WO2014076909A1 - (メタ)アクリル変性ポリブタジエンの製造方法 - Google Patents
(メタ)アクリル変性ポリブタジエンの製造方法 Download PDFInfo
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- WO2014076909A1 WO2014076909A1 PCT/JP2013/006549 JP2013006549W WO2014076909A1 WO 2014076909 A1 WO2014076909 A1 WO 2014076909A1 JP 2013006549 W JP2013006549 W JP 2013006549W WO 2014076909 A1 WO2014076909 A1 WO 2014076909A1
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- polybutadiene
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- modified polybutadiene
- acrylic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
- C08C19/34—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with oxygen or oxygen-containing groups
- C08C19/38—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with oxygen or oxygen-containing groups with hydroxy radicals
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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
- C08F18/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F18/14—Esters of polycarboxylic acids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/31—Aluminium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2347/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Derivatives of such polymers
Definitions
- the present invention relates to a method for producing acrylic-modified polybutadiene. More specifically, the present invention relates to a method for producing (meth) acryl-modified polybutadiene having no coloring or white turbidity without using a tin compound.
- This application claims priority to Japanese Patent Application No. 2012-249329 filed on November 13, 2012, the contents of which are incorporated herein by reference.
- Polybutadiene can be cured by heat, ultraviolet light, electron beam or the like.
- a cured product of polybutadiene is a resin material having excellent water resistance, moisture resistance, chemical resistance, electrical properties (high dielectric strength, low dielectric constant, arc resistance), transparency, and high toughness.
- modified polybutadiene has been proposed which has improved curability by heat, ultraviolet rays or electron beams by introducing a polymerizable functional group such as an acryloyl group or a methacryloyl group at the end of polybutadiene (Patent Documents 1 and 2).
- terminal (meth) acryl-modified polybutadiene is produced by reacting 1,2-polybutadienediol and (meth) acrylic acid ester in the presence of an acid catalyst such as p-toluenesulfonic acid.
- Patent Document 2 a (meth) acryl-modified polybutadiene is reacted by reacting a hydroxyl group-containing polybutadiene with a (meth) acrylic acid ester in the presence of a tetraalkoxytitanium catalyst, a dialkyltin dicarboxylate catalyst, or a dialkyltin oxide catalyst.
- Patent Document 1 has a problem that acidic substances such as p-toluenesulfonic acid remain in the target product.
- a dialkyltin dicarboxylate catalyst or a dialkyltin oxide catalyst described in Patent Document 2 is used, colorless and transparent (meth) acryl-modified polybutadiene can be obtained.
- organotin compounds have been strengthened.
- development of a production method that does not use an organotin compound has been desired.
- the present inventors have developed a method for producing a colorless and transparent terminal (meth) acryl-modified polybutadiene without using an organotin compound by using an organoaluminum compound as a catalyst for forming an ester bond.
- the headline and the present invention were completed.
- the present invention (1) A method for producing a (meth) acryl-modified polybutadiene, comprising reacting a polybutadiene having a hydroxyl group at a terminal with a (meth) acrylic acid ester in the presence of an organoaluminum compound. (2) The method for producing (meth) acryl-modified polybutadiene according to (1), wherein the organoaluminum compound is alkoxyaluminum. (3) The alkoxyaluminum has the formula (I)
- each of R 1 , R 2 , R 3 and R 4 independently represents a linear or branched C1-C30 alkyl group.
- the manufacturing method of the (meth) acryl modified polybutadiene as described in (2). (4) (meth) acrylic acid ester is represented by formula (II)
- R 5 represents a hydrogen atom or a methyl group
- R 6 represents a linear or branched C1-C6 alkyl group.
- the (meth) acryl-modified polybutadiene of the present invention is not particularly limited as long as the (meth) acryloyl group is bonded to at least one end of the polybutadiene chain by an ester bond.
- the polybutadiene chain of the (meth) acryl-modified polybutadiene of the present invention may be partially or entirely hydrogenated.
- (meth) acryl means acryl and methacryl.
- the (meth) acryl-modified polybutadiene of the present invention can be represented by the following formula (III).
- R 11 represents a hydrogen atom or a methyl group
- PB represents a polymer chain obtained by polymerizing butadiene or a polymer chain obtained by hydrogenating the polymer chain
- X represents an OH group or formula (IV).
- m 0 or 1.
- the double line portion of the solid line and the dotted line represents a single bond or a double bond
- the double line part of a solid line and a dotted line is a double bond, it is a polybutadiene not added with hydrogen, and when it is a single bond, it means a hydrogenated polybutadiene.
- the vinyl group need not be 100% hydrogenated, and the residual rate of the vinyl group is not particularly limited.
- the 1,4-bond repeating unit represented by the formula (V) has a double bond, a trans isomer, a cis isomer, or a mixture thereof may exist.
- the ratio of the repeating unit of 1,4-bond represented by the formula (V) to the 1,2-bond represented by the formula (VI) is 0 to 100 mol%. That is, in the present invention, the polymer chain represented by PB may be a polymer having only 1,4-bond or 1,2-bond, and 1,4-bond and 1,2-bond are mixed. It may be a polymer.
- the terminal acrylic-modified polybutadiene or terminal acrylic-modified hydrogenated polybutadiene of the present invention has a number average molecular weight of 500 to 10,000 according to GPC (gel filtration) method using polystyrene as an index.
- the (meth) acryl-modified polybutadiene of the present invention can be produced by reacting a polybutadiene having a hydroxyl group at a terminal with a (meth) acrylic ester in the presence of an organoaluminum compound.
- the polybutadiene having a hydroxyl group at the terminal is not particularly limited as long as at least one hydroxyl group is bonded to the terminal site of the polybutadiene chain. Of these, those in which hydroxyl groups are bonded to both terminal sites of the polybutadiene chain are preferred. Moreover, the structure of the site
- PB is the same as described above, and n is 1 or 2).
- a commercially available product can be used as the polybutadiene having a hydroxyl group at the terminal.
- NISSO-PB registered trademark
- -G-1000 manufactured by Nippon Soda Co., Ltd.
- NISSO-PB registered trademark
- -G-2000 manufactured by Nippon Soda Co., Ltd.
- NISSO-PB registered trademark
- -G-3000 Nippon Soda Co., Ltd.
- NISSO-PB registered trademark) -GI-1000 (manufactured by Nippon Soda Co., Ltd.)
- NISSO-PB registered trademark
- GI-2000 manufactured by Nippon Soda Co., Ltd.
- NISSO-PB registered trademark
- GI-3000 manufactured by Nippon Soda Co., Ltd.
- Poly bd R45HT manufactured by Idemitsu Kosan Co
- (Meth) acrylic acid ester means methacrylic acid alkyl ester or acrylic acid alkyl ester.
- (meth) acrylic acid ester of the present invention for example, the following formula (II)
- R 5 represents a hydrogen atom or a methyl group
- R 6 represents a linear or branched C1-C6 alkyl group
- “Straight or branched C1-C6 alkyl group” includes methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, and n-pentyl group. And isopentyl group, neopentyl group, t-pentyl group, 1-methylpentyl group, 2-methylpentyl group, n-hexyl group, isohexyl group and the like. Of these, a C1-C3 alkyl group is preferable, and a methyl group and an ethyl group are more preferable.
- Specific examples of the compound represented by the formula (II) include methyl methacrylate, ethyl methacrylate, methyl acrylate, and ethyl acrylate.
- the amount of the (meth) acrylic acid ester used is not particularly limited, but it is preferably 1 to 500 times mol, preferably 1 to 20 times mol, based on the hydroxyl group of the polybutadiene having a hydroxyl group at the terminal. Is more preferable.
- An organoaluminum compound is a compound in which an organic group is bonded to an aluminum atom.
- the group to be bonded is not particularly limited as long as it does not adversely influence the reaction.
- a preferred organoaluminum compound of the present invention is an aluminum alkoxide, for example of formula (I)
- R 1 , R 2 , R 3 and R 4 each independently represents a linear or branched C1-C30 alkyl group).
- “Straight or branched C1-C30 alkyl group” includes methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group , Isopentyl group, neopentyl group, t-pentyl group, 1-methylpentyl group, 2-methylpentyl group, n-hexyl group, isohexyl group, n-heptyl group, 6,6-dimethylheptyl group, 1,1-dimethyl Heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl,
- organoaluminum compound represented by the formula (I) include the following compounds.
- the amount of the organoaluminum compound used is 0.001 to 50 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of polybutadiene having a hydroxyl group at the terminal.
- the transesterification reaction between the polybutadiene having a hydroxyl group and (meth) acrylic acid ester may be allowed to react in the absence of a solvent or in a solvent.
- solvent used is not particularly limited as long as it is inert to the transesterification reaction.
- Solvents used include aromatic hydrocarbon solvents such as benzene, toluene, xylene, chlorobenzene and dichlorobenzene; alicyclic hydrocarbon solvents such as cyclohexane and cycloheptane; aliphatic hydrocarbon solvents such as hexane and heptane Ether solvents such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran and 1,2-dimethoxyethane; nitrile solvents such as acetonitrile and benzonitrile; N, N-dimethylformamide, N, N-dimethylacetamide, hexa Amide solvents such as methyl phosphoramide; ester solvents such as ethyl acetate, isopropyl acetate, n-
- the reaction temperature is preferably from 0 ° C to 200 ° C, more preferably from room temperature to 170 ° C.
- the reaction is usually completed within minutes to hours.
- a stabilizer may be added to the transesterification reaction. When a stabilizer is added, side reactions can be further suppressed.
- the stabilizer include a phenol-based stabilizer, a phosphorus-based stabilizer, and a sulfur-based stabilizer.
- the phenol-based stabilizer include 2,6-di-t-butyl-p-cresol (BHT), hydroquinone (HQ), methoquinone (MQ), 4-t-butylcatechol (TBC) and the like.
- BHT 2,6-di-t-butyl-p-cresol
- HQ hydroquinone
- MQ methoquinone
- TBC 4-t-butylcatechol
- phosphorus stabilizers include trinonyl phenyl phosphite (TNP) and phosphite.
- sulfur stabilizers examples include 2-methyl-4,6-bis-octylthiomethyl-phenol, dilauryl-3,3′-thiodipropionate (TPL), 4,4′-thiobis (3-methyl-6). -T-butylphenol) and the like.
- the addition amount of the stabilizer is 0.01 to 10 parts by weight, and more preferably 0.05 to 2 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid ester.
- Example 1 In a 500 mL separable flask, 300.0 g of NISSO-PB (registered trademark) -G-3000 (manufactured by Nippon Soda Co., Ltd.), 79.21 g of ethyl acrylate, 0.78 g of dibutylhydroxytoluene (BHT), and aluminum chelate M (river 6.86 g of Alkeneacetoacetate Aluminum Diisopropylate (manufactured by Ken Fine Chemical Co., Ltd.) was added, and the mixture was stirred at 115 ° C. to 120 ° C. for 5 hours. The reaction solution was concentrated under reduced pressure to obtain polybutadiene having a terminal portion that was acrylic-modified.
- NISSO-PB registered trademark
- BHT dibutylhydroxytoluene
- BHT dibutylhydroxytoluene
- aluminum chelate M river 6.86 g of Alkeneacetoacetate Aluminum Diisopropylate (
- the transesterification rate of the obtained terminal acrylic-modified polybutadiene was 97%.
- the appearance of the resulting acrylic-modified polybutadiene was transparent with no turbidity, and the APHA chromaticity was 30.
- the “ester exchange rate” means the rate at which the terminal hydroxyl group of NISSO-PB (registered trademark) -G-3000 is exchanged with an acrylic group.
- the transesterification rate can be calculated from the NMR integral value of methylene hydrogen adjacent to the hydroxyl group and the acrylic group.
- Example 2 Example except that the amount of aluminum chelate M added was 3.42 g and BHT was changed to 0.78 g of HP-400 (manufactured by Kawaguchi Chemical Industry Co., Ltd .; 2-methyl-4,6-bis-octylthiomethyl-phenol)
- HP-400 manufactured by Kawaguchi Chemical Industry Co., Ltd .
- 2-methyl-4,6-bis-octylthiomethyl-phenol terminal acrylic-modified polybutadiene was obtained.
- the transesterification rate of the obtained terminal acrylic-modified polybutadiene was 85%.
- the appearance of the resulting acrylic modified polybutadiene was clear with no turbidity, the APHA chromaticity was 30, and the Gardner chromaticity was ⁇ 1.
- Terminal acrylic modified polybutadiene was obtained in the same manner as in Example 2 except that the amount of aluminum chelate M added was 5.14 g. The transesterification rate of the obtained terminal acrylic-modified polybutadiene was 96%. The appearance of the resulting acrylic modified polybutadiene was clear with no turbidity, the APHA chromaticity was 40, and the Gardner chromaticity was ⁇ 1.
- Example 4 A terminal acrylic-modified polybutadiene was obtained in the same manner as in Example 2, except that the aluminum chelate M was 2.82 g of ALCH (manufactured by Kawaken Fine Chemical Co., Ltd .; ethyl acetoacetate aluminum diisopropylate). The transesterification rate of the obtained terminal acrylic-modified polybutadiene was 97%. The appearance of the resulting acrylic modified polybutadiene was clear with no turbidity, the APHA chromaticity was 30, and the Gardner chromaticity was ⁇ 1.
- Example 5 A terminal acryl-modified polybutadiene was obtained in the same manner as in Example 2 except that the aluminum chelate M was 1.72 g of ALCH (manufactured by Kawaken Fine Chemical Co., Ltd .; ethyl acetoacetate aluminum diisopropylate). The transesterification rate of the obtained terminal acrylic-modified polybutadiene was 94%. The appearance of the resulting acrylic modified polybutadiene was clear with no turbidity, the APHA chromaticity was 20, and the Gardner chromaticity was ⁇ 1.
- Example 6 In a 500 mL separable flask, 300 g of NISSO-PB (registered trademark) -G-3000 (manufactured by Nippon Soda Co., Ltd.), 79.24 g of methyl methacrylate, HP-400 (manufactured by Kawaguchi Chemical Industry Co., Ltd .; 2-methyl-4,6- Bis-octylthiomethyl-phenol (0.79 g) and ALCH (manufactured by Kawaken Fine Chemicals; 2.75 g of ethyl acetoacetate aluminum diisopropylate) were added and mixed, and then stirred at 115 ° C. to 120 ° C. for 5 hours.
- NISSO-PB registered trademark
- HP-400 manufactured by Kawaguchi Chemical Industry Co., Ltd .
- ALCH manufactured by Kawaken Fine Chemicals
- the reaction solution was concentrated under reduced pressure to obtain hydrogenated polybutadiene having a methacryl-modified end portion.
- the transesterification rate of the obtained terminal methacryl-modified hydrogenated polybutadiene was 97%.
- the appearance of the resulting methacryl-modified polybutadiene was transparent without turbidity, the APHA chromaticity was 30, and the Gardner chromaticity was ⁇ 1.
- the reaction solution was concentrated under reduced pressure to obtain hydrogenated polybutadiene having a methacryl-modified end portion.
- the transesterification rate of the obtained terminal methacryl-modified hydrogenated polybutadiene was 98%.
- the appearance of the resulting methacryl-modified polybutadiene was deep yellow and transparent, the APHA chromaticity was> 100, and the Gardner chromaticity was 4.
- the reaction solution was concentrated under reduced pressure to obtain hydrogenated polybutadiene having a methacryl-modified end portion.
- the transesterification rate of the obtained terminal methacryl-modified hydrogenated polybutadiene was 93%.
- the appearance of the resulting methacryl-modified polybutadiene was deep yellow and transparent, the APHA chromaticity was> 100, and the Gardner chromaticity was 4.
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Abstract
Description
本願は、2012年11月13日に出願された日本国特許出願第2012-249329号に対し優先権を主張し、その内容をここに援用する。
(1)有機アルミニウム化合物の存在下、末端にヒドロキシル基を有するポリブタジエンと、(メタ)アクリル酸エステルを反応させることを特徴とする(メタ)アクリル変性ポリブタジエンの製造方法。
(2)有機アルミニウム化合物が、アルコキシアルミニウムであることを特徴とする(1)に記載の(メタ)アクリル変性ポリブタジエンの製造方法。
(3)アルコキシアルミニウムが、式(I)
(4)(メタ)アクリル酸エステルが、式(II)
(5)末端にヒドロキシル基を有するポリブタジエンの一部または全部が水素添加されていることを特徴とする(1)~(4)のいずれかに記載の(メタ)アクリル変性ポリブタジエンの製造方法。
(6)末端にヒドロキシル基を有するポリブタジエンが、両端にヒドロキシル基を有していることを特徴とする(1)~(5)のいずれかに記載の(メタ)アクリル変性ポリブタジエンの製造方法。
本発明の(メタ)アクリル変性ポリブタジエンとしては、ポリブタジエン鎖の少なくとも一端に、エステル結合により、(メタ)アクリロイル基が結合しているものであれば特に制限されない。また、本発明の(メタ)アクリル変性ポリブタジエンのポリブタジエン鎖は、その一部又は全部が水素添加されていてもよい。なお、本発明において、(メタ)アクリルとは、アクリル及びメタクリルを意味する。
また、式(V)で表される1,4-結合繰り返し単位が、二重結合を有する場合には、トランス体、シス体、又はそれらの混合体が存在しうる。
本発明の(メタ)アクリル変性ポリブタジエンは、有機アルミニウム化合物の存在下、末端にヒドロキシル基を有するポリブタジエンと、(メタ)アクリル酸エステルを反応させることにより製造することができる。
使用する溶媒としては、ベンゼン、トルエン、キシレン、クロロベンゼン、ジクロロベンゼン等の芳香族炭化水素系溶媒;シクロヘキサン、シクロヘプタン等の脂環式炭化水素系溶媒;ヘキサン、ヘプタン等の脂肪族炭化水素系溶媒;ジエチルエーテル、ジイソプロピルエーテル、ジオキサン、テトラヒドロフラン、1,2-ジメトキシエタン等のエーテル系溶媒;アセトニトリル、ベンゾニトリル等のニトリル系溶媒;N,N-ジメチルホルムアミド、N,N-ジメチルアセタミド、ヘキサメチルホスホロアミド等のアミド系溶媒;酢酸エチル、酢酸イソプロピル、酢酸n-ブチル等のエステル系溶媒;エチルセロソルブアセテート、メチルセロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート(PGMEA)及びプロピレングリコールモノエチルエーテルアセテート等のグリコールエーテルエステル系溶媒;ジメチルスルホキシド、スルホラン等の含硫黄溶媒を挙げることができる。
フェノール系安定剤としては、2,6-ジ-t-ブチル-p-クレゾール(BHT)、ヒドロキノン(HQ)、メトキノン(MQ)、4-t-ブチルカテコール(TBC)等を挙げることができる。リン系安定剤としては、トリノニルフェニルフォスファイト(TNP)、亜リン酸エステル等を挙げることができる。硫黄系安定剤としては、2-メチル-4,6-ビス-オクチルチオメチル-フェノール、ジラウリル-3,3’-チオジプロピオネート(TPL)、4,4’-チオビス(3-メチル-6-t-ブチルフェノール)等を挙げることができる。
安定剤の添加量は、(メタ)アクリル酸エステル100重量部に対して、0.01~10重量部であり、0.05重量部~2重量部であるのがより好ましい。
500mLセパラブルフラスコにNISSO-PB(登録商標)-G-3000(日本曹達社製)300.0gと、エチルアクリレート79.21gと、ジブチルヒドロキシトルエン(BHT)0.78g、さらにアルミキレートM(川研ファインケミカル社製;アルキルアセトアセテートアルミニウムジイソプロピレート)6.86gを加えた後、115℃~120℃で、5時間攪拌した。反応溶液を減圧濃縮することにより、末端部をアクリル変性したポリブタジエンを得た。得られた末端アクリル変性ポリブタジエンのエステル交換率は97%であった。得られたアクリル変性ポリブタジエンの外観は濁りのない透明であり、APHA色度は30であった。
なお、「エステル交換率」とは、NISSO-PB(登録商標)-G-3000の末端水酸基がアクリル基で交換された率を意味する。エステル交換率は水酸基、アクリル基に隣接するメチレン水素のNMR積分値により算出することができる。
アルミキレートMの添加量を3.42gとし、BHTをHP-400(川口化学工業社製;2-メチル-4,6-ビス-オクチルチオメチル-フェノール)0.78gに変えた以外は実施例1と同様にして、末端アクリル変性ポリブタジエンを得た。得られた末端アクリル変性ポリブタジエンのエステル交換率は85%であった。得られたアクリル変性ポリブタジエンの外観は濁りのない透明であり、APHA色度は30であり、ガードナー色度は<1であった。
アルミキレートMの添加量を5.14gとした以外は実施例2と同様にして、末端アクリル変性ポリブタジエンを得た。得られた末端アクリル変性ポリブタジエンのエステル交換率は96%であった。得られたアクリル変性ポリブタジエンの外観は濁りのない透明であり、APHA色度は40であり、ガードナー色度は<1であった。
アルミキレートMをALCH(川研ファインケミカル社製;エチルアセトアセテートアルミニウムジイソプロピレート)2.82gとした以外は実施例2と同様にして、末端アクリル変性ポリブタジエンを得た。得られた末端アクリル変性ポリブタジエンのエステル交換率は97%であった。得られたアクリル変性ポリブタジエンの外観は濁りのない透明であり、APHA色度は30であり、ガードナー色度は<1であった。
アルミキレートMをALCH(川研ファインケミカル社製;エチルアセトアセテートアルミニウムジイソプロピレート)1.72gとした以外は実施例2と同様にして、末端アクリル変性ポリブタジエンを得た。得られた末端アクリル変性ポリブタジエンのエステル交換率は94%であった。得られたアクリル変性ポリブタジエンの外観は濁りのない透明であり、APHA色度は20であり、ガードナー色度は<1であった。
500mLセパラブルフラスコにNISSO-PB(登録商標)-G-3000(日本曹達社製)300gと、メチルメタクリレート79.24gと、HP-400(川口化学工業社製;2-メチル-4,6-ビス-オクチルチオメチル-フェノール)0.79g、ALCH(川研ファインケミカル社製;エチルアセトアセテートアルミニウムジイソプロピレート)2.75gを加えて混合した後、115℃~120℃で、5時間攪拌した。反応溶液を減圧濃縮することにより、末端部をメタクリル変性した水素添加ポリブタジエンを得た。得られた末端メタクリル変性水素添加ポリブタジエンのエステル交換率は97%であった。得られたメタクリル変性ポリブタジエンの外観は濁りのない透明であり、APHA色度は30であり、ガードナー色度は<1であった。
500mLセパラブルフラスコにNISSO-PB(登録商標)-G-3000(日本曹達社製)300gと、メチルメタクリレート79.26gと、HP-400(川口化学工業社製)0.79g、B-1(日本曹達社製;B-1;テトラ-n-ブトキシチタン)1.72gを加えて混合した後、115℃~120℃で、5時間攪拌した。反応溶液を減圧濃縮することにより、末端部をメタクリル変性した水素添加ポリブタジエンを得た。得られた末端メタクリル変性水素添加ポリブタジエンのエステル交換率は98%であった。得られたメタクリル変性ポリブタジエンの外観は濃黄色透明であり、APHA色度は>100であり、ガードナー色度は4であった。
500mLセパラブルフラスコにNISSO-PB(登録商標)-G-3000(日本曹達社製)300gと、メチルメタクリレート79.26gと、HP-400(川口化学工業社製)0.80g、T-60(日本曹達社製;T-60;プロパンジオキシチタンビス(エチルアセトアセテート))1.71gを加えて混合した後、115℃~120℃で、5時間攪拌した。反応溶液を減圧濃縮することにより、末端部をメタクリル変性した水素添加ポリブタジエンを得た。得られた末端メタクリル変性水素添加ポリブタジエンのエステル交換率は93%であった。得られたメタクリル変性ポリブタジエンの外観は濃黄色透明であり、APHA色度は>100であり、ガードナー色度は4であった。
500mLセパラブルフラスコにNISSO-PB(登録商標)-G-3000(日本曹達社製)300gと、メチルメタクリレート79.26gと、ジブチルヒドロキシトルエン(BHT)0.15g、TBP(日本曹達社製;n-ブチルリン酸エステルチタン)1.71gを加えて混合した後、115℃~120℃で、5時間攪拌した。しかし、エステル交換反応は進行しなかった。
Claims (6)
- 有機アルミニウム化合物の存在下、末端にヒドロキシル基を有するポリブタジエンと、(メタ)アクリル酸エステルを反応させることを特徴とする(メタ)アクリル変性ポリブタジエンの製造方法。
- 有機アルミニウム化合物が、アルコキシアルミニウムであることを特徴とする請求項1に記載の(メタ)アクリル変性ポリブタジエンの製造方法。
- 末端にヒドロキシル基を有するポリブタジエンの一部または全部が水素添加されていることを特徴とする請求項1~4のいずれかに記載の(メタ)アクリル変性ポリブタジエンの製造方法。
- 末端にヒドロキシル基を有するポリブタジエンが、両端にヒドロキシル基を有していることを特徴とする請求項1~5のいずれかに記載の(メタ)アクリル変性ポリブタジエンの製造方法。
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