JPH07173384A - Cross-linkable and cross-linked polyphenylene oxide composition - Google Patents

Abstract

PURPOSE: To provide a crosslinkable and crosslinked polyphenylene oxide compsn. which contains a silicon compd. having hydrosilylation-reactive groups and a polyphenylene oxide having hydrosilylation-reactive unsatd. groups and is useful for electronic parts, etc.

CONSTITUTION: This compsn. is prepd. by compounding (A) a silicon compd. having at least two hydrosilylation-reactive ≡SiH groups (e.g. a cyclic polysiloxane represented by formula I [wherein R is H, (substd.) alkyl, alkoxy, (substd.) arom., or the like provided R is H on at least two Si atoms; and n is 2-20] or a linear polysiloxane represented by formula II (wherein m is 0-1,000)) with (B) a polyphenylene oxide having at least two hydrosilylation-reactive unsatd. carbon-carbon bonds {e.g. one represented by formula I [wherein R is H, allyl, H₂CC≡CH, CH₂=CHC(O), or the like; and n is an integer of 5 or higher]}, at least either A or B having at least two hydrosilylation-reactive sites.

COPYRIGHT: (C)1995,JPO

Description

Detailed Description of the Invention

[0001]

This invention relates to unique crosslinkable and crosslinked polyphenylene oxide compositions and methods of making these compositions.

[0002]

The preparation of aromatic polyethers-by redox polymerization of 2,6-dimethylphenol in the presence of a copper-amine complex as a catalyst-is described in Hay '892, U.S. Pat. No. 3,262,892, Hay. '505, U.S. Pat. No. 3,378,505, and Hay' 466, U.S. Pat. No. 3,432,466. This reaction produces high molecular weight polyphenylene oxide (PPO).

Glass filled PPO is injection molded to provide excellent strength and stability to molded articles for a variety of applications where electrical resistance is required. The tensile strength and compressive modulus of this polymer are roughly equivalent (2.6 GPa) to those of other engineering thermoplastics such as polysulfone and polycarbonate. The dielectric constant of PPO is 2.58 at 60 Hz, and the dissipation factor is low, 0.0
0035 (60 Hz). The 24-hour water absorption is similarly low, 0.06%, while the volume resistivity is 1x10.
¹⁷ ohm-cm, which makes the overall properties very suitable for electronic applications.

The thermal and chemical resistance of PPO can be improved by crosslinking the PPO and converting it into a thermosetting material for use in composites and electronic components. Crosslinking of unsaturated PPO derivatives by free radical curing is described in this patent publication Nos.
2-208355, 2-233239, 4-9111
0, and 2-120357.

Parsec et al., US Pat. No. 4,871,8
No. 16 is a poly (α, ω-dihydropoly (dialkylsiloxane)) having a terminal reactive vinyl group capable of hydrosilation to form a thermally crosslinkable thermosetting linear triblock oligomer having a vinyl chain end. Arylene polyethers are disclosed. Shear et al., US Pat. No. 4,8
No. 14,392 discloses silicone-polyarylene ether block copolymers made by the reaction of amine-terminated polydiorganosiloxanes and anhydride functionalized polyarylene ethers. Snow et al., US Pat. No. 5,204,438, form thermosetting silicone-polyphenylene ether graft copolymers, 2,
Disclosed is an oxidative coupling of a 6-disubstituted phenol with a phenol-siloxane macromer. Krantz, U.S. Pat. No. 3,668,273 discloses block copolymers prepared by reacting a polyphenylene oxide segment with a polydiorganosiloxane segment whose chain terminates in an amine group.

In one aspect, the invention relates to a crosslinkable composition comprising a silicon compound and polyphenylene oxide. The silicon compound has at least two hydrosilation-reactive ≡SiH groups, and the polyphenylene oxide has at least two hydrosilation-reactive unsaturated carbon-carbon bonds, and further, of the silicon compound and the polyphenylene oxide. At least one has two or more hydrosilation reactive sites.

In another aspect, the invention relates to a crosslinkable composition comprising a polyene, a silicon compound, and polyphenylene oxide. The silicon compound has at least two hydrosilation-reactive ≡SiH groups,
And the polyene has at least two hydrosilation-reactive carbon-carbon double bonds, and the polyphenylene oxide has at least two hydrosilation-reactive unsaturated carbon-carbon bonds, and the polyene,
At least one of the silicon compound and polyphenylene oxide has two or more hydrosilation reactive sites.

In yet another aspect, the invention relates to a crosslinkable composition comprising a crosslinkable organosilicon prepolymer and a polyphenylene oxide having at least one hydrosilation reactive unsaturated carbon-carbon bond. . The crosslinkable organosilicon prepolymer can comprise the hydrosilation reaction product of a polyene and a silicon compound, as described above.

The present invention further relates to a crosslinked composition comprising a hydrosilation reaction product of a preceding crosslinkable composition, and achieving hydrosilation of a reactant comprising the crosslinkable composition. And a method of making these crosslinked compositions comprising: In yet another aspect, the invention relates to a product comprising the crosslinkable composition of the invention in the form of electronic components and a reinforced composite product.

The term "polyene" as used herein refers to a molecule having at least two carbon-carbon double bonds.

As used herein, the term "prepolymer" is either partially cured but not fully cured or its gel point (the gel point is the point at which the substance no longer Which does not flow and no longer dissolves in organic solvents.) Any liquid or solid composition crosslinkable by hydrosilation. It typically has from 5% to 60% of reacted reactive SiH groups.

As used herein, the term "crosslinked" includes less than complete crosslinking, in which context the crosslinked composition includes unreacted crosslinkable moieties (eg, for hydrosilation). Compositions carrying unreacted hydrosilation reactive ≡SiH groups, and unreacted hydrosilation reactive unsaturated carbon-carbon bonds). The cross-linking reactions discussed herein include hydrosilation, that is, the reaction of hydrosilation-reactive ≡SiH groups and hydrosilation-reactive carbon-carbon bonds.

As used herein, the terms "aliphatic,""cycloaliphatic," and "aromatic" are understood to include alkyl, cycloalkyl, and aryl groups, respectively, unless otherwise stated. It Furthermore, "aliphatic""alicyclic"
And "aromatic" include both unsubstituted aliphatic, cycloaliphatic, and aromatic groups, as well as substituted aliphatic, cycloaliphatic, and aromatic groups, the latter of which are additional substitutions other than carbon and hydrogen. Refers to aliphatic, cycloaliphatic, and aromatic moieties containing groups.

As used herein, the term "silicon compound" includes organosilicon compounds containing carbon in addition to silicon.

Vinyl-substituted benzyl groups discussed herein have the general formula:

[Chemical 11] It shows that the position of the vinyl group can exist at any open position of the phenyl ring.

Polyenes suitable for the present invention are those having at least two hydrosilation reactive carbon-carbon double bonds. Among such polyenes are Rave Fried '779, U.S. Pat. No. 4,900,779, Rave Fried' 731, U.S. Pat. No. 4,902,731.
No. 5, Bird, et al. '360, US Pat. No. 5,008,360.
And Rave Freed '809, US Pat. No. 5,01.
There are polycyclic polyenes, including those disclosed in 3,809.

A particular polycyclic polyene is a polycyclic hydrocarbon compound having at least two non-aromatic carbon-carbon double bonds in its ring. Exemplary compounds are cyclopentadiene oligomers [eg dicyclopentadiene (DC
PD), tricyclopentadiene, and tetracyclopentadiene], bicyclopentadiene (ie norbornadiene) and its Diels-Alder oligomers with cyclopentadiene (eg dimethanohexahydronaphthalene), norbornene dimers, hexahydronaphthalene, and substitutions thereof. Includes derivatives such as methyldicyclopentadiene.

The silicon compounds of the present invention include those having at least two hydrosilation reactive ≡SiH groups. Suitable silicon compounds include cyclic polysiloxanes having two or more hydrogen atoms bonded to silicon, especially at least two hydrosilation-reactive ≡SiH groups, tetrasiloxysilanes, linear polysiloxanes, and polyfunctional silanes. Included are compounds such as polycarbosilanes and crosslinkable organosilicon prepolymers. Two or more suitable silicon compounds can be used in combination, in particular one or more such cyclic polysiloxanes and / or one or more such tetrasiloxysilanes and / or one or more such Linear polysiloxane, and / or one or more such multifunctional silanes, and / or 1
Such polycarbosilane as described above can be adopted.

Suitable such silicon compounds are Rave Fried '779, Rave Fried' 731, and Rave Fried '809, and Cowan, US Pat. No. 4,8.
77,820, Rave Freed '134, US Pat. No. 5,077,134, Raymore Oaks' 432, US Patent 3,197,432, Raymore Oaks' 4.
33, U.S. Pat. No. 3,197,433 and Raymore Oaks' 936, U.S. Pat. No. 3,438,936. Suitable such polycarbosilanes are described by Weber et al. '390, US Pat. No. 5,130,3.
90, Weber et al. '916, US Pat. No. 5,16.
No. 9,916, Weber et al. '792, US Pat.
171,792, and those disclosed in Weber et al. '810, US Pat. No. 5,171,810.

Suitable cyclic polysiloxanes have the general formula:

[Chemical 12] [Wherein, R (which may be the same or different) is hydrogen, or a saturated substituted or unsubstituted alkyl or alkoxy group, or a substituted or unsubstituted aromatic or aryloxy group, and n Is an integer from 2 to about 20, and R is hydrogen on at least two silicon atoms in the molecule. ] Are included.

Methylhydrocyclosiloxane (also referred to herein as MHCS), and mixtures thereof, are suitable such cyclic polysiloxanes. Examples include tetraoctylcyclotetrasiloxane, and hexamethylcyclotetrasiloxane; tetra- and penta-methylcyclotetrasiloxane; tetra-, penta-, hexa-, and hepta-methylcyclopentasiloxane; tetra-, penta- and hexamethyl. -Including cyclohexasiloxane, tetraethylcyclotetrasiloxane, as well as tetraphenylcyclotetrasiloxane. Preferred are 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethyl-cyclopentasiloxane, and 1,3,5,7,
9,11-hexamethylcyclohexasiloxane or blends thereof.

The silicon compound may include a plurality of methylhydrocyclosiloxanes. In particular, in many cases, what is used is in fact a mixture of a large number of species in which n can vary widely, and such a mixture is hereinafter referred to as MHCS.

Generally, about 20 commercial MHCS mixtures are used.
% Or less (as low as 2% in pure form) low molecular weight linear methylhydrosiloxanes such as heptamethyltrisiloxane, octamethyltetrasiloxane and the like. One suitable commercial mixture is Huls M8830 MHCS available from Hals America of Pennsylvania, formerly Petralka, Bristol.

Tetrasiloxysilane has the general formula:

[Chemical 13] Where R is as defined above and is hydrogen on at least two silicon atoms in the molecule.

Examples include tetrakisdimethylsiloxysilane, tetrakisdiphenylsiloxysilane, and tetrakisdiethylsiloxysilane.

Suitable linear polysiloxanes have the general formula:

[Chemical 14] [Wherein, R (which may be the same or different) is hydrogen, or a substituted or unsubstituted saturated alkyl group, or a substituted or unsubstituted phenyl group, and at least two Rs are hydrogen, And m is an integer of about 0 to 1000. ] Are included.

Linear polysiloxanes often contain small amounts of branched polysiloxanes as impurities. Included in such branched polysiloxanes are those of the general formula

[Chemical 15] Where R and m are as defined above for the linear polysiloxane and n is an integer of about 3-100. If at least two R's in the molecule of such a branched polysiloxane are hydrogen, then these branched polysiloxanes are within the scope of this invention and such branched polysiloxanes and such branched polysiloxanes are included. Linear polysiloxanes containing siloxanes (eg, in minor amounts) are equivalent to linear polysiloxanes and are considered within the scope of linear polysiloxanes for purposes of this invention.

Further suitable for the linear polysiloxanes of the present invention, such linear polysiloxanes have the general formula:

[Chemical 16] (Rave Freed '134 and Rave Freed' 809
Wherein n is 0 to 1000 and R is alkyl or aryl, preferably methyl or phenyl. ) With a linear, short chain ≡SiH terminated polysiloxane.

These linear, short chain ≡SiH terminated polysiloxanes impart flexibility to the cured composition and can be used to make elastomers. Other short siloxane oligomers such as polysiloxanes, disiloxanes, trisiloxanes, and hexamethyltrisiloxanes are particularly useful for transfer molding operations where low viscosity, especially low viscosity, is most desirable.

Additional suitable linear polysiloxanes have the general formula:

[Chemical 17] (Wherein R is a substituted or unsubstituted saturated alkyl group, or a substituted or unsubstituted phenyl group, and 1
% Or about 1% to 50% or about 50%, or more preferably 5% or about 5% to 50% or about 50% R is hydrogen and m is 5 or about 5%.
~ 1000 or about 1000 or 3 or about 3 ~
100 or about 100, preferably 5 or about 5
100 or about 100, and the maximum value of m is most preferably about 60. Is a linear poly (organohydrosiloxane) having

Examples of linear poly (organohydrosiloxanes) are trimethylsiloxy-terminated methylhydropolysiloxane, trimethylsiloxy-terminated dimethylsiloxane methylhydrosiloxane copolymer, dimethylsiloxy-terminated dimethylsiloxane methylhydrosiloxane copolymer, dimethylsiloxy-terminated polydimethylsiloxane. , Trimethylsiloxy-terminated methyloctylsiloxane methylhydrosiloxane copolymer, dimethylsiloxy-terminated phenylmethylsiloxane methylhydro-siloxane copolymer, trimethylsiloxy-terminated methylcyanopropylsiloxane methylhydrosiloxane copolymer, trimethylsiloxy-terminated 3,3,3-trifluoropropylmethylsiloxane Methylhydrosiloxane copolymer, trimethylsiloxy End 3-aminopropyl methylsiloxane - methylhydrosiloxane copolymer, trimethylsiloxy-terminated 2-phenylethyl methyl siloxane - methylhydrosiloxane copolymer, and trimethylsiloxy-terminated 2- (4-methylphenyl) - ethyl methyl -
Includes siloxane-methylhydrosiloxane copolymer.

Poly (organohydrosiloxane) s that can be used include those disclosed in Cowan.

Suitable multifunctional silanes of the present invention have the general formula:

[Chemical 18] Wherein R'is a substituted or unsubstituted aliphatic, alicyclic, or aromatic group, and R (which may be the same or different) is hydrogen or a C _1-4 group. And at least two R in the molecule are hydrogen and n is an integer of 2-4. ], Aliphatic, cycloaliphatic, and aromatic multifunctional silanes.

Examples of polyfunctional silanes are 1,4-bis (dimethylsilyl) benzene, 4,4-bis (dimethylsilyl) diphenyl ether; 1,2-bis (dimethylsilyl) ethane, 1,6-bis (methylsilyl). ) Hexane,
Bis (methylsilyl) diisopropylbenzene, tris (dimethylsilyl) cyclohexane, and tris (dimethylsilyl) benzene. Among these, disilane, namely 1,4-bis (dimethylsilyl) benzene, 4,4′-bis (dimethylsilyl) diphenyl ether, 1,2-bis (dimethylsilyl) ethane, 1,6
-Bis (methylsilyl) hexane and bis (methylsilyl) diisopropylbenzene are preferred.

Suitable polycarbosilanes of the invention have the general formula:

[Chemical 19] [Wherein R ′ (which may be the same or different) is a substituted or unsubstituted aliphatic or aromatic group, and R (which may be the same or different) Is hydrogen or a substituted or unsubstituted alkyl or aryl group, and at least two R ′ are hydrogen, and m is an integer of 5 or greater. ] Or a saturated or unsaturated polycarbosilane having

Illustrative polycarbosilanes are poly (1-methyl-1-silapent-3-ene), poly (1-phenyl-1-silapent-3-ene), poly (1-silapent-3-ene), poly (1-silapent-3-ene). (1-Methyl-1-silaidane), poly (1-phenyl-1-silaidane), poly (1-phenyl-1-silabutane), poly (1-methyl-1-silabtan) and poly (1-methyl-1). -Shira-
1-ylidene-1,4-phenylene).

The polyphenylene oxides of the present invention include those having at least one hydrosilation reactive carbon-carbon unsaturated bond. In this context, hydrosilation-reactive carbon-carbon unsaturated bonds include double and triple bonds, of which double bonds are preferred.

These hydrosilation-reactive, polyphenylene oxides containing unsaturated carbon-carbon unsaturated bonds can have a high molecular weight so as to largely maintain the basic thermoplastic properties of the polymer. There is no upper limit to the molecular weight except when it affects the solubility of the polymer. In this context, above a certain molecular weight (which may be different for each polymer), the polymers become insoluble and / or very viscous and the crosslinking reaction becomes difficult to carry out. Therefore, the molecular weight of the polyphenylene oxide component is preferably lower than this limit.

The degree of unsaturation that characterizes the polyphenylene oxide also affects the properties of the thermoplastic polymer and can be adjusted to help protect the desired properties. In particular, the higher degree of substitution in the present invention leads to easier processability and greater compatibility with the organosilicon compound, and the unsaturated polyphenylene oxide derivative retains the desirable electrical properties and low water absorption of the starting polyphenylene oxide material. To do.

Suitable polyphenylene oxides of the present invention have the general formula:

[Chemical 20] [In the formula, R (which may be the same or different) is hydrogen or —CH ₂ CH═CH ₂ , —CH ₂ C≡CH, CH ₂
= CHC (O) -, CH 3 CH = CHC (O) -, or

[Chemical 21] The group and n are integers of 5 or more. ];as well as

[Chemical formula 22] Where R and n are as defined above, n is the same or different, and Q is a polycyclic aromatic residue.

With respect to the latter of the two above formulas, the polycyclic aromatic residue Q preferably comprises the residue of a diaryl, eg diphenolic compound. Such a residue has the formula:

[Chemical formula 23] (Where Y is

[Chemical formula 24] Is. A) can be included. Of these, the formula:

[Chemical 25] (Where Y is

[Chemical formula 26] Is. ) Is particularly preferable.

Suitable starting materials for preparing the polyphenylene oxides containing unsaturated, hydrosilation-reactive carbon-carbon bonds of the present invention include both homopolymers and copolymer polyphenylene oxides, and in this context copolymers Is understood to include polymers that incorporate two different monomer units as well as polymers that incorporate three or more different monomer units, such as terpolymers. It is further understood that such copolymers include polyphenylene oxide containing both different aromatic and different non-aromatic monomer units.

Suitable monomer units for preparing the polyphenylene oxide starting materials of the present invention are A.I. S. Hay, J. Poly. Sci. , 58, 581 (196
2 years) "Polymerization II by Oxidative Coupling II, Oxidation of 2,6-Disubstituted Phenols" and Hay'170, U.S. Pat. No. 3,546,170. Among the suitable compounds are 2,6 dimethylphenol, 2-methyl-6-ethylphenol, 2-methyl-6-isopropylphenol, 2,6-ciethylphenol, 2-methyl-6-chlorophenol, 2- Methyl-6-bromophenol, 2-methyl-6-methoxyphenol, 2-
Methyl-6-phenylphenol, 2-methyl-6-
(Thiomethoxymethyl) phenol, 2-methyl-6-
(Α-Phenylethyl) phenol, 2,6-bis (thiomethoxymethyl) phenol, 2-phenyl-6-
(Thiomethoxymethyl) phenol, 2-methyl-6-
(Methylthiophenol), 2-phenyl-6- (methylthio) phenol, and 2,6-diphenylphenol.

Homopolymers and copolymers of the requisite monomer units are suitable as polyphenylene oxide starting materials. One means for making these polymers is by redox polymerization, as disclosed in Hay '892, Hay' 505, and Hay '466.

The homopolymerizable starting material has the formula:

[Chemical 27] Wherein n is at least about 5. Poly (2,6)
-Dimethyl-1,4-phenylene oxide). These polymers are made by the indicated redox polymerization of 2,6-dimethylphenol.

If a comonomer having two aryl hydroxyls, in particular a phenolic hydroxyl such as tetramethylbisphenol, is used to prepare the polyphenylene oxide starting material, a polymer having free hydroxyl groups at both ends of the polymer chain. Can be manufactured. Whether or not the comonomer contains one or more aryl hydroxyls, the advantage of the comonomer is to reduce the crystallinity of the resulting polymer, thus improving its solubility and processability. In preparing the polyphenylene oxide starting material, a comonomer containing two phenolic groups can be included and has the general formula:

[Chemical 28] A copolymer having n, which may be the same or different, is 5 or more, and Q is a residue derived from a comonomer containing two phenol groups. Diphenol compounds that can be used for this purpose include 2,6-naphthalenediol, 4,4′-dihydroxybiphenyl, bisphenol A, bisphenol B,
p, p'-dihydroxydiphenyl sulfone, p, p '
-Dihydroxydiphenylketone, p, p'-dihydroxydiphenylether.

The polyphenylene oxide of the present invention is a metallation of the polyphenylene oxide starting material.
can be prepared by adding a group containing a hydrosilation-reactive carbon-carbon unsaturated bond at the metallation site by reaction with a compound supplying such a group. Metallization is Chark and Hay, Journal of Polymer S
science A-1, vol. 7, pp. 691-705 (1
969) and Hay '144, U.S. Pat. No. 3,402,
144; Chirk and Hay, and can be carried out according to the procedures taught in Hay '144.

In this connection, side chain and aryl ring lithiation can be provided by metallation with butyllithium in tetrahydrofuran, especially poly (2,6-dimethyl-
The methyl side chains of 1,4-phenylene ether) and phenyl ring lithiation are readily provided by this method. N, N, N ', N'-tetramethylenediamine complex of butyllithium can be used for the metallation reaction in other solvents. Metallation can be restricted to the side chains of polyphenylene oxide, especially poly (2,6-
When dimethyl-1,4-phenylene ether) is employed, sodium or potassium metallation agents can be used to limit, or at least substantially limit, the methyl side chain.

The metallated polyphenylene oxides can be modified by reaction with organic halides which are characterized by the requisite hydrosilation-reactive unsaturated carbon-carbon bonds, corresponding hydrosilation-reactive unsaturated carbons of the invention. Obtaining a polyphenylene oxide containing carbon bonds. Thus, when the metallated polyphenylene oxide features a mixture of side chains and aryl ring lithiation, the polyphenylene oxide so modified has a mixture of side chain unsaturation and aryl ring unsaturation. Correspondingly, if the metallation is essentially restricted to side chains, the hydrosilation-reactive unsaturated carbon-carbon bond consists essentially of side chain unsaturation.

Suitable compounds for reacting at the metallated site to give the required hydrosilation reactive carbon-carbon unsaturated bond containing group are allyl, propargyl,
Includes acrylyl, crotyl, and vinyl substituted benzyl halides. These of course give allyl, propargyl, acrylyl, crotyl, and vinyl-substituted benzyl groups, respectively. The halides that can be used are chloride, bromide,
I have iodide. The reaction is Japanese Patent Publication No. 1-1134.
25, 1-69628, 1-69629, 1-1134
26, 2-233757, 2-233759, 3-27
5718, and 2-232260.

As an additional means to obtain the hydrosilation-reactive unsaturated carbon-carbon bond containing polyphenylene oxides of this invention, the redox polymerization procedure disclosed in Hay '892, Hay' 505 and Hay '466 was used. Thus, 2,6 diallylphenol can be polymerized to obtain a homopolymer or copolymerized with 2,6 dimethylphenol as a comonomer to give a copolymer.

Another hydrosilation-reactive unsaturated carbon-carbon bond containing polyphenylene oxide of the present invention is
The unsaturation-providing groups are added only at the hydroxyl groups of the polyphenylene oxide, or at least essentially or substantially only at the hydroxyl groups of the polyphenylene oxide. In this method, there is provided a polyphenylene oxide of the invention having two hydrosilation-reactive unsaturated carbon-carbon bonds, one on each of the two end groups being attached to the opposite end of the polymer chain. And further provides a polyphenylene oxide of the present invention having only one hydrosilation reactive carbon-carbon bond.

The polyphenylene oxide containing two unsaturated groups shown is a polyphenylene oxide starting material,
In particular, it is obtained from a copolymer having free hydroxyl groups, in particular phenolic hydroxyl groups, at both ends of the polymer chain. Correspondingly, polyphenylene oxides containing a single unsaturated group are obtained from polyphenylene oxide starting materials having one such hydroxyl group, for example at one chain end, such monohydroxyl polymers being 2,6- Includes poly (2,6-dimethyl-1,4-phenylene oxide) produced from homopolymerization of dimethylphenol.

The hydroxylated polyphenylene oxide can be appropriately reacted with the required unsaturated halides, including those identified herein, according to the procedures set forth in Parsec et al. '816, and Japanese Patent Publication No. 2-323360. it can.

Hydrosilation catalysts provide the crosslinkable compositions of the present invention, such as blends, with the products that achieve their curing (including, in particular, crosslinking) and thereby the final cured (or crosslinked) product. Can be included to gain. For example, available ≡SiH groups and carbon-
The catalyst facilitates a hydrosilation reaction in which there are carbon double bonds, and conditions are otherwise suitable to support hydrosilation, where crosslinking is achieved.

If employed, the hydrosilation catalyst is about 5-60 pp, based on the total weight of the crosslinkable composition.
can be provided in an amount of m.

Hydrosilation catalysts include metal salts and complexes of Group VIII elements. Hydrosilation catalysts are platinum (eg, PtCl ₂ , dibenzonitrile platinum dichloride, platinum on carbon, dichloro (1,2-cyclooctadiene) platinum (II) (COD) PtCl ₂ ]: Newburyport, Massachusetts. (Available from Strem Chemical).

One such platinum catalyst suitable for both reactivity and cost is chloroplatinic acid (H ₂ PtCl ₆ .6H).
₂ O) and also the platinum complex of divinyltetramethyldi-siloxane available from Hals America as PC075, and the platinum containing catalysts PC072 (Platinum divinyl complex) and PC085 available from Hals America. One catalyst is a complex of chloroplatinic acid and dicyclopentadiene, such as Rave Fried '779.
And Bird et al. '360. The second catalyst is the indicated (COD) PtCl ₂ . As a hydrosilation catalyst for the crosslinkable blends of the present invention, Krivero et al., "New Platinum-Containing Initiators For Ring-Opening Polymerization", Jo.
internal of Polymer Science;
Part A: Polymer Chemistr
y, 29, 1853-1863 (1991) are also suitable.

The crosslinkable composition of the present invention may be provided in the form of a blend of individual components. The crosslinkable blend can be prepared by any suitable means such as conventional mixing of the necessary ingredients.

The cross-linking reaction may be solution or neat.
In and by any suitable means that supports the hydrosilation reaction. The temperature used in the crosslinking reaction is not critical and depends in part on the identity of the components and the presence or absence of solvent. Generally, temperatures as low as room temperature can be used. Alternatively, the crosslinking can be carried out thermally, which would require heating as high as 250 ° C. to maximize the glass transition temperature of the crosslinked composition.

For molding applications, especially for crosslinkable or crosslinked compositions, the neat polymer is warmed, poured into the interior of the mold, and then heated to form a cured molding. A catalytic retarder such as diethylenetriamine is required during this molding operation. The thermoset formulation can be cured at various temperatures, but typically can be cured 30-40 ° C above the glass transition temperature required in the cured coating. The thermally accelerated curing by the platinum hydrosilation catalyst can begin above 100 ° C., whereupon a gel can be formed immediately. If the curing is carried out at 250 ° C. for 2 hours, a glass transition temperature around 200 ° C. develops in the coating.

In the first embodiment, the crosslinkable composition comprises a hydrosilation catalyst and reactants, ie, a silicon compound and polyphenylene oxide. These reactants are properly blended and then subjected to suitable crosslinking procedures until a crosslinked product is achieved.

In this first embodiment, the silicon compound has at least two hydrosilation-reactive ≡SiH groups and the polyphenylene oxide has at least two hydrosilation-reactive unsaturated carbon-carbon bonds. Further, at least one of the silicon compound and polyphenylene oxide has two or more hydrosilation reactive sites. The crosslinking procedure is carried out to achieve the hydrosilation of such silicon compounds with polyphenylene oxide and to provide the crosslinking.

In a second embodiment, the crosslinkable composition comprises a polyene other than polyphenylene oxide having at least two hydrosilation-reactive carbon-carbon double bonds, and the indicated hydrosilation catalyst and silicon compound. Including. Since polyenes have at least two hydrosilation-reactive sites, polyphenylene oxide is not required to have two such sites in order to achieve the necessary cross-linking, especially the only hydrosilation-reactive saturated carbon- Polyphenylene oxide having carbon bonds as well as two or more of them may be employed.

Thus, in this second embodiment, the polyphenylene oxide has at least one hydrosilation-reactive unsaturated carbon-carbon bond. Consistent with the first aspect, at least one of a silicon compound, a polyene and a polyphenylene oxide has two or more hydrosilation reactive sites to support cross-linking,
The cross-linking can be carried out in the same way as for the first aspect.

In a third embodiment, the crosslinkable composition comprises a prepolymer (preferably a crosslinkable prepolymer, and more preferably a crosslinkable organosilicon prepolymer), and at least one hydrosilation reactive unsaturation. Comprising a polyphenylene oxide having carbon-carbon bonds, and in a particularly preferred embodiment, the polyene and silicon compound are the indicated crosslinkable organoorganic compounds prepared by hydrosilation from reactants containing such polyene and silicon compound. A crosslinkable composition is provided in the form of a silicon prepolymer. This crosslinkable composition (including hydrosilation catalysts) and such prepolymers, as well as polyphenylene oxide, similarly undergo a crosslinking procedure.

The same hydrosilation catalysts described above are likewise suitable for the preparation of the prepolymer. For such platinum catalysts, about 0.0005-based on the weight of monomers.
A catalyst concentration of about 0.05% by weight can be used.

With regard to this third aspect, the present invention provides that if the prepolymer of the crosslinkable composition comprises a sufficient amount of the hydrosilation catalyst used in its preparation to achieve crosslinking of the composition, the invention The crosslinked composition of can be prepared without an additional hydrosilation catalyst. instead of,
If desired, the curable composition can be provided with additional hydrosilation catalyst.

Crosslinkable organosilicon prepolymers suitable for the present invention are the Rave Fried '77 referenced above.
9, Rave Freed '731, Rave Freed '13
4, Bird et al. '360, and their prepolymers disclosed in Cowan. A suitable crosslinkable prepolymer for the present invention is Bird et al. '303, US Pat. No. 5,068, 303, Vernier' 048, US Pat. No. 5,025, 048, Vernier '735, US 5,118,735, Burnham et al. '979, U.S. Pat. No. 5,242,979, Burnham et al.' 817, U.S. Pat. No. 5,171,817, Rave Freed '498,
U.S. Pat. No. 5,196,498, and 1990, 10
U.S. Patent Application No. 593,168 filed on May 5
No. 6,058,049, including the prepolymers disclosed in US

Preferred crosslinkable organosilicon prepolymers are (a) at least one polyene having at least two hydrosilation reactive carbon-carbon double bonds and (b) at least two hydrosilation reactive. And having at least one member selected from the group consisting of cyclic polysiloxanes, tetrasiloxysilanes, and linear polysiloxanes.
At least one silicon compound, wherein at least one of the at least one polyene and the at least one silicon compound has two or more hydrosilation reactive sites. Most preferably, at least one silicon compound has 3 or more hydrosilation reactive ≡SiH groups.

Suitable polyenes and silicon compounds for such prepolymers include those discussed herein.

When the crosslinkable prepolymer of the present invention is the indicated crosslinkable organosilicon prepolymer,
Ie an organosilicon prepolymer comprising at least one polyene and one or another cyclic polysiloxane, and / or tetrasiloxysilane, and / or a linear polysiloxane as detailed above. , The ratio of total hydrosilation-reactive carbon-carbon double bonds (contributed by at least one polyene) to hydrosilation-reactive ≡SiH groups (contributed by at least one silicon compound) is preferably these Is defined according to the intended function of the prepolymer of.

In particular, the prepolymer is formulated for hydrosilation reaction with polyphenylene oxide,
If the polyphenylene oxide provides more than one hydrosilation reaction site, such hydrosilation causes it to participate in crosslinking. Since the hydrosilation-reactive site of polyphenylene oxide is an unsaturated carbon-carbon bond, the prepolymer must provide sufficient hydrosilation-reactive ≡SiH groups for reaction therewith, and the polyene and The relative proportion of hydrosilation reactive sites contributed by the silicon compound is determined accordingly.

From the above point of view, the prepolymer composition has at least a slight excess of hydrosilation-reactive ≡Si over the hydrosilation-reactive carbon-carbon double bonds.
It may have H groups. This ratio is preferably 1.1: 1 or greater. For example, higher molecular weight polyphenylene oxides such as those cross-linked with a slight excess of available hydrosilation reactivity ≡SiH groups can be employed.

With respect to the crosslinkable organosilicon prepolymers of the present invention, further included in such prepolymers are hydrosilation reactive ≡SiH groups that have been reacted with a polyene, preferably a polycyclic polyene. A crosslinkable linear poly (organohydrosiloxane) prepolymer comprising a contained linear poly (organohydrosiloxane). Suitable polyenes such as polycyclic polyenes include those discussed herein.

In these crosslinkable linear poly (organohydrosiloxane) prepolymers, preferably 5% to 90%, more preferably at least 30%, more preferably 3% of hydrosilation reactive ≡SiH groups.
0% to 60% is reacted with polyene. Suitable linear poly (organohydrosiloxanes) for these prepolymers are those discussed herein, and both general formulas and exemplary poly (organohydrosiloxanes) are applicable.

The crosslinkable prepolymers of this invention are Rave Fried '779, Rave Fried' 731, Rave Fried '134, Byrd et al' 360, Byrd et al '30.
3, Vernier '048, Vernier' 735, Cowan,
It can be prepared utilizing procedures and components including, but not limited to, the process steps and catalysts described in Burnham et al. '979 and Burnham et al.' 817, and US Pat. No. 5,340,644. The reaction for prepolymer formation is promoted thermally or by the addition of hydrosilation catalysts or radical generators such as peroxides and azo compounds.

One approach in the process for preparing the crosslinkable organosilicon prepolymers described above is, like the crosslinkable prepolymers of the present invention, simply the exact proportions of components: polyene, silicon compound and hydrosilation catalyst. Is simply mixed and the mixture is brought to the temperature at which the reaction begins. Appropriate temperature conditions are then maintained to drive the reaction to the extent of completion requirements to obtain the desired prepolymer.

In this regard, the reaction conditions utilized are prepolymers (within the meaning of the terms defined herein, such polymers are partially cured but not fully cured). Or not exceeding its gel point). For example, the mixture of components is maintained at about 30 ° C. to 80 ° C. for several hours, then the required ratio of effective hydrosilation reactivity ≡SiH.
The point at which the group reacts (preferably 5% to 60% thereof) is interrupted. More preferably, the polymerization is 30% to 60%,
Most preferably, 30% to 50% of the effective reactive ≡SiH groups are achieved to react.

The indicated preparation of the prepolymer is carried out as a two-step procedure, in which case in the final preparation of the prepolymer the polyene used is itself first prepared in the same way as the prepolymer. In this regard, it is obtained by heating a mixture of a hydrosilation catalyst, a silicon compound, and an initial polyene (such polyenes were discussed above as suitable in hydrosilation). More specifically, Polyene has Rave Fried '134 and Rave Fried' 809.
Can be produced by the method described in.

Except as appropriate in this two-step procedure, for the preparation of the prepolymer of the third aspect of the invention, the polyene is present in the case where no prepolymer is employed, ie in the second aspect of the invention. It should be noted that it is as suitable as the polyene for the crosslinkable composition of.

For the production of this polyene, the relative proportions of initial polyene and silicon compound employed are such that there is a large excess of hydrosilation-reactive carbon-carbon double bonds available for reaction with hydrosilation-reactive ≡SiH groups. It is like it exists. That is, the hydrosilation reactive carbon-carbon double bond of the initial polyene to the hydrosilation reactive ≡SiH group of the silicon compound is about 2: 1 to about 1.
It is between 0: 1. The excess initial polyene remaining after this reaction can be removed by any suitable method such as conventional stripping, for example distillation under vacuum.

In the resulting polyene, the ratio of total hydrosilation-reactive carbon-carbon double bonds contributed by the initial polyene to hydrosilation-reactive ≡SiH groups contributed by the silicon compound is preferably at least 1. 8: 1 or at least about 1.8: 1. More preferably, it is greater than 1.8: 1 or greater than about 1.8: 1. More preferably, this ratio is 1.8: 1 or about 1.8: 1 to 2.2: 1 or about 2.2: 1, and most preferably 1.8: 1 or about 1.8: 1. ~ 2.0: 1 or about 2.0: 1.

In the formation of the resulting polyene, the hydrosilation reactivity ≡SiH groups contributed by the silicon compound is sufficient, or at least substantially sufficient, as well as the hydrosilation reactivity contributed by the initial polyene. Reacts with carbon-carbon double bonds. In this context, "at least substantially enough" means ≡S
It is meant that approximately 90% or more of the iH groups are reactive.

For such hydrosilation-reactive carbon-carbon double bonds contributed by the initial polyene, those which have not reacted with the .tbd.SiH groups are effective for further hydrosilation. Thus, the resulting polyene contains at least two hydrosilation-reactive carbon-
Given a carbon double bond.

Of these hydrosilation-reactive carbon-carbon double bonds that are thus contributed but do not react with the ≡SiH groups, a part of the reacted initial polyene,
Such hydrosilation-reactive carbon-carbon double bonds, which are now part of the resulting polyene, can be combined with hydrosilation-reactive ≡SiH groups of additional silicon compounds in the second step of the two-step procedure shown. Can be used for reactions.
This second step is the production of the crosslinkable prepolymer,
The resulting polyene and the additional silicon compound can then be carried out in the manner described above for the preparation of the crosslinkable organosilicon prepolymer.

For such a two-stage prepolymer,
The ratio of total hydrosilation-reactive carbon-carbon double bonds contributed by the resulting polyene to hydrosilation-reactive ≡SiH groups contributed by the additional silicon compound is determined by the preparation of the crosslinkable organosilicon prepolymer. Is the same as that described above.

In particular, with respect to the preparation of the crosslinkable linear poly (organohydrosiloxane) prepolymers of the present invention, as discussed herein, the hydrosilation catalyst and polycyclic polyene are mixed and heated. Form a complex. The complex and poly (organohydrosiloxane) are then combined and, with respect to the organosilicon prepolymer discussed above, appropriate reaction conditions are utilized to obtain the required prepolymer.

In particular, as discussed above with respect to the organosilicon crosslinkable prepolymer, the reaction mixture is from about 40 ° C.
It is heated to 80 ° C., this reaction temperature is maintained for several hours, and then the required proportion of the effective hydrosilation-reactive ≡SiH groups are reacted (eg preferably for poly (organohydrosiloxane) prepolymers). 5% ~
It stops at the 60% point. More preferably, the polymerization is accomplished such that 30% to 60% of the available reactive .tbd.SiH groups are reacted.

As discussed immediately below, such a discussion is currently based on the best understanding of this issue regarding polycyclic polyenes suitable for obtaining the required poly (organohydrosiloxane) prepolymer from the lower temperatures shown. Provided. This discussion is not intended to limit the invention.

In particular, so that poly (organohydrosiloxane) prepolymers, which are preferably flowable and curable, can be obtained from such low temperature reactions,
Even if the ratio of hydrosilation-reactive carbon-carbon double bonds to hydrosilation-reactive ≡SiH groups is otherwise suitable for obtaining crosslinked polymers,
Appropriate polycyclic polyenes appear to be required, and suitable such polycyclic polyenes are those with chemically distinct hydrosilation reactive carbon-carbon double bonds. That is, one such bond is more reactive than the other during hydrosilation. These polycyclic polyenes include, for example, dicyclopentadiene and cyclopentadiene trimer, and cyclopentadiene oligomers such as methyldicyclopentadiene.

The crosslinking for the third aspect can be carried out according to the same conditions utilized for the first and second aspects.

Additional ingredients other than those previously specified may also be included in the present invention. Such components may be provided in the curable composition of the invention and / or, if a prepolymer is employed, in the preparation of the prepolymer, depending on the properties of the components of the prepolymer. . These specifically mentioned special additive ingredients are not given by limitation, but others not specifically mentioned may be suitable.

For example, those identified as at least one second silicon compound in Rave Freed '498 are suitable such additional components. This component is of particular interest as it can be provided as a starting material in the curable compositions of the invention and / or employed in the preparation of prepolymers.

Other additional ingredients include the kinetic modifiers disclosed in US Pat. No. 5,340,644 referenced above.

Still other ingredients are described in US Pat. No. 5,298,
Including flame retardants disclosed in No. 536.

Still other examples of additional components, carbon (graphite), quartz, aramid, and other polymeric fibers can be included in the curable compositions of the present invention, and these materials can be used in the present invention. Of the liquid prepolymers make them very good, making them excellent matrix materials. The fibers can be in the form of non-woven, unidirectional, woven, fabric, etc. Suitable fibers and prepregs include those discussed in Bird '360.

Additives such as fillers and pigments are also easily incorporated. Leucite, mica, wollastrite, calcium carbonate, sand, silica, fumed silica, fused silica,
Examples of fillers that can incorporate ceramic beads, hollow glass, glass spheres, glass beads, ground glass, waste glass, and other mineral fillers. Fillers can be supplied either as reinforcements or as fillers and extenders, reducing the cost of the molded product, especially glass spheres are useful for making low density composites. Fillers can also be used for other reasons, such as viscosity adjustment. Fillers can be present in amounts up to about 15% by weight of the curable composition of the present invention, and even higher amounts up to about 95% by weight when glass fibers are not used.

In this regard, a particularly useful reinforcing filler is spherical particles of fused silica, which can be included up to about 95% by weight. About 90% by weight of thermal conductive ceramic filler
Can be used up to. They are useful in electronic encapsulants for removing heat from electronic components.

Stabilizers (antioxidants, antiozonants, heat and light stabilizers) are storage stability of the monomers, prepolymers and polymers in the curable compositions of the present invention as well as the cured product. It is useful for maintaining thermo-oxidative stability. Among the preferred stabilizers are radical scavengers such as hindered phenols in combination with other stabilizers. A particularly useful example is bis (1,2,2,6
6-pentamethyl-4-piperidinyl)-(3,5-di-tert-butyl-4-hydroxybenzyl) butyl propanedioate (available as Tinuvin (TM) 144 from Ciba-Geigy, Inc., Hawthorne, NY). Or octadecyl 3,5-di-tert-butyl-
4-hydroxyhydrocinnamate (octadecyl 3-
Also known as (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate. ) (Available as Naugard ™ 76 from Uniroyal Chemical Company, Middlebury, Conn.) And bis (1,2,2,6,6-pentamethyl-4-piperidinyl-sebacate) (from Ciba-Geigy). Tin
Available as uvin ™ 765. ) Is included. Stabilizers are generally used in amounts of about 0.5% to about 3.0% based on the weight of prepolymer in the curable blend. Generally, Vernier '048 and Vernier' 7
The stabilizer disclosed in 35 can be adopted.

Also, one or more elastomers can be added, preferably prior to crosslinking, to improve toughness by incorporating elastomeric regions into the composition. Preferred are hydrocarbon elastomers having a molecular weight of less than 100,000 and low molecular weight siloxane elastomers. Exemplary hydrocarbon elastomers are low molecular weight ethylene-propylene-diene terpolymers, low molecular weight butyl rubber, partially hydrogenated low molecular weight polyisoprene or natural rubber, and partially hydrogenated low molecular weight polybutadiene or styrene-butadiene. It is a copolymer. Exemplary siloxane rubbers are low molecular weight vinyl or S
Includes iH-terminated polydimethyl / diphenylsiloxane copolymer. Preferred are low molecular weight ethylene-propylene-dicyclopentadiene and ethylene-propylene-ethylidene norbornene polymers having a molecular weight of 5500-7000. Most preferred is Trilen
e65 elastomer (available from Uniroyal Chemical Company). Elastomers are generally used in amounts of 0.5-20%, preferably 3-12%, and most preferably 5-10% by weight of the total composition, with higher levels useful in some applications. In general, the elastomers disclosed in Burnham et al. '979 and Burnham et al.' 817 can be employed.

In general, for the relative proportions and different types of components for use in the curable and cured compositions of the present invention, these are not undue tested by those skilled in the art according to various factors. Can be decided. Such factors include, but are not limited to, the compatibility of such components, whether they react with each other, the stoichiometry of the reactions that occur. Also, additional factors relate to the desired properties in the curable blend and the cured product.

In this regard, one set of ratios to consider is the ratio of all hydrosilation-reactive carbon-carbon double bonds to all hydrosilation-reactive ≡SiH groups, which ultimately results in the invention. All ingredients in the manufacture of the composition,
For example, it contributes from the polyene (if present) and the silicon compound, either contributing to the production of the prepolymer or to the final cured product. This ratio is preferably 0.1: 1 or about 0.1: 1 to 1.
5: 1 or about 1.5: 1, more preferably the ratio is 0.5: 1 or about 0.5: 1 to 1.
2: 1 or 1.2: 1, more preferably the ratio is 0.8 or about 0.8: 1 to 1.2: 1 or about 1 to 1.2: 1. Most preferably this ratio is 1: 1.1 or slightly higher.

For the range of the most preferred 1: 1.1 or slightly higher than specified, the considerations mentioned regarding the proportion of preferred hydrosilation sites for the crosslinkable prepolymer are of general applicability. Is the same as. There must be sufficient hydrosilation-reactive .ident.SiH groups available to react with the hydrosilation-reactive unsaturated carbon-carbon bonds of the polyphenylene oxide. Therefore, at least a slight excess of ≡SiH
Groups are preferred. Also, with respect to the discussion of the ratio of hydrosilation sites for crosslinkable prepolymers, the suitability of higher molecular weight polyphenylene oxide for crosslinking is generally found when a slight excess of hydrosilation reactive ≡SiH groups is available. It is similar to the one with specific applicability.

This amount is not critical, especially with respect to the relative amount of polyphenylene oxide with respect to the other components. The minimum amount of hydrosilation reactive component (excluding polyphenylene oxide) used is to achieve crosslinking. This amount is about 1% by weight of the composition, therefore
About 99% by weight or less of polyphenylene oxide can be used. The maximum amount of components other than polyphenylene oxide maintains the desirable properties imparted to the composition by the presence of polyphenylene oxide, which amount is about 60% by weight of the composition, so that polyphenylene oxide is preferably present. The minimum amount to do is 40% by weight.

The compositions of the present invention are coated, molded, or compounded to form useful processed forms. Inorganic, glass or metal coatings at ambient conditions provide corrosion protection for expensive assemblies.
This low polarity composition provides a cohesive and tacky coating with very low properties for absorption of atmospheric moisture. This and its low dielectric constant make them excellent protective coatings and encapsulants for sensitive electronic components.

The composition of the present invention may be used to obtain a reinforced composite material, product impregnated with a toughening agent. In addition, they can be coated onto fibers to make composite laminates and processed into useful structures. The fluid composition coats glass, aramid or carbon fiber as a filament, mat or cloth,
It can then be provided with a form that is especially cured and easily processed into laminates or other composite forms such as printed circuit board supports.

The composition can be poured directly into a die or mold to provide a rimtruded or molded part. Typically, a glass non-woven mat or cloth is placed in a mold and a fluid composition is injected to fill the mold and cure there to form a finished molded part. Rim truss
On) application, the glass or fiber roving is pulled through a die where the fluid polymer formulation is injected under pressure and thermally cured before it leaves the heating zone of the rimtrudder barrel. Make a solid rod from roving. rod,
Beams or other composite components can be made continuously by this method.

The invention is illustrated by the following examples, which are provided for purposes of illustration and should not be construed as limiting the scope of the invention. Unless stated otherwise, all percentages and parts are by weight.

[0110]

EXAMPLE 1 Polyphenylene oxide (PPO) having two hydroxyl groups on either end of the polymer.
-2OH) -α, ω-bis (2,6-dimethylphenol) -poly (2,6-dimethyl-1,4-phenylene oxide) 4-dimethylaminopyridine (28 g, in 740 mL methanol and 100 mL water. Cuprous chloride (7.2 g, 0.113 mol) was added to a solution of 0.23 mol). Air was bubbled through the reaction mixture for 15 minutes. Tetramethylbisphenol A (66.24 g, 0.233 mol) and 2,6
-A solution of dimethylphenol (113.77 g, 0.933 mol) in 1200 mL of methanol was added to the reaction mixture. Air was bubbled through the reaction mixture for 18 hours. The precipitated polymer was filtered and air dried at room temperature. Purification was carried out by precipitation of a solution of the crude polymer in chloroform in 2.4 L of methanol containing 40 mL of concentrated hydrochloric acid. The pale yellow precipitate that formed was collected and washed thoroughly with methanol to give 378 g.
Of PPO-2OH was obtained.

Preparation of Polyphenylene Oxide from PPO-2OH Having Two Hydrosilation-Reactive Carbon-Carbon Unsaturated Bonds at One of the Ends of the Polymer-Bis (vinylbenzyl ether) of PPO-2OH
(PPO-2VB) PPO-2OH (100 in 800 mL of chloroform.
g, 0.09 eq OH) solution in sodium hydroxide (1
0.8 g, 0.135 mol) of 50% aqueous solution was added dropwise. After the addition of tetrabutylammonium hydrogen sulfate (3.4 g, 0.01 mol) and 300 mL of water, the color of the reaction mixture changed from dark brown to yellow-green.
m, p-vinylbenzene chloride (25 g, 0.16
Mol) was added to the reaction mixture and stirring was continued for 18 hours. According to thin layer chromatography, PPO
The -2OH starting material had disappeared. The organic phase was separated from the aqueous phase and precipitated in 4.8 L of methanol. The precipitate that formed was collected, washed thoroughly with methanol and dried under vacuum. ¹ H NMR spectrum of the product shows σ = 5.2
It showed a clear separation pattern for vinyl olefinic protons at 5 ppm, 5.75 ppm, and 6.75 ppm.

Using a platinum hydrosilation catalyst,
Crosslinking of vinylbenzyl ether-terminated polyphenylene oxide (PPO-2VB) with methylhydrocyclosiloxane (MHCS) and dicyclopentadiene PPO-2VB (0.31 g) with dicyclopentadiene (8.77 meq olefin) and toluene 0.618.
g. 0.55 g of methylhydrocyclosiloxane and 0.08 g of chloroplatinic acid complexed with DCPD (1123 ppm Pt in dicyclopentadiene) were added to this solution.
Was added to bring the concentration to 59 ppm in the cross-linking formulation.

The formulation gelled after stirring for 72 hours at room temperature. The formulation formed a clear compatible gel at 154 ° C. in 3 minutes 15 seconds.

[0114]

Example 2 Production of Poly (2,6-dimethyl-1,4-phenylene oxide) PPO A catalyst was produced by dissolving 1.23 g of CuBr _{2 in} 15 mL of methanol. This solution is then toluene 1350 m
Transferred to a flask containing 3217 g of L and dibutylamine. The mixture was vigorously stirred while passing air at a rate of 3.7 L / min near the bottom of the flask. 2,6-dimethylphenol 210 dissolved in 210 g of toluene
g of solution was added over 15 minutes with continued stirring and introduction of air. The reaction was stopped by stopping the air flow and adding 200 mL of 50% acetic acid. Separate the organic phase,
Then, 3500 mL of methanol was poured to precipitate the polymer, and then the polymer was dried at 60 ° C. under vacuum.

Side group alkylation of PPO 6 g of poly (2,6-dimethyl-1,4-phenylene oxide) are added to 250 ml of dry toluene, and 2.3 g of sodium are added and the mixture is heated at 100 ° C. for 30 minutes. Dispersed by After cooling to room temperature, 1
-6 g of chlorohexane was added. The reaction mixture was heated to 65 ° C. for 1 hour, and 3.8 g of allyl chloride was added. The toluene solution was gradually added to 750 mL of methanol to precipitate the polymer. Polymer is toluene 250m
Redissolved in L and extracted 3 times with 250 mL portions of water. The polymer was reprecipitated by adding the toluene solution to 750 mL of methanol. The precipitated polymer was dried under vacuum.

Preparation of Crosslinkable Organosilicon Prepolymer from Methylhydrocyclosiloxane and Dicyclopentadiene (MHCS / DCPD) Methylhydrocyclosiloxane (Hals America, M8
803) 5.3 g, dicyclopentadiene 5.9 g, and chloroplatinic acid solution 0.75 in dicyclopentadiene.
g (0.15g CPA / 100g DCPD, 50 ° C
Heated for 1 hour) was added to the bottle. The reaction mixture was stirred at 25 ° C. until essentially 100% of the norbornene double bonds had reacted by NMR analysis. 5.5 mg (50 pp of tetramethylethylenediamine was added to the resulting prepolymer.
Stabilized by adding m) to the solution.

Crosslinking of Side Chain Allylated PPO with Crosslinkable Organosilicon Prepolymer 5.6 g of crosslinkable organosilicon prepolymer, 4.4 g of allylated PPO, PC in 10 g of tetrahydrofuran.
0.05 g of 072 platinum catalyst (Hals America) and 0.4 mg of tetramethylenediamine were dissolved. Spread 0.2 milcotting of this solution onto a glass plate,
Then, it was gradually heated to 250 ° C. to obtain a hard transparent non-polar coating having excellent electrical properties (low dielectric constant, low dielectric loss tangent, high resistance).

[0118]

Example 3 Aryl Ring and Side Chain Allylation of Poly (2,6-dimethyl-1,4-phenylene oxide) Butyl lithium (8.3 mL of a 1.6 M solution in hexane)
And 1.5 g of tetramethylethylenediamine were added to 370 g of benzene. Poly (2,6-dimethyl-1,4-
8 g of phenylene oxide) was added to the solution and stirred at 25 ° C. for 24 hours. The resulting lithiated polymer was reacted with 1.1 g of allyl chloride by stirring for 1 hour at 25 ° C. Methanol 1L
The polymer obtained by slowly adding was precipitated from solution. To purify the polymer, toluene 25
Redissolved in 0 mL and the resulting solution was extracted 3 times with 250 mL of water. The polymer was reprecipitated in methanol and dried under vacuum.

Crosslinking of Ring and Side Chain Allylated PPO with Crosslinkable Organosilicon Prepolymer Aryl ring and side chain allylated PPO (6.3 g) prepared according to the procedure described in Example 2, and crosslinkable organo 1.1 g of silicon prepolymer was dissolved in 10 g of tetrahydrofuran to give PC072 platinum complex 0.04
g, and 0.3 mg of tetramethylethylenediamine were added to this solution. A 0.3 mil coating of the solution was spread on a silicon wafer and cured at 200 ° C. for 2 hours. The coating was hard and transparent with excellent electrical properties.

Finally, although the invention has been described with respect to particular means, materials and embodiments, it is not limited to the particulars disclosed, and all equivalents within the scope of the claims. And it should be noticed.

Claims (19)

[Claims] 1. A method comprising: (a) a silicon compound having at least two hydrosilation-reactive ≡SiH groups, and (b) a polyphenylene oxide having at least two hydrosilation-reactive unsaturated carbon-carbon bonds. A crosslinkable composition, wherein at least one of a silicon compound and polyphenylene oxide has two or more hydrosilation reactive sites. 2. Further comprising a hydrosilation catalyst,
A crosslinkable composition according to claim 1. 3. The silicon compound comprises: (a) the following: (i) a polyene having at least two hydrosilation-reactive carbon-carbon double bonds, and (ii) at least two hydrosilation-reactive ≡SiH. A hydrosilation reaction product of a reactant comprising a silicon compound having a group and comprising a member selected from the group consisting of cyclic polysiloxanes, tetrasiloxysilanes, and linear polysiloxanes. A crosslinkable organosilicon prepolymer, wherein at least one of the polyene and silicon compound has two or more hydrosilation reactive sites (b) cyclic polysiloxane, (c) linear polysiloxane, ( selected from the group consisting of d) tetrasiloxysilane, (e) polycarbosilane, and (d) polyfunctional silane. Comprising membered, crosslinkable composition of claim 1. 4. The silicon compound has the formula: [In the formula, R (which may be the same or different) is hydrogen,
Alternatively, it is a saturated substituted or unsubstituted alkyl or alkoxy group, or a substituted or unsubstituted aromatic or aryloxy group, n is an integer from 2 to about 20, and R is at least 2 silicon atoms. It is hydrogen. ] Cyclic polysiloxane having
A crosslinkable composition according to claim 3. 5. The silicon compound has the formula: [In the formula, R (which may be the same or different) is hydrogen,
Or a substituted or unsubstituted saturated alkyl group, or a substituted or unsubstituted phenyl group, and at least 2
One R is hydrogen and m is an integer of about 0-1000. ] The crosslinkable composition of claim 3 comprising a linear polysiloxane having. 6. The silicon compound has the formula: [In the formula, R (which may be the same or different) is hydrogen,
Alternatively it is a saturated substituted or unsubstituted alkyl or alkoxy group, or a substituted or unsubstituted aromatic or aryloxy group, and R is hydrogen on at least two silicon atoms in the molecule. ] The crosslinkable composition of claim 3 comprising tetrasiloxysilane having. 7. The silicon compound has the formula: [Wherein R ′ (which may be the same or different) is a substituted or unsubstituted aliphatic or aromatic group, and R (which may be the same or different) is hydrogen or substituted or Is an unsubstituted alkyl or aryl group, and at least two R are hydrogen and m is an integer of at least 5. A crosslinkable composition according to claim 3 comprising a polycarbosilane selected from the group consisting of saturated or unsaturated polycarbosilanes having 8. The silicon compound is aliphatic, alicyclic, and a compound represented by the formula: [Wherein R ′ is a substituted or unsubstituted aliphatic, alicyclic or aromatic group, and R (which may be the same or different) is hydrogen or a C _1-4 alkyl group. , And at least two R are hydrogen, and n is an integer of 2-4. A crosslinkable composition according to claim 3, comprising a polyfunctional silane selected from the group consisting of aromatic polyfunctional silanes having 9. The crosslinkable composition of claim 1, wherein the polyphenylene oxide comprises a member selected from the group consisting of homopolymer and copolymer polyphenylene oxide. 10. The polyphenylene oxide is (a).
Formula: [In the formula, R (which may be the same or different) is hydrogen,
Or —CH ₂ CH═CH ₂ , —CH ₂ C≡CH, CH ₂
= CHC (O) -, CH 3 CH = CH (O) -, or embedded image And n is an integer of at least 5. ] And polyphenylene oxide having the formula (b): From the group consisting of polyphenylene oxide having R and n as defined above, n may be the same or different, and Q is a polycyclic aromatic residue. 10. The crosslinkable composition of claim 9, comprising a member selected. 11. The crosslinkable composition according to claim 10, wherein Q is a residue of a diphenol compound. 12. Q is (In the formula, Y is Is. A crosslinkable composition according to claim 11, comprising a member selected from the group consisting of: 13. Polyphenylene oxide having two hydrosilation-reactive unsaturated carbon-carbon bonds,
10. The crosslinkable composition according to claim 9, further comprising both ends each terminated by a group containing one of the two hydrosilation reactive unsaturated carbon-carbon bonds. 14. The crosslinkable composition of claim 9, wherein at least two hydrosilation reactive unsaturated carbon-carbon bonds consist essentially of side chain unsaturation. 15. The crosslinkable composition of claim 9, wherein the at least two hydrosilation reactive unsaturated carbon-carbon bonds comprise side chain unsaturation and cyclic unsaturation. 16. (a) A polyene having at least two hydrosilation-reactive carbon-carbon double bonds,
(B) at least two hydrosilation reactive ≡S
a silicon compound having an iH group and comprising at least one member selected from the group consisting of cyclic polysiloxanes, tetrasiloxysilanes, and linear polysiloxanes; and (c) at least one hydrosilation-reactive A crosslinkable composition comprising polyphenylene oxide having a saturated carbon-carbon bond, wherein at least one of a silicon compound and polyphenylene oxide has two or more hydrosilation reactive sites. 17. (a) having: (i) a polyene having at least two hydrosilation-reactive carbon-carbon double bonds, and (ii) having at least two hydrosilation-reactive ≡SiH groups. , And a crosslinkable composition comprising a hydrosilation reaction product of a reactant comprising a silicon compound comprising at least one member selected from the group consisting of cyclic polysiloxanes, tetrasiloxysilanes, and linear polysiloxanes. An organosilicon prepolymer, wherein at least one of the polyene and the silicon compound has two or more hydrosilation-reactive sites, and (b) at least one hydrosilation-reactive unsaturated carbon-
A crosslinkable composition comprising polyphenylene oxide having carbon bonds. 18. A crosslinked composition comprising a hydrosilation product of the crosslinkable composition according to any of claims 1-17. 19. A product comprising the crosslinked composition of claim 18, wherein the product comprises the crosslinked composition and an electronic component coated or encapsulated with the crosslinked composition. An article as described above, comprising a member selected from the group consisting of: electronic components.