JP2002212293A - Siloxane bond-containing polymer and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide siloxane bond-containing polymers excellent in heat resistance, and manufacturing method thereof. SOLUTION: The siloxane bond-containing polymers bear an Si-H bond represented by general formula (1) (wherein R1 is a hydrogen atom or a specific group; and R2 is a specific group) and at least one group selected among -C≡C-, -C=C-, a carbonyl group, an epoxy group, a hydroxyl group and an amino group. The manufacturing method of the polymers is also provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a compound having a highly reactive Si-H bond and at least one of -C−C-, -C = C-, a carbonyl group, an epoxy group and a hydroxyl group in a molecule. The present invention relates to a siloxane bond-containing polymer useful as a heat-resistant and flame-resistant material, and a method for producing the same.
Its applications include high heat-resistant adhesives, high heat-resistant release agents, high heat-resistant sealing materials, and the like.

[0002]

2. Description of the Related Art Many engineering plastics have been researched and developed as heat-resistant materials which are lightweight and have excellent mechanical properties and can be processed. The present inventors have found that a thermosetting silicon-based resin containing a repeating unit having a highly reactive carbon-carbon unsaturated bond and Si-H bond in the molecule has extremely high heat resistance. (Japanese Patent Laid-Open No. 7-
102609).

[0003] On the other hand, silicones containing a siloxane bond whose repeating unit is represented by Si-O even in the same silicon-based resin are used in a variety of fields such as mold release agents and sealing materials, but have a very high heat resistance. Absent. As a method for improving the heat resistance of silicones, it has been proposed to incorporate heat stabilizers such as iron oxides, cerium compounds, oxides and hydroxides of lanthanum-based rare earth metals, allyl urethane, and polyethynylpyridine. , All of which are for practical use
It was below 300 ° C. Therefore, polymers having a siloxane bond having high heat resistance have been desired.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have found that Si-
Reacting a dihydroxy compound with a hydrosilane compound containing an H bond to form a reactive Si-H bond and -C in the molecule;
It has been found that by using a siloxane bond-containing polymer having at least one of C-, -C = C-, a carbonyl group, an epoxy group, and a hydroxyl group, heat resistance and combustion resistance are greatly improved. The invention has been reached.

[0005]

The present invention provides a compound represented by the general formula (1):
(Formula 3)

Embedded image (Wherein, R ¹ is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group, an alkynyl group, an alkoxy group, or an aromatic group, and R ² is —C≡C—, —C ＝ C—, carbonyl Group, an epoxy group, a hydroxyl group, an amino group, an alkylene group having 1 to 50 carbon atoms, an alkenylene group, an alkynylene group, and a divalent aromatic group having at least one of these groups. Siloxane bond-containing polymers having a repeating unit represented by the formula:

The present invention relates to a compound represented by the general formula (2):

Embedded image (Wherein R ¹ has the same meaning as R ¹ in claim ¹ and X is a halogen atom and an alkoxy group having 1 to 30 carbon atoms), and a hydrosilane compound having a Si—H bond represented by the formula: R ¹ has the same meaning as R ¹ in claim 1, X is a halogen atom,
It is an alkoxy group having 1 to 30 carbon atoms. ) And a hydrosilane compound having a Si-H bond and R ² (OH) ₂
(Wherein R ² has the same meaning as R ² in claim 1.) The general formula of claim 1 which is obtained by reacting a dihydroxy compound represented by (1) siloxane bond-containing highly expressed in Method for producing molecules.

BEST MODE FOR CARRYING OUT THE INVENTION BEST MODE FOR CARRYING OUT THE INVENTION

[0007] The Si-H bond of the present invention and -C≡C-, -C
= A novel siloxane bond-containing polymer having at least one group of C-, a carbonyl group, an epoxy group and a hydroxyl group can be obtained by the reaction formula (3)

Embedded image As shown, a hydrosilane compound containing a Si—H bond represented by the general formula (2) and —C≡C— represented by R ² (OH) ₂ , —C ＝ C—, a carbonyl group, Epoxy group,
It can be produced by condensing a dihydroxy compound having at least one of the hydroxyl groups in the presence of a condensation reaction catalyst.

In the general formula (1), R¹1 carbon represented by
Alkyl groups which may have from 3 to 30 substituents include
Tyl, ethyl, propyl, hexyl, cyclohexyl
Xyl, octyl, dodecanyl, trifluoromethyl
Tyl group, 3,3,3-trifluoropropyl group, chloro
Methyl, aminomethyl, hydroxymethyl, silyl
A methyl group, a 2-methoxyethyl group and the like;
An alkenyl group optionally having 1 to 30 substituents
A vinyl group, a 2-propenyl group, an isopropenyl group,
3-butenyl group, 5-hexenyl group, 1,3-butadiene
Nyl group, 3,3,3-trifluoro-1-propenyl group
And may have a substituent having 1 to 30 carbon atoms.
Alkynyl groups include an ethynyl group, a 1-propynyl group,
2-propenyl group, butynyl group, trimethylsilylethyl
And a phenylethynyl group.
Examples of the alkoxy group which may have 30 substituents include
Xy, trifluoromethoxy, ethoxy, pheno
And a substituent having 1 to 30 carbon atoms.
The aromatic group which may be a phenyl group, a naphthyl group,
-Methylphenyl group, 4-chlorophenyl group, 4-metho
A xyphenyl group and the like. R^Two-C≡ represented by
C-, -C = C-, carbonyl group, epoxy group, hydroxyl
Number of carbon atoms having at least one of an amino group and an amino group
An alkylene group which may have 1 to 50 substituents is-
CH_Two-C≡C-CH_Two-CHF-, -CH_Two-CH = C
H-CH_Two-CHCl-, -CH_Two-CO-CH_Two-CH
F-, -CH_Two-COC-CH_Two-CHCl-, -CH_Two
-CHOH-CHF-, -CH_Two-NH-CHCl-C
H_TwoAnd the like, -C≡C-, -C = C-, carbo
At least one of a nyl group, an epoxy group, a hydroxyl group, and an amino group
Also has a substituent having 1 to 50 carbon atoms having one group
Alkenylene group is -CH_Two-C≡C-CH_Two-C
H = CH-CHF-, -CH_Two-CH = CH-CHCl
-CH = CH-CH_Two-, -CH_Two-CO-CHF-CH
= CH-CH_Two-, -CH_Two-COC-CHCl-CH =
CH-CH_Two-, -CH_Two-CH_TwoOH-CHF-CH =
CH-CH_Two-, -CH_Two-NH-CHCl-CH = CH
-CH_TwoAnd the like, -C≡C-, -C = C-,
A small number of rubonyl, epoxy, hydroxyl, and amino groups
At least one substituent having 1 to 50 carbon atoms
The alkynylene group which may be _Two-C≡C-CH
FC≡C-CH_Two-, -CH_Two-CH = CH-CHCl
-C≡C-CH_Two-, -CH_Two-CO-CHF-C≡C-
CH_Two-, -CH_Two-COC-CHCl-C @ C-CH_Two
-, -CH_Two-CHOH-C≡C-CHF-, -CH_Two−
NH—C≡C—CHCl— and the like, —C≡C—,
-C = C-, carbonyl group, epoxy group, hydroxyl group,
1 to 5 carbon atoms having at least one of the
And the divalent aromatic optionally having 0 substituents is -CH_Two−
C≡CC₆H_ThreeCl-, -CH_Two-CH = CH-C₆H_Three
Cl-, -CH_Two-CO-C₆H_ThreeCl, -CH_Two-COC
-CH_Two-C₆H_ThreeCl-, -C₆H_TwoClOH-, -C₆H
_TwoNH_TwoCl- and the like.

In the general formula (2), examples of the alkoxy group represented by X and having 1 to 30 carbon atoms which may have a substituent include a methoxy group, a trifluoromethoxy group, an ethoxy group and a phenoxy group. .

Examples of the hydrosilane compound containing a Si—H bond represented by the general formula (2) used as a raw material include dichlorosilane, methyldichlorosilane, ethyldichlorosilane, t-butyldichlorosilane, octyldichlorosilane, and cyclohexyldichlorosilane. , Dodecanyldichlorosilane, trifluoromethyldichlorosilane,
3,3,3-trifluoropropyldichlorosilane, silylmethyldichlorosilane, vinyldichlorosilane, allyldichlorosilane, 2-propenyldichlorosilane,
Isopropenyldichlorosilane, 3-butenyldichlorosilane, 5-hexenyldichlorosilane, 1,3-butadienyldichlorosilane, 3,3,3-trifluoro-
1-propenyldichlorosilane, ethynyldichlorosilane, 1-propynyldichlorosilane, 2-propenyldichlorosilane, butynyldichlorosilane, trimethylsilylethynyldichlorosilane, phenylethynyldichlorosilane, methoxydichlorosilane, ethoxydichlorosilane, phenoxydichlorosilane, phenyl Dichlorosilane, naphthyldichlorosilane, 4-methylphenyldichlorosilane, 4-chlorophenyldichlorosilane,
Bis (dichlorosilyl) methane, 1,1-dichloro-
3,3-dimethyl-1,3-disilabutane, diiodosilane, methyldimethoxysilane, methyldiethoxysilane, methyldiphenoxysilane, ethyldimethoxysilane, ethyldiethoxysilane, propyldimethoxysilane, propyldiethoxysilane, hexyldimethoxysilane, Hexyldiethoxysilane, cyclohexylmethoxysilane, octylmethoxysilane, trifluoromethyldimethoxysilane, hydroxymethyldimethoxysilane, silylmethyldimethoxysilane, vinyldimethoxysilane, vinyldiethoxysilane, vinyldiphenoxysilane, allyldimethoxysilane, 2-propenyl Dimethoxysilane, 3-butenyldichlorosilane, 3,
3,3-trifluoro-1-propenyldimethoxysilane; ethynyldimethoxysilane, ethynyldiethoxysilane, butynyldimethoxysilane, phenylethynyldimethoxysilane, trimethoxysilane, triethoxysilane, triphenoxysilane, phenyldimethoxysilane Phenyldiethoxysilane, naphthyldimethoxysilane, 4-chlorophenyldimethoxysilane and the like.

An aliphatic dihydroxy compound having at least one of -C≡C-, -C = C-, a carbonyl group, an epoxy group and a hydroxyl group represented by R ² (OH) ₂ which is another raw material. Is 2-butyne-1,4-diol, 3
-Hexyne-1,6-diol, 3-hexyne-2,5
-Diol, 4-octyne-1,8-diol, 2,5
-Dimethyl-3-hexyne-2,5-diol, 2-chloro-5-methyl-3-hexyne-2,5-diol,
3,6-dimethyl-4-octyne-3,6-diol,
2,4,7.9-tetramethyl-5-decyne-4,7-
Diols, 2,4-hexadiyne-1,6-diol,
3,5-octadyne-1,8-diol, 2,7-dimethyl-3,5-octadyne-2,7-diol,
1,4-bis (1′-hydroxycyclopentyl)-
1,3-butadiyne, 2-butene-1,4-diol,
3-hexene-1,6-diol, 3-hexene-2,
5-diol, 4-octene-1,8-diol, 2,
5-dimethyl-3-hexene-2,5-diol, 2-
Chloro-5-methyl-3-hexene-2,5-diol, 3,6-dimethyl-4-octene-3,6-diol, 2,4,7.9-tetramethyl-5-decene-4,
7-diol, hydroxypanaxidiol, 1-bromo-7-oxa-bicyclo (4.1.0) heptane-
2,3,4,5-tetraol, diethanolamine,
Diisopropanolamine, N, N'-bis (2-hydroxyethyl) ethylenediamine, 2-amino-4-octyne-1,8-diol, 2-amino-6-chloro-
4-octyne-1,8-diol, 2-hydroxy-4
-Octin-1,8-diol and the like, and the aromatic dihydroxy compound is 4- (3-hydroxy-3-methylbutyn-1-yl) benzyl alcohol, 1,1,4,
4-tetraphenyl-2-butyne-1,4 diol,
1,1,6,6-tetraphenyl-hexa-2,4-diyne-1,6-diol, 1,1,1,8,8,8-hexaphenyl-octa-3,5-diyne-2, 7-diol, 1,1,4,4-tetraphenyl-2-butene-
1,4 diol, tetrahydroxy-p-benzoquinone, 3,5-dihydroxyacetophenone, 1,4-dihydroxyanthraquinone, 2,6-dihydroxyanthraquinone, N-phenyldiethanolamine, N, N
-Bis (2-hydroxyethyl) -M-chloroamine,
3- (N-benzyl-N-methylamino) -1,2-propanediol, 8-hydroxy-4- (7-hydroxy-6-methoxy-2-oxo-1A, 2,7,7A-
Tetrahydronaphtho [2,3B] oxyline, 4-amino-catechol, 5-aminoresorcinol, 1,2,4
-Benzenetriol, pyrogallol, 4- (7-hydroxy-2naphthyl) pyrogallol and the like.

A method for producing a siloxane bond-containing polymer represented by the general formula (1) from hydrosilane having a Si—H bond and a dihydroxy compound will be described. The reactor includes a part for supplying raw materials, a stirring device inside the reactor, a part for controlling the temperature of the reactor, and the like. This reaction can be carried out without a solvent or in a solvent. The solvent is further charged into the container, if necessary, as the raw material, a hydro compound having a Si-H bond represented by the general formula (2), a dihydroxy compound represented by R ² (OH) ₂ , and a condensation reaction catalyst. . The condensation reaction catalyst can be charged in a solution state, a suspension state, or as it is without being dissolved in a solvent. The reaction solution is allowed to react for a predetermined time while being stirred while being controlled at a predetermined temperature. After a predetermined reaction time, a siloxane bond-containing polymer is obtained by removing the solvent or precipitating the polymer by distillation under reduced pressure or the like.

The catalyst for the decondensation reaction which can be used in the reaction formula (3) can be roughly classified into an acid catalyst and a basic catalyst. When the substituent X is a halogen atom, a basic catalyst can be used. When the substituent X of the hydro-compound having a Si-H bond represented by the general formula (2) represented by the general formula (2) is an alkoxy group which may have a substituent, an acid catalyst and a basic catalyst may be used.
Acid catalysts include HF, HCl, HBr, HI, H as inorganic acids.
₂ SO ₄ , HNO ₃ , H ₂ CO ₃ , HClO ₂ , H ₂ S, H ₂ S
O ₃ , H ₂ S ₂ O _{3 and the} like.
OH, CH ₃ COOH, C ₆ H ₅ COOH, oxalic acid, trifluoroacetic acid and the like.
₂ O ₃ , SiO ₂ —Al ₂ O ₃ , A-type zeolite, X-type zeolite, Y-type zeolite, L-type zeolite, molecular sieves, montmorillonite, acid clay, activated clay, diatomaceous earth, and the like. Sulfonic acid cation exchange resin, acrylic acid cation exchange resin and the like.

Examples of the basic catalyst which can be used in the reaction formula (3) include ammonia, methylamine, triethylamine, triethanolamine and pyridine as amine compounds, and lithium amide, sodium methylamide and potassium ethylamide as metal amide compounds. And the like.Examples of metal imide compounds include lithium imide, sodium methyl imide, and potassium ethyl imide.Alkoxy compounds include lithium methoxide, sodium methoxide, and potassium ethoxide. , Ethyl sodium, phenyl potassium, etc., as the metal oxide, MgO, SiO ₂ -MgO, etc., and as the ion exchange resin, a quaternary ammonium type anion exchange resin.

The ratio of the starting material, the hydrosilane compound having a Si--H bond represented by the general formula (2) to the dihydroxy compound is not particularly limited, but is preferably Si--H.
X group 100 m contained in the hydrosilane compound containing a bond
It is from 1 mmol to 500 mmol per mol. The acid catalyst or the basic catalyst, which is a catalyst, can be used alone or in combination of two or more. The amount of the catalyst used is 0.0001 m per 100 mmol of the dihydroxy compound.
mol to 200 mmol.

It is desirable to replace the inside of the container with an inert gas such as high-purity nitrogen or high-purity argon. Examples of the solvent include aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and mesitylene; diethyl ether, n-butyl ether, anisole, diphenyl ether, tetrahydrofuran, dioxane, bis (2-methoxyethyl) ether, 2-bis (2
Ether solvents such as -methoxyethoxy) ethane, halogen-containing solvents such as dichloromethane and chloroform, organic polar solvents such as N-methylpyrrolidone, dimethylformamide and dimethylacetamide, and mixed solvents thereof can be used. The amount of the solvent is 0.1 to 40 ml per 1 mmol of the raw material hydroxysilane compound.
Is preferred. Further, since water contained in the solvent may reduce the activity of the catalyst, it is preferable to use a solvent which has been previously dehydrated and dried.

The reaction temperature is -50 to 300 ° C, more preferably 0 to 150 ° C. The reaction pressure may be any of reduced pressure, normal pressure, and pressurized pressure. However, when the reaction temperature is higher than the boiling point of the solvent, it is desirable to perform the pressurized reaction using a pressure-resistant reaction vessel. Although the reaction time varies depending on the reaction temperature and the like, 0.1 to 200 hours is appropriate.

Isolation of the siloxane bond-containing polymer by removing the solvent may be performed without any treatment of the reaction solution, but may be performed by dispersing in a saturated aliphatic hydrocarbon, filtering, and treating with an aqueous solution. (JP-A-11-236388) or after the catalyst is separated by a method such as treatment with an anion exchange resin in the case of an acid catalyst or treatment with a cation exchange resin in the case of a basic catalyst.

As the saturated aliphatic hydrocarbon which can be used for separating the catalyst, pentane, hexane, heptane, octane and the like can be mentioned. The amount of saturated aliphatic hydrocarbon used is S
0.01 to 200 ml, more preferably 0.1 to 50 m per 1 g of the siloxane-containing polymer containing i-H bond
l.

The removal of the catalyst using an anion exchange resin or a cation exchange resin is performed by treating the reaction solution with an anion exchange resin or a cation exchange resin by a contact filtration method or a fixed bed method. Specifically, the contact filtration method is a method of mixing a reaction solution and an anion exchange resin or a cation exchange resin, stirring the mixture for a certain period of time, and removing the resin by filtration. The fixed bed method is a method in which the catalyst is removed from the reaction solution by passing the reaction solution through a fixed bed such as a column or a packed tower filled with an OH type anion exchange resin or an H type cation exchange resin. is there. The number of times of the processing is usually one, but may be two to 100 times. The reaction solution is usually treated as it is, but may be diluted 1.1 to 100 times with a solvent.

The anion exchange resins that can be used include, as exchange groups, —N (CH ₃ ) ₃ OH groups and —N (C ₂ H ₄ OH)
Strongly acidic OH type anion exchange resins having (CH ₃ ) ₂ OH groups, and weakly acidic OH type anion exchange resins having —NH ₂ — and —NH— groups as exchange groups are exemplified. Examples of the cation exchange resin that can be used include a strongly acidic H-type cation exchange resin having a sulfone group as an exchange group, a weakly acidic H-type cation exchange resin having a carboxyl group, a phenol group, and a phosphone group as an exchange group, and these. Silica resin,
What carried on the support | carriers, such as an alumina, is mentioned. These anion exchange resins or cation exchange resins can be used singly or in combination of two or more. The form of the anion exchange resin or the cation exchange resin may be granular or powder. Water content is 10wt%
Although an anion exchange resin or a cation exchange resin exceeding the above may be used as it is, it is preferable to keep the water content to 10 wt% or less by air drying, heating drying, vacuum drying or the like.

The amount of the anion exchange resin or the cation exchange resin to be used varies depending on the type of the resin, the exchange capacity, the type of the catalyst and the content of the catalyst in the reaction solution, but is 0.0001 to 10 g per 1 ml of the reaction solution. The processing time or residence time depends on the type of anion exchange resin or cation exchange resin,
The amount varies depending on the amount used and the concentration of the catalyst in the reaction solution.
1 to 400 hours. Processing temperature is -50 ~ 300 ℃,
More preferably, it is 0 to 150 ° C.

After the above-described catalyst removal operation, the siloxane bond-containing polymer is separated from the reaction solution by a method such as solvent removal, column separation, or precipitation.

【Example】

[0024]

Example 1 A magnetic stirrer was installed inside a 200 ml glass container, and the inside of the container was replaced with high-purity nitrogen gas. Subsequently, 4.6 g (4.
0 mmol), 8.3 g of triethylamine (82 mm
ol) and 40 ml of THF as a solvent and 3.5 g of 2-butyne-1,4-diol (4 g) while cooling with ice at 0 ° C.
0 mmol) in 40 ml of THF was added dropwise over 30 minutes under a nitrogen blanket. A white precipitate was deposited following the dropwise addition. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 4 hours. The reaction solution was filtered with a polyflon filter to remove a white precipitate. Further, the reaction solution was concentrated and dried in a vacuum at 60 ° C., and 4.7 g of the target product poly (methylsilylene-
1,4-dioxy-2-butynylene) was obtained. The yield was 92%. The weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography) was 3,200. Elemental analysis shows carbon 45.6%
(Theoretical value 46.9%) and hydrogen 6.7% (theoretical value 6.3%), and the measured value agrees well with the theoretical value within the range of the measurement error. ¹ H-NMR (ppm, CDCl ₃ ); 0.2 (-C H ₃ ), 4.4 (-C H _2- ), 4.7 (Si
H ). ¹³ C-NMR (ppm, CDCl ₃ ); -3.2 ( -C H ₃ ), 50.3 (C≡C- C H _2- ), 7
3.1 ( -C ≡ C- ). ²⁹ Si-NMR (ppm, CDCl ₃ ); -33.8 ( SiH ). IR (cm ^-1 ); 768 (m), 865 (s), 902 (s), 1063 (s), 1140
(s), 1261 (s), 1374 (m), 1458 (m), 2170 (s), 2875 (w),
2910 (w). Next, TGA-
Measured by DTA. Td ₅ in argon atmosphere
(5% weight loss temperature) was 451 ° C. 1000 ° C
Was 67% by weight.

[0025]

Example 2 Instead of dichloromethylsilane, dichloro
Using 7.1 g (40 mmol) of phenylsilane,
The reaction was carried out under the same conditions as in Example 1. 6.8g
Poly (phenylsilylene-1,4-)
Dioxy-2-butynylene) was obtained. 89% yield
Met. By GPC (gel permeation chromatography)
The weight average molecular weight in terms of polystyrene is 520
It was 0. Elemental analysis shows carbon 55.2% (theoretical 5
6.8%) and hydrogen 5.5% (theoretical 5.3%).
It is in good agreement with the theoretical value within the range of the fixed error.¹ H-NMR (ppm, CDCl_Three); 4.4 (-CH ₂ -), 4.8 (SiH), 7.3-7.7
(Ph-H).¹³ C-NMR (ppm, CDCl_Three) ； 50.5 (C≡C-CH _Two -), 73.4 (-C≡C
-), 128-136 (Ph).²⁹ Si-NMR (ppm, CDCl_Three);-47.2 (SiH). IR (cm^-1); 708 (m), 712 (m), 861 (s), 910 (s), 1063
(s), 1140 (s), 1261 (s), 1374 (m), 1458 (m), 1488 (m),
1607 (m), 2166 (s), 2872 (w), 2888 (w), 3012 (m). Next, TGA-
Measured by DTA. Td in argon atmosphere_Five
(5% weight loss temperature) was 462 ° C. 1000 ° C
Was 71% by weight.

[0026]

EXAMPLE 3 Instead of 2-butyne-1,4-diol, 3.5 g of 2-butene-1,4-diol (40 mmol) was used.
The reaction was carried out in the same manner as in Example 1 except for using l). 4.5 g of the desired product, poly (methylsilylene-1,4-dioxy-2-butenylene), were obtained.
The yield was 87%. The weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography) was 2,900. Elemental analysis shows carbon 4
It is 4.9% (theoretical value 46.2%) and hydrogen 8.0% (theoretical value 7.7%), and the measured value is in good agreement with the theoretical value within the range of measurement error. ¹ H-NMR (ppm, CDCl ₃ ); 0.2 (-C H ₃ ), 4.4 (-C H _2- ), 4.7 (Si
H ), 5.7 ( CH = CH ). ^{13 C-NMR (ppm, CDCl} 3); - 3.6 (- C H 3), 57.3 (C = CH- C H 2 -),
131.4 (- C H = C H -CH 2 -). ^{29 Si-NMR (ppm, CDCl} 3); - 33.4 (Si H). IR (cm ^-1 ); 771 (m), 869 (s), 889 (s), 1059 (s), 1241
(w), 1306 (m), 1410 (m), 2174 (s), 2873 (w), 2911 (w),
3010 (w). Next, TGA-
Measured by DTA. Td ₅ in argon atmosphere
(5% weight loss temperature) was 382 ° C. 1000 ° C
Was 57% by weight.

[0027]

EXAMPLE 4 Instead of 2-butyne-1,4-diol, 3.5 g of 2-butene-1,4-diol (40 mmol) was used.
The reaction was carried out in the same manner as in Example 2 except for using l). 6.9 g of the desired product, poly (phenylsilylene-1,4-dioxy-2-butenylene), were obtained. The yield was 90%. The weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography) was 5,100. The measured values of the elemental analysis were carbon 61.7% (theoretical value 62.5%) and hydrogen 6.4% (theoretical value 6.3%), and the measured values agreed well with the theoretical values within the range of measurement error. ¹ H-NMR (ppm, CDCl ₃ ); 4.4 (-C H _2- ), 4.7 (Si H ), 5.7 (C H = C
H- ), 7.2-7.7 (Ph-H). ^{13 C-NMR (ppm, CDCl} 3); 57.5 (C = CH- C H 2 -), 128~135 (- C H
_{= C H-CH 2 -,} Ph). ^{29 Si-NMR (ppm, CDCl} 3); - 47.4 (Si H). IR (cm ^-1 ); 699 (m), 720 (m), 759 (m), 863 (s), 911
(s), 1070 (s), 1239 (w), 1301 (m), 1404 (m), 1488 (m),
1607 (m), 2177 (s), 2869 (w), 2899 (w), 3012 (w). Next, TGA-
Measured by DTA. Td ₅ in argon atmosphere
(5% weight loss temperature) was 379 ° C. 1000 ° C
Was 54% by weight.

[0028]

According to the present invention, a siloxane bond-containing polymer having excellent heat resistance can be obtained by reacting a hydro compound having a Si-H bond with a dihydroxy compound using a catalyst for condensation reaction.

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Masayoshi Ito 580-32 Nagaura, Sodegaura-shi, Chiba F-term in Mitsui Chemicals, Inc. (reference) 4J035 BA02 CA021 CA032 CA142 EA01 HA01 HA03 HA06 HB01 LB02 LB03 LB09

Claims (2)

[Claims] 1. A compound represented by the general formula (1): (Wherein, R ¹ is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group, an alkynyl group, an alkoxy group, or an aromatic group, and R ² is —C≡C—, —C ＝ C—, carbonyl Group, an epoxy group, a hydroxyl group, an alkyl group having 1 to 50 carbon atoms, an alkenylene group, an alkynylene group and a divalent aromatic group having at least one of amino groups, and these groups include a substituent. Siloxane bond-containing polymers having a repeating unit represented by the formula: 2. A compound of the general formula (2) (Wherein R ¹ has the same meaning as R ¹ in claim ¹ and X is a halogen atom and an alkoxy group having 1 to 30 carbon atoms).
² (OH) ₂ (wherein R ² has the same meaning as R ² in claim 1.)
The method for producing a siloxane bond-containing polymer represented by the general formula (1) according to claim 1, which is obtained by reacting a dihydroxy compound represented by the following formula: