JPH0314047B2 - - Google Patents
Info
- Publication number
- JPH0314047B2 JPH0314047B2 JP17159182A JP17159182A JPH0314047B2 JP H0314047 B2 JPH0314047 B2 JP H0314047B2 JP 17159182 A JP17159182 A JP 17159182A JP 17159182 A JP17159182 A JP 17159182A JP H0314047 B2 JPH0314047 B2 JP H0314047B2
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- polymerization
- pmma
- vinyl
- monomers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000178 monomer Substances 0.000 claims description 24
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 6
- 229920001400 block copolymer Polymers 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 125000000217 alkyl group Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 41
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 238000000034 method Methods 0.000 description 20
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- -1 alkyl lithium Chemical compound 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010526 radical polymerization reaction Methods 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 229920006158 high molecular weight polymer Polymers 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- YFMFSCRSAWIWOP-UHFFFAOYSA-N phenyl(trityl)diazene Chemical compound C1=CC=CC=C1N=NC(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 YFMFSCRSAWIWOP-UHFFFAOYSA-N 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 239000012966 redox initiator Substances 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 238000010551 living anionic polymerization reaction Methods 0.000 description 2
- 238000010550 living polymerization reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920006132 styrene block copolymer Polymers 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- PCPYTNCQOSFKGG-ONEGZZNKSA-N (1e)-1-chlorobuta-1,3-diene Chemical compound Cl\C=C\C=C PCPYTNCQOSFKGG-ONEGZZNKSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- VFRMAHVDXYSEON-UHFFFAOYSA-N 1,1-diiodoethene Chemical compound IC(I)=C VFRMAHVDXYSEON-UHFFFAOYSA-N 0.000 description 1
- SXZSFWHOSHAKMN-UHFFFAOYSA-N 2,3,4,4',5-Pentachlorobiphenyl Chemical compound C1=CC(Cl)=CC=C1C1=CC(Cl)=C(Cl)C(Cl)=C1Cl SXZSFWHOSHAKMN-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 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
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- VLHDZWFQDCDKOX-UHFFFAOYSA-N [(4-methylphenyl)-diphenylmethyl]-phenyldiazene Chemical compound C1=CC(C)=CC=C1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)N=NC1=CC=CC=C1 VLHDZWFQDCDKOX-UHFFFAOYSA-N 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- GHXZPUGJZVBLGC-UHFFFAOYSA-N iodoethene Chemical compound IC=C GHXZPUGJZVBLGC-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
Description
【発明の詳細な説明】
本発明はビニルモノマーの重合方法に関するも
のである。さらに詳しくはビニルモノマーを特定
の触媒の存在下で重合させることによりブロツク
共重合体を効果的に製造する新規な方法に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for polymerizing vinyl monomers. More specifically, the present invention relates to a novel method for effectively producing block copolymers by polymerizing vinyl monomers in the presence of a specific catalyst.
ビニルモノマーの重合において“リビング重
合”としては、アルキルリチウムを重合開始剤と
して用いるリビングアニオン重合が古くから知ら
れている。このリビング重合法は、合成するポリ
マーの分子量や分子量分布の制御が容易であり、
またブロツクポリマーの分子設計も自由に行なう
ことができるという特徴をもつている。その一例
としてはｎ−ブチルリチウムによるポリブタジエ
ンの合成があり、このリビング性を生かしてブタ
ジエン−スチレンブロツク共重合体を合成するこ
とができる。これらの方法で合成されたポリブタ
ジエン、ブタジエン−スチレンブロツクコポリマ
ーは汎用合成ゴムおよび熱可塑性エラストマーと
して広く工業的に利用されている。 Living anionic polymerization using alkyl lithium as a polymerization initiator has long been known as "living polymerization" in the polymerization of vinyl monomers. This living polymerization method allows easy control of the molecular weight and molecular weight distribution of the synthesized polymer.
Another feature is that the molecular design of block polymers can be carried out freely. An example of this is the synthesis of polybutadiene using n-butyllithium, and this living property can be utilized to synthesize a butadiene-styrene block copolymer. Polybutadiene and butadiene-styrene block copolymers synthesized by these methods are widely used industrially as general-purpose synthetic rubbers and thermoplastic elastomers.
しかしながらｎ−ブチルリチウムによるリビン
グアニオン重合は、重合系における水分などの不
純物を非常に厳密に取除く必要がある。あるいは
重合させうるモノマーが無極性モノマーなどアニ
アン重合性モノマーに限られ、極性基を有するモ
ノマーに応用できないなどいくつかの制約があ
り、考えられる多くの重合反応の極く一部にしか
応用できないのが実情である。 However, living anionic polymerization using n-butyllithium requires very strict removal of impurities such as moisture in the polymerization system. Alternatively, the monomers that can be polymerized are limited to anionically polymerizable monomers such as non-polar monomers, and there are some restrictions such as the inability to apply to monomers with polar groups, so it can only be applied to a small portion of the many possible polymerization reactions. is the reality.
このような制約を克服するために種々の努力が
行なわれてきており、たとえばオゾン化ポリプロ
ピレンとアミンのレドツクス開始剤を用いて乳化
重合により単分散に近いポリマーとブロツクポリ
マーを合成する方法（mikula′sova′、堀江ら、
Europ.Polym.J.、10、1039（1974））がジアルキ
ルペルオキシドとアルキル第１級アミン、アルキ
ルアミノアルコール、アルキル第１級アミノスル
フオン酸およびそのアルカリ塩などのアミン類の
中の一つとを組み合わせたレドツクス開始剤を用
いて乳化重合により単分散超高分子量重合体を合
成する方法（特開昭52−84268）、ジアルキルペル
オキシドおよびジアルキルペルオキシエステルの
中の１つと第１級および／または第２級アミノ基
を有する高分子化合物およびアルキル第３級アミ
ンの中の少くとも１つとを組み合わせたレドツク
ス開始剤を用いて乳化重合により単分数超高分子
量重合体を合成する方法（特開昭52−84269）お
よび超高分子量ブロツク共重体を得る方法（特開
昭52−84275）などが見い出されている。しかし
ながらこれらの方法は水溶性モノマーや非共役モ
ノマーには適用が困難であり、また超高分子量重
合体しか得られないという欠点を有している。 Various efforts have been made to overcome these limitations, including a method of synthesizing nearly monodisperse polymers and block polymers by emulsion polymerization using ozonated polypropylene and an amine redox initiator (mikula'). sova′, Horie et al.
Europ.Polym.J., 10 , 1039 (1974)) combined a dialkyl peroxide with one of the amines such as alkyl primary amines, alkylamino alcohols, alkyl primary aminosulfonic acids and their alkali salts. A method for synthesizing monodisperse ultra-high molecular weight polymers by emulsion polymerization using a combination of redox initiators (JP 52-84268), one of dialkyl peroxides and dialkyl peroxy esters and primary and/or secondary A method for synthesizing single-fraction ultra-high molecular weight polymers by emulsion polymerization using a redox initiator in which a polymer compound having a primary amino group and at least one alkyl tertiary amine is combined 84269) and a method for obtaining an ultra-high molecular weight block copolymer (Japanese Patent Application Laid-Open No. 1984-84275). However, these methods have the disadvantage that they are difficult to apply to water-soluble monomers and non-conjugated monomers, and that only ultra-high molecular weight polymers can be obtained.
本発明者らは、これらの状況にかんがみリビン
グラジカル重合について鋭意努力を積み重ねた結
果、特定のアゾ化合物を開始剤として用いること
により均一系でリビングラジカル重合が起ること
を見い出し本発明に到達した。すなわち本発明は
一般式（）で表わされるアゾ系開始剤を用いて
ビニルモノマーをリビングラジカル重合させるこ
とにより有用なブロツク共重合体を合成する方法
を提供するものである。 In view of these circumstances, the present inventors have made extensive efforts to develop living radical polymerization, and as a result, they have discovered that living radical polymerization can occur in a homogeneous system by using a specific azo compound as an initiator, and have arrived at the present invention. . That is, the present invention provides a method for synthesizing useful block copolymers by subjecting vinyl monomers to living radical polymerization using an azo initiator represented by the general formula ().
ここでR1はフエニル基、またはアルキル置換
フエニル基、R2はフエニル基、アルキル置換フ
エニル基、またはアルキル基を表わす。 Here, R 1 represents a phenyl group or an alkyl-substituted phenyl group, and R 2 represents a phenyl group, an alkyl-substituted phenyl group, or an alkyl group.
本発明で用いられるビニルモノマーとしては特
に制限はなく、芳香族ビニル化合物、α，β不飽
和カルボン酸、α，β不飽和カルボン酸エステ
ル、α，β不飽和カルボン酸アミド、α，β不飽
和ニトリル化合物、カルボン酸ビニルエステル、
ハロゲン化ビニル、ハロゲン化ビニリテン、共役
ジエン化合物などラジカル重合が可能なものが挙
げられる
本発明で用いられる一般式（）のR1の例と
してはフエニル基、トリル基、などがあり、R2
にはフエニル基、トリル基、メチル基、エチル基
などがある。 The vinyl monomer used in the present invention is not particularly limited, and includes aromatic vinyl compounds, α, β unsaturated carboxylic acids, α, β unsaturated carboxylic acid esters, α, β unsaturated carboxylic acid amides, α, β unsaturated Nitrile compounds, carboxylic acid vinyl esters,
Examples of radical polymerization include vinyl halides, vinylitene halides, and conjugated diene compounds. Examples of R 1 in the general formula () used in the present invention include phenyl groups, tolyl groups, and
include phenyl, tolyl, methyl, and ethyl groups.
またビニルモノマーである芳香族ビニル化合物
の例としては、スチレン、α−メチルスチレン、
ｐ−メチルスチレン、ビニルトルエン（ｏ，ｍ，
ｐ−メチルスチレン混合物）などが、α，β不飽
和カルボン酸としてはアクリル酸、メタクリル酸
などが、α，β不飽和カルボン酸エステルとして
はアクリル酸メチル、アクリル酸エチル、アクリ
ル酸ブチルなどのアクリル酸アルキル、メタクリ
ル酸メチル、メタクリル酸エチル、メタクリル酸
ブチルなどのメタクリル酸アルキルおよびその誘
導体が、α，β不飽和カルボン酸アミドとしては
アクリルアミド、メタクリルアミドおよびその誘
導体が、α，β不飽和ニトリルとしてはアクリロ
ニトリル、メタクリロニトリル、α−クロロアク
リロニトリルなどが、カルボン酸ビニルエステル
としては酢酸ビニル、プロピオン酸ビニルなど
が、ハロゲン化ビニルとしては弗化ビニル、塩化
ビニル、臭化ビニル、沃化ビニルなどが、ハロゲ
ン化ビニリデンとしては弗化ビニリデン、塩化ビ
ニリデン、臭化ビニリデン、沃化ビニリデンなど
が、また共役ジエン化合物としてはブタジエン、
イソプレン、クロロプレン、ピペリレン、１−ク
ロルブタジエンなどが挙げられる。 Examples of aromatic vinyl compounds that are vinyl monomers include styrene, α-methylstyrene,
p-methylstyrene, vinyltoluene (o, m,
α, β unsaturated carboxylic acids include acrylic acid, methacrylic acid, etc. α, β unsaturated carboxylic acid esters include acrylic acids such as methyl acrylate, ethyl acrylate, and butyl acrylate. Alkyl methacrylates and their derivatives such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate are used as α,β unsaturated carboxylic acid amides, acrylamide, methacrylamide and their derivatives are used as α,β unsaturated nitriles. Acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, etc. are used as carboxylic acid vinyl esters, vinyl acetate, vinyl propionate, etc. are used as vinyl halides, vinyl fluoride, vinyl chloride, vinyl bromide, vinyl iodide, etc. Vinylidene halides include vinylidene fluoride, vinylidene chloride, vinylidene bromide, vinylidene iodide, etc., and conjugated diene compounds include butadiene,
Examples include isoprene, chloroprene, piperylene, and 1-chlorobutadiene.
重合は塊状重合、溶液重合、乳化重合、懸濁重
合など一般的にラジカル重合で行なわれる方式を
用いることができる。また本発明の方法によれば
開始剤およびモノマー量と重合転化率で分子量を
制御することが可能なため非常に簡単な系で重合
でき、工業化が極めて容易である。 Polymerization can be carried out by methods commonly used in radical polymerization, such as bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization. Furthermore, according to the method of the present invention, since the molecular weight can be controlled by controlling the amount of initiator and monomer and the polymerization conversion rate, polymerization can be carried out in a very simple system, and industrialization is extremely easy.
本発明の方法は単独重合体を得ることはもち
論、特に異なるモノマー単位からなるブロツクポ
リマーの合成にも非常に有用であり、第一段階で
得られたポリマーに第二のモノマーを加え熱をか
け重合を行わせしめると容易にブロツクポリマー
が得られる。熱としては重合温度を高めればよ
く、通常40℃〜150℃好ましくは50℃〜100℃で重
合が行なわれる。40℃以下では開始剤の分解が遅
すぎ150℃以上では速すぎる。さらにこのブロツ
クポリマーで第三、第四のモノマーを順次重合さ
せ、三元および四元ブロツクポリマーを得ること
もできる。これは生成するポリマーの一方の末端
に炭素−トリチル結合あるいはそれに類似の結合
が生成しており、それが熱により解離し再び重合
を開始するためと考えられる。したがつてブロツ
クポリマーの各成分の連鎖長も、末端に炭素−ト
リチル結合をもつたポリマー開始剤とブロツク重
合させるモノマーの量およびその重合転化率によ
り容易に調整することができる。また本法を実施
するに当り、重合転化率をほぼ100％に到達させ
た後、あるいは未反応モノマーを何らかの方法で
系から取り除いた後、次に反応させるモノマーを
添加すれば末端に炭素−トリチル結合を有するポ
リマーを系から取り出すことなくブロツクポリマ
ーを得ることができる。 The method of the present invention is very useful not only for obtaining homopolymers but also for synthesizing block polymers composed of different monomer units. Block polymers can be easily obtained by carrying out over-polymerization. As for the heat, it is sufficient to raise the polymerization temperature, and the polymerization is usually carried out at 40°C to 150°C, preferably 50°C to 100°C. Below 40°C, the decomposition of the initiator is too slow, and above 150°C, it is too fast. Furthermore, ternary and quaternary block polymers can be obtained by sequentially polymerizing third and fourth monomers with this block polymer. This is thought to be because a carbon-trityl bond or a bond similar thereto is formed at one end of the resulting polymer, which is dissociated by heat and starts polymerization again. Therefore, the chain length of each component of the block polymer can be easily adjusted by adjusting the amount of the monomer to be block-polymerized with the polymer initiator having a carbon-trityl bond at the end and the polymerization conversion rate thereof. In addition, when carrying out this method, after the polymerization conversion rate has reached almost 100%, or after removing unreacted monomers from the system by some method, the next monomer to be reacted can be added to form a carbon-trityl terminal. A block polymer can be obtained without removing the polymer having bonds from the system.
この際熱可塑性エラストマーを得るには共役ジ
エンとその他のモノマーの組合せが用いられ共役
ジエン以外のモノマー、共役ジエン、共役ジエン
以外のモノマーの順で重合される。 At this time, to obtain a thermoplastic elastomer, a combination of a conjugated diene and other monomers is used, and the monomer other than the conjugated diene, the conjugated diene, and the monomer other than the conjugated diene are polymerized in this order.
これらのモノマーの中では分子量などのコント
ロールの点では、特に１，１−ジ置換モノマーが
好ましい。このように本発明の方法は非常に多岐
に亘るブロツクポリマーの合成に利用することが
できる。 Among these monomers, 1,1-disubstituted monomers are particularly preferred from the viewpoint of controlling molecular weight and the like. Thus, the method of the present invention can be used to synthesize a wide variety of block polymers.
以下に本発明の実施例を示すが、本発明はその
要旨をこえない限り、本実施例により何ら制限さ
れるものではない。 Examples of the present invention are shown below, but the present invention is not limited by these Examples unless the gist thereof is exceeded.
実験１
完全に脱気させたビン中にメタクリル酸メチル
80mlおよびフエニルアゾトリフエニルメタンを
0.01mol／となるように秤量し、密栓後60℃の
光を遮断した温浴振とう槽にてメタクリル酸メチ
ルの重合を５時間および10時間行なつた。所定時
間反応後栓を開けメタノール中にポリマーを析出
させた。得られたポリメタクリル酸メチル（夫々
PMMA−ＡおよびPMMA−Ｂと略す。）の収量
および数平均分子量ｎ（ゲルパーミエーシヨン
クロマトグラフイーにより測定）は次のようなも
のであつた。Experiment 1 Methyl methacrylate in a completely degassed bottle
80ml and phenylazotriphenylmethane
Methyl methacrylate was weighed to be 0.01 mol/kg, and after being tightly capped, polymerization of methyl methacrylate was carried out for 5 hours and 10 hours in a warm bath shaking tank at 60° C. and shielded from light. After reacting for a predetermined period of time, the stopper was opened and the polymer was precipitated in methanol. The obtained polymethyl methacrylate (respectively
Abbreviated as PMMA-A and PMMA-B. ) and the number average molecular weight n (measured by gel permeation chromatography) were as follows.
収 量 ｎ
PMMA−Ａ 3.91ｇ 36600
PMMA−Ｂ 7.47ｇ 154000
これらのPMMA−ＡおよびPMMA−Ｂを用い
て以下の実験を行なつた。 Yield n PMMA-A 3.91g 36600 PMMA-B 7.47g 154000 The following experiment was conducted using these PMMA-A and PMMA-B.
実施例 １
完全に脱気された封管中にベンゼン10ml、
PMMA−A0.25ｇ、スチレン10mlを封入し80℃
の光を遮断した温浴振とう槽にて５時間反応させ
た。５時間後大量のメタノール中にポリマーを析
出させた。得られたポリマーの収量およびｎは
それぞれ0.72ｇ、148000であつた。Example 1 10 ml of benzene in a completely degassed sealed tube,
Enclose 0.25g of PMMA-A and 10ml of styrene at 80℃
The reaction was carried out for 5 hours in a warm bath shaking tank that was shielded from light. After 5 hours, the polymer was precipitated in a large amount of methanol. The yield and n of the obtained polymer were 0.72 g and 148000, respectively.
比較例 １
実施例１のPMMA−Ａ封入を除き他は実施例
１と同様にしてスチレンの熱重合を行なつた。得
られたポリマーは痕跡であつた。Comparative Example 1 Styrene was thermally polymerized in the same manner as in Example 1 except for the inclusion of PMMA-A in Example 1. The polymer obtained was traces.
比較例 ２
実施例１のスチレン封入を除き他は実施例１と
同様にしてPMMA−Ａの分子量増大があるかど
うかの確認を行なつた。回収されたポリマーは
0.23ｇであり、そのｎは37200と測定誤差内で
元のPMMA−Ａと同等であつた。Comparative Example 2 The same procedure as in Example 1 was carried out except for the inclusion of styrene in Example 1 to confirm whether there was an increase in the molecular weight of PMMA-A. The recovered polymer is
The weight was 0.23 g, and its n was 37200, which was equivalent to the original PMMA-A within the measurement error.
実施例 ２
実施例１のPMMA−ＡをPMMA−Ｂに変え封
入量を0.30ｇとした以外は実施例１と同様にして
重合を行なつた。得られたポリマー量は0.42ｇで
あり、そのｎは245000であつた。Example 2 Polymerization was carried out in the same manner as in Example 1, except that PMMA-A in Example 1 was replaced with PMMA-B and the amount enclosed was 0.30 g. The amount of polymer obtained was 0.42 g, and its n was 245,000.
比較例 ３
実施例２のスチレン封入を除き他は実施例２と
同様にしてPMMA−Ｂの分子量増大があるかど
うかの確認を行なつた。回収されたポリマーは
0.28ｇであり、そのｎは161000と測定誤差内で
元のPMMA−Ｂと同等であつた。Comparative Example 3 The same procedure as in Example 2 was carried out except for the inclusion of styrene in Example 2 to confirm whether there was an increase in the molecular weight of PMMA-B. The recovered polymer is
The weight was 0.28 g, and its n was 161,000, which was equivalent to the original PMMA-B within the measurement error.
実施例 ３
実施例１のスチレン10mlをブタジエン15mlに変
えた以外は実施例１と同様にして反応させた。５
時間後大量のメタノール中にポリマーを析出させ
た。得られたポリマーの収量およびｎは0.68
ｇ、136000であつた。Example 3 A reaction was carried out in the same manner as in Example 1 except that 10 ml of styrene in Example 1 was replaced with 15 ml of butadiene. 5
After some time, the polymer was precipitated into a large amount of methanol. The yield of the obtained polymer and n is 0.68
g, 136,000.
比較例 ４
実施例３のPMMA−Ａ封入を除き他は実施例
３と同様にしてブタジエンの熱重合を行なつた。
ポリマーはまつたく得られなかつた。Comparative Example 4 Butadiene was thermally polymerized in the same manner as in Example 3 except for the inclusion of PMMA-A in Example 3.
No polymer was obtained at all.
実施例 ４
完全に脱気された封管中にベンゼン15ml、実施
例２で得たポリマー0.30ｇ、メタクリル酸メチル
15mlを封入し光を遮断した80℃の温浴振とう槽に
て５時間反応させた。Example 4 In a completely degassed sealed tube, 15 ml of benzene, 0.30 g of the polymer obtained in Example 2, and methyl methacrylate.
15 ml of the mixture was sealed and reacted for 5 hours in a warm bath shaking tank at 80°C, shielded from light.
５時間後大量のメタノール中にポリマーを析出
させた。得られたポリマーの収量およびｎはそ
れぞれ0.39ｇ、336000であつた。 After 5 hours, the polymer was precipitated in a large amount of methanol. The yield and n of the obtained polymer were 0.39 g and 336,000, respectively.
比較例 ５
実施例４のメタクリル酸メチル封入を除き他は
実施例４と同様にして実施例２で得たポリマーの
分子量増大があるかどうかの確認を行なつた。回
収されたポリマーは0.29ｇであり、ｎは261000
と測定誤差範囲内で元のポリマーと同等であつ
た。Comparative Example 5 The same procedure as in Example 4 was repeated except for the encapsulation of methyl methacrylate in Example 4 to confirm whether the polymer obtained in Example 2 had an increase in molecular weight. The recovered polymer is 0.29g and n is 261000
and was equivalent to the original polymer within the measurement error range.
実施例 ５
完全に脱気された封管中にベンゼン15ml、実施
例３で得られたポリマー0.30ｇ、スチレン15mlを
封入し光を遮断した80℃の温浴振とう槽にて５時
間反応させた。Example 5 15 ml of benzene, 0.30 g of the polymer obtained in Example 3, and 15 ml of styrene were sealed in a completely degassed sealed tube, and the mixture was reacted for 5 hours in a hot bath shaking tank at 80°C that was shielded from light. .
５時間後大量のメタノール中にポリマーを析出
させた。得られたポリマーの収量およびｎはそ
れぞれ0.37ｇ、207000であつた。 After 5 hours, the polymer was precipitated in a large amount of methanol. The yield and n of the obtained polymer were 0.37 g and 207000, respectively.
以上本法により効率よくブロツクポリマーが得
られることがわかる。 The above shows that block polymers can be efficiently obtained by this method.
実験２
フエニルアゾトリフエニルメタンの代わりにｐ
−メチル−フエニルアゾトリルフエニルメタンを
用いる以外は実験１と同様にして、メタクリル酸
メチルの重合を５時間行つた。反応後栓を開け、
メタノール中にポリマーを析出させた。得られた
ポリメタクリル酸メチル（PMMA−Ｃと略す）
の収量およびｎは下記のとおりであつた。Experiment 2 p instead of phenyl azotriphenylmethane
Polymerization of methyl methacrylate was carried out for 5 hours in the same manner as in Experiment 1 except that -methyl-phenylazotolylphenylmethane was used. After the reaction, open the stopper and
The polymer was precipitated in methanol. Obtained polymethyl methacrylate (abbreviated as PMMA-C)
The yield and n were as follows.
収 量 ｎ
PMMA−Ｃ 3.78ｇ 34000
実施例 ６
PMMA−ＡをPMMA−Ｃに変えた以外は実施
例３と同様にして反応させた。得られたポリマー
の収量およびｎはそれぞれ0.59ｇ、113000であ
つた。 Yield n PMMA-C 3.78g 34000 Example 6 The reaction was carried out in the same manner as in Example 3 except that PMMA-A was changed to PMMA-C. The yield and n of the obtained polymer were 0.59 g and 113000, respectively.
実験３
フエニルアゾトリフエニルメタンの代わりにｐ
−メチル−フエニルアゾメチルジフエニルメタン
を用いる以外は実験１と同様にして、メタクリル
酸メチルの重合を５時間行つた。反応後栓を開
け、メタノール中にポリマーを析出させた。得ら
れたポリメタクリル酸メチル（PMM−Ｄと略
す）の収量およびｎは下記のとおりであつた。Experiment 3 p instead of phenylazotriphenylmethane
Polymerization of methyl methacrylate was carried out for 5 hours in the same manner as in Experiment 1 except that -methyl-phenylazomethyldiphenylmethane was used. After the reaction, the stopper was opened and the polymer was precipitated in methanol. The yield and n of the obtained polymethyl methacrylate (abbreviated as PMM-D) were as follows.
収 量 ｎ
PMMA−Ｄ 3.96ｇ 37000
実施例 ７
PMMA−ＡをPMMA−Ｄに変えた以外は実施
例３と同様にして反応させた。得られたポリマー
の収量およびはそれぞれ0.51ｇ、102000であつ
た。 Yield n PMMA-D 3.96g 37000 Example 7 The reaction was carried out in the same manner as in Example 3 except that PMMA-A was changed to PMMA-D. The yield of the obtained polymer was 0.51 g and 102000, respectively.
実験４
フエニルアゾトリフエニルメタンの代わりにフ
エニルアゾｐ−メチルフエニルジフエニルメタン
用い、メタクリル酸エチルを重合させた以外は実
験１と同様にして５時間重合を行つた。反応後栓
を開け、メタノール中にポリマーを析出させた。
得られたポリメタクリル酸エチル（PEMA−Ａ
と略す）の収量およびｎは下記のとおりであつ
た。Experiment 4 Polymerization was carried out for 5 hours in the same manner as in Experiment 1 except that phenylazo p-methylphenyldiphenylmethane was used instead of phenylazotriphenylmethane and ethyl methacrylate was polymerized. After the reaction, the stopper was opened and the polymer was precipitated in methanol.
The obtained polyethyl methacrylate (PEMA-A
The yield of (abbreviated as) and n were as follows.
収 量 ｎ
PEMA−Ａ 4.03ｇ 38000
実施例 ８
PMMA−ＡをPEMA−Ａに代えた以外は実施
例１と同様にして反応させた。得られたポリマー
の収量およびｎはそれぞれ0.54ｇ、98000であ
つた。 Yield n PEMA-A 4.03g 38000 Example 8 The reaction was carried out in the same manner as in Example 1 except that PMMA-A was replaced with PEMA-A. The yield and n of the obtained polymer were 0.54 g and 98000, respectively.
Claims (1)
フエニル基、R2はフエニル基、アルキル置換フ
エニル基、またはアルキル基を表わす。） で表わされるアゾ系開始剤の存在下、 重合温度40〜150℃で異種ビニルモノマーを順
次重合 せしめることを特徴とする新規なブロツク共重合
体の製造法。[Claims] 1. General formula (Here, R 1 represents a phenyl group or an alkyl-substituted phenyl group, and R 2 represents a phenyl group, an alkyl-substituted phenyl group, or an alkyl group.) In the presence of an azo initiator represented by: polymerization temperature of 40 to 150°C A novel method for producing a block copolymer, characterized by sequentially polymerizing different vinyl monomers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17159182A JPS5959713A (en) | 1982-09-30 | 1982-09-30 | Production of novel block copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17159182A JPS5959713A (en) | 1982-09-30 | 1982-09-30 | Production of novel block copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5959713A JPS5959713A (en) | 1984-04-05 |
| JPH0314047B2 true JPH0314047B2 (en) | 1991-02-25 |
Family
ID=15925993
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17159182A Granted JPS5959713A (en) | 1982-09-30 | 1982-09-30 | Production of novel block copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5959713A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0527004U (en) * | 1991-03-06 | 1993-04-06 | 正雄 山田 | Orifu |
| JP2002348340A (en) * | 2001-05-28 | 2002-12-04 | Denki Kagaku Kogyo Kk | Block copolymer and method for producing the same |
-
1982
- 1982-09-30 JP JP17159182A patent/JPS5959713A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5959713A (en) | 1984-04-05 |
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