JP2007211240A - Acrylic-modified polybutadiene - Google Patents
Acrylic-modified polybutadiene Download PDFInfo
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- JP2007211240A JP2007211240A JP2007003891A JP2007003891A JP2007211240A JP 2007211240 A JP2007211240 A JP 2007211240A JP 2007003891 A JP2007003891 A JP 2007003891A JP 2007003891 A JP2007003891 A JP 2007003891A JP 2007211240 A JP2007211240 A JP 2007211240A
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- acrylic
- modified polybutadiene
- polybutadiene
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- hydroxyl group
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- 239000005062 Polybutadiene Substances 0.000 title claims abstract description 67
- 229920002857 polybutadiene Polymers 0.000 title claims abstract description 67
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 37
- 229920000642 polymer Polymers 0.000 claims abstract description 33
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 23
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 28
- 238000001723 curing Methods 0.000 abstract description 14
- 238000010894 electron beam technology Methods 0.000 abstract description 9
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000001029 thermal curing Methods 0.000 abstract description 4
- 230000000704 physical effect Effects 0.000 abstract description 3
- 230000001747 exhibiting effect Effects 0.000 abstract 2
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000012442 inert solvent Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- NIDNOXCRFUCAKQ-UMRXKNAASA-N (1s,2r,3s,4r)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1[C@H]2C=C[C@@H]1[C@H](C(=O)O)[C@@H]2C(O)=O NIDNOXCRFUCAKQ-UMRXKNAASA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- LNBMZFHIYRDKNS-UHFFFAOYSA-N 2,2-dimethoxy-1-phenylethanone Chemical compound COC(OC)C(=O)C1=CC=CC=C1 LNBMZFHIYRDKNS-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- LQRUPWUPINJLMU-UHFFFAOYSA-N dioctyl(oxo)tin Chemical compound CCCCCCCC[Sn](=O)CCCCCCCC LQRUPWUPINJLMU-UHFFFAOYSA-N 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- -1 methacryloyl group Chemical group 0.000 description 1
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
本発明は、アクリル変性ポリブタジエンに関し、詳しくは、安全な方法により製造されるアクリル変性ポリブタジエンに関する。 The present invention relates to acrylic-modified polybutadiene, and more particularly to acrylic-modified polybutadiene produced by a safe method.
従来から、電着塗装材料、塗料、注型樹脂、成型樹脂、接着剤等として有用な、重合体鎖の末端部に水酸基やカルボキシル基等の官能基が結合したポリマーが知られている。例えば、液状ポリブタジエンは、硬化させることによって、耐水・耐湿性、耐薬品性、電気特性（高絶縁耐力、低誘電率、耐アーク性）、透明性に優れ、高い靭性のある物性を示す樹脂となる。 Conventionally, polymers having a functional group such as a hydroxyl group or a carboxyl group bonded to an end portion of a polymer chain, which are useful as an electrodeposition coating material, a paint, a casting resin, a molding resin, an adhesive, and the like are known. For example, liquid polybutadiene is a resin that exhibits excellent water and moisture resistance, chemical resistance, electrical properties (high dielectric strength, low dielectric constant, arc resistance), transparency, and high toughness by curing. Become.
ポリマーの硬化方法としては、例えば、有機過酸化物を触媒として用いる熱硬化法、紫外線・電子線を用いる硬化方法等がある。熱硬化法によれば架橋密度の高い硬化樹脂が得られるが、硬化を精密に制御することが困難である。一方、紫外線・電子線を用いる硬化方法では硬化の精密な制御は容易であるものの、十分な架橋密度を有する硬化樹脂を得ることが困難である場合が多い。 Examples of the polymer curing method include a thermal curing method using an organic peroxide as a catalyst, and a curing method using an ultraviolet ray and an electron beam. Although a cured resin having a high crosslinking density can be obtained by the thermosetting method, it is difficult to precisely control the curing. On the other hand, in the curing method using ultraviolet rays / electron beams, although precise control of curing is easy, it is often difficult to obtain a cured resin having a sufficient crosslinking density.
そこで、熱、紫外線又は電子線による硬化性を高めるために水酸基等の官能基を有する高分子の該官能基をアクリロイル基やメタクリロイル基等の重合性官能基で修飾したポリマー（以下、「高分子（メタ）アクリレート」という。）が提案されている（特許文献１〜７参照。）。この高分子（メタ）アクリレートは、紫外線又は電子線の硬化物性が高められており、硬化反応をより精密に制御することができ、例えば、精密機械や光学器械等の接着剤等として用いることができる。 Therefore, in order to enhance curability by heat, ultraviolet rays or electron beams, a polymer in which the functional group of a polymer having a functional group such as a hydroxyl group is modified with a polymerizable functional group such as an acryloyl group or a methacryloyl group (hereinafter referred to as “polymer”). ("Meth) acrylate") has been proposed (see Patent Documents 1 to 7). This polymer (meth) acrylate has enhanced cured properties of ultraviolet rays or electron beams, and can control the curing reaction more precisely. For example, it can be used as an adhesive for precision machines or optical instruments. it can.
前記高分子（メタ）アクリレートとしては、下記液状ポリブタジエンアクリレート（Ｄ）（以下、化合物（Ｄ）という。）が知られており、例えばイソシアネ−ト基を有する化合物（Ａ）（以下、化合物（Ａ）という。）、アクリレート（Ｂ）、及び分子末端に水酸基を有する１，２−液状ポリブタジエン（Ｃ）を無溶媒又は不活性溶媒中で所定温度に加熱することにより、簡便かつ高収率で得ることができる（下記反応式参照。）。 As the polymer (meth) acrylate, the following liquid polybutadiene acrylate (D) (hereinafter referred to as compound (D)) is known. For example, compound (A) having an isocyanate group (hereinafter referred to as compound (A) ), Acrylate (B), and 1,2-liquid polybutadiene (C) having a hydroxyl group at the molecular end are heated to a predetermined temperature in a solvent-free or inert solvent to obtain a simple and high yield. (See the following reaction formula.)
このようにして得られた化合物（Ｄ）は、物品表面に化合物（Ｄ）又は化合物（Ｄ）を含む組成物の塗膜を形成し、熱硬化のみならず、硬化部位に紫外線又は電子線を照射することにより硬化させることができる。 The compound (D) thus obtained forms a coating film of the composition containing the compound (D) or the compound (D) on the surface of the article, and not only heat curing but also ultraviolet rays or electron beams at the cured site. It can be cured by irradiation.
しかしながら、上記高分子（メタ）アクリレートは、原料にトルエンジイソシアネート（化合物（Ａ））を使用しており、かかるトルエンジイソシアネートは感作性物質であって、発ガン性があると考えられるなど極めて有害な物質であることから、作業環境を含め、環境安全性の改善が望まれている。 However, the above polymer (meth) acrylate uses toluene diisocyanate (compound (A)) as a raw material, and such toluene diisocyanate is a sensitizing substance and is considered to be carcinogenic. Therefore, it is desired to improve the environmental safety including the working environment.
本発明の課題は、環境安全性を改善し、しかも、熱硬化や、紫外線や電子線による硬化物性が極めて高く、硬化反応を精密に制御することができるアクリル変性ポリブタジエン、及びその製造方法を提供することにある。 An object of the present invention is to provide an acrylic-modified polybutadiene that improves environmental safety, has extremely high cured properties by heat curing, ultraviolet rays, and electron beams, and can precisely control the curing reaction, and a method for producing the same. There is to do.
本発明者らは、上記課題を解決するために鋭意研究した結果、重合体鎖を構成するブタジエン単位の８０％以上が１，２結合からなる直鎖上の重合体鎖の末端に、直接、（メタ）アクリル酸をエステル結合させることにより、上記課題を解決できることを見い出し、本発明を完成するに至った。 As a result of diligent research to solve the above problems, the inventors of the present invention directly, at the end of a linear polymer chain in which 80% or more of the butadiene units constituting the polymer chain are composed of 1,2 bonds, It has been found that the above problem can be solved by ester-linking (meth) acrylic acid, and the present invention has been completed.
すなわち、本発明は、（１）重合体鎖を構成するブタジエン単位の８０％以上が１，２結合からなる重合体鎖の少なくとも一端に、直接、（メタ）アクリル酸がエステル結合していることを特徴とするアクリル変性ポリブタジエンや、（２）重合体鎖の両端に、直接、（メタ）アクリル酸がエステル結合していることを特徴とする（１）に記載のアクリル変性ポリブタジエンや、（３）数平均分子量が、５００〜１００００であることを特徴とする（１）又は（２）に記載のアクリル変性ポリブタジエンに関する。 That is, according to the present invention, (1) (meth) acrylic acid is directly ester-bonded to at least one end of a polymer chain in which 80% or more of butadiene units constituting the polymer chain are composed of 1,2 bonds. (2) Acrylic modified polybutadiene as described in (1), wherein (meth) acrylic acid is ester-bonded directly to both ends of the polymer chain, and (3) ) The number average molecular weight is 500 to 10,000. The present invention relates to the acrylic-modified polybutadiene described in (1) or (2).
また、本発明は、（４）重合体鎖を構成するブタジエン単位の８０％以上が１，２結合からなる重合体鎖の少なくとも一端に水酸基を有している水酸基含有ポリブタジエンに、触媒存在下、（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アクリル変性ポリブタジエンの製造方法や、（５）水酸基含有ポリブタジエンが、両端に水酸基を有していることを特徴とする（４）に記載のアクリル変性ポリブタジエンの製造方法や、（６）触媒が、テトラアルコキシチタンであることを特徴とする（４）又は（５）に記載のアクリル変性ポリブタジエンの製造方法や、（７）触媒がジアルキルスズジカルボン酸塩又はジアルキルスズオキサイドであることを特徴とする（４）又は（５）に記載のアクリル変性ポリブタジエンの製造方法に関する。 Further, the present invention provides (4) a hydroxyl group-containing polybutadiene in which 80% or more of the butadiene units constituting the polymer chain have a hydroxyl group at least at one end of the polymer chain in the presence of a catalyst. A process for producing an acrylic-modified polybutadiene characterized by reacting a (meth) acrylic acid ester, or (5) a hydroxyl group-containing polybutadiene has hydroxyl groups at both ends. A method for producing modified polybutadiene, (6) the method for producing acrylic modified polybutadiene according to (4) or (5), wherein the catalyst is tetraalkoxytitanium, and (7) the catalyst is a dialkyltin dicarboxylic acid The method for producing an acrylic-modified polybutadiene according to (4) or (5), which is a salt or a dialkyltin oxide. To.
本発明のアクリル変性ポリブタジエンは、製法変更で環境安全性が改善された上に、熱硬化のみならず、紫外線や電子線による硬化物性が極めて高く、硬化反応を精密に制御することができる。しかも、低粘度であるので、ハンドリング性に極めて優れている。さらに、本発明のアクリル変性ポリブタジエンの製造方法によれば、本発明のアクリル変性ポリブタジエンを容易に製造することができる。 The acrylic-modified polybutadiene of the present invention is improved in environmental safety by changing the production method, and has not only thermal curing but also extremely high cured physical properties by ultraviolet rays and electron beams, so that the curing reaction can be precisely controlled. And since it is low-viscosity, it is very excellent in handling property. Furthermore, according to the method for producing the acrylic modified polybutadiene of the present invention, the acrylic modified polybutadiene of the present invention can be easily produced.
本発明のアクリル変性ポリブタジエンとしては、重合体鎖を構成するブタジエン単位の８０％以上が１，２結合からなる重合体鎖の少なくとも一端に、直接、（メタ）アクリル酸がエステル結合しているものであれば特に制限されるものではなく、本発明のアクリル変性ポリブタジエンは、塗料、注型樹脂、成型樹脂、接着剤等として用いることができる。また、製法変更で環境安全性が改善された上に、熱硬化のみならず、紫外線や電子線による硬化物性が極めて高く、硬化反応を精密に制御することができるので、精密機械等のように精密で微細な構造を有する物品の接着剤や塗料等に好適に用いることができる。なお、本発明において、（メタ）アクリル酸とはアクリル酸及びメタクリル酸を意味する。 As the acrylic-modified polybutadiene of the present invention, (meth) acrylic acid is directly ester-bonded to at least one end of a polymer chain in which 80% or more of the butadiene units constituting the polymer chain are composed of 1,2 bonds. If it is, it will not restrict | limit in particular, The acrylic modified polybutadiene of this invention can be used as a coating material, casting resin, molding resin, an adhesive agent, etc. In addition to improving environmental safety by changing the manufacturing method, not only thermal curing but also curing properties by ultraviolet rays and electron beams are extremely high, and the curing reaction can be precisely controlled. It can be suitably used for adhesives and paints for articles having a precise and fine structure. In the present invention, (meth) acrylic acid means acrylic acid and methacrylic acid.
本発明のアクリル変性ポリブタジエンにおける重合体鎖は、上記のように、重合体鎖を構成するブタジエン単位の８０％以上が１，２結合からなる直鎖状のものであり、硬化反応をより精密に制御することができる点から、ブタジエン単位の８５％以上が１，２結合からなるものが好ましく、ブタジエン単位の９０％以上が１，２結合からなることがより好ましく、ブタジエン単位の９５％以上が１，２結合からなることがさらに好ましい。 As described above, the polymer chain in the acrylic-modified polybutadiene of the present invention is a linear chain in which 80% or more of the butadiene units constituting the polymer chain are composed of 1,2 bonds, and the curing reaction is made more precise. In terms of controllability, 85% or more of the butadiene units are preferably composed of 1,2 bonds, more preferably 90% or more of the butadiene units are composed of 1,2 bonds, and 95% or more of the butadiene units are 95% or more. More preferably, it consists of 1,2 bonds.
また、本発明のアクリル変性ポリブタジエンにおける他端は、無置換（水素原子）であってもよいし、置換基を有していてもよく、置換基としては、例えば、水酸基、カルボキシル基、（メタ）アクリル酸エステル基等を挙げることができ、（メタ）アクリル酸エステル基が好ましい。これにより、低粘度でありながら、硬化物性がさらに向上し、硬化反応をさらに精密に制御することが可能となる。 The other end of the acrylic-modified polybutadiene of the present invention may be unsubstituted (hydrogen atom) or may have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, (meta ) Acrylic acid ester group and the like can be mentioned, and a (meth) acrylic acid ester group is preferable. Thereby, the cured physical properties are further improved while the viscosity is low, and the curing reaction can be controlled more precisely.
すなわち、重合体鎖の両端に、直接、（メタ）アクリル酸がエステル結合している下記に示す構造のものが好ましい。なお、下記で示すブタジエンの重合体鎖部分は、８０％以上が１，２結合からなるものであればよい。また、一端にアクリル酸が直接エステル結合し、他端にメタクリル酸が直接エステル結合したものであってもよい。 That is, the structure shown below in which (meth) acrylic acid is ester-bonded directly to both ends of the polymer chain is preferable. In addition, the polymer chain portion of butadiene shown below may be one in which 80% or more is composed of 1,2 bonds. Alternatively, acrylic acid may be directly ester-bonded to one end and methacrylic acid may be directly ester-bonded to the other end.
また、本発明のアクリル変性ポリブタジエンの数平均分子量としては、通常、５００〜１００００程度であり、１０００〜５０００であることが好ましい。 In addition, the number average molecular weight of the acrylic-modified polybutadiene of the present invention is usually about 500 to 10,000, and preferably 1,000 to 5,000.
このような本発明のアクリル変性ポリブタジエンは、重合体鎖を構成するブタジエン単位の８０％以上が１，２結合からなる重合体鎖の少なくとも一端に水酸基を有している水酸基含有ポリブタジエンに、触媒存在下、（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。（メタ）アクリル酸エステルの添加量としては、その種類により一概にはいえないが、通常、水酸基含有ポリブタジエンに対して、９〜２００重量％であることが好ましく、１４〜１００重量％であることがより好ましい。これにより、末端の水酸基に対して、５０％以上、好ましくは７０％以上、より好ましくは９０％以上、さらに好ましくは９５％の割合で、（メタ）アクリル酸を末端に導入することができる。 Such an acrylic-modified polybutadiene of the present invention has a catalyst in a hydroxyl group-containing polybutadiene in which 80% or more of the butadiene units constituting the polymer chain have a hydroxyl group at least at one end of the polymer chain. Below, it can manufacture by making (meth) acrylic acid ester react. The amount of (meth) acrylic acid ester added is generally unrecognizable depending on its type, but is usually preferably 9 to 200% by weight, and preferably 14 to 100% by weight, based on the hydroxyl group-containing polybutadiene. Is more preferable. Thereby, (meth) acrylic acid can be introduced into the terminal at a ratio of 50% or more, preferably 70% or more, more preferably 90% or more, and still more preferably 95% with respect to the terminal hydroxyl group.
また、本発明の製造方法において用いる水酸基含有ポリブタジエンは、少なくとも一端に水酸基を有しており、両端に水酸基を有していることが好ましく、これにより、両端に、直接、（メタ）アクリル酸がエステル結合したアクリル変性ポリブタジエンを製造することができる。水酸基含有ポリブタジエンと反応させる（メタ）アクリル酸エステルとしては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル等を挙げることができる。 Further, the hydroxyl group-containing polybutadiene used in the production method of the present invention preferably has a hydroxyl group at at least one end and preferably has a hydroxyl group at both ends, whereby (meth) acrylic acid is directly attached to both ends. Ester-linked acrylic modified polybutadiene can be produced. Examples of the (meth) acrylic acid ester to be reacted with the hydroxyl group-containing polybutadiene include methyl (meth) acrylate and ethyl (meth) acrylate.
本発明の製造方法における水酸基含有ポリブタジエンの製造方法としては、例えば、ブタジエンを溶液中でナトリウム触媒の存在下に重合させてポリブタジエンを調製し、これに、エチレンオキサイド、プロピレンオキサイド等のエポキシ化合物を添加する方法が挙げられる。これにより、ポリブタジエンの末端に、８０％以上、好ましくは９０％以上の割合で、水酸基を導入することができる。このような水酸基含有ポリブタジエンとしては、具体的に、日本曹達株式会社製の商品名：Ｇ−２０００ を挙げることができる。なお
、この水酸基含有ポリブタジエンは、水添処理を施していない非水添物である。
As a method for producing a hydroxyl group-containing polybutadiene in the production method of the present invention, for example, polybutadiene is prepared by polymerizing butadiene in a solution in the presence of a sodium catalyst, and an epoxy compound such as ethylene oxide or propylene oxide is added thereto. The method of doing is mentioned. Thereby, a hydroxyl group can be introduced into the terminal of polybutadiene at a ratio of 80% or more, preferably 90% or more. Specific examples of such a hydroxyl group-containing polybutadiene include trade name: G-2000 manufactured by Nippon Soda Co., Ltd. This hydroxyl group-containing polybutadiene is a non-hydrogenated product that has not been subjected to hydrogenation treatment.
水酸基含有ポリブタジエンと（メタ）アクリル酸エステルとの反応は、無溶媒又は適当な不活性溶媒中、適当な触媒の存在下で行うことができる。かかる触媒としては、例えば、テトラメトキシチタン、テトラエトキシチタン、テトラプロポキシチタン、テトラブトキシチタン等のテトラアルコキシチタンを含む有機チタン化合物、ジブチルスズジラウレート、ジオクチルスズジラウレート等のジアルキルスズジカルボン酸塩、ジブチルスズオキサイド、ジオクチルスズオキサイド等のジアルキルスズオキサイドを含む有機スズ化合物等を挙げることができる。かかる触媒の使用量としては、水酸基含有ポリブタジエンの水酸基に対して、０．０１〜１０ｍｏｌ％であることが好ましく、０．１〜３．５ｍｏｌ％であることがより好ましい。この範囲で使用することにより、効率的に本発明のアクリル変性ポリブタジエンを製造することができる。 The reaction between the hydroxyl group-containing polybutadiene and the (meth) acrylic acid ester can be carried out in the absence of a solvent or in a suitable inert solvent in the presence of a suitable catalyst. Examples of such catalysts include organic titanium compounds containing tetraalkoxytitanium such as tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium and tetrabutoxytitanium, dialkyltin dicarboxylates such as dibutyltin dilaurate and dioctyltin dilaurate, dibutyltin oxide, An organic tin compound containing a dialkyltin oxide such as dioctyltin oxide can be used. The amount of the catalyst used is preferably 0.01 to 10 mol%, more preferably 0.1 to 3.5 mol%, based on the hydroxyl group of the hydroxyl group-containing polybutadiene. By using in this range, the acrylic modified polybutadiene of the present invention can be produced efficiently.
また、水酸基含有ポリブタジエンと（メタ）アクリル酸エステルとの反応は、副生物であるメタノール等のアルコールや、目的物であるアクリル変性ポリブタジエンを反応系から除去（留去）することにより、平衡を偏らせ、反応を促進することが好ましい。 In addition, the reaction between the hydroxyl group-containing polybutadiene and the (meth) acrylic acid ester is biased by removing (distilling off) the by-product alcohol such as methanol and the target product acrylic-modified polybutadiene from the reaction system. It is preferable to promote the reaction.
また、反応に用いられる溶媒としては、反応に不活性な溶媒であれば特に制限されないが、例えば、ベンゼン、トルエン、キシレン等の芳香族炭化水素；ジエチルエーテル、テトラヒドロフラン、１，２−ジメトキシエタン、１，４−ジオキサ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；ジメチルスルホキシド等が挙げられ、これらの中でも、ベンゼン、トルエン、キシレン等の芳香族炭化水素が好ましい。 The solvent used in the reaction is not particularly limited as long as it is an inert solvent for the reaction. For example, aromatic hydrocarbons such as benzene, toluene and xylene; diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, Examples include ether solvents such as 1,4-dioxane; nitrile solvents such as acetonitrile and benzonitrile; dimethyl sulfoxide and the like. Among these, aromatic hydrocarbons such as benzene, toluene and xylene are preferable.
反応温度としては、通常、０〜１３０℃であり、室温〜１２０℃の範囲であることが好ましい。反応は、通常、数分〜数時間で完結する。反応終了後、この反応液から未反応の（メタ）アクリル酸エステル及び溶媒を除去することにより、本発明のアクリル変性ポリブタジエン（を主成分とする液体）を得ることができる。 As reaction temperature, it is 0-130 degreeC normally, and it is preferable that it is the range of room temperature-120 degreeC. The reaction is usually completed in a few minutes to a few hours. After the completion of the reaction, the unreacted (meth) acrylic acid ester and the solvent are removed from the reaction solution, whereby the acrylic-modified polybutadiene (a liquid mainly composed of the present invention) of the present invention can be obtained.
本発明の製造方法により得られるアクリル変性ポリブタジエンは、白濁のない透明な液状のものであるため、光学器械等のように透明性が要求される物品の接着剤、塗料としても有用である。また、本発明のアクリル変性ポリブタジエンは、前記水酸基含有ポリブタジエン、又は水酸基を有していないポリブタジエンと混合して使用することもできる。 Since the acrylic-modified polybutadiene obtained by the production method of the present invention is a transparent liquid without white turbidity, it is also useful as an adhesive or paint for articles that require transparency such as optical instruments. The acrylic-modified polybutadiene of the present invention can be used by mixing with the hydroxyl group-containing polybutadiene or polybutadiene having no hydroxyl group.
以下、実施例により本発明をより具体的に説明するが、本発明の技術的範囲はこれらの例示に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, the technical scope of this invention is not limited to these illustrations.
［実施例１］
３００ｍｌのガラス製反応容器に、ブタジエンが１，２−結合で重合した液状ポリブタジエン（商品名：Ｇ−２０００ 日本曹達（株）製 数平均分子量＝１，１００，（１））１５０．０ｇ、２，６−ジ−ｔ−ブチル−４−メチルフェノール（ＢＨＴ）０．１５ｇ、及びテトラブトキシチタン１．６ｇ（２）を仕込み、攪拌しながら、メチルメタクリレート（３）３０．０ｇをトルエン５０．０ｇに溶解したメチルメタクリレート溶液を添加して反応を行った。次いで、ドライエア中、１２０℃で５時間保持し、副生したメタノール、メチルメタクリレート（３）及び溶媒の留去を行った。さらに、１２０℃で１時間減圧留去して、透明な液体１５８．２ｇを得た。１Ｈ−ＮＭＲ測定（日本電子株式会社製、ＥＣＰ−５００）では、３．６ｐｐｍ付近にある水酸基が結合したメチレンプロトンのスペクトルが、エステル交換によって４．１ｐｐｍ付近にシフトしていた。また、ＦＴ−ＩＲ測定（Ｐｅｒｋｉｎ Ｅｌｍｅｒ社製、Ｓｐｅｃｔｒｕｍ Ｏｎｅ）でも、３３００ｃｍ−２付近の水酸基の吸収が消失しており、得られた液体は、上記アクリル変性ポリブタジエン（４）を主成分として含有していた。 150.0 g of liquid polybutadiene (trade name: G-2000 Nippon Soda Co., Ltd. number average molecular weight = 1,100, (1)) in which butadiene is polymerized with 1,2-bonds in a 300 ml glass reaction vessel , 6-di-t-butyl-4-methylphenol (BHT) 0.15 g and tetrabutoxytitanium 1.6 g (2) were charged, and 30.0 g of methyl methacrylate (3) was added to 50.0 g of toluene while stirring. The reaction was carried out by adding a methyl methacrylate solution dissolved in. Subsequently, it hold | maintained at 120 degreeC in dry air for 5 hours, and distilled methanol, methyl methacrylate (3), and a solvent byproduced. Furthermore, it distilled under reduced pressure at 120 degreeC for 1 hour, and obtained 158.2g of transparent liquids. In 1 H-NMR measurement (manufactured by JEOL Ltd., ECP-500), the spectrum of methylene protons to which a hydroxyl group in the vicinity of 3.6 ppm was bonded was shifted to about 4.1 ppm by transesterification. Further, even in FT-IR measurement (Perkin Elmer, Spectrum One), the absorption of hydroxyl groups in the vicinity of 3300 cm −2 has disappeared, and the obtained liquid contains the above acrylic-modified polybutadiene (4) as a main component. It was.
[実施例２］
３００ｍｌのガラス製反応容器に、ブタジエンが１，２−結合で重合した液状ポリブタジエン（商品名：Ｇ−２０００ 日本曹達（株）製 数平均分子量＝１，１００，（１））１５０．０ｇ、２，６−ジ−ｔ−ブチル−４−メチルフェノール（ＢＨＴ）０．１５ｇ、及びジーｎーブチルスズジラウレート２．６ｇを仕込み、攪拌しながら、メチルメタクリレート（３）３０．０ｇをトルエン５０．０ｇに溶解したメチルメタクリレート溶液を添加して反応を行った。次いで、ドライエア中、１２０℃で３時間保持し、副生したメタノール、メチルメタクリレート（３）及び溶媒の留去を行い、半応液１９４．３ｇを得た。この反応液１６０．０ｇを用いて、さらに、１２０℃で２時間減圧留去して、透明な液体９９．４ｇを得た。１Ｈ−ＮＭＲ測定（日本電子株式会社製、ＥＣＰ−５００）では、３．６ｐｐｍ付近にある水酸基が結合したメチレンプロトンのスペクトルが、エステル交換によって４．１ｐｐｍ付近にシフトしていた。また、ＦＴ−ＩＲ測定（Ｐｅｒｋｉｎ Ｅｌｍｅｒ社製、Ｓｐｅｃｔｒｕｍ Ｏｎｅ）でも、３３００ｃｍ−２付近の水酸基の吸収が消失しており、得られた液体は、上記アクリル変性ポリブタジエン（４）を主成分として含有していた。
[Example 2]
150.0 g of liquid polybutadiene (trade name: G-2000 Nippon Soda Co., Ltd. number average molecular weight = 1,100, (1)) in which butadiene is polymerized with 1,2-bonds in a 300 ml glass reaction vessel , 6-di-t-butyl-4-methylphenol (BHT) 0.15 g and di-n-butyltin dilaurate 2.6 g, and 30.0 g of methyl methacrylate (3) into 50.0 g of toluene while stirring. The dissolved methyl methacrylate solution was added to carry out the reaction. Subsequently, it hold | maintained at 120 degreeC in dry air for 3 hours, methanol, methyl methacrylate (3) byproduced, and the solvent were distilled off, and 194.3g of semi-reaction liquid was obtained. Using 160.0 g of this reaction solution, the solution was further distilled off under reduced pressure at 120 ° C. for 2 hours to obtain 99.4 g of a transparent liquid. In 1 H-NMR measurement (manufactured by JEOL Ltd., ECP-500), the spectrum of methylene protons to which a hydroxyl group in the vicinity of 3.6 ppm was bonded was shifted to about 4.1 ppm by transesterification. Further, even in FT-IR measurement (Perkin Elmer, Spectrum One), the absorption of hydroxyl groups in the vicinity of 3300 cm −2 has disappeared, and the obtained liquid contains the above acrylic-modified polybutadiene (4) as a main component. It was.
［比較例１］
３００ｍｌガラス製反応器に、ブタジエンが１，２−結合で重合した液状ポリブタジエン〔商品名：Ｇ−２０００ 日本曹達（株）製 数平均分子量＝１，１００（６）〕２００．０ｇ、２，６−ジ−ｔ−ブチル−４−メチルフェノール（ＢＨＴ）０．１４ｇ、２，４−トルエンジイソシアネート（７）２２．０ｇ、２−ヒドロキシエチルメタクリレート（８）１６．０ｇを仕込み、全容を６０〜７０℃で５時間反応することにより、透明な粘稠液体（９）を得た。反応の追跡は、反応液を少量抜き取り、このもののＩＲスペクトルを測定することにより行い、ＩＲスペクトルの２，１００〜２，６００ｃｍ−１（イソシアネート基）のピークが消失した時点で、反応を終了させた。得られた粘稠な液体であって、上記（９）で示される化合物を含有していた。 Liquid polybutadiene in which butadiene is polymerized with 1,2-bonds in a 300 ml glass reactor [trade name: G-2000 Nippon Soda Co., Ltd. number average molecular weight = 1,100 (6)] 200.0 g, 2,6 -Di-t-butyl-4-methylphenol (BHT) 0.14 g, 2,4-toluene diisocyanate (7) 22.0 g, 2-hydroxyethyl methacrylate (8) 16.0 g were charged, and the total volume was 60-70. By reacting at 5 ° C. for 5 hours, a transparent viscous liquid (9) was obtained. The reaction is traced by extracting a small amount of the reaction solution and measuring the IR spectrum of the reaction solution. When the 2,100-2,600 cm-1 (isocyanate group) peak of the IR spectrum disappears, the reaction is terminated. It was. It was the obtained viscous liquid, Comprising: The compound shown by said (9) was contained.
（評価）
（１）粘度評価
実施例１で得られた液体、比較例１で得られた液体、及びこれらの製造に用いた液状ポリブタジエン〔商品名：Ｇ−２０００ 日本曹達（株）製 数平均分子量＝１，１００〕について、東京計器製Ｂ型粘度計を用いて粘度の測定（測定温度４５℃）を行った。その結果を表１に示す。
(Evaluation)
(1) Viscosity evaluation The liquid obtained in Example 1, the liquid obtained in Comparative Example 1, and the liquid polybutadiene used in the production thereof [trade name: G-2000 Nippon Soda Co., Ltd. number average molecular weight = 1 , 100], the viscosity was measured (measurement temperature: 45 ° C.) using a B-type viscometer manufactured by Tokyo Keiki. The results are shown in Table 1.
表１から明らかなように、本発明のアクリル変性ポリブタジエンを主成分とする実施例１で得られた液体は、ウレタン結合を介してメタクリル酸が結合しているポリブタジエンを主成分とする比較例１で得られた液体や、末端に水酸基を有する液状ポリブタジエンに比して、粘度が非常に低くなっていることがわかる。 As can be seen from Table 1, the liquid obtained in Example 1 whose main component is the acrylic modified polybutadiene of the present invention is Comparative Example 1 whose main component is polybutadiene in which methacrylic acid is bonded via a urethane bond. It can be seen that the viscosity is very low compared to the liquid obtained in the above and liquid polybutadiene having a hydroxyl group at the terminal.
（２）ＵＶ硬化性評価
実施例１で得られた液体、及び比較例１で得られた液体について、ＵＶ硬化性について確認した。具体的には、Nicolet Magna社製 760 FTIR spectrometerを用いて、ラジカル
開始剤としてジメトキシアセトフェノンを４ｐｈｒ添加し、２５℃で測定を行った。波長８１４ｃｍ−１での吸光度の変化率を反応率として比較した。
(2) UV Curability Evaluation About the liquid obtained in Example 1 and the liquid obtained in Comparative Example 1, the UV curability was confirmed. Specifically, using a 760 FTIR spectrometer manufactured by Nicolet Magna, 4 phr of dimethoxyacetophenone was added as a radical initiator, and the measurement was performed at 25 ° C. The change rate of absorbance at a wavelength of 814 cm −1 was compared as the reaction rate.
その結果を図１に示す。図１に示すように、実施例１で得られた液体は、比較例１で得られた液体に比べて、ＵＶ硬化特性が高いことがわかる。 The result is shown in FIG. As shown in FIG. 1, it can be seen that the liquid obtained in Example 1 has higher UV curing characteristics than the liquid obtained in Comparative Example 1.
Claims (7)
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| WO2011045918A1 (en) * | 2009-10-14 | 2011-04-21 | 日本曹達株式会社 | Method for producing polybutadiene |
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| US20140005317A1 (en) * | 2010-01-15 | 2014-01-02 | Nippon Soda Co., Ltd. | Polybutadiene derivative composition |
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| WO2023053816A1 (en) | 2021-09-30 | 2023-04-06 | 住友理工株式会社 | Radical-curable sealing member for fuel cells |
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