CN1844247A - Method for stabilization of mould made of silicone elastomer - Google Patents
Method for stabilization of mould made of silicone elastomer Download PDFInfo
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- CN1844247A CN1844247A CNA2005100817738A CN200510081773A CN1844247A CN 1844247 A CN1844247 A CN 1844247A CN A2005100817738 A CNA2005100817738 A CN A2005100817738A CN 200510081773 A CN200510081773 A CN 200510081773A CN 1844247 A CN1844247 A CN 1844247A
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Abstract
The invention relates to the use of an addition agent stabilized relative to moulding material of siloxane elastomer composing the die assembly in increasing the service life of the die obtained through siloxane elastomer cross-linking of polycondensation reaction, wherein the addition agent is selected from: (1) at least a symmetrical multiple silicon sulfide alkane, (2) at least a poly(alkylphenol sulphide), (3) at least an alkyl thiuram sulfide.
Description
The present invention relates to be used for the purposes of the additive of stable moiety silicone elastomer by the crosslinked gained mould of condensation polymerization composite.
Another theme of the present invention is to be used to the condensation polymerization composite of these silicone elastomer preparations.
That the further theme of the present invention is so to obtain, be used for mould by molding is decorated and industrial article duplicate.
Another theme of the present invention is the preparation method of silicone mold.
Silicone composition, especially siloxanes condensation polymerization composite are used to duplicating by molding decoration and industrial article.Duplicating of article comprises, in the first step, makes the former of the article that will duplicate.This former is by the silicone elastomer preparation and be called as " diaphragm ".After silicone cross-linked, this diaphragm is separated with initial article.This diaphragm constitutes the mould that duplicates that will be used to duplicate article.
This type of mould is widely used in duplicating of the article made by resin such as vibrin, and it can verily duplicate the meticulousst details.Yet in this application process, the experience sex change gradually easily of this mould: the composition of vibrin, especially vinylbenzene diffuse into polymerization take place in the diaphragm.The physical chemistry structural modification of the mould that contacts with described resin: it hardens gradually, loses its antiseized character and tearing strength simultaneously.These sex change finally cause when the described polyester article demoulding, and this die surface fragment is shut down.This moment, this mould was die on.
This has related to multiple degradation mechanism.They may depend on the standard relevant with silicone elastomer as depending on resin or condition of moulding.Possible is that polymerization mechanism is a free radical mechanism: the formation of free radical, the initiation of cinnamic radical polymerization and growth.High vinylbenzene or peroxide level, the exothermal nature of resin polymerization and the existence of oxygen all are degradation factors.The diversity that can influence the silicone mold factors of degradation means that the solution that is provided also was not entirely satisfactory up to now.
Improving silicone mold introduces in this elastomerics the derivative that a kind of method of vibrin resistibility is to suppress one or more stages of radical polymerization.
Therefore European patent application EP-A-787766 provides improvement to the silicone mold life-span by introduce additive in condensation polymerization composite, and it maybe can be the bulky amine with sebacic acid 1-alkyl ester of NR end group that this additive is selected from sterically hindered phenol, steric hindrance bis-phenol, steric hindrance thiobisphenol, zinc dialkyl dithiophosphate, diaryl zinc dithiophosphate, aromatic amine.
Among the FR-A-2 773 165, additive is selected from:
-(a) in its structure, comprise at least one R-S
qThe antioxidant addn of-R ' group, wherein R and R ' are for having the monovalence alkyl of at least 3 carbon atoms or having the monovalence alkyl of ester bond, perhaps R and R ' form ring together, q be comprise end value 1 to 3 between integer,
-(b) additive, it is the inhibitor of free radical and it can produce at least one group under condition of moulding:
(a)+(b) synergistic combination,
(a) and/or (b) and the synergistic combination of phosphoric acid salt (c).
The additive of FR-A-2 773 165 comprises:
The carbothioic acid ester of+following formula:
R wherein
5For having the alkyl of 1-15 the carbon atom that comprises end value, the integer that x is an end value between interior 1 to 4, and thiodipropionate (x=2) preferably, wherein the compound that can mention is:
● thio-2 acid two (13) ester (CAS 10595-72-9),
● 3,3 '-thio-2 acid distearyl ester (CAS 693-36-7),
● 3,3 '-thiodipropionate dilauryl (CAS 123-28-4);
+ comprise several sulfide groups R-S that is connected on the tetravalence carbon
qThe compound of-R ', preferred four (thioether) tetramethylolmethane, for example tetramethylolmethane four (lauryl thiopropionate) or PETL (CAS 29598-76-3).
EP-A-854 167 provides a few class additives, comprises phenol, thiodipropionate, polysulfide, phosphonic acid ester etc., and described phenol is sterically hindered.
For the improvement in silicone mold life-span and thus for making the needs of the additive may realize this purpose still exist.
Therefore one object of the present invention is to provide additive; it makes with respect to the resin of the goods that are used to prepare the molding of wanting especially vibrin; can protect the elastomerics that constitutes silicone mold; so that make it possible to achieve than the molding of the bigger quantity of crossing the realization of deenergizing and the appearance of protection moulded product.
Applicant company has been found that the use of specific sulfide makes can increase the life-span of silicone mold with unexpected ratio, and when described silicone mold came from condensation polymerization composite crosslinked, situation promptly was like this.
Theme of the present invention is, a kind ofly can make the silicone elastomer that constitutes mould with respect to the purposes for the treatment of the stable additive of moulding material and be used to increase by the life-span by the crosslinked mould of making of the silicone elastomer of polycondensation, and this additive is selected from:
-(a) at least a " symmetry " that meets following general formula vulcanized silane more:
(G
2)
a(G
1)
3-aSi-R
0-(S
x-R
0)
m-Si(G
1)
3-a(G
2)
x (I)
Wherein:
+ a represents to be selected from 1 or 2 number;
+ m represents to be selected from 1 and 2 number;
+ x is integer or the mark in the 2-6 scope;
+ symbol G
1, it can be identical or different, separately expression: saturated or unsaturated aliphatic alkyl group; Saturated, undersaturated and/or aromatics, monocycle or polycyclic carbon ring group; Or comprise the group of saturated or unsaturated aliphatic carbon based moiety and the isocyclic part that are defined as above;
+ symbol G
2, it can be identical or different, separately expression: hydroxyl or hydrolyzable univalent perssad;
+ symbol R
0The expression divalent group is selected from: saturated or unsaturated aliphatic alkyl group; Saturated, undersaturated and/or aromatic group, monocycle or polycyclic carbon ring group; And the group that comprises saturated or unsaturated aliphatic hydrocarbyl portion and the isocyclic part that are defined as above; Described divalent group randomly replaces with Sauerstoffatom and/or sulphur atom and/or the nitrogen-atoms that has 1 univalent perssad or at interval, this univalent perssad is selected from: hydrogen atom: saturated or unsaturated aliphatic alkyl group; Saturated, undersaturated and/or aromatics, monocycle or polycyclic carbon ring group; With the group that comprises saturated or unsaturated aliphatic hydrocarbyl portion and the isocyclic part that are defined as above;
-(b) at least a poly-(alkylphenol sulfide) with following general formula:
R wherein
1Represent saturated aliphatic hydrocarbyl group, y is integer or the mark in the 1-4 scope, and repeating unit n can be 0,1,2 or higher number;
-(c) at least a alkyl thiuram sulfide with following general formula:
Wherein, R
2, R
3, R
4, R
5, identical or different, represent hydrogen atom separately, saturated aliphatic hydrocarbyl group or saturated monocyclic groups, R
2Or R
3And R
4Or R
5In at the most only one can represent hydrogen atom; Z can be integer or the mark in the 2-6 scope.
More specifically, theme of the present invention is described purposes
In particularly preferred mode, this purposes target is that the quantity that obtains each mould molding increases more than 10%, and is preferred more than 20%, more preferably more than 30%.
Another theme of the present invention is that silicone mold maybe can be used to the preparation method of the silicone elastomer of above-mentioned mould preparation, in the method, is added in the conventional elastomer precursor silicone composition according to disclosed one or more additives above.
The whole features that hereinafter provide all are applicable to these themes.
Above, phrase " aliphatic hydrocarbyl group " refers to the straight or branched group of the optional replacement that preferably comprises 1-25 carbon atom.
Advantageously, described aliphatic hydrocarbyl group comprises 1-15 carbon atom, is more preferably 1-8 carbon atom under some situation.
The radical of saturated aliphatic alkyl group that can be mentioned comprises alkyl such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, isopentyl, neo-pentyl, the 2-methyl butyl, the 1-ethyl propyl, hexyl, isohexyl, new hexyl, the 1-methyl amyl, the 3-methyl amyl, 1, the 1-dimethylbutyl, 1, the 3-dimethylbutyl, the 2-ethyl-butyl, 1-methyl isophthalic acid-ethyl propyl, heptyl, 1-methyl hexyl, 1-propyl group butyl, 4,4-dimethyl amyl group, octyl group, the 1-methylheptyl, the 2-ethylhexyl, 5,5-dimethyl hexyl, nonyl, decyl, 1-methyl nonyl, 3,7-dimethyl octyl group and 7,7-dimethyl octyl group, hexadecyl, tridecyl, stearyl, lauryl.
Described unsaturated aliphatic alkyl group comprises one or more degrees of unsaturation, preferred one, two or three olefinics (two key) and/or acetylene series (triple bond) unsaturated.
The example for by the above-mentioned alkyl that limits by removing two or more hydrogen atom deutero-alkenyl or alkynyls.Preferably, described unsaturated aliphatic alkyl group only comprises a degree of unsaturation.
In the context of the present invention, term " carbon ring group " refers to randomly and to replace, preferred C
3-C
50Monocycle or many cyclic groups.Advantageously, it is C
3-C
18Base is preferably monocyclic, bicyclic or tricyclic.When described carbon ring group comprised more than a nucleolus (under many ring isocyclic situations), those nucleolus condensed in couples.Two condensed are endorsed to be monolateral condensing or peri-condensed.
Unless otherwise mentioned, described carbon ring group can comprise saturated part and/or aromatics part and/or unsaturated part.
The saturated carbon ring examples of groups is a cycloalkyl.Preferably, described cycloalkyl is C
3-C
18And C better
5-C
10What especially can mention is cyclopentyl, cyclohexyl, suberyl, ring octyl group, adamantyl or norborneol alkyl.
Any unsaturated part of described unsaturated carbocyclic or carbocyclic ring class comprises one or more olefinic degrees of unsaturation, preferred one, two or three.Advantageously, it comprises 6-50 and is more preferably 6-20 carbon atom, for example 6-18 carbon atom.The example of unsaturated carbocyclic is C
6-C
10Cycloalkenyl group.
The example of aromatic carbocyclic group is (C
6-C
18) aryl and particularly phenyl, naphthyl, anthryl and phenanthryl.
Not only comprised as defined above alkyl aliphatic series part but also comprised as defined above that the group of isocyclic part for example is that aralkyl adds benzyl, or alkaryl such as tolyl.
The substituting group of described alkyl aliphatic group or part and described carbon ring group or part is an alkoxyl group for example, and wherein moieties is preferably as defined above.
Above about symbol G
2Mentioned phrase " hydrolyzable univalent perssad " refers to such group, for example: halogen atom, particularly chlorine; Group-O-G
3With-O-CO-G
3, G wherein
3Expression: saturated or unsaturated aliphatic alkyl group, or saturated, undersaturated and/or aromatics, monocycle or polycyclic carbon ring group, or comprise group saturated as defined above or unsaturated aliphatic hydrocarbyl portion and isocyclic part, G
3May be halo and/or replace with one or more alkoxyl groups; Group-O-N=CG
4G
5, G wherein
4And G
5Adopt the above-mentioned G that provides independently
3In the implication any, G
4And G
5May be halo and/or randomly replace with one or more alkoxyl groups; Group-O-NG
4G
5, G wherein
4And G
5As above limit.
Advantageously, so hydrolyzable univalent perssad is to be selected from following group: optional halo and/or randomly with one or more (C
1-C
8) the straight or branched C that replaces of alkoxyl group
1-C
8Alkoxyl group; Optional halo or randomly with one or more (C
1-C
8) C that replaces of alkoxyl group
2-C
9Acyloxy; C
5-C
10Cycloalkyloxy; Or C
6-C
18Aryloxy.As an example, described hydrolyzable group is methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, methoxymethoxy, ethoxy ethoxy, methoxy ethoxy, β-chlorine propoxy-or β-chloroethoxy or as the acetoxyl group of selecting.
Many sulfurations silane of formula (I) preferably among the compound (a), wherein:
+ a=1 or 2;
+m＝1；
+ x is 2-4;
+ symbol G
1, identical or different, expression separately: straight or branched C
1-C
8Alkyl; C
5-C
10Cycloalkyl or C
6-C
18Aryl;
+ symbol G
2, identical or different, expression separately: hydroxyl; Randomly with one or more (C
1-C
8) the straight or branched C that replaces of alkoxyl group
1-C
8Alkoxyl group;
+ symbol R
0, identical or different, represent separately: C
1-C
8Alkylidene chain; C
5-C
10Cycloalkylidene; Or comprise in these groups the divalent group of at least two kinds combination.
As many sulfurations silane of formula (I), the example that can mention comprises:
Two-monosubstituted ethoxy dimetylsilyl propyl group the tetrasulfide (being called MESPT) of-following formula:
(C
2H
5O)(CH
3)
2Si-(CH
2)
3-S
4-(CH
2)
3-Si(CH
3)
2(OC
2H
5) (I-1)
Two-diethoxymethyl silyl propyl group the tetrasulfide (being called DESPT) of-following formula:
(C
2H
5O)
2(CH
3)Si-(CH
2)
3-S
4-(CH
2)
3-Si(CH
3)(OC
2H
5)
2 (I-2)
Two-monosubstituted ethoxy dimetylsilyl propyl disulfide the thing (being called MESPD) of-following formula:
(C
2H
5O)(CH
3)
2Si-(CH
2)
3-S
2-(CH
2)
3-Si(CH
3)
2(OC
2H
5) (I-3)
Two-monohydroxy dimetylsilyl propyl group the tetrasulfide of-following formula:
(HO)(CH
3)
2Si-(CH
2)
3-S
4-(CH
2)
3-Si(CH
3)
2(OH) (I-4)
Poly-(alkylphenol sulfide) of formula (II) preferably among the compound (b), wherein: R
1Expression straight or branched C
1-C
8Alkyl; Y is 1-3; With n be 3-8.
The alkyl thiuram sulfide of formula (III) preferably among the compound (c), wherein: the substituent R of nitrogen-atoms
2, R
3, R
4And R
5, identical or different, represent hydrogen atom or straight or branched C separately
1-C
8Alkyl, condition are described substituent R
2Or R
3And R
4Or R
5In at the most only one the expression hydrogen atom; Z is 2-5.
As formula (II) and polysulfide (III), the example that can mention comprises the compound of following formula:
Y=2 wherein, 1 and n=5 (being called TB7);
-and the compound of following formula:
(III-1 is called TRA)
(III-2 is called TETD)
First embodiment that especially is fit to according to the present invention, used additive belongs to (a) class of formula (I), wherein:
+ a=1 or 2;
+m＝1；
+ x is 2-4;
+ symbol G
1, identical or different, expression separately: methyl, ethyl, propyl group, sec.-propyl, cyclohexyl and/or phenyl;
+ symbol G
2, identical or different, expression separately: hydroxyl, methoxyl group, oxyethyl group, positive propoxy and/or isopropoxy;
+ symbol R
0, identical or different, expression separately: the methylene radical of divalence, ethylidene and propylidene.
In such group of preferable additives have described formula (I-1) for being selected from, (I-2), (I-3), (I-4), many sulfurations silane and composition thereof.
Described (a) compounds, and described (b) and (c) whole compounds of class, their usage ratio all especially is per 100 parts of silicone composition 0.2-5 weight parts, preferred 0.5-3 part comprises end value.
Second embodiment that especially is fit to according to the present invention, used additive belongs to (b) class of formula (II), wherein symbol R
1Expression methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl or amyl group.
Such preferred additives is the polysulfide of formula (II-1).
The 3rd embodiment that especially is fit to according to the present invention, used additive belongs to the additive of (c) class, wherein substituent R
2, R
3, R
4And R
5, identical or different, represent hydrogen atom, methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl and/or amyl group separately, condition is described substituent R
2Or R
3And R
4Or R
5In at the most only one the expression hydrogen atom.
The group of such preferable additives is selected from formula (III-1) and polysulfide (III-2).
The more specially suitable embodiment according to the present invention, used additive are selected from many sulfurations silane (a) of formula (I).
The present invention can easily be applied to and can at room temperature (can promote crosslinked under heating condition) by the crosslinked silicone composition of polycondensation.
The present invention is particularly useful for the silicone composition as the silicone elastomer precursor, and it comprises:
-(A) diorganopolysiloxanecompositions oil, but it has the condensation that is selected from that is bonded in silicon, the reactive group of hydrolyzable or hydroxyl end groups;
-(B) randomly, but be selected from the compound of the silane that comprises condensation or hydrolysable group;
-(C) catalyzer;
-(D) randomly, any other additive in the types of compositions that is generally used for being considered.
Therefore one group of siloxanes of available comprises the diorganopolysiloxanecompositions compositions that can be solidified into silicone elastomer by polycondensation according to the present invention, comprising:
-(A) but at least a each end at chain has the diorganopolysiloxanecompositions oil of at least two condensations or hydrolysable group or single hydroxyl,
-(B) be when having hydroxyl end groups oily as (A), but comprise the silane of at least three condensations or hydrolysable group and/or be derived from the product of this silane moiety hydrolysis,
-(C) be used for the catalyzer of described oily polycondensation.
Above or hereinafter, unless otherwise mentioned, per-cent by weight.
Can be used for diorganopolysiloxanecompositions oil (A) in the present composition and meet those of formula (1) more specifically:
Y
nSiR
3-nO(SiR
2O)
xSiR
3-nY
n (1)
Wherein:
-R represents identical or different monovalence alkyl, but Y represents the group or the hydroxyl of identical or different hydrolyzable or condensation,
-n is selected from 1,2 and 3, n=1 when Y is hydroxyl, and x for greater than 1, be preferably greater than 5 integer.
The oil viscosity of 25 ℃ of following formulas (1) is between 10-10
6Between the mPas.As the R examples of groups, can mention alkyl with 1-8 carbon atom, such as methyl, ethyl, propyl group, butyl, hexyl and octyl group, vinyl or phenyl.
As replacing the R examples of groups, can mention 3,3,3-trifluoro propyl, chloro-phenyl-and beta-cyano ethyl.
In the product of industrial used formula (1) usually, the R group of at least 60% number is a methyl, and other groups generally are phenyl and/or vinyl.
As the example of hydrolyzable Y group, can mention amino, amido, aminooxy, ketoimine oxygen base, inferior aminooxy, alkene oxygen base, alkoxyl group, alkoxyl group-alkylene oxide group, acyloxy and bound phosphate groups (phosphato) and, for example, wherein:
-for amino Y group: normal-butyl amino, sec-butyl amino and cyclohexyl amino,
-the amido that replaces for N-: benzoyl-amino,
-for aminooxy: dimethyl aminooxy, diethyl aminooxy, dioctyl aminooxy and phenylbenzene aminooxy,
-for inferior aminooxy and ketoimine oxygen base: derived from those of acetophenone oxime, acetoxime, diphenylketoxime, methyl ethyl ketone oxime, di-isopropyl ketoxime and chlorine cyclohexanone-oxime,
-for the alkoxyl group Y group: have the group of 1-8 carbon atom, as methoxyl group, propoxy-, isopropoxy, butoxy, hexyloxy and octyloxy,
-for alkoxyl group alkylene oxide group Y group: the methoxyl group inferior ethoxyl,
-for the acyloxy Y group: have the group of 1-8 carbon atom, as methanoyl, acetoxyl group, propionyloxy and 2-ethyl hexanoyl oxygen base,
-for the phosphoric acid ester Y group: derived from those of dimethyl phosphate, diethyl phosphoric acid and dibutyl phosphate group.
But as the condensation Y group, can mention hydrogen atom and halogen atom, be preferably chlorine.
When Y group was hydroxyl described in the following formula (1), n equaled 1 so, and for the polymer manufacture organopolysiloxane elastomerics by following formula (1), except described condensation catalyst, must use linking agent (B), and this linking agent (B) is the silane of following formula:
R
4-aSiY’
a (2)
Wherein R has the above meaning that provides in formula (1), Y ' but identical or different hydrolyzable of expression or condensation group and a equal 3 or 4.
The example that provides at Y group is applicable to Y ' group.
Even Y is not under the situation of hydroxyl in oil (A), it is desirable to the silane of use formula (2).
In this case, it is desirable to adopt the Y group of the described oil (A) identical with the Y ' group of described silane (B).
The α of described formula (1), alpha, omega-dihydroxy diorganopolysiloxanecompositions generally are that viscosity is 25 ℃ following 10mPas to 25 ℃ down 500, and 000mPas, preferred 25 ℃ are 20-300, the oil of 000mPas down.They are basically by formula (R
2SiO) linear polymer that two organosiloxy unit constitute.
Yet, do not get rid of other unit that generally exist, such as RSiO as impurity
3/2, RSiO
1/2And SiO
4/2, especially exist with at least 1% ratio with respect to two organosiloxy unit number.
Organic group on the Siliciumatom of being represented by described symbol R that is bonded in this base oil can be selected from alkyl such as methyl, ethyl or the n-propyl with 1-3 carbon atom, vinyl, phenyl, 3,3,3-trifluoro propyl and beta-cyano ethyl.
Preferably, at least 60% of all R groups is methyl and 1% is vinyl at the most.
As by formula R
2The unitary example that SiO represents can be mentioned those of following formula: (CH
3)
2SiO; CH
3(CH
2=CH) SiO; CH
3(C
6H
5) SiO; CF
3CH
2CH
2(CH
3) SiO; NC-CH
2CH
2(CH
3) SiO; NC-CH
2(C
6H
5) SiO.
In most cases, these base oils are to be sold by the manufacturer of siloxanes.And its production technology is known; It is for example at French Patent FR-A-1, and 134,005, FR-A-1 has obtained in 198,749 and FR-A-1,226,745 open.
As the example of the monomeric silanes (B) of formula (2), especially can mention polyamides TMOS, polyalkoxysilane, polyketone imines TMOS and poly-imido TMOS, and particularly following silane: CH
3Si (OCOCH
3)
3C
2H
5Si (OCOCH
3)
3(CH
2=CH) Si (OCOCH
3)
3C
6H
5Si (OCOCH
3)
3CF
3CH
2CH
2Si (OCOCH
3)
3NC-CH
2CH
2Si (OCOCH
3)
3CH
2ClSi (OCOCH
2CH
3)
3CH
3Si (ON=C (CH
3) C
2H
5)
2OCH
2CH
2OCH
3CH
3Si (ON=CH-CH
3)
2OCH
2CH
2OCH
3
The α of above-mentioned silane (B) and formula (1), the alpha, omega-dihydroxy polydiorganosiloxane is in conjunction with being used to the stable single-component composition of performance under the secluding air situation.
As with the α of formula (1), the alpha, omega-dihydroxy polydiorganosiloxane in conjunction with and can be advantageously used in the example of monomeric silanes shown in the formula (2) in the two-component composition, can mention polyalkoxysilane, and these of following formula particularly: Si (OCH
2H
5)
4Si (O-n-C
3H
7)
4Si (O-isoC
3H
7)
4Si (OC
2H
4OCH
3)
4CH
3Si (OCH
3)
3CH
2=CHSi (OCH
3)
3CH
3Si (OC
2H
4OCH
3)
3ClCH
2Si (OC
2H
5)
3CH=CHSi (OC
2H
4OCH
3)
3
Monomeric silanes mentioned above can be whole or in part had other valence links of at least two, preferred three Y ' atoms and silicon to replace with the poly-alkoxyl group polysiloxane that SiO and SiR siloxane bond satisfy by each molecule.
As the example of polymeric cross-linker, can mention poly-(tetraethyl silicate) and poly-(silicic acid propyl ester).
The polymkeric substance of the formula of per 100 weight parts (1) uses the linking agent of the formula (2) of 0.1-20 weight part usually.
With respect to the polysiloxane of the formula (1) of per 100 weight parts, can be solidified into the condensation catalyst (C) that the elastomeric constituent polyorganosiloxane composition of the above-mentioned type comprises 0.001-10 weight part, preferred 0.05-3 weight part.
The content of condensation catalyst is usually than used much lower in the two-component composition in the single-component composition, and with respect to the polysiloxane of the formula (1) of per 100 weight parts generally between the 0.001-0.05 weight part.
The linking agent (B) of formula (2), no matter it is used to the preparation of single component or two-component composition, all is handy product on the siloxanes market; In addition, it is known in the purposes that begins from room temperature in the cured compositions; It is particularly in French Patent FR-A-1,126,411, FR-A-1,179,969, FR-A-1,189,216, FR-A-1,198,749, FR-A-1,248,826, FR-A-1,314,649, FR-1,423,477, FR-A-1 has obtained description in 432,799 and FR-A-2,067,636.
Composition of the present invention can comprise the enhancing or half that is preferably selected from siliceous filler in addition to be strengthened or loose filler.
Described reinforcing filler is preferably selected from pyrogenic silica and precipitated silica.It has the 50m that is at least according to BET method mensuration
2/ g, be preferably greater than 70m
2The specific surface area of/g is less than the primary particle mean sizes of 0.1 μ m (micron) and less than the tap density of 200g/l.
These silicon-dioxide can be introduced with former state, or introduce after handling with the silicoorganic compound that are generally used for this purposes.Among these compounds methyl polysiloxane is arranged, such as hexamethyldisiloxane, prestox sily oxide or octamethylcyclotetrasiloxane, the methyl polysilicon azane, such as hexamethyldisilazane or pregnancy basic ring three silazane, chlorosilane, such as dimethylchlorosilane, trimethylchlorosilane, methyl ethylene dichlorosilane or dimethyl vinyl chlorosilane, and organoalkoxysilane, such as dimethyldimethoxysil,ne, dimethyl vinyl Ethoxysilane or trimethylammonium methoxy silane.
In this treating processes, described silicon-dioxide can make its starting weight increase at most about 20%, preferably approximately 18%.
The size of particles of described half enhancing or loose filler is greater than 0.1 μ m (micron) and be selected from grinding quartz, calcined clay and diatomite.
Per 100 parts of oil (A) use 0-100 part, preferred 5-80 part filler usually.
Above the basal component of the silicone composition that briefly limits is known to those skilled in the art.It has obtained detailed description in the literature, and great majority can obtain on market.
These compositions at room temperature and crosslinked in the presence of the moisture in atmospheric moisture and/or composition.It is divided into two big classes.
The first kind is made of single-component composition or the composition that comprises unitary package, its shelf-stable and be solidified into elastomerics with atmospheric moisture under isolated atmospheric moisture situation.In this case, used condensation catalyst (C) is a metallic compound, is generally tin, titanium or zirconium compounds.
It is acid, neutral or alkaline that but the character that depends on described condensation or hydrolysable group, these single-component compositions are considered to.
As acidic composition, can mention for example patent US-A-3,035,016, US-A-3,077,465, US-A-3,133,891, US-A-3,409,573, US-A-3,438,930, US-A-3, disclosed composition in 647,917 and US-A-3,886,118.
As neutral composite, can mention for example patent US-A-3,065,194, US-A-3,542,901, US-A-3,689,454, US-A-3,779,986, GB-A-2,052,540, US-A-4, disclosed composition in 417,042 and EP-A-69,256.
As alkaline compositions, can mention for example patent US-A-3,378,520, US-A-3,364,160, US-A-3,417,047, US-A-3, the composition that is melted in 742,004 and US-A-3,758,441.
According to preferred alternative form, also can use the single-component flow composition, patent US-A-3 for example, 922,246, US-A-3, those disclosed in 956,280 and US-A-4,143,088.
As a preferred class in the context of the invention, second class is by two-component composition or comprises two packaged composition and constitute, it comprises α usually, alpha, omega-dihydroxy diorganopolysiloxanecompositions oil (A), silane (B) or the product and the catalyzer (C) that obtain by this silane moiety hydrolysis, it is metallic compound, preferred tin compound, and/or amine.
The example of this based composition is at patent US-A-3, obtained in 678,002, US-A-3,888,815, US-A-3,933,729, US-A-4,064,096 and GB-A-2,032,936 open.
More particularly preferably be the two-component composition that comprises following substances in these compositions:
-(A): 100 parts of viscosity are 20-300, the α of 000mPas, alpha, omega-dihydroxy diorganopolysiloxanecompositions oil, its organic group is selected from methyl, ethyl, vinyl, phenyl and 3,3,3-trifluoro propyl, wherein at least 60% number is a methyl, 20% number is a phenyl at the most, and 2% is vinyl at the most
-(B): 0.5-15 part polyalkoxysilane or poly-oxyalkylsiloxane,
-(C): 0.01-1 part catalysis tin compound,
-0-150 part, preferred 10-120 part siliceous inorganic filler.
Described tin catalyst (C) has obtained detailed description in above-mentioned document; It especially can be the pink salt of monobasic or di-carboxylic acid.The description of these carboxylic acid tin is especially referring to the works (chemistry and technology of siloxanes (Chemistry and Technology of Silicones), the 337th page, Academic Press, 1968, second edition) of No11.
Can mention naphthenate, octylate, oleate, butyrates, dibutyl tin laurate or dibutyltin diacetate especially.
As the catalysis tin compound, also can use pink salt (especially di-carboxylic acid tin) and the reaction product of gathering (tetraethyl silicate), as patent US-A-3, described in 186,963.
As patent US-A-3, disclosed in 862,919, also can use the reaction product of dialkyl dialkoxy silicane and carboxylic acid tin.
As belgian patent BE-A-842, disclosed in 305, also can use the reaction product of alkyl silicate or alkyltrialkoxysilaneand and dibutyltin diacetate.
In the described linking agent (B), more special preferred alkyl trialkoxy silane, alkyl silicate and poly-(alkyl silicate), wherein organic group is the alkyl with 1-4 carbon atom.
Described alkyl silicate can be selected from methyl silicate, tetraethyl silicate, isopropyl silicate, silicic acid n-propyl and be selected from the polysilicates of these silicon ester partial hydrolysates; They are by a high proportion of formula (R
4O)
3SiO
0.5, R
4OSiO
1.5, (R
4O)
2SiO and SiO
2The polymkeric substance formed of unit, R
4Expression methyl, ethyl, sec.-propyl or n-propyl.It characterizes normally and passes through the quantitative assay of sample hydrolysate and definite dioxide-containing silica based on it.
With respect to per 100 parts of oil (A), described condensation polymerization composite can comprise in addition the 10-130 weight part at each end of the chain with (CH
3)
3SiO
0.5Unit terminated, viscosity is one or more polydimethyl siloxane oil of 10-5000mPas 25 ℃ the time.
Composition of the present invention can be able to moulding according to different shape, extrude or molding particularly, and can be at room temperature with atmospheric moisture or add entry and then be solidified into elastomerics.Mild heat can be quickened to solidify under 20-150 ℃ temperature.
Another theme of the present invention is to comprise as the silicone composition of the precursor of silicone elastomer:
-(A) diorganopolysiloxanecompositions oil, but it has and is bonded in being selected from of silicon reactive group condensation, hydrolyzable or hydroxyl end groups;
-(B) randomly, but be selected from the compound of the silane that comprises condensation or hydrolysable group;
-(C) catalyzer;
-(D) randomly, any other additive in the types of compositions that is generally used for being considered;
-(E) can make constitute described mould silicone elastomer with respect to the additive for the treatment of that moulding material is stable, described additive is selected from:
+ (a) many sulfurations silane of at least a formula (I),
+ (b) poly-(alkylphenol sulfide) of at least a formula (II),
+ (c) the alkyl thiuram sulfide of at least a formula (III),
Described formula (I), (II) and compound (III) as above limit.
Particular topic of the present invention is silicone composition, and it is for the precursor of silicone elastomer and can be able to crosslinkedly by polycondensation, and said composition comprises:
-(A): at least a diorganopolysiloxanecompositions oil, but it has at least two condensations or hydrolyzable group or single hydroxyl at each end of the chain,
-(B): when (A) when comprising hydroxyl end groups oily, but comprise the silane of at least three condensations or hydrolysable group and/or be derived from the product of this silane moiety hydrolysis,
-(C): be used for the catalyzer of described oily polycondensation, and
-(E): the additive that is limited as mentioned.
For most preferred form, can be with reference to above-mentioned about component (A), (B), (C) and the given information of described additive (E).All combinations all are acceptable.
The further theme of the present invention is the prepared mould of silicone elastomer that can obtain by crosslinked aforesaid condensation polymerization composite.Another theme of the present invention is resulting silicone elastomer.
The present invention will illustrate in greater detail by the embodiment as non-limiting example.
Embodiment 1-4
The preparation by the crosslinked silicone composition of polycondensation at room temperature
1) basic mixture:
Prepare basic mixture by mediating following material:
The BET specific surface area of-17.1 parts (weight) is 300m
2/ g, the pyrogenic silica of handling with hexamethyldisilazane,
-25.7 parts at each end of the chain with (CH
3)
3SiO
0.525 ℃ of unit terminated polydimethyl siloxane oil that following viscosity is 500mPas,
-34.4 parts at each end of the chain with (CH
3)
2(OH) SiO
0.525 ℃ of unit terminated following viscosity are 14, the hydroxylation polydimethyl siloxane oil of 000mPas,
-2.3 parts at each end of the chain with (CH
3)
2(OH) SiO
0.5The hydroxylation polydimethyl siloxane oil that 25 ℃ of unit terminated following viscosity are 750mPas,
-20.1 parts of median sizes are the grinding quartz of 10 μ m,
-0.2 part of water
-0.2 part at each end of the chain with (CH
3)
2(OH) SiO
0.5The hydroxylation polydimethyl siloxane oil that 25 ℃ of unit terminated following viscosity are 75mPas, and
The additive of-aequum (E).
2) catalytic mixtures:
Above-mentioned basic mixture is 23 ℃ of following homogenizing 1 hour, and 5 parts of catalyzer are joined in 100 parts of these mixtures, and this catalyzer is based on being dissolved at each end of the chain with (CH
3)
3SiO
0.5Poly-(tetraethyl silicate) in the polydimethyl siloxane oil (54.8% weight) that 25 ℃ of unit terminated following viscosity are 50mPas and poly-(silicic acid propyl ester) (41% weight) and di-n-butyltin dilaurate (4.2% weight).
3) processing of siloxanes:
Catalytic as mentioned above basic mixture is about 1 minute of 23 ℃ of following homogenizing, then 20 * 10
2The degassing is about 10 minutes under the vacuum of Pa.So the product of the degassing is then cast in suitable mould.This layered product is in room temperature (23 ℃) the crosslinked and demoulding after 4 days down.
4) compare test (table 1) based on different additives.
The casting unsaturated polyester resin is up to observing siloxanes distortion on this mould, and/or described diaphragm has little surface patches to be shut down during the demoulding.This test method is very sensitive and consistent with the addition of PE additive for monomeric polymerization in the described mould.The infiltration of solvent has reduced the connection of siloxane network, and has finally reduced mechanical property.
Test-results provides with the number of foundry resin before the described silicone mold distortion.
The vibrin that is used for molding is the resin of being sold with trade(brand)name 2126AP by ChangXing Chemical Co..Its processing is as follows: per 100 parts of these resins add 2 weight part solidifying agent.
Table 1
| 0 couple of embodiment in the same old way | Additive | Content umber with respect to per 100 parts of silicone compositions | The result | |
| Foundry resin is observed | The copies of foundry resin | |||
| To in the same old way 1 | Blank | - | Well | 28 |
| Embodiment 1 | MESPT(I-1) | 2.5 | Well | 101 |
| Embodiment 2 | TB7(II-1) | 2.5 | Pratically is good | 93 |
| Embodiment 3 | TRA(III-1) | 2.5 | Pratically is good | 91 |
| Embodiment 4 | TETD(III-2) | 2.5 | Pratically is good | 83 |
Claims (12)
1, a kind ofly can make the silicone elastomer that constitutes mould with respect to the purposes for the treatment of the stable additive of moulding material and be used to increase by the life-span by the crosslinked mould of making of the silicone elastomer of polycondensation, this additive is selected from:
-(a) at least a " symmetry " that meets following general formula vulcanized silane more:
(G
2)
a(G
1)
3-aSi-R
0-(S
x-R
0)
m-Si(G
1)
3-a(G
2)
x (I)
Wherein:
+ a represents to be selected from 1 or 2 number;
+ m represents to be selected from 1 and 2 number;
+ x is integer or the mark in the 2-6 scope;
+ described symbol G
1, it can be identical or different, separately expression: saturated or unsaturated aliphatic alkyl group; Saturated, undersaturated and/or aromatics, monocycle or polycyclic carbon ring group; Or comprise the group of saturated or unsaturated aliphatic carbon based moiety and the isocyclic part that are defined as above;
+ described symbol G
2, it can be identical or different, separately expression: hydroxyl or hydrolyzable univalent perssad;
+ described symbol R
0The expression divalent group is selected from: saturated or unsaturated aliphatic alkyl group; Saturated, undersaturated and/or aromatic group, monocycle or polycyclic carbon ring group; And the group that comprises saturated or unsaturated aliphatic hydrocarbyl portion and the isocyclic part that are defined as above; Described divalent group randomly replaces with Sauerstoffatom and/or sulphur atom and/or the nitrogen-atoms that has 1 univalent perssad or at interval, this univalent perssad is selected from: hydrogen atom: saturated or unsaturated aliphatic alkyl group; Saturated, undersaturated and/or aromatics, monocycle or polycyclic carbon ring group; With the group that comprises saturated or unsaturated aliphatic hydrocarbyl portion and the isocyclic part that are defined as above;
-(b) at least a poly-(alkylphenol sulfide) with following general formula:
R wherein
1Represent saturated aliphatic hydrocarbyl group, y is integer or the mark in the 1-4 scope, and repeating unit n can be 0,1,2 or higher number;
-(c) at least a alkyl thiuram sulfide with following general formula:
Wherein: R
2, R
3, R
4, R
5, identical or different, represent hydrogen atom separately, saturated aliphatic hydrocarbyl group or saturated monocyclic groups, R
2Or R
3And R
4Or R
5In at the most only one can represent hydrogen atom; Z can be integer or the mark in the 2-6 scope.
2, the purposes of claim 1, be used for the stable moiety silicone elastomer that is used for the mould of polyester article molding, especially the cinnamic polymerization in order to prevent from silicone elastomer, to produce by described vibrin, and can not produce interference to the core of described polyester and the polymerization of surface.
3, claim 1 or 2 purposes is characterized in that described compound (a) is for being selected from many sulfurations silane of formula (I), wherein:
+ a=1 or 2;
+m＝1；
+ x is 2-4;
+ described symbol G
1, identical or different, expression separately: straight or branched C
1-C
8Alkyl; C
5-C
10Cycloalkyl or C
6-C
18Aryl;
+ described symbol G
2, identical or different, expression separately: hydroxyl; Randomly with one or more (C
1-C
8) the straight or branched C that replaces of alkoxyl group
1-C
8Alkoxyl group;
+ described symbol R
0, identical or different, represent separately: C
1-C
8Alkylidene chain; C
5-C
10Cycloalkylidene; Or comprise in these groups the divalent group of at least two kinds combination.
4, the purposes of claim 3 is characterized in that described compound (a) comprises:
Two-monosubstituted ethoxy dimetylsilyl propyl group the tetrasulfide (being called MESPT) of-following formula:
(C
2H
5O)(CH
3)
2Si-(CH
2)
3-S
4-(CH
2)
3-Si(CH
3)
2(OC
2H
5) (I-1)
Two-diethoxymethyl silyl propyl group the tetrasulfide (being called DESPT) of-following formula:
(C
2H
5O)
2(CH
3)Si-(CH
2)
3-S
4-(CH
2)
3-Si(CH
3)(OC
2H
5)
2 (I-2)
Two-monosubstituted ethoxy dimetylsilyl propyl disulfide the thing (being called MESPD) of-following formula:
(C
2H
5O)(CH
3)
2Si-(CH
2)
3-S
2-(CH
2)
3-Si(CH
3)
2(OC
2H
5) (I-3)
Two-monohydroxy dimetylsilyl propyl group the tetrasulfide of-following formula:
(HO)(CH
3)
2Si-(CH
2)
3-S
4-(CH
2)
3-Si(CH
3)
2(OH) (I-4)。
5, claim 1 or 2 purposes is characterized in that described compound (b) is selected from poly-(alkylphenol sulfide) of formula (II), wherein: R
1Expression straight or branched C
1-C
8Alkyl; Y is 1-3; With n be 3-8.
6, the purposes of claim 5 is characterized in that described compound (b) comprises the compound of following formula:
Y=2 wherein, 1 and n=5 (being called TB7).
7, claim 1 or 2 purposes is characterized in that described compound (c) is selected from the alkyl thiuram sulfide of formula (III), wherein: the substituent R of nitrogen-atoms
2, R
3, R
4And R
5, identical or different, represent hydrogen atom or straight or branched C separately
1-C
8Alkyl, condition are described substituent R
2Or R
3And R
4Or R
5In at the most only one the expression hydrogen atom; Z is 2-5.
8, the purposes of claim 7 is characterized in that described compound (c) comprises the compound of following formula:
(III-2; Be called TETD).
9, silicone composition, it is the precursor of silicone elastomer, said composition comprises:
-(A) diorganopolysiloxanecompositions oil, but it has the condensation that is selected from that is bonded on the silicon, the reactive group of hydrolyzable or hydroxyl end groups;
-(B) randomly, but be selected from the compound of the silane that comprises condensation or hydrolysable group;
-(C) catalyzer;
-(D) randomly, any other additive in the types of compositions that is generally used for being considered; And
-(E) can make constitute described mould silicone elastomer with respect to the additive for the treatment of that moulding material is stable, described additive is selected from:
+ (a) many sulfurations silane of at least a formula (I),
+ (b) poly-(alkylphenol sulfide) of at least a formula (II),
+ (c) the alkyl thiuram sulfide of at least a formula (III),
Defined in described formula (I), (II) and one of compound (III) such as above-mentioned claim 1-8.
10, the silicone composition of claim 9 is characterized in that described silicone composition is the precursor of silicone elastomer and can be able to crosslinkedly by polycondensation that said composition comprises:
-(A): at least a diorganopolysiloxanecompositions oil, but it has at least two condensations or hydrolyzable group or single hydroxyl at each end of the chain,
-(B): when (A) when comprising hydroxyl end groups oily, but comprise the silane of at least three condensations or hydrolysable group and/or be derived from the product of the partial hydrolysis of this silane,
-(C): be used for the catalyzer of described oily polycondensation, and
-(E): as the additive defined in one of above-mentioned claim 1-8.
11, claim 9 or 10 silicone composition is characterized in that used additive (E) is selected from the many sulfurations silane (a) as the formula (I) defined in the claim 1, one of 3 and 4.
12, the mould that makes by the silicone elastomer that can obtain by the condensation polymerization composite that limits among one of crosslinked as above-mentioned claim 9-11.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2005100817738A CN1844247A (en) | 2005-04-07 | 2005-04-07 | Method for stabilization of mould made of silicone elastomer |
| TW095112270A TW200708553A (en) | 2005-04-07 | 2006-04-06 | Process for the stabilization of molds made of silicone elastomer |
| PCT/FR2006/000765 WO2006106237A1 (en) | 2005-04-07 | 2006-04-06 | Method for stabilizing molds composed of a siliconized elastomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2005100817738A CN1844247A (en) | 2005-04-07 | 2005-04-07 | Method for stabilization of mould made of silicone elastomer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1844247A true CN1844247A (en) | 2006-10-11 |
Family
ID=36650827
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2005100817738A Pending CN1844247A (en) | 2005-04-07 | 2005-04-07 | Method for stabilization of mould made of silicone elastomer |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN1844247A (en) |
| TW (1) | TW200708553A (en) |
| WO (1) | WO2006106237A1 (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5814695A (en) * | 1995-09-08 | 1998-09-29 | General Electric Company | Silicone molding compositions having extended useful life |
| FR2739863B1 (en) * | 1995-10-16 | 1997-11-21 | Elf Antar France | PROCESS FOR THE PREPARATION OF BITUMEN / POLYMER COMPOSITIONS WITH REINFORCED MULTIGRADE CHARACTER AND APPLICATION OF THE COMPOSITIONS OBTAINED IN THE PRODUCTION OF BITUMEN / POLYMER BINDERS FOR COATINGS |
| FR2773165B1 (en) * | 1997-12-26 | 2001-06-08 | Rhodia Chimie Sa | STABILIZATION OF SILICONE ELASTOMER MOLDS |
| JP3914390B2 (en) * | 2001-01-15 | 2007-05-16 | 信越化学工業株式会社 | Room temperature curable organopolysiloxane composition for molding |
| FR2861082B1 (en) * | 2003-10-15 | 2005-12-30 | Arkema | VULCANIZATION AGENT FOR USE WITH EPDM-TYPE RUBBER |
-
2005
- 2005-04-07 CN CNA2005100817738A patent/CN1844247A/en active Pending
-
2006
- 2006-04-06 TW TW095112270A patent/TW200708553A/en unknown
- 2006-04-06 WO PCT/FR2006/000765 patent/WO2006106237A1/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| TW200708553A (en) | 2007-03-01 |
| WO2006106237A1 (en) | 2006-10-12 |
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