JP3471010B2 - Modified polysiloxane compound and method for producing the same - Google Patents

Description

Detailed Description of the Invention 【Technical field】

The present invention relates to a modified polysiloxane compound and a method for producing the modified polysiloxane compound, and more specifically, to a modified polysiloxane compound having a phenol skeleton and obtained by block-copolymerizing a p-alkenylphenol unit and an organosiloxane unit as an essential constituent unit. It relates to a manufacturing method. The modified polysiloxane compound of the present invention has a controlled molecular weight and structure, and has a highly reactive phenolic hydroxyl group in the molecule. Therefore, it is used as a modifier for photosensitive resins, various thermosetting resins, and thermoplastic resins. It is expected to be used in a wide range of technical fields.

[Background technology]

BACKGROUND OF THE INVENTION Organopolysiloxane compounds are widely used in various fields because they have excellent interfacial properties such as thermal stability, water repellency, defoaming properties, and releasability. In particular, in recent years, the use as a film-forming agent has been expanded by taking advantage of its unique interface characteristics, while a modifier for imparting the temperature characteristics and interface characteristics of the organopolysiloxane compound to various resins. The application as is being actively developed. That is, for improving the performance of synthetic resins such as paints and molded articles, for example, dimethylpolysiloxane, methylphenylpolysiloxane, fatty acid-modified polysiloxane,
Polyether-modified polysiloxane or the like is used.
However, their compatibility with resins is insufficient, and their heat resistance is insufficient, so that their use range is limited. In order to improve these drawbacks, various reactive polysiloxane compounds, for example, a low molecular weight dimethylsiloxane compound having a functional group such as an epoxy group, an amino group, a hydroxyl group and a (meth) acryl group at the molecular end is commercially available. ing. Also, reaction products of them with other resins, for example,
Reaction product of polysiloxane containing terminal epoxy group and phenol resin (JP-A-61-73725, JP-A-62-174222)
(Japanese Patent Laid-Open Publication No. 62-242242), a reaction product of a polysiloxane containing a terminal hydrogen group and an epoxy resin containing an alkenyl group (JP-A-62-62
-212417 gazette) is proposed.

DISCLOSURE OF THE INVENTION

In recent years, as a resist material having a submicron resolution capability necessary for the production of VLSI, as a modifier of mechanical properties, moisture resistance, surface properties, etc. of various thermosetting resins and thermoplastic resins, As a separation membrane or biocompatible polymer material,
A polysiloxane compound having a controlled structure and having an arbitrary number of functional groups in a molecule is craving. In the above-mentioned method, the method of using a low molecular weight dimethylsiloxane compound having a functional group in the molecule, which is commercially available, has a drawback that the moldability and the mechanical strength are deteriorated because the compatibility with other resins is not sufficient. Have. Also,
The method using a reaction product of a polysiloxane having a functional group at the terminal and another resin tends to cause an unfavorable phenomenon such as abnormal thickening or gelation during the modification reaction, and unreacted components remain, resulting in As a result, there is a problem that the compatibility is lowered. An object of the present invention is to provide a modified polysiloxane compound having a phenol skeleton having a controlled molecular weight and structure and a narrow molecular weight distribution. As a result of intensive studies to achieve the above object, the present inventors have conducted an anionic polymerization method on a compound obtained by protecting the phenolic hydroxyl group of p-alkenylphenol with a saturated aliphatic protective group, or a compound copolymerizable therewith. Polymerized by
Then, after adding a cyclic siloxane compound and copolymerizing it, it is possible to easily produce a modified polysiloxane compound having a narrow molecular weight distribution and introducing a phenol skeleton whose structure is controlled by a method of eliminating a saturated aliphatic protective group. Heading, completed the present invention. The present invention provides a compound represented by the following general formula [I] X (Y) n ... [I] (where X is a p-alkenylphenol unit represented by the following general formula [II] as an essential structural unit. The unit block, Y is a polymer block having an organosiloxane represented by the following general formula [III] as a repeating unit, and n is 1 or 2.), and the weight ratio of X and Y is 1 / 99 ≦ X / Y ≦ 90/10, modified polysiloxane compound having a number average molecular weight of 1,000 to 100,000, (In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydrogen atom.) (In the formula, R ³ and R ⁴ each represent a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group. In the formula, R ³ and R ⁴ are the same as each other. Or may be different.) Or, X is a random or block copolymer comprising a p-alkenylphenol unit and a repeating unit of one or more conjugated dienes and / or one or more vinyl compounds. It is a modified polysiloxane compound represented by the general formula [I] and a method for producing the same. That is, the modified polysiloxane compound of the present invention is obtained by homopolymerizing a compound in which the hydroxyl group of the phenol residue represented by the following general formula [IV] is protected by a saturated aliphatic protecting group in the presence of an anionic polymerization initiator, Alternatively, it is produced by copolymerizing it with a copolymerizable compound, then adding a cyclic siloxane compound and copolymerizing, and then removing the saturated aliphatic protective group. (In the formula, R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents a linear or branched alkyl group having 1 to ⁶ carbon atoms.) Hereinafter, the present invention will be described in more detail. X in the above general formula [I] of the present invention is a polymer block having a p-alkenylphenol unit represented by the above general formula [II] as an essential constituent unit, and more specifically,
From a polymer block having one or more p-alkenylphenol repeating units, or from a repeating unit of a p-alkenylphenol unit and one or more conjugated dienes and / or one or more vinyl compounds And a block composed of a random copolymer or a block copolymer, and also includes a block represented by the following general formula [V]. (In the formula, R ¹ and R ² have the same meanings as described above, and a and b are arbitrary natural numbers depending on the degree of polymerization.) In the above general formula [I] of the present invention, Y is It is a polymer block having an organosiloxane represented by the general formula [III] as a repeating unit, and at least one of the blocks constituting the molecular chain of the compound represented by the general formula [I] is Y. The compound represented by I] is represented by X-Y or Y-X-Y. Examples of the compound represented by the general formula [IV] used in the present invention include pn-butoxystyrene and p-sec.
-Butoxystyrene, p-tert-butoxystyrene, p
-Tert-butoxy-α-methylstyrene and the like are exemplified,
Particularly, p-tert-butoxystyrene and p-tert-butoxy-α-methylstyrene are preferable. As the conjugated diene or vinyl compound copolymerizable with the general formula (IV) used in the present invention, 1,3-butadiene,
Isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-
Conjugated dienes such as pentadiene and 1,3-hexadiene;
Styrene, p-methylstyrene, α-methylstyrene,
Vinyl aromatic compounds such as p-tert-butylstyrene, vinylnaphthalene, divinylbenzene, and 1,1-diphenylethylene; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, etc. ) Acrylic acid esters; vinyl pyridines such as 2-vinyl pyridine and 4-vinyl pyridine; acrylonitrile and the like, and they are used as one kind or as a mixture of two or more kinds. The compound represented by the general formula [IV] of the present invention, or the compound represented by the general formula [IV] and the copolymerizable compound are under vacuum or an inert gas atmosphere such as nitrogen or argon under an organic solvent. In, the alkali metal and / or organic alkali metal compound as a polymerization initiator, -100 ℃ ~ 150 ℃
By conducting anionic polymerization at the temperature of 1, the polymer having a controlled molecular weight and a narrow molecular weight distribution can be obtained. The alkali metal of the anionic polymerization initiator is lithium, sodium, potassium or the like, and as the organic alkali metal compound, an alkylated product of the alkali metal,
Allyl compounds, aryl compounds and the like are used. Specific examples of the organic alkali metal compound include ethyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, ethyl sodium, butadienyl dilithium,
Butadienyl disodium, lithium biphenyl, lithium naphthalene, lithium fluorene, sodium biphenyl, sodium naphthalene, sodium triphenyl, α-methylstyrene sodium dianion and the like can be mentioned, and these are used alone or as a mixture of two or more kinds. Organic solvents include aliphatic hydrocarbons such as n-hexane and n-heptane; alicyclic hydrocarbons such as cyclohexane and cyclopentane; aromatic hydrocarbons such as benzene and toluene; diethyl ether, dioxane, tetrahydrofuran and the like. The organic solvents usually used in anionic polymerization, such as ethers, are used as one kind or as a mixed solvent of two or more kinds. The morphology of the copolymer obtained by the anionic polymerization is a random copolymer obtained by adding a mixture of the compound represented by the general formula [IV] and the monomer to a reaction system and polymerizing the mixture. Part is prepolymerized, then a mixture of both is added to obtain a partial block copolymer by continuing the polymerization, and also the general formula [IV]
A complete block copolymer is synthesized by sequentially adding the compound represented by and the above monomer to the reaction system to carry out polymerization. After homopolymerization of the compound represented by the general formula [IV], or after copolymerization reaction with the monomers, a cyclic siloxane compound is added to the reaction system, and anionic polymerization reaction is continued under the same conditions as those exemplified above. By doing so, with a chain of the compound represented by the general formula [IV], or a chain composed of the compound represented by the general formula [IV] and the monomers, and a block copolymer composed of a polysiloxane chain ( Hereinafter, referred to as a precursor) is produced. The cyclic siloxane compound used here is a compound represented by the following general formula [VI]. (Here, each of R ⁷ and R ⁸ is a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and c is a positive integer of 3 to 7. or,
R ⁷ and R ⁸ may be the same or different from each other. ) Specific examples of the compound represented by the general formula [VI] include, for example, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, hexaethylcyclotrisiloxane, octa Examples thereof include ethylcyclotetrasiloxane and hexaphenylcyclotrisiloxane, which can be used alone or as a mixture of two or more kinds. In this sequential anionic polymerization reaction, the polymerization conditions such as reaction temperature and reaction solvent can be appropriately changed within the set range. In addition, the modified polysiloxane compound of the present invention is a method other than the above-mentioned method, for example, after homopolymerization of the compound represented by the above [IV], or after a copolymerization reaction with the above-mentioned monomers, the above-mentioned reaction system is added to the reaction system. A chain of the compound represented by the general formula [IV] is added by adding an organosiloxane compound having a functional group capable of reacting with the growth end of the polymer, and performing a coupling reaction under the same conditions as those exemplified above.
Alternatively, a precursor composed of a chain composed of the compound represented by the general formula [IV] and the monomers and a polysiloxane chain is produced. The organosiloxane compound used here is not particularly limited in structure as long as it has a functional group capable of coupling reaction with the growth end of the polymer, and specific examples include the following general formula [VII] and [VII] VIII] and the like are used. (In the formula, R ⁹ and R ¹⁰ are each a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and X ₁ and X ₂ are halogen atoms and epoxy. A group, a carbonyl group, a chlorocarbonyl group, or a hydrocarbon group having 1 to 20 carbon atoms containing a halogen atom, an epoxy group, a carbonyl group, a chlorocarbonyl group or the like, provided that d is an integer of 1 or more. ) (In the formula, R ⁹ , R ¹⁰ , X ¹ and d have the same meanings as described above, and R ¹¹
Represents a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group. ) Specific examples of the compounds represented by the general formulas [VII] and [VIII] include, for example, commercially available α, ω-bis (chloromethyl) polydimethylsiloxane and 1- (3-chloropropyl) -1,1. , 3,3,3-pentamethyldisiloxane, α,
Examples include ω-bis (3-glycidoxypropyl) polydimethylsiloxane and α, ω-dichloropolydimethylsiloxane. In this sequential polymerization reaction and coupling reaction, the conditions such as the reaction temperature and the reaction solvent can be appropriately changed within the set range. The reaction for removing the saturated aliphatic protective group from the precursor thus obtained to form the p-alkenylphenol skeleton is carried out in the presence of a solvent exemplified in the above-mentioned polymerization reaction or a chlorine-based solvent such as carbon tetrachloride. Under, add hydrogen chloride gas to 150
It can be carried out at a temperature of not higher than 0 ° C, preferably room temperature to 100 ° C. According to the method described above, the modified polysiloxane compound of the present invention in which the molecular weight and structure are controlled and a phenol skeleton having a narrow molecular weight distribution is introduced can be produced.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention will be described more specifically with reference to Examples and Comparative Examples. However, the scope of the present invention is not limited by the following examples. In the following examples, "%" is based on weight unless otherwise specified. Further, m, n, l, k, p in the following general formulas [IX] to [XV] are
The corresponding natural numbers are shown. Example 1 Tetrahydrofuran (hereinafter referred to as THF) solution 6 containing 0.01 mol of sec-butyllithium under a nitrogen atmosphere 6
To 50 g, 130 g of a THF solution containing 0.25 mol of p-tert-butoxystyrene (trade name, Hokuko PTBST, manufactured by Hokuko Kagaku Co., Ltd., hereinafter referred to as PTBST) while stirring at -70 ° C was added over 1 hour, After continuing the reaction for another 3 hours, 200 g of a THF solution containing 0.45 mol of hexamethylcyclotrisiloxane (hereinafter referred to as D3) was added to the reaction solution over 1 hour, and the reaction temperature was kept at 30 ° C for 8 hours. The reaction was continued.
Next, water was added to the reaction solution to stop the reaction, and then liquid separation was performed, and the solvent was distilled off from the organic layer under reduced pressure to obtain a precursor A. The obtained precursor A had a number average molecular weight (Mn) of 15100 measured by the VPO method and a Si content of 25.3% measured by elemental analysis, which were all in good agreement with the set values. It shows a peak with a weight average molecular weight (M
w) / number average quantity (Mn) = 1.15. From this result, it was confirmed that the copolymerization was performed as expected and a poly-PTBST-polydimethylsiloxane copolymer was produced. 10 g of the obtained precursor A was dissolved in methyl ethyl ketone.
A 10% solution was prepared, and hydrogen chloride gas was blown into the solution at room temperature for 30 minutes, water was added to the solution, the solution was separated, and the solvent was distilled off from the organic layer under reduced pressure to obtain a copolymer P-1. ¹ H-NMR of the precursor A and the copolymer P-1 used in this reaction were measured and compared.
The peak of 1.31 ppm derived from t-butyl group disappeared in the latter, and the Mn by the VPO method of the latter was 13000, which was in good agreement with the set value, and the GPC elution curve was a monodisperse polymer with Mw / Mn = 1.18. Met. From the above, it was confirmed that the debutylation reaction from the precursor A proceeded as expected without causing any side reaction, and the target poly-p-vinylphenol-polydimethylsiloxane copolymer was obtained. did. The estimated structural formula of the copolymer P-1 obtained in Example 1 is shown in [IX] below. Further, various spectrum data are shown below. ¹ H-NMR [δ (ppm), internal standard: THF, solvent: THF-d ⁸ ]: 0
~ 0.3 (Si-CH ₃ ), 1.3 to 1.7 (CH ₂ ), 1.8 to 2.1 (CH), 6.
3 to 6.8 (C ₆ H ₄ ), 7.7 to 7.9 (OH) ¹³ C-NMR [δ (ppm), internal standard: THF, solvent: THF-d ⁸ ]:
_{1.4 (Si-CH 3),} 35~50 (CH 2, CH), 116~156 (C 6 H 4) 29 Si-NMR [δ (ppm), internal standard: TMS, solvent: THF-d ^8, mitigation reagents: Fe _{(acac) 3]:} 4.8 (CH-Si (CH 3) 2 -O),
-22.5~-21.6 (O-Si ( CH 3) 2 -O), - 14.9 (O
_{-Si (CH 3) 2 -OH)} 4) IR (cm -1): 3150~3400 (OH), 3020~3100 (C
₆ H ₄ ), 1260 (Si—CH ₃ ), 1020 to 1120 (Si—O) (Example 2) 300 g of a THF solution in which a sodium-kerosene dispersion containing 0.02 mol of metallic sodium was dissolved under a nitrogen atmosphere.
While stirring at −40 ° C., 30 g of a THF solution containing 0.05 mol of p-tert-butyl-α-methylstyrene (hereinafter referred to as PTBMST) was added over 1 hour, and the reaction was further continued for 2 hours. 90 g of THF solution containing 0.15 mol of D3 in the reaction solution 1
The mixture was added over a period of time, and the reaction temperature was raised to 30 ° C. to continue the reaction for 8 hours. Then, trimethylsilyl chloride was added to the reaction solution to stop the reaction, water was further added to separate the layers, and the solvent was distilled off from the organic layer under reduced pressure to obtain a precursor B. The obtained precursor B had Mn = 4300 and Si content = 30.0%, which were in good agreement with the set values, and the GPC elution curve showed a unimodal peak and Mw / Mn = 1.25. . From this result, it was confirmed that the copolymerization was performed as expected and a polydimethylsiloxane-poly-PTBMST-polydimethylsiloxane copolymer was obtained. 10 g of the obtained precursor B was treated in the same manner as in Example 1 to obtain a copolymer P-2. The precursor B and the copolymer P-2 used in this reaction were measured and compared by ¹ H-NMR.
The 1.31 ppm peak derived from the ert-butyl group disappeared in the latter, and the latter had a good match with the set value at Mn = 4000.The GPC elution curve shows a monodisperse distribution of Mw / Mn = 1.25. It was a polymer. From the above, the debutylation reaction from the precursor B proceeds as expected without causing any side reaction, and the target polydimethylsiloxane-poly-p-isopropenylphenol-polydimethylsiloxane copolymer is obtained. I was confirmed. Copolymer P-2 obtained in Example 2
The estimated structural formula of is shown in [X] below. In addition, ¹ H-NMR spectrum data is shown below. ¹ H-NMR [δ (ppm), internal standard: THF, solvent: THF-d ⁸ ]: 0
_{~0.3 (Si-CH 3),} 0.0~0.8 (C-CH 3), 1.0~1.9 (C
H ₂ ), 6.2 to 7.1 (C ₆ H ₄ ), 7.8 to 8.1 (OH) (Example 3) In a nitrogen atmosphere, 1000 g of a THF solution containing 0.01 mol of sec-butyllithium was stirred at -70 ° C. PTBST
After adding 130 g of a THF solution containing 0.25 mol over 1 hour and continuing the reaction for 3 hours, a THF solution containing 0.28 mol of styrene was added.
The F solution was added over 1 hour, and the reaction was continued for another 3 hours. A THF solution containing 0.67 mol of D3 was added to the reaction solution over 1 hour, and the reaction temperature was further raised to 30 ° C. to continue the reaction for 8 hours. Next, trimethylsilyl chloride was added to the reaction solution to stop the reaction, and then liquid separation was performed, and the solvent was distilled off from the organic layer under reduced pressure to obtain a precursor C. The obtained precursor C has Mn = 23100, Si content = 24.5%
Well, the GPC elution curve showed a unimodal peak, and Mw / Mn was 1.2. From this result, it was confirmed that the copolymerization was carried out as expected and a poly-PTBST-polystyrene-polydimethylsiloxane copolymer was produced. The thus-obtained precursor C10g was treated in the same manner as in Example 1 to obtain a copolymer P-3. When the precursor C and the copolymer P-3 used in this reaction were measured and compared with each other by ¹ H-NMR, the former was 1.31 ppm derived from the p-tert-butyl group.
Peak disappears in the latter, and Mn = 2080
The value of 0 is in good agreement with the set value, and the GPC elution curve shows Mw / Mn =
It was 1.30 monodisperse polymer. From the above, the debutylation reaction from the precursor C proceeded as expected without causing any side reaction, and the target poly-p-vinylphenol-polystyrene-polydimethylsiloxane copolymer was obtained. It was confirmed. The estimated structural formula of the copolymer P-3 obtained in Example 3 is shown in [XI] below. In addition, ¹ H-NMR spectrum data is shown below. ¹ H-NMR [δ (ppm), internal standard: THF, solvent: THF-d ⁸ ]: 0
_{~0.3 (Si-CH 3),} 1.3~2.0 (CH 2), 1.8~2.5 (CH), 6.
3 to 7.5 (C ₆ H ₄ , C ₆ H ₅ ) (Example 4) In a nitrogen atmosphere, 600 g of a THF solution in which a sodium-kerosene dispersion containing 0.02 mol of sodium was dissolved,
0.53 mol PTBMST and 1. Butadiene with stirring at -60 ° C.
480 g of THF solution containing 10 mol was added over 2 hours,
After continuing the reaction for another 2 hours, 90 g of a THF solution containing 0.20 mol of D3 was added to the reaction solution over 1 hour, and the reaction temperature was further raised to 30 ° C. and the reaction was continued for 8 hours. Then, the reaction solution was poured into a large amount of methanol, and the precipitated polymer was dried under reduced pressure to obtain a precursor D. The obtained precursor D was in good agreement with the set values at Mn = 21000 and Si content = 8.1%, the GPC elution curve showed a unimodal peak, and Mw / Mn = 1.28. From this result, the copolymerization was performed as expected, and polydimethylsiloxane- (polyPT
It was confirmed that a BMST / polybutadiene) -polydimethylsiloxane copolymer was produced. The thus obtained precursor D10 was treated in the same manner as in Example 1 to obtain a copolymer P-4. The precursor D and the copolymer P-4 used in this reaction were measured and compared by ¹ H-NMR.
The peak around 1.31 ppm derived from the ert-butyl group disappeared in the latter, and the latter had a good match with the set value at Mn = 17500, and the GPC elution curve was a monodisperse polymer with Mw / Mn = 1.28. It was From the above, the debutylation reaction from the precursor D proceeds as expected without causing any side reaction, and the target polydimethylsiloxane- (poly-p-isopropenylphenol / polybutadiene) -polydimethylsiloxane It was confirmed that a polymer was obtained. The estimated structural formula of the copolymer P-4 obtained in Example 4 is shown in [XII] below. (In the formula, the p-isopropenylphenol block and the butadiene block are randomly copolymerized.) In addition, ¹ H-NMR spectrum data is shown below. ¹ H-NMR [δ (ppm), internal standard: THF, solvent: THF-d ⁸ ]: 0
_{~0.3 (Si-CH 3),} 0.0~0.8 (C-CH 3), 1.0~1.9 (C
H ₂ ), 1.8 to 2.2 (CH), 4.8 to 5.0 (CH = CH ₂ ), 5.2 to 5.6
_{(CH = CH 2), 7.8~8.1} (C 6 H 4) ( Example 6) Under a nitrogen atmosphere, a THF solution 550g containing α- methylstyrene 0.15 mol, stirring n- butyllithium 0.01 at 25 ° C. 5 g of a hexane solution containing moles was added over 30 minutes, and the reaction was continued for another hour. The reaction solution is -70
After cooling to ℃ and continuing the reaction for another 3 hours, PTBST
1 g of 100 g of THF solution containing 0.15 mol and 0.10 mol of styrene
It was added over time and the reaction was continued for another 3 hours. Next, 300 g of a THF solution containing 0.45 mol of D3 was added to the reaction solution over 1 hour, the reaction temperature was set to 30 ° C., and the reaction was continued for 8 hours. After the reaction was stopped by adding water to the reaction solution, the solution was separated and the solvent was distilled off from the organic layer under reduced pressure to obtain a precursor F. The obtained precursor F was in good agreement with the set values at Mn = 15700 and Si content = 24.2%, the GPC elution curve showed a unimodal peak, and Mw / Mn = 1.28. From this result, it was confirmed that the copolymerization was carried out as expected and a poly-α-methylstyrene- (polystyrene / polyPTBST) -polydimethylsiloxane copolymer was produced. The thus obtained precursor F10 was treated in the same manner as in Example 1 to obtain a copolymer P-6. The precursor F and the copolymer P-6 used in this reaction were measured and compared by ¹ H-NMR.
The peak around 1.31 ppm derived from et-butyl group disappeared in the latter, and the Mn of the latter was 15000, which was in good agreement with the set value, and the GPC elution curve was a monodisperse polymer with Mw / Mn = 1.28. . From the above, the debutylation reaction from the precursor F proceeds as expected without causing any side reaction, and the desired poly-α-methylstyrene- (polystyrene / poly-p
-Vinylphenol) It was confirmed that a polydimethylsiloxane polymer was obtained. The estimated structural formula of the copolymer P-6 obtained in Example 6 is shown in [XIV] below. (In the formula, the styrene block and the p-vinylphenol block are randomly copolymerized.) In addition, ¹ H-NMR spectrum data is shown below. ¹ H-NMR [δ (ppm), internal standard: THF, solvent: THF-d ⁸ ]: 0
_{~0.3 (Si-CH 3),} 0.0~0.8 (C-CH 3), 1.3~2.0 (C
H _2), 1.8 to 2.5 (CH), in _{6.3~7.5 (C 6 H 4, C} 6 H 5) ( Example 7) Under a nitrogen atmosphere, a THF solution 600g containing n- butyllithium 0.01 mol, -70 PTBST 0.15 with stirring at ℃
100 g of THF solution containing 1 mol and 0.20 mol of butadiene was added over 1 hour and the reaction was continued for another 3 hours. Next, 300 g of a THF solution containing 0.45 mol of D3 was added to the reaction solution over 1 hour, the reaction temperature was set to 30 ° C., and the reaction was continued for 8 hours. After water was added to the reaction solution to stop the reaction, the solution was separated and the solvent was distilled off from the organic layer under reduced pressure to obtain a precursor G. The obtained precursor G had Mn = 15200 and Si content = 24.1%, which were in good agreement with the set values, and the GPC elution curve showed a unimodal peak, and Mw / Mn = 1.17. From this result, the copolymerization was carried out as expected, and (polybutadiene / polyPTBS
It was confirmed that a T) -polydimethylsiloxane copolymer was produced. Copolymer P-7 was obtained in the same manner as in Example 1 except that 10 g of the obtained precursor G was used. When the precursor G and the copolymer P-7 used in this reaction were measured and compared by ¹ H-NMR, the peak around 1.31 ppm derived from t-butyl group in the former disappeared in the latter, and The latter Mn is 14
Good agreement with the set value at 500, GPC elution curve Mw / Mn = 1.17
Was a monodisperse polymer. From the above, the debutylation reaction from the precursor G proceeds as expected without producing any side reaction, and is aimed at.
It was confirmed that a (polybutadiene / poly-p-vinylphenol) -polydimethylsiloxane copolymer was obtained. The estimated structural formula of the copolymer P-7 obtained in Example 7 is shown in [XV] below. (In the formula, the butadiene block and the p-vinylphenol block are randomly copolymerized.) In addition, ¹ H-NMR spectrum data is shown below. ¹ H-NMR [δ (ppm), internal standard: THF, solvent: THF-d ⁸ ]: 0
~ 0.3 (Si-CH ₃ ), 1.0 to 1.9 (CH ₂ ), 1.8 to 2.2 (CH), 4.
_{8~5.0 (CH = CH 2),} 7.8~8.1 (C 6 H 4)

[Industrial availability]

As shown in the above examples, according to the method of the present invention,
A modified polysiloxane compound in which a phenol skeleton having a narrow molecular weight distribution with controlled molecular weight and structure is introduced can be easily synthesized. Therefore, the modified polysiloxane compound is used as a resist material having a submicron resolution ability necessary for the production of VLSI, as a modifier of various thermosetting resins and thermoplastic resins, and further as a separation membrane. It is expected to be used as a biocompatible material in a wide range of fields, and its industrial significance is extremely large.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP 62-277417 (JP, A) JP 59-199705 (JP, A) JP 5-271518 (JP, A) JP 5- 170920 (JP, A) JP 47-4099 (JP, A) JP 47-4100 (JP, A) JP 47-4195 (JP, A) JP 48-28592 (JP, A) JP-A-50-44249 (JP, A) JP-B-46-9355 (JP, B1) US Patent 3678125 (US, A) US Patent 3483270 (US, A) US Patent 3051684 (US, A) UK Patent Application Publication 1267644 (GB, A) UK patent application publication 1308459 (GB, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 77/00-77/62 CA (STN) REGISTRY (STN)

Claims (4)

(57) [Claims] 1. A compound represented by the following general formula [I] X (Y) n ... [I] (where X is a p-alkenylphenol unit represented by the following general formula [II] as an essential constituent unit. A polymer block, Y is a polymer block having an organosiloxane represented by the following general formula [III] as a repeating unit, and n is 1
Or 2. ), And the weight ratio of X and Y is 1/99 ≦
A modified polysiloxane compound having X / Y ≦ 90/10 and a number average molecular weight of 1,000 to 100,000. (In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydrogen atom.) (In the formula, R ³ and R ⁴ each represent a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group. Further, R ³ and R ⁴ are the same or It may be different.) 2. A random or block copolymer block in which X is a p-alkenylphenol unit and a repeating unit of one or more conjugated dienes and / or vinyl compounds other than p-alkenylphenol.
The modified polysiloxane compound described. 3. A compound in which a hydroxyl group of a phenol residue represented by the following general formula [IV] is protected by a saturated aliphatic protecting group in the presence of an anionic polymerization initiator, is homopolymerized, or is copolymerized therewith. In the presence of an aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, ethers, or a chlorine-based solvent, after copolymerizing with a possible compound and then copolymerizing with a cyclic siloxane compound. The method for producing a modified polysiloxane compound according to claim 1, wherein the saturated aliphatic protective group is eliminated by using hydrogen chloride gas. (Here, R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ is
It represents a linear or branched alkyl group having 1 to 6 carbon atoms. ) 4. The method for producing a modified polysiloxane compound according to claim 3, wherein the copolymerizable compound is a vinyl compound other than one or more kinds of conjugated dienes and / or p-alkenylphenols.