JP2013082823A - Polymer, polymer composition, method for producing polymer, and method for producing block copolymer - Google Patents
Polymer, polymer composition, method for producing polymer, and method for producing block copolymer Download PDFInfo
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- JP2013082823A JP2013082823A JP2011224219A JP2011224219A JP2013082823A JP 2013082823 A JP2013082823 A JP 2013082823A JP 2011224219 A JP2011224219 A JP 2011224219A JP 2011224219 A JP2011224219 A JP 2011224219A JP 2013082823 A JP2013082823 A JP 2013082823A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 119
- 238000004519 manufacturing process Methods 0.000 title claims description 27
- 229920001400 block copolymer Polymers 0.000 title claims description 17
- 239000000203 mixture Substances 0.000 title claims description 13
- 239000000178 monomer Substances 0.000 claims abstract description 62
- -1 thiocarbonylthio group Chemical group 0.000 claims abstract description 48
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 46
- 239000003960 organic solvent Substances 0.000 claims abstract description 23
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007870 radical polymerization initiator Substances 0.000 claims abstract description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000010526 radical polymerization reaction Methods 0.000 claims description 14
- 238000001542 size-exclusion chromatography Methods 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 9
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- 238000005160 1H NMR spectroscopy Methods 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
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- 238000005227 gel permeation chromatography Methods 0.000 claims 2
- 125000004432 carbon atom Chemical group C* 0.000 description 27
- FFYWKOUKJFCBAM-UHFFFAOYSA-N ethenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC=C FFYWKOUKJFCBAM-UHFFFAOYSA-N 0.000 description 17
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- 238000000034 method Methods 0.000 description 15
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- 125000000217 alkyl group Chemical group 0.000 description 10
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- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 8
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- 125000000623 heterocyclic group Chemical group 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 5
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- IDSLBLWCPSAZBL-UHFFFAOYSA-N 2-cyanopropan-2-yl benzenecarbodithioate Chemical compound N#CC(C)(C)SC(=S)C1=CC=CC=C1 IDSLBLWCPSAZBL-UHFFFAOYSA-N 0.000 description 4
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- 125000005842 heteroatom Chemical group 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
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- 229920005989 resin Polymers 0.000 description 4
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
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- 239000007787 solid Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
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- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
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- FNBPLKKPMRILKY-UHFFFAOYSA-N (4-ethenylphenyl)methyl benzenecarbodithioate Chemical compound C1=CC(C=C)=CC=C1CSC(=S)C1=CC=CC=C1 FNBPLKKPMRILKY-UHFFFAOYSA-N 0.000 description 1
- FLLHZLOYVPKTTJ-UHFFFAOYSA-N (benzyltetrasulfanyl)methylbenzene Chemical group C=1C=CC=CC=1CSSSSCC1=CC=CC=C1 FLLHZLOYVPKTTJ-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- VBQCFYPTKHCPGI-UHFFFAOYSA-N 1,1-bis(2-methylpentan-2-ylperoxy)cyclohexane Chemical compound CCCC(C)(C)OOC1(OOC(C)(C)CCC)CCCCC1 VBQCFYPTKHCPGI-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
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Images
Abstract
Description
本発明は、重合体、重合体組成物、重合体の製造方法およびブロック共重合体の製造方法に関する。 The present invention relates to a polymer, a polymer composition, a method for producing a polymer, and a method for producing a block copolymer.
分子中に二重結合などの反応活性点を有する重合体は、その反応活性点に基づく反応性、重合性、架橋・硬化性などの特性を利用して、接着剤、塗料、各種処理剤、成形材料などの種々の用途に用いられている。 A polymer having a reactive active site such as a double bond in the molecule is used for adhesives, paints, various treating agents, utilizing properties such as reactivity, polymerizability, cross-linking and curability based on the reactive active site, It is used for various applications such as molding materials.
分子中に反応活性点を導入する方法としては、１分子中に２つの二重結合を有するモノマーを重合する方法が挙げられる。
特許文献１（特開２００７−２９７５２６号公報）には、アリル（メタ）アクリレートおよびビニル（メタ）アクリレートから選ばれる少なくとも１種の２官能性（メタ）アクリレートを含む不飽和単量体を、ルイス酸の存在下でラジカル重合する方法が記載されている。この重合方法によると、２官能性（メタ）アクリレートを１０質量％以上の高い割合で用いた場合にも、分子間架橋のない、熱可塑性の重合体が得られることが記載されている。このように、１分子中に２つの二重結合を有するモノマーを重合すると、側鎖に複数の二重結合を有する重合体が得られる。
Examples of a method for introducing a reactive site in a molecule include a method of polymerizing a monomer having two double bonds in one molecule.
Patent Document 1 (Japanese Patent Application Laid-Open No. 2007-297526) discloses an unsaturated monomer containing at least one bifunctional (meth) acrylate selected from allyl (meth) acrylate and vinyl (meth) acrylate. A method for radical polymerization in the presence of an acid is described. According to this polymerization method, it is described that even when a bifunctional (meth) acrylate is used at a high ratio of 10% by mass or more, a thermoplastic polymer having no intermolecular crosslinking can be obtained. Thus, when a monomer having two double bonds in one molecule is polymerized, a polymer having a plurality of double bonds in the side chain is obtained.
また、分子中に反応活性点を導入する他の方法としては、特定のチオカルボニルチオ化合物を連鎖移動剤として実施する可逆的付加脱離連鎖移動（ＲＡＦＴ）重合法が挙げられる（例えば特許文献２、３参照）。このＲＡＦＴ重合法を用いると、分子末端にチオカルボニルチオ基を有するポリマーを得ることができる。分子末端のチオカルボニルチオ基は、反応活性点として働く。そのため、このチオカルボニルチオ基末端を開始点として新たな重合をおこなうことができ、さまざまなブロック共重合体を得られるとされている。 In addition, as another method for introducing a reactive site into a molecule, there is a reversible addition / elimination chain transfer (RAFT) polymerization method in which a specific thiocarbonylthio compound is used as a chain transfer agent (for example, Patent Document 2). 3). When this RAFT polymerization method is used, a polymer having a thiocarbonylthio group at the molecular end can be obtained. The thiocarbonylthio group at the molecular end serves as a reaction active site. Therefore, it is said that new polymerization can be carried out starting from the terminal of this thiocarbonylthio group, and various block copolymers can be obtained.
また、非特許文献１（Journal of Polymer Science Part A：Polymer Chemistry, Vol.45, Issue 1, 26-40 (2007)）には、アリルメタクリレ―トのＲＡＦＴ重合が記載されている。この文献によれば、特定のチオカルボニルチオ化合物を連鎖移動剤として、アリルメタクリレ―トのＲＡＦＴ重合をおこなうことにより、重合末端にチオカルボニルチオ基と、側鎖に複数の二重結合であるアリル基とを備え、有機溶媒に可溶な重合体が得られるとされている。なお、アリル基にはラジカル反応性はない。 Non-Patent Document 1 (Journal of Polymer Science Part A: Polymer Chemistry, Vol. 45, Issue 1, 26-40 (2007)) describes RAFT polymerization of allyl methacrylate. According to this document, by performing RAFT polymerization of allyl methacrylate using a specific thiocarbonylthio compound as a chain transfer agent, there are a thiocarbonylthio group at the polymerization terminal and a plurality of double bonds in the side chain. It is said that a polymer having an allyl group and soluble in an organic solvent can be obtained. The allyl group has no radical reactivity.
一方、重合末端にチオカルボニルチオ基と、側鎖に複数のラジカル重合が可能な二重結合とを有する重合体は知られていない。 On the other hand, a polymer having a thiocarbonylthio group at a polymerization end and a double bond capable of radical polymerization at a side chain is not known.
本発明は上述のような課題に鑑みてなされたものであり、重合末端にチオカルボニルチオ基と、側鎖に複数のラジカル重合が可能な二重結合とを備え、有機溶媒に可溶な重合体を提供することにある。 The present invention has been made in view of the above-mentioned problems, and includes a thiocarbonylthio group at a polymerization terminal and a double bond capable of radical polymerization at a side chain, and is soluble in an organic solvent. To provide coalescence.
本発明者らは上記の課題を達成すべく鋭意検討を重ねてきた。その結果、チオカルボニルチオ基を有する連鎖移動剤と、ラジカル重合開始剤とを特定の割合で重合系に添加し、それらの存在下で、１分子中に２つのラジカル重合が可能な二重結合を有し、かつ、非対称構造であるモノマーを重合することにより、重合末端にチオカルボニルチオ基と、側鎖に複数のラジカル重合が可能な二重結合とを備え、有機溶媒に可溶な重合体が得られることを見出した。 The present inventors have intensively studied to achieve the above-described problems. As a result, a chain transfer agent having a thiocarbonylthio group and a radical polymerization initiator are added to the polymerization system at a specific ratio, and in the presence thereof, a double bond capable of two radical polymerizations in one molecule. And a monomer having an asymmetric structure is polymerized to have a thiocarbonylthio group at the polymerization terminal and a double bond capable of radical polymerization at the side chain, and is soluble in an organic solvent. We found that coalescence was obtained.
すなわち、本発明によれば、
重合末端にチオカルボニルチオ基と、
側鎖にラジカル重合が可能な複数の二重結合と、を備え、アセトン、テトラヒドロフラン、クロロホルム、トルエンのいずれかに溶解する、重合体が提供される。
That is, according to the present invention,
A thiocarbonylthio group at the polymerization terminal;
Provided is a polymer having a plurality of double bonds capable of radical polymerization in a side chain and dissolved in any one of acetone, tetrahydrofuran, chloroform, and toluene.
さらに、本発明によれば、
上記本発明の重合体を有機溶媒に溶解して得られる、重合体組成物が提供される。
Furthermore, according to the present invention,
There is provided a polymer composition obtained by dissolving the polymer of the present invention in an organic solvent.
さらに、本発明によれば、上記本発明の重合体の製造方法であって、
前記チオカルボニルチオ基を有する連鎖移動剤と、ラジカル重合開始剤との存在下で、
１分子中に２つのラジカル重合が可能な二重結合を有し、かつ、非対称構造である第１モノマーを含む、モノマー成分をラジカル重合する工程を備え、
前記モノマー成分１００モル部に対して、
前記チオカルボニルチオ基を有する連鎖移動剤の添加量が０．２モル部以上２０モル部以下であり、
前記ラジカル重合開始剤の添加量が０．１モル部以上１０モル部以下である、重合体の製造方法が提供される。
Furthermore, according to the present invention, there is provided a process for producing the polymer of the present invention,
In the presence of the chain transfer agent having the thiocarbonylthio group and a radical polymerization initiator,
A step of radically polymerizing a monomer component including a first monomer having a double bond capable of two radical polymerizations in one molecule and having an asymmetric structure;
For 100 mole parts of the monomer component
The addition amount of the chain transfer agent having a thiocarbonylthio group is 0.2 to 20 parts by mole,
Provided is a method for producing a polymer, wherein the radical polymerization initiator is added in an amount of 0.1 to 10 mol parts.
さらに、本発明によれば、上記本発明の製造方法で得られた重合体のチオカルボニルチオ基末端を開始点として、１分子中に１つの二重結合を有する第３モノマーを重合する工程を備える、ブロック共重合体の製造方法が提供される。 Furthermore, according to the present invention, the step of polymerizing a third monomer having one double bond in one molecule starting from the thiocarbonylthio group terminal of the polymer obtained by the production method of the present invention described above. A method for producing a block copolymer is provided.
本発明によれば重合末端にチオカルボニルチオ基と、側鎖に複数のラジカル重合が可能な二重結合とを備え、有機溶媒に可溶な重合体を提供することができる。 According to the present invention, it is possible to provide a polymer that has a thiocarbonylthio group at a polymerization terminal and a double bond capable of radical polymerization at a side chain and is soluble in an organic solvent.
以下、本発明について説明するが、本発明は、以下の具体的形態に限定されるものではなく、技術的思想の範囲内で任意に変形することができる。 Hereinafter, the present invention will be described, but the present invention is not limited to the following specific embodiments, and can be arbitrarily modified within the scope of the technical idea.
本発明の重合体は、重合末端にチオカルボニルチオ基と、側鎖にラジカル重合が可能な複数の二重結合とを備えている。そして、本発明の重合体は、アセトン、テトラヒドロフラン、クロロホルム、トルエンのいずれかに溶解する。 The polymer of the present invention comprises a thiocarbonylthio group at the polymerization terminal and a plurality of double bonds capable of radical polymerization at the side chain. And the polymer of this invention melt | dissolves in any of acetone, tetrahydrofuran, chloroform, and toluene.
（重合体の製造方法）
以下、本発明の重合体の製造方法について、具体例を用いて説明するが、本発明は以下に限定されるものではない。
(Method for producing polymer)
Hereinafter, although the manufacturing method of the polymer of this invention is demonstrated using a specific example, this invention is not limited to the following.
本実施形態の重合体の製造方法は、チオカルボニルチオ基を有する連鎖移動剤と、ラジカル重合開始剤との存在下で、１分子中に２つのラジカル重合が可能な二重結合を有し、かつ、非対称構造である第１モノマーを含む、モノマー成分をラジカル重合する工程を備えている。 The polymer production method of the present embodiment has a double bond capable of two radical polymerizations in one molecule in the presence of a chain transfer agent having a thiocarbonylthio group and a radical polymerization initiator, And it has the process of radical-polymerizing the monomer component containing the 1st monomer which is an asymmetrical structure.
そして、モノマー成分１００モル部に対して、チオカルボニルチオ基を有する連鎖移動剤の添加量は、好ましくは０．２モル部以上であり、さらに好ましくは０．８モル部以上であり、とくに好ましくは１．５モル部以上である。連鎖移動剤の添加量を上記下限値以上とすることにより、重合体のゲル化を抑制し重合物を得ることができる。
なお、本実施形態において、モノマー成分とは、後述する第一モノマーおよび第二モノマーを表す。第二モノマーを添加しない場合は、第一モノマーのみを表す。
And the addition amount of the chain transfer agent having a thiocarbonylthio group is preferably 0.2 mol parts or more, more preferably 0.8 mol parts or more, particularly preferably 100 mol parts of the monomer component. Is 1.5 mol parts or more. By making the addition amount of a chain transfer agent more than the said lower limit, gelatinization of a polymer can be suppressed and a polymer can be obtained.
In addition, in this embodiment, a monomer component represents the 1st monomer and 2nd monomer which are mentioned later. When no second monomer is added, only the first monomer is represented.
また、モノマー成分１００モル部に対して、チオカルボニルチオ基を有する連鎖移動剤の添加量は好ましくは２０モル部以下であり、さらに好ましくは１０モル部以下であり、とくに好ましくは５モル部以下である。連鎖移動剤の添加量を上記上限値以下とすることにより、重合体の収率の低下を抑制することができる。 The amount of the chain transfer agent having a thiocarbonylthio group added is preferably 20 parts by mole or less, more preferably 10 parts by mole or less, and particularly preferably 5 parts by mole or less with respect to 100 parts by mole of the monomer component. It is. The fall of the yield of a polymer can be suppressed by making the addition amount of a chain transfer agent below the said upper limit.
また、モノマー成分１００モル部に対して、ラジカル重合開始剤の添加量は好ましくは０．１モル部以上であり、さらに好ましくは０．４モル部以上であり、とくに好ましくは０．８モル部以上である。ラジカル重合開始剤の添加量を上記下限値以上とすることにより、重合体の収率を増加させることができる。 Further, the amount of radical polymerization initiator added is preferably 0.1 mol parts or more, more preferably 0.4 mol parts or more, particularly preferably 0.8 mol parts with respect to 100 mol parts of the monomer component. That's it. By making the addition amount of the radical polymerization initiator more than the above lower limit value, the yield of the polymer can be increased.
また、モノマー成分１００モル部に対して、ラジカル重合開始剤の添加量は好ましくは１０モル部以下であり、さらに好ましくは５モル部以下であり、とくに好ましくは３モル部以下である。ラジカル重合開始剤の添加量を上記上限値以下とすることにより、重合体の分子量の低下を抑制することができる。 Moreover, the addition amount of the radical polymerization initiator is preferably 10 parts by mole or less, more preferably 5 parts by mole or less, and particularly preferably 3 parts by mole or less with respect to 100 parts by mole of the monomer component. By making the addition amount of a radical polymerization initiator below the said upper limit, the fall of the molecular weight of a polymer can be suppressed.
本実施形態の重合体の製造方法において、重合開始剤の添加量は、チオカルボニルチオ基を有する連鎖移動剤の添加量よりも少ないことが好ましい。
チオカルボニルチオ基を有する連鎖移動剤の添加量に対する重合開始剤の添加量の比は、とくに限定はされないが、０．０３以上１．０以下の範囲にあるのが好ましく、０．０５以上０．８以下の範囲にあるのがさらに好ましく、０．１以上０．６以下の範囲にあるのがとくに好ましい。連鎖移動剤と重合開始剤の添加量の比が上記範囲内にあると、重合体のゲル化を抑制しつつ、重合体の分子量の低下を抑制することができる。
In the polymer production method of the present embodiment, the addition amount of the polymerization initiator is preferably smaller than the addition amount of the chain transfer agent having a thiocarbonylthio group.
The ratio of the addition amount of the polymerization initiator to the addition amount of the chain transfer agent having a thiocarbonylthio group is not particularly limited, but is preferably in the range of 0.03 to 1.0, preferably 0.05 to 0. Is more preferably in the range of 0.8 or less, and particularly preferably in the range of 0.1 to 0.6. When the ratio of the addition amount of the chain transfer agent and the polymerization initiator is within the above range, it is possible to suppress a decrease in the molecular weight of the polymer while suppressing gelation of the polymer.
反応温度は、５０℃以上８０℃以下で行うことが好ましい。さらに好ましくは６０℃以上７０℃以下である。反応温度が上記範囲内にあると、重合体のゲル化を抑制しつつ、重合体の収率の低下を抑制することができる。 The reaction temperature is preferably 50 ° C or higher and 80 ° C or lower. More preferably, it is 60 degreeC or more and 70 degrees C or less. When the reaction temperature is within the above range, it is possible to suppress a decrease in the yield of the polymer while suppressing gelation of the polymer.
溶媒はモノマー１００体積部に対して、５００体積部以下で行うことが好ましい。さらに好ましくは１００体積部以下である。重合系における溶媒が上記範囲内にあると、重合体のゲル化を抑制しつつ、重合体の収率の低下を抑制することができる。 The solvent is preferably used at 500 parts by volume or less with respect to 100 parts by volume of the monomer. More preferably, it is 100 volume parts or less. When the solvent in the polymerization system is within the above range, it is possible to suppress a decrease in the yield of the polymer while suppressing gelation of the polymer.
つづいて、本実施形態の重合体の製造方法で使用する各成分について説明する。 Next, each component used in the polymer production method of the present embodiment will be described.
（第１モノマー）
本実施形態における第一モノマーとしては、１分子中に２つのラジカル重合が可能な二重結合を有し、かつ、非対称構造であればとくに限定はされないが、入手容易性の点から、（メタ）アクリル酸ビニルが好ましい。なお、（メタ）アクリル酸とはアクリル酸、メタクリル酸の両方を示す。
本実施形態では、第１モノマーとして上記モノマーのうちの１種類のみを使用しても、２種類以上を使用してもよい。
(First monomer)
The first monomer in the present embodiment is not particularly limited as long as it has a double bond capable of two radical polymerizations in one molecule and has an asymmetric structure. ) Vinyl acrylate is preferred. In addition, (meth) acrylic acid shows both acrylic acid and methacrylic acid.
In the present embodiment, only one type of the above monomers may be used as the first monomer, or two or more types may be used.
なお、第１モノマーが非対称構造であるのが好ましい理由は必ずしも明らかではないが、以下のように推察される。１分子中に２つのラジカル重合が可能な二重結合を有し、かつ、非対称構造であるモノマーは、分子内の２つの二重結合の反応性がそれぞれ異なる。そのため、ラジカルは反応性がより高い二重結合に付加して重合が進んでいく。その結果、反応性がより低い二重結合は反応せず重合体中に残り、側鎖に二重結合を有する重合体を得ることができると考えられる。 The reason why the first monomer preferably has an asymmetric structure is not necessarily clear, but is presumed as follows. A monomer having a double bond capable of radical polymerization in one molecule and an asymmetric structure has different reactivity of the two double bonds in the molecule. For this reason, the radical is added to a double bond having higher reactivity, and polymerization proceeds. As a result, it is considered that a double bond having a lower reactivity does not react and remains in the polymer, and a polymer having a double bond in the side chain can be obtained.
（第２モノマー）
本実施形態のモノマー成分には、１分子中に１つの二重結合を有する第２モノマーをさらに含んでいてもよい。本実施形態における第２モノマーとしては、１分子中に１つの二重結合を有していればとくに限定はされない。
(Second monomer)
The monomer component of this embodiment may further include a second monomer having one double bond in one molecule. The second monomer in this embodiment is not particularly limited as long as it has one double bond in one molecule.
本実施形態における第２モノマーとしては、例えば、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸イソブチル、アクリル酸２−エチルヘキシル、アクリル酸ラウリルなどのアルキル基の炭素数が１〜２０のアクリル酸アルキルエステル；アクリル酸シクロヘキシルなどのシクロアルキル基の炭素数が３〜２０のアクリル酸シクロアルキルエステル；アクリル酸トリシクロデシル、アクリル酸トリシクロデシロキシエチル、アクリル酸トリシクロデシロキシプロピルなどのトリシクロアルキル基の炭素数が５〜２０のアクリル酸トリシクロアルキルエステル；アクリル酸アミノメチル、アクリル酸Ｎ，Ｎ−ジメチルアミノエチルなどのアルキル基の炭素数が１〜２０のアクリル酸アミノアルキルエステル；メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ブチル、メタクリル酸イソブチル、メタクリル酸ｔ−ブチル、メタクリル酸２−エチルヘキシル、メタクリル酸ラウリルなどのアルキル基の炭素数が１〜２０のメタクリル酸アルキルエステル；メタクリル酸シクロヘキシルなどのシクロアルキル基の炭素数が３〜２０のメタクリル酸シクロアルキルエステル；メタクリル酸トリシクロデシル、メタクリル酸トリシクロデシロキシエチル、メタクリル酸トリシクロデシロキシプロピルなどのトリシクロアルキル基の炭素数が５〜２０のメタクリル酸トリシクロアルキルエステル；メタクリル酸アミノメチル、メタクリル酸Ｎ，Ｎ−ジメチルアミノエチルなどのアルキル基の炭素数が１〜２０のメタクリル酸アミノアルキルエステル；スチレン、ビニルトルエン、α−メチルスチレン、ｔ−ブチルスチレンなどのスチレン系単量体；塩化ビニル、塩化ビニリデン、酢酸ビニル、酢酸イソプロペニル、アクリル酸グリシジル、メタクリル酸グリシジル、アクリルアミド、メタクリルアミドなどのビニル誘導体；メタクリル酸３−（トリメトキシシリル）プロピル、アクリル酸３−（トリメトキシシリル）プロピルなどの（メタ）アクリロキシ基を有するシラン化合物；マレイン酸ジメチルエステル、マレイン酸ジエチルエステルなどの不飽和二塩基酸のジアルキルエステル、ヒンダートアミノ基を有するアクリル酸エステル若しくはメタクリル酸エステル、ベンゾトリアゾール基を有するアクリル酸エステル若しくはメタクリル酸エステル、アクリロニトリル、メタクリロニトリルなどグリシジル基を含有する（メタ）アクリル酸グリシジルアルキルエステル、水酸基を含有する(メタ)アクリル酸ヒドロキシアルキルエステルなどが挙げられる。
これらの中でも、（メタ）アクリル酸エステルがとくに好ましい。
本実施形態では、第２モノマーとして上記モノマーのうちの１種類のみを使用しても、２種類以上を使用してもよい。
Examples of the second monomer in the present embodiment include an acrylic having 1 to 20 carbon atoms in an alkyl group such as methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, and the like. Acid alkyl ester; cycloalkyl group having 3 to 20 carbon atoms in the cycloalkyl group such as cyclohexyl acrylate; trialkyl such as tricyclodecyl acrylate, tricyclodecyloxyethyl acrylate, tricyclodecyloxypropyl acrylate, etc. Acrylic acid tricycloalkyl ester having 5 to 20 carbon atoms in the cycloalkyl group; aminoalkyl ester acrylic acid having 1 to 20 carbon atoms in the alkyl group such as aminomethyl acrylate and N, N-dimethylaminoethyl acrylate; Methacryl An alkyl methacrylate having 1 to 20 carbon atoms in the alkyl group such as methyl, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate; A cycloalkyl group having 3 to 20 carbon atoms of a cycloalkyl group such as cyclohexyl methacrylate; a tricycloalkyl group such as tricyclodecyl methacrylate, tricyclodecyloxyethyl methacrylate, or tricyclodecyloxypropyl methacrylate; Methacrylic acid tricycloalkyl ester having 5 to 20 carbon atoms; aminoalkyl methacrylate having 1 to 20 carbon atoms in the alkyl group such as aminomethyl methacrylate and N, N-dimethylaminoethyl methacrylate Steal; Styrene monomers such as styrene, vinyltoluene, α-methylstyrene, t-butylstyrene; vinyl chloride, vinylidene chloride, vinyl acetate, isopropenyl acetate, glycidyl acrylate, glycidyl methacrylate, acrylamide, methacrylamide, etc. Silane compounds having a (meth) acryloxy group such as 3- (trimethoxysilyl) propyl methacrylate and 3- (trimethoxysilyl) propyl acrylate; unsaturated compounds such as dimethyl maleate and diethyl maleate Dialkyl esters of dibasic acids, acrylic or methacrylic esters having hindered amino groups, acrylic or methacrylic esters having benzotriazole groups, acrylonitrile, Containing a glycidyl group such as Ronitoriru (meth) acrylic acid glycidyl esters, containing a hydroxyl group (meth) acrylic acid hydroxyalkyl esters.
Among these, (meth) acrylic acid esters are particularly preferable.
In this embodiment, only one type of the above monomers may be used as the second monomer, or two or more types may be used.
本実施形態の第２モノマーの添加量はとくに限定されず、目的に応じて任意の量を添加することができる。 The addition amount of the 2nd monomer of this embodiment is not specifically limited, According to the objective, arbitrary amounts can be added.
（チオカルボニルチオ基を有する連鎖移動剤）
本実施形態におけるチオカルボニルチオ基を有する連鎖移動剤としては、とくに限定されないが、一般的にＲＡＦＴ重合法に用いられるものを使用できる。例えば、下記一般式（１）で表されるものを用いることができる。
Although it does not specifically limit as a chain transfer agent which has a thiocarbonyl thio group in this embodiment, The thing generally used for the RAFT polymerization method can be used. For example, what is represented by the following general formula (1) can be used.
（上記一般式（１）において、Ｚは水素原子、塩素原子、カルボキシル基、シアノ基、炭素数１〜２０のアルキル基、炭素数６〜２０の１価の芳香族炭化水素基、炭素原子と異項原子との合計原子数３〜２０の１価の複素環式基、−ＯＨ、−ＳＲ１、―Ｎ（Ｒ１）２、―ＯＣ（＝Ｏ）Ｒ１、−Ｃ（＝Ｏ）ＯＲ１、−Ｃ（＝Ｏ）Ｎ（Ｒ１）２、−Ｐ（＝Ｏ）（ＯＲ１）２、または−Ｐ（＝Ｏ）（Ｒ１）２を示す。上記Ｒ１は、炭素数１〜２０のアルキル基、炭素数３〜２０の１価の脂肪族炭化水素基、炭素数６〜２０の１価芳香族炭化水素基、炭素原子と異項原子との合計数３〜２０の１価の複素環式基、−ＯＲ'、−ＳＲ'、−Ｎ（Ｒ'）２または重合体鎖を有する１価の基を示す。各Ｒ'は炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、炭素数６〜１８の１価の芳香族炭化水素基または炭素原子と異項原子との合計原子数３〜１８の１価の複素環式基を示す。上記Ｒは炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、炭素数６〜１８の１価の芳香族炭化水素基または炭素原子と異項原子との合計数３〜１８の１価の複素環式基を示す。上記Ｚの炭素数１〜２０のアルキル基、炭素数６〜２０の１価の芳香族炭化水素、合計原子数３〜２０の１価の複素環式基、カルボキシル基、Ｒ１の水素はそれぞれ置換されていてもよく、前記Ｒの炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、炭素数６〜１８の１価の芳香族炭化水素基、合計数３〜１８の１価の複素環式基の水素はそれぞれ置換されていてもよい。） (In the general formula (1), Z represents a hydrogen atom, a chlorine atom, a carboxyl group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a carbon atom, Monovalent heterocyclic group having 3 to 20 atoms in total with the hetero atom, -OH, -SR1, -N (R1) 2, -OC (= O) R1, -C (= O) OR1,- C (= O) N (R1) 2, -P (= O) (OR1) 2, or -P (= O) (R1) 2 wherein R1 is an alkyl group having 1 to 20 carbon atoms, carbon A monovalent aliphatic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a monovalent heterocyclic group having a total of 3 to 20 carbon atoms and hetero atoms, —OR ′, —SR ′, —N (R ′) 2 or a monovalent group having a polymer chain, wherein each R ′ is an alkyl group having 1 to 18 carbon atoms and an alkenyl having 2 to 18 carbon atoms. N represents a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms or a monovalent heterocyclic group having 3 to 18 total atoms of carbon atoms and hetero atoms, wherein R is 1 to C carbon atoms. 18 alkyl groups, alkenyl groups having 2 to 18 carbon atoms, monovalent aromatic hydrocarbon groups having 6 to 18 carbon atoms, or monovalent heterocyclic groups having 3 to 18 carbon atoms and hetero atoms in total. The alkyl group having 1 to 20 carbon atoms, the monovalent aromatic hydrocarbon having 6 to 20 carbon atoms, the monovalent heterocyclic group having 3 to 20 atoms in total, the carboxyl group, and the hydrogen atom of R1. Each may be substituted, the alkyl group having 1 to 18 carbon atoms, the alkenyl group having 2 to 18 carbon atoms, the monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and the total number of 3 to 18 In the monovalent heterocyclic group may be substituted.)
連鎖移動剤として具体的には、ジチオ安息香酸ベンジル、１−フェニルエチルジチオ安息香酸塩、２−フェニルプロプ−２−イルジチオ安息香酸塩、１−アセトキシルエチルジチオ安息香酸塩、ヘキサキス（チオベンゾイルチオメチル）ベンゼン、１，４−ビス（チオベンゾイルチオメチル）ベンゼン、１，２，４，５−テトラキス（チオベンゾイルチオメチル）ベンゼン、１，４−ビス−（２−（チオベンゾイルチオ）プロプ−２−イル）ベンゼン、１−（４−メトキシフェニル）エチルジチオ安息香酸塩、ジチオ酢酸ベンジル；エトキシカルボニルメチルジチオアセタート、２−（エトキシカルボニル）プロプ−２−イルジチオベンゾアート、２−シアノプロプ−２−イルジチオベンゾアート、第三ブチルジチオベンゾアート、２，４，４−トリメチルペント−２−イルジチオベンゾアート、２−（４−クロロフェニル）プロプ−２−イルジチオベンゾアート、３−および４−ビニルベンジルジチオベンゾアート、Ｓ−ベンジルジエトキシホスフィニルジチオフォルマート、第三ブチルトリチオペルベンゾアート、２−フェニルプロプ−２−イル４−クロロジチオベンゾアート、２−フェニルプロプ−２−イル１−ジチオナフタラート、４−シアノペンタン酸ジチオベンゾアート、ジベンジルテトラチオテレフタラート、ジベンジルトリチオカーボネート、カルボキシメチルジチオベンゾアートなどのジチオベンゾアート末端基を持つポリ（酸化エチレン）；１−ピロールカルボジチオ酸ベンジル、１−（２−ピロリジノン）カルボジチオ酸ベンジル、（１，２−ベンゼンジカルボキシイミド）カルボジチオ酸ベンジル、１−ピロールカルボジチオ酸２−シアノプロプ−２−イル、１−ピロールカルボジチオ酸２−シアノブト−２−イル、１−イミダゾールカルボジチオ酸ベンジル、Ｎ，Ｎ−ジメチルジチオカルバミン酸Ｓ−（２−シアノプロプ−２−イル）、Ｎ，Ｎ−ジエチルジチオカルバミン酸Ｓ−ベンジル、１−（２−ピロリジノン）カルボジチオ酸、Ｎ，Ｎ−ジエチルジチオカルバミン酸Ｓ−（２−エトキシカルボニルプロプ−２−イル）、キサントゲン酸Ｏ−エチルＳ−（１−フェニルエチル）、キサントゲン酸Ｏ−エチルＳ−（２−（エトキシカルボニル）プロプ−２−イル）、キサントゲン酸Ｏ−エチルＳ−（２−シアノプロプ−２−イル）、キサントゲン酸Ｏ−エチルＳ−シアノメチル、キサントゲン酸Ｏ−フェニルＳ−ベンジル、キサントゲン酸Ｏ−ペンタフルオロフェニルＳ−ベンジル、３，３−ジ（ベンジルチオ）プロプ−２−エンジチオ酸ベンジルなどが挙げられる。 Specific examples of the chain transfer agent include benzyl dithiobenzoate, 1-phenylethyldithiobenzoate, 2-phenylprop-2-yldithiobenzoate, 1-acetoxylethyldithiobenzoate, hexakis (thiobenzoylthio) Methyl) benzene, 1,4-bis (thiobenzoylthiomethyl) benzene, 1,2,4,5-tetrakis (thiobenzoylthiomethyl) benzene, 1,4-bis- (2- (thiobenzoylthio) prop- 2-yl) benzene, 1- (4-methoxyphenyl) ethyldithiobenzoate, benzyl dithioacetate; ethoxycarbonylmethyldithioacetate, 2- (ethoxycarbonyl) prop-2-yldithiobenzoate, 2-cyanoprop-2 -Ildithiobenzoate, tert-butyldithiobenzoate, 2,4, -Trimethylpent-2-yldithiobenzoate, 2- (4-chlorophenyl) prop-2-yldithiobenzoate, 3- and 4-vinylbenzyldithiobenzoate, S-benzyldiethoxyphosphinyldithioformate, Tert-butyltrithioperbenzoate, 2-phenylprop-2-yl 4-chlorodithiobenzoate, 2-phenylprop-2-yl 1-dithionaphthalate, 4-cyanopentanoic acid dithiobenzoate, dibenzyltetrathio Poly (ethylene oxide) having dithiobenzoate end groups such as terephthalate, dibenzyltrithiocarbonate, carboxymethyldithiobenzoate; benzyl 1-pyrrolecarbodithioate, benzyl 1- (2-pyrrolidinone) carbodithioate, (1 , 2-Benzenedica Boxyimido) benzyl carbodithioate, 2-cyanoprop-2-yl 1-pyrrolecarbodithioate, 2-cyanobut-2-yl 1-pyrrolecarbodithioate, benzyl 1-imidazolecarbodithioate, N, N-dimethyldithiocarbamic acid S -(2-cyanoprop-2-yl), N-N-diethyldithiocarbamate S-benzyl, 1- (2-pyrrolidinone) carbodithioate, N, N-diethyldithiocarbamate S- (2-ethoxycarbonylprop-2- Yl), O-ethyl S- (1-phenylethyl) xanthate, O-ethyl S- (2- (ethoxycarbonyl) prop-2-yl) xanthate, O-ethyl S- (2-cyanoprop-Xanthate) 2-yl), O-ethyl S-cyanomethyl xanthate, xanthogen Acid O-phenyl S-benzyl, xanthate O-pentafluorophenyl S-benzyl, benzyl 3,3-di (benzylthio) prop-2-enedithioate and the like.
なお、本実施形態において、上記一般式（１）で表される連鎖移動剤のＺ基およびＲ基は、重合体の末端部分に取り込まれることとなる。 In the present embodiment, the Z group and R group of the chain transfer agent represented by the general formula (1) are incorporated into the terminal portion of the polymer.
（ラジカル重合開始剤）
本実施形態におけるラジカル重合開始剤としては、とくに限定はされないが、通常の重合法に用いられるものを使用できる。例えば、有機過酸化物またはアゾビス系化合物などを使用できる。
(Radical polymerization initiator)
Although it does not specifically limit as a radical polymerization initiator in this embodiment, The thing used for a normal polymerization method can be used. For example, an organic peroxide or an azobis compound can be used.
有機過酸化物としては、例えば、イソブチルパーオキサイド、ラウロイルパーオキサイド、３，５，５−トリメチルヘキサノイルパーオキサイド、オクタノイルパーオキサイド、ベンゾイルパーオキサド、ｔ−ブチルクミルパーオキサイド、ジシクロベンゾイルパーオキサイド、ジクミルパーオキサイド、ジ−ｔ−ブチルパーオキサイド、１、１−ビス（ｔ−ブチルパーオキシ）−３，３，５−トリメチルシクロヘキサン、３，３，５−トリメチルシクロヘキサノンパーオキサイド、メチルシクロヘキサノンパーオキサド、ジイソブチルパーオキシジカーボネート、２−ジエチルヘキシルパーオキシジカーボネート、２，５−ジメチル−２，５−ビス（２−エチルヘキサノイルパーオキシ）ヘキサン、１，１−ビス（ｔ−ヘキシルパーオキシ）−３，３，５−トリメチルシクロヘキサン、１，１−ビス（ｔ−ヘキシルパーオキシ）シクロヘキサン、１，１−ビス（ｔ−ブチルパーオキシ）シクロヘキサン、２，２−ビス（ｔ−ブチルパーオキシ）ブタン、ｔ−ブチルハイドロパーオキサイド、クメンハイドロパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、メチルエチルケトンパーオキサイド、シクロヘキサノンパーオキサイド、ｔ−ブチルパーオキシ−２−エチルヘキサノエート、１，１，３，３−テトラメチルブチルパーオキシ−２−エチルヘキサノエート、ｔ−ヘキシルパーオキシ−２−エチルヘキサノエート、ｔ−ブチルパーオキシイソブチレートなどが挙げられる。 Examples of the organic peroxide include isobutyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, benzoyl peroxide, t-butylcumyl peroxide, dicyclobenzoyl peroxide. Oxide, dicumyl peroxide, di-t-butyl peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone Peroxide, diisobutyl peroxydicarbonate, 2-diethylhexyl peroxydicarbonate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1,1-bis (t-hexyl) Peroxy -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) Butane, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, t-butylperoxy-2-ethylhexanoate, 1,1,3,3-tetra Examples thereof include methylbutyl peroxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, and t-butylperoxyisobutyrate.
アゾビス系化合物としては、例えば、２，２'−アゾビスイソブチロニトリル、ジメチルアゾジイソブチレート、２，２'−アゾビス（２，４−ジメチルバレロニトリル）、２，２'−アゾビス（２−メチルブチロニトリル）、２，２'−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）、（１フェニルエチル）アゾジフェニルメタン、ジメチル−２，２'−アゾビスイソブチレート、１，１'−アゾビス（１−シクロヘキサンカルボニル）、２，２'−アゾビス（２，２，４−トリメチルペンタン）、２−フェニルアゾ−２，４−ジメチル−４−メトキシバレロニトリル、２，２'−アゾビス（２−メチルプロパン）などが挙げられる。
これらの重合開始剤は、単独でまたは２種類以上を組み合わせて使用することができる。
本実施形態の重合体の製造方法においては、ラジカル開始種として、アゾビス系化合物が好ましく、２，２'−アゾビスイソブチロニトリルなどが重合温度条件下で有効にラジカルを発生できる点からとくに好ましい。
Examples of the azobis compound include 2,2′-azobisisobutyronitrile, dimethylazodiisobutyrate, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2 -Methylbutyronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), (1 phenylethyl) azodiphenylmethane, dimethyl-2,2'-azobisisobutyrate, 1, 1'-azobis (1-cyclohexanecarbonyl), 2,2'-azobis (2,2,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2'-azobis (2-methylpropane) and the like.
These polymerization initiators can be used alone or in combination of two or more.
In the method for producing the polymer of the present embodiment, an azobis-based compound is preferable as the radical initiating species, and in particular, 2,2′-azobisisobutyronitrile and the like can effectively generate radicals under polymerization temperature conditions. preferable.
（重合条件）
本実施形態の重合体は、溶液重合、バルク重合、懸濁重合などで得られる。
本実施形態の重合体は、有機溶媒の存在下で溶液重合をすることが好ましい。この場合に使用できる有機溶媒としては、モノマーと本実施形態の重合体を溶解し、一定値以下の連鎖移動係数を有するものが好ましく用いられる。
例えば、トルエン、キシレン、または「ソルベッソ１００もしくは１５０」（芳香族炭化水素混合物、エクソン社製の商品名）などの芳香族炭化水素類；へプタン、ヘキサン、オクタンなどの脂肪族系炭化水素類；ミネラルスピリット、ホワイトスピリット、ミネラルターペンなどの芳香族―脂肪族炭化水素類混合溶媒；酢酸エチル、酢酸ブチル、酢酸イソブチルなどの酢酸エステル類；メチルエチルケトン、メチルイソブチルケトンなどのケトン類；イソプロパノール、ノルマルブタノール、イソブタノールなどの脂肪族アルコール類；エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテルなどのアルキレングリコールモノアルキルエーテル類；非プロトン系溶媒としてＮ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、テトラメチル尿素、ヘキサメチルホスホルアミド、アセトニトリル、ジメチルスルホキシド、アルキルエーテル、テトラヒドロフラン、ジエチルエーテル、ジオキサンなどが挙げることができ、これらの有機溶媒は単独または混合溶媒として使用される。
(Polymerization conditions)
The polymer of this embodiment is obtained by solution polymerization, bulk polymerization, suspension polymerization, or the like.
The polymer of this embodiment is preferably subjected to solution polymerization in the presence of an organic solvent. As the organic solvent that can be used in this case, a solvent that dissolves the monomer and the polymer of the present embodiment and has a chain transfer coefficient of a certain value or less is preferably used.
For example, aromatic hydrocarbons such as toluene, xylene, or “Sorvesso 100 or 150” (aromatic hydrocarbon mixture, trade name manufactured by Exxon); aliphatic hydrocarbons such as heptane, hexane, and octane; Aromatic-aliphatic hydrocarbons such as mineral spirits, white spirits and mineral terpenes; acetates such as ethyl acetate, butyl acetate and isobutyl acetate; ketones such as methyl ethyl ketone and methyl isobutyl ketone; isopropanol, normal butanol, Aliphatic alcohols such as isobutanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl Alkylene glycol monoalkyl ethers such as ether; N, N-dimethylformamide, N, N-dimethylacetamide, tetramethylurea, hexamethylphosphoramide, acetonitrile, dimethyl sulfoxide, alkyl ether, tetrahydrofuran, diethyl as aprotic solvents Ether, dioxane and the like can be mentioned, and these organic solvents are used alone or as a mixed solvent.
重合に際して、上記各成分は、あらかじめ混合物とした上で重合系に添加してもよいし、別々に重合系に添加してもよい。また、この混合物を分割して重合系に添加してもよい。 In the polymerization, each of the above components may be added to the polymerization system in the form of a mixture in advance, or may be added separately to the polymerization system. Further, this mixture may be divided and added to the polymerization system.
本実施形態の重合体の製造方法では、重合時間、攪拌条件などの重合条件、精製溶媒などの精製方法は、公知の方法が用いられる。 In the method for producing a polymer of the present embodiment, a known method is used as a polymerization method such as polymerization time and stirring conditions, and a purification method such as a purification solvent.
（重合体）
以下、本実施形態の重合体について説明する。
本実施形態の重合体は、サイズ排除クロマトグラフィー（ＳＥＣ）により測定したポリスチレン換算の数平均分子量（Ｍｎ１）が好ましくは３，０００以上３０，０００以下であり、さらに好ましくは３，０００以上２５，０００以下である。数平均分子量（Ｍｎ１）が上記上限値以下であると、本実施形態の重合体は、有機溶媒に対する溶解性がより一層優れる。
(Polymer)
Hereinafter, the polymer of this embodiment will be described.
The polymer of this embodiment preferably has a polystyrene-equivalent number average molecular weight (Mn1) measured by size exclusion chromatography (SEC) of 3,000 to 30,000, more preferably 3,000 to 25,000. 000 or less. When the number average molecular weight (Mn1) is not more than the above upper limit, the polymer of the present embodiment is further excellent in solubility in an organic solvent.
本実施形態の重合体は、ＳＥＣにより測定したポリスチレン換算の数平均分子量（Ｍｎ１）に対する重量平均分子量（Ｍｗ）の比（Ｍｗ／Ｍｎ１）が１０．０以下であるのが好ましく、５．０以下であるのがとくに好ましい。Ｍｗ／Ｍｎ１が上記上限値以下であると、本実施形態の重合体は、有機溶媒に対する溶解性がより一層優れる。 In the polymer of this embodiment, the ratio (Mw / Mn1) of the weight average molecular weight (Mw) to the number average molecular weight (Mn1) in terms of polystyrene measured by SEC is preferably 10.0 or less, and 5.0 or less. Is particularly preferred. When the Mw / Mn1 is not more than the above upper limit, the polymer of the present embodiment is further excellent in solubility in an organic solvent.
本実施形態の重合体は、ＳＥＣにより測定したポリスチレン換算の数平均分子量（Ｍｎ１）と、１Ｈ−ＮＭＲより測定した分子総末端数から算出される数平均分子量（Ｍｎ２）との比（Ｍｎ１／Ｍｎ２）で表される分岐度が、好ましくは２．０以上９．０以下である。分岐度が上記範囲内であると、本実施形態の重合体は、有機溶媒に対する溶解性がより一層優れる。 The polymer of this embodiment has a ratio (Mn1 /) of the number average molecular weight (Mn1) in terms of polystyrene measured by SEC and the number average molecular weight (Mn2) calculated from the total number of molecular ends measured by 1 H-NMR. The degree of branching represented by Mn2) is preferably 2.0 or more and 9.0 or less. When the degree of branching is within the above range, the polymer of this embodiment is further excellent in solubility in an organic solvent.
（重合体組成物）
本実施形態の重合体は有機溶媒に溶解するため、有機溶媒に溶解させることにより、重合体組成物として用いることができる。有機溶媒はとくに限定されず、一般的に公知の有機溶媒を用いることができる。
なお、本実施形態の重合体が有機溶媒に溶解しているかどうかの確認は、重合体溶液が透明かどうかで確認してもよいし、重合体溶液が孔径０．２μｍ以下のフィルターを通過するかどうかで確認してもよい。
(Polymer composition)
Since the polymer of this embodiment dissolves in an organic solvent, it can be used as a polymer composition by dissolving in an organic solvent. The organic solvent is not particularly limited, and generally known organic solvents can be used.
Whether the polymer of this embodiment is dissolved in an organic solvent may be confirmed by checking whether the polymer solution is transparent, or the polymer solution passes through a filter having a pore size of 0.2 μm or less. You may check whether or not.
また、本実施形態の重合体組成物には、安定剤、滑剤、顔料、耐衝撃性改良剤、加工助剤、補強剤、着色剤、難燃剤、耐候性改良剤、紫外線吸収剤、酸化防止剤、防かび剤、抗菌剤、光安定剤、耐電防止剤、シリコンオイル、ブロッキング防止剤、離型剤、発泡剤、香料などの各種添加剤；ガラス繊維、ポリエステル繊維などの各種繊維；タルク、マイカ、モンモリロナイト、シリカ、木粉などの充填剤；各種カップリング剤などの任意成分を必要に応じて配合することができる。 Further, the polymer composition of the present embodiment includes a stabilizer, a lubricant, a pigment, an impact resistance improver, a processing aid, a reinforcing agent, a colorant, a flame retardant, a weather resistance improver, an ultraviolet absorber, and an antioxidant. Agents, fungicides, antibacterial agents, light stabilizers, antistatic agents, silicone oil, antiblocking agents, mold release agents, foaming agents, fragrances, and other additives; glass fibers, polyester fibers, and other fibers; talc, Fillers such as mica, montmorillonite, silica, and wood powder; optional components such as various coupling agents can be blended as necessary.
（ブロック共重合体の製造方法）
本実施形態の重合体は、重合末端にチオカルボニルチオ基を有している。そのため、このチオカルボニルチオ基末端を開始点として新たな重合をおこなうことができ、さまざまなブロック共重合体を得ることができる。
(Method for producing block copolymer)
The polymer of this embodiment has a thiocarbonylthio group at the polymerization terminal. Therefore, new polymerization can be performed starting from this thiocarbonylthio group terminal, and various block copolymers can be obtained.
以下、本実施形態の重合体を用いたブロック共重合体の製造方法について説明する。
本実施形態のブロック共重合体の製造方法では、本実施形態の重合体のチオカルボニルチオ基末端を開始点として、１分子中に１つの二重結合を有する第３モノマーを重合する。
Hereinafter, the manufacturing method of the block copolymer using the polymer of this embodiment is demonstrated.
In the block copolymer production method of the present embodiment, the third monomer having one double bond in one molecule is polymerized starting from the thiocarbonylthio group end of the polymer of the present embodiment.
（第３モノマー）
本実施形態における第３モノマーとしては、１分子中に１つの二重結合を有していればとくに限定はされない。具体的には、上記第２モノマーで挙げたモノマーを使用することができる。
(Third monomer)
The third monomer in this embodiment is not particularly limited as long as it has one double bond in one molecule. Specifically, the monomers mentioned in the second monomer can be used.
本実施形態の重合体を用いてブロック共重合体を作製する場合は、本実施形態の重合体には上記第２モノマー成分を共重合していることが好ましい。
この場合、第２モノマーの含有量はとくに限定されないが、第１モノマーと第２モノマーの合計量を１００モル％としたとき、好ましくは５モル％以上９５モル％以下であり、さらに好ましくは２０モル％以上８０モル％以下であり、とくに好ましくは４０モル％以上６０モル％以下である。第２モノマー成分を含有することにより、得られるブロック共重合体は、有機溶媒に対する溶解性がより一層優れる。
When producing a block copolymer using the polymer of this embodiment, it is preferable to copolymerize the said 2nd monomer component in the polymer of this embodiment.
In this case, the content of the second monomer is not particularly limited, but when the total amount of the first monomer and the second monomer is 100 mol%, it is preferably 5 mol% or more and 95 mol% or less, and more preferably 20 mol%. It is from mol% to 80 mol%, particularly preferably from 40 mol% to 60 mol%. By containing a 2nd monomer component, the block copolymer obtained is further excellent in the solubility with respect to an organic solvent.
本実施形態の重合体およびブロック共重合体は反応活性点を有するため、その反応活性点に基づく反応性、重合性、架橋・硬化性などの特性を利用して、例えば、樹脂改質剤、樹脂表面改質剤、アスファルト改質剤、相容化剤、粘着剤、接着剤、制振材料、分散剤、分散安定剤、乳化剤、界面活性剤、ハイドロゲル、塗料、コーティング剤、バインダー、インキなどの用途に適用できる。 Since the polymer and block copolymer of the present embodiment have a reactive site, utilizing properties such as reactivity, polymerizability, crosslinking / curing property based on the reactive site, for example, a resin modifier, Resin surface modifier, asphalt modifier, compatibilizer, adhesive, adhesive, vibration damping material, dispersant, dispersion stabilizer, emulsifier, surfactant, hydrogel, paint, coating agent, binder, ink It can be applied to other uses.
以上、本発明の実施形態について述べたが、これらは本発明の例示であり、上記以外の様々な構成を採用することもできる。 As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above are also employable.
以下に、実施例および比較例を挙げて本発明を更に具体的に説明するが、本発明は、その要旨を超えない限りこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples unless it exceeds the gist.
＜試薬＞
実施例および比較例で使用した試薬を以下に示す。
（１）２，２'−アゾビスイソブチロニトリル（ＡＩＢＮ、和光純薬工業社製）
（２）メタクリル酸ビニル（ＶＭＡ、和光純薬工業社製）
（３）２−シアノプロプ−２−イルジチオベンゾアート（ＣＴＡ、シグマアルドリッチジャパン社製）
（４）メタクリル酸メチル（ＭＭＡ、和光純薬工業社製）
（５）スチレン（和光純薬工業社製）
（６）１，４‐ジオキサン（和光純薬工業社製）
なお、２，２'−アゾビスイソブチロニトリルは、メタノールにより再結晶を行った。
各種モノマーおよび１，４‐ジオキサンは水素化カルシウムを添加して一昼夜攪拌した後に蒸留を行い精製して用いた。
２−シアノプロプ−２−イルジチオベンゾアートは市販品の試薬をそのまま使用した。
<Reagent>
The reagents used in Examples and Comparative Examples are shown below.
(1) 2,2′-azobisisobutyronitrile (AIBN, manufactured by Wako Pure Chemical Industries, Ltd.)
(2) Vinyl methacrylate (VMA, Wako Pure Chemical Industries, Ltd.)
(3) 2-cyanoprop-2-yldithiobenzoate (CTA, manufactured by Sigma-Aldrich Japan)
(4) Methyl methacrylate (MMA, manufactured by Wako Pure Chemical Industries, Ltd.)
(5) Styrene (Wako Pure Chemical Industries, Ltd.)
(6) 1,4-dioxane (manufactured by Wako Pure Chemical Industries, Ltd.)
2,2′-Azobisisobutyronitrile was recrystallized from methanol.
Various monomers and 1,4-dioxane were used after adding calcium hydride and stirring for a whole day and after distillation for purification.
For 2-cyanoprop-2-yldithiobenzoate, a commercially available reagent was used as it was.
＜測定＞
（ＮＭＲの測定）
ＶＡＲＩＡＮ製、ＵＮＩＴＹＩＮＯＶＡ−４００Ｓ（１Ｈ＝４００ＭＨｚ）を用い、内部標準テトラメチルシラン（ＴＭＳ）入りの重クロロホルム中、室温で測定を行った。
<Measurement>
(NMR measurement)
Measurement was performed at room temperature in deuterochloroform containing internal standard tetramethylsilane (TMS) using a unit made by VARIAN, UNITYINOVA-400S (1H = 400 MHz).
（ＳＥＣ測定）
ＴＨＦを溶出溶媒として東ソー社製ＨＰＬＣ−８２２０を用いてサイズ排除クロマトグラフィー測定をおこなった。カラムはガードカラムＴＳＫ−ｇｕａｒｄ ｃｏｌｕｍｎ ＨｘＬ−Ｌ（４ｃｍ）と分析カラムＧ４０００ＨｘＬ（５μｍ、４×１０５）、Ｇ３０００ＨｘＬ（５μｍ、６×１０４）、Ｇ２０００ＨｘＬ（５μｍ、１×１０４）を直列に繋いで４０℃、１．０ｍＬ／ｍｉｎの流速にて測定してポリスチレン換算による相対分子量を求めた。また、検出にはＲＩを用いた。
(SEC measurement)
Size exclusion chromatography was measured using HPLC-8220 manufactured by Tosoh Corporation with THF as an elution solvent. Columns are guard column TSK-guard column H xL -L (4 cm) and analytical column G4000H xL (5 μm, 4 × 10 5 ), G3000H xL (5 μm, 6 × 10 4 ), G2000H xL (5 μm, 1 × 10 4 ) Were connected in series and measured at a flow rate of 40 ° C. and 1.0 mL / min to obtain a relative molecular weight in terms of polystyrene. In addition, RI was used for detection.
＜重合体＞
（実施例１）
重合管に、モノマーとして、メタクリル酸ビニル（ＶＭＡ、９.４ｍｍｏｌ）と、連鎖移動剤として、２−シアノプロプ−２−イルジチオベンゾアート（ＣＴＡ、０．０３７６ｍｍｏｌ）と、開始剤として、ＡＩＢＮ（０．０１８８ｍｍｏｌ）と、溶媒として、１，４−ジオキサン（０．５ｍＬ）と、攪拌子とをそれぞれ添加した。すなわち、ＶＭＡ：ＣＴＡ：ＡＩＢＮ＝１００：０．４：０．２になるように各成分を重合管に添加した。凍結脱気を３回行った後、封管し、６０℃で７時間反応させた。
反応後、反応溶液を液体窒素で冷却して反応を止め、室温に戻した後、過剰量のメタノールで再沈殿を行った。その後、析出したポリマーをろ過回収後、減圧下、４０℃で乾燥させ、紫色の固体を、収率２０．２％で得た。収率は後述の方法で算出した。
なお、同様の条件で重合時間を１６時間まで延ばしてみたところ、重合体はゲル化してしまった。
<Polymer>
Example 1
Into the polymerization tube, vinyl methacrylate (VMA, 9.4 mmol) as a monomer, 2-cyanoprop-2-yldithiobenzoate (CTA, 0.0376 mmol) as a chain transfer agent, and AIBN (0 0.188 mmol), 1,4-dioxane (0.5 mL) and a stirrer were added as solvents. That is, each component was added to the polymerization tube so that VMA: CTA: AIBN = 100: 0.4: 0.2. After performing freeze deaeration three times, it was sealed and reacted at 60 ° C. for 7 hours.
After the reaction, the reaction solution was cooled with liquid nitrogen to stop the reaction, returned to room temperature, and then reprecipitated with an excessive amount of methanol. Thereafter, the precipitated polymer was collected by filtration and dried at 40 ° C. under reduced pressure to obtain a purple solid with a yield of 20.2%. The yield was calculated by the method described later.
When the polymerization time was extended to 16 hours under the same conditions, the polymer was gelled.
（収率の算出方法）
以下の式（１）により収率を算出した。
収率（％）＝１００×（反応後に回収された紫色の固体の質量）／（仕込んだＶＭＡの質量） （１）
(Yield calculation method)
The yield was calculated by the following formula (1).
Yield (%) = 100 × (mass of purple solid recovered after reaction) / (mass of charged VMA) (1)
得られた重合体の数平均分子量Ｍｎ１および分子量分布（Ｍｗ／Ｍｎ１）は、ＳＥＣで測定した。また、１Ｈ−ＮＭＲを用いて測定した分子総末端数から算出される数平均分子量Ｍｎ２を測定した。具体的には、Ｍｎ２は以下のようにして算出した。 The number average molecular weight Mn1 and molecular weight distribution (Mw / Mn1) of the obtained polymer were measured by SEC. Moreover, the number average molecular weight Mn2 calculated from the total number of molecular terminals measured using 1 H-NMR was measured. Specifically, Mn2 was calculated as follows.
（数平均分子量Ｍｎ２の算出方法）
以下の式（２）により数平均分子量Ｍｎ２を算出した。
(Calculation method of number average molecular weight Mn2)
The number average molecular weight Mn2 was calculated by the following formula (2).
ここで、Ｍｎ２は数平均分子量、∫S 7.9ppmはＣＴＡに由来するプロトン一つ分の１Ｈ−ＮＭＲスペクトルのピーク面積、∫S 0.2-2.9ppmはポリマーの主鎖とメチル基に由来するプロトン五つ分の１Ｈ−ＮＭＲスペクトルのピーク面積、１１２はモノマーであるＶＭＡの分子量である。 Here, Mn2 number average molecular weight, ∫S 7.9ppm peak area of the 1 H-NMR spectrum of the proton one fraction derived from CTA, the ∫S 0.2-2.9ppm from the main chain and the methyl groups of the polymer protons 1 H-NMR peak areas of the spectrum of five minutes, 112 is the molecular weight of VMA is a monomer.
（実施例２〜４、比較例１〜２）
ＶＭＡ、ＣＴＡおよびＡＩＢＮの添加量の比を表１に示した値にそれぞれ変えた以外は実施例１と同様に所定時間重合をおこなった。なお、ＶＭＡの添加量は９．４ｍｍｏｌにそろえた。
(Examples 2-4, Comparative Examples 1-2)
Polymerization was carried out for a predetermined time in the same manner as in Example 1 except that the ratio of the addition amounts of VMA, CTA and AIBN was changed to the values shown in Table 1, respectively. The amount of VMA added was adjusted to 9.4 mmol.
実施例１〜４、比較例１〜２の重合結果を表１に示す。実施例１〜４の重合体は、有機溶媒に溶解した（重合時間を延ばしてゲル化したものを除く）。また、ＣＴＡとＡＩＢＮの添加量を増やすと、重合時間を延ばしても重合体のゲル化が抑制された。その結果、ＣＴＡとＡＩＢＮの添加量が多いほど収率が向上した。 The polymerization results of Examples 1-4 and Comparative Examples 1-2 are shown in Table 1. The polymers of Examples 1 to 4 were dissolved in an organic solvent (excluding those that were gelated by extending the polymerization time). Moreover, when the addition amount of CTA and AIBN was increased, the gelation of the polymer was suppressed even if the polymerization time was extended. As a result, the yield increased as the amount of CTA and AIBN added increased.
なお、実施例４（重合時間１６時間）で得られた重合体は、１Ｈ−ＮＭＲスペクトルにより、構造を確認した（図１、２）。図１より、重合体の側鎖には、メタクリル酸ビニル（ＶＭＡ）由来の二重結合が存在することを確認できた。また、図２より、重合体の末端には、２−シアノプロプ−２−イルジチオベンゾアート（ＣＴＡ）由来のチオカルボニルチオ基が存在することを確認できた。
一方、比較例１〜２の重合体は重合初期でゲル化し、有機溶媒に不溶なものしか得られなかった。
The structure of the polymer obtained in Example 4 (polymerization time 16 hours) was confirmed by 1 H-NMR spectrum (FIGS. 1 and 2). From FIG. 1, it was confirmed that a double bond derived from vinyl methacrylate (VMA) was present in the side chain of the polymer. Further, from FIG. 2, it was confirmed that a thiocarbonylthio group derived from 2-cyanoprop-2-yldithiobenzoate (CTA) was present at the end of the polymer.
On the other hand, the polymers of Comparative Examples 1 and 2 gelled at the initial stage of polymerization, and only insoluble in organic solvents were obtained.
（実施例５〜７）
モノマーとして、メタクリル酸ビニル（ＶＭＡ）に加えてメタクリル酸メチル（ＭＭＡ）を添加し、モノマー（ＶＭＡ＋ＭＭＡ）、ＣＴＡおよびＡＩＢＮの添加量の比を表２に示した値にそれぞれ変えた以外は実施例１と同様にして、７時間重合をおこなった。
(Examples 5-7)
Example in which methyl methacrylate (MMA) was added as a monomer in addition to vinyl methacrylate (VMA), and the ratio of the addition amount of monomer (VMA + MMA), CTA and AIBN was changed to the values shown in Table 2, respectively. In the same manner as in Example 1, polymerization was carried out for 7 hours.
実施例５〜７の重合結果を表２に示す。実施例５〜７の重合体は、いずれも有機溶媒に溶解した。なお、実施例６で得られた重合体は、１Ｈ−ＮＭＲスペクトルにより構造を確認した（図３）。図３より、ＶＭＡとＭＭＡの仕込み比は、重合体中の組成比と一致することが確認できた。 The polymerization results of Examples 5 to 7 are shown in Table 2. All the polymers of Examples 5 to 7 were dissolved in an organic solvent. In addition, the structure of the polymer obtained in Example 6 was confirmed by 1 H-NMR spectrum (FIG. 3). From FIG. 3, it was confirmed that the charging ratio of VMA and MMA coincided with the composition ratio in the polymer.
＜ブロック共重合体＞
（実施例８）
重合管に、実施例４において１６時間重合をおこなって得られた重合体（４．７ｍｍｏｌ）と、モノマーとして、スチレン（８．６ｍｍｏｌ）と、開始剤として、ＡＩＢＮ（０．１４１ｍｍｏｌ）と、溶媒として、１，４−ジオキサン（０．５ｍＬ）と、攪拌子とをそれぞれ添加した。凍結脱気を３回行った後、封管し、６０℃で所定時間反応させた。
反応後、反応溶液を液体窒素で冷却して反応を止め、室温に戻した後、過剰量のメタノールで再沈殿を行った。その後、析出したポリマーをろ過回収後、減圧下、４０℃で乾燥させ、紫色の固体を得た。なお、同様の条件で重合時間を１２時間まで延ばしてみたところ、重合体はゲル化してしまった。数平均分子量Ｍｎ１および分子量分布（Ｍｗ／Ｍｎ１）はＳＥＣで測定した。
<Block copolymer>
(Example 8)
In the polymerization tube, the polymer (4.7 mmol) obtained by polymerization in Example 4 for 16 hours, styrene (8.6 mmol) as the monomer, AIBN (0.141 mmol) as the initiator, solvent 1,4-dioxane (0.5 mL) and a stirrer were added respectively. After performing freeze deaeration three times, the tube was sealed and reacted at 60 ° C. for a predetermined time.
After the reaction, the reaction solution was cooled with liquid nitrogen to stop the reaction, returned to room temperature, and then reprecipitated with an excessive amount of methanol. Thereafter, the precipitated polymer was collected by filtration and then dried at 40 ° C. under reduced pressure to obtain a purple solid. When the polymerization time was extended to 12 hours under the same conditions, the polymer gelled. The number average molecular weight Mn1 and the molecular weight distribution (Mw / Mn1) were measured by SEC.
（実施例９）
実施例４において１６時間重合をおこなって得られた重合体を、実施例６において７時間重合をおこなって得られた重合体に変えた以外は実施例８と同様に１６時間重合をおこなった。
Example 9
Polymerization was carried out for 16 hours in the same manner as in Example 8, except that the polymer obtained by carrying out the polymerization for 16 hours in Example 4 was changed to the polymer obtained by carrying out the polymerization for 7 hours in Example 6.
実施例８〜９の重合結果を表３に示す。実施例８〜９のブロック共重合体は、有機溶媒に溶解した（重合時間を延ばしてゲル化したものを除く）。また、ＶＭＡとＭＭＡの共重合体を用いた実施例９の方が重合体のゲル化が抑制され、その結果、収率が向上した。
なお、実施例９で得られた重合体の構造は、１Ｈ−ＮＭＲスペクトルにより確認した（図４）。図４より、ブロック共重合体が得られたことが確認できた。
The polymerization results of Examples 8 to 9 are shown in Table 3. The block copolymers of Examples 8 to 9 were dissolved in an organic solvent (excluding those that were gelated by extending the polymerization time). Further, in Example 9 using a copolymer of VMA and MMA, gelation of the polymer was suppressed, and as a result, the yield was improved.
The structure of the polymer obtained in Example 9 was confirmed by 1 H-NMR spectrum (FIG. 4). From FIG. 4, it was confirmed that a block copolymer was obtained.
本実施形態の重合体およびブロック共重合体は、反応活性点に基づく反応性、重合性、架橋・硬化性などの特性を利用して、樹脂改質剤、樹脂表面改質剤、アスファルト改質剤、相容化剤、粘着剤、接着剤、制振材料、分散剤、分散安定剤、乳化剤、界面活性剤、ハイドロゲル、塗料、コーティング剤、バインダー、インキなど幅広い応用が可能であり、産業上の利用価値は高いといえる。 The polymer and block copolymer of the present embodiment utilize properties such as reactivity, polymerizability, cross-linking / curing property based on the reaction active point, resin modifier, resin surface modifier, asphalt modification. Wide range of applications such as agents, compatibilizers, adhesives, adhesives, vibration damping materials, dispersants, dispersion stabilizers, emulsifiers, surfactants, hydrogels, paints, coating agents, binders, inks, etc. The above utility value is high.
Claims (11)
側鎖にラジカル重合が可能な複数の二重結合と、
を備え、
アセトン、テトラヒドロフラン、クロロホルム、トルエンのいずれかに溶解する、重合体。 A thiocarbonylthio group at the polymerization terminal;
A plurality of double bonds capable of radical polymerization in the side chain;
With
A polymer that dissolves in acetone, tetrahydrofuran, chloroform, or toluene.
サイズ排除クロマトグラフィー（ＳＥＣ）により測定したポリスチレン換算の数平均分子量（Ｍｎ１）と、１Ｈ−ＮＭＲより測定した分子総末端数から算出される数平均分子量（Ｍｎ２）との比（Ｍｎ１／Ｍｎ２）で表される分岐度が、２．０以上９．０以下である、重合体。 The polymer of claim 1,
Ratio (Mn1 / Mn2) between the number average molecular weight (Mn1) in terms of polystyrene measured by size exclusion chromatography (SEC) and the number average molecular weight (Mn2) calculated from the total number of molecular ends measured by 1 H-NMR The polymer whose branch degree represented by these is 2.0 or more and 9.0 or less.
ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定したポリスチレン換算の数平均分子量（Ｍｎ１）が３，０００以上３０，０００以下である、重合体。 The polymer according to claim 1 or 2,
A polymer having a polystyrene-reduced number average molecular weight (Mn1) measured by gel permeation chromatography (GPC) of 3,000 or more and 30,000 or less.
当該重合体が、（メタ）アクリル酸ビニルに由来する繰り返し単位を含む、重合体。 In the polymer according to any one of claims 1 to 3,
The polymer in which the said polymer contains the repeating unit derived from vinyl (meth) acrylate.
当該重合体組成物は、孔径０．２μｍ以下のフィルターを通過する、重合体組成物。 The polymer composition according to claim 5, wherein
The polymer composition passes through a filter having a pore size of 0.2 μm or less.
前記チオカルボニルチオ基を有する連鎖移動剤と、ラジカル重合開始剤との存在下で、
１分子中に２つのラジカル重合が可能な二重結合を有し、かつ、非対称構造である第１モノマーを含む、モノマー成分をラジカル重合する工程を備え、
前記モノマー成分１００モル部に対して、
前記チオカルボニルチオ基を有する連鎖移動剤の添加量が０．２モル部以上２０モル部以下であり、
前記ラジカル重合開始剤の添加量が０．１モル部以上１０モル部以下である、重合体の製造方法。 A method for producing a polymer according to any one of claims 1 to 4,
In the presence of the chain transfer agent having the thiocarbonylthio group and a radical polymerization initiator,
A step of radically polymerizing a monomer component including a first monomer having a double bond capable of two radical polymerizations in one molecule and having an asymmetric structure;
For 100 mole parts of the monomer component
The addition amount of the chain transfer agent having a thiocarbonylthio group is 0.2 to 20 parts by mole,
The method for producing a polymer, wherein an addition amount of the radical polymerization initiator is 0.1 mol part or more and 10 mol part or less.
前記第１モノマーが、（メタ）アクリル酸ビニルである、重合体の製造方法。 In the manufacturing method of the polymer of Claim 7,
The method for producing a polymer, wherein the first monomer is vinyl (meth) acrylate.
前記モノマー成分が、１分子中に１つの二重結合を有する第２モノマーをさらに含む、重合体の製造方法。 In the manufacturing method of the polymer of Claim 7 or 8,
The method for producing a polymer, wherein the monomer component further comprises a second monomer having one double bond in one molecule.
前記第２モノマーが（メタ）アクリル酸エステルである、重合体の製造方法。 In the method for producing a polymer according to claim 9,
The method for producing a polymer, wherein the second monomer is a (meth) acrylic acid ester.
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| US20100317816A1 (en) * | 2009-06-16 | 2010-12-16 | Bausch & Lomb Incorporated | Biomedical devices |
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| WO2005116097A1 (en) * | 2004-05-14 | 2005-12-08 | Rhodia Chimie | Synthesis of copolymers in the form of a mikto star by controlled radical polymerization |
| JP2008176218A (en) * | 2007-01-22 | 2008-07-31 | Jsr Corp | Radiation-sensitive resin composition and color filter |
| JP2008216489A (en) * | 2007-03-01 | 2008-09-18 | Jsr Corp | Radiation-sensitive resin composition and method for forming spacer |
| US20100317816A1 (en) * | 2009-06-16 | 2010-12-16 | Bausch & Lomb Incorporated | Biomedical devices |
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