JPH07149907A - Sih-terminated chain extender for organosilicone polymer - Google Patents

Abstract

PURPOSE: To obtain a composition useful for electronic use by combining an organosilicone crosslinked (pre)polymer, which is obtained by allowing a specific cyclic polysiloxane or a tetrahedral siloxysilane, a specific polycyclic polyene and a specific chain extender or undergo hydrosilylation, with an elastomer.

CONSTITUTION: This organosilicone polymer is an organosilicone crosslinked (pre)polymer which is a hydrosilylation product of the following components (a), (b) and (c). (a) At least one cyclic polysiloxane or tetrahedral siloxysilane having at least two ≡SiH groups, (b) at least one polycyclic polyene having in its ring at least two non-aromatic carbon-carbon double bonds reactive in hydrosilylation, and (c) at least one compound (chain extender) of the formula: R₁-R₂-R₃ (wherein R₁ and R₃ are each an -SiH terminal group which may be the same or different; and R₂ is a substituted- or unsubstituted aliphatic- or aromatic group). Here, at least one of components (a) and (b) has more than two reactive sites.

COPYRIGHT: (C)1995,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an elastomer and a crosslinkable organosilicone prepolymer produced by a hydrosilation reaction or a composition containing the crosslinked organosilicone polymer, and a method for producing the organosilicone polymer and the prepolymer.

[0002]

BACKGROUND OF THE INVENTION Organosilicone polymers such as those described in US Pat. Nos. 4,900,779 and 4,902,731 are too brittle for some applications. The brittleness of the polymer results from the short distance between the cyclic siloxane moieties, ie the high crosslink density. Such a high crosslink density decisively interferes with the energy-absorbing molecular motion before breaking. Mixing certain polymers with these polymers results in US Pat.
It becomes slightly tenacious as shown in 5,171,817 and 5,242,979. However, in order to obtain significant tenacity, the crosslink density of the cured polymer must be reduced. For reaction with organosilicone prepolymers made from cyclic polysiloxanes and polycyclic polyenes, chain extenders having terminal unsaturated groups are disclosed in US Pat. Nos. 5,068,303 and 5,008,360. These chain extenders are used to increase the viscosity of the prepolymer.

[0003]

The composition of the present invention comprises:
(1) a discontinuous phase elastomer and (2) a continuous phase of an organosilicone crosslinked polymer or crosslinkable prepolymer which is a reaction product of the following components (a), (b) and (c): (a) At least one cyclic polysiloxane having at least two ≡SiH groups or tetrahedral siloxysilane,
(B) Non-aromatic carbon that reacts in hydrosilation-
At least one polycyclic polyene having at least two carbon double bonds in the ring, and (c) formula R ₁ -R ₂ -R
_At least one of the compounds having ₃ (in the formula, R ₁ and R ₃ are the same or different —SiH terminal groups, and R ₂ includes a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group).
The species, at least one of (a) and (b), has more than two reactive sites.

The present invention also relates to a method of making organosilicone prepolymers and articles containing elastomers and crosslinked organosilicone polymers. Low molecular weight Si
Incorporation of the H-terminal chain extender into the prepolymer results in a composition with significantly increased toughness. If the chain extender has hard molecular chains, the shear modulus G'also increases.
The tenacity of the polymer improves properties such as adhesion of the polymer laminate to copper on the printed circuit board, as well as processability such that the printed circuit board made from the rubber / polymer composition has improved piercing capability.
By "prepolymer" is meant a viscous liquid or solid hydrosilanated crosslinkable composition that has been partially cured but not cured to or above its gel point. The gel point is that when the material is heated it no longer flows and is no longer soluble in organic solvents.

The elastomer shown as component (1) of the composition of the present invention is added to improve the toughness of the organosilicone polymer. Although many elastomers can be added to impart toughness, hydrocarbon elastomers having a weight average molecular weight of less than 10,000 are preferred. An ethylene-propylene-diene terpolymer having a weight average molecular weight of about 5500 to 7000 ("EP
DM "or" EPDM rubber "), for example TRILENE 65 or TRILENE 67 elastomers (Uniroya
l Chemical Company, Middlebury, CT) is most preferred.
Other suitable hydrocarbon elastomers are, for example, partially hydrogenated low molecular weight polyisoprene (90% hydrogenated L1R
290, Nissho Iwai America, Inc., New York, NY), partially hydrogenated low molecular weight styrene-butadiene or butadiene polymers (eg RICON 184 or 131, Colorado Chem
ical Specialties, Grand Junction, CO,
Must be hydrogenated after purchase) and low molecular weight butyl rubber (isobutylene-isoprene copolymer, KALENE 8
00, Hardman, Belleville, NJ). Low molecular weight (weight average molecular weight less than 200,000) vinyl or-
Siloxane rubbers such as SiH-terminated polydimethyl / diphenylsiloxane copolymers can also be used.

The elastomer is usually used in an amount of 0.5 to 20%, preferably 3 to 12%, based on the total amount of the composition. The elastomer can be added to the monomers or prepolymers used to make the organosilicone polymer. Elastomers useful in the present invention include U.S. Pat. Nos. 5,171,817 and 5,242,979 and "Organosilicon Compositions Containing Hydrocar".
bon Elastomers, Research Disclosure 33082 (Octob
er 1991). There are several requirements for the elastomer to be effective in toughening the polymer without significantly affecting other properties. First, there must be a reaction between the organosilicone prepolymer and the elastomer. Second, the polymer and elastomer must form two phases. In order to obtain the desired product, the elastomer should preferably have more than one hydrosilanation-reactive carbon-carbon double bond. Since elastomers with multiple double bonds tend to react with the prepolymer to form a one-phase system, the hydrocarbon elastomer is hydrogenated to reduce the number of carbon-carbon double bonds so that phase separation occurs. be able to. The carbon-carbon double bonds of the elastomer should preferably not exceed 50 mol%, more preferably 25 mol% and most preferably 15 mol%.

The elastomer is preferably present within the cured or crosslinked polymer as micron-sized particles forming the second phase. The particles preferably have a diameter of 0.001
.About.50 microns, more preferably 0.01 to 10 microns in diameter, most preferably 0.1 to 5 microns. Appropriate results have been obtained with elastomers that are soluble or insoluble in the liquid prepolymer. However, the dispersibility of the liquid prepolymer is desirable for storage stability, as it is preferred that the mixture does not separate during storage. Component (a) used to prepare the prepolymers and polymers of the present invention can be a cyclic polysiloxane having at least two silicon-bonded hydrogen atoms or a tetrahedral siloxysilane. Suitable cyclic polysiloxanes have the general formula:

[0008]

[Chemical 1]

(Wherein R is hydrogen, a substituted or unsubstituted saturated alkyl or alkoxy group or a substituted or unsubstituted aryl or aryloxy group, and n is an integer of 2 to 20. However, R is an intramolecular silicon. Hydrogen for at least two of the atoms.) Suitable cyclic polysiloxanes include US Pat.
It is disclosed in No. 8,360 and No. 5,068,303. Examples include trimethylcyclotrisiloxane;
Hexamethylcyclotetrasiloxane; Tetraoctylcyclotetrasiloxane; Tetra and pentamethylcyclotetrasiloxane; Tetra, penta, hexa and heptamethylcyclopentasiloxane; Tetra, penta and hexamethylcyclohexasiloxane, tetraethylcyclotetrasiloxane and terraphenylcyclo Tetrasiloxane may be mentioned. Preferred cyclic polysiloxanes are methylhydrocyclosiloxanes such as 1,3,5,7-
Tetramethylcyclotetrasiloxane; 1,3,5,7,9-pentamethylcyclopentasiloxane and 1,3,5,6,9,11-
Hexamethylcyclohexasiloxane or a mixture thereof. In most cases many mixtures of these compounds are used and n can vary widely. "Methylhydrocyclosiloxane" means a mixture thereof.

The tetrahedral siloxysilane has the following general structural formula: Si- [OSi (R) ₃ ] ₄ (In the formula, R is as defined above, and at least two of the silicon atoms in the molecule are hydrogen.) As an example of the reaction component of the formula (Ib), Examples include tetrakisdimethylsiloxysilane, tetrakisdiphenylsiloxysilane and tetrakisdiethylsiloxysilane. Of these, tetrakisdimethylsiloxysilane is the most well known and preferred compound. The polycyclic polyenes that can be used as component (b) in preparing the prepolymers and polymers of the present invention are polycyclic polyenes having at least two non-aromatic carbon-carbon double bonds in the ring that react in hydrosilation. It is a cyclic hydrocarbon compound.
Specific examples of these compounds are cyclopentadiene oligomers (such as dicyclopentadiene, tricyclopentadiene and tetracyclopentadiene) and their substituted derivatives such as methyldicyclopentadiene.
Cyclopentadiene oligomers such as dicyclopentadiene and tricyclopentadiene are preferred. It is also possible to use two or more polycyclic polyenes in combination.
At least one of component (a) or (b) has more than two reactive sites. Reactive sites are defined as carbon-carbon double bonds or ≡SiH groups that react in hydrosilation.

Component (c) used in preparing the polymers and prepolymers of the present invention is a low molecular weight compound having a molecular weight of less than 3,000 and having the formula R ₁ -R ₂ -R ₃
(Wherein R ₁ and R ₃ are the same or different SiH terminal groups, and R ₂ includes an aliphatic or aromatic group). This component is called "chain extender". R ₁ and R ₃ is -SiR ₄ R ₅ H or _{- (O-SiR 4 R 5} ) x
It is preferably an H group (x is 1 to 6). R
₄ and R ₅ may be the same or different and are selected from substituted or unsubstituted alkyl, alkoxy, aryl, aryloxy and siloxy groups. A siloxy group does not have a hydrogen atom bonded to a silicon atom, such as trimethylsiloxy,
Mention may be made of pentamethyldisiloxy, phenylmethylsiloxy and cyclosiloxane groups. R ₁ and R ₃ are preferably derived from tetramethyldisiloxane or p-bis (dimethylsilyl) benzene. Any functionality that does not substantially react with the .tbd.SiH groups or carbon-carbon double bonds or interfere with the hydrosilation catalyst under the hydrosilanization conditions used can be attached to any R group. Suitable functional groups include, for example, ester, amide, sulfone, sulfoxide, ketone and ether groups. Examples of functional groups which cannot be present because they react with .tbd.SiH groups or interfere with the hydrosilation catalysts are, for example, olefins, alcohols, sulphides and some amines having carbon-carbon double bonds which react in hydrosilation. And phosphine. R
Examples of ₂ aliphatic or aromatic groups include substituted or unsubstituted straight chain, cyclic or branched chain alkyl, alkoxy, aryl and aryloxy, and combinations thereof. R ₂ may also contain a siloxane bond unless it is composed solely of the following siloxane bond.

[0012]

[Chemical 2]

Component (c) is typically a compound containing a double bond that reacts in the hydrosilation (eg vinyl, allyl or norbornenyl) and an excess of two .tbd.SiH groups preferably having a molecular weight> 600. Is a hydrosilation reaction product with a low-molecular weight monomer. Examples of the compound having two reactive double bonds are 5-vinyl-2-norbornene; o-, m- or p-diisopropenylbenzene; o-, m- or p-divinylbenzene; diallyl ether; Diallylbenzene; norbornadiene; dimethanohexahydronaphthalene; diallyl ether of bisphenol A; vinylbenzyl ether of tetramethylbisphenol A; 1,3-divinyltetramethyldisiloxane; 1,4-divinyl-1,1,4,4- Tetramethyldisilylethylene; divinyldimethylsilane and 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane. Examples of low molecular weight monomers containing two ≡SiH groups include 1,1,3,3-tetramethyl-1,3-disiloxane; o- or p-bis (dimethylsilyl) benzene; 3,3,5,5-hexamethyltrisiloxane; o- or p-bis (diethylsilyl) benzene; 1,3-diphenyl-1,3-dimethyldisiloxane; 1,3-bis (trimethylsiloxy) -1 , 3-dimethyldisiloxane and 1,1,
4,4-tetramethylnidisilylethylene may be mentioned.

The component (c) is o- or p-bis (dimethylsilyl) benzene; o- or p-bis (diethylsilyl).
It can be benzene; or a compound such as 1,1,4,4-tetramethylnidisilylethylene. Component (a),
(B) and (c) are usually present in the following amounts. 0.7 <(b) number of double bonds / (a) and (c) ≡
SiH bond moles <1.6 and 0.03 <(c) ≡SiH bond moles / (a) ≡Si
For toughness values higher than the H bond mole number <0.30, the amounts are preferably as follows: 0.8 <(b) number of double bonds / (a) and (c) ≡
SiH bond moles <1.4 and 0.05 <(c) ≡SiH bond moles / (a) ≡Si
H bond mole number <0.25 Further, in the case of a higher toughness value in combination with a high glass transition temperature, the following amounts are preferable. 0.9 <(b) double bond mole number / (a) and (c) ≡
SiH bond moles <1.2 and 0.07 <(c) ≡SiH bond moles / (a) ≡Si
Molar H-bonds <0.20 The preferred ratio of each component depends on the individual components used and the amount used.

The reaction to form the prepolymers and polymers of the present invention can be facilitated thermally or by the addition of hydrosilation catalysts or radical generators such as peroxides or azo compounds. Hydrosilation catalysts include metal salts and complexes of Group VIII elements. Preferred hydrosilation catalysts include platinum, such as bis (acetonitrile) platinum dichloride, bis (benzonitrile) platinum dichloride, platinum-divinyl complex, platinum / carbon,
Mention may be made of platinum dichloride, cyclooctadiene platinum dichloride, dicyclopentadiene platinum dichloride and chloroplatinic acid. The catalyst concentration was 0.0005 platinum based on the weight of the monomer.
% To 0.05% by weight is preferred, 0.0010 to 0.02% is more preferred, and 0.002 to 0.01% is most preferred. In order to obtain a truly tenacious polymer, it is important that the chain extender (c) reacts completely into the polymer, ie both chain ends are chemically bonded to the polymer. Unreacted or "hanging" chain ends reduce the degree of toughness imparted by the chain extender. The present invention provides one of the following methods
Done by seed.

If the carbon-carbon double bond of (b) is "chemically distinct", ie the two bonds have significantly different reactivities in the hydrosilation reaction, the polymer is prepared in two steps. It is preferable. First, by reacting reagents (a) and (b) together such that the more reactive carbon-carbon double bond of (b) reacts completely,
A prepolymer rich in olefins is produced. Carbon-
The carbon double bond / Si-H bond ratio is 1.1 / 1.0 to 1.4 / 1.
It varies from 0, preferably from 1.2 / 1.0 to 1.3 / 1.0.
Here, the total carbon-carbon double bond / Si-H bond ratio is 1.0.
This prepolymer can be mixed with component (c), a chain extender, so that Si-H remaining in (a)
The bond competes with the Si-H bond in (c) for the remaining carbon-carbon double bonds in (b). Since the Si-H bond in (c) is less sterically packed than in (a), the former tends to react more than the latter. This allows most or all of the .tbd.Si--H bonds of the chain extender to react in the final cured polymer. When all three reagents are reacted together at the same time, (c) Si-H
Some of the bonds react with the more reactive bonds of (b),
The less reactive double bond produces a chain extender with less reactive end. During curing some of these bonds remain unreacted, which results in "hanging" chain ends.

However, if the carbon-carbon double bond of (b) is not "chemically distinct", ie both bonds have similar or equivalent reactivity in the hydrosilation reaction, the reagent (A), (b) and (c)
Can all be mixed at the same time. The above mixture is 1
It is suitably catalyzed and thermally polymerized at a preferred temperature of 00 to 260 ° C. A wide range of toughness and thermal properties can be obtained by varying the type of chain extender (rigid or flexible, short or long). For example, 4-8% Trilene 65
Using the composition of the present invention in the presence of EPDM rubber, 18
Fracture toughness values of 0-650 J / m ² were obtained. Polymer prepared from prepolymer prepared from methylhydrocyclosiloxane (mixture with 4 and 5 silicon atoms in the ring) with 7% Trilene 65 EPDM rubber without chain extender and dicyclopentadiene Indicates a breaking energy value of 110 J / m ² . In addition to acting as a toughening agent, SiH-terminated chain extenders can function as reactive diluents, for example in molding operations. Addition to the prepolymer prepared from (a) and (b) can make the mixture less viscous and flowable or easier to process, as the mixture does not react until heated.

For all of the above steps, alkyldiamines and alkyltriamines such as N, N, N ', N'
-Low level cure rate retarders (composites) such as tetramethylethylenediamine and diethylenetriamine or'Phosphorus Based Catalyst Retardants for Silicon
Carbon Resin Systems 』, Research Disclosure 32610
3 (June 1991) and the use of phosphorus compounds as described in European Patent Application No. 479,310 makes it possible to control the reaction rate and the associated increase in viscosity. The addition of small amounts of catalyst inhibitors to formulations containing SiH end chain extenders extends the pot life of the catalyst resin formulations by preventing the hydrosilation reaction from occurring at room temperature. The stabilizer (antioxidant) is effective for maintaining the storage stability and curing of the prepolymer, that is, the thermooxidative stability of the crosslinked polymer. Bis (1,2,2,6,6-pentamethyl-
4-piperidinyl)-(3,5-di-tert-butyl-4-
Hydroxybenzyl) butyl propanedioate (TINU
VIN (registered trademark) 144, Ciba-Geigy, Hawthorne, NY)
Or octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate (octadecyl 3- (3 ',
5'-di-tert-butyl-4'-hydroxyphenyl)
NAUGARD® 7, also known as propionate
6, Uniroyal Chemical Co., Middlebury, CT) and bis (1,2,2,6,6-pentamethyl-4-piperidinyl sebacate (TINUVIN (registered trademark) 765, Ciba-Geigy) Stabilizers and their use are described in US Pat.
25,048 and 5,118,735.

Glass, carbon (graphite), quartz, metals, ceramics, aramids and other polymeric fibers can be wetted with a liquid prepolymer, which can be used as a matrix material in the production of prepregs and composites. The fibers can be, for example, in the form of woven or non-woven materials or tows of unidirectional fibers. The compositions of the present invention are particularly well suited for impregnating glass or other fibrous fillers for printed circuit boards. Generally, prepregs (ie, laminates and printed circuit boards made from the prepregs) have a fibrous filler of 2 based on the total amount of the composition.
5 to 90%, preferably 30 to 60%, depending on weave. The fibers can be treated with a finish to enhance wetting and binding of the prepolymer to the fibers. Pigments and other types of fillers are easily mixed. Examples of non-fibrous fillers that can be used are vermiculite, mica, wollastonite, carbon black, calcium carbonate, silica, fumed silica, glass beads, frosted glass, scrap glass, ceramic beads, hollow glass spheres and others. Is a mineral fiber. The filler can act as a reinforcing agent or a bulking agent that reduces cost.
It can also be used for other reasons such as viscosity adjustment. The non-fibrous filler may range from 20 to
It can be present in an amount of 95% by weight.

The composition of the present invention has excellent electrical insulation and water resistance. Many have high glass transition temperatures. It is therefore well suited for electronic applications such as composites, adhesives, encapsulants, potting compounds and coatings. It is particularly useful in preparing laminates and prepregs such as those used in printed circuit boards. This prepreg and laminate are described in US Pat. No. 5,008,360. The product of the present invention is selected from the group consisting of electronic parts containing the organosilicone composition or electronic parts coated or encapsulated (embedded or sealed) with the organosilicone composition. The component is typically selected from the group consisting of electronic circuit boards, circuit board laminates, circuit board prepregs, semiconductor components, capacitors, resistors, diodes, transistors, transformers, coils, wires, hybrid circuits and multichip modules. It contains at least one kind.

When the prepolymer used in the composition of the present invention is mixed with a low molecular weight SiH terminated chain extender,
This produces a polymer with significantly increased toughness. The tenacious polymer can improve properties such as adhesion of the polymer laminate to copper on the printed circuit board and improve processability such as perforating printed circuit boards made from the polymer. The chain extender comprises a rigid molecular chain, eg R _{2 comprises} a substituted or unsubstituted polyaromatic moiety such as a bisphenol, biphenyl, naphthyl or anthracenyl group, or R ₂
The shear modulus G ′ is also increased when has a substituted or unsubstituted fused fused polycyclic moiety such as a di, tri or tetradicyclopentadienyl group. Examples of the chain extender containing a hard chain include excess bis (dimethylsilyl) benzene and vinylbenzene-terminated bisphenol A.
And the hydrosilation reaction product of excess 1,1,3,3-tetramethyl-1,3-disiloxane with allyl ether terminated bisxylenol P.

The organosilicone crosslinked polymers and crosslinkable prepolymers containing the --SiH end chain extenders of this invention are also useful in the absence of a discontinuous elastomeric phase. However, compositions containing the polymers and prepolymers are "tougher" than organosilicone compositions that are not as tough as those having an elastomeric phase, but without chain extenders. That is, the presence of a chain extender allows these compositions to be toughened by various means such as particulate fillers or thermoplastics. However, these additives are not as effective in increasing the toughness of chain extender-free polymers and prepolymers. All parts and percentages herein are by weight and based on the total prepolymer, unless otherwise specified. The catalysts and catalyst inhibitors used in the examples below are prepared as follows.

Catalyst A PC075, a complex of platinum with 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is described by Huls America, Bristol,
Available from PA. 20% PC07 with toluene
Dilute to 5 solution. This solution is called catalyst A. Catalyst B 1,500 ppm of chloroplatinic acid / dicyclopentadiene (CPA / DCPD) catalyst complex was added to a glass container in an amount of 0.
Sparge 150 parts of CPA with nitrogen for 5 minutes, then 10
It was prepared by adding 0 part of DCPD and stirring at 50 to 70 ° C. for 1 hour. Then, the composite was cooled to room temperature. This catalyst is called catalyst B. Catalyst inhibitor N, N, N ', N'-tetramethylethylenediamine (TMEDA) / toluene 2000 ppm solution ("catalyst inhibitor solution") was added to 0.10 parts TMEDA and 49.
It was prepared by placing 90 parts of toluene in a glass container and mixing them well.

[0024]

Example A This example demonstrates the preparation of a SiH-terminated chain extender having the formula:

[0025]

[Chemical 3]

(N ≦ 3, Me = methyl) Distilled 5-vinyl-2-norbornene (100.0 parts,
0.83 mol), 340.0 parts (2.5 mol) of 1,1,3,3-tetramethyl-1,3-disiloxane (TMDS) and 0.7
3 parts of catalyst A were added to a glass container. The vessel was placed in a water bath at 25 ° C. and stirred for 12 hours until all double bonds were hydrosilanated as shown by ¹ H-NMR. After distilling off excess TMDS, vacuum distillation was carried out to 475
Some chain extender was recovered. SiH analysis of the distilled product showed that the product contained 5.027 meq SiH / g.

[0027]

Example B This example demonstrates the preparation of a SiH-terminated chain extender having the formula:

[0028]

[Chemical 4]

(N ≦ 3, Me = methyl) Dimethanohexahydronaphthalene (DMHN) (25.0)
Part, 0.16 mol), 42.4 parts (0.32 mol) 1,1,3,3
-Tetramethyl-1,3-disiloxane (TMDS) and
0.22 parts of catalyst A were added to a glass container. Container at 25 ° C
And stirred for 7 hours until all of the double bonds were hydrosilanated as shown by ¹ H-NMR. Excess TMDS was decompressed using a rotary evaporator (1 mm
Hg) at 25 ° C for 20 minutes and 35 ° C for 15 minutes. SiH analysis of the distilled product revealed that it was 4.254 meq Si
It was shown to contain H / g.

[0030]

Example C This example demonstrates the preparation of an olefin-rich prepolymer. Methylhydrosiloxane (111.3 parts) (MHCS, predominantly 8 and 10 member polysiloxane rings), 145.7 parts dicyclopentadiene (DCPD), 13.0 parts catalyst B, 70.0 parts 30% T.
RILENE 65 Toluene solution (TRILENE 65 is a Uniroyal Chemi
made by cal, Middlebury, CT EPDM rubber),
1.25 parts TINUVIN® 765 hindered amine antioxidant (Ciba Geigy, Hawthorne, NY), 6.22 parts N
AUGARD® 76 Interfering Phenolic Antioxidants (Uniro
yal Chemical Co., Ltd.) and 7.5 parts of toluene were added to a glass container. The vessel was placed in a water bath at 25 ° C. to keep the temperature of the reactants 1-5 ° C. above the bath temperature and stirring was continued until all of the norbornene linkages of DCPD were hydrosilanated as shown by ¹ H-NMR. went. This prepolymer had a double bond / SiH ratio of 1.30.

[0031]

Example D This example demonstrates the preparation of an olefin-rich prepolymer using the procedure of Example C. The amounts of the components in the starting mixture are varied so that the prepolymer double bond / SiH ratio is lower than in Example C. M
HCS (140.4 copies), 169.7 copies of DCPD, 15.2
Parts of catalyst B, 90.1 parts of 30% TRILENE 65 EPDM rubber in toluene solution, 1.53 parts of TINUVIN® 765 antioxidant, 7.83 parts of NAUGARD® 76 antioxidant and 9 parts 0.0 part of toluene was added to a glass container. This prepolymer had a double bond / SiH ratio of 1.20.

[0032]

Example E This example demonstrates the preparation of an olefin-rich prepolymer using the procedure of Example C. The amounts of the components in the starting mixture are varied such that the prepolymer double bond / SiH ratio is lower than in Examples C or D. MHCS (61.2 parts), 67.3 parts DCPD, 6.5
Parts of catalyst B, 37.5 parts of 30% TRILENE 65 EPDM rubber in toluene solution, 0.64 parts of TINUVIN® 765 antioxidant, 3.11 parts of NAUGARD® 76 antioxidant and 9 parts 0.0 part of toluene was added to a glass container. This prepolymer had a double bond / SiH ratio of 1.10.

[0033]

Example F This example describes the preparation of a chain extender having the formula:

[0034]

[Chemical 5]

Tetramethylbisphenol A (TMBPA-2VB) (20.6) in 100 ml toluene in a glass container.
4 g, 0.04 mol) bis (vinylbenzyl ether)
P-Bis (dimethylsilyl) benzene (PBMS
B) (18.2 g, 0.094 mol) and 0.07 from Huls America.
88 ml of catalyst PC075 was added. Add this reaction mixture to 4
Stir overnight at 0 ° C., thin layer chromatography (TLC)
I monitored it at. The solvent and excess PBMSB were removed under reduced pressure to give 35 g of the desired compound, a greenish viscous liquid (yield 96.8%). The structure of this substance is ¹ H-NM
Confirmed with R.

[0036]

Example G This example describes the preparation of a chain extender having the formula:

[0037]

[Chemical 6]

TMB in 100 ml toluene in a glass container
To a solution of PA-2VB (20.64 g, 0.04 mol) 1,1,
3,3-Tetramethyl-1,3-disiloxane (16.08
g, 0.12 mol) and 0.83 ml of catalyst from Huls America
PC075 was added. The reaction mixture was stirred at 40 ° C overnight.
Stir and monitor by thin layer chromatography (TLC)
It was Remove solvent and excess tetramethyldisiloxane under reduced pressure
0.58 g of the desired compound, a yellowish viscous liquid, removed by
A substance (yield 97.5%) was obtained. The structure of this substance ¹H-
Confirmed by NMR.

[0039]

EXAMPLE 1 The present invention demonstrates the preparation of a series of cured plaques from a chain extender prepared as in Example A and an olefin-rich prepolymer prepared as in Example C. The resin was mixed with catalyst solution A and catalyst inhibitor solution to obtain a gel time of 3-5 minutes at 130 ° C. Gel time was determined by dropping 4 drops of prepolymer solution directly from an 18 gauge syringe onto a hot plate preheated to 130 ° C. The resin was agitated with an applicator stick until the resin gelled. The solvent was removed on a rotary evaporator under reduced pressure of 1-2 mm Hg at 50 ° C.
The neat prepolymer was poured into a 0.3 cm (1/8 ") thick Teflon coated mold and cured in an oven under an inert atmosphere. The prepolymer was heated to 165 ° C, held for 1 hour and heated to 250 ° C. Then hold for 4 hours, then slowly cool to room temperature.The sample was then cut into 0.5 ″ × 2.5 ″ rectangular pieces for breaking energy testing. Preliminary destruction, SAMPE Journal, January / Febru
Tested by the 3-point blending method described in ary 1988, p.42. Also, 0.6 × 0.6 cm (0.25 ″ ×
The 0.25 ") specimen was tested by thermomechanical analysis (TMA) to determine the glass transition temperature (Tg) of the cured sample.

The TMA data is converted to TMA analyzer, 943
Mold, made by DuPont, obtained in Wilmington, DE. The sample was run under a liquid nitrogen atmosphere with a load of 500 mg. Sample at 0 ° C for 10
Equilibrate for 2 minutes, heat to 260 ° C at 10 ° C / min, 26
Hold at 0 ° C for 1 minute, cool to 20 ° C at 10 ° C / min,
Hold at 20 ° C. for 30 minutes. The effect of the first heating was to relieve the thermal stress in the sample. Then, the sample at 10 ° C /
Second heating was done to 300 ° C. in minutes. The glass transition temperature (Tg) of the sample was obtained from this second heating. The Tg was recorded against temperature and the slope change of the polymer was shown in the thermal expansion curve.
Formulation tested and resulting fracture energy and Tg
Is shown in Table 1. The breaking energy in the table is the average value obtained for 5 or 6 samples. Fracture energies of 470 to 640 J / m ² were obtained with formulations incorporating 13.7 to 26.9 wt% chain extender in the formulation. This is compared to the rupture energy of 110 J / m ^{2 of} cured plaque produced without the chain extender. The glass transition temperature was 90-122 ° C, compared to 160-190 ° C for polymers made without the chain extender.

[0041]

[Table 1] Table 1 Inhibitor of Example A of Example C Catalyst Catalytic Average Breakdown Energy TMA Tg Prepolymer Chain extender Solution A Solution (J / m ² ) (° C) ───────────── ───────────────────────── 38.4 g 11.9 g 0.58 ml 0.53 g 505 90 38.4 g 11.9 g 0.58 ml 0.68 g 470 103 40.8 g 10.0 g 0.58 ml 0.66 g 525 102 40.8 g 10.0 g 0.58 ml 0.71 g 475 104 43.2 g 8.1 g 0.58 ml 0.60 g 636 106 43.2 g 8.1 g 0.58 ml 0.64 g 641 107 45.7 g 6.1 g 0.58 ml 0.83 g 592 112 45.7 g 6.1 g 0.58 ml 0.94 g 492 122 ────────────────────────────────────

[0042]

Example 2 This example illustrates the preparation of a series of cured plaques of chain extender prepared as in Example A and an olefin-rich prepolymer prepared as in Example D. . The resin was mixed with catalyst inhibitor solution and catalyst solution A to obtain a gel time of 3-6 minutes at 130 ° C. Polymer plaques were prepared and tested as described in Example 1. The formulations tested and the resulting fracture energy and Tg results are shown in Table 2. The breaking energy in the table is an average value obtained from 5 or 6 samples. 18
The breaking energy of 1 to 513 J / m ² is 5.2 to ² during prescription.
It was obtained with a formulation in which 0.4% by weight of chain extender was mixed. This is compared to the rupture energy of 110 J / m ^{2 of} cured plaque produced without the chain extender. The glass transition temperature was 84-143 ° C, compared to 160-190 ° C for polymers made without the chain extender.

[0043]

[Table 2] Table 2 Inhibitor of Example A of Example D Catalyst Average Destruction Energy TMA Tg Prepolymer Chain extender Solution Solution A Ruge (J / m ² ) (° C) ──────────── ───────────────────────── 47.8 g 10.2 g 0.58 ml 0.42 g 513 84 47.8 g 10.2 g 0.58 ml 0.50 g 501 92 50.7 g 7.7 g 0.58 ml 0.33 g 444 110 50.7 g 7.7 g 0.58 ml 0.54 g 414 125 53.8 g 5.2 g 0.58 ml 0.33 g 253 133 53.8 g 5.2 g 0.58 ml 0.54 g 231 136 56.8 g 2.6 g 0.58 ml 0.38 g 181 142 56.8 g 2.6 g 0.58 ml 0.63 g --- 143 ────────────────────────────────────

[0044]

EXAMPLE 3 This example illustrates the preparation of a series of cured plaques of a chain extender prepared as in Example A and an olefin-rich prepolymer prepared as in Example E. . Resin as catalyst inhibitor and catalyst solution A
When mixed with, the gel time at 130 ° C. was 3 to 5 minutes. Polymer plaques were prepared and tested as described in Example 1. The formulations tested and the resulting fracture energies and Tg's are shown in Table 3. The breaking energy in the table is an average value obtained from 5 or 6 samples. 128-4
A break energy of 46 J / m ² was obtained with a formulation incorporating 5.9 to 17.2 wt% chain extender in the formulation. This is compared to the rupture energy of 110 J / m ^{2 of} cured plaque produced without the chain extender. The glass transition temperature was 89-142 ° C compared to 160-190 ° C for polymers made without the chain extender.

[0045]

[Table 3] Table 3 Inhibitor of Example A of Example E Catalyst average breaking energy TMA Tg prepolymer chain extender solution Solution A Ruge (J / m ² ) (° C) ──────────── ───────────────────────── 49.7 g 8.6 g 0.58 ml 0.08 g 435 89 49.7 g 8.6 g 0.58 ml 0.33 g 383 68 52.9 g 5.9 g 0.58 ml 0.21 g 259 134 52.9 g 5.9 g 0.58 ml 0.42 g 190 145 58.5 g 3.1 g 0.60 ml 0.25 g 128 126 58.5 g 3.1 g 0.60 ml 0.67 g --- 142 ────────────── ───────────────────────

[0046]

EXAMPLE 4 This example illustrates a chain extender prepared as in Example B and 2 of the olefin rich prepolymer.
Figure 4 shows the preparation of a sheet of hardened plaque. Furthermore, it is shown that the toughness obtained with chain extension additives is only possible in the presence of rubbers such as TRILENE 65 EPDM rubber. That is, the rubber makes the polymer truly tenacious because the chain extender reduces the crosslink density of the cured polymer. MHCS (100.0 parts), 71.0 parts DCPD,
89.2 parts of tricyclopentadiene (TCPD), 13.
7 parts of Catalyst B, 0.86 parts of TINUVIN® 765 antioxidant and 4.2 parts of NAUGARD® 76 antioxidant were added to two glass vessels. In the first container (label A) 5.1 parts toluene and 134.3 parts 30% TRILENE
65 EPDM rubber toluene solution was added. To a second container (label B) was added 139.4 parts of toluene. The procedure used is described in Example C. These prepolymers had a double bond / SiH ratio of 1.29. When prepolymers A and B were mixed with the chain extender of Example B and catalyst solution A, the gel time was 130 minutes and 2 minutes 30 seconds to 3 minutes. 220 ℃ instead of 250 ℃
Polymer plaques were prepared and tested as described in Example 1, except that

[0047]

[Table 4] Table 4 Prepolymer Prepolymer Chain extender Catalyst Average breaking energy TMA Tg-AB Example B Solution A Ruge (J / m ² ) (° C) ─────────────── ────────────────────── 100.5 g 46.3 g 0.84 g 586 90 102.5 g 47.3 g 0.32 g 58 117 ──────────── ────────────────────────

[0048]

Example 5 This example illustrates the preparation of a cured plaque of a chain extender p-bis (dimethylsilyl) benzene and an olefin-rich prepolymer prepared as in Example D. Prepolymer (71.4 parts) prepared as in Example D, 8.85 parts p-bis (dimethylsilyl).
Benzene, 0.88 parts inhibitor solution A and 2.17 parts catalyst solution A were mixed in a glass jar. The gel time was 130 minutes and 4 minutes and 30 seconds. Polymer plaques were prepared and tested as described in Example 1. 13.6
The breaking energy of the formulation incorporating wt.% Chain extender was 207 J / m ² on average for 5 specimens. This is 110 J / m ^{2 of} hardened plaque produced without chain extender
Compare with the destructive energy of. The glass transition temperature of the cured polymer is 160 times that of the polymer prepared without the chain extender.
115 ° C compared to ~ 190 ° C.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor John Kennis Bird, Delaware, United States 19808 Wilmington Brandywine Springs Manor Addison Drive 3210 (72) Inventor Julia Schmidt Vernier, Delaware, United States 19806 Wilmington West Sixth Street 2427 ( 72) Inventor Jiang Jian Tuan 19807 Delaware, United States Wilmington Wooddale Fox Hill Lane 22

Claims (16)

[Claims] 1. An organosilicone crosslinked polymer or crosslinkable prepolymer which is a hydrosilation reaction product of the following components (a), (b) and (c): (a) Cyclic polysiloxane having at least two ≡SiH groups. Or at least one tetrahedral siloxysilane,
(B) Non-aromatic carbon that reacts in hydrosilation-
At least one polycyclic polyene having at least two carbon double bonds in the ring, and (c) formula R ₁ -R ₂ -R
_At least one compound having ₃ (wherein R ₁ and R ₃ are the same or different —SiH terminal groups, and R ₂ is a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group).
The species, at least one of (a) and (b), has more than two reactive sites. 2. A method for producing an organosilicone polymer or prepolymer, which comprises (1) at least one of (a) a cyclic polysiloxane having at least two ≡SiH groups or a tetrahedral siloxysilane in the presence of a hydrosilation catalyst. Reacting the species with (b) at least one polycyclic polyene having at least two chemically distinct non-aromatic carbon-carbon bonds that react in hydrosilation ((a) and (b)). At least one of which has more than two reactive sites.), Producing an intermediate reaction product, and (2) the intermediate reaction product and (c) a compound of formula R ₁ -R in the presence of an additional catalyst. _2- R ₃ (wherein R ₁ and R ₃ are the same or different —SiH terminal groups, and R ₂ is a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group). At least Which method comprises reacting one. 3. (c) comprises o- and p-bis (dimethylsilyl) benzene; o- and p-bis (diethylsilyl) benzene; and 1,1,4,4-tetramethyldisilylethylene The method of claim 2 selected from the group. 4. (c) is a compound containing two carbon-carbon double bonds which react in hydrosilation, and .tbd.SiH.
The process of claim 2 which is the hydrosilation reaction product of an excess of low molecular weight monomer containing two groups. 5. A compound containing two reactive carbon-carbon double bonds is 5-vinyl-2-norbornene; o-, m- or p-diisopropenylbenzene; o-, m- or p-divinylbenzene. Diallyl ether; diallylbenzene; norbornadiene; dimethanohexahydronaphthalene; diallyl ether of bisphenol A; vinylbenzyl ether of tetramethylbisphenol A; 1,3-divinyltetramethyldisiloxane; 1,4-divinyl-1,1, 4,4-tetramethyldisilylethylene; divinyldimethylsilane;
And the method of claim 4 selected from the group consisting of 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane. 6. The low molecular weight monomer is 1,1,3,3-tetramethyl-1,3-disiloxane; o- or p-bis (dimethylsilyl) benzene; 1,1,3,3,5,5. -Hexamethyltrisiloxane; o- or p-bis (diethylsilyl) benzene; 1,
3-diphenyl-1,3-dimethyldisiloxane; 1,3-
The method of claim 4 selected from the group consisting of bis (trimethylsiloxy) -1,3-dimethyldisiloxane; and 1,1,4,4-tetramethyldisilylethylene. 7. The method according to claim 2, wherein R _{2 in} (c) is a bisphenol group. 8. A method for producing an organosilicone polymer or prepolymer, which comprises (a) at least one cyclic polysiloxane or tetrahedral siloxysilane having at least two ≡SiH groups in the presence of a hydrosilation catalyst.
Species, (b) at least one polycyclic polyene having at least two non-aromatic carbon-carbon bonds in the ring that are chemically indistinguishable and that react in hydrosilation (note that
At least one of (a) and (b) has more than two reactive sites. ) And (c) Formula R ₁ —R ₂ —R ₃ (wherein R ₁ and R ₃ are the same or different —SiH terminal groups, and R ₂ is a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group). A group having a group) is reacted with at least one compound having a group. 9. An organosilicone crosslinked polymer or a crosslinkable prepolymer continuous phase which is (1) a discontinuous phase of an elastomer and (2) a hydrosilation reaction product of the following components (a), (b) and (c). A composition containing: (a) at least one cyclic polysiloxane having at least two ≡SiH groups or tetrahedral siloxysilane,
(B) Non-aromatic carbon that reacts in hydrosilation-
At least one polycyclic polyene having at least two carbon double bonds in the ring, and (c) formula R ₁ -R ₂ -R
_At least one compound having ₃ (wherein R ₁ and R ₃ are the same or different —SiH terminal groups, and R ₂ is a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group).
Species; Note that at least one of (a) and (b) has more than two reactive sites. 10. A group of (c) consisting of o- and p-bis (dimethylsilyl) benzene; o- and p-bis (diethylsilyl) benzene; and 1,1,4,4-tetramethyldisilylethylene. The composition of claim 9 selected from: 11. The hydrosilation reaction product of (c) is a compound containing two carbon-carbon double bonds which react in hydrosilation and an excess amount of a low molecular weight monomer containing two ≡SiH groups. The composition as described. 12. A compound containing two reactive carbon-carbon double bonds is 5-vinyl-2-norbornene; o-, m- or p-.
Diisopropenylbenzene; o-, m- or p-divinylbenzene; diallyl ether; diallylbenzene; norbornadiene; dimethanohexahydronaphthalene; diallyl ether of bisphenol A; vinylbenzyl ether of tetramethylbisphenol A; 1,3-divinyl From tetramethyldisiloxane; 1,4-divinyl-1,1,4,4-tetramethyldisilylethylene; divinyldimethylsilane; and 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane The method according to claim 11 selected from the group consisting of
The composition as described. 13. The low molecular weight monomer is 1,1,3,3-tetramethyl-1,3-disiloxane; o- or p-bis (dimethylsilyl) benzene; 1,1,3,3,5,5. -Hexamethyltrisiloxane; o- or p-bis (diethylsilyl) benzene;
1,3-diphenyl-1,3-dimethyldisiloxane; 1,3
12. The composition of claim 11 selected from the group consisting of: -bis (trimethylsiloxy) -1,3-dimethyldisiloxane; and 1,1,4,4-tetramethyldisilylethylene. 14. The composition according to claim 9, wherein R _{2 in} (c) is a bisphenol group. 15. A product comprising an elastomer and a crosslinked organosilicone polymer, the crosslinked organosilicone polymer comprising (1) a discontinuous phase of the elastomer and (2) the following components (a), (b) and (c). A product selected from the group consisting of an electronic component containing a composition containing the continuous phase or an electronic component coated or encapsulated with the composition: (a) Cyclic polysiloxane having at least two ≡SiH groups or tetrahedral siloxysilane At least one of
(B) Non-aromatic carbon that reacts in hydrosilation-
At least one polycyclic polyene having at least two carbon double bonds in the ring, and (c) formula R ₁ -R ₂ -R
_At least one compound having ₃ (wherein R ₁ and R ₃ are the same or different —SiH terminal groups, and R ₂ is a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group).
The species, at least one of (a) and (b), has more than two reactive sites. 16. The product of claim 15, wherein the product further comprises a filler.