WO1992021712A1 - Compose de polysiloxane modifie et elaboration de ce compose - Google Patents

Compose de polysiloxane modifie et elaboration de ce compose Download PDF

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Publication number
WO1992021712A1
WO1992021712A1 PCT/JP1992/000686 JP9200686W WO9221712A1 WO 1992021712 A1 WO1992021712 A1 WO 1992021712A1 JP 9200686 W JP9200686 W JP 9200686W WO 9221712 A1 WO9221712 A1 WO 9221712A1
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WIPO (PCT)
Prior art keywords
group
compound
reaction
general formula
modified polysiloxane
Prior art date
Application number
PCT/JP1992/000686
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English (en)
Japanese (ja)
Inventor
Hiroo Muramoto
Hideo Kubo
Original Assignee
Nippon Soda Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Soda Co., Ltd. filed Critical Nippon Soda Co., Ltd.
Priority to JP50989292A priority Critical patent/JP3471010B2/ja
Publication of WO1992021712A1 publication Critical patent/WO1992021712A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences

Definitions

  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • their use was limited due to insufficient compatibility with the resin and insufficient heat resistance.
  • 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.
  • 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. %
  • 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.
  • 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.
  • the present invention was completed:
  • the present invention relates to the general formula C
  • 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.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a hydrogen atom
  • 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.
  • R 3 and R 4 are each other
  • 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.
  • 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;
  • 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.
  • 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].
  • 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 ⁇ 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 ⁇ -methylstyrene and the like, and particularly preferred are p-tert-butoxystyrene and .p-tert-butoxy ⁇ -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, ⁇ -methylstyrene, ⁇ -methylstyrene, ⁇ -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.
  • 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.
  • organic solvents aliphatic hydrocarbons such as ⁇ -hexane and ⁇ -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.
  • 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.
  • 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.
  • 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.
  • polymerization conditions such as reaction temperature and reaction solvent are It can be changed appropriately within the set range.
  • 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.
  • 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.
  • 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
  • the reaction for removing the saturated aliphatic protecting group from the precursor obtained in this manner to generate a ⁇ -alkenylphenol skeleton is carried out by the solvent exemplified in the polymerization reaction or a chlorine-based compound such as carbon tetrachloride.
  • a solvent 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.
  • 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:
  • n, n, 1, k, and p in the following general formulas [IX] to [XV] each represent a corresponding natural number.
  • PTBST p-tert-butoxystyrene
  • the obtained ⁇ -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 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.
  • 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.
  • the obtained precursor C10g was treated in the same manner as in Example 1 to obtain a copolymer P-3.
  • ⁇ - ⁇ R was measured and compared.
  • Mn 20800 agreed well with the set value
  • the debutylation reaction from the precursor E proceeds as expected without any side reaction, and the desired poly- ⁇ -methylstyrene-poly- ⁇ -vinylphenol-polydimethylsiloxane polymer is obtained. I confirmed that it was done.
  • the thigh R was measured and compared.
  • 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 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.
  • 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.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Silicon Polymers (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)

Abstract

Composé de polysiloxane modifié présentant un squelette phénole d'un poids moléculaire et d'une structure moléculaire déterminés. Ce composé peut être élaboré en réalisant l'homopolymérisation anionique d'un composé représenté par la formule générale (I) dans laquelle le groupe hydroxyle phénolique est protégé par un groupe de protection aliphatique saturé ou une copolymérisation anionique de ce groupe avec un composé copolymérisable, en ajoutant un composé siloxane cyclique au polymère obtenu pour réaliser une copolymérisation, et en extrayant le groupe de protection (a) dans laquelle R1 représente l'hydrogène ou un méthyle.
PCT/JP1992/000686 1991-05-31 1992-05-27 Compose de polysiloxane modifie et elaboration de ce compose WO1992021712A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP50989292A JP3471010B2 (ja) 1991-05-31 1992-05-27 変性ポリシロキサン化合物及びその製造方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP15600491 1991-05-31
JP3/156004 1991-05-31
JP4/143383 1992-05-08
JP14338392A JPH05156023A (ja) 1991-05-31 1992-05-08 変性ポリシロキサン化合物及びその製造方法

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WO1992021712A1 true WO1992021712A1 (fr) 1992-12-10

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2468799A1 (fr) * 2009-08-21 2012-06-27 Nippon Soda Co., Ltd. Procédé de production de composé polysiloxane modifié

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5663146B2 (ja) * 2009-05-29 2015-02-04 株式会社ブリヂストン 変性共役ジエン系重合体の製造方法、変性共役ジエン系重合体、ゴム組成物、空気入りタイヤ

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5372100A (en) * 1976-12-09 1978-06-27 Dow Corning Improved block copolymer and its manufacture
JPS59123502A (ja) * 1982-12-28 1984-07-17 Nissan Motor Co Ltd 選択透過膜
JPS62212440A (ja) * 1986-03-04 1987-09-18 バイエル・アクチエンゲゼルシヤフト ポリシロキサンセグメント含有ブロツクコポリマ−

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5372100A (en) * 1976-12-09 1978-06-27 Dow Corning Improved block copolymer and its manufacture
JPS59123502A (ja) * 1982-12-28 1984-07-17 Nissan Motor Co Ltd 選択透過膜
JPS62212440A (ja) * 1986-03-04 1987-09-18 バイエル・アクチエンゲゼルシヤフト ポリシロキサンセグメント含有ブロツクコポリマ−

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2468799A1 (fr) * 2009-08-21 2012-06-27 Nippon Soda Co., Ltd. Procédé de production de composé polysiloxane modifié
EP2468799A4 (fr) * 2009-08-21 2013-02-27 Nippon Soda Co Procédé de production de composé polysiloxane modifié
US8420744B2 (en) 2009-08-21 2013-04-16 Nippon Soda Co., Ltd. Process for the production of modified polysiloxanes

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JPH05156023A (ja) 1993-06-22
JP3471010B2 (ja) 2003-11-25

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