JPH0340047B2 - - Google Patents
Info
- Publication number
- JPH0340047B2 JPH0340047B2 JP57096183A JP9618382A JPH0340047B2 JP H0340047 B2 JPH0340047 B2 JP H0340047B2 JP 57096183 A JP57096183 A JP 57096183A JP 9618382 A JP9618382 A JP 9618382A JP H0340047 B2 JPH0340047 B2 JP H0340047B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- vinyl aromatic
- conjugated diene
- styrene
- aromatic compound
- 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 - Lifetime
Links
- 229920002554 vinyl polymer Polymers 0.000 claims description 28
- -1 vinyl aromatic compound Chemical class 0.000 claims description 25
- 229920001400 block copolymer Polymers 0.000 claims description 22
- 150000001993 dienes Chemical class 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 229920001577 copolymer Polymers 0.000 claims description 8
- 229920005604 random copolymer Polymers 0.000 claims description 7
- 150000003512 tertiary amines Chemical class 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 4
- 150000003377 silicon compounds Chemical class 0.000 claims description 4
- 150000002900 organolithium compounds Chemical class 0.000 claims description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 44
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 31
- 238000006116 polymerization reaction Methods 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 238000005299 abrasion Methods 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical class Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 125000002897 diene group Chemical group 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000001979 organolithium group Chemical group 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001268 conjugating effect Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002641 lithium Chemical group 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- CETVQRFGPOGIQJ-UHFFFAOYSA-N lithium;hexane Chemical compound [Li+].CCCCC[CH2-] CETVQRFGPOGIQJ-UHFFFAOYSA-N 0.000 description 1
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- IBOKZQNMFSHYNQ-UHFFFAOYSA-N tribromosilane Chemical class Br[SiH](Br)Br IBOKZQNMFSHYNQ-UHFFFAOYSA-N 0.000 description 1
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Polymerization Catalysts (AREA)
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は新規な分岐状ビニル芳香族化合物−共
役ジエンブロツク共重合体（以下単に分岐状ブロ
ツク共重合体と称す。）に関し、さらに詳しくは
柔軟性と耐摩耗性と機械的強度が改良された、ビ
ニル芳香族化合物重合体部分と少量のビニル芳香
族化合物と大量の共役ジエンとのランダム共重合
体部分から成る分岐状ブロツク共重合体に関する
ものである。
最近感触と実用性の両面から履物分野では柔軟
性にとみ、耐摩耗性が優れ、、しかも力学的強度
に優れた熱可塑性エラストマーの要求が高まつて
いる。
ポリスチレン部分とポリブタジエン部分からな
る分岐状のブロツク共重合体はアニオン重合の技
術の分野では公知のものであり、例えば特開昭54
−94597に開示されている。
しかしこの方法では(B)o−Ｘまたは（Ａ−Ｂ）o
−Ｘで表わされる(B)ブロツク（ポリ共役ジエン）
中のスチレンのランダム性に関する記載なく、ま
たその効果として履物遥としての柔軟性と耐摩耗
性、力学的強度のバランスの点で未だ十分満足出
来るものではない。
本発明の目的は柔軟性にとみ、耐摩耗性と力学
的強度に優れた分岐状ブロツク共重合体を提供す
ることにある。
本発明の分岐状ブロツク共重合体は、炭化水素
溶媒中で有機リチウム化合物を開始剤としてエー
テルまたは第３級アミンの存在下でビニル芳香族
化合物を重合し、更にビニル芳香族化合物と共役
ジエンを共重合したのち、ハロゲン化ケイ素化合
物でカツプリングして得られる
一般式（Ａ−Ｂ）−oＸ
（式中、
Ａ：ビニル芳香族化合物重合体ブロツク、
Ｂ：結合ビニル芳香族化合物が２〜10重量％のビ
ニル芳香族化合物と共役ジエンとのランダム共
重合体ブロツク、
Ｘ：ハロゲン化ケイ素化合物残基、
ｎ：３〜６の整数。）
で表わされ、かつ該共重合体の全結合ビニル芳香
族化合物が20〜55重量％であることを特徴とする
分岐状ブロツク共重合体である。
本発明の分岐状ブロツク共重合体は全結合ビニ
ル芳香族化合物が20〜55重量％、好ましくは25〜
50重量％である。全結合ビニル芳香族化合物量が
20重量％未満では機械的強度が劣り、55重量％を
超えると硬度が高すぎて柔軟性の点で好ましくな
い。
本発明の分岐状ブロツク共重合体の最も大きな
特徴は、一般式（Ａ−Ｂ）−oＸで表わされる分岐
状ブロツク共重合体においてＢ部分が特定範囲の
結合ビニル芳香族化合物含量のランダムな共重合
体であることにある。すなわちＢ部分の結合ビニ
ル芳香族化合物は２〜10重量％、好ましくは３〜
８重量％である。２重量％未満では耐摩耗性が劣
り、10重量％を超えると機械的強度が劣る。
更にＢ部分が共役ジエンを主体とするビニル芳
香族化合物のテーパー型共重合体では耐摩耗性が
劣る。すなわちこのＢ部分を少量のビニル芳香族
化合物と大量の共役ジエンの完全ランダム共重合
体にすることによつて柔軟性、耐摩耗性及び機械
的強度のバランスがとれる。
Ｂ部分のビニル芳香族化合物と共役ジエンのラ
ンダム共重合体は炭化水素溶媒中にランダマイザ
ーとしてエーテルまたは第３級アミンを添加して
重合することによつて得られる。従つてかかるラ
ンダマイザーを使用しない重合方法では本発明の
目的とするＢ部分のビニル芳香族化合物と共役ジ
エンのランダム性は得られない。
エーテルまたは第３級アミンを添加するとポリ
共役ジエン部分のビニル結合が増加するが、この
ビニル結合は15〜30重量％であることが好まし
い。ビニル結合が15重量％以上であれば、Ｂ部分
のビニル芳香族化合物と共役ジエンは実質的にラ
ンダム共重合体である。しかしビニル結合が30重
量％を超えると機械的強度が極端に悪くなり好ま
しくない。またビニル結合が15重量％未満ではＢ
部分のビニル芳香族化合物がテーパーブロツクに
なつて好ましくない。かかる観点からエーテルま
たは第３級アミンの使用量はモノマー100部当り
0.5〜20部が好ましい。
分岐を生成するケイ素−炭素結合はケイ素−ビ
ニル芳香族化合物結合であるよりはケイ素−共役
ジエン結合である方が柔軟性と機械的強度が改良
され好ましい。ケイ素以外のカツプリング剤では
機械的強度が劣り好ましくない。
このため本発明の分岐状ブロツク共重合体は炭
化水素溶媒中、エーテルまたは第３級アミンの存
在下で有機リチウム開始剤を用いてビニル芳香族
化合物ブロツクを生成した後、ビニル芳香族化合
物と共役ジエンのランダム共重合体ブロツクを生
成し、ついで有機リチウム開始剤のLi1グラム原
子当り１〜20モルの共役ジエンを添加し、ハロゲ
ン化ケイ素化合物でカツプリング反応を実施する
ことにより最も好ましい共重合体が得られる。
本発明に使用するビニル芳香族化合物として
は、スチレン、α−メチルスチレン、ｐ−メチル
スチレン、ｍ−メチルスチレン、ｏ−メチルスチ
レン、ｐ−tert−ブチルスチレン、ジメチルスチ
レン、ビニルナフタレンなどが使用できる。この
うちスチレンが好ましい。また共役ジエンとして
はブタジエン、イソプレン、ピペリレンなどが使
用できる。このうちブタジエンが好ましい。
本発明の分岐状ブロツク共重合体の重量平均分
子量は10000〜1000000、好ましくは30000〜
800000である。この中Ａ部分の重量平均分子量は
3000〜80000であり、Ｂ部分の重量平均分子量は
4500〜120000である。
本発明の分岐状ブロツク共重合体は等温重合法
でも断熱重合法でも得られるが、特に断熱重合法
が好ましい。また好ましい重合温度範囲は０℃〜
120℃である。
本発明の分岐状ブロツク共重合体の製造に用い
られる炭化水素溶媒として、例えばシクロペンタ
ン、シクロヘキサン、ベンゼン、エチルベンゼ
ン、キシレン及びこれらとペンタン、ヘキサン、
ヘプタン、ブタンなどの混合物が用いられる。
有機リチウム化合物としては例えば、ｎ−ブチ
ルリチウム、sec−ブチルリチウム、tert−ブチ
ルリチウム、ｎ−ヘキシルリチウム、イソプロピ
ルリチウム、フエニルリチウム、ナフチルリチウ
ム等があり、モノマー100重量部当り0.04〜1.0重
量部で用いられる。
エーテル及び第３級アミンはランダム化剤であ
り、同時に共役ジエン部分のミクロ構造の調節剤
でもある。
例えばジエチルエーテル、ジブチルエーテル、
アニソール、テトラヒドロフラン、ジメトキシベ
ンゼン、エチレングリコールジメチルエーテル、
エチレングリコールジブチルエーテル、トリエチ
ルアミン、Ｎ−ジメチルアニリン、ピリジン、
NNN′N′−テトラメチルエチレンジアミンなど
のエーテル化合物及び第３級アミン化合物が用い
られる。
ハロゲン化ケイ素化合物としてはトリブロムシ
ラン、テトラクロロシラン、ビストリクロロスタ
ニルエタン等が用いられ、ブロツク重合体末端リ
チウム原子１当量に対しハロゲン化ケイ素化合物
のハロゲン原子0.90〜1.10当量の割合で用いられ
る。
ハロゲン化ケイ素化合物添加直前に少量の共役
ジエンを加えて分岐部分の結合をケイ素−共役ジ
エン結合としとものがより好ましい。
本発明の分岐状ブロツク共重合体はポリスチレ
ン、1.2ポリブタジエン等とブレンドして、必要
ならば油展して履物をはじめ自動車部品、電気器
具部品にも用いられる。
以下に本発明の実施例をあげて詳細に説明する
が、本発明の主旨を越えない限り、本発明が限定
されるものではない。
なお各種測定は下記の方法によつた。
柔軟性の指標として硬度（HS）を用い、JIS
K6301に従つて求めた。
耐摩耗性はDIN摩耗試験機で測定した。
機械的強度は引張強度（TB）を用い、JIS
K6301に従つて求めた。
スチレンとブタジエンのランダム性はスチレン
とブタジエンの反応速度比r1、r2を使つて求め
た。
ミクロ構造は赤外法（モレロ法）により求め
た。
実施例１〜３、比較例１〜７
実施例 １
洗條、乾燥した撹拌機、ジヤケツト付きのオー
トクレーブに窒素雰囲気下でシクロヘキサン６
、テトラハイドロフラン１ｇを仕込んだ後、内
温を50℃に昇温した。
次にｎ−ブチルリチウムを１ｇ含むヘキサン溶
液を添加後、スチレンを380ｇ添加し60分重合し
た。スチレンの重合転化率は100％であつた。
次いでスチレン20ｇ、ブタジエン600ｇの混合
体を添加して120分重合した。スチレン、ブタジ
エンの重合転化率は100％であつた。
次いでテトラクロロシランを0.66ｇ含むヘキサ
ン溶液を添加し、20分間カツプリング反応を行つ
た。
なお重合中は温度を常に50℃になる様コントロ
ールした。
重合体溶液に2.6−ジtert−ブチル−ｐ−クレゾ
ールを添加し、更に伸展油（ナフテン系
NONALIC（富士興産(株)製））を50PHR添加後、
シクロヘキサンを加熱除去してブロツク共重合体
を得た。
なおスチレン・ブタジエンのランダム性につい
て次のような測定を行なつた。
(1) まず種々のモノマー組成のスチレン・ブタジ
エンの混合体を転化率５％以下まで重合させ、
生成した種々のコポリマーのスチレン・ブタジ
エン含量を赤外線分析で測定した。
J.POLYMER SCIENCE、５（’50）に開
示されたFINEMAN ＆ ROSSの方法に従
い、ブタジエン、スチレンの反応性比r1、r2を
求めた。
(2) 次に定常状態を仮定したスチレンとブタジエ
ンの共重合速度から下記の式を導き出した。
ｄ〔Ｓ〕／ｄ〔Ｂ〕＝〔Ｓ〕／〔Ｂ〕（r1〔Ｓ
〕＋〔Ｂ〕／〔Ｓ〕＋r2〔Ｂ〕）
ｄ〔Ｓ〕：コポリマー中のスチレン部分の増加速
度
ｄ〔Ｂ〕：コポリマー中のブタジエン部分の増加
速度
〔Ｓ〕：モノマーブレンド中のスチレンの重量
〔Ｂ〕：モノマーブレンド中のブタジエンの重
量
r1：スチレンの反応性比
r2：ブタジエンの反応性比
この式によりコポリマー中のスチレン差分百分
率を算出し、スチレンがランダムに共重合してい
るか検討した。
例えば実施例１と同様の条件でシクロヘキサン
６、テトラハイドロフラン１ｇを添加し、50℃
で上記の重合を行い、r1＝0.10、r2＝1.15の値を
得た。
このr1、r2を用いて実施例１のブロツクＢのス
チレンの結合状態（ブロツク性）を差分百分率で
図示すると第１図のようになり、実質的に完全ラ
ンダム共重合している。
実施例２、３、比較例１〜５
表−１に示した所定量のシクロヘキサン、ｎ−
ブチルリチウム、テトラハイドロフラン、スチレ
ン、ブタジエン、テトラクロロシランを用いて実
施例１と同様に重合した。
但し、実施例３はテトラクロロシランを添加す
る直前に少量のブタジエンを添加した。
また実施例２についてランダム性をr1＝0.10、
r2＝1.15を用いて測定したところ第２図のように
なり、実質的にランダムに共重合していることが
わかつた。
比較例 ６、７
比較例６はランダマイザーのテトラハイドロフ
ランを使用しなかつた。
比較例７はテトラクロロシランの代りにテトラ
クロロスズを用いてカツプリング反応を行つた。
また比較例６の場合50℃でのr1、r2を求めそれ
ぞれ0.03、28.0の値を得た。このr1、r2を用いて
図示すれば第３図が得られ、これはスチレンがテ
ーパーブロツクになつていることを示す。
分岐状ブロツク共重合体の性質を表−２に示
す。
実施例１〜３は比較例１〜７に比較し、柔軟
性、耐摩耗性、機械的強度のバランスの点で優れ
ている。
特に分岐状ブロツク共重合体を生成するために
テトラクロロシランを添加する直前に少量のブタ
ジエンを添加した実施例３が柔軟性、耐摩耗性、
機械的強度のバランスの点で最も優れている。
実施例 ４
スチレンに替えてｐ−メチルスチレンを用いた
他は実施例１と同様にして重合した。結果は表−
２に示したが、柔軟性、耐摩耗性、機械的強度に
おいてバランスのとれた特性を示すことがわか
る。
The present invention relates to a novel branched vinyl aromatic compound-conjugated diene block copolymer (hereinafter simply referred to as a branched block copolymer), and more specifically, it relates to a novel branched vinyl aromatic compound-conjugated diene block copolymer (hereinafter simply referred to as a branched block copolymer), and more specifically, it has improved flexibility, abrasion resistance, and mechanical strength. , a branched block copolymer consisting of a vinyl aromatic compound polymer portion and a random copolymer portion of a small amount of a vinyl aromatic compound and a large amount of a conjugated diene. Recently, there has been an increasing demand in the footwear field for thermoplastic elastomers that are flexible, have excellent abrasion resistance, and have excellent mechanical strength, both in terms of feel and practicality. A branched block copolymer consisting of a polystyrene portion and a polybutadiene portion is well known in the field of anionic polymerization technology, for example, as disclosed in JP-A-54
-94597. But in this method (B) o -X or (A-B) o
(B) block represented by -X (polyconjugated diene)
There is no description of the randomness of the styrene inside, and the effect of this is that the balance between flexibility, abrasion resistance, and mechanical strength for footwear is still not fully satisfactory. An object of the present invention is to provide a branched block copolymer that is flexible, has excellent abrasion resistance and mechanical strength. The branched block copolymer of the present invention is obtained by polymerizing a vinyl aromatic compound in a hydrocarbon solvent using an organolithium compound as an initiator in the presence of an ether or a tertiary amine, and then polymerizing the vinyl aromatic compound and a conjugated diene. After copolymerization, the general formula (A-B) -o % by weight of a random copolymer block of a vinyl aromatic compound and a conjugated diene; It is a branched block copolymer characterized by containing 20 to 55% by weight of aromatic compounds. The branched block copolymer of the present invention has a total bonded vinyl aromatic compound content of 20 to 55% by weight, preferably 25 to 55% by weight.
50% by weight. The amount of total bonded vinyl aromatic compounds is
If it is less than 20% by weight, the mechanical strength will be poor, and if it exceeds 55% by weight, the hardness will be too high, making it undesirable in terms of flexibility. The most significant feature of the branched block copolymer of the present invention is that in the branched block copolymer represented by the general formula (A-B) -o The reason is that it is a copolymer. That is, the amount of bound vinyl aromatic compound in part B is 2 to 10% by weight, preferably 3 to 10% by weight.
It is 8% by weight. If it is less than 2% by weight, the wear resistance will be poor, and if it exceeds 10% by weight, the mechanical strength will be poor. Furthermore, a tapered copolymer of a vinyl aromatic compound in which the B portion is mainly composed of a conjugated diene has poor wear resistance. That is, by making the B portion a completely random copolymer of a small amount of vinyl aromatic compound and a large amount of conjugated diene, flexibility, abrasion resistance, and mechanical strength can be balanced. The random copolymer of a vinyl aromatic compound and a conjugated diene, which is part B, can be obtained by polymerizing by adding an ether or a tertiary amine as a randomizer to a hydrocarbon solvent. Therefore, in a polymerization method that does not use such a randomizer, the randomness of the vinyl aromatic compound and conjugated diene of the B portion, which is the object of the present invention, cannot be obtained. Addition of an ether or tertiary amine increases the vinyl bonds in the polyconjugated diene moiety, preferably from 15 to 30% by weight. If the vinyl bond is 15% by weight or more, the vinyl aromatic compound and conjugated diene of the B portion are substantially random copolymers. However, if the vinyl bond exceeds 30% by weight, the mechanical strength becomes extremely poor, which is not preferable. Also, if the vinyl bond is less than 15% by weight, B
The vinyl aromatic compound in the portion becomes a tapered block, which is not preferable. From this point of view, the amount of ether or tertiary amine used should be determined per 100 parts of monomer.
0.5 to 20 parts is preferred. The silicon-carbon bond that forms the branch is preferably a silicon-conjugated diene bond rather than a silicon-vinyl aromatic compound bond because flexibility and mechanical strength are improved. Coupling agents other than silicon are not preferred because they have poor mechanical strength. Therefore, the branched block copolymer of the present invention is produced by forming a vinyl aromatic compound block using an organolithium initiator in a hydrocarbon solvent in the presence of an ether or a tertiary amine, and then conjugating it with a vinyl aromatic compound. The most preferred copolymers are produced by forming random copolymer blocks of dienes, then adding 1 to 20 moles of conjugated diene per gram atom of Li organolithium initiator, and carrying out a coupling reaction with a silicon halide compound. can get. As the vinyl aromatic compound used in the present invention, styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, p-tert-butylstyrene, dimethylstyrene, vinylnaphthalene, etc. can be used. . Among these, styrene is preferred. Moreover, butadiene, isoprene, piperylene, etc. can be used as the conjugated diene. Among these, butadiene is preferred. The weight average molecular weight of the branched block copolymer of the present invention is from 10,000 to 1,000,000, preferably from 30,000 to
800000. The weight average molecular weight of this part A is
3000 to 80000, and the weight average molecular weight of part B is
4500-120000. The branched block copolymer of the present invention can be obtained by isothermal polymerization or adiabatic polymerization, but adiabatic polymerization is particularly preferred. The preferred polymerization temperature range is 0°C to
The temperature is 120℃. Hydrocarbon solvents used in the production of the branched block copolymer of the present invention include, for example, cyclopentane, cyclohexane, benzene, ethylbenzene, xylene, and combinations thereof with pentane, hexane,
Mixtures of heptane, butane, etc. are used. Examples of organic lithium compounds include n-butyllithium, sec-butyllithium, tert-butyllithium, n-hexyllithium, isopropyllithium, phenyllithium, naphthyllithium, etc., and the amount is 0.04 to 1.0 parts by weight per 100 parts by weight of monomer. used in Ethers and tertiary amines are randomizing agents and at the same time modifiers of the microstructure of the conjugated diene moieties. For example, diethyl ether, dibutyl ether,
Anisole, tetrahydrofuran, dimethoxybenzene, ethylene glycol dimethyl ether,
Ethylene glycol dibutyl ether, triethylamine, N-dimethylaniline, pyridine,
Ether compounds and tertiary amine compounds such as NNN'N'-tetramethylethylenediamine are used. As the halogenated silicon compound, tribromosilane, tetrachlorosilane, bistrichlorostannylethane, etc. are used, and the halogen atom of the halogenated silicon compound is used in a ratio of 0.90 to 1.10 equivalents per 1 equivalent of the terminal lithium atom of the block polymer. More preferably, a small amount of conjugated diene is added immediately before addition of the halogenated silicon compound to form a silicon-conjugated diene bond at the branched portion. The branched block copolymer of the present invention can be blended with polystyrene, 1.2 polybutadiene, etc. and, if necessary, oil-extended for use in footwear, automobile parts, and electrical appliance parts. The present invention will be described in detail below with reference to examples, but the present invention is not limited unless it goes beyond the gist of the present invention. In addition, various measurements were conducted according to the following methods. Using hardness ( HS ) as an index of flexibility, JIS
Obtained according to K6301. Abrasion resistance was measured using a DIN abrasion tester. For mechanical strength, tensile strength (T B ) is used, and JIS
Obtained according to K6301. The randomness of styrene and butadiene was determined using the reaction rate ratios r 1 and r 2 of styrene and butadiene. The microstructure was determined by an infrared method (Morello method). Examples 1 to 3, Comparative Examples 1 to 7 Example 1 Cyclohexane 6 was placed in an autoclave equipped with a washed, dry stirrer and jacket under a nitrogen atmosphere.
After charging 1 g of tetrahydrofuran, the internal temperature was raised to 50°C. Next, a hexane solution containing 1 g of n-butyllithium was added, and then 380 g of styrene was added and polymerized for 60 minutes. The polymerization conversion rate of styrene was 100%. Next, a mixture of 20 g of styrene and 600 g of butadiene was added and polymerized for 120 minutes. The polymerization conversion rate of styrene and butadiene was 100%. Next, a hexane solution containing 0.66 g of tetrachlorosilane was added, and a coupling reaction was performed for 20 minutes. During the polymerization, the temperature was always controlled at 50°C. 2.6-di-tert-butyl-p-cresol was added to the polymer solution, and extender oil (naphthene-based
After adding 50 PHR of NONALIC (manufactured by Fuji Kosan Co., Ltd.),
Cyclohexane was removed by heating to obtain a block copolymer. The randomness of styrene and butadiene was measured as follows. (1) First, a mixture of styrene and butadiene with various monomer compositions is polymerized to a conversion rate of 5% or less,
The styrene-butadiene content of the various copolymers produced was determined by infrared analysis. The reactivity ratios r 1 and r 2 of butadiene and styrene were determined according to the FINEMAN & ROSS method disclosed in J. POLYMER SCIENCE, 5 ('50). (2) Next, the following equation was derived from the copolymerization rate of styrene and butadiene assuming a steady state. d[S]/d[B]=[S]/[B](r 1 [S
]+[B]/[S]+ r2 [B]) d[S]: Rate of increase in styrene moieties in the copolymer d[B]: Rate of increase in butadiene moieties in the copolymer [S]: Styrene in the monomer blend Weight of [B]: Weight of butadiene in the monomer blend r 1 : Reactivity ratio of styrene r 2 : Reactivity ratio of butadiene Calculate the differential percentage of styrene in the copolymer using this formula, I considered whether there was one. For example, under the same conditions as in Example 1, add 6 cyclohexane and 1 g of tetrahydrofuran, and
The above polymerization was carried out, and the values of r 1 =0.10 and r 2 =1.15 were obtained. When the bonding state (blockability) of styrene in block B of Example 1 is plotted as a percentage difference using r 1 and r 2 , it is as shown in FIG. 1, indicating that substantially completely random copolymerization has occurred. Examples 2 and 3, Comparative Examples 1 to 5 Predetermined amounts of cyclohexane shown in Table 1, n-
Polymerization was carried out in the same manner as in Example 1 using butyllithium, tetrahydrofuran, styrene, butadiene, and tetrachlorosilane. However, in Example 3, a small amount of butadiene was added immediately before adding tetrachlorosilane. In addition, for Example 2, the randomness is r 1 = 0.10,
When measured using r 2 =1.15, the results were as shown in Figure 2, indicating that copolymerization was substantially random. Comparative Examples 6 and 7 Comparative Example 6 did not use tetrahydrofuran as a randomizer. In Comparative Example 7, a coupling reaction was carried out using tetrachlorotin instead of tetrachlorosilane. In addition, in the case of Comparative Example 6, r 1 and r 2 at 50°C were determined to be 0.03 and 28.0, respectively. If this r 1 and r 2 are used to illustrate, Figure 3 is obtained, which shows that styrene forms a tapered block. Table 2 shows the properties of the branched block copolymer. Examples 1 to 3 are superior to Comparative Examples 1 to 7 in terms of the balance of flexibility, abrasion resistance, and mechanical strength. In particular, Example 3, in which a small amount of butadiene was added immediately before adding tetrachlorosilane to produce a branched block copolymer, showed excellent flexibility, abrasion resistance, and
It has the best balance of mechanical strength. Example 4 Polymerization was carried out in the same manner as in Example 1, except that p-methylstyrene was used instead of styrene. The results are in the table-
2, it can be seen that it exhibits well-balanced characteristics in flexibility, abrasion resistance, and mechanical strength.
【表】【table】
【表】【table】
第１図は実施１のスチレン含量とモノマー転化
率の関係を示すグラフ、第２図は実施例２のスチ
レン含量とモノマー転化率の関係を示すグラフ、
第３図は比較例６のスチレン含量とモノマー転化
率の関係を示すグラフで、本発明の一般式（Ａ−
Ｂ）−ＸのＢ部分のランダム性か否かを示すもの
である。
FIG. 1 is a graph showing the relationship between styrene content and monomer conversion rate in Example 1, FIG. 2 is a graph showing the relationship between styrene content and monomer conversion rate in Example 2,
FIG. 3 is a graph showing the relationship between the styrene content and the monomer conversion rate of Comparative Example 6, which shows the general formula (A-
B) This shows whether the B part of -X is random or not.
Claims (1)
剤としてエーテルまたは第３級アミンの存在下で
得られる分岐状ビニル芳香族化合物−共役ジエン
ブロツク共重合体において、該共重合体が 一般式（Ａ−Ｂ）−oＸ （式中、 Ａ：3000〜80000の重量平均分子量を有するビニ
ル芳香族化合物重合体ブロツク、 Ｂ：4500〜120000の重量平均分子量を有する、結
合ビニル芳香族化合物含量が２〜10重量％のビ
ニル芳香族化合物と共役ジエンとのランダム共
重合体ブロツク、 Ｘ：ハロゲン化ケイ素化合物残基、 ｎ：３〜６の整数） で表わされ、30000〜1000000の重量平均分子量を
有しており、かつ該共重合体の全結合ビニル芳香
族化合物が20〜55重量％であることを特徴とする
分岐状ビニル芳香族化合物−共役ジエンブロツク
共重合体。[Scope of Claims] 1. A branched vinyl aromatic compound-conjugated diene block copolymer obtained in a hydrocarbon solvent using an organolithium compound as an initiator in the presence of an ether or a tertiary amine; is a general formula (A-B) -o A random copolymer block of a vinyl aromatic compound and a conjugated diene with a compound content of 2 to 10% by weight, X: a halogenated silicon compound residue, n: an integer of 3 to 6), A branched vinyl aromatic compound-conjugated diene block copolymer having a weight average molecular weight and characterized in that the copolymer contains 20 to 55% by weight of total bonded vinyl aromatic compounds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9618382A JPS58213010A (en) | 1982-06-07 | 1982-06-07 | Branched block copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9618382A JPS58213010A (en) | 1982-06-07 | 1982-06-07 | Branched block copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58213010A JPS58213010A (en) | 1983-12-10 |
| JPH0340047B2 true JPH0340047B2 (en) | 1991-06-17 |
Family
ID=14158196
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9618382A Granted JPS58213010A (en) | 1982-06-07 | 1982-06-07 | Branched block copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58213010A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0686562B2 (en) * | 1985-03-01 | 1994-11-02 | シエル・インターナシヨナル・リサーチ・マートスハツペイ・ベー・ヴエー | Resin composition |
| JPH07116273B2 (en) * | 1991-12-17 | 1995-12-13 | 旭化成工業株式会社 | Block copolymer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4148771A (en) * | 1977-06-23 | 1979-04-10 | Phillips Petroleum Company | Method of making novel rubbery block copolymers and pressure-sensitive adhesives |
| JPS56115309A (en) * | 1980-02-15 | 1981-09-10 | Asahi Chem Ind Co Ltd | Thermosetting resin composition and its preparation |
-
1982
- 1982-06-07 JP JP9618382A patent/JPS58213010A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4148771A (en) * | 1977-06-23 | 1979-04-10 | Phillips Petroleum Company | Method of making novel rubbery block copolymers and pressure-sensitive adhesives |
| JPS56115309A (en) * | 1980-02-15 | 1981-09-10 | Asahi Chem Ind Co Ltd | Thermosetting resin composition and its preparation |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58213010A (en) | 1983-12-10 |
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