JPS6223004B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a new type of silicone-modified phenolic resin prepolymer. The silicone-modified phenolic resin prepolymer according to the present invention not only provides a cured product with excellent electrical properties, heat resistance, and moisture resistance, but is also extremely useful as a curing agent for various silicone resins or as a modifying resin. Conventionally, organosilane-modified phenolic resins similar to the silicone-modified phenolic resin prepolymer according to the present invention have been disclosed, for example, in British Patent No. 1044149, US Pat.
No. 50-129699, etc., and the organosilane-modified phenolic resins described therein are all synthesized by dealkoxylation or dehalogenation reaction between a phenol/borac resin and an alkoxysilane or halogenosilane. However, since the silicon atoms and carbon atoms in the modified resins obtained by these methods are bonded via oxygen atoms (〓Si-O-C〓 bond), the modified resins have the disadvantage of poor moisture resistance. has. In addition, such conventional silane or silosaquin-modified phenols use silicone for the sole purpose of increasing heat resistance, and are not intended to perform various reactions using the functional groups of silicone. Since it is also a phenolic hydroxyl group, it is difficult to apply it to a wide range of reactions. On the other hand, JP-A-56-45491 discloses an organosilane compound which is effective as a coupling agent or a sizing agent for glass fibers and is obtained by the reaction of phenol, thiophenol, hydroxypyridine or thiopyridine with a halogenated alkylsilane. However, since this type of compound is a monomer, it is extremely difficult to make a cured product that can be used practically, not only by itself but also by blending it with other resins. The present invention aims to provide a novel silicone-modified phenolic resin prepolymer, which has the formula [Here A is the expression or expression A group represented by, B is the formula or expression A group represented by R is a hydrogen atom or a methyl group, X
is a halogen atom, R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms, R ² is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, Y is a hydroxyl group or a hydrolyzable group other than a halogen atom group, a is an integer from 0 to 3, n
is an integer of 0 to 10, m is an integer of 0 to 70, and when a is 3, at least one of R ² contains an unsaturated group]
The present invention relates to a silicone-modified phenolic resin prepolymer shown in the following. The silicone-modified phenolic resin prepolymer represented by the above formula (i) according to the present invention has phenols and organosilicon groups.

Because it is bonded with [formula], it has very good moisture resistance, and is a monovalent group containing a hydroxyl group, a hydrolyzable group, or an aliphatic unsaturated bond as a reactive group that directly connects to silicon atoms. Since it has a hydrocarbon group, it can be cured with only this prepolymer, and can also be co-crosslinked with various silicone resins. Hereinafter, the silicone-modified phenolic resin prepolymer according to the present invention will be explained in detail. A in the above formula (i) is or expression Residues from which the phenolic hydroxyl group is removed include, for example, phenol derivatives such as catechol, resorcinol, hydroquinone, or phloroglucinol;
2,2-bis(2-hydroxyphenyl)propane, 2,4'-dihydroxydiphenylmethane,
2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)
Propane, 2,2-bis(4-hydroxyphenyl)pentane, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxybenzophenone, 4,
4'-dihydroxydiphenyl sulfone, 4,4'-
Dihydric phenols such as dihydroxydiphenyl sulfide, phenol novolac resins, resol type phenolic resins, isopropenylphenol oligomers, or groups obtained by removing hydroxyl groups from compounds containing phenolic hydroxyl groups such as polyparavinylphenols. (residue) can be given. Some of these residues are illustrated below.

【formula】 【formula】 【formula】

(R′; H, CH ₃ , C ₂ H ₅ , etc.) (u; 0 or 1) In the above general formula (i), R is a hydrogen atom or a methyl group, and the C ₁ to _{C 10} divalent hydrocarbon group represented by R ¹ includes an alkylene group such as a methylene group, an ethylene group or a propylene group, and a phenylene group. arylene group, 1,4-xylylene group, phenethylene group or

Examples of the C ₁ to _{C 10} monovalent hydrocarbon groups represented by R ² and R ³ include methyl, ethyl, propyl, butyl, and pentyl groups. , lower alkyl group such as hexyl group or octyl group, vinyl group, allyl group or 1-
Lower alkenyl groups such as propenyl groups, mononuclear and dinuclear aryl groups such as phenyl, xylyl, tolyl, naphthyl or benzyl groups, cycloalkyl groups such as cyclobutyl, cycloheptyl or cyclohexyl groups, cyanoethyl groups, Cyano group-substituted lower alkyl group such as cyanopropyl group or cyanobutyl group, chlorine atom-substituted alkyl group such as chloromethyl group, chloropropyl group or chlorophenyl group, or aryl group, aryl group-substituted alkyl group such as phenylethyl, (CF) ₃ CFOCH ₂ CH ₂ CH ₂ ―, (CF ₃ ) ₂ CF
(CF ₃ ) ₂ COCH ₂ CH ₂ CH ₂ - or CF ₃ CH ₂ CH ₂ -
Examples include fluorine atom-substituted alkyl groups such as. It goes without saying that R ² and R ³ do not necessarily have to be the same and may be different types. Y represents a hydroxyl group or a hydrolyzable group (however, this Y excludes a halogen atom); Examples include alkenyloxy groups such as an acyloxy group and a propenoxy group. a, l, m and n are as described above. The prepolymer according to the present invention has a formula bonding to a phenolic residue in the molecule, (where R ¹ , R ² , a, and n are the same as above) (l+m≧2), and a group that can be converted into a group that can be condensed into the molecule (hydroxyl group or It is essential to have a hydrolyzable group) and/or an addition-polymerizable group (a monovalent hydrocarbon group containing an aliphatic unsaturated bond). Note that the prepolymer may have a phenolic hydroxyl group in its molecule. Specific examples of the silicone-modified phenolic resin prepolymer represented by the above formula (i) include those shown below. (p, p' are positive integers) The silicone-modified phenolic resin prepolymer according to the present invention can be obtained by reacting a phenolic compound with an organosilane or an organosiloxane, for example, starting from a phenol novolak resin. The reaction formula when used as a raw material is as follows. A hydrolyzable group (when a is 0, 1, 2) or an aliphatic unsaturated bond-containing monovalent hydrocarbon group (a
silicone-modified phenolic resin prepolymer with 3). A silicone-modified phenolic resin prepolymer having a hydroxyl group (when a is 0, 1, or 2) or an aliphatic unsaturated bond-containing monovalent hydrocarbon group (when a is 3) (wherein R ¹ , R ² , R ³ , Y, a, n, and m have the same meanings as above, and X is a halogen atom.) By the reaction used as a starting material in the above reaction, a phenolic residue (A in formula (i) It is desirable to have a phenolic hydroxyl group in one molecule as a compound that can be converted into a phenolic hydroxyl group, such as phenol derivatives such as catechol, resorcinol, hydroquinone or phloroglucinol, phenyl)propane, 2,4'-dihydroxydiphenylmethane, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4 -hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)pentane, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylsulfone, Phenol resins synthesized from divalent phenols such as 4,4'-dihydroxydiphenyl sulfide, phenol derivatives such as phenol novolak resins, resol type phenolic resins, and formaldehyde, and furthermore, phenolic resins with the chemical structural formula below. Examples include isopropenylphenol oligomers and polyparavinylphenols shown below. (m′; integer from 0 to 18) (m''; an integer of 20 to 70) Examples of phenols used to obtain the above-mentioned phenolic resins include alkyl phenols such as phenol, cresol, xylenol, propylphenol, amylphenol, butylphenol, octylphenol, and phenylphenol. or aryl group-substituted phenols, halogen-substituted phenols, and polyhydric alcohols such as bisphenol A. In addition, the substitution position of the propyl group in the above-mentioned substituted phenols such as propylphenol is o- with respect to the hydroxyl group. It may be in either the , m- or p-position.Formaldehydes that are raw materials for obtaining phenolic resins may include formaldehyde, paraformaldehyde, formalin, or other formaldehyde that can be supplied. There is no restriction on the type, and various conventionally known ones can be used.On the other hand, as the organosilane or organosiloxane used as a starting material together with the above-mentioned phenol compound, for example, (In the formula, R ¹ , R ² , R ³ , X, Y, a and n have the same meanings as above.) Specifically, the following compounds can be mentioned. be able to. Note that when such an organosilane or organosiloxane is reacted with a phenol compound, it reacts according to the reaction formula (i) described above, and then, by hydrolyzing this reaction product, it is directly bonded to the silicon atom. The hydrolyzable groups are easily converted to hydroxyl groups. The silicone-modified phenolic resin prepolymer in the present invention is obtained by reacting a phenol compound with an organosilane or organosiloxane, and the ratio of the phenol compound and organosilane or organosiloxane to be used is determined depending on the desired reaction product. Therefore, it can be selected arbitrarily. For example, when all the hydroxyl groups of the above-mentioned phenolic compound are completely modified with organosilane or organosiloxane, it is sufficient to use 1 to 1.5 moles of organosilane or organosiloxane per equivalent of phenolic hydroxyl group; In the case of partially modifying with organosilane or organosiloxane, it is possible to partially modify by reacting 1 mole or less of organosilane or organosiloxane per equivalent of phenolic hydroxyl group. This silicone-modified phenolic resin prepolymer can be produced by reacting a phenol compound in advance with a predetermined amount of an alkali metal compound to form an alkali metal phenoxide, and adding organosilane or organosiloxane to the alkali metal phenoxide. Lithium, sodium or potassium is preferred as the alkali metal. These alkali metals can be used in the form of compounds such as alkali metal hydrides and alkoxides of hydroxides. Alkali metal phenoxide can be easily synthesized by reacting a predetermined amount of an alkali metal compound with a phenol compound in an appropriate solvent. However, when using an alkali metal hydroxide, the water generated by the reaction is completely removed from the reaction system by a known method in order to hydrolyze the organosilane or organosiloxane containing a hydrolyzable group. Needs to be removed. This also applies to water contained in raw materials. The ratio of the alkali metal compound to the phenolic hydroxyl group can be selected arbitrarily, but for example, when the phenolic hydroxyl group is completely modified with silane,
It is sufficient to use 1 to 1.3 moles of the alkali metal compound per equivalent of phenolic hydroxyl group. The above-mentioned reactions are usually carried out in various solvents, but particularly favorable results are obtained when carried out in polar solvents. Solvents that can be used here include N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphoramide, N-methyl-2-pyrrolidone, dimethylsulfone, N-acetyl-2-pyrrolidone. Examples include polar solvents such as Note that nonpolar solvents such as benzene, toluene, xylene, methyl ethyl ketone, and methyl isobutyl ketone can also be used in combination with the above polar solvents. In the above reaction, after dissolving the phenolic compound in these solvents, an alkali metal compound is added to convert the phenolic hydroxyl group into a metal salt, and then organosilane or organosiloxane is added dropwise to react. When an alkali metal hydroxide is used as a compound, it is usually preferable to use it as an aqueous solution of the alkali metal hydroxide. After metal salt formation, water contained in the reaction system is removed from the reaction system using an azeotrope forming agent such as toluene, benzene, xylene, etc., and the organosilane or organosiloxane is produced in a substantially completely anhydrous state. It is necessary to drip. The reaction between the metal salt of the phenolic resin and the organosilane or organosiloxane is preferably carried out at a temperature of 50 to 150°C, preferably 80 to 130°C. The reaction time depends on the reaction temperature, but 80
When the reaction is carried out at ~130°C, the reaction time is usually in the range of 6 to 10 hours. The end point of the reaction is determined by measuring the pH of the reaction system using litmus paper, etc.
However, if the reaction is not completed, the reaction system is alkaline, so it is easily hydrolyzed by moisture in the air and further condensed, resulting in gelation. Because of this disadvantage, it is necessary to complete the reaction completely. The silicone-modified phenolic resin prepolymer thus obtained can be obtained by separately removing the alkali halide produced by the reaction and then distilling off the reaction solvent. In the case of the silicone-modified phenolic resin prepolymer containing a hydrolyzable group obtained in this way, it can be obtained as a hydroxyl group-containing silicone-modified phenolic resin prepolymer by reacting with water. Hydrolysis methods include a method in which a phenol compound is reacted with an organosilane or organosiloxane containing a hydrolyzable group, and then water is continuously added without taking out the reaction product; Examples of methods include taking out the material, dissolving it in a solvent, and adding water. It goes without saying that this hydrolysis reaction may be carried out using a solvent. Solvents that can be used here include methanol, ethanol, propanol,
Alcohol solvents such as isopropyl alcohol and butanol, acetone, methyl ethyl ketone,
Examples include ketone solvents such as methyl isobutyl ketone, and solvents such as benzene, toluene, xylene, hexane, and hepetane. Among these, alcohol-based solvents and ketone-based solvents are particularly suitable from the viewpoint of contact with water. The amount of water used for hydrolysis is not particularly limited as long as it is at least the required minimum amount. The hydrolysis reaction can be carried out by simply adding water, but generally various catalysts can be used to accelerate the reaction, such as acetic acid, hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, etc. can. Further, the reaction temperature must be in the range of -20°C to 40°C, preferably -5°C to 25°C, in order to prevent condensation of hydroxyl groups. Completion of the above reaction can be easily confirmed by analyzing the disappearance of hydrolyzable groups by infrared absorption spectroscopy or the like. Further, after the reaction is completed, the reaction system is made completely neutral by washing with water, and then the solvent is distilled off to obtain a phenolic resin prepolymer modified with an organosilane or organosiloxane containing a hydroxyl group. The silicone-modified phenolic resin prepolymer having various reactive functional groups thus obtained can be cured by employing various methods. For example, in the case of silicone-modified phenolic resin prepolymers containing hydrolyzable groups and silicone-modified phenolic resin prepolymers containing hydroxyl groups, lead, tin, zirconium, zinc,
By using metal salts, metal chelates, or amine derivatives of metals such as iron, cadmium, barium, aluminum, titanium, and magnesium with organic acids as catalysts, these silicone-modified phenolic resin prepolymers can be hydrolyzed alone. It is possible to cure the resin at room temperature or under heat by blending it with a silicone resin containing a group or a silicone resin containing a hydroxyl group. Furthermore, in the case of a silicone-modified phenolic resin prepolymer having a monovalent hydrocarbon group containing an aliphatic unsaturated bond, only the silicone-modified phenolic resin prepolymer can be cured by using an organic peroxide. It can also be cured by a hydrosilylation reaction with an organopolysiloxane containing an SiH group, and it can also be cured by using an organopolysiloxane containing a thiol group. The silicone-modified phenolic resin prepolymer of the present invention can be used by blending various inorganic fillers, such as fumed silica, silica aerogel, precipitated silica, separated silica, crystalline silica, etc. silica, aluminum oxide, aluminum silicate, zirconium silicate, magnesium oxide, diatomaceous earth, calcium carbonate, clay, titanium dioxide, calcined clay, glass fiber, carbon fiber, talc, glass powder, wood powder, cement, etc. I can do it. Furthermore, depending on the application, anti-aging agents, various flame retardant imparting agents, flame retardant imparting aids, coloring agents such as pigments such as dyes or carbon black, and flexibility imparting agents may be added as necessary. It can also be blended. The silicone-modified phenolic resin prepolymer according to the present invention has a wide range of properties, from a low-viscosity material that can easily flow at room temperature to a solid material, by arbitrarily selecting various conditions during its synthesis. The prepolymer of the present invention has a wide range of uses, including various casting resins, paints, varnishes, sealants,
It is useful as a coating agent, electrical insulating material, insulating protective film, general molding material, and encapsulating material for electronic components. Furthermore, the prepolymer can be used as an intermediate material for reactions with other silanes or polysiloxanes having functional groups. Specifically, by combining with carbon functional silanes, amino groups, acrylic groups, etc. , a functional group such as an epoxy group or a mercapto group can be introduced, and a thermoplastic block polymer having a phenolic resin as a hard segment can be obtained by reacting with a linear (both terminals) functional polysiloxane. These secondarily synthesized modified compounds can be widely applied as base components or additives in various compositions. Hereinafter, embodiments of the present invention will be illustrated by Examples, but these are for explaining the present invention in more detail and are not intended to limit the present invention. Example 1 Phenol novolac resin (trade name MP-120, manufactured by Gunei Chemical Co., Ltd.) 79 was placed in a four-necked flask with an internal volume of 2 equipped with a thermometer, reflux condenser, and stirring bar.
g, 400ml of toluene and dimethyl sulfoxide
After charging 400 ml and uniformly dissolving it, an aqueous solution of 29 g of sodium hydroxide dissolved in 30 g of water was gradually added dropwise using a dropping funnel over a period of 10 minutes. After the dropwise addition was completed, the reaction was carried out at reflux temperature for 1 hour, and then water in the reaction system was completely removed by azeotropic dehydration. After keeping the reaction temperature between 100℃ and 110℃, Eq. 128 g of the silane represented by was added dropwise from the dropping funnel over a period of 30 minutes. After dropping, increase the temperature to 115°C to 120°C.
The reaction was carried out for 10 hours while the temperature was maintained at 0.degree. C., and then the precipitate was separated, and the solvent was distilled off under a reduced pressure of 2 mmHg and an oil bath temperature of 150.degree. C., yielding 127 g of a red and transparent product. This product was confirmed to be a polymer having the structure of the following formula and a molecular weight of 1700 by infrared absorption spectroscopy.

[Table] Example 2 75g of isopropoxysilane-modified phenolic resin prepolymer obtained in Example 1, 400ml of toluene,
150 ml of acetone, 400 ml of water, and 32.5 g of concentrated hydrochloric acid were stirred at room temperature for 1 hour, washed with water until neutral, and the solvent was distilled off under reduced pressure (5 mmHg) at an oil bath temperature of 130°C. 58 g of product was obtained.
The softening point of this product was 67°C. It was confirmed from infrared absorption spectrum and nuclear magnetic resonance spectrum that this product had the following structure and a molecular weight of 1280.

【table】

[Table] Example 3 Phenol novolak resin (product name MP-
120 (manufactured by Gunei Kagaku Co., Ltd.) was dissolved in a mixed solvent of 200 ml of toluene and 200 ml of dimethyl sulfoxide, and an aqueous solution of 16 g of sodium hydroxide dissolved in 16 g of water was added dropwise thereto, followed by reaction at reflux temperature for 1 hour. Thereafter, water in the reaction system was completely distilled off by azeotropic dehydration. After that, the reaction temperature was raised to 110℃, and from the dropping funnel, 55 g was added dropwise over 10 minutes, and the reaction was allowed to proceed for 9 hours while maintaining this temperature. After the reaction, the precipitate was separated and washed with water, and then
When the solvent was distilled off under a reduced pressure of mmHg and an oil bath temperature of 150℃, 75g of a semi-solid red and transparent product was obtained.
Obtained. This product has a molecular weight of the following structure based on infrared absorption spectrum and nuclear magnetic resonance spectrum.
It was confirmed that it was a 1500 polymer.

【table】

[Table] Example 4 20 g of the methoxysilane-modified phenolic resin prepolymer synthesized in Example 3, 100 g of acetone, 100 g of toluene, 100 g of water, and 1.5 g of acetic acid were reacted at room temperature for 3 hours, and then washed with water until neutral. The solvent was distilled off under reduced pressure (5 mmHg) at an oil bath temperature of 130°C to obtain 15 g of a red and transparent product. The softening point of this product was 63°C. This substance has a structure of the following formula and a molecular weight of 1400 according to infrared absorption spectra and nuclear magnetic resonance spectra.
It was confirmed that the polymer was

【table】

[Table] Example 5 Phenol novolac resin (trade name MP-
After dissolving 90 g of 120 L (manufactured by Gunei Kagaku Co., Ltd.) in a mixed solvent of 200 ml of dimethylformamide and 200 ml of toluene, an aqueous solution of 34.3 g of sodium hydroxide dissolved in 34.3 g of water was added dropwise, and the mixture was reacted at 110° C. for 1 hour. After the reaction was completed, water in the system was completely removed by azeotropic dehydration. This formula After dropping 170 g of the silane shown by and reacting at 120°C for 10 hours, the precipitate was separated and the
Hg), when the solvent was distilled off at an oil bath temperature of 150℃,
169 g of a highly viscous liquid red and transparent product was obtained. This product was confirmed to be a polymer with a molecular weight of 2500 and the following structure based on infrared absorption spectrum and nuclear magnetic resonance spectrum.

[Table] Example 6 169g of dimethoxysilane-modified phenolic resin prepolymer synthesized in Example 5, 200g of acetone,
200g toluene, 150g methyl ethyl ketone, water
After reacting 200 g and 1 g of acetic acid at room temperature for 8 hours, washing with water until neutral, and distilling off the solvent under reduced pressure (5 mmHg) and an oil bath temperature of 90°C, a red and transparent color remained sticky at room temperature. 125g of solid product
Obtained. This product was confirmed to be a polymer with a molecular weight of 1600 and a structure shown by the following formula from infrared absorption spectra and nuclear magnetic resonance spectra.

【table】

【table】 \
○●−Si〓OH content /
Measured value 15.5 weight〓
Theoretical value 15.2 〓
Example 7 Polyparavinylphenol resin (product name M-
Resin (manufactured by Maruzen Oil Co., Ltd.) (120 g) was dissolved in 300 ml of dimethyl sulfoxide and 300 ml of methyl isobutyl ketone, and an aqueous solution of 40 g of sodium hydroxide and 40 g of water was added dropwise thereto to synthesize the sodium salt of phenol resin. After the reaction is complete, the water present in the system is removed by azeotropic dehydration, and the reaction temperature is maintained at 110°C. 167 g of silane represented by was added dropwise. After the dropwise addition was completed, the reaction was further carried out at 110°C for 10 hours, and the precipitate was separated and the solvent was distilled off under reduced pressure (2 mmHg) and an oil bath temperature of 150°C, resulting in the formation of a red and transparent solid at room temperature. 170g of material was obtained. The softening point of the product was 115°C. This product was confirmed to be a polymer with a molecular weight of 11,000 and a structure shown by the following formula from an infrared absorption spectrum.

[Table] Example 8 100g of isopropoxysilane-modified polyparavinylphenol resin synthesized in Example 7, acetone
500g, toluene 500g, water 500g and acetic acid 10g
After reacting at room temperature for 5 hours, the reaction mixture was washed with water to neutrality, and the solvent was distilled off under reduced pressure (5 mmHg) at an oil bath temperature of 150°C to obtain 70 g of a transparent product. The softening point of this product was 135°C. This substance has a structure of the following formula and a molecular weight of 8900 according to infrared absorption spectrum and nuclear magnetic resonance spectrum.
It was confirmed that the polymer was

[Table] Example 9 100 g of orthocresol novolak resin was dissolved in a mixed solvent of 200 ml of toluene and 200 ml of dimethylformamide, and 33.3 g of sodium hydroxide was dissolved in water.
An aqueous solution dissolved in 33.3 g was added dropwise and reacted for 1 hour at reflux temperature, and then water in the reaction system was completely distilled off by azeotropic dehydration. After that, the reaction temperature was raised to 110℃, and the formula was 140 g of the silane represented by was added dropwise, and the reaction was allowed to proceed for 9 hours while maintaining this temperature. After the reaction was completed, the precipitate was separated and washed with water.
When the solvent was distilled off under reduced pressure of Hg at an oil bath temperature of 150°C, 106 g of a semi-solid red and transparent product was obtained.
Obtained. It was confirmed from infrared absorption spectrum and nuclear magnetic resonance spectrum that this product had the structure shown by the following formula.

【table】

[Table] Example 10 106 g of methoxysilane-modified orthocresol novolak resin synthesized in Example 9, 200 g of acetone
g, toluene 150g, methyl isobutyl ketone 70g
After stirring 200 g of water and 2 g of acetic acid at room temperature for 1 hour, the mixture was washed with water until neutral, and the solvent was removed under reduced pressure (5 g).
mmHg) and an oil bath temperature of 130°C, 75g of a red and transparent reaction product was obtained. This product was found to be a polymer with a molecular weight of 1650 and a structure shown by the following formula according to infrared absorption spectroscopy and nuclear magnetic resonance spectroscopy.

[Table] ○●Nuclear magnetic resonance spectrum

[Table] Example 11 90g of phenol novolac resin was mixed with 300g of toluene.
ml, dissolved in a mixed solvent of 300 ml of dimethyl sulfoxide, and 34.3 g of sodium hydroxide and 34.3 g of water.
After adding dropwise an aqueous solution dissolved in , and reacting for 1 hour at reflux temperature, water in the reaction system was completely distilled off by azeotropic dehydration. After that, the reaction temperature was raised to 120℃, and 3-chloropropyltrimethoxysilane was added through the dropping funnel.
160 g was added dropwise, and the reaction was carried out for 14 hours while maintaining this temperature. After the reaction was completed, the precipitate was separated, washed with water, and the solvent was distilled off under a reduced pressure of 2 mmHg and an oil bath temperature of 160°C, to obtain 174 g of a red and transparent product that was fluid at room temperature. This product was confirmed to be a polymer with a molecular weight of 2000 and a structure shown by the following formula from an infrared absorption spectrum and a nuclear magnetic resonance spectrum.

[Table] Example 12 After dissolving 27g in 100ml of toluene and 100ml of dimethyl sulfoxide, the temperature was maintained at 110℃,
This formula 25 g of the silane shown was added dropwise. After that, while maintaining the reaction temperature at 115-120℃,
Allowed time to react. After the reaction was completed, the precipitate was separated, and the solvent was distilled off under a reduced pressure of 2 mmHg at an oil bath temperature of 150°C, resulting in a red and transparent product with high viscosity at room temperature.
g was obtained. This product was confirmed to have the following structure from its infrared absorption spectrum.

[Table] Example 13 20g of methoxysilane-modified phenol resin obtained in Example 12, 100g of acetone, 100g of toluene, water
After stirring 100 g and 5 g of acetic acid at room temperature for 2 hours to react, the reaction solution was made neutral by washing with water. After that, the solvent was removed under reduced pressure (5 mmHg) and the oil bath temperature was
Distillation at 130° C. gave 14 g of a highly viscous product that was red and transparent and flowed at room temperature. This product was confirmed to have the following structure from infrared absorption spectrum and nuclear magnetic resonance spectrum.

[Table] / disappears

【table】 \
−Si〓OH content
/
Measured value 8.2 weight〓
Theoretical value 8.4 〃
Example 14 53g of phenol novolac resin was mixed with 200g of toluene.
ml, dissolved in a mixed solvent of 200 ml of dimethyl sulfoxide, and to this, 18.4 g of sodium hydroxide and 18.4 g of water.
An aqueous solution dissolved in was added dropwise and the reaction was carried out for 1 hour at reflux temperature, after which the water in the reaction system was completely distilled off by azeotropic dehydration. After that, the reaction temperature was lowered to 80℃, and the formula Drop 85g of the silane shown in from the dropping funnel,
The reaction was continued for 9 hours while maintaining this temperature. After the reaction was completed, the precipitate was separated and the solvent was distilled off under reduced pressure to obtain 57 g of a highly viscous, red and transparent product. This product was confirmed to be a polymer with a molecular weight of 1900 and a structure shown by the following formula from infrared absorption spectra and nuclear magnetic resonance spectra.

【table】

[Table] Example 15 106g of phenol novolac resin was added to 400g of toluene.
ml and dimethyl sulfoxide in a mixed solvent of 400 ml, and an aqueous solution of 41 g of sodium hydroxide dissolved in 41 g of water was added dropwise thereto. After reacting for 1 hour at reflux temperature, the water in the reaction system was removed by azeotropic dehydration. Completely removed. After that, the reaction temperature was raised to 120℃, and the formula Drop 145g of the silane shown in
Allowed time to react. After the reaction was completed, the precipitate was separated, washed with water, and the solvent was distilled off under reduced pressure to obtain 153 g of a highly viscous, red and transparent product. This product was confirmed to be a polymer with a molecular weight of 1500 and a structure shown by the following formula from an infrared absorption spectrum.

[Table] Example 16 20 g of the methoxy group-containing silicone-modified phenolic resin prepolymer obtained in Example 11 and 0.2 g of dibutyltin dilaurate were mixed uniformly, and 4 g of this mixture was placed in an aluminum shear and left at room temperature for 48 hours. Afterwards, it was almost completely cured. The surface hardness of the cured product was 80 on the Shore D hardness tester, and the cured product was transparent in color. Example 17 From 15 g of the methoxy group-containing silicone-modified phenolic resin prepolymer obtained in Example 5, 40 mol% of dimethylsiloxane units, 20 mol% of methylsiloxane units, 20 mol% of diphenylsiloxane units, and 20 mol% of phenylsiloxane units. After uniformly mixing 5 g of organopolysiloxane having a silanol content of 5% by weight and 0.2 g of dibutyltin dilaurate, the mixture was heated at 120° C. for 5 hours to obtain a cured product. This cured product has excellent flexibility, is pale and transparent, and has a surface hardness of Shore D.
It was 50. Example 18 100 g of silanol group-containing silicone-modified phenolic resin prepolymer obtained in Example 4, 250 g of fused silica, 1 g of calcium stearate, lead carbonate
A molding material was obtained by uniformly kneading 1.5 g of benzoic acid and 2.5 g of benzoic acid using two heated rolls. A molded article was obtained by transfer molding this molding material at 175° C., molding pressure of 70 kg/cm ² , and molding time of 3 minutes. This molded article was further post-cured at 180°C for 4 hours. This material had a bending strength of 10 Kg/mm ² at room temperature. Example 19 4 g of the vinyl group-containing silicone-modified phenolic resin prepolymer obtained in Example 15 and 0.5 g of dicumyl peroxide as an organic peroxide catalyst were uniformly mixed and heated at a temperature of 150°C for 4 hours under a nitrogen gas atmosphere. Upon reaction, a cured product with a surface hardness of Shore D of 75 and a transparent color was obtained. Example 20 20 g of the vinyl group-containing silicone-modified phenolic resin prepolymer obtained in Example 15, When 12 g and 0.03 g of alcohol-modified chloroplatinic acid containing 2% platinum were mixed uniformly and heated at 120°C for 2 hours and then further heated at 150°C for 4 hours, it showed a surface hardness of Shore D of 80 and a pale A cured product with a transparent color was obtained.

[Brief explanation of the drawing]

Figures 1 to 15 show Examples 3, 4, 5, 6,
This figure shows the measurement results of infrared absorption spectrum (IR), nuclear magnetic resonance spectrum (NMR), and molecular weight distribution (GPC) of the silicone-modified phenolic resin prepolymers obtained in 11 and 13. [GPC measurement conditions GPC name: Toyo Sotachi HL-801A Measurement column: TSK-GEL; G2000H6 (7.5mmφ×
600mm x 2) + G4000H6 (7.5mmφ x 600mm) +
GMH6 (7.5mmφ×600mm) Detector UV and refractive index solvent THF Flow rate 1.2ml/min Sample concentration 0.5% by weight] Figure 1...IR of silicone-modified phenolic resin prepolymer obtained in Example 3, Figure 2 ...Example 3
NMR of the silicone-modified phenolic resin prepolymer obtained in Example 3, Fig. 3...GPC of the silicone-modified phenolic resin prepolymer obtained in Example 3, Fig. 4
Figure: IR of the silicone-modified phenolic resin prepolymer obtained in Example 4. Figure 5: IR of the silicone-modified phenolic resin prepolymer obtained in Example 4.
NMR, Fig. 6...GPC of the silicone-modified phenolic resin prepolymer obtained in Example 4, Fig. 7...
NMR of the silicone-modified phenolic resin prepolymer obtained in Example 5, Figure 8... NMR of the silicone-modified phenolic resin prepolymer obtained in Example 5
IR, Fig. 9...GPC of the silicone-modified phenolic resin prepolymer obtained in Example 5, Fig. 10...
NMR of the silicone-modified phenolic resin prepolymer obtained in Example 6, Figure 11... NMR of the silicone-modified phenolic resin prepolymer obtained in Example 6
IR, Fig. 12...NMR of the silicone-modified phenolic resin prepolymer obtained in Example 11, Fig. 13...IR of the silicone-modified phenolic resin prepolymer obtained in Example 11, Fig. 14...NMR of the silicone-modified phenolic resin prepolymer obtained in Example 13 silicone modified phenolic resin prepolymer
IR, Figure 15...NMR of the silicone-modified phenolic resin prepolymer obtained in Example 13.

Claims (1)

[Claims] 1 formula [Here A is the expression or expression A group represented by, B is the formula or expression A group represented by R is a hydrogen atom or a methyl group, X
is a halogen atom, R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms, R ² is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, Y is a hydroxyl group or a hydrolyzable group other than a halogen atom group, a is an integer from 0 to 3, n
is an integer of 0 to 10, m is an integer of 0 to 70, and when a is 3, at least one of R ² contains an unsaturated group]
A silicone-modified phenolic resin prepolymer represented by: