WO2017043373A1 - 片末端に置換基を有する(メタ)アクリル系重合体の製造方法 - Google Patents
片末端に置換基を有する(メタ)アクリル系重合体の製造方法 Download PDFInfo
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- WO2017043373A1 WO2017043373A1 PCT/JP2016/075331 JP2016075331W WO2017043373A1 WO 2017043373 A1 WO2017043373 A1 WO 2017043373A1 JP 2016075331 W JP2016075331 W JP 2016075331W WO 2017043373 A1 WO2017043373 A1 WO 2017043373A1
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- 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
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/38—Esters containing sulfur
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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
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/12—Esters of monohydric alcohols or phenols
- C08F20/14—Methyl esters, e.g. methyl (meth)acrylate
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- 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
- C08F2/00—Processes of polymerisation
- C08F2/02—Polymerisation in bulk
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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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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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
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/12—Esters of monohydric alcohols or phenols
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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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
- C08F4/74—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals
- C08F4/76—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals selected from titanium, zirconium, hafnium, vanadium, niobium or tantalum
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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
- C08F2810/00—Chemical modification of a polymer
- C08F2810/40—Chemical modification of a polymer taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains
Definitions
- the present invention relates to a method for producing a (meth) acrylic polymer having a functional group at one end of a molecule, preferably by bulk polymerization, while having a high polymerization rate and a high functional group introduction rate and suppressing disulfide formation. .
- the (meth) acrylic polymer having a substituent at one end of the molecule can be used as a raw material for the block polymer or graft polymer.
- a method for producing a (meth) acrylic polymer having a substituent at one end of a molecule a compound having a thiol and a functional group described in Patent Document 1 and Patent Document 2 is used as a starting species (meta )
- a method of polymerizing an acrylic monomer, a method of polymerizing a halide described in Patent Document 3 as a starting species, and then substituting the halogen with a substituent are known.
- the methods described in Patent Document 1 and Patent Document 2 employ a bulk polymerization reaction, and since the reaction is slow, the reaction control is easy and there is an advantage that it is suitable for mass production.
- the (meth) acrylic polymer produced by such a method has a low polymerization stability and tends to have a low blocking rate and a grafting rate during the production of the block polymer and graft polymer.
- the polymerization reaction is carried out in an inert gas atmosphere, resulting in a low introduction rate of substituents.
- the present invention has a high functional group introduction rate of a (meth) acrylic polymer having a functional group at the end of a molecular piece, and suppresses the formation of disulfide as an impurity, and is preferably efficiently produced by a bulk polymerization method. It aims to provide a method.
- the present invention provides a (meth) acrylic monomer using as a starting species a compound having a functional group other than a thiol group and a thiol group in the presence of an inert gas containing 0.01 to 6.0 vol% oxygen.
- a method for producing a (meth) acrylic polymer having a functional group at one end by polymerization reaction of a monomer mixture containing is a method for producing a (meth) acrylic monomer having a functional group at one end by polymerization reaction of a monomer mixture containing.
- the polymerization reaction of the (meth) acrylic monomer is preferably performed in the presence of a metallocene catalyst.
- the functional group is preferably at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an alkoxysilyl group, an allyl group, and an amino group.
- a compound having a functional group other than a thiol group and a thiol group has a monomer mixture containing the (meth) acrylic monomer, and a functional group other than the thiol group and a thiol group. It is preferably used in an amount within the range of 0.1 to 50 parts by weight with respect to 100 parts by weight of the total amount of the compound.
- the polymerization reaction is usually a bulk polymerization reaction.
- the polymerization reaction is preferably carried out at a temperature within the range of 60 to 200 ° C.
- the metallocene catalyst is added in an amount of 0. 1 to 100 parts by weight in total of the monomer mixture containing the (meth) acrylic monomer and the compound having a functional group other than the thiol and a thiol group. It is preferably used in an amount within the range of 001 to 5.0 parts by weight.
- the polymerization reaction of a (meth) acrylic monomer is preferably carried out by a bulk polymerization method using a compound having a functional group other than a thiol group and a thiol group as a starting species.
- a compound having a functional group other than a thiol group and a thiol group as a starting species.
- the block ratio and the graft ratio can be improved in the production of the block and graft polymer using the obtained (meth) acrylic polymer.
- the compound serving as the starting species is a compound having a functional group other than a thiol group and a thiol group.
- the functional group is preferably at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an alkoxysilyl group, an allyl group, and an amino group. These functional groups may be contained singly or in combination in the compound.
- Examples of such a compound having a functional group and a thiol group include mercaptomethanol, 1-mercaptoethanol, 2-mercaptoethanol, 1-mercaptopropanol, 3-mercaptopropanol, 1-mercapto-2,3-propanediol, 1-mercapto-2-butanol, 1-mercapto-2,3-butanediol, 1-mercapto-3,4-butanediol, 1-mercapto-3,4,4′-butanetriol, 2-mercapto-3- A hydroxyl group-containing thiol compound whose functional group is a hydroxyl group such as butanol, 2-mercapto-3,4-butanediol, 2-mercapto-3,4,4′-butanetriol, and thioglycerol; ⁇ -mercaptopropionic acid, ⁇ -mercaptopropionic acid, 2,3-dimercaptopropionic acid, thioglycolic acid, o-
- the above compound when used as a starting species, the above compound is usually used alone.
- the compound that is polymerized using the above compound as the starting species is a compound having an ethylenically unsaturated double bond, and a typical example includes a (meth) acrylic monomer.
- (Meth) acrylic monomer used in the present invention is mainly composed of (meth) acrylic acid alkyl ester.
- the alkyl chain in the (meth) acrylic acid alkyl ester may be linear or branched, and examples thereof include an alkyl chain having 1 to 36 carbon atoms.
- alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, (meth ) Hexyl acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, Stearyl (meth) acrylate, icosyl (meth) acrylate, docosyl (meth) acrylate, isostearyl (meth) acrylate, octadecyl (meth) acrylate, heptadecyl (meth) acrylate, behenyl (meth) acrylate
- the (meth) acrylic monomer used in the present invention may be one monomer of (meth) acrylic acid alkyl ester, but may be a combination of two or more monomers.
- the alkyl acrylate ester is in an amount of 50 to 100 parts by weight, preferably 70 to 100 parts by weight, more preferably 90 to 100 parts by weight, based on 100 parts by weight of the monomer mixture.
- salts such as (meth) acrylic acid and alkali metal salts of (meth) acrylic acid;
- acrylic acid aryl esters such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate;
- acrylic acid alkoxyalkyl esters such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxypropyl (meth) acrylate ;
- (Meth) acrylonitrile vinyl acetate;
- Vinyl halide compounds such as vinyl chloride, vinylidene chloride, 2-chloroethyl (meth) acrylate;
- macromonomer having a radical polymerizable vinyl group at the terminal of the monomer obtained by polymerizing vinyl group for example, fluorine-based macromonomer, silicon-containing macromonomer, etc.
- Such a monomer other than (meth) acrylic acid alkyl ester is 0 to 50 parts by weight, preferably 0 to 30 parts by weight, more preferably 0 to 10 parts by weight with respect to 100 parts by weight of the monomer mixture. It is.
- the polymerization reaction using the starting species as described above is usually performed by a bulk polymerization method without using a solvent.
- the compound having a thiol group and a functional group other than a thiol group used as a starting species is a monomer mixture containing the (meth) acrylic monomer and a functional group other than the thiol group. Is used in an amount in the range of 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight with respect to 100 parts by weight of the total of the compound having a thiol group. If the compound having the functional group and thiol group used as the starting species is below the lower limit, the polymerization reaction may not proceed efficiently, and if the upper limit is exceeded, the polymerization reaction proceeds too quickly and the reaction is controlled. There are things that cannot be done.
- the reaction proceeds by heating the reaction system, but in the present invention, it is preferable to use a metallocene catalyst as the catalyst.
- a metallocene catalyst used in the present invention, a compound represented by the following formula (I) can be used.
- M is a metal selected from the group consisting of Group 4, Group 5, Group 14 and Group 15 metals, Cobalt, Chromium, Ruthenium and Palladium, and R1 and R2 are each independently
- an aliphatic hydrocarbon group which may have a substituent an alicyclic hydrocarbon group which may have a substituent, an aromatic hydrocarbon group which may have a substituent and a silicon which may have a substituent
- a 5-membered ring may be bonded, and a plurality of adjacent R 1 or R 2 may jointly form a cyclic structure, and a and b are each independently an integer of 1 to 5 Yes
- X is hydrogen At least a part of the atoms is a hydrocarbon group or a halogen atom that may be substituted with a halogen
- metallocene catalysts include dicyclopentadiene-Ti-dichloride, dicyclopentadiene-Ti-bisphenyl, dicyclopentadiene-Ti-bis-2,3,4,5,6-pentapentane.
- Fluorophen-1-yl dicyclopentadiene-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, dicyclopentadiene-Ti-bis-2,5,6-trifluorophen-1 -Yl, dicyclopentadiene-Ti-bis-2,6-difluorophen-1-yl, dicyclopentadiene-Ti-bis-2,4-difluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis -2,3,4,5,6-pentafluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis-2,3,5 6-tetrafluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis-2,6-difluoro-3- ( Titanocene compounds such as pyr
- the metallocene catalyst is usually 0.001 to 5.0 parts by weight, preferably 0.001 parts by weight with respect to a total of 100 parts by weight of the monomer mixture containing the (meth) acrylic monomer and the starting species. Used in an amount in the range of 005 to 0.5 parts by weight. If the amount of the metallocene catalyst falls below the lower limit, the effect of using the metallocene catalyst may not appear. May not be obtained.
- the polymerization reaction is usually carried out by a bulk polymerization method using the above components.
- the reaction is carried out in an inert gas atmosphere containing a small amount of oxygen. That is, in the copolymerization using the above components, the reaction is generally performed after sufficiently replacing the air present in the reaction system with an inert gas such as nitrogen gas.
- an inert gas such as nitrogen gas.
- the polymer obtained by carrying out the polymerization reaction in an inert gas atmosphere in the absence of oxygen tends to have a reduced grafting rate during the production of the graft polymer.
- the polymerization reaction is carried out using an inert gas containing 0.01 to 6.0 vol% oxygen. Further, it is preferable to use an inert gas containing 0.05 to 1.0 vol% oxygen.
- the inert gas used here include nitrogen gas, argon gas, xenon gas, and carbon dioxide gas. In the present invention, nitrogen gas is preferably used.
- oxygen contained in the inert gas becomes a tray for protons released from the —SH group, stabilizes the reaction system, and suppresses the formation of disulfide.
- Such an action of oxygen is recognized within an oxygen concentration range of 0.01 to 6.0 vol%, preferably 0.05 to 1.0 vol%. Below this lower limit, the above-described effects are obtained. unacceptable. Also, the polymerization rate tends to be low. On the other hand, when the above upper limit is exceeded, the polymerization reaction is affected, and the formation reaction of the (meth) acrylic polymer having one terminal functional group is not stabilized.
- the inert gas containing 0.01 to 6.0 vol% of oxygen is sufficient if the air in the container is sufficiently substituted, and is usually 2 to 20 times, preferably 3 times the volume of the reaction container.
- the gas in the reaction vessel is replaced by circulating an inert gas containing oxygen up to 10 times.
- a polymerization reaction is carried out using a compound having a functional group and a thiol group in the group under the above conditions as an initiator.
- This polymerization reaction is usually performed under normal pressure conditions, but may be performed under pressure or reduced pressure.
- the reaction temperature is usually set to a temperature in the range of 60 to 200 ° C, preferably 60 to 150 ° C, more preferably 60 to 120 ° C.
- the reaction temperature may be set in multiple stages. That is, the reaction may be performed at a relatively low temperature immediately after the start of the reaction, and then the reaction temperature may be increased.
- the reaction time is usually set in the range of 30 minutes to 24 hours, preferably 1 hour to 15 hours.
- Said polymerization rate can be calculated
- the temperature of the reaction product can be returned to room temperature, and the reaction product can be completely stopped by adding a reaction inhibitor such as benzoquinone.
- This reaction inhibitor is usually dissolved in an organic solvent such as tetrahydrofuran (THF) and added to the reaction.
- the reaction product is obtained as a THF solution, and this THF solution contains the reaction product, unreacted monomer, unreacted starting species, disulfide and the like. Unreacted monomers, unreacted starting species, and THF as a solvent can be distilled off by vacuum distillation using a vacuum evaporator or the like.
- the reactant obtained as described above is a (meth) acrylic polymer having a functional group derived from the starting species at one end of the molecule.
- a (meth) acrylic polymer having a functional group derived from the starting species at one end of the molecule For example, when 2-mercaptoethanol is used as the starting species. Thus, a polymer having a thioethanol group at one end of the polymer molecule can be obtained.
- 3-mercaptopropanol is used as a starting species, a polymer having a thiopropanol group at one end of the polymer molecule is obtained.
- ⁇ -mercaptopropionic acid is used as the starting species, a polymer having a thiopropionic acid group bonded to one end of the polymer molecule can be obtained, and 2- (dimethylamino) ethanethiol can be obtained.
- the functional group bonded to one end of such a polymer is determined based on the amount of the starting seed and the introduction rate at one end of the polymer obtained from the measurement according to the functional group such as hydroxyl value, acid value, and amine value. Can be calculated and confirmed.
- the reaction product thus obtained has a weight average molecular weight measured by gel permeation chromatography (GPC) in the range of usually 500 to 100,000, preferably 1,000 to 30,000.
- GPC gel permeation chromatography
- the polymerization rate is 80% or more and the functional group introduction rate is 90% or more.
- the amount of disulfide contained can be suppressed within the range of 5 to 20 ppm. This is 1/2 to 1/4 of the amount of disulfide contained in the polymer obtained by carrying out in an inert atmosphere containing no oxygen.
- the (meth) acrylic polymer having a polar group at one end obtained by the production method of the present invention has a high polymerization rate and substituent introduction rate, and a graft polymer using this polymer has high grafting. Have a rate.
- GCM degree of branching
- This degree of branching can be measured with a gel permeation chromatograph-multi-angle light scattering photometer (GPC-MALS).
- a polymerization reaction that has been conventionally performed in an inert gas atmosphere in the absence of oxygen is performed in an inert gas atmosphere to which a small amount of oxygen is added, thereby providing high uniformity (meta).
- An acrylic polymer can be produced efficiently.
- the (meth) acrylic polymer obtained by the production method of the present invention can be suitably used as a raw material for a block polymer or a graft polymer without causing a decrease in the blocking rate and grafting rate.
- Example 1 A 1-liter flask equipped with a stirrer, a gas inlet tube, a thermometer and a reflux condenser was charged with 90 parts by weight of 2-ethylhexyl acrylate (2EHA) and 0.3 part by weight of titanocene dichloride as a catalyst. Nitrogen gas containing oxygen in an amount of 0.3 vol% from the tube was 0.1 liter / min. The gas in the flask was replaced by continuing to flow at a speed of 60 minutes, and the contents in the flask were heated to 95 ° C.
- 2EHA 2-ethylhexyl acrylate
- titanocene dichloride titanocene dichloride
- the residual monomer ratio was measured using gas chromatography, and the polymerization rate was determined.
- the polymerization rate was 86.2%.
- the obtained reaction product was transferred to an evaporator, and the residual monomer and residual thiol compound were removed while gradually heating to 80 ° C. under reduced pressure.
- the molecular weight of the polymer thus obtained measured using gel permeation chromatography (GPC) was 1,100. Moreover, when the hydroxyl group introduction rate was calculated as a ratio of the amount of the starting species used and the amount of the hydroxyl group obtained from the measured value of the hydroxyl value of the obtained polymer, it was 98.2%, with a high probability at one end.
- the polymer was introduced with a hydroxyl group.
- Examples 2 to 12 Comparative Examples 1 and 2
- Polymerization was carried out in the same manner as in Example 1 except that the monomer composition and the oxygen content were changed as shown in Table 1.
- the functional group introduction rate for Example 5 was calculated from the measured value of the acid value
- the functional group introduction rate for Example 7 was calculated from the measured value of the amine value. The results are shown in Table 1.
- Example 13 A 1 liter flask equipped with a stirrer, a thermometer and a reflux condenser was charged with the polymer obtained in Example 2 and Karenz AOI manufactured by Showa Denko K.K. The mixture was heated and stirred at ° C for 6 hours to obtain a polymer (macromonomer) having an acryloyl group.
- a 1 liter flask equipped with a stirrer, gas inlet tube, thermometer and reflux condenser was charged with 30 parts by weight of macromonomer, 70 parts by weight of 2EHA, and 100 parts by weight of ethyl acetate. The contents in the flask were heated to 75 ° C. while continuing to introduce in an amount of 10 liters per part per hour.
- 0.1 part by weight of azoisobutyronitrile (AIBN) was added to the flask with stirring. After the AIBN addition, cooling and heating were performed for 2 hours so that the contents in the stirring flask could be maintained at 75 ° C. Thereafter, 0.3 part by weight of AIBN was added with stirring, and the contents in the flask were heated and cooled so that the contents in the flask could be maintained at 75 ° C., and further reacted for 6 hours.
- Example 3 A macromonomer was obtained in the same manner as in Example 13, except that the polymer obtained in Example 2 was replaced with the polymer obtained in Comparative Example 1. When the obtained macromonomer was used to prepare a graft polymer in the same manner as in Example 13, the degree of branching gM was 0.65.
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Abstract
Description
ここで、分子の片末端に置換基を有する(メタ)アクリル系重合体を製造する方法としては、特許文献1および特許文献2に記載のチオールと官能基とを有する化合物を開始種として(メタ)アクリル系単量体を重合反応させる方法、特許文献3に記載のハロゲン化物を開始種として重合反応させた後、ハロゲンを置換基に置き換える方法等が知られている。
特に特許文献1および特許文献2に記載の方法は、塊状重合反応を採用しており、反応が緩やかであるために反応制御が容易であり、大量生産に適しているとの利点がある。
この原因について本発明者は慎重に検討した結果、不活性ガス雰囲気下で重合反応を行うことにより、置換基の導入率が低いことに起因していることがわかった。
本発明では、上記官能基が、水酸基、カルボキシル基、アルコキシシリル基、アリル基、アミノ基よりなる群から選ばれる少なくとも一種類の基であることが好ましい。
本発明では、上記重合反応の反応温度を、60~200℃の範囲内の温度で行うことが好ましい。
本発明の(メタ)アクリル系ポリマーの製造方法において、開始種となる化合物は、チオール基以外の官能基およびチオール基を有する化合物である。
α-メルカプトプロピオン酸、β-メルカプトプロピオン酸、2,3-ジメルカプトプロピオン酸、チオグリコール酸、o-メルカプト安息香酸、m-メルカプト安息香酸、チオリンゴ酸、チオール炭酸、o-チオクマル酸、α-メルカプトブタン酸、β-メルカプトブタン酸、γ-メルカプトブタン酸、チオヒスチジンおよび11-メルカプトウンデカン酸のように官能基がカルボキシル基である化合物;
3-メルカプトプロピル-トリメトキシシラン、3-メルカプトプロピル-トリエトキシシラン、3-メルカプトプロピル-モノメチルジメトキシシラン、3-メルカプトプロピル-モノフェニルジメトキシシラン、3-メルカプトプロピル-ジメチルモノメトキシシラン、3-メルカプトプロピル-モノメチルジエトキシシラン、4-メルカプトブチル-トリメトキシシラン及び3-メルカプトブチル-トリメトキシシラン等のアルコキシシリル基含有チオール化合物;
アリルメルカプタンのように官能基がアリル基である化合物;
2-(ジメチルアミノ)エタンチオール、システアミン、2-アミノチオフェノール、4-アミノチオフェノール、6-アミノ-1-ヘキサンチオール、11-アミノ-1-ウンデカンチオールのように官能基がアミノ基である化合物;を挙げることができる。
上記化合物を開始種として重合する化合物は、エチレン性不飽和二重結合を有する化合物であり、代表的な例としては(メタ)アクリル系単量体を挙げることができる。
(メタ)アクリル酸および(メタ)アクリル酸アルカリ金属塩などの塩;
(メタ)アクリル酸フェニル、(メタ)アクリル酸ベンジル、(メタ)アクリル酸フェノキシエチルのような(メタ)アクリル酸アリールエステル;
(メタ)アクリル酸メトキシエチル、(メタ)アクリル酸エトキシエチル、(メタ)アクリル酸プロポキシエチル、(メタ)アクリル酸ブトキシエチル、(メタ)アクリル酸エトキシプロピルのような(メタ)アクリル酸アルコキシアルキルエステル;
(メタ)アクリロニトリル;酢酸ビニル;
塩化ビニル、塩化ビニリデン、(メタ)アクリル酸-2-クロロエチルのようなハロゲン化ビニル化合物;
(メタ)アクリル酸シクロヘキシルのような脂環式アルコールの(メタ)アクリル酸エステル;
2-ビニル-2-オキサゾリン、2-ビニル-5-メチル-2-オキサゾリン、2-イソプロペニル-2-オキサゾリンのようなオキサゾリン基含有重合性化合物;
(メタ)アクリロイルアジリジン、(メタ)アクリル酸-2-アジリジニルエチルのようなアジリジン基含有重合性化合物;
アリルグリシジルエーテル、(メタ)アクリル酸グリシジルエーテル、(メタ)アクリル酸-2-エチルグリシジルエーテルのようなエポキシ基含有ビニル単量体;
(メタ)アクリル酸-2-ヒドロキシエチル、(メタ)アクリル酸-2-ヒドロキシプロピル、(メタ)アクリル酸ポリプロピレングリコールとポリエチレングリコールとのモノエステル、ラクトン類と(メタ)アクリル酸-2-ヒドロキシエチルとの付加物のようなヒドロキシル基含有ビニル化合物;
フッ素置換(メタ)アクリル酸アルキルエステル等の含フッ素ビニル単量体;
(メタ)アクリル酸を除く、イタコン酸、 クロトン酸、マレイン酸、フマル酸のような不飽和カルボン酸、これらの塩並びにこれらの(部分)エステル化合物および酸無水物;
2-クロルエチルビニルエーテル、モノクロロ酢酸ビニルのような反応性ハロゲン含有ビニル単量体;
(メタ)アクリルアミド、N-メチロール(メタ)アクリルアミド、N-メトキシ エチル(メタ)アクリルアミド、N-ブトキシメチル(メタ)アクリルアミドのようなアミド基含有ビニル単量体;
ビニルトリメトキシシラン、γ-メタクリロキシプロピルトリメトキシシラン、アリルトリメトキシシラン、トリメトキシシリルプロピルアリルアミン、2-メトキシエトキシトリメトキシシランのような有機ケイ素基含有ビニル化合物単量体;ならびに、
エチルデンノルボルネン、ピペリジン、イソプレン、ペンタジエン、ビニルシクロヘキセン、クロロプレン、ブタジエン、メチルブタジエン、シクロブタジエン、メチルブタジエンのようなジエン化合物等を挙げることができる。
上記のような開始種を用いた重合反応は、通常は、溶媒を用いない塊状重合法により行われる。
本発明に使用するメタロセン系触媒としては次式(I)で表される化合物を用いることができる。
即ち、上記のような成分を用いた共重合に際しては、反応系に存在する空気を窒素ガスなどの不活性ガスで充分に置換した後、反応を行うのが一般的である。しかしながら、酸素が不存在の不活性ガス雰囲気下で重合反応を行って得られた重合体は、グラフトポリマーの製造時にグラフト化率が低下するという傾向がある。
この置換基導入率低下を抑制するために、不活性ガス中に微量の酸素を含有させることが有効である。
この重合反応は、通常は常圧条件で行われるが、加圧条件下あるいは減圧条件下で行ってもよい。
上記のようにして重合反応を行うことにより、通常は使用した原料の50重量%以上、好ましくは80重量%以上が反応する(重合率)。
上記の反応時間が経過後、反応物の温度を室温まで戻し、反応物にベンゾキノンのような反応禁止剤を加えることにより完全に停止させることができる。この反応禁止剤は通常はテトラヒドロフラン(THF)のような有機溶媒に溶解して反応物に添加する。
〔実施例1〕
攪拌装置、ガス導入管、温度計および還流冷却管を備えた容量1リットルのフラスコに、2-エチルヘキシルアクリレート(2EHA)90重量部および触媒としてチタノセンジクロライド0.3重量部の量で仕込み、ガス導入管から酸素を0.3vol%の量で含む窒素ガスを0.1リットル/min.の速度で60分間流し続けることでフラスコ内のガスを置換し、フラスコ内の内容物を95℃に加熱した。
2-メルカプトエタノール添加後、攪拌中のフラスコ内の内容物が95℃を維持できるように冷却および加熱を2時間行った。その後、フラスコ内の内容物を100℃に維持できるように加熱および冷却を行ってさらに8時間反応させた。
次いで、得られた反応物をエバポレータに移し、減圧下に80℃まで徐々に加熱しながら残存モノマーおよび残存チオール化合物を除去した。
また得られた重合体について、用いた開始種量と、水酸基価の測定値から得られた水酸基量の割合として水酸基導入率を計算したところ、98.2%であり、高い確率で片末端に水酸基が導入されたポリマーであった。
結果を表1に示す。
実施例1において、モノマー組成及び酸素量を表1のように変更した以外は同様にして重合を行った。また、実施例5についての官能基導入率は酸価の測定値から、実施例7についての官能基導入率はアミン価の測定値から算出を行った。
結果を表1に示す。
攪拌装置、温度計および還流冷却管を備えた容量1リットルのフラスコに実施例2において得られたポリマーと昭和電工(株)製カレンズAOIを水酸基とイソシアネート基が等量となるように仕込み、70℃で6時間加熱攪拌し、アクリロイル基を有するポリマー(マクロモノマー)を得た。攪拌装置、ガス導入管、温度計および還流冷却管を備えた容量1リットルのフラスコにマクロモノマー30重量部、2EHA70重量部、酢酸エチル100重量部を仕込み、ガス導入管から窒素ガスをモノマー100重量部当たり1時間に10リットルとなる量で導入し続けながら、フラスコ内の内容物を75℃に加熱した。次いでアゾイソブチロニトリル(AIBN)を0.1重量部を攪拌下にフラスコ内に添加した。AIBN添加後、攪拌中のフラスコ内の内容物が75℃を維持できるように冷却および加熱を2時間行った。その後、AIBN0.3重量部を攪拌下に添加し、フラスコ内の内容物を75℃に維持できるように加熱および冷却を行ってさらに6時間反応させた。こうして得られた重合体についてゲルパミエーションクロマトグラフィ(GPC)を用いて測定した分子量はMwが50万であった。また、GPC-MALSによって分岐度gMを測定したところ、gM=0.55であった。
実施例13において、実施例2で得られたポリマーを比較例1で得られたポリマーに置き換えたこと以外は同様にしてマクロモノマーを得た。得られたマクロモノマーを実施例13と同様にして、グラフトポリマーを作成したところ、分岐度gMは0.65であった。
Claims (5)
- 酸素を0.01~6.0vol%含有する不活性ガスの存在下に、チオール基以外の官能基とチオール基とを有する化合物を開始種として、(メタ)アクリル系単量体を含有する単量体混合物を重合反応させて、片末端に官能基を有する(メタ)アクリル系重合体を製造する方法。
- 上記(メタ)アクリル系単量体を含有する単量体混合物の重合反応を、メタロセン系触媒の存在下に行い、前記メタロセン系触媒が(メタ)アクリル系単量体を含有する単量体混合物および、上記チオール基以外の官能基とチオール基とを有する化合物の合計100重量部に対して0.001~5.0重量部の範囲で使用することを特徴とする、請求項1に記載の(メタ)アクリル系重合体の製造方法。
- 上記官能基が、水酸基、カルボキシル基、アルコキシシリル基、アリル基、アミノ基よりなる群から選ばれる少なくとも一種類の基であることを特徴とする請求項1または請求項2に記載の(メタ)アクリル系重合体の製造方法。
- 上記(メタ)アクリル系単量体を含有する単量体混合物および、前記チオール基以外の官能基とチオール基とを有する化合物の合計100重量部に対して、上記チオール基以外の官能基とチオール基とを有する化合物を0.1~50重量部の範囲内の量で使用することを特徴とする請求項1ないし請求項3のいずれかの項に記載の(メタ)アクリル系重合体の製造方法。
- 上記重合反応が、塊状重合反応であることを特徴とする請求項1または請求項4に記載の(メタ)アクリル系重合体の製造方法。
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