represented by the above formula (XI)
In terms of ease of obtaining raw materials, ease of synthesis, and manufacturing cost, the substitution grave has 0 to 3, preferably 0 to 2, of d and e in the formula (Xlll), and RO has 1 carbon atom. ~6 hydrocarbon groups are required.

In the present invention, the alkoxy group-containing substituent represented by R1 in the formula (m) is a methoxy group, an ethoxy group,
Preferably, it is a phenoxy group or a 2-methoxyethoxy group.

When the alkoxy group in the alkoxy group-containing substituent represented by R1 in the formula (III) is one of these groups, it is possible to obtain a synthetic resin that is easy to incorporate and whose properties are less likely to deteriorate over time. In addition, it is possible to use a paint that has excellent adhesion to the base material and has the characteristics of fluorine.

In the alkoxy group-containing siloxane compound of the present invention represented by the formula (X[I), s, t, and U in the formula (Xll) each represent the number of units in the polysimethylsiloxane linear chain portion, and the range thereof is as follows: When the alkoxy group-containing siloxane compound of the present invention is introduced into, for example, a synthetic resin or paint, it is possible to clearly express the functional properties of polydimethylsiloxane, and to facilitate its introduction into the synthetic resin or paint #1. Further, from the viewpoint of ease of synthesis, it is 1 to 2,000, preferably 4 to 700. For example, the alkoxy group-containing siloxane compound of the present invention,
When used for the purpose of introducing into synthetic resins and paints,
Although it is not possible to make a general rule because it varies depending on the type of synthetic resin or paint being used, the required functional properties, etc., it is usually the case that the linear chain unit of polydimethylsiloxane is
Those in which the number of ~700 or less can be particularly preferably used.

In any case, in the alkoxy group-containing siloxane compound of the present invention, even if s, t, and U in the formula (XII) have a large polymer, the terminal alkoxy group and the terminal alkoxy group in the molecule are There is no difference in that the polymer has a substituent moiety containing a fluorine atom at the same time, and it is easy to easily control the molecular weight distribution such that the dispersity of the polymer is 1.1 to 1.2. It has the advantage that it can be obtained easily.

And the ninth or first one has such excellent features.
The alkoxy group-containing siloxane compound of the invention () can be produced, for example, by the method detailed below.

Manufacturing method An example of manufacturing the alkoxy group-containing siloxane compound of the ninth or tenth invention will be described below with reference to the reaction formula.

First, using one or more of the above lithium syralate compounds (A26) as an initiator, hexamethylcyclotrisiloxane, octamethylcyclotetrahexane, or a mixture of these two is injected into a polar compound that does not have active hydrogen. The intermediate compound IeJ is obtained by living polymerization in a solvent.
(A27) is obtained.

Next, one or more of the lithium syralate compound (A26) and the intermediate compound (A27) are reacted with a trichlorosilane compound containing a fluorine atom-containing substituent (A32). As a result, raw material siloxane compound (A:13)Q is obtained.

(A25) (A26) andlor + C1zsi -R'''(A2
7) (A 32) (A 33) (In the formula, R2, R3, RI3, R'', ■, W, S, t and U each represent the same meaning as above.) Here, as, 1 .2.20 Silane, Ran, 3°Rorosilane The above trichlorosilane compound (A 32) For example, (Tritecafluoro I).

3.3-1-lifluoropropyl trichloride (heptadecafluoro-1,1).

1.2-tetrahy)herodecyl)trichlorosilane,
3-(heptafluoroisopropoxy)propyl 1~lichlorosilane, l, l, 2.2-de1~lafluoro1~
Examples include lychlorosilane.

The raw material siloxane compound (A33
The alkoxy group-containing siloxane compound (A:14) of the present invention can be obtained by adding 14 to the compound (A6) represented by the following formula through a hydrosilylation reaction.

(A6) (A34) In addition, the control of the non-mercury solvent used in the Ribbink polymerization, the reaction temperature, the reaction time, the molecular weight of the resulting alkoxy group-containing siloxane compound, and the hydrogen silal used as a polymerization initiator. The catalysts and the like that can be used in the hydrosilylation reaction are the same as those used in the production of the alkoxy group-containing siloxane compound of the first or second invention.

Furthermore, the compound of the ninth or tenth invention (
A56) is a process for producing (A48) starting from the above compounds (A41), (A42) and (A4:I), in which the following siloxane compound (A55) is substituted for (A45). It can also be manufactured by using

(Raiko, hereafter in the margin) (A 55) (A 56) For example, the compound obtained in the following manner has a fluorine atom-containing substituent at the α position and ω, ω′, ω″
It is a siloxane compound that has an alkoxy group in the position, and when used for example to modify synthetic resins or as a raw material for coating compositions,
Significantly improves target properties such as interfacial properties such as water repellency, mold releasability, stain resistance, and oil repellency, heat resistance, water resistance, weather resistance, chemical resistance, and low abrasion without causing deterioration of other physical properties. It can be improved.

In addition, in the alkoxy group-containing siloxane compound of the first or second invention, the number of siloxane chain trees is one tree based on the alkoxy group, and the number of siloxane chain trees is one tree based on the fluorine atom-containing substituent. be. In contrast, in the alkoxy group-containing siloxane compound of the third or fourth invention, the number of siloxane chains based on the alkoxy group is 2, and in the alkoxy group-containing siloxane compound of the fifth or sixth invention II, represents an alkoxy group; x
The number of siloxane chains in the ti type is 3. Also,
In the alkoxy-based siloxane compound of the seventh or eighth invention, the number of siloxane chains is 2 based on the fluorine atom-containing substituent, and in the alkoxy group-containing siloxane compound of the ninth or tenth invention, , the number of siloxane chain trees based on the fluorine atom-containing substituent is three.

Because of these structural differences, the alkoxy group-containing siloxane compound of the present invention should be selected to have the optimal structure, depending on the properties of the desired synthetic resin or paint and the desired functional properties. For example, it is possible to impart desired functional properties to synthetic resins and paints.

Also, the number of siloxane chains based on the alkoxy group or 2
an alkoxy group-containing siloxane compound according to the third or fourth invention, which is a book, an alkoxy group-containing siloxane compound according to the fifth or sixth invention, in which the number of siloxane chains is 3 based on the alkoxy group, a fluorine atom-containing substituent The alkoxy group-containing siloxane compound of the seventh or eighth invention, which has a base type of siloxane chains of two, and the ninth or tenth invention, which has a siloxane button of three based on the fluorine atom-containing substituent. For example, when the alkoxy group-containing siloxane compound of the present invention is used for the purpose of improving the properties of synthetic resins or paints, the length of each siloxane chain in the alkoxy group-containing siloxane compound of the present invention is usually determined by the length of each siloxane chain. Although the lengths are preferably the same, depending on the purpose, different siloxane chain lengths may be set.

Furthermore, in the alkoxy group-containing siloxane compound of the third invention, R8 and R9 in the formula (V),
In the alkoxy group-containing siloxane compound of the seventh invention, different substituents may be introduced into the substituents represented by R10R'' and R12 in the formula (■), or the alkoxy group-containing siloxane compound of the seventh invention In the containing siloxane compound, x4 and x in the formula (X+)
5 In the alkoxy group-containing siloxane compound of the ninth invention, X 6 , X ? Although it is possible to introduce substituents different from each other to the substituents represented by Since this increases the tolerance of the synthesis conditions, it is preferable that the siloxane chains have the same length and the same substituents.

[Example] Next, Examples of the present invention will be shown to further specifically explain the present invention.

(Example 1) A reaction apparatus equipped with a stirring device and a condenser was
(tridecafluoro-1,1,2.2tetrahydrooctyl)dimethylsilanol (100 g) and butyllidium hexane solution (1,5 mol/m) J58++1 were combined with N
After charging and reacting under 2 gas streams, 100++ lj of tetrahydrofuran (TIIF) previously dried and 52.9 g of hexamethylcyclotrisiloxane were added, and after polymerization at a temperature of 20°C for 10 hours, 24.5 g of dimethylchlorosilane was added. 7 g was added and stirred for 1 hour to stop the polymerization.

The produced lithium chloride was removed by washing with water, and then dried over anhydrous sodium sulfate.

The low boiling point of the reactant thus obtained is 1 g'C/100+
The sake was thickened for 2 hours under uiHg conditions, and the target siloxane compound was obtained in the residue in an almost quantitative yield.

'H-NMR spectrum of the obtained siloxane compound,
The respective analysis results of IR spectrum, GPC (gel permeation chromatography), and 5i-H adjuvant amount data are as follows, and 1 having the structure of the following formula
It was confirmed that it was -()-sodecafluoro-1.1,2.2-tetrahydrooctyl)-9-hydrodecamethylpentasiloxane.

'H-NMR (CDC statement: l) δppmG, 1.
8 (S i C!LL, s, 3 (IH) 0.
5~2.2 (SiC dan, c dan, , broad, 4H) 4
．． 55 (Si-dan, m, IH) IR (KBr) 2970co+-' (C-H) 2250cm-' (S i-H) 1250cm-' (S i -CHt ) 125
0~1150cm-' (CF2.CFi)1
120-105105O' (S i -0) GPC (
) Luene) Polystyrene equivalent molecular weight Number average molecular weight (Mn
) 850 Weight average molecular weight (Mw) 930 Polydispersity (Mw
/Mn) 1.1i Quantitative data of H group H [ppm] Calculated molecular weight from 1442 [ppffil H [ppm1] In a reaction apparatus equipped with a stirrer and a condenser,
1-(tridecafluoro-1,1,2) obtained above
．． 20 g of 2-tetrahydrooctyl)-9-hydrodecamethylpentasiloxane was charged and heated to 110°C.

Then 1.5 x 10-'g of chloroplatinic acid was added followed by 3.8g of dimethylvinylethoxysilane dropwise. After the dropwise addition was completed, the reaction temperature was maintained at 110°C and the mixture was allowed to stand for 10 hours.

The low boiling point of the reaction product thus obtained is 100℃/10++
The sake was brewed under conditions of +mHg for 2 hours, and the target siloxane compound was obtained in the residue in an almost quantitative yield.

'H-NMR spectrum of the obtained siloxane compound,
The analysis results of IR spectrum, GPC (gel permeation chromatography), and viscosity are as follows, and the structure of the following formula is I-(tridecafluoro-1,12,2 -tetrahydrooctyl)
It was confirmed that it was -9-(2(dimethylethoxysilyl)ethyl)decamethylpentasiloxane.

'H-NMR, (CDC statement 3 0.18-0.22 (SiC tanyu 1m.

0.50 (SiC tan, C tan" δppm 36H) S 1 , s, 4H) 0.7 to 2.6 (SiC tan 2 CH2CF 2-, broa
d.

1.1-1.3, -DCII2C11,,t,
7 H) 3.60-4.10 (-0CH2cH3, ci, 2H) IR (KBr) 2970cm-' (C-H) 1260cm-' (S 1-CH3) 1250-11
50cm-' (CF2, CF3)1
150~1.120c+a-' (S I CH2CH2S t )1120~10
5105O' (S i -0)960~940cm-
(S
w/Mn) 1,4 Viscosity (25℃
) 12 cm voice (Example 2) A reaction apparatus equipped with a stirring device and a condenser was
12 g of (tridecafluoro-1,1,2,2 detrahytrooctyl)dimethylsilanol and 19+nJ1 of butyllithium hexane solution (1.5 mol/M) were charged and reacted under a N2 stream, and then dried in advance. 2000 ml of tetrahydrofuran and 1980 g of hexamethylcyclotrisiloxane were added. After polymerizing at a temperature of 20° C. for 20 hours, 2.97 g of dimethylchlorosilane was added and stirred for 1 hour to terminate the polymerization.

Next, the produced lithium chloride was removed by washing with water, and then dried over anhydrous sodium sulfate.

The low boiling point of the reaction product thus obtained was reduced to 150°C/1 n
Distillation was carried out over a period of 2 hours under the condition of 1 g of ++at, and the desired siloxane compound was obtained in the residue in an almost quantitative yield.

The results of GPC (gel permeation chromatography) and viscosity analysis and 5i-H adjudication data of the obtained siloxane compound were as follows.

GPC () Luene) Polystyrene equivalent molecular weight Number average molecular weight (Mn) 634] 0 Weight average molecular weight (Mw)
75930Si-H group quantitative data H [ppm1 15.1 [ppI
Calculated molecular weight from I]H [ppm] 66200 Viscosity (25°C) 3540 centipoise In a reactor equipped with a stirrer and a condenser,
100 g of the siloxane compound obtained in step (1) above, 0.18 g of dimethylvinylmethoxysilane, and 200 g of toluene.
mJ1 was charged and heated to 110°C.

Next, 18 x 10-'g of chloroplatinic acid was added, and the mixture was aged for 10 hours while maintaining the reaction temperature at 110°C.

The low boiling point of the reaction product thus obtained was reduced to 120°C/1no
Distillation was carried out over 2 hours under the condition of 1 g of ol, and the target siloxane compound was obtained in the residue in a nearly quantitative yield. The results of analysis of IR spectrum, GPC (Kölpermeation chromatography) and viscosity of the obtained siloxane compound are as follows, and it was confirmed that it had the structure of the following formula.

IR (KBr) 2970c+n-' (C-H) 2840c+n-' (S i OCH:+)12
[i[1cm-' (S i -CH:l )1
250~]]50cm-' (CF2, CF3
) 1150-1120cm (S 1-CH2CH2-3i ) 1120-105105O' (S i -0) GPC
(Toluene) Polystyrene equivalent molecular weight Number average molecular weight (M
n) 64100 weight average molecule ii1 (M w
) 782 [ ] [1 Dispersity (Mw/M n )
1.2 viscosity (25°C) 3710 centivoise (Example 3) In a reactor equipped with a stirrer and a condenser,
1-(tridecafluoro-
Charge 20 g of 1,l,2,2-tetrahytroocdyle)-9-hydrodecamethylpentasiloxane, 11
Heated to 0°C.

Next, 1.5×10-'g of chloroplatinic acid was added, followed by dropwise addition of 9.7g of vinyltriphenoxysilane.

After the dropwise addition was completed, the mixture was aged for 1 hour while maintaining the reaction temperature at 110°C.

The low boiling point of the reaction product thus obtained was 100'C/11
Thicken the oil for 2 hours under the conditions of 1 mm and 11 g, and add 11 g to the remaining pot.
The target siloxane compound was obtained in almost quantitative yield.

The analysis results of 'H-NMR spectrum, IR spectrum, GPC (gel permeation chromatography), and viscosity of the obtained siloxane compound are as follows, and the structure of the following formula l-(+-Lidecafluoro 1.l.

It was confirmed that it was 2.2-tetrahydrooctyl)-9-(2(triphenoxysilyl)ethyl)decamethylpentasiloxane.

NMR (CDC statement 3) = δppm0118~f1
, 22 (SiC tan,, m, 30H) 0.5-2.6 (SiC tan, C tanzsi, m.

5iCHU Cdan, CF2-, broad.

8H) 6.6-7.4 (-0@'3, m, 15H) I R(KBr) H 2970cm-' (C-H) 1260cIm-' (S i -CH31250-1
150cm-' (CF 21150~1120cm-
' (S I CH2CH2 112 fl ~]050 cm-' (S iCF3 Si) O) GPC (1 Heluene) Polystyrene equivalent molecular weight Number average molecular weight (M n ) Positive weight average molecular weight (M w ) Dispersity (M w / M n ) Viscosity (25°C) 28 centivoise (Example 4) In a reactor equipped with a stirrer and a condenser,
1-(1-lidecafluoro-1.1,2.2-detrahy-1-rooctyl)-9- obtained in Example 1
Hill ~ Prepare 20g of rhodecamethylbentasiloxane,
It was heated to 110°C.

Then, 1.5 x 10'' g of chloroplatinic acid was added, followed by dropwise addition of 7.3 g of Cyphenylvinylethyl-xysilane. After the dropwise addition, while maintaining the reaction temperature of 110°C,
Aged for 0 hours.

The low boiling point of the reaction product thus obtained is 1()0°C/10
The sake was thickened over 2 hours under conditions of 0.1 1 g, and the target siloxane compound was obtained in the residue in a nearly quantitative yield.

'H-NMR spectrum of the obtained siloxane compound,
The analysis results of IR spectrum, GPC (gel permeation chromatography), and viscosity are as follows, and l-(tridecafluoro-1,l) has the structure of the following formula.

It was confirmed that it was 2.2-tetrahydrooctyl)-9-(2(cyphenyle-1hexysilyl)ethyl)decamethylpentasiloxane.

H NMR (CDC sentence 3 0.18-0.22 (SiCdan” 9m.

0.3-2.6 (S ICH2C Danyu δppm 30H) Si, m.

SiC 2C 2 CF 2-, broad
l, 1~1.3, -QC)I2C1(:4.t
, IIH') 3.60-4. lo (-○C Danyo CH: l, q, 2H) 7.0~7.6 (-tatami, m, l0H) IR (KBr) 3100c11-' (→D) 2970cm-' (C-H) 1260cm -' (S 1-CH5) 1250~11
50cm-' (CF2.CF:+)11
50~1120cm-' (S I CH2CH2S i )1120~I[
150cm-' (S i -0)960~940c+
w-' (S i 0CH2CH:l) 700cm-', 720cm-' (S i◎)GP
C (toluene) polystyrene equivalent molecular weight number average molecular weight (
Mn) 970 Weight average molecular weight (Mw) 1130 Dispersity (M w / M n ) 1.3 Viscosity (25°C) 28 centivoise (Example 5) In a reaction apparatus equipped with a stirring device and a condenser,
10 g of (3,3,3-trifluoropropyl)dimethylsilanol and 38.7 iu of butyl lithium hexane solution (1.5 mol/view) were charged under a N2 stream and reacted, then pre-dried tetrahydrofuran 800
Hogami and hexamethylcyclotrisiloxane 567.2
g was added. After polymerizing for 15 hours at a temperature of 20°C, 6.04 g of dimethylchlorosilane was added and stirred for 1 hour to stop the polymerization.

Next, the produced lithium chloride was removed by washing with water, and then dried over anhydrous sodium sulfate.

The low boiling point of the reaction product thus obtained was reduced to 150°C/l m
The mixture was distilled off over 2 hours under the conditions of (g+)Ig, and the desired siloxane compound was obtained in the residue in an almost quantitative yield.

The results of GPC (gel permeation chromatography) and viscosity analysis of the obtained siloxane compound, as well as the 5i-H adjudication data, are as follows.

GPC (Toluene) Polystyrene equivalent molecular weight Number average molecular weight (Mn) 9520 Weight average molecular weight (M w ) l[]490Si-
Quantitative data of H group H [ppn] ] 12.5 [p
pm1H [calculated molecular weight from ppm1 8890 viscosity (
25°C) in a reactor equipped with a 116 centivoise stirrer and a condenser.
100 g of the siloxane compound obtained above, 3.2 g of vinyltris(2-methoxyethoxy)silane, and 100 mM of toluene were charged and heated to 110°C.

Next, 10-5 g of chloroplatinic acid (5.8X) was added, and the mixture was aged for 10 hours while maintaining the reaction temperature at 110°C.

The low boiling point of the reaction product thus obtained was reduced to 120°C/1 m
Distillation was carried out over 2 hours under conditions of 1-1 g of ml, and the target siloxane compound was obtained in the residue in a nearly quantitative yield.

IR spectrum of the obtained siloxane compound, GPC (
The analysis results of gel permeation chromatography) and viscosity were as shown below, and it was confirmed that the structure was as shown in the following formula.

R (KBr) 2970cm-' (C old 1250cal-' (S i -CH,) 1250~
]150cm-' (CF:+)] 15(1-
] 120cI11-'(S iCH2CH2S 1
) 1120~1050c+a-' (S i -0)GP
C (toluene) polystyrene equivalent molecular weight number average molecular weight (
Mn) 9590 Weight average molecular weight (M w ) 1.3400 Dispersity (M w / M n ) 1.4 Viscosity (2
5°C) 181 centivoice (Example 6) In a reactor equipped with a stirrer and a condenser,
20 g of 1(1-lidecafluoro-1.1,2.2-tetrahy-1-looctyl)-9-hydrodecamethylpentasiloxane obtained in Example 1 was charged.
Heated to 10°C.

Next, 10-'g of chloroplatinic acid t,sx was added, and then 4.6g of methylvinyljethoxysilane was added dropwise. After the dropwise addition was completed, the mixture was allowed to ripen for 10 hours while maintaining the reaction temperature at 110°C.

The low-boiling content of the reaction product thus obtained was reduced to 100°C/1h+
The sake was thickened under conditions of st+g for 2 hours, and the desired siloxane compound was obtained in the residue in an almost quantitative yield.

'H-NMR spectrum of the obtained siloxane compound,
The analysis results of IR spectrum, GPC (gel permeation chromatography), and viscosity are as follows, and l-(tridecafluoro-1,l) has the structure of the following formula.

It was confirmed that it was 2.2-tetrahydrooctyl)-9-(2-(methyljethoxysilyl)ethyl)decamethylpentasiloxane.

(The following is a margin) 'H-NMR (CDC statement 3) = δppm0.18
~0.22 (SiC Dan, m, 33H) 0.55 (S I CH2C Danyu Si, d, 4H) 0.7 to 2.
5 (SiCtan, Cdan2 CF2-, broad
.

1.1-1. :l, -QC:1I2c11. ,
m, IOH) 3.60-4. ] f1 (-0CH, CH3, m, 4H) IR (KBr) 2970cm-' (C-H) ]]260cm-' (S 1-CH3) 1250-11
50cm-' (CF2, CF,)115
11-1121] c+a-' (S I CN2 CN2 S x ) 11
2[] ~]050ci+-' (S i -0)96
0 to 940 cm-' (S i 0CH2CH3) GPC ()-Luene) Polystyrene equivalent molecular weight Number average molecular weight (Mn) 890 Weight average molecular weight (Mw) 1:100 Molecule B! ,
Viscosity (M w / M n ) 1.4 Viscosity (
25°C) 13 centivoise (Example 7) In a reactor equipped with a stirrer and a condenser,
(tridecafluoro-1,1,2,2tetrahydrooctyl)dimethylsilanol (50.0 g) and 79 vsl of tutyllithium hexane solution (1.5 mol/l) were charged under a N2 stream and reacted, and then 10flOnlj of dried tetrahydrofuran and 1130g of hexamethylcyclolisiloxane were added. temperature 20
After polymerization for 15 hours at °C, methylchlorosilane 7.5
1. g was added thereto, and the mixture was stirred for 1 hour to stop the polymerization.

Next, the produced lithium chloride was removed by washing with water, and then dried with anhydrous sulfuric acid and 1 helium.

The low boiling point of the reactant thus obtained was 150'C/1m
Distillation was carried out over a period of 2 hours under the condition of 1 g of +llt, and the target siloxane compound was obtained in the residue in an almost quantitative yield.

The respective analysis results of GPC (Kel permeation chromatography) and viscosity of the obtained siloxane compound and the 5i-H adjudication amount data are as follows,
It was confirmed that it has the following structure.

(Laikong, blank space below) GPC (1 to luene) polystyrene equivalent molecular weight Number average molecular weight (Mn) l! 1740 weight average molecular weight (M
w) 2:1720H group quantitative data H [ppm3 53.9 [ppn
Calculated molecular weight from lH[ppm1 18550 viscosity (
25°C) 423 centipoise i Into the reactor, the stirrer and condenser were removed.
100 g of the siloxane compound obtained in step ①, vinyl 1
~ 1 hexysilane 0.8 [] g and 1 hexysilane 1
Prepare 00m, Q, 1. ] Heated to 11'C.

Next, 10-5 g of 2.8X chloroplatinic acid was added, and the mixture was aged for 10 hours while maintaining the reaction temperature at 110°C.

The low boiling point of the reaction product thus obtained was 120°C/lIl.
Distillation was carried out over a period of 2 hours under conditions of lIIHg, and the desired siloxane compound was obtained in the residue in a nearly quantitative yield.

IR spectrum of the obtained siloxane compound, GPC (
The analysis results of gel permeation chromatography) and viscosity were as shown below, and it was confirmed that the structure was as shown in the following formula.

IR (KBr) 2970cm-' (C-H) 2840cm-' (S i OCH3) 1260cm
-' (S i -CH3)1250~11511cm
-' (CF 2. CF 3) 1150-1120
cn+' bow (S 1-CH2CH2-3i) 1120~1050c+s-' (S i-0) GPC
(Toluene) Polystyrene equivalent molecular weight Number average molecular weight (M
n ) 1.9900 weight average molecular weight (M w
) 25900 Dispersity (Mw/Mn)
1.3 viscosity (25°C) 508 centiboise (Example 8) In a reactor equipped with a "stirring"! A position and a condenser, After preparing and reacting 1.0 g of dimethylsilanol 5 and butyl lithium hexane solution (15 mol/17911 g) under a N2 stream, react with 1.000 ml of pre-dried Te1-Rahy1-Lofuran. 1130 g of hexamethylcyclotrisiloxane was added thereto. After polymerization at a temperature of 20° C. for 15 hours, 5.90 g of 1-lichlorosilane was added, and the polymerization was stopped by stirring for 14 hours.

Next, the produced lithium chloride was removed by washing with water, and then anhydrous sodium sulfate to thulium was dried.

The low boiling point of the reaction product thus obtained is 1[]0'C/10
Distillation was carried out over a period of 2 hours under conditions of 1 g/mm, and the desired siloxane compound was obtained in the residue in an almost quantitative yield.

The GPC (gel permeation chromatography) and viscosity analysis results and 5i-H method quantitative data of the obtained siloxane compound are as follows.
It was confirmed that it has the following structure.

GPC (1-luene) polystyrene equivalent molecular weight Number average molecular weight (Mn): 13790 Weight average molecular weight (Mw
) 37710H group quantitative data H [ppm] 33.8 [ppm]
Calculated molecular weight from m1H [ppm] 29590 Viscosity (25°C) 681 centiboise ■ α α′ α″ Tridecafluoro stirrer and condenser] 100 g of the compound, 64 g of vinyltriethoxysilane (), and 150 m of 1-toluene were charged and heated to 110°C.

Then, 1.8×10 −5 g of chloroplatinic acid was added and the mixture was aged for 10 hours while maintaining the reaction temperature at 110° C.

The low boiling point of the reaction product thus obtained was reduced to 120°C/l m
Distillation was carried out over a period of 2 hours under the condition of n+lIg, and the target siloxane compound was obtained in the residue in an almost quantitative yield.

IR spectrum of the obtained siloxane compound, GPC (
The analysis results of Gel Permeation Chroma 1 to Craffy) and viscosity are as follows, and it was confirmed that the structure was as shown in the following formula.

I R(KBr) 2970cm-' (C-H) 1260c+n-' (S i -CH:l)12
50~l15Dcm-' (CF2, CF,)1
120-105[]cn-' (S i -0)GPC
(1-Luene) Polystyrene equivalent molecular weight Number average molecular weight (
M n ) 33800 weight average molecular weight (M w
) 4271.0 Dispersity (Mw/Mn)
], :1 Viscosity (25°C) 795 centivoice (Example 9) Production In a reactor equipped with a stirrer and a condenser,
After charging 100 g of (heptadecafluoro-1,1,2゜2-te-1-helahy-1-lodecyl) dimethylsilanol and 128 m of tutyllithium hexane solution (1.5 mol/liter) under a N2 stream and allowing them to react. , 2 Tl [Igl] of pre-dried tetrahydrofuran and 1804 g of hexamethylcyclo-wasiloxane were added. temperature 20
After polymerization for 15 hours at °C, dimethylchlorosilane 19
．． 9 g was added and stirred for 1 hour to stop the polymerization.

Next, the produced lithium chloride was removed by washing with water, and then dried over anhydrous sodium sulfate.

The low boiling point of the reaction product thus obtained was reduced to 150°C/1 a
Distillation was carried out over 2 hours under the condition of +ml11g, and the target siloxane compound was obtained in the residue in a nearly quantitative yield.

The results of GPC (gel permeation chromatography) and viscosity analysis and 5i-H method quantitative data of the obtained siloxane compound are as follows.

GPC () Luene) Polystyrene equivalent molecular weight Number average molecular weight (Mn) 11710 Weight average molecular weight (M w
) 12896Si-H group quantitative data H[ppm1 103.3[ppm
]H[ppm1 Calculated molecular weight 968° Viscosity (25
°C) 100 g of the siloxane compound obtained in step 611, (
m, p-) styryl ethyl trime 1-xysilane 2,6
g and 100 nl of toluene were charged and heated to 110°C.

Next, 5.4×10-'g of chloroplatinic acid was added, and the mixture was aged for 10 hours while maintaining the reaction temperature at 11.0°C.

The low boiling point of the reaction product thus obtained was reduced to 120°C/1mm.
Distillation was carried out over 2 hours under the conditions of 1 g, and a monosiloxane compound was obtained in the residue in an almost quantitative yield.

IR spectrum of the obtained siloxane compound, GPC
(Gel Permeation Chroma 1 to Claffy) and viscosity analysis results are as shown below, and it was confirmed that the structure was as shown in the following formula.

IR (KBr) 2970c "' (C-H) 2840cm-' (S i OCH: l )], ]
260cm-'(S i CH:+)1250
~1]50c1' (CF2, CF:+)112
0~105105O' (S i -0)GPC(1
-luene) Polystyrene equivalent molecular weight Number average molecular weight (Mn
) 9590 Weight average molecular weight (M w ) +3400 Dispersity (
Mw/Mn) 1. ．． 4 Viscosity (25°C) 181 centivoise (Example 10) Remove the stirrer and condenser and place the 1-(l~sdecafluoro-1 ,1,2,2-tetrahydrooctyl)-9
-Prepare 20g of hydrodecamethylpentasiloxane,
It was heated to 110°C.

Next, 1.5xlO-'g of chloroplatinic acid was added, and then 5.9g of Allyltrier 1-xysilane was added dropwise.

After the dropwise addition, while maintaining the reaction temperature of 11.0°C,
Aged for time.

The low boiling point of the reaction product thus obtained is 100°C/]0+
Distillation was carried out over a period of 2 hours under the condition of nm11g, and the target siloxane compound was obtained in the residue in an almost quantitative yield.

'H-NMR spectrum of the obtained siloxane compound,
The analysis results of IR spectrum, GPC (Gelper knee chromatography), and viscosity are as follows, and the structure of l-(tridecafluoro-1,l) is shown below.

It was confirmed that it was 2.2-tetrahydrooctyl)-9-(3(1-xysilyl)propyl)decamethylpentasiloxane.

'HNMR(CDCM:+)' δppm0
．． 18-0.22 (SiC, m, 30H) 0.3-2.6 (SiC, CH2, broad.

0.3-1.0, 5iCI1. CH2Cl1. S
i1.1~IJ, -0C112CH3,j.

5iCH2C)I, CH2Si, 19H)3.
60-4.10 (-0CHUCH3,q,6H IR (KBr) 2970cm-' (C-H) 1260cm-' (S 1-CH:l) 1250
~1150cm-' (CF2, CF:
+1120~1050cm"" (S i-0)960
~940co+-' (S iOCH2CH:+) GPC (toluene) polystyrene equivalent molecular weight Number average molecular weight (M n ) 10[]0 Weight average molecular weight (Mw
) 1300 Dispersity (Mw/Mn)
1.3 viscosity (25°C) 13 centimeter voice (Example 11) In a reactor equipped with a stirrer and a condenser,
20 g of 1-(1-lidecafluoro-1,1,2,2-tetrahydrooctyl)-9-hydrodecamethylpentasiloxane obtained in Example 1 was charged, and 1
Heated to 10°C.

Then, 5×10 −′ g of chloroplatinic acid] were added, followed by dropwise addition of 4.7 g of allyltrimethoxysilane.

After the dropwise addition was completed, the mixture was aged for 10 hours while maintaining the reaction temperature at 1106C.

The low-boiling content of the reaction product thus obtained is 1 g'C/+0 ■l.
Distillation was carried out over 2 hours under the conditions of 1 g, and the target siloxane compound was obtained in a nearly quantitative yield in the residue.

IH-NMR spectrum of the obtained siloxane compound,
The analysis results of IR spectrum, GPC (Gelper knee chromatography), and viscosity are as shown below, and it was confirmed that the structure was as shown in the following formula.

H N M R (CD Cl :+) δppm0
．． 18-0.22 (S i CH3, m, 30H) 0.3-2.6 (5iCH, CIl, CF2-, broad
.

[1,:l ~], [], 5ic11. cl1
2c11. si, nx.

5icl12c11. cl12si, IOH)
3.6 (-octanyo, s, 9H) IR (KBr) 2970cm-' (C-H) 2840cn+-' (S i OCH3) 1260c
'(S i -CH:+)1250~1150
cm-' (CF2, CF:+)1120~1
05[1c+a-' (S i-0) GPC () Luene) Polystyrene equivalent molecular weight number average molecule! (Mn)
870 Weight average molecular weight (Mw) 1200 Dispersity (Mw
/Mn) 1.4 viscosity (25°C) 13 centiboise (Example 12) In a reactor equipped with a stirrer and a condenser,
(pentafluorophenyl)dimethylsilanol 0.2
4g and phthyllithium hexane solution (1.5 mol/statement)
After preparing and reacting 0.66m carbon under N2 gas flow, pre-dried Tel-Rahi I ~ Rofuran 50+++
M and 49.2 g of hexamethylcyclo I disiloxane were added. After polymerizing for 24 hours at a temperature of 20°C, 0.13 g of vinyldimethylchlorosilane was added and stirred for 1 hour to terminate the polymerization.

Next, the produced lithium chloride was removed by washing with water, and then dried over anhydrous sodium sulfate.

The low-boiling content of the reaction product thus obtained was reduced to 150°C/tau.
Distillation was carried out over a period of 2 hours under aHg conditions, and the target siloxane compound was obtained in a nearly quantitative yield in the residue.

IR spectrum of the obtained siloxane compound, GPC (
The analysis results of Gelber knee chromatography) and viscosity were as follows.

IR (KBr) 2970cm-' (C 1250c1M-' (S 1 1250-1150cIIl-+ 1120-105105O') GPC (Toluene) Number average molecular weight Weight average molecular weight Viscosity (25°C) 3680 centiboise former CH,) (CF2. CF3 (Sl-O) Molecular weight in terms of polystyrene (M n ) 4: I400 (M w ) 52200 A stirrer and a condenser were taken (=J digits) into a reactor, 40 g of the siloxane compound obtained in step 1 above, and 0.15 g of triethoxysilane. and 1110 mM of toluene were added and heated to IIO'C.

Next, 4.8 x 10-6 g of chloroplatinic acid was added, and the mixture was aged for 10 hours while maintaining the reaction temperature at 110°C.

The low boiling point of the reaction product thus obtained is 120°C/]vn
Distillation was carried out over a period of 2 hours under Hg conditions, and the target siloxane compound was obtained in a nearly quantitative yield in the residue.

IR spectrum of the obtained siloxane compound, GPC (
The analysis results of gel permeation chromatography) and viscosity were as shown below, and it was confirmed that the structure was as shown in the following formula.

■ R (KBr) 2970cn-' (C +250c+o-' (S 1 1150~1.120cm-' (S lCH2CH2 1120~101050c1') (S 1690~9
40 cm-' (S i 0CH2C1(lO) Si) Old CH3 GPC (1~luene) Polystyrene equivalent molecular weight Number average molecular weight (M n ) 475 [ft1 Weight average molecular i
(Mw) 5:ll[]O dispersity (Mw/M
n) IJ cakeness (25°C) 4250 centiboise (Example 13) Take a stirring device and a condenser (=J order reactor), (tridecafluoro-1,1,2,2 Tel to ) Dimethylsilanol 17.3g and methyllithium hexane solution (15 mol/liter) 27IIlfL
were charged under a N2 stream and allowed to react, and then 106 g of tetrahydrofuran [00+eu] which had been dried in advance and hexamethylcyclotrisiloxane were added. Temperature 20°C
After polymerization for 15 hours, 9.25 g of 7-octynyldimethylchlorosilane was added, and the mixture was stirred for 1 hour to terminate the polymerization.

Next, the produced lithium chloride was removed by washing with water, and then dried over anhydrous sodium sulfate.

The low boiling point of the reaction product thus obtained was reduced to 150℃/1m+m
11 g of the product was poured into oil over a period of 2' to obtain the desired siloxane compound in a nearly quantitative yield in the residue.

The analysis results of the IR spectrum, GPC (gel permeation chromatography) and viscosity of the obtained siloxane compound were as follows.

IR (KBr) 2970cm-' (C-H) 12611cm-' (S i -CH:l) 125
0~1150cn-' (CF2, CF3)1
120-105105O' (S i -0) GPC (
1 to Luene) Polystyrene equivalent molecular weight Number average molecular weight (M
n) 3300 Weight average molecular weight (Mw) 4000 Viscosity (25°C) 35 centimeters Remove the stirrer and condenser and add the siloxane compound lug obtained in step 1 above and 0.32 g of methyldimethoxysilane to the 1-digit reactor. Prepare and heat to +10°C
heated to.

Next, 1.5 x 1o-'g of chlorinated metallic acid was added, and the mixture was aged for 10 hours while maintaining the reaction temperature at 110°C.

The low boiling point of the reaction product thus obtained was reduced to 120°C/1mm.
1 g was poured into oil over a period of 2 hours, and the desired siloxane compound was obtained in a nearly quantitative yield in the residue.

IR spectrum of the obtained siloxane compound, GPC (
The analysis results of gel permeation chroma 1) and viscosity are as shown below, and it was confirmed that the structure was as shown in the following formula.

l R(KBr) 2970cm-' (C-H) 2840cm-' (S i OCH3) 1260cm
-' (S i CH: l ) 1250-115
0 cm-' (CF2, CF:l)1120
~105105O' (S i -0) GPC (toluene) polystyrene equivalent molecular weight number average molecule ft (Mn)
:1000 weight average molecular ft (Mw) 47
20 Dispersity (M w / M n ) 1.
4 viscosity (25°C) 52 centipoise (Example 14) In a reactor equipped with a stirrer and a condenser,
(Tridecafluoro-1,1,2,2tetrahydrooctyl)dimethylsilanol 17,: Ig and butyl lithium hexane solution (1.5 mol/liter) 2711 tons were charged under a N2 stream and reacted. , 100 mM of previously dried tetrahydrofuran and 106 g of hexamethylcyclotrisiloxane were added. 15 at temperature 20℃
After polymerization for an hour, 8.26 g of methylphenylvinylchlorosilane was added and stirred for 1 hour to stop the polymerization.

Next, the produced lithium chloride was removed by washing with water, and then dried over anhydrous sodium sulfate.

The low boiling point of the reaction product thus obtained was reduced to 150°C/ln+
m1l) z condition 2 II! The distillate was thickened over a period of time, and a monosiloxane compound was obtained in the residue in an almost quantitative yield.

IR spectrum of the obtained siloxane compound, GPC (
The analysis results of gel permeation chromatography) and viscosity were as follows.

IR (KBr) 2970cn+-' (C-H) 1260c"' (S i -CH3) 1250~11
50cIM-' (CF2.CF:+)112
0 to 1050c "' (S i -0) GPC () Luene) Polystyrene equivalent molecular weight Number average molecular weight (Mn)
3100 Weight average molecular weight (Mw) 3820 Viscosity (25°
C) Into a 1-digit reactor equipped with a 38 centipoise stirrer and a condenser, 1 (2) g of the siloxane compound obtained above and 1 to 0.0 g of dimethyl ether to xysilane were added. : Prepare 14g 110
heated to ℃.

Next, 1-5 g of chloroplatinic acid], 7X] was added, and the mixture was aged for 10 hours while maintaining the reaction temperature at 110°C.

The low boiling point of the reaction product thus obtained was reduced to 120°C/1 y.
R Stiffen the sake for 2 hours under IIHg conditions, and add 1 to the remainder of the pot]
The target siloxane compound was obtained in almost quantitative yield.

IR spectrum of the obtained siloxane compound, GPC (
The analysis results of gel permeation chromatography) and viscosity were as shown below, and it was confirmed that the structure was as shown in the following formula.

R (KBr) 2970 cm (C old 1260 cm' (S 1-CH3) 1251] ~
]151]cm-' (CF2, CF3)
1150-1120cm-' (S I CH2CH2S 1 ) 1120-10
50C[l-' (S i -0)960~940c
m-' (S i 0CH2CH,)GPC()-Luene> Polystyrene equivalent molecular weight Number average molecular weight (Mn)
3:120 Weight average molecular weight (Mw) 45
80 Dispersity (Mw/M n ) 1.4 Viscosity (25°C) 49 centipoise (Example 15) In a reactor equipped with a stirrer and a condenser,
(tridecafluoro-1,1,2,2de)~lahytrooctyl)dimethylsilanol 17,:Ig and methyllithium hexane solution (1.5 mol/text) 27111
were charged under a N2 stream and reacted, and then pre-dried tetrahydrofuran]001IJ1 and hexamethylcyclo1 to lysiloxane1 (Ill) were added. Temperature 2
After polymerizing at 0° C. for 15 hours, 11.1 g of diphenylvinylchlorosilane was added and stirred for 1 nr7 to stop the polymerization.

Next, the produced lithium chloride was removed by washing with water, and then dried over anhydrous sodium sulfate.

The low boiling point of the reaction product thus obtained is +50°C/1+
The sake was thickened for 2 hours under conditions of nllHg, and the desired siloxane compound was obtained in the residue in an almost quantitative yield.

IR spectrum of the obtained siloxane compound, GPC (
The analysis results of gel permeation chromatography) and viscosity were as follows.

I R (KBr) 2970cm' (C-H) 1250cm-' (S i CH3 1250-1150cm-' (CF2, CF3) 1120-105105O' (S1O) GPC ()-Luene) Polystyrene equivalent molecular weight Number average molecular weight (Mn) 3520 Weight average molecular weight (M W ) 421S (1 viscosity (25°C) 45 cm voice In a reactor equipped with a stirrer and a condenser,
10 g of the siloxane compound obtained in the above (1) and 0.47 g of triethoxysilane were charged and heated to 110°C.

Next, 10-5 g of 1.5X chloroplatinic acid was added, and the mixture was aged for 10 hours while maintaining the reaction temperature at 110°C.

The low boiling point of the reaction product thus obtained is 120°C/]+n
The sake was thickened over 2 hours under conditions of 11 g of ml, and a monosiloxane compound was obtained in the residue in an almost quantitative yield.

IR spectrum of the obtained siloxane compound, GPC
(Gerber knee chromatography) and viscosity analysis results are as follows, and it was confirmed that the structure was as shown in the following formula.

IR (KBr) 297Gcm' (C-H) 1250c' (Si 125(1-)]50cn+-' (CF 21150
~1120 cIB-' (S i -CH2 1120 ~ IQ5Gcl' 960-940 cm-' (S i -0) CH.

(S i 0CH2CH.

CH, -3j F 3 700c+m-' (S i◎2> GPC ()-Luene) Polystyrene equivalent molecular weight Number average molecular weight (Mn) 3740 Weight average molecular weight (Mw) 5140 Dispersity (Mw
/Mn) 1.4 viscosity (25°C) 67 centivoise (Example 16) In a reactor equipped with a stirrer and a condenser,
After preparing 17.3 g of (tridecafluoro-1,1,2,2 tetrahydrooctyl)dimethylsilanol and 2711 grams of methyllithium hexane solution (1.5 mol/liter) under a N2 gas flow and reacting, 100 mJ1 of pre-dried tetrahydrofuran and 1 hexamethylcyclo
~106g of resiloxane were added. After polymerizing for 15 hours at zo'c temperature, ethylvinyldichlorosilane 3
．． 50 g was added and stirred for 1 hour to stop the polymerization.

Next, the produced lithium chloride was removed by washing with water, and then dried over anhydrous sulfuric acid.

The low-boiling content of the reaction product thus obtained was 15g1°C/1
The distillate was thickened over 2 hours under conditions of 11 g of mm, and the objective siloxane compound was obtained in the residue in a nearly quantitative yield.

IR spectrum of the obtained siloxane compound, GPC (
The analysis results of gel permeation chromatography) and viscosity are as follows, and it was confirmed that the structure was as shown below.

IR (KBr) 2'170cm-' (C ]260c11' (S 1 1250-1150cm-'1120-105105O' GPC (+Heluene) Number average molecular weight Weight average molecular weight Viscosity (25°C) 75 centivoise H) CH,) (CF2, CF3) (S i -0) Polystyrene equivalent molecular weight (Mn) 6420 (Mw) 7280 In a reaction apparatus equipped with a stirring device and a condenser,
10 g of the siloxane compound obtained in step (1) above and 0.26 g of triethoxysilane were charged and heated to 110°C.

Next, Ji4platinic acid 8. 10-6 g of 1X was added and the mixture was aged for 1 hour while maintaining the reaction temperature at 110°C.

The low boiling point of the reaction product thus obtained was reduced to 120°C/1 m
The sake was thickened over 2 hours under conditions of 1 g of sake, and the target siloxane compound was obtained in the residue in a nearly quantitative yield.

111 IR spectrum of siloxane compound, GP
The analysis results of C (gel permeation chromatography) and viscosity are as follows, and it was confirmed that the structure was as shown in the following formula.

R (KBr) 2970c++1-' (C 12C126O' (S 1 1250~1150cm-' (CF 2H3 old C.F.

]]5[1~]]20cm-' (S I CH2CH2S l )1120~10
5105O' (S i -0)960~940cm-
'(S i 0CH2CH3)GPC (Toluene) Polystyrene equivalent molecular weight Number average molecular weight (Mn) 65
70 Weight average molecular weight (M w ) 8740 Dispersity (
M w / M n ) ], , 3 viscosity 3
C25°C> 110 centimeter voice (Example 17) A reaction apparatus equipped with a stirring device and a condenser,
(tridecafluoro-1,l,2.2tetrahy-1-looctyl)dimethylsilanol 17Jg and tutyllithium hexane solution (1.5mol/u) 27+n solution were mixed with N2
After charging and reacting under a stream of air, 106 g of hexamethylcyclotrisiloxane and 106 g of dried tetrahydrofuran [00m, Q] were added. After polymerizing for 15 hours at a temperature of 20°C, 8.89 g of p-edenylphenyldimethylchlorosilane was added and the mixture was stirred for 1 hour to terminate the polymerization.

Next, the produced lithium chloride was removed by washing with water, and then dried over anhydrous sodium sulfate.

The low boiling point of the reaction product thus obtained was 150'C/1nv.
The distillation was carried out under Hg conditions for 2 hours, and the desired siloxane compound was obtained in the residue in an almost quantitative yield.

IR spectrum of the obtained siloxane compound, GPC (
The analysis results of gel permeation chromatography) and viscosity were as follows.

IR (KBr) 2970cm-' (C-H) 1260cm' (S 1-CH:+) 1250~
]]50cm-' (CF 2. CF 3) 1120
~l050c1' (S i-0) GPC (1-luene) Polystyrene equivalent molecular weight Number average molecular weight (Mn)
336 (1 weight average molecular weight (Mw) 4150
Viscosity (25°C) 38 centipoise In a reactor equipped with a stirrer and a condenser,
10 g of the siloxane compound obtained in step (1) above and 0.49 g of triethoxysilane were charged and heated to 110°C.

Next, 1.5 x 10-'g of chloroplatinic acid was added, and the mixture was aged for 10 hours while maintaining the reaction temperature at 110°C.

The low boiling point of the reaction product thus obtained was reduced to 120°C/l m
The sake was thickened over 2 days under the conditions of 11 g of ml, and the desired siloxane compound was obtained in the residue in an almost quantitative yield.

IR spectrum of the obtained siloxane compound, GPC (
The analysis results for gel perk knee chromatography) and viscosity are as shown below, and it was confirmed that the structure was as shown in the following formula.

IR (KBr) 2970c+s-' (C-H) +260cIm-' (S i -CHz) 125
0~l150cm-' (CF2, CF3)112
0~1(150c1' (S i -0)960~94
0cm-' (S i 0CH2CH:l ) GPC
(Toluene) Polystyrene equivalent molecular weight Number average molecular weight (M
n) :I5]0 Weight average molecular weight (Mw)
4980 Dispersity (Mw/M n ) 1
．． 4 viscosity (25°C) 58 centivoise (Example 18) In a reactor equipped with a stirrer and a condenser,
0.42 g of vinyldimethylsilanol and 2.7 tssL of butyllithium hexane solution (1.5 mol/l)
were charged under a N2 stream and allowed to react, and then 4 fJml of tetrahydrofuran, which had been dried in advance, and 39.0 g of hexamethylcyclotrisiloxane were added. Temperature 20°C
After polymerization for 20 hours, (tridecafluoro-1,1
, 2,2-tetrahydrooctyl)trichlorosilane was added thereto, and the mixture was stirred for 1 hour to terminate the polymerization.

Next, the produced lithium chloride was removed by washing with water, and then dried over anhydrous sodium sulfate.

The low boiling point of the reaction product thus obtained was reduced to 15[]°C/1m
The liquor was thickened for 2 hours under +mHg conditions, and the objective siloxane compound was obtained in almost quantitative yield in the residue.

IR spectrum of the obtained siloxane compound, GPC (
The analysis results of Gelver Mini-Stain Chroma 1 to Craffy) and viscosity were as shown below, and it was confirmed that the structure was as shown in the following formula.

I R (KBr) 970cm + (C old 16]Ocm-' (CH=CH2)]]260c+
n-' (S i -CH,) 1250-1150c
m-' (CF 2 , CF z ) 1120-10
50all' (S i -0) GPC (Toluene) Polystyrene equivalent molecular weight Number average molecular weight (Mn) 341
20 Weight average molecular weight (M w ) 38770 Viscosity (2
5°C) in a reactor equipped with a 686 centivoise stirrer and a condenser.
30 g of the siloxane compound obtained in step (1) above, 0.43 g of triethoxysilane, and 50 rnJ1 of toluene were charged and heated to 110°C.

Next, 4×10 −5 g of chloroplatinic acid was added, and the mixture was aged for 10 hours while maintaining the reaction temperature at 110° C.

The low boiling point of the reaction product thus obtained was +20°C/18
The distillation was carried out under conditions of 11 g over 2 sowing periods, and the desired siloxane compound was obtained in the residue in a nearly quantitative yield.

IR spectrum of the obtained siloxane compound, GPC
(Gel Permeation Chroma 1 to Claffy) and viscosity analysis results are as shown below, and it was confirmed that the structure was as shown in the following formula.

(Raikō, blank space below) IR (KBr) 2970c+a-' (C-H) 1260cm-' (S 1 1250~1150co+-' (CF 21150~
1.120co+-' (SI CH2 11211~I[150cm-'960-940cm-' GPC () Luene) Number average molecular weight Weight average molecular weight CH3 CH2S t ) (S i -0) (SiOCH2CH3) Polystyrene equivalent molecular weight (M n ) 34900 (Mw) 47520, CF,) Dispersity (Mw/Mn) 1.4 Viscosity (25°C) 1239 centivoise (Example 1.9) In a reactor equipped with a stirrer and a condenser,
(tridecafluoro-1,1,2.2tetrahydrooctyl)dimethylsilanol 5.0g and butyllithium hexane solution (1.5 mol/liter) 7.9mliter and N
After preparing and reacting under 2 gas flows, 1110 mM of tetrahydrofuran and 1 to 100 ml of hexamethylcyclo, which had been dried in advance, were added.
113 g of lisiloxane were added. 15 at a temperature of 20℃
After polymerization for an hour, 2.6 g of triethoxychlorosilane
was added and stirred for 1 hour to stop the polymerization.

Next, the produced lithium chloride was removed by washing with water, and then dried over anhydrous sodium sulfate.

The low-boiling content of the reaction product thus obtained was reduced to 150°C/1, m
Distillation was carried out over a period of 2 hours under conditions of 11 g of ml, and the target siloxane compound was obtained in the residue in an almost quantitative yield.

IR spectrum of the obtained siloxane compound, GPC (
The analysis results of gel permeation chromatography) and viscosity are as follows, and it was confirmed that the structure was as shown below.

IR (KBr) 2970cm-' (C 1260cm-' (S 1 1250~1150c11-'1120~105105O' 960 to 940cm-' GPCl toluene) H) CH3) (CF2, CF:+) (S i -0) ( S x OCH2CH:I ) Polystyrene equivalent molecular weight Number average molecular weight (Mn) Weight average molecular weight (M w ) Dispersity (M w / M n ) Viscosity (25°C) 232 centipoise + 5420 1.3 (Example 20) Stirring device 7. Remove the condenser and add 50 g of (tridecafluoro-1.1, 2.2 detrahytrooctyl) dimethylsilanol and a butyl lithium hexane solution (1.5 mol/liter) to a single-digit reactor. ! After reacting, 1 mJlj of tetrahydrofuran, which had been dried in advance, and 113 g of hexamethylcyclotrisiloxane were added. After polymerizing for 15 hours at a temperature of 20° C., 1.6 g of dimethylmethyl-oxychlorosilane was added and stirred for 1 hour to terminate the polymerization.

Next, the produced lithium chloride was removed by washing with water, and then dried over anhydrous sodium sulfate.

The low boiling point of the reaction product thus obtained was reduced to 150°C/1 m
Distillation was carried out over a period of 2 hours under mHg conditions, and the target siloxane compound was obtained in a nearly quantitative yield in the residue.

IR spectrum of the obtained siloxane compound, GPC (
The analysis results of gel permeation chromatography) and viscosity are as follows, and it was confirmed that the structure was as shown below.

IR (KBr) 2970cm-' (C-H) 2840cn+-' (S i OCH3) 1260c
m-' (S 1-CH,) 1250~l] 50cm
'(CF2, CF3)1120~IO5
0 cm-' (S i-0) GPC (+- toluene) polystyrene equivalent molecular weight number average molecule i (Mn) 12
010 Weight average molecular weight (M w ) ] 519 [
] Dispersity (M w / M n ) 1,
3 Viscosity (25°C> 206 centivoids) [Effects of the Invention] According to the present invention, (1) Since the molecular chain has a fluorine atom-containing substituent at the end and an alkoxy group at the other end, these However, for example, it chemically bonds with synthetic resins, base materials to which paint is applied, etc., and causes the fleet phenomenon and 44+ after aging.
It has excellent weather resistance and durability with almost no decrease in fU property, and (2) Since there is a fluoroalkyl group in the same molecule, it cannot be fU in conventional polysiloxane compounds with trimethylsiloxane group terminals. , or even better water repellency, stain resistance, mold releasability, non-adhesion,
It is possible to impart various functions such as oil repellency, low friction, snow and icing resistance, etc. without impairing the properties of polysiloxane, (3) Molecular weight In (dispersity) 1.1 to 1.2
(4) If the molecular chain length is uniform and the structure is uniform, it is easy to obtain surface properties with controlled functional properties. The disadvantages of conventional polysiloxane compounds produced by equilibration reactions using acidic or basic catalysts are deterioration of physical properties due to the formation of dimethylsiloxane cyclic substances that cannot be removed during production and stickiness due to fleeting. In addition to suppressing variations in quality and properties, it also has the potential to improve properties by reducing substituents containing alkoxy groups, which are reactive groups with synthetic resins, base materials to which paints are applied, etc. (The number of siloxane chains in the mold is 1 to 3, and the number of siloxane chains based on the fluorine atom-containing substituent, which is also a reactive group, is 1 to 3, so it can be controlled as required.) Functional properties can be imparted by appropriately selecting the chain length of the siloxane button, the type of fluorine atom-containing substituent at the end of the siloxane button, and the ratio of the molecular chain length between the siloxane button and the fluorine atom-containing substituent. according to the desired characteristics of the purpose,
It is possible to precisely control the properties, especially water repellency, oil repellency, chemical resistance, stain resistance, mold releasability, non-adhesion, low friction,
An industrially useful alkoxy-based siloxane that has various advantages such as being suitable for a wide range of applications that require high performance due to snow and icing resistance, such as in the fields of synthetic resins and paints. Compounds can be provided.

Claims (10)

[Claims] (1) The following general formula (I): ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (However, in formula (I), j is an integer from 1 to 2000, and R^5 is pentafluorophenyl group, 3-(heptafluoroisopropoxy)propyl group, 1,1,2,2
-tetrafluoroethyl group or the following formula (II); C_bH
_cF_2_b_−_c_+_1 (II) [Formula (II) In the formula, b is an integer from 3 to 18, and c represents an integer from 0 to 2b. ] represents a linear or branched fluoroalkyl group, where X^1 is the following formula (3); ▲There are numerical formulas, chemical formulas, tables, etc.▼(III) The following formula (XIII); -O-(CH_2CH_2O)_d(CH_2CH(C
H_3)O)_e-R^0(XIII) [In formula (XIII),
d and e each independently represent an integer of 0 to 3, and R
^0 represents a hydrocarbon group having 1 to 6 carbon atoms. ] represents an alkoxy group-containing substituent represented by R^2, R^
3 and R^4 each independently represent an alkyl group having 1 to 4 carbon atoms or a phenyl group, and X has 2 carbon atoms.
~12 linear or branched divalent hydrocarbon groups or the following formula (XIV); ▲Mathematical formulas, chemical formulas, tables, etc. are available▼(XIV) [In formula (XIV), R^6 and R^7 are Each independently represents a divalent hydrocarbon group having 0 to 3 carbon atoms. represents a divalent substituent represented by ], and a represents an integer of 0 to 2. ] or the following formula (IV); ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) [In formula (IV), R^1, R^4 and a each represent the same meaning as above. . ] It is a substituent shown by these. ) An alkoxy group-containing siloxane compound represented by (2) In the formula (I), the substituent represented by R^5 is a 3,3,3-trifluoropropyl group, a tridecafluoro-1,1,2,2-tetrahydrooctyl group,
3-(heptafluoroisopropoxy)propyl group, 1
, 1,2,2-tetrafluoroethyl group or heptadecafluoro-1,1,2,2-tetrahydrodecyl group, and in the formula (III) or the formula (IV), R
The alkoxy-containing substituent represented by ^1 is a methoxy group,
The alkoxy group-containing siloxane compound according to claim 1, which is an ethoxy group, a phenoxy group, or a 2-methoxyethoxy group. (3) The following general formula (V); ▲There are mathematical formulas, chemical formulas, tables, etc.▼(V) (However, in formula (V), k and l each independently represent 1.
Represents an integer of ~2000, R^8 is a pentafluorophenyl group, 3-(heptafluoroisopropoxy)propyl group, 1,1,2,2-tetrafluoroethyl group or a straight chain represented by the above formula (II) or a branched fluoroalkyl group, where R^9 is an alkyl group having 1 to 6 carbon atoms, a phenyl group, a pentafluorophenyl group, a 3-
(heptafluoroisopropoxy)propyl group, 1,1
, 2,2-tetrafluoroethyl group or the above formula (II)
It is a linear or branched fluoroalkyl group represented by the following formula (VI); ▲ Numerical formula, chemical formula, table, etc. ▼ (VI) ^2, R^4, X and a each have the same meaning as in formula (III) above. ] Or the following formula (VII); ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (VII) [Formula (VII) Formula, R^1 represents the same meaning as above. ] represents a substituent represented by ) An alkoxy group-containing siloxane compound represented by (4) In the above formula (V), R^8 is a pentafluorophenyl group, 3,3,3-trifluoropropyl group, tridecafluoro-1,1,2,2-tetrahydrooctyl group, 3-( heptafluoroisopropoxy)propyl group, 1,1,2,2-tetrafluoroethyl group, or heptadecafluoro-1,1,2,2-tetrahydrodecyl group, and R^9 has 1 to 1 carbon atoms. 6 alkyl group, phenyl group, pentafluorophenyl group, 3,3
, 3-trifluoropropyl group, tridecafluoro-1
, 1,2,2-tetrahydrooctyl group, 3-(heptafluoroisopropoxy)propyl group, 1,1,2,
It is a 2-tetrafluoroethyl group or a heptadecafluoro-1,1,2,2-tetrahydrodecyl group, and R^1 in the formula (VI) or the formula (VII) is a methoxy group, an ethoxy group, or a phenoxy group. The alkoxy group-containing siloxane compound according to claim 3, which is a group or a 2-methoxyethoxy group. (5) The following general formula (VIII); ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (VIII) (However, in formula (VIII), m, n and p each independently represent an integer from 1 to 2000, R^1^0 is a pentafluorophenyl group, a 3-(heptafluoroisopropoxy)propyl group, a 1,1,2,2-tetrafluoroethyl group, or a linear or branched fluorocarbon group represented by the above formula (II). Represents an alkyl group, R^1^1 and R
^1^2 each independently represents an alkyl group having 1 to 6 carbon atoms, phenyl group, pentafluorophenyl group, 3-(heptafluoroisopropoxy)propyl group, 1,1,2
, 2-tetrafluoroethyl group or a linear or branched fluoroalkyl group represented by the above formula (II), and X^3 is the following formula (IX); ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (IX ) [In formula (IX), R^1, R^4, X and a each represent the same meaning as in the above formula (III). ] or the following formula (X); ▲There are mathematical formulas, chemical formulas, tables, etc.▼(X) [In formula (X), R^1 represents the same meaning as above. ] represents a substituent. ) An alkoxy group-containing siloxane compound represented by (6) In the formula (VIII), R^1^0 is a pentafluorophenyl group, 3,3,3-trifluoropropyl group, tridecafluoro-1,1,2,2-tetrahydrooctyl group, 3 -(heptafluoroisopropoxy)
A propyl group, a 1,1,2,2-tetrafluoroethyl group, or a heptadecafluoro-1,1,2,2-tetrahydrodecyl group, where R^1^1 and R^1^2 are each independently Alkyl group having 1 to 6 carbon atoms, phenyl group, pentafluorophenyl group, 3,3,3-trifluoropropyl group, tridecafluoro-1,1,2,2
-tetrahydrooctyl group, 3-(heptafluoroisopropoxy)propyl group, 1,1,2,2-tetrafluoroethyl group or heptadecafluoro-1,1,2
, 2-tetrahydrodecyl group, and the alkoxy group-containing substituent represented by R^1 in the formula (IX) or the formula (X) is a methoxy group, ethoxy group, phenoxy group or 2-methoxyethoxy group. The alkoxy group-containing siloxane compound according to claim 5. (7) The following general formula (X I ); ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (X I ) [However, in formula (X I), q and r each independently represent an integer from 0 to 2000. , R^1^3 is a pentafluorophenyl group, a 3-(heptafluoroisopropoxy)propyl group, a 1,1,2,2-tetrafluoroethyl group, or a linear or branched group represented by the above formula (II). represents a fluoroalkyl group, R^1^4 represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, and X^
4 and X^5 each represent a substituent represented by the above formula (III). ] An alkoxy group-containing siloxane compound. (8) In the formula (X I), the substituent represented by R^1^3 is a 3,3,3-trifluoropropyl group, a tridecafluoro-1,1,2,2-tetrahydrooctyl group, 3-(heptafluoroisopropoxy)propyl group, 1,1,2,2-tetrafluoroethyl group or heptadecafluoro-1,1,2,2-tetrahydrodecyl group, and in the formula (III), R The alkoxy group-containing siloxane compound according to claim 7, wherein the alkoxy group-containing substituent represented by ^1 is a methoxy group, an ethoxy group, a phenoxy group, or a 2-methoxyethoxy group. (9) The following general formula (XII); ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (XII) [However, in formula (XII), s, t, and u each independently represent an integer from 0 to 2000. , R^1^3 is a pentafluorophenyl group, a 3-(heptafluoroisopropoxy)propyl group, a 1,1,2,2-tetrafluoroethyl group, or a linear or branched group represented by the above formula (II). It represents a fluoroalkyl group, and X^6, X^7 and X^8 each represent a substituent represented by the above formula (III). ] An alkoxy group-containing siloxane compound represented by: (10) In the formula (XII), the substituent represented by R^1^3 is a 3,3,3-trifluoropropyl group, a tridecafluoro-1,1,2,2-tetrahydrooctyl group, a 3 -(heptafluoroisopropoxy)propyl group, 1,1,2,2-tetrafluoroethyl group, or heptadecafluoro-1,1,2,2-tetrahydrodecyl group, and in the formula (III), R^ The alkoxy group-containing siloxane compound according to claim 9, wherein the alkoxy group-containing substituent represented by 1 is a methoxy group, an ethoxy group, a phenoxy group, or a 2-methoxyethoxy group.