JPS63125527A - Silicone polymer and its production - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to fluorosilicone compositions and, more particularly, to methods of making fluorosilicone polymers by polymerizing fluoro-substituted cyclic polysiloxanes in the presence of certain superior chain terminators. It is.

Processes for making diorganopolysiloxane polymers, particularly high molecular weight diorganopolysiloxane polymers, are well known. In the case of alkyl and aryl substituted polymers,
The method of manufacture involves using a suitable diorganodichlorosilane and hydrolyzing it. Then, a large potash metal hydroxide is added from the resulting hydrolyzate. The mixture is then heated to an elevated temperature for a period of time sufficient to preferentially distill out the desired cyclic polysiloxane. Although a process known as the decomposition process produces cyclic polysiloxanes containing from 3 to 10 repeating 810 units, most cyclic polysiloxanes are cyclotrisiloxanes or cyclotetrasiloxanes. Additionally, this decomposition process can be carried out such that the majority of the polysiloxane formed is either cyclotetrasiloxane or cyclotrisiloxane.

When it is desired to produce diorganopolysiloxane polymers with methyl and phenyl substituents, it is desirable to form the maximum amount of cyclic tetrasiloxane. The cyclic tetrasiloxane is then collected in relatively pure form, a small amount of basic equilibration catalyst and a suitable amount of chain terminator are added to it, and the mixture of these components is heated to an elevated temperature for a suitable period of time. High molecular weight IT diorganopolysiloxane heptapolymer, 500,000~s o at 25°C
Polymers with viscosities in the range of n, o o o, o o o centiboise, more preferably 1,000,
A polymer having a viscosity in the range of 000 to 30 Q, OOO, 000 centivoise is prepared. *After the combination reaches its maximum level, the mixture is cooled and a neutralizing agent is added to it to neutralize the basic catalyst and remove excess cyclic tetrasiloxane to form the desired diorganopolysiloxane. Obtain a polymer. It should be noted that such methods are those conventionally used in the production of high molecular weight diorganopolysiloxane polymers.

However, it is 500,000-1°o at 25°C
The viscosity of o o o o o centiboids can be utilized to produce low molecular weight diorganopolysiloxane polymers.

It should be noted that it is the amount of chain terminator present in the reaction mixture that determines the molecular weight of the final diorganopolysiloxane polymer formed during the polymerization reaction. Such chain terminators are usually dicappolysiloxane polymers chain terminated with low molecular weight triorganosiloxy end groups such as disiloxanes and trisiloxanes.

An example of a chain terminator suitable for such a process is, for example, hexamethyldisiloxane.

The amount of chain terminating agent in the reaction mixture determines the amount of chain terminating agent available for end-terminating the cyclic polysiloxane (1) produced from the cyclic polysiloxane; Determine the molecular weight of the final polymer.The lower the relative sparseness of the chain terminator, the higher the molecular weight of the final polymer, and the higher the presence of chain terminator, the lower the molecular weight of the final polymer. I would be able to get a job.

One method for producing silanol-terminated diorganopolysiloxane polymers with molecular weights in the viscosity range of 1.000 to 10 G, 000 centivoids or higher at 25°C is to use low molecular weight polymers suitable as chain terminators. A silanol material is used and the desired amount of such chain terminator is added to a mixture of the desired cyclotetrasiloxane and an appropriate amount of acidic or basic equilibration catalyst and the mixture is equilibrated to form the desired polymer. It is a turtle that manufactures. Such low molecular weight silanol-terminated diorganopolysiloxane polymers are preferred as chain terminators for the production of high viscosity diorganopolysiloxane polymers.

This is because, in the presence of a filler, prior to curing of the composition, the silanol groups present in the polymer render the composition so overly structured that it becomes substantially useless. This is because it acts as a force. therefore,
Silanol group''!!, 9 means the presence of moisture means heat vulcanization (crosslinking)
It is desirable to prepare high viscosity diorganopolysiloxane polymers having organic groups selected from alkyl and aryl groups, particularly methyl and phenyl groups, for use in silicone rubber compositions.

Therefore, the fact that silanol groups could be advantageously introduced into a 2g combination of high molecular weight diorganopolysiloxanes containing fluorinated substituents was surprising. However, regarding the production of diorganopolysiloxane polymers having fluorinated substituents, it is necessary to consider conventional methods for producing such polymers. The triorganosiloxy-terminated high viscosity diorganopolysiloxane summer polymer containing four fluorinated substituents is prepared by first selecting a suitable fluorinated substituent-containing diorganodichlorosilane and hydrolyzing it. The acidity of the collected hydrolyzate is then reduced to a suitable level and the hydrolyzate is then separated from excess water. A suitable amount of an alkali metal hydroxide catalyst is then added to the purified hydrolyzate and the hydrolyzate is heated to a temperature of about 200° C. or higher to form a cyclic trisiloxane with a fluorinated lf substituent. In the chemistry of monofluorosilicone, which is preferentially distilled out as an overhead distillate, it is known that cyclic trisiloxanes react more easily to form polymers than the corresponding cyclic tetrasiloxanes. There is. Therefore, a cyclic trisiloxane with a suitably formed fluorinated substituent was selected, and a basic polymerization catalyst was added thereto with an appropriate amount of a triorganosiloxy-terminated low molecular weight polymer. The resulting mixture is heated to an elevated temperature IfIC to form the desired diorganopolysiloxane 1. However, from the start, such fluorinated substituent-containing cyclic trisiloxanes rapidly polymerize to form the desired high or low molecular weight IIE'M.

Thus, conventional low molecular weight triorganosiloxy-terminated diorganopolysiloxane chain terminators are fluorinated and react quickly enough to form a cyclic trisiloxane reaction mixture. It was found that he was not responding inside.

That is, such conventional chain terminators are suitable for reacting with the cyclic trisiloxane reaction mixture to form diorganopolysiloxane polymers of the desired molecular weight.
It was recognized that time was required. Without the use of such interlocking low molecular weight triorganosiloxy-terminated chain terminators, low or high viscosity fluorinated bamboo group-containing diorganopolysiloxane polymers will eventually undergo biofluorinated substitution. It is formed and destroyed within one hour by equilibration reaction of the group-containing cyclic trisiloxane. Furthermore, if the chain terminator can react more rapidly in the fluorinated substituent-containing cyclic trisiloxane reaction mixture, then the reaction at 25° C.
High viscosity polymers with viscosities of 0 to 30 CLOOQOOOO centipoise, more preferably 1,000.000-50 (LUOo, 000 centipoise) could be prepared with equilibration reaction times as short as one hour. Therefore, when presenting a fluorinated substituent-containing cyclic trisiloxane,
50 at 25°C (LOOO~s o ao o Q, o
It would be highly desirable to find a chain terminator suitable for producing highly viscous polymers with a viscosity of 0 centiboise in a short time of about 1 hour. This would provide a more efficient and economical method for the production of fluorinated substituent-containing silicone polymers, and thus for the production of fluorinated substituent-containing silicone elastomer compositions. In this respect, the chain terminator selected for such a process is a polymer that exhibits good physical properties comparable to polymers containing fluorinated #I substituents produced by prior art processes. It was desirable to give

The present invention is based on the formula (a): %Formula %) (wherein R and 1 represent a group selected from a monovalent hydrocarbon group and a fluorinated side-attached hydrogen group, and 1 is a cyclic group) When the polysiloxane is a mixture, a part of it is a fluorinated side hydrogen group, and t represents 3 gold), or a mixture thereof, (tl): (in the formula , ? and R1 are monovalent hydrocarbon groups and halogenated -
A first step of reacting a chain terminator (representing a group selected from side-attached hydrogenated groups and representing an integer from 2 to 50) with a basic polymerization catalyst and (c) a basic polymerization catalyst, and a second step of neutralizing the basic polymerization catalyst. The present invention provides a method for producing a fluorosilicone polymer comprising two steps. In the method, the cyclic polysiloxane is a cyclic polysiloxane having the formula or represents a phenyl group R1
It is preferable to use a corresponding cyclic tridimxane when represents a fluoroallic group, such as a [u-trifluoropropyl group.

Furthermore, as another gist of the present invention, (aJ formula: % formula %
Cyclic polysiloxane of [31 (wherein - and - represent a side hydrogen group, a fluorinated side hydrogen group, and a mixed group thereof, and t represents 3), (b) formula ni〇 A first step of reacting a chain terminator of H (in the formula, - represents an aliphatic-side hydrogenated group having 6 carbon atoms with # atoms) and (0) a basic polymerization catalyst; The present invention provides a method for producing a fluorosilicone polymer, which includes a second step of neutralizing a basic polymerization catalyst.

This second method of the invention allows the use of four fluorinated substituents in the preparation of polymers other than diorganopolysiloxane polymers. However, this process is particularly advantageously used for the preparation of diorganopolysiloxane polymers containing fluorinated substituents. Both of the above two methods of the present invention involve the preparation of high molecular weight diorganopolysiloxanes containing fluorinated substituents, e.g.
It is particularly preferred for the production of polymers with viscosities in the range of 00 to 30 centiboise. In either method, the cyclic siloxane is preferably a cyclic trisiloxane, since the advantages of using the novel chain terminator described above are particularly relevant for fluorinated substituents in the equilibration reaction of cyclic tridicuxanes. This is because it is remarkable in the polymerization reaction of tricyclic trisiloxane.

In the first process of the present invention for the production of the entire diorganopolysiloxane type, the process is limited to the production of diorganopolysiloxane polymers containing fluorinated substituents. Therefore, in formula (1), R is preferably an argyl group having 1 to 8 carbon atoms; examples include methyl, ethyl, propyl; aryl groups; examples include phenyl, methyl-phenyl, ethyl-phenyl; cyclo It is a monovalent hydrocarbon group selected from alkyl, S, 1 and 7#kenyl groups such as cyclohexyl and cyclohexyl, for example, vinyl. It is preferable that KR is an alkyl group having 1 to 8 carbon atoms, such as a methyl group, or a phenyl group. Also formula] 1
), R breath is a fluorinated side hydrogen group, particularly preferably a fluoroalkyl group such as he-43-trifluoroglobyl group. In this method it is particularly preferred that t is 3, ie the cyclic siloxane is a cyclic trisiloxane.

In the chain terminator of formula 12), P and R'' are groups selected from the group consisting of -side hydrogen groups and norogenated -valent hydrocarbon groups, such as alkyl groups having 1 to 8 carbon atoms; phenyl , aryl groups such as methylphenyl; cycloalkyl groups; pulkenyl groups such as vinyl, allyl, etc.;
and 3. It is a fluoroalkyl group such as 3-trifluoropropyl. It will be clear that , I and P can be essentially alkyl groups, or groups chosen from alkyl and aryl groups, such as methyl and phenyl groups. However, in particularly preferred embodiments, one of y and y is an alkyl or aryl group of 1 to 8 carbon atoms, such as methyl or phenyl, and the other is a fluoroalkyl group, such as 5- In formula (2), which is preferably a trifluoropropyl group, e is an integer of 2 to 50. Typically, one method for producing diorganopolysiloxane polymers having low molecular weight silanol end groups of formula (2), as described below, consists of approximately 70% siloxy units having three siloxy units, disiloxy, tetra A polymer mixture containing 30% of a diorganopolysiloxy polymer mixture with silanol end groups such as siloxy, pentasiloxy, hexasiloxy, heptasiloxy, octasiloxy, etc. is obtained.

Therefore, in the method of the present invention, it is of course possible to use one type of polymer, but a mixture of diorganopolysiloxane polymers containing silanol end groups in which B in formula (2) takes a uniform integer value can be used. It should be understood that mixtures can be used and that such mixtures are usually used.
In the following, a method for producing a cyclic polysiloxane having a fluorinated group is specifically explained. In the first step, as is known in the prior art, a suitable fluorine substituent is added to a diorganodichlorosiloxane. and hydrolyze it in water. After hydrolyzing these diorganodichlorosilanes in water, excess water and acid are separated from the hydrolyzate (hereinafter abbreviated as hydrolyzate). The hydrolyzate can then be washed with water and treated with a weak base such as sodium bicarbonate to neutralize the acid. If the acid content of the hydrolyzate is below the standard value, collect the hydrolyzate and add an alkali metal hydroxide such as sodium hydroxide to it.
5% by weight and heating the hydrolyzate mixture to a high temperature of 200° C. or higher under atmospheric or reduced pressure to preferentially convert the hydrolyzate to a cyclic siloxane and to convert it as an overhead distillate. Distillate. In this way, from the hydrolyzate, 3~
Cyclic polysiloxanes containing 10 SiO groups, mainly cyclic trisiloxanes and cyclic tetrasiloxanes, can be distilled off from the top of the column. In the process of the invention, this decomposition step is carried out in such a way that the cyclic trisiloxane is preferentially obtained as an overhead distillate, since it is particularly easy to carry out when applying VC to the polymerization of cyclic trisiloxane. . This increases the temperature of the decomposition reactor to a point where K is high enough to boil cyclic trisiloxanes with fluorinated a substituents, but not high enough to boil cyclic tetrasiloxanes and higher boiling cyclic polysiloxanes. This is achieved by maintaining the temperature at a high temperature. Therefore, using such a method, a large portion of the hydrolyzate can be converted into cyclic trisiloxane, which can be separated and collected from the hydrolyzate mixture by distillation. These cyclic trisiloxanes are then used as main reactants for the preparation of the tetrafluorinated substituent polymers which are the object of this invention. It will be appreciated that diorganodichlorosilanes and therefore cyclic trisiloxanes usually have methyl, penta-3-trifluoropropylsiloxy groups as basic substituents or siloxy groups in their molecules. This is because such groups are included in the fluorinated W substituent-containing cyclic trisiloxane, which can be easily prepared. Expression +
It may be necessary to explain the method for producing the chain terminator No. 21. The method for producing the chain terminator is described in U.S. Pat.
No. 53,832. However, to explain the description of the patent #14F, firstly, the above-mentioned cyclic trisiloxane may be dimethyl or diphenyl cyclic trisiloxane or preferably methyl&45-)lifluoroprobyl cyclic trisiloxane. The weight of Km trisiloxane, acetone and 19% distilled water were added to the mixture, and 11-5% weight activated clay (Filtrol 0orfo, Los Angeles, California) was added to the mixture.
(commercially available from Ration). It will be appreciated that the acid-activated clay acts as a catalyst in the reaction mixture. The resulting mixture is heated under reflux for 16 hours, during which time an additional amount of water is added. Heating IS! The temperature is in the range of 50475°C. After heating for a total of 16-24 hours, acetone, the above formula) 2
), a mixture of a low molecular weight diorganopolysiloxane polymer with four silanol end groups, water and clay is obtained.

The resulting mixture was passed through F through Celite (-S of diatomaceous earth) to separate the white clay. The mixture is then heated to remove the solvent mixture, namely acetone and water, by stripping. Finally, mix the mixture in a nitrogen stream at 70-10
Heat to 0°C to remove residual acetone and water.

Thus 70-90% of polymers with 3 siloxy units
The silanol end group of formula (2) consisting of a mixture of polymers with the remainder having 2.4, 5.6 and 7 siloxy units and a trace amount of a polymer having 8 siloxy potentials is added. A reaction mixture is obtained which is a low molecular weight diorganopolysiloxane polymer. The polymer usually has a temperature of 100 to 2 at 25°C.
The viscosity is in the range of 0.00 cm to 5 to 7%.
It has a silanol content of The method explained above is based on the formula (2
It should be noted that other methods for the preparation of chain terminators with silanol end groups () are also available. For example, diorganodichlorosilane The hydrolyzate obtained by hydrolyzing and ffa can be used as a chain terminator in the method of the present invention. 4 It should be noted that the presence of substituents is not essential, so simply a methyl substituent or methylphenyl or diphenylAle
Silanol-type chain terminators of formula (2) having only groups or four substituents other than fluoroalkyl substituents can be used as b-chain terminators in the process of the invention. Additionally, cyclic polysiloxanes, preferably cyclic trisiloxanes or Fi cyclic tetrasiloxanes, may be used in the process of the invention. Cyclic trisilophenes having fluorinated substituents are preferred in the process of the present invention for the production of both low molecular weight and high molecular weight fluorinated substituent-containing diorganopolysiloxanes. Particular preference is given to using cyclic trisiloxanes. Accordingly, the desired amount of chain terminator is mixed into the cyclic polysiloxane of formula (1) and mixed to give at least 10 pp.
Add m basic polymerization catalyst. It is particularly preferred that the basic polymerization catalyst is an alkali gold hydroxide such as potassium hydroxide.

See, for example, U.S. Pat. No. 4,002,951. However, other basic polymerization catalysts, such as alkali metal silates and also complex alkali metal salts, can also be used in the process of the invention as well as in the prior art. The resulting mixture is then heated to a high temperature, e.g.
The linear fluorinated substituent-containing diorganopolysiloxane is heated to remove the silanol end groups by heating at a temperature VC of 20 to 180°C, preferably 14° to 80°C, for 5 minutes to 4 hours, optimally 30 minutes to 1 hour. Produces a polymer. The process of the present invention has been found to be useful in preparing high viscosity linear diorganopolysiloxane polymers containing fluorinated mono-substituents. Such a polymer has a viscosity of 500°000 to 30°C (LOOO centiboise) at 25°C. In the production of such a high viscosity fluorinated substituent-containing electropolymer, the viscosity is approximately 400°C. It should be noted that preference is given to using a mixture containing 1000 ppm silanol-type chain terminator and at least 410 ppm basic polymerization catalyst.4
00 to 2000 ppm (7) It is more preferable to use a silanol type chain terminator and 20 to 50 ppm of a basic polymerization catalyst. The reaction time can be varied within the range of 5 minutes to 4 hours, but is usually 5 minutes to 2 hours, more preferably 30 minutes to 1 hour.
It should be noted that it is about 4 hours. After this polymerization time, a neutralizing agent is added to the reaction mixture to neutralize the catalyst. Such neutralizing agents may be silyl phosphates, such as those described in US Pat. No. 854,562 (Ragzano et al.), filed November 25, 1977. Chlorosilane, acetic acid, and various other weak acids can also be used as neutralizing agents.The advantage of usyryl phosphate is that, similar to acetic acid neutralizing agents, it is a buffering agent that does not require back titration to reach substantial benefits in the polymerization mixture. This is the point where it acts as After neutralizing the reaction mixture, the mixture is heated to a temperature of at least 150 DEG C. for at least 1 hour and excess cyclic polysiloxane is removed by stripping to yield the desired polymer. It should be noted that this method can be used to obtain desired polymers containing 5X or less of volatile or cyclic polysiloxane in the equilibrium mixture.

500,000 to 30 o, o, o at 25°C.

, 0 centivoise viscosity, more preferably 1.00
α000~s o a, o o o, o o a A linear diorganoborisilocyanate 71 polymer containing a substituent was used, and various fluorinated silanol terminal groups were used as described above, with a viscosity of α000~s o a, o o o, o o a centipoise. It has been found that fillers of the type can be incorporated to form core pounds, particularly from 5 to 300 parts of filler per 100 parts of polymeric base.

The filler is selected from silica fillers and extender fillers.

Examples of silica fillers, particularly reinforcing silica fillers, include fumed silica and precipitated silica and particularly U.S. Pat.
Cyclic tetrasiloxane treated silica as described in &009 and further treated with silazane and diethylhydroxylamine reinforced silica fillers. Processing aids, such as those described in U.S. Pat. No. 4,089,933, are typically added to the mixture of polymeric base and filler that is compounded in a dough mixer. Such processing aids prevent the resulting composition from undergoing structural changes prior to curing and from sticking to compounding mills, as described in the US patent. Various other additives may be added to these ingredients, such as oil resistance additives, flame retardants such as carbon black and platinum, and compression set prevention additives such as rare earth octoates. can. An organic peroxide type catalyst such as dicumyl peroxide, dibenzoyl peroxide, etc., such as those described in U.S. Pat. The composition is cured to form a silicone elastomer having fluorinated substituents. Silicone rubber compositions containing fluorinated substituents, especially silicone rubber compositions containing thermally crosslinkable fluorinated substituents, have excellent solvent resistance (especially useful because they produce silicone/elastomers). be.

All conventional methylphenyl type polymer bases intended for the production of thermally crosslinkable silicone rubber compositions are combined with water or, if the polymer base has silanol groups, with fillers and compounds. It should be noted that compounding is not possible as this results in a composition that disintegrates into embedding rags or that causes structure formation when chemically processed.

Furthermore, it should be noted that in the X11 product which contains a peroxide catalyst, the peroxide catalyst is activated by heating it to a temperature of 100° C. or higher. The present invention also provides fluorinated substituent-containing 81H olefin platinum-catalyzed compositions such as those described in U.S. Pat. No. 4.06'i, '609.
established 5i) (olefin plati)
nQm catalyzed compoaitow)
It can also be used to make polymeric bases that are useful for. In the method of the present invention described above, the siloxane of the formula (110) does not necessarily have to be a pure substance, but may be a mixture of a cyclic trisiloxane and a cyclic tetrasiloxane, and its n
Formula Q trisiloxane is a trisiloxane containing a fluorine substituent,
It can also be a cyclic tetrasiloxane containing 11 vinyl substituents or menarvinyl ash substituents. The cyclic tetrasiloxane or methylvinyl N-tri'7xane is present in the reaction mixture to introduce vinyl groups into the final polymer formed, whereby the composition is cross-linked with a peroxide catalyst. Although the method of the present invention can be advantageously used to form a thermally crosslinkable fluorinated substituent-containing silicone elastomer capable of forming Tk bonds, the improved insulator expansion according to the present invention can be applied to Siloxanes also more commonly have fluorinated substituents and have a strong formula (
3) has at least 6 carbon atoms, more preferably at least 1
High molecular weight alcohols with 0 carbon atoms, such as aliphatic side-chained hydrogen radicals with 10 to 30 carbon atoms, such as octadecanol, hexadecanol, tetradecanol, oleyl alcohol, etc. This can be accomplished by reacting a chain terminator.

High molecular weight alcohols, especially high viscosity linear diorganopolysiloxa heptapolymers, such as 5011 at 25°C
1.000~300. OOQ, 000-t Nchiboiz,
More preferably 1.00 (L00G~30QOOO,0
It has been found advantageous to use VC4 as a chain terminator in processes for the preparation of polymers having viscosities of 0.000 centivoise or more. These high molecular weight chain terminators will be incorporated into the mixture at substantially the same rate as the silanol type chain terminators of formula (2). These alcohol-type chain terminators are less expensive to obtain and require special methods for their manufacture. Such higher alcohol type chain terminators can be utilized as chain terminators in equilibration reactions in the preparation of both polymers containing fluorinated substituents and polymers with many fluorinated substituents.

Therefore, in equation (3)? and t represent a group selected from the group consisting of a monovalent hydrocarbon group, a fluorinated side-attached hydrogen group, and a mixed group thereof, and t represents 3; 6R4
and 1 carbon number, such as methyl, ethyl, propyl, etc.
~8 alkyl groups, alkenyl groups such as vinyl, allyl, cycloalkyl groups such as cyclohexyl, cycloheptyl, aryl groups such as phenyl, methyl-phenyl, ethylphenyl, and carbon such as 4A3-)realolpropyl. It can be a group selected from several 3 to 8 fluoroalkyl groups. Additionally, cyclic trisiloxanes and cyclic tetrasiloxanes or higher cyclic siloxanes may be included in the reaction mixture of cyclic polysiloxanes. Preferably, the cyclic siloxane is either a cyclic trisiloxane or a mixture of a cyclic trisiloxane and a cyclic tetrasiloxane. In a particularly preferred embodiment in this case, in the compound of formula (3), ν is an alkyl group having 1 to 8 carbon atoms, for example a methyl group, and ax is a 43-trifluoropropyl group, and t
It is. In such a cyclic trisiloxane, t is 4 and -
is methyl and - is vinyl. The mixture is fluorinated! ! This substituent is necessary for the production of high molecular weight vinyl group-containing fluorinated substituent-containing diorganopolysiloxane polymers which are useful in the production of thermally cross-linking silicone elastomers.

The method for preparing the fluorinated substituent-containing cyclic trisiloxane is the same as described above in this embodiment. Methyl vinyl cyclic tetrasiloxa 7 is prepared in a similar manner by using the appropriate diorganodichlorosilane. The difference between the two methods is that in the decomposition step the reaction mixture is heated to a higher temperature in order to preferentially distill off the cyclic tetrasiloxane from the top of the column. An improved method allows the cyclic tetrasilokidane to be distilled overhead at maximum efficiency by condensing the boiling cyclic trisilokane and returning it to the cracking reactor for use in the reaction again. Can be separated.

Thus, after a suitable cyclic siloxane is obtained, it is mixed together in the appropriate proportions and a commercially available higher alcohol type chain terminator is added to the mixture in the desired proportion. Then, an appropriate amount of basic polymerization catalyst is added. Concerning the concentration of the chain terminator, the higher alcohol type chain terminator should be at least 450 ppm to 2.000 ppm.
pm, and the basic polymerization catalyst is used at a concentration of at least 10 ppm, more preferably from 20 to 50 ppm.
used at a concentration of In the production of polymers containing fluorinated substituents, only Shin-style tetrasiloxanes are used with higher alcohol-type chain terminators and basic equilibration catalysts such as alkali metal hydroxides. Dew.

The resulting mixture is heated to a temperature above 140 DEG C. for a period ranging from 2 to 24 hours until the desired high viscosity polymer maximum is obtained. The reaction mixture is then cooled and the basic equilibrated catalyst is mildly removed! The desired polymer is neutralized with an acid such as silyl phosphate or acetic acid and the unreacted cyclic siloxane is removed by stripping to leave the desired polymer. In the production of polymers with four fluorinated substituents, cyclic trisiloxanes with fluorinated substituents are used alone or in the form of mixtures with vinyl group-containing cyclic trisiloxanes or methyl-vinyl cyclic trisiloxanes. , in the presence of an appropriate amount of an alcohol-type 8-chain terminator and a basic polymerization catalyst at the concentration shown below, such as potassium hydroxide or potassium syralate, at a temperature of 120 to 180°C +1, usually for 5 minutes to Polymerization is carried out by heating for 4 hours, more preferably 5 minutes to 2 hours, particularly preferably 30 minutes to 1 hour. After said polymerization time has elapsed, the basic polymerization catalyst is treated with a mild acid, such as silyl phosphate, or other OA, preferably for the reasons mentioned above.
Neutralize with a mild acid, such as acetic acid. The same basic polymerization catalyst used in Embodiment 9 above and described in the aforementioned US Pat. No. 4,002,951 may be used in this embodiment. Further, as a chain terminator, any high molecular weight aliphatic alcohol, preferably having 6 to 30 carbon atoms, more preferably 10 to 30 carbon atoms, can be used in this method. -It should be E. After the polymerization reaction is completed, the reaction mixture is cooled, a neutralizing agent is added, and the reaction is preferably terminated within 30 minutes to 1 hour. The reaction mixture is then cooled and a neutralizing agent for the basic polymerization catalyst, such as silyl phosphate, is added for the reasons mentioned above. Unreacted cyclic siloxane is then removed to leave the desired R(combination). Removal of unreacted cyclic siloxane is carried out by heating the reaction mixture to a temperature of 150° C. for at least 41 hours. The second embodiment can be used in the production of diorganopolysiloxane polymers of various viscosities, but is particularly suitable for use in the production of high molecular weight linear diorganopolysiloxane polymers containing fluorinated ti1a groups. It should be noted that preference is given to the formula: (wherein ? and I represent groups selected from monovalent hydrocarbon groups and halogenated side-attached hydrogen groups, and RlO represents at least 6 and more preferably represents an aliphatic group having at least 410, usually from 10 to 30 carbon atoms, where n is such that the viscosity of the polymer is 50+ at 25°C.
A polymer of 1,000-30 G, 00 Q, OOO centivoise is an integer varying within a range is obtained. Usually, and t in the cyclic trisiloxane of formula (3)? and - can be any group or substituent, where I is preferably an alkyl group having 1 to 8 carbon atoms, and t is A! %3-trifluoropropyl group, R10 is preferably an octadecyl group.

1. Preferably at 25°C. dOQOOOO~
500.00 (LOOO centiboise viscosity) is selected as the polymer base, and for every 100 parts thereof, 5 to 300 parts of filler, particularly preferably selected from fumed silica and precipitated silica, are used for reinforcement. Optionally, a silica filler, preferably a silica filler treated with a cyclic polysiloxane or a silica filler treated with silazane or diethyl-hydroxylamine as described in the aforementioned U.S. Pat. Various processing aids, such as those described in the aforementioned U.S. Pat. Processing aids such as and other components of the scale described in the first aspect of the invention are added, a peroxide catalyst is incorporated into the resulting mixture, and the resulting mixture is heated to a temperature of 100° C. or higher, as described above. Thus, it is possible to produce a silicone elastomer containing a fluorinated w1 substituent which has excellent solvent resistance.

It is observed that the fluorinated substituent-containing silicone elastomers produced by the above process have good physical properties comparable to elastomers produced by prior art processes. Additionally, the fluorinated substituent-containing polymers and dimethyl polymers prepared by the process of the present invention may be used in olefin platinum-catalyzed compositions as described in U.S. Pat. No. 4,061,609. It is possible.

Next, the present invention will be further explained by examples. Needless to say, these are additional limitations to the present invention. In the examples, all sections are repeated sections.

Example 1 Methylfluoropropylcyclotrisiloxane and octadecanol as shown in Table 1 below were charged into a reactor, and the resulting mixture was heated to 155°C and purged in a chamber to remove traces. water was removed. Methylvinylcyclotrisiloxa/hydroxide) IJium catalyst was added to initiate the polymerization reaction. After 38 minutes, the reaction was stopped by removing the heating bath and introducing carbon dioxide gas. , and finally the polymer was neutralized by mixing with silyl phosphate in a dough mixer. Volatile content was measured as described in Table 1. The volatile content was determined by heating the polymer in a shallow dish at 155 DEG C. under 15 m vacuum for 45 minutes and measuring the weight loss. The Williams plasticity of the resulting polymer before and after removal of volatiles is shown in Table 1. The experimental results are shown in Table 1.

Table 1 Two of these polymers were combined with 100 parts of polymer, 3 parts of dimethylsilanol oil processing aid, 4 parts of tin cane vinyl rubber processing aid with high vinyl content containing 155 moles of vinyl groups, and tetramer. Compounding was performed by mixing 23 parts of the treated fumed silica filler and 12 parts of red iron oxide. The compounded components were pressure cured with 1.6 parts of bis(2,4-dichlorobenzoyl) peroxide having an active content of 50% by weight. These compositions are shown as Compositions C and D in Table 2 below. The physical properties of these crosslinked cured compositions cured under the conditions in Table 2 are shown in Table 2.

Table 2 Example 2 Polymers were prepared by the method of the present invention using silanol-type chain terminators with fluorinated substituents and by the prior art method. After preparing the polymers by the prior art method and the method of the present invention, the polymers were heated to 350° C. for 15 minutes in the presence of moist nitrogen acting as a hydrolyzing agent to increase the tendency of the polymers to decompose. The results are shown in Table 3. Table 3 shows the 1ffl weight loss of the polymer under the above test.

Polymer Williams plasticity terminal group heavy didynamics %K 251
-51 (c) Crow OH11,9F 281
-5t (cFI3) (on) (a given 0 & (M)
1[LOa 332, -
81(C%X0HX(%C%C1%) fL7
H250-81 (C-)! 1
2.4I 267-81 (C! Crow h7.3J
276-81 (C! Karasu) 3 & 5 The results in Table 5 show that polymers produced using silanol-type chain terminators, particularly fluorinated substituent-containing silanol-type chain terminators, are less likely to be produced using trimethylsiloxy-type chain terminators. Comparison with the produced polymer shows that it has the same stability as that of the polymer.

Example 3 Into a clean, dry reactor, 500 parts (1
, 06 mol), 1. to 5,7-titramethyl-1.3.
5.7-Titravinylsiloxane cyclic tetra? −(V
T) 1.43 parts ([1001 mol), and 1°3.5
-) 149 parts (1001 mol) of samethyl-1,45-tris(sim'3'-)lifluoroprobyl)trisiloxane-1,5-diol were charged. The reactor contents were heated to 120-140°C and purged with nitrogen until 25 parts of trimer were removed and the water content was reduced to less than 10 ppm. The reactor temperature was adjusted to 140°C and when this temperature was reached, the sodium fluorosilal-)CL9
13 parts (sodium hydroxide [gives 1025g])
was added.

The polymerization was allowed to proceed for 8-10 minutes under stirring, and then the silyl phosphate (corresponding to a 13% solution of T3sPOa) was added.
The catalyst was allowed to stand for up to 35 minutes before being neutralized. The polymer was then held at 150-160°C until the volatile content reached a level VC of α8 to α5X to remove the volatile content. A highly tough rubber with a Williams plasticity of 255 was obtained. This polymer is in the bath of 2.112! 1. It had a viscosity If (measured under 77 for a 92% ethyl acetate solution). Compounding gave this rubber a crosslinked (vulcanized) rubber with good properties.

Composition: Polydimethyl containing 155 moles of vinyl groups on 100 chains
4HO (=Si(Me)z-0-+-H3 fumed silica*123 rare earth metal octo-) a2TS
-501)21.6 Bone11. ! Fumed silica treated with 1,5.8-octamethylsiloxane tetramer 2 bis(z4-dichlorobenzoyl) peroxide, 50% active paste; Bottle 0adox TS-50, Novr
Manufactured by yChemical Corp., located in New York)*
Lupereo (Lubel: I) C! BT, L
ucidol Div.

Hardness: Shorem 4143 Tensile Strength: psi 1076 1145
Elongation % 670 630 Tear strength Type C) Bond 118 102 Hardness Shore A 40 44 Tensile strength psi N40 995 Elongation %
690 590 Tear strength type C) Bond 115 105 Boishyore (Bo
yshore) 40 Example 4 500 parts (1,06 mol) of fluorosilicone trimer, methyl and nitrimer t4 were added to a dry reactor.
3 parts ((LD 01 mol) and 1. Molar trimethyl-
161 parts of 1,45-tris(A'3.i'-trifluorobropyl)trisiloxane-1,5-diol ((L
12 moles of OO) were charged. Reactor contents '1120
The reactor temperature was adjusted to 140°C by heating to ~140°C and drying the system as in Example 1. As a catalyst, sodium fluorosyralate was added in an amount equivalent to 0017 parts (α00042 mol) of sodium hydroxide. , the polymerization was terminated after 35 minutes by neutralization with silyl phosphate. Add the obtained rubber to 15
The volatile content was reduced to [18
±α5%. Thus, Williams plasticity is 258.
I got a rubber band with a hermitage. This polymer has a solution viscosity of 2.177 [
(measured at 77? as a 2N ethyl acetate solution) and 37°C
had a torque reading of 800 m·V on the graveender at a shear rate of 40 rpm. This rubber was compounded and crosslinked according to the method of Example 5 to give the following physical properties.

Properties Hardness Shore A 41 Tensile strength psi 1095 Elongation%
650 Tear strength C) Bond 135 Example 5 Fluorosilicone trimmer 2 in a dry reactor
10 parts ((145 mol), 16 parts (α007-el) of methyl and niltrimer and 1.5-trimethyl-1,4
5-tris(4'8'3'-trifluoropropyl)trisiloxa/-1,5-diol (1104 parts ((10
002-1-le) was charged. The polymerization mixture was dried according to the method described in Examples 3 and 4 to remove 10 parts of fluorosilicone trimer. 1.3.5.7-Octamethyl-siloxane cyclic tetramer in colloidal sodium hydroxide (particle size 25-30
micron) was added as a catalyst. , the polymerization was carried out for 35 minutes, and then Example 1
The catalyst was neutralized and the rubber was devolatilized according to the method described in . A rubber with a Williams plasticity of 305 was obtained, a shear rate of 40 rpm, 57°C.
A torque of 880 m-9 was recorded on the Gravender. This polymer gave a solution viscosity of 2.541 (measured under 77 for a 2% solution in ethyl acetate).

Claims (1)

[Claims] 1. Formula (a): (R^4R^5SiO)_3 (wherein R^4 and R^5 are a monovalent hydrocarbon group, a fluorinated monovalent hydrocarbon group, or a mixture thereof (b) a chain of the formula; The first step is to react the terminator and (c) the basic polymerization catalyst at a temperature of 120-180°C for 5 minutes to 4 hours, and the second step is to neutralize the basic polymerization catalyst.
500,000-300,000 at 25℃
A method for producing a fluorosilicone polymer having a viscosity of 0,000 centipoise. 2. The manufacturing method according to claim 1, wherein R^4 is a group selected from an alkyl group and a phenyl group, and R^5 is a 3,3,3-trifluoropropyl group. 3. The manufacturing method according to claim 1, wherein R^6 contains 10 to 30 carbon atoms. 4. The production method according to claim 1, wherein the basic polymerization catalyst is an alkali metal hydroxide. 5. The production method according to claim 1, wherein the chain terminator (b) is used in a proportion of at least 50 ppm and the basic polymerization catalyst in a proportion of at least 10 ppm. 6. Further heat the mixture to at least 150°C for at least 1
The manufacturing method according to claim 1, further comprising a step of heating for a period of time and removing volatile components by stripping. 7. Prior to the first step, diorganodichlorosilane having the same organic groups as R^4 and R^5 is hydrolyzed in water to produce a hydrolyzate, and the hydrolyzate is mixed with water and most of the The process of separating the polysiloxane from the acid, adding an alkali metal hydroxide catalyst to the hydrolyzate, and heating the mixture to 200°C or higher to preferentially distill off the desired cyclic polysiloxane from the top of the column is claimed. The manufacturing method described in Scope 1. 8. Formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^8 and R^9 represent groups selected from monovalent hydrocarbon groups and halogenated monovalent hydrocarbon groups, and R^1^ 0
represents an aliphatic group having at least 10 carbon atoms, and n is such that the viscosity of the polymer is 500,000 to 300 at 25°C.
,000,000 centipoise). 9. A patent claim in which R^8 is selected from a mixed group of alkyl and alkenyl groups, R^9 is a 3,3,3-trifluoropropyl group, and R^1^0 is an octadecyl group. Polymer according to scope item 8.