JP2012184364A - Acrylic resin and method for producing the same - Google Patents
Acrylic resin and method for producing the same Download PDFInfo
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- JP2012184364A JP2012184364A JP2011049453A JP2011049453A JP2012184364A JP 2012184364 A JP2012184364 A JP 2012184364A JP 2011049453 A JP2011049453 A JP 2011049453A JP 2011049453 A JP2011049453 A JP 2011049453A JP 2012184364 A JP2012184364 A JP 2012184364A
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- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 44
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 125000005370 alkoxysilyl group Chemical group 0.000 claims abstract description 18
- 239000011347 resin Substances 0.000 claims abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims description 23
- 239000003505 polymerization initiator Substances 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 9
- 238000007711 solidification Methods 0.000 abstract description 3
- 230000008023 solidification Effects 0.000 abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 19
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 14
- 239000008096 xylene Substances 0.000 description 14
- -1 2-ethylhexyl Chemical group 0.000 description 12
- 239000002904 solvent Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 238000003915 air pollution Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229940065472 octyl acrylate Drugs 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- YHYCMHWTYHPIQS-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-methoxyethanol Chemical compound COC(O)COCCO YHYCMHWTYHPIQS-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- SHJIJMBTDZCOFE-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]-1-methoxyethanol Chemical compound COC(O)COCCOCCOCCO SHJIJMBTDZCOFE-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- UMSUVRQADXVIDD-UHFFFAOYSA-N ethyl 2-acetyloxyprop-2-enoate Chemical compound CCOC(=O)C(=C)OC(C)=O UMSUVRQADXVIDD-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BBNYLDSWVXSNOQ-UHFFFAOYSA-N oxolane-2-carbaldehyde Chemical compound O=CC1CCCO1 BBNYLDSWVXSNOQ-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明はアクリル樹脂とその製造方法に関し、さらに詳しくは、常温で液体あるいは高粘稠な低分子量であるアクリル樹脂に関する。 The present invention relates to an acrylic resin and a method for producing the same, and more particularly to an acrylic resin that is liquid at room temperature or has a high molecular weight and low molecular weight.
従来から、アクリル樹脂は透明性に優れ、耐油性、耐候性が高いために様々な分野で利用されている。 Conventionally, acrylic resins have been used in various fields because of their excellent transparency and high oil resistance and weather resistance.
通常使われるアクリル樹脂は、分子量が数千から数万であり、それを固化したものである。そのため、適当な溶剤で希釈し溶液とすることが作業性を上げるために必要である。
これに対し、数平均分子量１５００〜５０００を有し、かつ、常温で固体あるいは高粘稠である低分子量アクリル樹脂が開示されている（例えば、特許文献１）。
A commonly used acrylic resin has a molecular weight of several thousand to several tens of thousands, and is a solidified product. Therefore, it is necessary to increase the workability by diluting with a suitable solvent to obtain a solution.
On the other hand, a low molecular weight acrylic resin having a number average molecular weight of 1500 to 5000 and being solid or highly viscous at room temperature is disclosed (for example, Patent Document 1).
これは、連鎖移動剤としてチオール類を用いるものであり、合成されたアクリル樹脂はチオール類による異臭を持つことが欠点として上げられる。
また、省資源、省エネルギー、更には、職場環境の改善を目的に様々な分野においてアクリル樹脂の優れた性能を有した無溶剤、又は低溶剤の素材が求められている。
This uses a thiol as a chain transfer agent, and the synthesized acrylic resin has a bad odor due to the thiol.
In addition, there is a need for a solvent-free or low-solvent material having excellent performance of acrylic resins in various fields for the purpose of resource saving, energy saving, and improvement of the workplace environment.
本発明の目的は、１分子中に１個以上のアルコキシシリル基を有する数平均分子量８００〜２５００、重量平均分子量／数平均分子量が２．５以下で、アルコキシシリル基の濃度が１．５モル／Ｋｇ樹脂以上であるアクリル樹脂を提供することを目的としている。 The object of the present invention is to provide a number average molecular weight of 800 to 2500 having one or more alkoxysilyl groups in one molecule, a weight average molecular weight / number average molecular weight of 2.5 or less, and an alkoxysilyl group concentration of 1.5 mol It aims at providing the acrylic resin which is more than / Kg resin.
上述した課題を解決するために、本発明は以下の手段を提供する。
本発明に係るアクリル樹脂は、１分子中に１個以上のアルコキシシリル基を有するアクリル樹脂であって、数平均分子量が８００〜２５００であり、重量平均分子量／数平均分子量が２．５以下であり、かつ前記アルコキシシリル基の濃度が１．５モル／Ｋｇ樹脂以上であることを特徴とする。
本発明により、アクリル樹脂において、固化して作業性が悪化することを防止できる。
In order to solve the above-described problems, the present invention provides the following means.
The acrylic resin according to the present invention is an acrylic resin having one or more alkoxysilyl groups in one molecule, having a number average molecular weight of 800 to 2500, and a weight average molecular weight / number average molecular weight of 2.5 or less. And the concentration of the alkoxysilyl group is 1.5 mol / Kg resin or more.
According to the present invention, in an acrylic resin, it is possible to prevent solidification and deterioration of workability.
従って、通常のアクリル樹脂に比べて、粘性を調整するために溶剤を使用しないので大気汚染が抑制できる。また、エネルギー（熱）を節約でき、設備を簡素化できる。
また、本発明に係るアクリル樹脂の製造方法は、アクリルモノマーを有機溶剤に溶解もしくは分散させるとともに、前記アクリルモノマー１００重量部に対して重合開始剤２〜１０重量部を前記有機溶剤に滴下し、１３０℃以上で重合反応を行う工程と、前記有機溶剤を除去する工程と、を備えることを特徴とする。
Therefore, as compared with a normal acrylic resin, since no solvent is used for adjusting the viscosity, air pollution can be suppressed. In addition, energy (heat) can be saved and equipment can be simplified.
In addition, in the method for producing an acrylic resin according to the present invention, an acrylic monomer is dissolved or dispersed in an organic solvent, and 2 to 10 parts by weight of a polymerization initiator is dropped into the organic solvent with respect to 100 parts by weight of the acrylic monomer. The method includes a step of performing a polymerization reaction at 130 ° C. or higher and a step of removing the organic solvent.
これにより、１分子中に１個以上のアルコキシシリル基を有し、数平均分子量が８００〜２５００であり、重量平均分子量／数平均分子量が２．５以下であり、かつ前記アルコキシシリル基の濃度が１．５モル／Ｋｇ樹脂以上であるアクリル樹脂を形成することができる。 Thus, one molecule has one or more alkoxysilyl groups, the number average molecular weight is 800 to 2500, the weight average molecular weight / number average molecular weight is 2.5 or less, and the concentration of the alkoxysilyl group Can form an acrylic resin of 1.5 mol / Kg resin or more.
本発明により、アクリル樹脂において、固化して作業性が悪化することを防止できる。
従って、通常のアクリル樹脂に比べて、溶剤を使用しないので大気汚染が抑制できる。また、エネルギー（熱）を節約でき、設備を簡素化できる。
According to the present invention, in an acrylic resin, it is possible to prevent solidification and deterioration of workability.
Therefore, air pollution can be suppressed because no solvent is used as compared with a normal acrylic resin. In addition, energy (heat) can be saved and equipment can be simplified.
以下、本発明を詳細に説明する。
本発明のアクリル樹脂は、１分子中に１個以上のアルコキシシリル基を有するアクリル樹脂であって、数平均分子量が８００〜２５００であり、重量平均分子量／数平均分子量が２．５以下であり、かつ前記アルコキシシリル基の濃度が１．５モル／Ｋｇ樹脂以上である。
Hereinafter, the present invention will be described in detail.
The acrylic resin of the present invention is an acrylic resin having one or more alkoxysilyl groups in one molecule, the number average molecular weight is 800 to 2500, and the weight average molecular weight / number average molecular weight is 2.5 or less. And the density | concentration of the said alkoxysilyl group is 1.5 mol / Kg resin or more.
本発明のアクリル樹脂の製造方法を説明する。
まず、複数のアクリルモノマーの成分を有機溶剤に溶解もしくは分散させ、重合温度を１３０℃以上に保ちながら、アクリルモノマー１００重量部に対して、重合開始剤であるラジカル重合開始剤２〜１０重量部をアクリルモノマーの撹拌下に滴下し、重合反応を行う。
The manufacturing method of the acrylic resin of this invention is demonstrated.
First, a plurality of acrylic monomer components are dissolved or dispersed in an organic solvent, and while maintaining the polymerization temperature at 130 ° C. or higher, 2 to 10 parts by weight of a radical polymerization initiator as a polymerization initiator with respect to 100 parts by weight of the acrylic monomer Is dropped with stirring of the acrylic monomer to carry out the polymerization reaction.
重合温度が１３０℃よりも低い場合には数平均分子量が２５００より大きくなり、かつ、未重合のモノマーが多くなり好ましくない。
また、ラジカル重合開始剤が２重量部よりも少ないと、未反応のモノマーが多く残存することとなり好ましくない。
また、１０重量部よりも多くなると、得られた樹脂中の開始剤の残基の割合が高くなる。そのため、アクリル樹脂の本来持つ特性、透明性、耐油性、耐候性等が損なわれ好ましくない。
When the polymerization temperature is lower than 130 ° C., the number average molecular weight is more than 2500, and unpolymerized monomers increase, which is not preferable.
On the other hand, if the radical polymerization initiator is less than 2 parts by weight, a large amount of unreacted monomer remains, which is not preferable.
Moreover, when it exceeds 10 weight part, the ratio of the residue of the initiator in the obtained resin will become high. Therefore, the inherent properties, transparency, oil resistance, weather resistance, etc. of the acrylic resin are impaired, which is not preferable.
反応時間は通常、１〜１０時間とすればよい。重合終了後、常圧、又は減圧下に有機溶媒を除去する。
これにより、１分子中に１個以上のアルコキシシリル基を有するアクリル樹脂であって、数平均分子量が８００〜２５００であり、重量平均分子量／数平均分子量が２．５以下であり、かつ前記アルコキシシリル基の濃度が１．５モル／Ｋｇ樹脂以上であるアクリル樹脂が作製できる。
The reaction time is usually 1 to 10 hours. After completion of the polymerization, the organic solvent is removed under normal pressure or reduced pressure.
Thus, an acrylic resin having one or more alkoxysilyl groups in one molecule, having a number average molecular weight of 800 to 2500, a weight average molecular weight / number average molecular weight of 2.5 or less, and the alkoxy resin An acrylic resin having a silyl group concentration of 1.5 mol / Kg resin or more can be produced.
アクリル樹脂の数平均分子量があまりに低い場合、アクリル樹脂の持つ特性が損なわれ強靭な硬化物が得られなくなる。また、アクリル樹脂の数平均分子量があまり高いと粘度が高くなり無溶剤化の妨げになる。したがって、アクリル樹脂の数平均分子量は、８００〜２５００であることが好ましい。 If the number average molecular weight of the acrylic resin is too low, the properties of the acrylic resin are impaired and a tough cured product cannot be obtained. On the other hand, if the number average molecular weight of the acrylic resin is too high, the viscosity becomes high and the solvent-free state is hindered. Therefore, the number average molecular weight of the acrylic resin is preferably 800 to 2500.
本発明に使用される（メタ）アクリルモノマーとしては特に限定されるものではなく、一般的に（メタ）アクリルモノマーとして知られているものであればいかなるものであってもよい。 The (meth) acrylic monomer used in the present invention is not particularly limited and may be any as long as it is generally known as a (meth) acrylic monomer.
この化合物の具体例としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ブチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、ラウリル（メタ）アクリレート、２−ヒイドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、２−ヒドロキシ−３−フェノキシプロピル（メタ）アクリレート、テトラヒドロフルフラル（メタ）アクリレート、メトキシジエチレングリコール（メタ）アクリレート、メトキシテトラエチレングリコール（メタ）アクリレート、フェノキシエチルオキシエチル（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、３−クロロ−２−ヒドロキシプロピル（メタ）アクリレート等があげられる。 Specific examples of this compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, and 2-ethylhexyl (meth). Acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxy Propyl (meth) acrylate, tetrahydrofurfural (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, phenoxyethyloxy Chill (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate and the like.
また、本発明に使用できるアルコキシシリル基を有するアクリルモノマーの具体例としては、下記のように表わされる化合物がある。 Further, specific examples of the acrylic monomer having an alkoxysilyl group that can be used in the present invention include compounds represented as follows.
（Ｒ1＝水素またはメチル、Ｒ2＝メチルまたはエチル、ｎ＝３〜１０の整数）
本発明で用いることができるラジカル重合開始剤としては、通常使用されているものを用いることができる。また、好ましくは１０時間半減期温度が５０℃から１２５℃までのものである。
(R 1 = hydrogen or methyl, R 2 = methyl or ethyl, n = integer of 3-10)
As the radical polymerization initiator that can be used in the present invention, those generally used can be used. Also preferably, the 10 hour half-life temperature is from 50 ° C to 125 ° C.
具体例としては、ｔ−ブチルパーオキシピバレ−ト、ｔ−ブチルパーオキシネオデカネート、ｔ−ブチルパーオキシ−２−エチルヘキサノエート、ｔ−ブチルパーオキシ−３，５，５−トリメチルヘキサノエート等である。
また、その他、アゾイソブチルニトリル，アゾビスジメチルバレロニトリル等があげられる。
Specific examples include t-butyl peroxypivalate, t-butyl peroxyneodecanate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxy-3,5,5-trimethyl. Such as hexanoate.
Other examples include azoisobutyl nitrile and azobisdimethylvaleronitrile.
有機溶媒としては、アルコール系溶媒、エーテル系溶媒、炭化水素系溶媒を用いることができる。また、炭化水素系溶媒を用いた場合には、溶解性の点から他の溶媒を併用することが好ましい。特に好ましくはキシレン、トルエンである。
なお、本発明のアクリル樹脂にはその他共重合可能な不飽和モノマーを共重合させることができる。
As the organic solvent, an alcohol solvent, an ether solvent, or a hydrocarbon solvent can be used. When a hydrocarbon solvent is used, it is preferable to use another solvent in combination from the viewpoint of solubility. Particularly preferred are xylene and toluene.
The acrylic resin of the present invention can be copolymerized with other copolymerizable unsaturated monomers.
共重合可能な不飽和モノマーの具体例としてはアクリロニトリル、酢酸ビニル、スチレン、メチルスチレン、クロルスチレン、等のスチレン誘導体、ビニリデンクロライド、アクリルアミド、エチルα−アセトキシアクリレ−ト等の重合性モノマーがある。
以下、実験例により本発明をさらに具体的に説明するが、本発明は以下の実験例に限定されるものではない。
Specific examples of the copolymerizable unsaturated monomer include styrene derivatives such as acrylonitrile, vinyl acetate, styrene, methylstyrene, chlorostyrene, and polymerizable monomers such as vinylidene chloride, acrylamide, and ethyl α-acetoxyacrylate. .
Hereinafter, the present invention will be described more specifically with experimental examples, but the present invention is not limited to the following experimental examples.
「実験例１」
撹拌機、コンデンサー及び滴下ロート２基を備えた２リットルセパラブルフラスコにキシレン１０００ｇを計り取り、オイルバスにより１４０℃に加熱した。８−（トリメトキシシリル）オクチルメタクリレート１７７ｇ、メチルメタクリレート５６ｇ、ｎ−ブチルアクリレート７７ｇをはかりとり、よく混合して滴下ロートに仕込んだ。
また、キシレン２００ｇとｔ−ブチルパーオキシー２−エチルヘキサノエート３１ｇをよく混合し別の滴下ロートに仕込んだ。
"Experiment 1"
1000 g of xylene was measured into a 2 liter separable flask equipped with a stirrer, a condenser and two dropping funnels, and heated to 140 ° C. with an oil bath. 177 g of 8- (trimethoxysilyl) octyl methacrylate, 56 g of methyl methacrylate and 77 g of n-butyl acrylate were weighed, mixed well, and charged into a dropping funnel.
Further, 200 g of xylene and 31 g of t-butylperoxy-2-ethylhexanoate were mixed well and charged into another dropping funnel.
これらモノマーと重合開始剤とを重合温度１４０℃を維持するようにキシレン中に約３時間で滴下した。滴下終了後、更に１４０℃で３時間熟成した。
熟成終了後、ガスクロマト分析によりモノマー成分が０．５％以下であることを確認した。つぎに減圧下にキシレンを除去し、目的のアクリル樹脂３４５ｇを得た。
得られたアクリル樹脂の性状はアルコキシシリル基濃度１．６ｍｏｌ／ｋｇ、数平均分子量Ｍｎ１０８０、重量平均分子量／数平均分子量＝１．９であった。
These monomers and a polymerization initiator were dropped into xylene in about 3 hours so as to maintain a polymerization temperature of 140 ° C. After completion of dropping, the mixture was further aged at 140 ° C. for 3 hours.
After completion of aging, it was confirmed by gas chromatography analysis that the monomer component was 0.5% or less. Next, xylene was removed under reduced pressure to obtain 345 g of the desired acrylic resin.
The properties of the obtained acrylic resin were alkoxysilyl group concentration 1.6 mol / kg, number average molecular weight Mn 1080, weight average molecular weight / number average molecular weight = 1.9.
「実験例２」
撹拌機、コンデンサー及び滴下ロート２基を備えた２リットルセパラブルフラスコにキシレン１０００ｇを計り取り、オイルバスにより１４０℃に加熱する。８−（トリメトキシシリル）オクチルメタクリレート１２６ｇ、メチルメタクリレート２９ｇ、ｎ−ブチルアクリレート６０ｇ、２−ヒドロキシエチルアクリレート３６ｇ、８−（トリメトキシシリル）オクチルアクリレート５９ｇを計り取り、よく混合して滴下ロートに仕込んだ。
また、キシレン２００ｇと重合開始剤ｔ−ブチルパーオキシ−２−エチルヘキサノエート３１ｇをよく混合し別の滴下ロートに仕込んだ。
"Experimental example 2"
1000 g of xylene is measured into a 2 liter separable flask equipped with a stirrer, a condenser and two dropping funnels, and heated to 140 ° C. with an oil bath. Weigh 126 g of 8- (trimethoxysilyl) octyl methacrylate, 29 g of methyl methacrylate, 60 g of n-butyl acrylate, 36 g of 2-hydroxyethyl acrylate, 59 g of 8- (trimethoxysilyl) octyl acrylate, mix well, and charge into the dropping funnel. It is.
Further, 200 g of xylene and 31 g of a polymerization initiator t-butylperoxy-2-ethylhexanoate were mixed well and charged into another dropping funnel.
これらモノマーと重合開始剤を重合温度１４０℃を維持するようにキシレン中に約３時間で滴下した。
滴下終了後、１４０℃で１時間熟成し、重合開始剤ｔ−ブチルパーオキシ−２−エチルヘキサノエート１．６ｇを再度追加した。その後、更に同温で２時間熟成した。
These monomers and a polymerization initiator were dropped into xylene in about 3 hours so as to maintain a polymerization temperature of 140 ° C.
After completion of dropping, the mixture was aged at 140 ° C. for 1 hour, and 1.6 g of a polymerization initiator t-butylperoxy-2-ethylhexanoate was added again. Thereafter, it was further aged for 2 hours at the same temperature.
ガスクロマト分析によりモノマー成分が０．５％以下であることを確認した。つぎに減圧下にキシレンを除去し、目的のアクリル樹脂３５０ｇを得た。
得られたアクリル樹脂はアルコキシシリル基濃度１．６ｍｏｌ／ｋｇ、数平均分子量Ｍｎ１１００、重量平均分子量／数平均分子量＝１．９であった。
以下、本発明に対する比較例を説明する。
It was confirmed by gas chromatography analysis that the monomer component was 0.5% or less. Next, xylene was removed under reduced pressure to obtain 350 g of the desired acrylic resin.
The obtained acrylic resin had an alkoxysilyl group concentration of 1.6 mol / kg, a number average molecular weight Mn of 1100, and a weight average molecular weight / number average molecular weight of 1.9.
Hereinafter, comparative examples for the present invention will be described.
「比較例１」
撹拌機、コンデンサー及び滴下ロートを備えた２リットルセパラブルフラスコにトルエン８２０ｇ、８−（トリメトキシシリル）オクチルメタクリレート３１１ｇ、メチルメタクリレート３１１ｇ、ｎ−ブチルアクリレート１９７ｇ、２−メルカプトエタノール１０５ｇをはかりとり、オイルバスで１１０℃に加熱した。
“Comparative Example 1”
820 g of toluene, 311 g of 8- (trimethoxysilyl) octyl methacrylate, 311 g of methyl methacrylate, 197 g of n-butyl acrylate, and 105 g of 2-mercaptoethanol are weighed in a 2 liter separable flask equipped with a stirrer, a condenser and a dropping funnel. Heated to 110 ° C. in bath.
また、重合開始剤ｔ−ブチルパーオキシ−２−エチルヘキサノエート７８ｇを滴下ロートを用いて２時間かけて滴下した。
滴下終了後、重合温度１１０℃で３時間熟成した。ガスクロマト分析によりモノマー成分が０．７％以下であることを確認した。この比較例では、重合温度を１３０度より低くしている。
Further, 78 g of a polymerization initiator t-butylperoxy-2-ethylhexanoate was dropped over 2 hours using a dropping funnel.
After completion of dropping, the mixture was aged at a polymerization temperature of 110 ° C. for 3 hours. It was confirmed by gas chromatography analysis that the monomer component was 0.7% or less. In this comparative example, the polymerization temperature is lower than 130 degrees.
つぎに減圧下にキシレンを除去しアクリル樹脂９００ｇを得た。
得られたアクリル樹脂の性状はアルコキシシリル基濃度１．１ｍｏｌ／ｋｇ、数平均分子量Ｍｎ７６０、重量平均分子量／数平均分子量＝１．６であった。なお、連鎖移動剤を有しているため、数平均分子量Ｍｎは７６０となっている。
また、連鎖移動剤を有しているため、このアクリル樹脂は特異なメルカプタン臭を有していた。
Next, xylene was removed under reduced pressure to obtain 900 g of an acrylic resin.
The properties of the obtained acrylic resin were alkoxysilyl group concentration 1.1 mol / kg, number average molecular weight Mn760, weight average molecular weight / number average molecular weight = 1.6. In addition, since it has a chain transfer agent, the number average molecular weight Mn is 760.
Moreover, since it had a chain transfer agent, this acrylic resin had a unique mercaptan odor.
「比較例２」
撹拌機、コンデンサー及び滴下ロート２基を備えた２リットルセパラブルフラスコにキシレン１０００ｇをとり、オイルバスにより１４０℃に加熱した。８−（トリメトキシシリル）オクチルメタクリレート１２６ｇ、メチルメタクリレート２９ｇ、ｎ−ブチルアクリレート６０ｇ、２−ヒドロキシエチルアクリレート３６ｇ、８−（トリメトキシシリル）オクチルアクリレート５９ｇをはかりとり良く混合して滴下ロ−トに仕込んだ。
"Comparative Example 2"
1000 g of xylene was placed in a 2 liter separable flask equipped with a stirrer, a condenser and two dropping funnels, and heated to 140 ° C. with an oil bath. 126 g of 8- (trimethoxysilyl) octyl methacrylate, 29 g of methyl methacrylate, 60 g of n-butyl acrylate, 36 g of 2-hydroxyethyl acrylate and 59 g of 8- (trimethoxysilyl) octyl acrylate are mixed and mixed well into a dropping funnel. Prepared.
キシレン２００ｇと重合開始剤ｔ−ブチルパーオキシ−２ー−エチルヘキサノエート３ｇを良く混合して別の滴下ロートに仕込んだ。
これらモノマーと重合開始剤を重合温度１４０℃を維持するようにキシレン中に３時間かけて滴下した。
200 g of xylene and 3 g of a polymerization initiator t-butylperoxy-2-ethylhexanoate were mixed well and charged into another dropping funnel.
These monomers and a polymerization initiator were dropped into xylene over 3 hours so as to maintain a polymerization temperature of 140 ° C.
滴下終了後、さらに１４０℃で３時間熟成した。熟成終了後、減圧下キシレンを除去し、アクリル樹脂３４０ｇを得た。この比較例では、アクリルモノマー１００重量部に対して重合開始剤１重量部である。
得られたアクリル樹脂の性状はアルコキシシリル基濃度１．７ｍｏｌ／ｋｇ、数平均分子量Ｍｎ２７５０、重量平均分子量／数平均分子量＝２．１であった。
After completion of dropping, the mixture was further aged at 140 ° C. for 3 hours. After completion of aging, xylene was removed under reduced pressure to obtain 340 g of an acrylic resin. In this comparative example, the polymerization initiator is 1 part by weight with respect to 100 parts by weight of the acrylic monomer.
The properties of the obtained acrylic resin were alkoxysilyl group concentration 1.7 mol / kg, number average molecular weight Mn2750, weight average molecular weight / number average molecular weight = 2.1.
この比較例では、得られたアクリル樹脂の数平均分子量Ｍｎが２５００より大きい。このため、未重合のモノマーが多くなっている。これは、重合開始剤の滴下量が２重量部よりも小さいためである。
以上より、本実験例は、比較例と比較し、重合反応を精度良く行うことができた。また、溶剤を使用しないので大気汚染が抑制でき、またエネルギー（熱）を節約できるといった効果が得られる。
In this comparative example, the number average molecular weight Mn of the obtained acrylic resin is larger than 2500. For this reason, there are many unpolymerized monomers. This is because the dripping amount of the polymerization initiator is smaller than 2 parts by weight.
From the above, this experimental example was able to carry out the polymerization reaction with higher accuracy than the comparative example. In addition, since no solvent is used, air pollution can be suppressed and energy (heat) can be saved.
Claims (2)
数平均分子量が８００〜２５００であり、重量平均分子量／数平均分子量が２．５以下であり、かつ前記アルコキシシリル基の濃度が１．５モル／Ｋｇ樹脂以上であることを特徴とするアクリル樹脂。 An acrylic resin having one or more alkoxysilyl groups in one molecule,
An acrylic resin having a number average molecular weight of 800 to 2500, a weight average molecular weight / number average molecular weight of 2.5 or less, and a concentration of the alkoxysilyl group of 1.5 mol / Kg resin or more. .
前記有機溶剤を除去する工程と、
を備えることを特徴とするアクリル樹脂の製造方法。 A step of dissolving or dispersing an acrylic monomer in an organic solvent, dropping 2 to 10 parts by weight of a polymerization initiator into the organic solvent with respect to 100 parts by weight of the acrylic monomer, and performing a polymerization reaction at 130 ° C. or higher;
Removing the organic solvent;
A method for producing an acrylic resin, comprising:
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| JP2018002970A (en) * | 2016-07-08 | 2018-01-11 | 信越化学工業株式会社 | Thermosetting silicone resin composition and optical semiconductor device using the molded body |
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