WO1992021712A1

WO1992021712A1 - Modified polysiloxane compound and production thereof

Info

Publication number: WO1992021712A1
Application number: PCT/JP1992/000686
Authority: WO
Inventors: Hiroo Muramoto; Hideo Kubo
Original assignee: Nippon Soda Co., Ltd.
Priority date: 1991-05-31
Filing date: 1992-05-27
Publication date: 1992-12-10
Also published as: JPH05156023A; JP3471010B2

Abstract

A modified polysiloxane compound having a phenol skeleton controlled in molecular weight and molecular structure. It can be produced by conducting the anionic homopolymerization of a compound represented by general formula (I) wherein the phenolic hydroxyl group is protected with a saturated aliphatic protective group or the anionic copolymerization thereof with a compound copolymerizable therewith, adding a cyclic siloxane compound to the formed polymer to effect copolymerization, and removing the protective group (a) wherein R1 represents hydrogen or methyl.

Description

Specification

Modified polysiloxane compound and method for producing the same

【Technical field】

The present invention relates to a modified polysiloxane compound and a method for producing the same. More specifically, the present invention relates to a modified polysiloxane compound having a phenol skeleton, which is obtained by block copolymerizing a phenol phenol unit and an organosiloxane unit as essential constituent units, and It relates to the manufacturing method.

Since the modified polysiloxane compound of the present invention is controlled in molecular weight and structure and has a highly reactive fininol hydroxyl group in the molecule, it can be 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]

Organopolysiloxane compounds are widely used in various fields because of their excellent interfacial properties such as heat stability, water repellency, defoaming properties, and mold release properties. In particular, in recent years, while its use as a film-forming agent has been expanding by taking advantage of its unique interface characteristics, it has been modified to impart the temperature characteristics and interface characteristics of organopolysiloxane compounds to various resins. Application as an agent is also being actively developed.

That is, dimethyl polysiloxane, methylphenyl polysiloxane, fatty acid-modified polysiloxane, polydiene-modified polysiloxane, and the like have been conventionally used for improving the performance of synthetic resins such as paints and molded articles. However, their use was limited due to insufficient compatibility with the resin and insufficient heat resistance. In order to remedy these drawbacks, various reactive polysiloxane compounds, for example, low-molecular-weight dimethylsiloxane compounds having a functional group such as an epoxy group, an amino group, a hydroxyl group, or a (meth) acrylic group at a molecular terminal are known. It is commercially available. Further, a reaction product of these with another resin, for example, a reaction product of a polysiloxane having a terminal epoxy group and a phenol resin (Japanese Patent Application Laid-Open No. 61-73725, Japanese Patent Application Laid-Open No. 174,222, etc.), and a reaction product of a polysiloxane containing a terminal hydroxyl group and an alkenyl group-containing epoxy resin (Japanese Patent Application Laid-Open No. 62-212,417). ing. %

[Disclosure of the Invention]

In recent years, as a resist material having submicron resolution required for the production of VLSI, it has been used as a modifier for mechanical properties, moisture resistance, surface properties, etc. of various thermosetting resins and thermoplastic resins. As a separation membrane or a biocompatible polymer material, a polysiloxane compound having a controlled structure and having an arbitrary number of functional groups in a molecule has been desired.

In the above-mentioned method, the method using a commercially available low-molecular-weight dimethylsiloxane compound having a functional group in the molecule is disadvantageous in that the compatibility with other resins is not sufficient and the moldability and the mechanical strength are reduced. Having. In addition, the method of reacting a polysiloxane having a functional group at the end with other fats tends to cause undesired phenomena such as abnormal thickening and gelation during the denaturation reaction, and unreacted components are not easily produced. There was a problem such as remaining, resulting in a decrease in phase S compatibility.

An object of the present invention is to provide a modified polysiloxane compound in which the molecular weight and structure are controlled and a phenol skeleton having a narrow molecular weight distribution is introduced.

The present inventors have conducted intensive studies to achieve the above object, and as a result, obtained a compound in which the phenolic 7k acid group of P-alkenylphenol was protected by a saturated aliphatic protecting group, or a compound copolymerizable therewith. Is polymerized by an anion polymerization method, and then a cyclic siloxane compound is added thereto for copolymerization, and then a saturated aliphatic protecting group is eliminated by a method in which the molecular weight distribution is narrow and the structure is controlled. In view of the fact that a modified polysiloxane compound having a skeleton introduced therein can be easily produced, the present invention was completed:

The present invention relates to the general formula C

X (Y) n (1;

(Where X is a polymer block having a P-alkenyl phenol unit represented by the following general formula [II] as an essential constituent unit, and Y is a repeating unit represented by an organosiloxane represented by the following general formula [II I]. And n is 1 or 2.)

Wherein the weight ratio between X and Y is 1 / 99≤X / Y≤90 / 10, and the number average molecular weight is from 1,000 to 100; Siloxane compounds, [II:

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydrogen atom.)

[I I I]

(Wherein, R ³ and R ⁴ each represent a linear or branched alkyl group, cycloalkyl group, aryl group or aralkyl group having 1 to 20 carbon atoms. In the formula, R ³ and R ⁴ are each other Or X is a random or block composed of a p-alkenylphenol unit and one or more conjugated gens and / or one or more vinyl compound repeating units. A modified polysiloxane compound represented by the general formula [I], which is a polymer, and a method for producing the same.

That is, the modified polysiloxane compound of the present invention is a compound in which the hydroxyl group of a phenol residue represented by the following general formula [IV] is protected by a saturated aliphatic protecting group alone in the presence of an anion polymerization initiator. It is characterized in that it is produced by polymerizing or copolymerizing it with a copolymerizable compound, then adding a cyclic siloxane compound and copolymerizing, followed by elimination of a saturated aliphatic protecting group. I do. ■ 0 R ⁽ : iv;

H

c

Eleven

(Wherein, R ⁵ represents a hydrogen Rc t-atom or a methyl group, R ^e represents an alkyl group of straight-chain or branched technique of i~ 6 carbon atoms.) / The present invention will be described in further detail.

X in the general formula [I] of the present invention is a polymer block having a p-alkenyl phenol unit represented by the general formula [II] as an essential constituent unit. A polymer block having two or more p-alkenylphenol as a repeating unit, or a p-alkenylphenol unit and one or more conjugated gens and / or one or more vinyl compounds It is a block composed of a random copolymer or a block copolymer composed of a repeating unit, and also includes a block represented by the following general formula [V].

[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 general formula [I] of the present invention, Y is A polymer block having an organosiloxane represented by the general formula [I II] as a repeating unit, and at least one of the blocks constituting the branch の of the compound represented by the general formula [I] is Y. The compound represented by the general formula [I] is represented by X—Y or Y—X—Y.

The compound represented by the general formula [IV] used in the present invention includes, for example, Examples include xylstyrene, p-sec-butoxystyrene, p-tert-butoxystyrene, p-tert-butoxy α-methylstyrene and the like, and particularly preferred are p-tert-butoxystyrene and .p-tert-butoxyα-methylstyrene. .

Examples of the conjugated or vinyl compound copolymerizable with the general formula [IV] used in the present invention include 1,3-butadiene, isoprene, 2,3-dimethyl3-1,3-butadiene, and 1,3-pentadiene. Conjugated dienes such as 1,3-hexadiene; vinyl aromatics such as styrene, ρ-methylstyrene, α-methylstyrene, ρ-tert-butylstyrene, vinylnaphthalene, divinylbenzene, 1,1-diphenylethylene Group compounds; methyl (meth) acrylate,

(Meth) acrynolate esters such as (meth) ethyl acrylate and (meth) butyl acrylate; vinylpyridines such as 2-vinylpyridine and 4-vinylpyridine; and acrylonitrile; Used as a mixture of two or more.

The compound of the present invention represented by the general formula [IV] or the compound represented by the general formula [IV] and the copolymerizable compound may be used in an organic gas atmosphere under an inert gas atmosphere such as nitrogen or argon. In a solvent, the molecular weight is controlled by performing anionic polymerization at a temperature of −100 ° C. to 150 ° C. using a metal salt of an alkali metal and / or an organic metal salt of a metal as a polymerization initiator. A polymer having a narrow molecular weight distribution can be obtained.

Examples of the alkali metal of the anion polymerization initiator include lithium, sodium, and potassium, and examples of the organic alkali metal compound include alkylated, arylated, and arylated compounds of the alkali metal. Specific examples of organic alkali metal compounds include ethyl lithium, n-butyl lithium, sec-butyl lithium, teri-butyl lithium, ethyl sodium, butadienyl dilithium, butadienyl disodium, lithium biphenyl, lithium naphthalene, and lithium fluorene. And sodium biphenyl, sodium naphthalene, sodium triphenyl, α-methylstyrene sodium dianion and the like, and these are used as one kind or as a mixture of two or more kinds.

As organic solvents, aliphatic hydrocarbons such as η-hexane and η-heptane; alicyclic hydrocarbons such as cyclohexane and cyclopentane; aromatic hydrocarbons such as benzene and toluene; getyl ether Organic solvents usually used in anionic polymerization, such as ethers such as dioxane and tetrahydrofuran, are used as one kind or a mixture of two or more kinds. The form of the copolymer obtained by the anion polymerization may be such that a random copolymer is formed by adding a mixture of the compound represented by general formula [IV] and the monomer to a reaction system and polymerizing the mixture. Is partially polymerized in advance, and then a mixture of the two is added and polymerization is continued to obtain a partial block copolymer, and the compound represented by the general formula (IV) and the monomer are converted into a reaction system. A complete block copolymer is synthesized by sequentially adding and polymerizing.

After the homopolymerization of the compound represented by the general formula [IV] or after the copolymerization reaction with the monomers, a cyclic siloxane compound is added to the reaction system, and the anion polymerization reaction is carried out under the same conditions as those described above. Thus, a block copolymer composed of the compound represented by the general formula [IV] or a chain composed of the compound represented by the general formula [IV: and the monomer] and a polysiloxane chain Combined (hereinafter, referred to as a precursor << manufactured: The cyclic siloxane compound used herein is a compound represented by the following general formula VC.

(Where, R ^: and R ⁸ are a straight-chain or branched alkyl group, a cycloalkyl group, an aryl group or an aralkyl group having i to 20 carbon atoms, respectively, and c is a positive integer of 3 to 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 and octamethylcyclo. Tetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, hexethylcyclotrisiloxane, octaethylcyclotetrasiloxane, hexaphenylcyclotrisiloxane, and the like. It can be used as a mixture of two or more.

In this successive anion polymerization reaction, polymerization conditions such as reaction temperature and reaction solvent are It can be changed appropriately within the set range.

Further, modified polysiloxane compounds of the present invention, persons other than the methods described ^above;: removed by, for example, after homopolymerization of the represented by (IV) compound, or after the copolymerization reaction between the monomer One class, the reaction An organosiloxane compound having a functional group capable of reacting with the growth terminal of the polymer is added to the system, and a coupling reaction is carried out under the same conditions as those described above to obtain a compound represented by the general formula (IV). A precursor comprising a chain, or a chain comprising the compound represented by the general formula [IV] and the above-mentioned monomer, and a polysiloxane chain is produced.

The structure of the organosiloxane compound used herein is not particularly limited as long as it has a functional group capable of performing a coupling reaction with the growth terminal of the polymer. Specific examples include the following general formulas (VII) and (VII). VIII] is used.

Xl [VII]

(Wherein, R ^s and R ¹ 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 Xi and X ₂ are a halogen atom, Represents an epoxy group, a carbonyl group, a carbonyl group, or a hydrocarbon group having 1 to 20 carbon atoms containing a halogen atom, an epoxy group, a carbonyl group, a carbonyl group, etc., where d is an integer of 1 or more Represents.)

Xi R (VIII)

(Wherein, R ⁸ , R ¹⁰ , X ¹ and d represent the same meaning 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. Is shown.) Specific examples of the compound represented by the general formula mi] or in include, for example, commercially available o

, ω-bis (chloromethyl) polydimethylsiloxane, 1- (3-crocopropyl) 1,1,1,3,3,3-pentamethyldisiloxane, ω-bis (3-glycidoxypropyl) polydimethylsiloxane, α , —Dichloro mouth polydimethylsiloxane and the like.

In the polymerization reaction and the coupling reaction performed sequentially, conditions such as a reaction temperature and a reaction solvent can be appropriately changed within a set range.

The reaction for removing the saturated aliphatic protecting group from the precursor obtained in this manner to generate a ρ-alkenylphenol skeleton is carried out by the solvent exemplified in the polymerization reaction or a chlorine-based compound such as carbon tetrachloride. In the presence of a solvent, at least one kind of proton donor such as hydrochloric acid, hydrogen chloride gas, hydrobromic acid, 1,1,1-trifluoroacetic acid and the like is added to 150 or less, preferably at room temperature to 100 ° C. It can be done at temperature.

According to the above-mentioned method, the modified polysiloxane compound of the present invention in which the molecular weight and the structure are controlled and the phenol skeleton having a narrow molecular weight distribution is introduced is 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 at all by the following;

In the following examples, “%” is by weight unless otherwise specified.

Further, m, n, 1, k, and p in the following general formulas [IX] to [XV] each represent a corresponding natural number.

(Example 1)

In a nitrogen atmosphere, p-tert-butoxystyrene (trade name; Hokuko-Ichi PTBST, Hokuko Chemical Co., Ltd., hereinafter referred to as PTBST) Add 130 g of 0.25 mol THF solution over 1 hour, continue the reaction for 3 hours, and add hexamethylcyclotrisiloxane (hereinafter, 200 g of a THF solution containing 0.45 mol was added over 1 hour, and the reaction was continued for 8 hours while maintaining the reaction temperature at 30 ° C. Then, add water to the reaction solution Three

After the reaction was stopped, the mixture was separated and the solvent was distilled off from the organic layer under reduced pressure to obtain a precursor A.

The obtained β-form A had a number average molecular weight (Mn :) of 15100 as measured by the VP0 method and an Si content of 25.3% as measured by elemental analysis, and all agreed well with the set values. The curve showed a unimodal peak, and the weight average molecular weight (Mw) / number average molecular weight (Mn) = 1.15. From these results, it was confirmed that the copolymerization was performed as expected and that a poly-PTBST-polydimethylsiloxane copolymer was produced.

10 g of the obtained precursor A is dissolved in methyl ethyl ketone to form a 10% solution, hydrogen chloride gas is blown at room temperature for 30 minutes, water is added, liquid separation is performed, and the solvent is distilled off from the organic layer under reduced pressure. Copolymer

—P— I got 1.

For the precursor A and the copolymer P-1 used in this reaction, the thigh R was measured and compared, and the 1.31 ppm peak derived from the tert-butyl group in the former disappeared in the latter, and then disappeared. In addition, the latter Mn by the VP0 method was 13000, which was in good agreement with the set value, and the GPC elution curve was a monodisperse polymer of M / Mn-1.18.

From the above, it was confirmed that the debutylation reaction from precursor A proceeded as expected without any side reaction, and that the desired poly (p-vinylphenol-polydimethylsiloxane) copolymer was obtained. confirmed.

The deduced structural formula of copolymer P-1 obtained in Example 1 is shown in [IX] below.

CH _S

C 11 CH ₂ H · · · [IX:

Various spectrum data are shown below.

'HN R [δ (pm) , internal standard: THF, solvent: THF-d ^8]:

_{~0.3 (Si- CH 3), 1.3~1.7} (CH 2), 1.8 -2.1 (CH), 6.3-6.8 (C 6 H 4), 7.7 ~ 7.9 (OH) 13 C-NMR [5 (ppm), Internal standard: THF, solvent: THF—d ⁸ ]:

.4 (Si-CH ₃ ), 35 to 50 (CH ₂ , CH), 116 to 156 (C ₈ H ₄ ) ^2B Si-M [S (pp), internal standard: TMS, solvent: THF-d ^8, relaxation _{reagent: Fe (acac) 3::} 4.8 (CH-Si (CH 3) 2 -0), -22.5~- 21.6 (0- Si (C¾) ₂ -0), -14.9 (G-Si (CH ₃ ) _: -OH.

4) IR (cm- ¹ ):

3150～ ed (OH), 3020 -3100 (> , 1260 (Si- CH 3), image ~ 1120 (Si - (Example 2)

Under a nitrogen atmosphere, 30 g of a THF solution containing 0.05 mol of PTBST was added over 1 hour to 300 g of a THF solution containing a sodium-kerosene dispersion containing 0.02 mol of metallic sodium while stirring at 140 ° C. After the reaction was continued for 90 hours, 90 g of a THF solution containing 0.15 mol of D3 was added to the reaction solution over 1 hour, and the reaction was continued at a reaction temperature of 30 ° C. for 8 hours. Next, after adding trimethylsilyl chloride to the reaction solution to terminate the reaction, water was further added and the solution was separated, and the solvent was distilled off under reduced pressure from the organic layer to obtain a precursor B.

In the obtained former body B, M n = 4300, Si content = 30.Ο ό · = 1.25. From these results, it was confirmed that the copolymerization ability 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.

When the precursor B and the copolymer P-2 used in this reaction were compared by defining: H—R, the peak at 1.31 ppm derived from the tert-butyl group in the former disappeared in the latter. In the latter case, Mn = 4000 was in good agreement with the set value, and the GPC elution efficiency was 泉 ν ·· _ΖΜη = 1.25, which was a monodisperse polymer.

From the above, the debutylation reaction from the predecessor Β does not cause any side reaction: it proceeds as expected, and the desired polydimethylsiloxane-poly-p-isopropenylfuninol-polydimethylsiloxane copolymer It was confirmed that coalescence was obtained. The deduced structural formula of the copolymer P-2 obtained in Example 2 is shown in [X] below.

(CH ₃ )) _s

The NMR spectrum data is shown below.

^ -NMR Co (ρριπ), Internal standard: THF, Solvent: THF— d ⁸ :

0 -0.3 (Si-CH ,,). 0.0 -0.8 (C-CH ₃ ), 1.0 to 1.9 (CH ₂ ), 6.2-7.1 (C ₆ H.,), 7.8 to 8.1 (OH)

(Example 3)

Under a nitrogen atmosphere, 130 g of a THF solution containing 0.25 mol of PTBST was added over 1 hour to 1000 g of a THF solution containing 0.01 mol of sec-butyllithium while stirring at -70 ° C, and the reaction was further continued for 3 hours. Thereafter, a THF solution containing 0.28 mol of styrene was added over 1 hour, and the reaction was further continued for 3 hours. To the reaction solution, a THF solution containing 0.67 mol of D30 was added over 1 hour, and the reaction was continued at a reaction temperature of 30 ° C. for 8 hours. Next, trimethylsilyl chloride was added to the reaction solution to stop the reaction, and then the layers were separated. The solvent was distilled off from the organic layer under reduced pressure to obtain the former H form C.

The obtained precursor C had good agreement with the set values at Mn = 23100 and Si content = 24.5%, and the GPC elution curve showed a monomodal peak, with a force of Mw / Mn = 1.2. Was. From these results, it was confirmed that the copolymerization was performed as expected, and that a poly-PTBST-polystyrene-polydimethylsiloxane copolymer was formed.

The obtained precursor C10g was treated in the same manner as in Example 1 to obtain a copolymer P-3. For the precursor C and the copolymer P-3 used in this reaction, ^-丽 R was measured and compared. As a result, the peak at 1.31 ppm derived from the p-tert-butyl group in the former disappeared in the latter. Mn = 20800 agreed well with the set value, and the GPC elution curve was a monodisperse polymer with Mw / Mn = 1.30. ―

From the above, the debutylation reaction from precursor C proceeded as expected without any side reaction, and the desired poly (p-vinylphenol-polystyrene-polydimethylsiloxane) copolymer was obtained. I confirmed that.

The deduced structural formula of copolymer F-3 obtained in Example 3 is shown in the following [XI. L2,

C4H9-CH ₂ -CH — (CH2-CH — i-0 S i (CH ₃ ) 3 i:

i

OH and-Spectral data is shown below.

'E-MR [5 (ppm), internal standard: THF, solvent: THF—d ⁸ ]:

0 -0.3 (Si-CH ₃ ), 1.3 to 2.0 (CH ₂ ), 1.8 to 2.5 (CH), 6.3 to 7.5 (C ₆ H ₄ 'C _e H ₅ )

(Implementation ^ 4) H

Five

Under a nitrogen atmosphere, 480 g of a THF solution in which 0.53 mol of PTBMST and 10 mol of butadiene L are dissolved is added to 600 g of a THF solution containing a sodium-containing lium-kecosin dispersion containing 0.02 mol of sodium while stirring at 160 ° C for 2 hours. The reaction was continued for another 2 hours, and then 90 g of a THF solution containing 0.20 mol of D30 was added to the reaction solution over 1 hour, and the reaction was continued for 8 hours at a reaction temperature of 30. . Next, 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 resulting precursor D had good agreement with the set values at Mn = 21000 and Si content = 8.1, and the GPC; elution curve showed a unimodal peak, and the force was Mw "Mn = 1.28: From this result, it was confirmed that the copolymerization ability was performed as expected, and that polydimethylsiloxane-poly (poly-PTE ST 'Po · "phthazinine.-polydimethylsiloxane copolymer was formed."

10 g of the obtained precursor D was treated in the same manner as in Example 1 to obtain a copolymer P-4.

NMR measurement of the precursor D and the copolymer P-4 used in this reaction showed that the peak force at around 1.31 ppm derived from the tert-butyl group in the former <disappeared in the latter, Mn = 17500, 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 D proceeded as expected without any side reaction, and the desired polydimethylsiloxane-1 (poly-1p-isoprobenylfuninol Z polybutadiene) -1 polydimethyl It was confirmed that the siloxane copolymer strength was obtained.

The deduced structural formula of the copolymer obtained in Example 4 is shown in the following (XII). (CH ₃ ) ₃ Si (CH ₃ ) 3 an)

(Random)

(In the formula, p-isopropenylphenol block and butadiene block are randomly copolymerized.) ¹ H-NMR spectrum data is shown below.

^ -NMR (δ (ρρα), internal standard: THF, solvent: THF—d ⁸ ]:

_{0 ~ 0.3 (Si- CH 3)} , 0.0 ~ 0.8 (C-CH 3), 1.0~1.9 (CH 2), 1.8 -2.2 (CH), 4.8 -5.0 (CH = CH 2), 5.2 ~ 5.6 (CH = CH ₂ ), 7,8 ~ 8.1 (C ₆ H ₄ )

(Example 5)

Under a nitrogen atmosphere, 5 g of a hexane solution containing 0.01 mol of n-butyllithium was added dropwise to the 550 g of THF solution containing 0.15 mol of methylstyrene while stirring at 25 ° C over 30 minutes. The reaction was continued for hours. The reaction solution was cooled to 170 ° C, and the reaction was read for another 3 hours.After that, 100 g of a THF solution containing 0.15 mol of PTBST was added over 1 hour, and the reaction temperature was kept at 30 ° C for another 8 hours. Continued. 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 E.

The obtained precursor E had a Mn = 14700 and a Si content of 26.3%, which were in good agreement with the set values, the GPC elution curve showed a unimodal peak, and MwZMn = 1.28. From this result, it was confirmed that the copolymerization was performed as expected, and a poly (methyl styrene) -poly (PTBST) -polydimethylsiloxane copolymer was produced.

The obtained precursor ElOg was treated in the same manner as in Example 1 to obtain a copolymer P-5.

When the precursor E and the copolymer P-5 used in this reaction were compared by -NMR measurement, the peak force around 1.31 ppm derived from the tet-butyl group in the former disappeared in the latter. 1 person

In addition, the latter Mn was 14000, which was in good agreement with the set value, and the GPC elution curve was a monodisperse polymer with Mw / Mn = 1.2S.

As described above, the debutylation reaction from the precursor E proceeds as expected without any side reaction, and the desired poly-α-methylstyrene-poly-ρ-vinylphenol-polydimethylsiloxane polymer is obtained. I confirmed that it was done.

_C showing the estimated structural formula of the copolymer one .rho. 5 obtained in Example 5 in the following [XI II]

Chs (iz

C ₄ H ₉ -CH ₂ -CH — (CH ₂ -CH--Si-0 ^ — H · · · (XI II:

Γ to CHs

OH Also! The H-NMR spectrum data is shown below.

^-MR C5 (ppm), Internal standard: THF, Solvent: THF—d ⁸ ]:

0 to 0.3 (Si-CH ₃ ), 0.0 to 0.8 (C-CH ₃ ), 1.3 to 2.0 (CH ₂ ), 1.8 -2.1 (CH), 6.3 -7.2

(Le 6, CsH

(: Example 6)

Under a nitrogen atmosphere, to a 550 g of THF solution containing 0.15 mol of methylstyrene, 5 g of a hexane solution containing 0.01 mol of n-butyllithium stirred at 25 ° C. was added over 30 minutes. The reaction was continued for hours. The reaction solution was cooled to 0 ° C, and the reaction was continued for another 3 hours. Then, 100 g of a THF solution containing 0.15 mol of PTBST and 0.10 mol of styrene was added over 1 hour, and the reaction was continued for another 3 hours. did. Next, 300 g of a THF solution containing 0.45 mol of D 3 was added to the reaction solution over 1 hour, and the reaction temperature was set to 30 ° C., and the reaction was continued for another 8 hours. After the reaction was stopped by adding water to the reaction solution, the mixture was separated and the solvent was distilled off from the organic layer under reduced pressure to obtain a precursor F.

The obtained precursor F had a good agreement with the set value at Mn = 15700 and Si content = 24.2%, and the GPC elution curve showed a monomodal peak. I did. From this result, it was confirmed that the copolymerization was performed as expected, and a poly-α-methylstyrene-mono (polystyrene / poly-PTBST) -polydimethylsiloxane polymer was produced.

The obtained pre-IS form FlOg was treated in the same manner as in Example 1 to obtain a copolymer P-6. IB

For the precursor F and copolymer P-6 used in this reaction, the thigh R was measured and compared. The peak around 1.31 ppm derived from the tet-butyl group in the former disappeared in the latter. The latter Mn was 15000, which was in good agreement with the set value, and the GPC elution curve was a monodisperse polymer with Mv / Mn = 1.28.

From the above, the debutylation reaction from precursor Ε proceeds as expected without any side reaction, and the desired poly-α-methylstyrene-mono (polystyrene / poly-ρ-vinylphenol) polydimethyl It was confirmed that a siloxane polymer was obtained.

The estimated structural formula of copolymer-6 obtained in Example 6 is shown in the following [XIV]. H [XIV]

(In the formula, the styrene block and the p-vinylphenol block are randomly copolymerized.) Also, -brain (Spectral data is shown below.

Ή-NMR [(5 (ρριη), internal standard: TH F, solvent: TH F— d ⁸ ]:

0 -0.3 (Si-CHa), 0.0 -0.8 (C- CH 3), 1.3~2.0 (CH 2), 1.8 ~ 2.5 (CH), 6.3 -7.5

(Example 7)

Under a nitrogen atmosphere, 100 g of a THF solution containing 0.15 mol of PTB ST and 0.20 mol of butadiene was added to 600 g of a THF solution containing 0.01 mol of η-butyllithium for 1 hour while stirring at 170 ° C. The reaction was continued over a further 3 hours. Next, 300 g of a THF solution containing 0.44 mol of D30 was added to the reaction solution over 1 hour, and the reaction temperature was increased to 30 ° C. 1G

The reaction was continued for 8 hours. After the reaction was stopped by adding water to the reaction solution, the mixture was separated, and the solvent was distilled off from the organic layer under reduced pressure to obtain a precursor G.- The obtained pre-IS form G contained Mn = 15200 and contained Si. The amount was 24.1, which was in good agreement with the set value. The GPC elution curve showed a unimodal peak, and Μ Ζλίη = Ι.1Τ. From this result, it was confirmed that the copolymerization was carried out as expected, and that a (polybutadiene / poly PTBS S—polydimethylsiloxane copolymer was produced.

10 g of the obtained precursor G was used to obtain a copolymer P-7 in the same manner as in Example 1. The precursor G used in this reaction was compared with the copolymer P-7 by ¹ H-NMR measurement. However, the peak around 1.31 ppm derived from the t-butyl group in the former disappeared in the latter, and the Mn of the latter was 14500, which was in good agreement with the set value, and the GPC elution curve was MwZM n = I There were 17 monodisperse polymers:

As described above, the debutylation reaction from the precursor G proceeds as expected without any side reaction, and the desired (polybutadiene poly-P-vinylphenol) -polydimethylsiloxane copolymer is obtained. I confirmed that.

The deduced structural formula of the copolymer P-7 obtained at m7 is shown in the following [XV].

(Random)

(In the formula, it indicates that the butadiene block and the P-vinylphenol block are randomly copolymerized.) The H-MR spectrum data is shown below.

^ -MR [6 (ppm), internal standard: THF, solvent: THF-d ^8]:

_{~0.3 (Si- CH 3), 0.0~} 0.8 (C-CH 3), 1.0 ~ 1.9 (CH 2), 1.8~2 · 2 (CH), 4.8~5.0 (C 1?

H = CH ₂ ), 7.8 ~ 8.1 (Ce H ₄ ) [Industrial applicability]

As described in the above examples, according to the method of the present invention, a modified polysiloxane compound having a controlled molecular weight and structure and having a phenol skeleton having a narrow molecular weight distribution can be easily synthesized.

Therefore, the modified polysiloxane compound is used as a resist material having a resolution of a sub-micron opening required for the production of an VLSI, and as a modifier for various thermosetting resins and thermoplastic resins. Is expected to be used in a wide range of fields as separation membranes and biocompatible materials, and its industrial significance is extremely large.

Claims

IS

The scope of the claims

i. The following general formula C I]

X (Y) n

(Where X is a polymer block having p-alkenylphenol unit ii represented by the following general formula [π] as a monomer unit, and Y is an organosiloxane represented by the following general formula [III: Is a polymer block as a unit, and n is 1 or 2.) is represented by the following formula, wherein the weight ratio between X and Y is 1/990/10, and the number average molecular weight is 1, 000. ~ 1 0 0,

A modified polysiloxane compound which is 100.

C αι]

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom.)厂R ³

— S i-0 [I I I]

One R ⁴

(Wherein, R ³ and R ⁴ are straight鎮又of C 1-2 0 each represents an alkyl group, a cycloalkyl group, § Li one Norre group or Ararukiru group branched. Further, R ³ and R ⁴ May be the same or different.)

2. The modified polysiloxane compound according to claim 1, wherein X is a random or block copolymer block consisting of a p-alkenylphenol unit and one or more kinds of conjugated dinin and / or vinyl compound repeating units. .

3. In the presence of an anion polymerization initiator, it is possible to homopolymerize or copolymerize a compound represented by the following general formula [IV], in which the hydroxyl group of a funinol residue is protected with a saturated aliphatic protecting group. 13

The modified polysiloxane compound according to claim 1, wherein the compound is copolymerized with a cyclic compound, and then the cyclic siloxane compound is added and copolymerized, and then a saturated aliphatic protecting group is eliminated. Method.

(IV)

(Here, 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.)

4. The process for producing a modified polysiloxane compound according to claim 3, wherein the copolymerizable compound is one or more conjugated gens and ^/ or vinyl compounds.