JPH0340727B2 - - Google Patents
Info
- Publication number
- JPH0340727B2 JPH0340727B2 JP3834283A JP3834283A JPH0340727B2 JP H0340727 B2 JPH0340727 B2 JP H0340727B2 JP 3834283 A JP3834283 A JP 3834283A JP 3834283 A JP3834283 A JP 3834283A JP H0340727 B2 JPH0340727 B2 JP H0340727B2
- Authority
- JP
- Japan
- Prior art keywords
- vinyl aromatic
- weight
- aromatic compound
- amount
- block copolymer
- 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
- 229920002554 vinyl polymer Polymers 0.000 claims description 45
- -1 vinyl aromatic compound Chemical class 0.000 claims description 44
- 229920001400 block copolymer Polymers 0.000 claims description 25
- 150000001993 dienes Chemical class 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 3
- 150000002900 organolithium compounds Chemical class 0.000 claims description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 18
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000004793 Polystyrene Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229920002223 polystyrene Polymers 0.000 description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 150000003512 tertiary amines Chemical class 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 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
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 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
- 238000005516 engineering process Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 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
- 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
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229920001198 elastomeric copolymer Polymers 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
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 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
- 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- FLESAADTDNKLFJ-UHFFFAOYSA-N nickel;pentane-2,4-dione Chemical compound [Ni].CC(=O)CC(C)=O FLESAADTDNKLFJ-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 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
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
Description
本発明は新規な直鎖状ビニル芳香族化合物−共
役ジエンブロツク共重合体に関し、さらに詳しく
は、引張強度と伸びのバランスのとれた両端に非
エラストマー性ビニル芳香族化合物ブロツクを有
し、中央に共役ジエンを主体としたビニル芳香族
化合物と共役ジエンのエラストマー性共重合体ブ
ロツクを有する直鎖状ブロツク共重合体に関する
ものである。
最近、感覚と実用性の両面からポリスチレン改
質分野では、引張強度と伸びのバランスのとれた
熱可塑性エラストマーの要求が高まつている。
ビニル芳香族化合物と共役ジエンから成る直鎖
状ブロツク共重合体はアニオン重合の技術分野で
は公知のものであり、例えば特公昭40−23798、
特公昭46−32415に開示されている。しかしこれ
らの方法で得られるブロツク共重合体は引張強度
と伸びのバランスの点で未だ十分満足出来るもの
ではない。
そこで本発明者らは引張強度と伸びのバランス
のとれた直鎖状ブロツク共重合体を得るべく鋭意
検討した結果本発明に到達した。即ち本発明は炭
化水素溶媒中で有機リチウム化合物を開始剤とし
て重合して得られるビニル芳香族化合物含量が25
〜55重量％の直鎖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−Ａ
（式中Ａはビニル芳香族化合物重合体ブロツクで
あつて、両端のＡの合計量はビニル芳香族化合物
全体の50〜97重量％を含み、Ｂは共役ジエンを主
体とするビニル芳香族化合物との共重合体であつ
て、(a)ビニル芳香族化合物が漸増するテーパーブ
ロツクを３〜10個有し、(b)ビニル芳香族化合物／
共役ジエンの重量比が３〜15／97〜85である。）
であつて、モノマー単位で１〜４個連らなつたビ
ニル芳香族化合物の連鎖の量が全ビニル芳香族化
合物含量の５〜30重量％であることを特徴とする
直鎖状ブロツク共重合体である。
本発明の直鎖状ブロツク共重合体はビニル芳香
族化合物が25〜55重量％、好ましくは28〜50重量
％である。ビニル芳香族化合物が25重量％未満で
は引張強度が劣り、55重量％を超えると伸びが劣
る。
本発明のブロツク共重合体の特徴は一般式Ａ−
Ｂ−ＡにおいてＢ部分が特定範囲のビニル芳香族
化合物を有し、更に特定範囲のテーパーブロツク
数を有し、しかも該直鎖状ブロツク共重合体は特
定範囲のビニル芳香族化合物の連鎖分布を有した
共重合体であることにある。これらの特徴によ
り、引張強度と伸びのバランスが著しく改善され
る。
すなわち本発明のブロツク共重合体のＢ部分の
ビニル芳香族化合物含量は３〜15重量％、好まし
くは５〜10重量％であり、かつＡ部分のビニル芳
香族化合物が全ビニル芳香族化合物の50〜97％
で、好ましくは70〜96％である。Ｂ部分のビニル
芳香族化合物の含量が３重量％未満では引張強度
が劣り、15重量％を超えると伸びが劣る。さらに
Ｂ部分はビニル芳香族化合物が漸増するテーパー
ブロツクからなり、そのテーパーブロツクの数は
３〜10個、好ましくは３〜７個が良い。テーパー
ブロツクの数が３未満では伸びが劣り、10を超え
ると引張強度が劣る。
直鎖状ブロツク共重合体のビニル芳香族化合物
の連鎖分布はモノマー単位で１〜４個連らなつた
ビニル芳香族化合物の連鎖の量が全ビニル芳香族
化合物含量の５〜30重量％、好ましくは15〜30重
量％である。４以下の連鎖が５重量％未満では伸
びが劣り、30重量％を超えると引張強度が劣る。
本発明のブロツク共重合体は次の様な方法で製
造することが出来る。
すなわち、炭化水素溶媒中にエーテルまたは第
３級アミンを添加し、有機リチウム化合物を開始
剤として用い、
(1) まずビニル芳香族化合物を全モノマー使用量
の８〜40重量％、好ましくは10〜25重量％を重
合し、重合反応が実質的に終了した後
(2) 共役ジエン85〜97重量％とビニル芳香族化合
物３〜15重量％の混合物を３〜10回に分けて重
合し、必要ならその後１回添加分と等量の共役
ジエンを添加して重合する。
(3) 最後にビニル芳香族化合物を全モノマー使用
量に対し８〜40重量％、好ましくは10〜25重量
％を重合する方法が使用できる。
上記の共役ジエンとビニル芳香族化合物の混合
物を３回〜10回に分けて重合する工程において各
回の単量体使用量は同程度の方が好ましく、また
各回においてほぼ100％の重合を行なうことが望
ましい。また３〜10回に分けてモノマーを添加す
る方法としてモノマー混合物を添加する方法、ま
たは共役ジエンとビニル芳香族化合物を同時に添
加する方法等が用いられる。
好ましいビニル芳香族化合物の連鎖分布を有す
るビニル芳香族化合物と共役ジエンの共重合体
は、炭化水素溶媒中にエーテルまたは第３級アミ
ンを添加して重合することによつて得られる。エ
ーテルまたは第３級アミンを添加するとビニル芳
香族化合物の１〜４の連鎖量が増加するが、この
連鎖量はビニル芳香族化合物含量の５〜30重量％
が好ましく、更に好ましくは15〜30重量％であ
る。５重量％未満では伸びが劣り、30重量％を超
えると引張強度が劣る。
ビニル芳香族化合物の連鎖分布を調節する観点
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重量部当り0.005〜５重量部が好まし
く、更に好ましくは0.005〜0.5重量部である。
0.005重量部未満の場合も５重量部を超えた場合
も、ビニル芳香族化合物の連鎖量が所望通りに得
られず、引張強度が劣る。
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、ビニルナフタレン等が使用出来る。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
使用出来る。このうちブタジエンが好ましいもの
として挙げられる。
本発明の直鎖状ブロツク共重合体の重量平均分
子量は好ましくは10000〜800000、更に好ましく
は50000〜500000である。このうちＡ部分の重量
平均分子量は3000〜80000、Ｂ部分の重量平均分
子量は44000〜340000が好ましい。
本発明の直鎖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。また好ましい重
合温度範囲は30〜120℃である。
本発明の直鎖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、iso−ヘキシ
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。
エーテルまたは第３級アミンとしては例えばテ
トラハイドロフラン、ジエチルエーテル、アニソ
ール、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、トリエチルアミン、Ｎ−ジメ
チルアニリン、ピリジ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。
本発明の直鎖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食
品容器包装類、玩具、日常雑貨品類、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。
そのほか本発明のブロツク共重合体の用途は広
範囲な領域にわたるが、その例を示すならば履
物、容器などの射出成形品、玩具、家庭用品など
のフロー成形品、パッキング、シート、プレート
などの圧搾成形品等に好適に使用することができ
る。また炭化水素溶剤に溶解するので接着剤とし
ても有効に用いられる。更に本発明のブロツク共
重合体はSBRやNBRなどの他のゴム、ポリスチ
レンなどのプラスチック等に混合しその物性を改
変されるのにも用いられる。例えばゴム用途とし
てはクレープ調スポンジ、プラスチック用途とし
て汎用ポリスチレンの耐衝撃性等の向上剤として
利用される。
また本発明のブロツク共重合体は水素添加して
耐熱性、耐候性を向上させることができる。水素
添加したブロツク共重合体も上記各用途に使用で
き、またポリスチレン、ポリオレフインなどの樹
脂類やゴム類とブレンドすることもできる。
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。
引張強度（TB）と伸び（EB）は、JISK6301に
従つて測定した。
透明性試験はASTM・Ｄ−1003に準拠した。
スチレン連鎖は農工大田中教授等によつて開発
された方法（高分子学会予稿集、第29巻７号2055
頁）に準拠した。
全スチレン含量は赤外法により求めた。
実施例 １
洗滌、乾燥した攪拌機、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4500
ｇ、テトラハイドロフラン１ｇを仕込んだ後、内
温を70℃にした。
次にｎ−ブチルリチウム0.5ｇを含むヘキサン
溶液を添加後スチレンを130ｇ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15ｇ、ブタジエン115ｇの混合物
を添加して60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。更にこの操作を
２回繰返した。次いでブタジエンを115ｇ添加し
て重合転化率100％まで重合させた。その後更に
スチレンを130ｇ添加して60分重合した。転化率
は100％であつた。
なお重合中は温度を常に70℃になる様に調節し
た。重合終了後、重合体溶液に２，６−ジ−tert
−ブチルｐ−クレゾールを添加した後、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。
実施例２〜８、比較例１〜10
表−１に示した所定量のスチレン、ブタジエ
ン、テトラハイドロフラン等を用い、実施例１と
同様の処方によつて重合した。
The present invention relates to a novel linear vinyl aromatic compound-conjugated diene block copolymer, and more specifically, it has non-elastomeric vinyl aromatic compound blocks at both ends with a well-balanced tensile strength and elongation, and has a non-elastomeric vinyl aromatic compound block in the center. The present invention relates to a linear block copolymer having an elastomeric copolymer block of a vinyl aromatic compound and a conjugated diene, mainly composed of a conjugated diene. Recently, there has been an increasing demand for thermoplastic elastomers with a well-balanced tensile strength and elongation in the field of polystyrene modification, both for aesthetic and practical reasons. Linear block copolymers consisting of vinyl aromatic compounds and conjugated dienes are well known in the technical field of anionic polymerization, such as those described in Japanese Patent Publication No. 40-23798,
It is disclosed in Japanese Patent Publication No. 46-32415. However, the block copolymers obtained by these methods are still not fully satisfactory in terms of the balance between tensile strength and elongation. Therefore, the present inventors conducted intensive studies to obtain a linear block copolymer having a well-balanced tensile strength and elongation, and as a result, they arrived at the present invention. That is, the present invention has a vinyl aromatic compound content of 25% by polymerization using an organolithium compound as an initiator in a hydrocarbon solvent.
~55% by weight of a linear vinyl aromatic compound-conjugated diene block copolymer, the copolymer has the general formula A-B-A (where A is a vinyl aromatic compound polymer block, and The total amount of A includes 50 to 97% by weight of the entire vinyl aromatic compound, and B is a copolymer with a vinyl aromatic compound mainly consisting of a conjugated diene, in which (a) the vinyl aromatic compound gradually increases. It has 3 to 10 tapered blocks, and (b) vinyl aromatic compound/
The weight ratio of the conjugated diene is 3-15/97-85. ), characterized in that the amount of chains of 1 to 4 vinyl aromatic compounds in monomer units is 5 to 30% by weight of the total vinyl aromatic compound content. It is a combination. The linear block copolymer of the present invention has a vinyl aromatic compound content of 25 to 55% by weight, preferably 28 to 50% by weight. If the vinyl aromatic compound is less than 25% by weight, the tensile strength will be poor, and if it exceeds 55% by weight, the elongation will be poor. The block copolymer of the present invention is characterized by the general formula A-
In B-A, the B portion has a vinyl aromatic compound in a specific range, and further has a taper block number in a specific range, and the linear block copolymer has a chain distribution of vinyl aromatic compounds in a specific range. The reason is that it is a copolymer with These features significantly improve the balance between tensile strength and elongation. That is, the vinyl aromatic compound content of the B part of the block copolymer of the present invention is 3 to 15% by weight, preferably 5 to 10% by weight, and the vinyl aromatic compound content of the A part is 50% by weight of the total vinyl aromatic compounds. ~97%
and preferably 70 to 96%. If the content of the vinyl aromatic compound in the B portion is less than 3% by weight, the tensile strength will be poor, and if it exceeds 15% by weight, the elongation will be poor. Further, part B consists of tapered blocks in which the vinyl aromatic compound gradually increases, and the number of tapered blocks is 3 to 10, preferably 3 to 7. If the number of taper blocks is less than 3, the elongation will be poor, and if it exceeds 10, the tensile strength will be poor. The chain distribution of vinyl aromatic compounds in the linear block copolymer is such that the amount of chains of 1 to 4 vinyl aromatic compounds in monomer units is preferably 5 to 30% by weight of the total vinyl aromatic compound content. is 15-30% by weight. If the number of chains of 4 or less is less than 5% by weight, the elongation will be poor, and if it exceeds 30% by weight, the tensile strength will be poor. The block copolymer of the present invention can be produced by the following method. That is, an ether or a tertiary amine is added to a hydrocarbon solvent, and an organolithium compound is used as an initiator. After polymerizing 25% by weight and substantially completing the polymerization reaction, (2) polymerize a mixture of 85 to 97% by weight of a conjugated diene and 3 to 15% by weight of a vinyl aromatic compound in 3 to 10 batches to obtain the necessary amount. Then, an amount of conjugated diene equivalent to the amount added once is added and polymerized. (3) Finally, a method can be used in which a vinyl aromatic compound is polymerized in an amount of 8 to 40% by weight, preferably 10 to 25% by weight based on the total amount of monomers used. In the process of polymerizing the mixture of conjugated diene and vinyl aromatic compound in 3 to 10 times, it is preferable that the amount of monomer used each time is about the same, and approximately 100% polymerization should be carried out each time. is desirable. Further, as a method of adding the monomer in 3 to 10 times, a method of adding a monomer mixture, a method of adding a conjugated diene and a vinyl aromatic compound at the same time, etc. are used. A copolymer of a vinyl aromatic compound and a conjugated diene having a preferred vinyl aromatic compound chain distribution can be obtained by polymerization in a hydrocarbon solvent by adding an ether or a tertiary amine. The addition of ethers or tertiary amines increases the chain content of 1-4 vinyl aromatics, which ranges from 5 to 30% by weight of the vinyl aromatic content.
is preferred, and more preferably 15 to 30% by weight. If it is less than 5% by weight, the elongation will be poor, and if it exceeds 30% by weight, the tensile strength will be poor. From the viewpoint of controlling the chain distribution of the vinyl aromatic compound, the amount of ether or tertiary amine used is preferably 0.005 to 5 parts by weight, more preferably 0.005 to 0.5 parts by weight per 100 parts by weight of monomer.
If the amount is less than 0.005 parts by weight or more than 5 parts by weight, the desired chain amount of the vinyl aromatic compound cannot be obtained, resulting in poor tensile strength. 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. Further, as the conjugated diene, butadiene, isoprene, piperylene, etc. can be used. Among these, butadiene is preferred. The weight average molecular weight of the linear block copolymer of the present invention is preferably 10,000 to 800,000, more preferably 50,000 to 500,000. Among these, the weight average molecular weight of the A part is preferably 3,000 to 80,000, and the weight average molecular weight of the B part is preferably 44,000 to 340,000. The linear block copolymer of the present invention can be obtained by isothermal polymerization or adiabatic polymerization. Further, a preferable polymerization temperature range is 30 to 120°C. Hydrocarbon solvents used in the production of the linear 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, iso-hexyllithium, phenyllithium, naphthyllithium, etc., and the amount is 0.04 to 1.0 per 100 parts by weight of monomer.
Used in parts by weight. Examples of the ether or tertiary amine include ether compounds such as tetrahydrofuran, diethyl ether, anisole, dimethoxybenzene, ethylene glycol dimethyl ether, triethylamine, N-dimethylaniline, and pyridine;
and tertiary amine compounds are used. The linear block copolymer of the present invention can be blended with polystyrene, 1,2-polybutadiene, etc. to produce food containers and packaging, toys, miscellaneous goods, etc. If necessary, it can be oil-extended to produce footwear, automobile parts, and electrical appliance parts. Also used for In addition, the block copolymer of the present invention can be used in a wide range of areas, including injection molded products such as footwear and containers, flow molded products such as toys and household goods, and compressed products such as packing, sheets, and plates. It can be suitably used for molded products and the like. Also, since it dissolves in hydrocarbon solvents, it can be effectively used as an adhesive. Furthermore, the block copolymer of the present invention can be mixed with other rubbers such as SBR and NBR, plastics such as polystyrene, etc., and used to modify their physical properties. For example, in rubber applications, it is used as a crepe-like sponge, and in plastic applications, it is used as an impact resistance improver for general-purpose polystyrene. Furthermore, the block copolymer of the present invention can be hydrogenated to improve its heat resistance and weather resistance. Hydrogenated block copolymers can also be used for each of the above applications, and can also be blended with resins such as polystyrene and polyolefins and rubbers. 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. Tensile strength (T B ) and elongation (E B ) were measured according to JISK6301. The transparency test was based on ASTM D-1003. The styrene chain was developed by Professor Tanaka et al. of the University of Agriculture and Technology (Proceedings of the Society of Polymer Science and Technology, Vol. 29, No. 7, 2055).
page). Total styrene content was determined by infrared method. Example 1 Cyclohexane 4500 ml under nitrogen atmosphere in a washed, dry, stirred, and jacketed autoclave.
After charging 1 g of tetrahydrofuran and 1 g of tetrahydrofuran, the internal temperature was brought to 70°C. Next, a hexane solution containing 0.5 g of n-butyllithium was added, and then 130 g of styrene was added and polymerized for 60 minutes. The polymerization conversion rate of styrene was 100%.
Next, a mixture of 15 g of styrene and 115 g of butadiene was added and polymerized for 60 minutes. The polymerization conversion rate of styrene and butadiene was 100%. This operation was further repeated twice. Next, 115 g of butadiene was added and polymerization was carried out to a polymerization conversion rate of 100%. Thereafter, 130 g of styrene was further added and polymerized for 60 minutes. The conversion rate was 100%. During the polymerization, the temperature was always adjusted to 70°C. After polymerization, add 2,6-di-tert to the polymer solution.
After adding -butyl p-cresol, cyclohexane was removed by heating to obtain a block copolymer. Examples 2 to 8, Comparative Examples 1 to 10 Polymerization was carried out according to the same recipe as in Example 1 using predetermined amounts of styrene, butadiene, tetrahydrofuran, etc. shown in Table 1.
【表】 ブロツク共重合体の性質を表−２に示す。【table】 The properties of the block copolymer are shown in Table 2.
【表】
実施例１〜７は比較例１〜８に比べ、引張強度
および伸びのバランスの点で優れている。
また図に実施例１、比較例５および比較例６の
共重合体について田中等の方法によるオゾン使用
の酸化分解法によるスチレン連鎖分布曲線を示
す。
この結果は表−３のとおりであつた。[Table] Examples 1 to 7 are superior to Comparative Examples 1 to 8 in terms of balance between tensile strength and elongation. The figure also shows styrene chain distribution curves for the copolymers of Example 1, Comparative Example 5, and Comparative Example 6 obtained by the oxidative decomposition method using ozone according to Tanaka's method. The results were as shown in Table 3.
【表】
実施例８、比較例９
実施例１のブロツク共重合体12重量％とポリス
チレン（三井東圧(株)製トーポレックス−525）88
重量％との混合組成物を製造し、成形温度180℃
で厚さ0.2mmのシートについて物性を調べた。ま
た比較のため上記ポリスチレン単独の物性を調べ
た。
結果を表−４に示す。[Table] Example 8, Comparative Example 9 12% by weight of the block copolymer of Example 1 and polystyrene (Toporex-525 manufactured by Mitsui Toatsu Co., Ltd.) 88
Producing a mixed composition with wt%, molding temperature 180℃
The physical properties of a 0.2 mm thick sheet were investigated. For comparison, the physical properties of the polystyrene alone were investigated. The results are shown in Table 4.
【表】
応用例
実施例１のブロツク共重合体1000ｇをシクロヘ
キサン5000ｇに溶解し、テトラヒドロフラン13ｇ
を加えた後、ニツケルアセチルアセトン2.5ｇを
含むシクロヘキサン溶液100mlと、トリイソブチ
ルアルミニウム40ｇを含むシクロヘキサン溶液
300mlを加え、15Kg／cm2、100℃にて60分間反応を
行つた。反応終了後、塩酸水溶液で数回洗浄した
後、実施例１と同様にして溶媒を除き、重合体を
得た。重合体の引張強度は350Kg／cm2、伸びは345
％、アイゾツト衝撃強度8.2Kgcm／cm、ロツクウ
エル硬度46であつた。[Table] Application example: Dissolve 1,000 g of the block copolymer of Example 1 in 5,000 g of cyclohexane, and add 13 g of tetrahydrofuran.
After adding 100 ml of cyclohexane solution containing 2.5 g of nickel acetylacetone and cyclohexane solution containing 40 g of triisobutylaluminum.
300 ml was added and the reaction was carried out at 15 Kg/cm 2 and 100° C. for 60 minutes. After the reaction was completed, the mixture was washed several times with an aqueous hydrochloric acid solution, and then the solvent was removed in the same manner as in Example 1 to obtain a polymer. The tensile strength of the polymer is 350Kg/cm 2 and the elongation is 345
%, Izod impact strength was 8.2 Kgcm/cm, and Rockwell hardness was 46.
図は実施例１、比較例５および６の共重合体に
ついて、オゾンによる酸化分解法によるスチレン
連鎖分布曲線を示す。
The figure shows styrene chain distribution curves for the copolymers of Example 1 and Comparative Examples 5 and 6 obtained by oxidative decomposition using ozone.
Claims (1)
剤として重合して得られるビニル芳香族化合物含
量が25〜55重量％の直鎖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−Ａ （式中、Ａは重量平均分子量が3000〜80000のビ
ニル芳香族化合物重合体ブロツクであつて、両端
のＡの合計量はビニル芳香族化合物全量の50〜97
％重量であり、Ｂは重量平均分子量が44000〜
340000でありかつビニル芳香族化合物／共役ジエ
ンの重量比が３〜15／97〜85である共役ジエンと
ビニル芳香族化合物との共重合体ブロツクであつ
て、Ｂ部分はビニル芳香族化合物の量がその鎖に
沿つて漸増するテーパーブロツクを３〜10個有す
る） を有し、モノマー単位で１〜４個連なつたビニル
芳香族化合物の連鎖の量が全ビニル芳香族化合物
含量の５〜30重量％であり、かつ重量平均分子量
が50000〜500000であることを特徴とする直鎖状
ブロツク共重合体。[Scope of Claims] 1. A linear vinyl aromatic compound having a vinyl aromatic compound content of 25 to 55% by weight, obtained by polymerization in a hydrocarbon solvent using an organolithium compound as an initiator.
In the conjugated diene block copolymer, the copolymer has the general formula A-B-A (where A is a vinyl aromatic compound polymer block having a weight average molecular weight of 3,000 to 80,000, and The amount is 50 to 97 of the total amount of vinyl aromatic compounds.
% weight, and B has a weight average molecular weight of 44000~
340,000 and a vinyl aromatic compound/conjugated diene weight ratio of 3 to 15/97 to 85, wherein part B is the amount of the vinyl aromatic compound. has 3 to 10 tapered blocks increasing gradually along the chain), and the amount of chains of vinyl aromatic compounds with 1 to 4 monomer units is 5 to 30 of the total vinyl aromatic compound content. % by weight and a weight average molecular weight of 50,000 to 500,000.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3834283A JPS59166518A (en) | 1983-03-10 | 1983-03-10 | Straight-chain block copolymer |
| US06/586,442 US4603155A (en) | 1983-03-10 | 1984-03-05 | Alkenyl aromatic compound-conjugated diene block copolymer and process for the production thereof |
| NLAANVRAGE8400773,A NL185781C (en) | 1983-03-10 | 1984-03-09 | Block copolymer of an alkenyl-aromatic compound and a conjugated diene, process for its preparation and shaped articles therefrom. |
| GB08406429A GB2138009B (en) | 1983-03-10 | 1984-03-12 | Block copolymer of an alkenyl aromatic compound and a conjugated diene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3834283A JPS59166518A (en) | 1983-03-10 | 1983-03-10 | Straight-chain block copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59166518A JPS59166518A (en) | 1984-09-19 |
| JPH0340727B2 true JPH0340727B2 (en) | 1991-06-19 |
Family
ID=12522608
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3834283A Granted JPS59166518A (en) | 1983-03-10 | 1983-03-10 | Straight-chain block copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59166518A (en) |
Families Citing this family (32)
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|---|---|---|---|---|
| JPS63270718A (en) * | 1988-03-22 | 1988-11-08 | Asahi Chem Ind Co Ltd | Block copolymer |
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| JPWO2022209235A1 (en) | 2021-03-31 | 2022-10-06 | ||
| JPWO2023013772A1 (en) | 2021-08-06 | 2023-02-09 | ||
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-
1983
- 1983-03-10 JP JP3834283A patent/JPS59166518A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59166518A (en) | 1984-09-19 |
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