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WO2011070880A1 - Procédé de production d'un polymère d'éther vinylique en forme d'étoile - Google Patents

Procédé de production d'un polymère d'éther vinylique en forme d'étoile Download PDF

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Publication number
WO2011070880A1
WO2011070880A1 PCT/JP2010/069795 JP2010069795W WO2011070880A1 WO 2011070880 A1 WO2011070880 A1 WO 2011070880A1 JP 2010069795 W JP2010069795 W JP 2010069795W WO 2011070880 A1 WO2011070880 A1 WO 2011070880A1
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group
vinyl ether
monomer
oxystyrene
star polymer
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Japanese (ja)
Inventor
憲弘 吉田
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Maruzen Petrochemical Co Ltd
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Maruzen Petrochemical Co Ltd
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Priority to JP2011545153A priority Critical patent/JP5731401B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
    • C08F261/06—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated ethers

Definitions

  • the present invention relates to a method for producing a vinyl ether type star polymer. More specifically, the present invention relates to a method for producing a star polymer having an arm in which a vinyl ether polymer and an oxystyrene polymer are sequentially copolymerized from a nucleus.
  • Oxystyrene-based polymers such as hydroxystyrene are used as functional polymer materials in various industrial fields, and in particular, in the field of electronic materials, particularly as a raw material for resin components for semiconductor resists.
  • the use as a photosensitive resin component used for an interlayer insulating film or a surface protective film of a semiconductor element or the like has been studied.
  • the star polymer that has both oxystyrene polymer and vinyl ether polymer in the arm has low viscosity and fine particle property, which is unique to star polymer, in addition to oxystyrene polymer and vinyl ether polymer. Since a unique function can be simultaneously provided, it can be suitably used as a raw material for a photosensitive resin component suitable for applications such as an interlayer insulating film and a surface protective film of a semiconductor element.
  • a diblock copolymer as the arm, microphase separation is possible, leading to the creation of materials controlled on the nano-order.
  • the oxystyrene arm when the oxystyrene arm is arranged in the shell, it can be a material advantageous for the crosslinking reaction.
  • a method for producing a star polymer a method in which a polyfunctional starting species is synthesized in advance and an arm is extended therefrom (core first method), and a living polymer to be an arm is produced by crosslinking with a divinyl compound or the like. (Arm first method) is common.
  • Patent Document 1 a method for synthesizing a star polymer using a diblock polymer of a vinyl ether polymer and an oxystyrene polymer as an arm using a polyfunctional starting species is disclosed (Patent Document 1).
  • this method requires the synthesis of the multifunctional starting species in a step separate from the step of polymerizing the star polymer, so that the one-pot production is difficult and the production method is complicated.
  • the multifunctional initiating species is a compact initiating species, the vicinity of the reaction starting point is likely to be spatially crowded and an arm loss is likely to occur.
  • the maximum number of arms of the star polymer obtained by this method is 4, and there is a problem that it is difficult to sufficiently develop the low viscosity depending on the fineness of the star polymer and the number of branches.
  • a vinyl ether monomer is living cationically polymerized with a starting acid such as alkoxyethyl acetate and a Lewis acid, and then a divinyl ether is added to the resulting living polymer to form a nucleus and stimulate
  • a method for producing a responsive vinyl ether-based star polymer is disclosed (Patent Document 2).
  • Patent Document 2 since the arm and the nucleus can be polymerized in one pot, the manufacturing method is simpler than the core-first method.
  • the production method itself is simple, the number of arms can be easily increased, and development of a production method of a star polymer in which a vinyl ether arm and an oxystyrene arm are sequentially copolymerized from the core is required.
  • An object of the present invention is to provide a production method in which a vinyl ether star polymer in which an arm made of a vinyl ether polymer and an arm made of an oxystyrene polymer are sequentially copolymerized from the core can be continuously carried out in a series of steps. Is to provide.
  • the present inventors first formed a nucleus by living cationic polymerization of a divinyl compound using a starting species in the presence of a Lewis acid, followed by crosslinking, and then The inventors have found that a vinyl ether-based star polymer can be easily obtained by living cationic polymerization of a vinyl ether-based monomer and an oxystyrene-based monomer, and the present invention has been completed.
  • the present invention synthesizes a vinyl ether polymer having a vinyl group in a side chain by adding a Lewis acid in a reaction solution containing at least an initiating species, a solvent and a divinyl compound, and nuclei are obtained by intermolecular crosslinking of the vinyl group side chain.
  • a vinyl ether monomer and an oxystyrene monomer are added and living cationic polymerization is performed in the order of the vinyl ether monomer and the oxystyrene monomer.
  • a method for producing a vinyl ether-based star polymer is provided.
  • a vinyl ether star polymer in which a vinyl ether arm and an oxystyrene arm are sequentially copolymerized from a nucleus which has been complicated in the conventional synthesis, can be produced by a simple method.
  • the manufacturing method of the vinyl ether-type star polymer of the present invention can be carried out in one pot, the manufacturing process and the manufacturing equipment can be greatly simplified, which is extremely advantageous industrially compared with various conventional methods. .
  • a Lewis acid is added to a reaction solution containing at least an initiating species, a solvent and a divinyl compound to synthesize a vinyl ether polymer having a vinyl group in a side chain, and a nucleus is formed by intermolecular crosslinking of the vinyl group side chain.
  • a vinyl ether monomer and an oxystyrene monomer are added and living cationic polymerization is performed in the order of the vinyl ether monomer and the oxystyrene monomer.
  • a method for producing a vinyl ether-based star polymer is provided.
  • a starting species, a solvent, and a divinyl compound are sequentially added to a reaction vessel, and then an appropriate Lewis acid is added to the reaction (hereinafter, this step is referred to as “nucleation step”). ).
  • the star polymer core is first synthesized in this process.
  • the divalent organic group R 2 includes a group represented by the following formula. Wherein n, l and p are each an integer of 1 or more, R 7 is —O—, —O—Ph—O— or —O—Ph—C (CH 3 ) 2 —Ph—O— or carbon A cycloalkyl group having a number of 3 or more, wherein Ph represents a phenylene group)
  • divinyl compound represented by the formula (1) examples include ethylene glycol divinyl ether, bisphenol A bis (vinyloxyethylene) ether, bis (vinyloxyethylene) ether, hydroquinone bis (vinyloxyethylene) ether, 1 , 4-bis (vinyloxymethyl) cyclohexane.
  • starting species that can be used in the method of the present invention include compounds that generate protons such as water, alcohol, and protonic acids, or compounds that generate carbocations such as alkyl halides. Further, it may be a cation supply compound such as an adduct of the vinyl ether and a compound that generates protons. Examples of the compound that generates such a carbocation include 1-alkoxyethyl acetate such as 1-isobutoxyethyl acetate.
  • Lewis acid (I) As the Lewis acid used in the living cation polymerization reaction in the nucleation step (hereinafter referred to as “Lewis acid (I)”), it is generally possible to use a Lewis acid used for cationic polymerization of vinyl ether monomers. it can.
  • the organic aluminum halide compound or aluminum halide compound represented by these is mentioned.
  • examples of the monovalent organic group include an alkyl group, an aryl group, an aralkyl group, an alkenyl group, and an alkoxy group, but are not particularly limited.
  • examples of the halogen atom for Y include a chlorine atom, a bromine atom, and a fluorine atom, and q and r are preferably such that q is in the range of 1 to 2 and r is in the range of 1 to 2.
  • Examples of the organic aluminum halide compound or aluminum halide compound represented by the general formula (4) include diethylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride, methylaluminum sesquichloride, ethylaluminum sesquichloride, ethylaluminum.
  • Examples include sesquibromide, isobutylaluminum sesquichloride, methylaluminum dichloride, ethylaluminum dichloride, ethylaluminum dibromide, ethylaluminum difluoride, isobutylaluminum dichloride, octylaluminum dichloride, ethoxyaluminum dichloride, phenylaluminum dichloride.
  • the solvent used in the method of the present invention includes aromatic hydrocarbon solvents such as benzene, toluene and xylene; propane, n-butane, isobutane, n-pentane, n-hexane, n-heptane, n-octane and isooctane.
  • aromatic hydrocarbon solvents such as benzene, toluene and xylene
  • the amount of divinyl compound used in the nucleation step is preferably 1 to 1000 equivalents, more preferably 1 to 100 equivalents per equivalent of the starting species. If the amount of divinyl compound used is less than the above range, the reaction starting point in the formed nucleus is reduced, so that sufficient arm introduction cannot be performed. Moreover, when the usage-amount of a divinyl compound will exceed the said range, it will become easy to gelatinize at the time of nucleation. Moreover, there is no restriction
  • the amount of Lewis acid added in the nucleation step is usually 0.1 to 100 mol%, preferably 1 to 50 mol%, based on the divinyl compound.
  • the end point of the crosslinking reaction for forming nuclei can be confirmed, for example, by monitoring the RI chart of gel permeation chromatography (GPC) in a time-sharing manner and the change in the GPC waveform converges. It is preferable to do so.
  • GPC gel permeation chromatography
  • a vinyl ether monomer and an oxystyrene monomer are added, and living cationic polymerization is sequentially performed to form a diblock arm (hereinafter referred to as a “diblock arm”). , Referred to as “arm formation process”).
  • each polymerization reaction in said nucleation process and the arm formation process demonstrated from now on can be continuously advanced as a series of processes within the same reaction container.
  • the polymerization rate of the oxystyrene monomer is increased by adding a Lewis acid (Lewis acid (II)) suitable for this as described later. be able to.
  • R 4 is a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched alkyl group having 1 to 6 carbon atoms, in which all or part of hydrogen is substituted with fluorine.
  • the vinyl ether monomer represented by these can be mentioned.
  • Examples of the linear or branched alkyl group having 1 to 6 carbon atoms in the definition of R 4 in the general formula (2) include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, Examples thereof include a tert-butyl group, an isobutyl group, an n-amyl group, and an isoamyl group.
  • Examples of the fluoroalkyl group having 1 to 6 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, and 2,2,2-trifluoroethyl. Groups and the like.
  • alkoxyalkyl group having 2 to 6 carbon atoms examples include a methoxymethyl group, an ethoxymethyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group, a 2-tetrahydropyranyl group, and a 2-tetrahydrofuranyl group.
  • Examples of the cycloalkyl group having 5 to 10 carbon atoms include cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, bicyclo [2.2.1] heptyl group, bicyclo [2.2.2] octyl group, tricyclo [ 5.2.1.0 2,6 ] decanyl group, adamantyl group and the like.
  • examples of the aryl group represented by the group (2a) include a phenyl group, a methylphenyl group, an ethylphenyl group, a methoxyphenyl group, an ethoxyphenyl group, a fluorophenyl group, and a trifluoromethylphenyl group.
  • examples include benzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, ethoxybenzyl group, fluorobenzyl group, trifluoromethylbenzyl group and the like.
  • the alkoxypolyoxyalkyl group represented by the group (2b) includes 2- (2-methoxyethoxy) ethyl group, 2- (2-ethoxyethoxy) ethyl group, 2- (2- (2-methoxyethoxy) ) Ethoxy) ethyl group, 2- (2- (2-ethoxyethoxy) ethoxy) ethyl group, 2- (2- (2- (2-methoxyethoxy) ethoxy) ethyl group, 2- (2- (2- (2- (2-methoxyethoxy) ethoxy) ethyl group, 2- (2- (2 And-(2-ethoxyethoxy) ethoxy) ethoxy) ethyl group.
  • Examples of the vinyl ether monomer represented by the formula (2) include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, sec-butyl vinyl ether, tert-butyl vinyl ether, isobutyl vinyl ether, alkyl vinyl ethers such as n-amyl vinyl ether and isoamyl vinyl ether; fluoroalkyl vinyl ethers such as trifluoromethyl vinyl ether, pentafluoroethyl vinyl ether and 2,2,2-trifluoroethyl vinyl ether; 2-methoxyethyl vinyl ether and 2-ethoxyethyl Alkoxy compounds such as vinyl ether, 2-tetrahydropyranyl vinyl ether, 2-tetrahydrofuranyl vinyl ether Kill vinyl ethers: cyclopentyl vinyl ether, cyclohexyl vinyl ether, cycloheptyl vinyl ether
  • Examples include alkoxy polyoxyalkyl vinyl ethers.
  • vinyl ether monomers may be used alone or in combination of two or more.
  • the oxystyrene monomer used in this arm formation step the following general formula (3) (Wherein R 5 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 6 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group having 2 to 6 carbon atoms, an acyl group, an alkoxy group) A carbonyl group, an alkoxycarbonylalkyl group or an alkylsilyl group)
  • R 5 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 6 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group having 2 to 6 carbon atoms, an acyl group, an alkoxy group
  • a carbonyl group, an alkoxycarbonylalkyl group or an alkylsilyl group The oxystyrene type monomer represented by these can be mentioned.
  • the alkyl group having 1 to 4 carbon atoms includes a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, An isobutyl group etc. are mentioned.
  • the alkyl group having 1 to 6 carbon atoms includes a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, Examples thereof include an isobutyl group, an n-amyl group, an isoamyl group, etc.
  • the alkoxyalkyl group having 2 to 6 carbon atoms include a methoxymethyl group, an ethoxymethyl group, a 1-methoxyethyl group, a 1-ethoxyethyl group, and a 1-methoxypropyl group.
  • Examples of the acyl group having 2 to 6 carbon atoms include acetyl group, propionyl group, tert-butylcarbonyl group and the like.
  • alkoxycarbonyl group methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, tert-butoxy And the like.
  • alkoxycarbonylalkyl group having 2 to 6 carbon atoms include tert-butoxycarbonylmethyl group.
  • Examples of the alkylsilyl group having 2 to 6 carbon atoms include trimethylsilyl group and tert-butyldimethylsilyl group. Groups and the like.
  • Examples of the oxystyrene monomer represented by the general formula (3) include p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, o Hydroxystyrenes such as isopropenylphenol; p-methoxystyrene, m-methoxystyrene, p-ethoxystyrene, m-ethoxystyrene, p-propoxystyrene, m-propoxystyrene, p-isopropoxystyrene, m-isopropoxy Alkoxystyrenes such as styrene, pn-butoxystyrene, mn-butoxystyrene, p-isobutoxystyrene, m-isobutoxystyrene, p-tert-but
  • oxystyrene monomers may be used alone or in combination of two or more.
  • the vinyl ether monomer and the oxystyrene monomer are sequentially subjected to living cationic polymerization to form a diblock arm.
  • the vinyl ether monomer is added to the reaction system to perform living cationic polymerization, Addition of oxystyrene monomer into the reaction system and living cationic polymerization (Method A), or addition of a mixture of vinyl ether monomer and oxystyrene monomer into the reaction system A method of performing living cationic polymerization (Method B) under a condition in which the reaction rate constant ratio between the monomer reaction rate constant k OS and the vinyl ether monomer reaction rate constant k VE is k VE / k OS ⁇ 1650 Can be mentioned.
  • living cationic polymerization of vinyl ether monomers proceeds by adding vinyl ether monomers to the reaction system.
  • a Lewis acid (I) suitable for living cationic polymerization of a vinyl ether monomer may be further added.
  • the Lewis acid (I) the same Lewis acid as the Lewis acid used in the nucleation step may be added, or a different Lewis acid may be added.
  • an oxystyrene monomer is added and polymerized, and bonded to the arm portion which is a vinyl ether polymer.
  • Lewis acid (II) a Lewis acid suitable for the living cationic polymerization of the monomer.
  • Examples of the Lewis acid (II) include metal halide compounds or organometallic halogen compounds composed of elements other than Al, and these compounds include TiCl 4 , TiBr 4 , BCl 3 , BF 3 , BF 3 .OEt. 2 , SnCl 2 , SnCl 4 , SbCl 5 , SbF 5 , WCl 6 , TaCl 5 , VCl 5 , FeCl 3 , ZnBr 2 , ZrCl 4 and the like. Of these, SnCl 4 , FeCl 3 and the like are preferably used as the Lewis acid (II).
  • Et 1.5 AlCl 1.5 is used as a Lewis acid in the nucleation step and vinyl ether monomer polymerization, and then SnCl 4 is additionally used in oxystyrene monomer polymerization to add oxystyrene monomer.
  • SnCl 4 is additionally used in oxystyrene monomer polymerization to add oxystyrene monomer.
  • a mixture of a vinyl ether monomer and an oxystyrene monomer is added to the reaction system.
  • a Lewis acid (I) suitable for living cationic polymerization of a vinyl ether monomer may be further added.
  • the same Lewis acid as the Lewis acid used in the nucleation step may be added, or a different Lewis acid may be added.
  • Lewis acid (II) may be added when a mixture of vinyl ether monomer and oxystyrene monomer is added to the reaction system, or added when the reaction of the vinyl ether monomer is completed. You may do it.
  • the amount of Lewis acid added in the arm formation step is not particularly limited, but can be set in consideration of the polymerization characteristics or polymerization concentration of the vinyl ether monomer and oxystyrene monomer used. Usually, it can be used in an amount of 0.1 to 100 mol%, preferably 1 to 50 mol%, based on various monomers.
  • Each polymerization condition varies depending on the kind of Lewis acid, starting species, monomer, solvent and the like used, but the polymerization temperature is usually preferably in the range of ⁇ 80 ° C. to 150 ° C., and in the range of ⁇ 78 ° C. to 80 ° C. The inside is more preferable.
  • the polymerization time is usually in the range of 10 hours to 250 hours.
  • the reaction rate constant ratio between the reaction rate constant k OS of the oxystyrene monomer and the reaction rate constant k VE of the vinyl ether monomer is k VE / k OS ⁇
  • the reaction rate constant k OS of the oxystyrene monomer and the reaction rate constant k VE of the vinyl ether monomer are the conversion of each monomer under the polymerization conditions in which the oxystyrene monomer and the vinyl ether monomer coexist.
  • the rate is obtained by monitoring the rate and varies depending on various factors such as the monomer, the polymerization temperature, the initiator, the Lewis acid, the type of the solvent, and so on.
  • the combination of monomer, polymerization temperature, initiator, Lewis acid, and solvent is not particularly limited as long as conditions such that k VE / k OS ⁇ 1650 can be expressed.
  • a vinyl ether monomer having a larger reaction rate constant and an oxystyrene monomer having a lower reaction rate because the reaction rate constant ratio is increased.
  • Suitable combinations of monomers include, for example, a combination of ethyl vinyl ether and p-tert-butoxystyrene.
  • k VE / k OS ⁇ 1650 can be satisfied by performing living cationic polymerization at ⁇ 30 ° C. or lower, preferably ⁇ 40 ° C. or lower, and a diblock arm is formed quantitatively. can do.
  • a polymerization terminator is added at a desired degree of polymerization to stop the polymerization reaction. If necessary, catalyst residues such as metal compounds are removed, and (1) volatile matter is removed from the polymer solution. It can be isolated by a method of evaporating, or (2) a method of adding a large amount of a poor solvent and precipitating and separating the polymer.
  • reaction terminator examples include alcohols such as methanol, ethanol, and propanol; amines such as dimethylamine and diethylamine; compounds that act as end terminators such as water, aqueous ammonia, and aqueous sodium hydroxide, and / or Lewis.
  • alcohols such as methanol, ethanol, and propanol
  • amines such as dimethylamine and diethylamine
  • compounds that act as end terminators such as water, aqueous ammonia, and aqueous sodium hydroxide, and / or Lewis.
  • a compound having a function of deactivating the acid activity is used.
  • a method of removing the metal compound which is a Lewis acid a method of treating with water or an aqueous solution containing an acid such as hydrochloric acid, nitric acid, sulfuric acid; a method of treating with an inorganic oxide such as silica gel, alumina, silica-alumina; The method etc. which process with an ion exchange resin are mentioned.
  • a method of treating with an ion exchange resin is most preferable.
  • Cation exchange resin is effective for removing metal ions.
  • the cation exchange resin may be used as a cation exchange resin.
  • a mixture of resin and anion exchange resin may be used.
  • Examples of the cation exchange resin include strongly acidic cation exchange such as Amberlyst 15DRY (trade name) manufactured by Organo Corporation, Diaion SK1BH, SK104H, PK208H, PK216H, PK228H (trade name) manufactured by Mitsubishi Chemical Corporation. Resin etc. are mentioned.
  • Examples of the mixed bed ion exchange resin include a mixture of a strongly acidic cation exchange resin such as Amberlyst MSPS2-1 ⁇ DRY (trade name) manufactured by Organo Corporation and a weakly basic anion exchange resin.
  • the substituent R 5 and the substituent R 6 of the oxystyrene monomer (3) may be easily removed by acid or alkali to give a hydroxyl group.
  • the oxystyrene having such a substituent It is also possible to deprotect a star polymer obtained by using a monomer and obtain a star polymer having a hydroxystyrene-based repeating unit in the arm.
  • a star-shaped polymer having a hydroxystyrene-based polymer as an arm obtained by deprotecting such a protecting group for example, in a solvent, under an acid catalyst such as hydrochloric acid or sulfuric acid, or an aqueous sodium hydroxide solution
  • the reaction may be carried out under alkaline conditions at a reaction temperature of 50 to 150 ° C. for a reaction time of 1 to 30 hours to remove the protecting group.
  • Weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) It was determined from a standard polystyrene calibration curve by gel permeation chromatography (GPC) method [RI detector; columns are LF804 ⁇ 3 manufactured by Shodex; eluent is tetrahydrofuran].
  • GPC gel permeation chromatography
  • Absolute molecular weight (Mwavesolute) The absolute molecular weight was determined by gel permeation chromatography (GPC) -viscosity method. [RI detector; viscometer; column, Shodex KF-800D + KF-805L ⁇ 2; eluent is tetrahydrofuran].
  • Number of branches (f) The number of branches (f) was calculated according to the following formula.
  • f A ⁇ B / C
  • Particle size The particle size was analyzed by dynamic light scattering (DLS) (manufactured by Otsuka Electronics Co., Ltd.) [eluent is tetrahydrofuran].
  • DLS dynamic light scattering
  • Example 1 Core-ethyl vinyl ether-p-tert-butoxystyrene copolymer Production of a star polymer (arm formation by method A): A glass container with a three-way stopcock was prepared, and after substituting with argon, it was heated in an argon atmosphere to remove adsorbed water in the glass container.
  • IBEA 1-isobutoxyethyl acetate 14.8 millimolar (hereinafter abbreviated as “mM”), 1,4-bis (vinyloxymethyl) cyclohexane (hereinafter referred to as “CHDVE”) 29.5 mM, ethyl acetate 3.7 moler (hereinafter abbreviated as “M”) and 185 ml of toluene were cooled.
  • EVE ethyl vinyl ether
  • PTBOS p-tert-butoxystyrene
  • SnCl 4 186 mM
  • methanol was added to the polymerization system to stop the reaction.
  • Example 2 Core-ethyl vinyl ether-p-tert-butoxystyrene copolymer Production of a star polymer (arm formation by method B): A glass container with a three-way stopcock was prepared, and after substituting with argon, it was heated in an argon atmosphere to remove adsorbed water in the glass container. IBEA 14.8 mM, CHDVE 29.5 mM, ethyl acetate 3.7 M, and toluene 185 ml were placed in a container and cooled.
  • Example 3 Core-ethyl vinyl ether-p-isopropenylphenol copolymer system Production of star polymer (arm formation by method A): A glass container with a three-way stopcock was prepared, and after substituting with argon, it was heated in an argon atmosphere to remove adsorbed water in the glass container. IBEA 14.8 mM, CHDVE 29.5 mM, ethyl acetate 3.7 M, and toluene 185 ml were placed in a container and cooled.
  • PIPP p-isopropenylphenol
  • Comparative Example 1 Core-p-tert-butoxystyrene-ethyl vinyl ether copolymer type production of star polymer (when oxystyrene monomer and vinyl ether monomer are reacted in this order): A glass container with a three-way stopcock was prepared, and after substituting with argon, it was heated in an argon atmosphere to remove adsorbed water in the glass container. IBEA 14.8 mM, CHDVE 29.5 mM, ethyl acetate M, and 185 ml of toluene were placed in the container and cooled.
  • k EVE / k TBOS which is the ratio of the reaction rate constant k TBOS of PTBOS and the reaction rate constant k EVE of EVE , was calculated to be 1600. Further, it was confirmed that the reaction of PTBOS had occurred before the conversion rate of EVE reached 100%, and it was not possible to obtain the target star polymer.
  • a vinyl ether star polymer in which a vinyl ether arm and an oxystyrene arm are sequentially copolymerized from a nucleus which has been complicated in the conventional synthesis, can be produced by a simple method.
  • the manufacturing method of the vinyl ether-type star polymer of the present invention can be carried out in one pot, the manufacturing process and the manufacturing equipment can be greatly simplified, which is extremely advantageous industrially compared with various conventional methods. .
  • the arm is a diblock copolymer of an oxystyrene polymer and a vinyl ether polymer, and the photosensitivity suitable for applications such as an interlayer insulating film and a surface protective film of a semiconductor element.
  • a vinyl ether-based star polymer that can be suitably used as a raw material for the resin component can be produced with high economic efficiency, and can be widely used in the field of electronic material production.

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Abstract

La présente invention concerne un procédé de production qui peut être exécuté en continu en une série d'étapes et qui est à destination d'un polymère d'éther vinylique en forme d'étoile dans lequel un bras comprenant un polymère d'éther vinylique et un bras comprenant un polymère d'oxystyrène sont co-polymérisés en séquence à partir d'un noyau. Ledit procédé de production est caractérisé par l'adjonction d'un acide de Lewis à la solution réactionnelle contenant au moins un germe de départ, un solvant, et un composé divinylique, la synthèse d'un polymère d'éther vinylique ayant uniquement des groupes vinyle sur les chaînes latérales, la production d'un noyau par réticulation intermoléculaire desdites chaînes latérales de groupes vinyle, puis par l'adjonction d'un monomère d'éther vinylique et d'un monomère d'oxystyrène, provoquant la polymérisation cationique vivante du polymère d'éther vinylique et du polymère d'oxystyrène en séquence, formant des bras di-séquencés.
PCT/JP2010/069795 2009-12-09 2010-11-08 Procédé de production d'un polymère d'éther vinylique en forme d'étoile Ceased WO2011070880A1 (fr)

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