JPS634579B2 - - Google Patents
Info
- Publication number
- JPS634579B2 JPS634579B2 JP55177697A JP17769780A JPS634579B2 JP S634579 B2 JPS634579 B2 JP S634579B2 JP 55177697 A JP55177697 A JP 55177697A JP 17769780 A JP17769780 A JP 17769780A JP S634579 B2 JPS634579 B2 JP S634579B2
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- rubber composition
- rubber
- butadiene
- weight
- 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
- 229920001971 elastomer Polymers 0.000 claims description 40
- 239000005060 rubber Substances 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 38
- 229920000642 polymer Polymers 0.000 claims description 38
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 10
- 230000009477 glass transition Effects 0.000 claims description 7
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 claims description 7
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 150000002900 organolithium compounds Chemical class 0.000 claims description 3
- 150000002901 organomagnesium compounds Chemical class 0.000 claims description 3
- 125000002897 diene group Chemical group 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 239000003701 inert diluent Substances 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 description 19
- 150000001993 dienes Chemical class 0.000 description 16
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 229910052788 barium Inorganic materials 0.000 description 5
- 229920003051 synthetic elastomer Polymers 0.000 description 5
- 239000005061 synthetic rubber Substances 0.000 description 5
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 229920003052 natural elastomer Polymers 0.000 description 4
- 229920001194 natural rubber Polymers 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- -1 tributyllithium Chemical compound 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- GIKVREQPOYIWFC-UHFFFAOYSA-L barium(2+);2,3-di(nonyl)phenolate Chemical compound [Ba+2].CCCCCCCCCC1=CC=CC([O-])=C1CCCCCCCCC.CCCCCCCCCC1=CC=CC([O-])=C1CCCCCCCCC GIKVREQPOYIWFC-UHFFFAOYSA-L 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- AFVDZBIIBXWASR-UHFFFAOYSA-N (e)-1,3,5-hexatriene Chemical compound C=CC=CC=C AFVDZBIIBXWASR-UHFFFAOYSA-N 0.000 description 1
- JKTAIYGNOFSMCE-UHFFFAOYSA-N 2,3-di(nonyl)phenol Chemical compound CCCCCCCCCC1=CC=CC(O)=C1CCCCCCCCC JKTAIYGNOFSMCE-UHFFFAOYSA-N 0.000 description 1
- MBOHKEXXDOWLDA-UHFFFAOYSA-N 4,6-ditert-butyl-6-methylcyclohexa-1,3-dien-1-ol Chemical compound CC(C)(C)C1=CC=C(O)C(C)(C(C)(C)C)C1 MBOHKEXXDOWLDA-UHFFFAOYSA-N 0.000 description 1
- UWKKBEQZACDEBT-UHFFFAOYSA-N CCCC[Mg] Chemical compound CCCC[Mg] UWKKBEQZACDEBT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000006237 Intermediate SAF Chemical class 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- BBCDCWSBHCIZJI-UHFFFAOYSA-L barium(2+);2-dodecylbenzenesulfonate Chemical compound [Ba+2].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O BBCDCWSBHCIZJI-UHFFFAOYSA-L 0.000 description 1
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 1
- 238000009835 boiling Methods 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
- 238000013329 compounding Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 1
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- GMKLFLBFWRBGBG-UHFFFAOYSA-L strontium;2,3-di(nonyl)phenolate Chemical compound [Sr+2].CCCCCCCCCC1=CC=CC([O-])=C1CCCCCCCCC.CCCCCCCCCC1=CC=CC([O-])=C1CCCCCCCCC GMKLFLBFWRBGBG-UHFFFAOYSA-L 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Description
本発明は高い割合でトランス―１，４結合を有
する溶液重合ジエン類重合体と高いガラス転位温
度を有するジエン類重合体とからなる新規なゴム
組成物に関するものであり、各種ゴム用途、特に
タイヤ用途に適した改良されたゴム組成物を提供
することを目的とする。
高い割合でトランス―１，４結合を有する溶液
重合ジエン類重合体は比較的最近までゴム弾性を
有する重合体が知られていなかつたが、Ａ族金
属の化合物と有機リチウム化合物及び／又は有機
マグネシウム化合物を主成分とする複合触媒の発
見によつて得ることが可能になつた。得られた高
い割合でトランス―１，４結合を有する重合体は
極めて優れた特性、高いグリーン強度、引張強
度、反発弾性及び耐摩耗性を示し、種々のゴム用
途、特にタイヤ用途の原料ゴムとして期待される
ものである。
しかしながらこれら高い割合でトランス―１，
４結合を有する溶液重合ジエン類重合体は一般に
加工性、特に粘着性で劣り、又、タイヤトレツド
用途として用いるにはウエツトスキツド抵抗性が
十分でなく、重合体中へのイソプレン単位の導入
等の試み（特開昭55−27337号公報）もなされて
いるが、未だその改良は十分なものではない。
本発明は上述の高い割合でトランス―１，４結
合を有する溶液重合ジエン類重合体の優れた特徴
を維持しつつ加工性、ウエツトスキツド抵抗性等
の欠点の改良を目的とするものである。
すなわち、本発明は、(A)溶液重合で得られる、
ジエン部分のトランス―１，４結合60ないし95モ
ル％の、ブタジエン重合体、イソプレン―ブタジ
エン共重合体又はスチレンブタジエン共重合体20
〜80重量％と、
(B)−60℃ないし−10℃のガラス転位温度を有す
るブタジエン重合体、スチレン―ブタジエン共重
合体又はイソプレン重合体80〜20重量％からなる
ゴム組成物を提供するものである。
本発明の高い割合でトランス―１，４結合を有
する溶液重合ジエン類重合体(A)はそのジエン部分
のトランス―１，４結合が60ないし95モル％、好
ましくは70ないし90モル％のジエン類重合体であ
る。60％より低いトランス―１，４結合では改良
すべき高い割合でトランス―１，４結合を有する
溶液重合ジエン類重合体としての特徴、例えば高
いグリーン強度、引張強度、反発弾性、耐摩耗性
等が十分でなく、一方、95モル％を越える場合は
トランス―１，４結合の長い連鎖を生じ、これに
起因する結晶性が発現し、ゴム弾性体として好ま
しいものではない。
本発明の重合体(A)は溶液重合によつてジエン類
単量体を単独重合又は共重合するか、あるいはジ
エン類と他の共重合可能な単量体との共重合を行
なうことによつて得られるものである。
本発明の高い割合でトランス―１，４結合を有
する上述のジエン類重合体を得るのに使用する触
媒としてはＡ族金属の化合物と有機リチウム化
合物及び／又は有機マグネシウム化合物を主成分
とする複合開始剤を用いる。本発明で使用する
Ａ族金属の化合物はカルシウム、ストロンチウム
又はバリウムの化合物であり、その例としてはバ
リウムジステアレート、バリウム―ジ―tert―ブ
チルアルコラート、バリウムジアリルアルコラー
ト、ストロンチウムジアリルアルコラート、バリ
ウムジベンジルアルコラート、バリウムジノニル
フエノラート、ドデシルベンゼンスルホン酸バリ
ウム、ストロンチウムジノニルフエノラート及び
カルシウムジノフエノラートなどがあげられる。
又、複合触媒の第２の成分である有機リチウム及
び／又は有機マグネシウム化合物としては、その
例としてｎ―（sec又はtert―）ブチルリチウム、
ジブチルマグネシウム、トリブチルリチウム、マ
グネシウム、トリエチルブチルリチウム、マグネ
シウムがあげられる。複合開始剤はこれらの成分
を主成分とするものであるが更に有機アルミニウ
ム化合物、有機亜鉛化合物ないしは各種ルイス塩
基が共存するものであつても良い。
本発明の組成物を構成する第２の成分であるジ
エン類重合体Ｂは高いガラス転位温度を有するも
のであり、その温度は−60℃ないし−10℃好まし
くは−50℃ないし−20℃の重合体である。−60℃
以下の温度では本発明の目的とする加工性、ウエ
ツトスキツド抵抗性の改良が不十分である。ガラ
ス転位温度の上限は用途によつてゴムを使用する
温度が変化することにもより定められないが、一
般にその使用温度以下、すなわちタイヤ用途の場
合には−10℃以下、好ましくは−20℃以下の温度
が好ましい。ジエン類重合体としてはこの温度範
囲にあるものであれば良く各種の乳化重合又は溶
液重合ジエン類重合体があり、ブタジエン重合
体、スチレン―ブタジエン共重合体、イソプレン
―ブタジエン共重合体等が例としてあげられ好ま
しいものである。更に具体的な例としては結合ス
チレン30ないし50重量％の乳化重合スチレン―ブ
タジエン重合体、結合スチレン15ないし50重量％
の溶液重合スチレン―ブタジエン共重合体、１，
２―ビニル結合40ないし80重量％のシデイアムビ
ニルブタジエン重合体等である。
本発明のゴム組成物を構成する重合体Ａと重合
体Ｂの比率は重量比で20対80ないし80対20に限定
される。この比率は上述した本発明の効果を得る
に必須であり、この比率の範囲外では改良すべき
加工性、ウエツトスキツド抵抗性と維持すべき引
張強度、反発弾性、耐摩耗性等のバランスがくず
れ本発明の目的を達成しない。又、組成物のムー
ニー粘度は30ないし150、分子量分布は重量平均
分子量と数平均分子量の比で表示して1.2ないし
5.0であることが好ましい。あまりにも高い又は
低い分子量、あまりも狭い又は広い分子量分布を
有する原料ゴムは本発明の組成物としての加工性
ないし物性がかたよつたものとなり好ましくな
い。
本発明の原料ゴムを構成する上記２成分は他の
ゴム組成物を構成する成分とともにオープンロー
ル，インターナルミキサー等で混合されても良
く、又、あらかじめ上記２成分のみないしは原料
ゴム成分のみをこれらゴム混合機で混合するかあ
るいは溶液状で混合し、これより溶剤を除去する
方法によつても良い。好ましい一つの方法は、重
合体Ｂが溶液重合による場合にのみ適用できるも
ので、両者を重合時に一挙に混合された状態で得
ることであり、直列ないしは並列に連結された２
以上の重合域を有する重合機による異なる反応条
件下での重合により達成される。
本発明のゴム組成物は上述の特徴を生かし、単
独又は他の合成ゴムないしは天然ゴムとブレンド
して公知の種々の配合及び加硫を経てタイヤ、特
にタイヤトレツド、カーカス用途、あるいは押出
製品、自動車窓枠、工業用品等の種々の用途に使
用することができる。又、場合によつては種々の
プラスチツクとグラフト又はブレンドして耐衝撃
性等の改良の用途にも供することができる。
本発明の特に好ましい用途の一つはタイヤ特に
タイヤトレツドの原料ゴムとしての用途であり、
単独で使用されても良いが、タイヤの種類および
使用用途によつては天然ゴム又は（及び）他の合
成ゴムと混合しても使用される。
本発明のゴム組成物と混合して使用される他の
合成ゴムとしては、ガラス転位温度が−50℃以下
の乳化重合スチレン―ブタジエン共重合ゴム、乳
化重合ポリブタジエンゴム、溶液重合低シス及び
高シスポリブタジエンゴム、アルフイン触媒で重
合されたポリブタジエンゴム又はスチレン―ブタ
ジエン共重合体ゴム、ポリイソプレンゴム、ブタ
ジエン―イソプレン共重合ゴム等がある。なお、
これらの合成ゴム又は（及び）天然ゴムは１種又
は２種以上併用して使用されるが、本発明のゴム
組成物の特性を生かすためには、原料ゴム中、少
なくとも30重量％は本発明のゴム組成物であるこ
とが必要である。
本発明により得られるゴム組成物を単独か、も
しくは天然ゴム又は（及び）他の合成ゴムと混合
してタイヤ用ゴム組成物とする場合に特に重要な
ものはカーボンブラツクである。使用されるカー
ボンブラツクの種類と量は本発明のゴム組成物の
用途に合せ自由に選択でき、一般にはFEF級、
HAF級、ISAF級、GPF級ないしはSAF級と通
称されるカーボンブラツクの中から選択される。
又、その量はゴム100重量部に対し20ないしは120
重量部であることが好ましい。20重量部以下では
引張強度、耐摩耗性等が十分でなく、逆に120重
量部以上では反発弾性の著しい低下をもたらし好
ましくない。又プロセス油としては通常ゴム配合
用として用いられている石油留分のうちの高沸点
部分から成るもので、その炭水素分子の化学構造
によつてパラフイン系ナフテン系及びアロマチツ
ク系として知られるプロセス油を目的、用途に合
せ用いることができその量も自由に選択できる。
本発明のゴム組成物には使用に際して更に必要
に応じてプロセス油、カーボンブラツク以外の他
の充填剤、酸化亜鉛、ステアリン酸、酸化防止
剤、オゾン劣化防止剤、ワツクス等を加えること
ができる。又加硫剤としてはイオウ及びイオウ化
合物が各種の加硫促進剤と共に用いられる。これ
らの種類と量はゴム組成物の用途に合わせ自由に
選択することができる。
以上の諸配合剤と本発明のゴム組成物よりなる
タイヤ用ゴム組成物はタイヤ特にタイヤトレツド
配合物として従来のいかなるゴム組成物に比して
も実用物性上、加工操作上、極めてバランスのと
れた、しかも優れた性質を示すものである。
次に若干の実施例によつて本発明の効果を説明
するが、これらは本発明を限定するものではな
い。
参考例 １
高い割合でトランス―１，４結合を有する各種
ジエン類重合体Ａは次の重合処法により得た。
乾燥した窒素で満たされた容量８の反応器に
希釈剤としてｎ―ヘキサン3.6Kg及び単量体とし
てブタジエン0.9Kgを仕込み撹拌しながら70℃に
加熱した。次いで重合開始剤としてバリウムジノ
ニルフエノキシド3.4ミリモル、リチウムマグネ
シウムトリブチル5.0ミリモル、トリエチルアル
ミニウム6.7ミリモルを順次加え重合を開始させ
た。反応は90分間続け重合系の温度は重合時の発
熱により最高95℃まで昇温した。重合終了後重合
体溶液に２，４―ジ―tert―ブチルクレゾールを
重合体100ｇに対して0.5ｇになるよう混合後、ｎ
―ヘキサンを揮発させてブタジエン重合体を得
た。得られた重合体のムーニー粘度、分子量分
布、ミクロ構造等を表１に示す。
又、類似の重合処法によつて得たイソプレン―
ブタジエン共重合体、スチレン―ブタジエン共重
合体の分析値も表１に示した。
又、表２には本発明の組成物を構成するもう一
つの成分である高いガラス転位温度を有するジエ
ン類重合体で実施例に使用した種々の重合体の分
析値を示した。
実施例 １〜８
実施例の組成物１〜８は種々の重合体Ａ及び重
合体Ｂを表３に示す比でオープンロールにて混合
することによつて得た。得られた組成物のムーニ
ー粘度及び分子量分布も併せて表３中に示した。
実施例 ９〜11
実施例の組成物９〜11は種々の重合体Ａ及び重
合体Ｂの重合終了後、溶液状態にて混合し、これ
より溶剤を除去させることによつて得た。重合体
Ａと重合体Ｂの混合比、得られた組成物のムーニ
ー粘度及び分子量分布を表３に示す。
The present invention relates to a novel rubber composition comprising a solution-polymerized diene polymer having a high proportion of trans-1,4 bonds and a diene polymer having a high glass transition temperature. The purpose is to provide an improved rubber composition suitable for various uses. Solution-polymerized diene polymers having a high proportion of trans-1,4 bonds have not been known to have rubber elasticity until relatively recently; This became possible with the discovery of composite catalysts whose main components are compounds. The obtained polymer having a high proportion of trans-1,4 bonds exhibits extremely excellent properties, high green strength, tensile strength, impact resilience, and abrasion resistance, and is useful as a raw material rubber for various rubber applications, especially for tires. This is to be expected. However, in these high proportions, trans-1,
Solution-polymerized diene polymers having 4 bonds are generally inferior in processability, particularly in adhesiveness, and do not have sufficient wet skid resistance for use in tire tread applications. Japanese Patent Application Laid-open No. 55-27337) has also been made, but the improvement is still not sufficient. The object of the present invention is to maintain the excellent characteristics of the solution-polymerized diene polymer having a high proportion of trans-1,4 bonds as described above, while improving the drawbacks such as processability and wet skid resistance. That is, the present invention provides (A) obtained by solution polymerization,
Butadiene polymer, isoprene-butadiene copolymer or styrene-butadiene copolymer containing 60 to 95 mol% of trans-1,4 bonds in the diene moiety20
~80% by weight, and (B) 80 to 20% by weight of a butadiene polymer, styrene-butadiene copolymer, or isoprene polymer having a glass transition temperature of -60°C to -10°C. It is. The solution-polymerized diene polymer (A) having a high proportion of trans-1,4 bonds according to the present invention has a diene moiety containing 60 to 95 mol%, preferably 70 to 90 mol% of trans-1,4 bonds. It is a similar polymer. If the trans-1,4 bond is lower than 60%, the characteristics of a solution-polymerized diene polymer having a high proportion of trans-1,4 bonds should be improved, such as high green strength, tensile strength, impact resilience, abrasion resistance, etc. On the other hand, if the amount exceeds 95 mol %, long chains of trans-1,4 bonds occur, resulting in crystallinity, which is not preferable as a rubber elastic body. The polymer (A) of the present invention can be produced by homopolymerizing or copolymerizing diene monomers by solution polymerization, or by copolymerizing dienes with other copolymerizable monomers. It is something that can be obtained. The catalyst used to obtain the above-mentioned diene polymer having a high proportion of trans-1,4 bonds according to the present invention is a composite mainly composed of a group A metal compound and an organolithium compound and/or an organomagnesium compound. Use an initiator. The compound of Group A metal used in the present invention is a compound of calcium, strontium or barium, examples of which include barium distearate, barium di-tert-butyl alcoholate, barium diallyl alcoholate, strontium diallyl alcoholate, barium dibenzyl Examples include alcoholate, barium dinonyl phenolate, barium dodecylbenzenesulfonate, strontium dinonyl phenolate, and calcium dinophenolate.
Examples of the organolithium and/or organomagnesium compounds that are the second component of the composite catalyst include n-(sec or tert-)butyllithium,
Examples include dibutylmagnesium, tributyllithium, magnesium, triethylbutyllithium, and magnesium. The composite initiator mainly contains these components, but may also contain an organoaluminum compound, an organozinc compound, or various Lewis bases. Diene polymer B, which is the second component constituting the composition of the present invention, has a high glass transition temperature, and its temperature is -60°C to -10°C, preferably -50°C to -20°C. It is a polymer. −60℃
At temperatures below, the improvements in workability and wet skid resistance, which are the objectives of the present invention, are insufficient. The upper limit of the glass transition temperature is not set because the temperature at which the rubber is used changes depending on the application, but it is generally below the usage temperature, i.e. -10°C or less in the case of tire applications, preferably -20°C. The following temperatures are preferred. Diene polymers that fall within this temperature range include various emulsion-polymerized or solution-polymerized diene polymers, such as butadiene polymers, styrene-butadiene copolymers, isoprene-butadiene copolymers, etc. This is a preferable example. More specific examples include emulsion polymerized styrene-butadiene polymers containing 30 to 50% by weight of bound styrene; 15 to 50% by weight of bound styrene;
solution polymerized styrene-butadiene copolymer, 1,
Such as cidium vinyl butadiene polymer containing 40 to 80% by weight of 2-vinyl bonds. The ratio of polymer A and polymer B constituting the rubber composition of the present invention is limited to 20:80 to 80:20 by weight. This ratio is essential to obtain the above-mentioned effects of the present invention; outside this ratio, the balance between workability and wet skid resistance to be improved and tensile strength, impact resilience, abrasion resistance, etc. to be maintained will be lost. Does not achieve the purpose of the invention. In addition, the Mooney viscosity of the composition is 30 to 150, and the molecular weight distribution is 1.2 to 1.2, expressed as the ratio of weight average molecular weight to number average molecular weight.
Preferably it is 5.0. A raw material rubber having an excessively high or low molecular weight or an excessively narrow or wide molecular weight distribution is not preferable because the processability or physical properties of the composition of the present invention will be uneven. The above two components constituting the raw rubber of the present invention may be mixed together with other components constituting the rubber composition using an open roll, an internal mixer, etc. Alternatively, only the above two components or only the raw rubber component may be mixed in advance. They may be mixed in a rubber mixer or mixed in the form of a solution, and the solvent may be removed from the mixture. One preferred method is applicable only when polymer B is produced by solution polymerization, and is to obtain both polymers in a mixed state at once during polymerization.
This is achieved by polymerization under different reaction conditions using a polymerizer having the above polymerization zones. Taking advantage of the above-mentioned characteristics, the rubber composition of the present invention can be used alone or blended with other synthetic rubber or natural rubber and subjected to various known formulations and vulcanization to be used in tires, particularly tire treads, carcass applications, extruded products, and automobile windows. It can be used for various purposes such as frames and industrial supplies. In some cases, it can also be grafted or blended with various plastics to improve impact resistance and the like. One of the particularly preferred uses of the present invention is as a raw material rubber for tires, especially tire treads.
It may be used alone, but depending on the type of tire and intended use, it may also be used in combination with natural rubber or/and other synthetic rubber. Other synthetic rubbers that can be used in combination with the rubber composition of the present invention include emulsion polymerized styrene-butadiene copolymer rubber with a glass transition temperature of -50°C or lower, emulsion polymerized polybutadiene rubber, solution polymerized low cis and high cis Examples include polybutadiene rubber, polybutadiene rubber polymerized with an Alfin catalyst, styrene-butadiene copolymer rubber, polyisoprene rubber, butadiene-isoprene copolymer rubber, and the like. In addition,
These synthetic rubbers or (and) natural rubbers may be used alone or in combination of two or more, but in order to take advantage of the characteristics of the rubber composition of the present invention, at least 30% by weight of the raw rubber should be the rubber composition of the present invention. It is necessary that the rubber composition is Carbon black is particularly important when the rubber composition obtained according to the present invention is used alone or mixed with natural rubber and/or other synthetic rubber to form a rubber composition for tires. The type and amount of carbon black used can be freely selected depending on the use of the rubber composition of the present invention, and generally FEF grade,
It is selected from carbon black commonly known as HAF class, ISAF class, GPF class or SAF class.
Also, the amount is 20 to 120 per 100 parts by weight of rubber.
Parts by weight are preferred. If it is less than 20 parts by weight, the tensile strength, abrasion resistance, etc. will not be sufficient, and if it is more than 120 parts by weight, it will result in a significant decrease in impact resilience, which is undesirable. Processing oils are usually made of high-boiling parts of petroleum fractions used for rubber compounding, and are known as paraffinic, naphthenic and aromatic processing oils, depending on the chemical structure of their hydrocarbon molecules. can be used depending on the purpose and application, and the amount can be freely selected. Processing oil, fillers other than carbon black, zinc oxide, stearic acid, antioxidants, antiozonants, wax, etc. can be added to the rubber composition of the present invention as required. As the vulcanizing agent, sulfur and sulfur compounds are used together with various vulcanization accelerators. The types and amounts of these can be freely selected depending on the use of the rubber composition. The rubber composition for tires comprising the above-mentioned compounding agents and the rubber composition of the present invention has extremely well-balanced properties for tires, especially tire tread compounds, compared to any conventional rubber compositions in terms of practical physical properties and processing operations. Moreover, it shows excellent properties. Next, the effects of the present invention will be explained using some examples, but these are not intended to limit the present invention. Reference Example 1 Various diene polymers A having a high proportion of trans-1,4 bonds were obtained by the following polymerization process. A reactor with a capacity of 8 filled with dry nitrogen was charged with 3.6 kg of n-hexane as a diluent and 0.9 kg of butadiene as a monomer and heated to 70° C. with stirring. Next, 3.4 mmol of barium dinonyl phenoxide, 5.0 mmol of lithium magnesium tributyl, and 6.7 mmol of triethylaluminum were sequentially added as polymerization initiators to initiate polymerization. The reaction continued for 90 minutes, and the temperature of the polymerization system rose to a maximum of 95°C due to heat generated during polymerization. After the polymerization was completed, 2,4-di-tert-butylcresol was mixed into the polymer solution in an amount of 0.5g per 100g of polymer, and then
- Butadiene polymer was obtained by volatilizing hexane. Table 1 shows the Mooney viscosity, molecular weight distribution, microstructure, etc. of the obtained polymer. Also, isoprene obtained by a similar polymerization process
Table 1 also shows the analytical values for the butadiene copolymer and styrene-butadiene copolymer. Further, Table 2 shows the analytical values of various polymers used in the examples, which are diene polymers having a high glass transition temperature, which are another component constituting the composition of the present invention. Examples 1-8 Compositions 1-8 of Examples were obtained by mixing various polymers A and B in the ratios shown in Table 3 on an open roll. The Mooney viscosity and molecular weight distribution of the obtained composition are also shown in Table 3. Examples 9 to 11 Compositions 9 to 11 of Examples were obtained by mixing various polymers A and B in a solution state after completion of polymerization, and removing the solvent from the mixture. Table 3 shows the mixing ratio of Polymer A and Polymer B, and the Mooney viscosity and molecular weight distribution of the resulting composition.
【表】【table】
【表】【table】
【表】【table】
【表】
実施例 12
実施例12の組成物は次の重合処理法により重合
段階で一挙に作成した。
参考例で用いた希剤としてｎ―ヘキサン1.8Kg
及び単量体としてブタジエン0.34Kg、スチレン
0.113Kgを仕込み撹拌しながら50℃に加熱した。
次いで１，２―ジメトキシエタン10ミリモル，ｎ
―ブチルリチウム5.0ミリモルを加えて重合反応
を開始させた。反応は60分間続けた。重合系の温
度は重合時の発熱によつて、65℃となつた。この
時点の重合系の転化率及び重合体の結合スチレン
量、ブタジエン部のミクロ構造を表４に示す。[Table] Example 12 The composition of Example 12 was prepared all at once in the polymerization step using the following polymerization treatment method. 1.8Kg of n-hexane as a diluent used in the reference example
and 0.34Kg of butadiene and styrene as monomers
0.113Kg was charged and heated to 50°C while stirring.
Then 10 mmol of 1,2-dimethoxyethane, n
- 5.0 mmol of butyllithium was added to initiate the polymerization reaction. The reaction lasted for 60 minutes. The temperature of the polymerization system was 65°C due to heat generation during polymerization. Table 4 shows the conversion rate of the polymerization system, the amount of bound styrene in the polymer, and the microstructure of the butadiene moiety at this point.
【表】
次いで、反応器に解媒成分として、バリウム―
ジ―ノニルフエノキシド3.4ミリモル，ジ―ｎ―
ブチルマグネシウム5.0ミリモル，トリエチルア
ルミニウム6.7ミリモルを追加し、さらにｎ―ヘ
キサン1.5Kg，ブタジエン0.3Kgを仕込み、120分
間重合を継続した。重合系の温度は重合時の発熱
により最高72℃まで昇温した。最終的に得られた
組成物の結合スチレン量、ムーニー粘度ブタジエ
ン部のミクロ構造を表５に示す。[Table] Next, barium was added to the reactor as a decomposition component.
Di-nonyl phenoxide 3.4 mmol, di-n-
5.0 mmol of butylmagnesium and 6.7 mmol of triethylaluminum were added, and 1.5 kg of n-hexane and 0.3 kg of butadiene were added, and the polymerization was continued for 120 minutes. The temperature of the polymerization system rose to a maximum of 72°C due to heat generation during polymerization. Table 5 shows the amount of bound styrene, Mooney viscosity, and microstructure of the butadiene portion of the finally obtained composition.
【表】
得られた実施例１〜12のゴム組成物と比較例と
して重合体Ａ、重合体Ｂ各々単独及びエマルジヨ
ンSBR1502とを表６に示す配合にて、加工性及
び加硫物物性を測定した。結果を表７に表す。
表６から明らかなように本発明のゴム組成物は
いずれも比較例の各種重合体Ａに比べ加工性とウ
エツトスキツド抵抗性で優れ、しかも引張強度、
反発弾性、耐摩耗性等の加硫物性は維持されてお
り、両者のバランスのとれた優れたゴム組成物で
あることを示す。[Table] Processability and vulcanizate physical properties were measured using the obtained rubber compositions of Examples 1 to 12 and Comparative Examples: Polymer A, Polymer B each alone, and emulsion SBR1502 in the formulations shown in Table 6. did. The results are shown in Table 7. As is clear from Table 6, all of the rubber compositions of the present invention are superior in processability and wet skid resistance compared to various polymers A of comparative examples, and are superior in tensile strength and
The vulcanized physical properties such as impact resilience and abrasion resistance were maintained, indicating that the rubber composition had an excellent balance between the two.
【表】【table】
【表】【table】
【表】【table】
Claims (1)
ンス―１，４結合60ないし95モル％の、ブタジ
エン重合体、イソプレン―ブタジエン共重合体
又はスチレンブタジエン共重合体20〜80重量％
と、 (B) −60℃ないし−10℃のガラス転位温度を有す
るブタジエン重合体、スチレン―ブタジエン共
重合体又はイソプレン重合体80〜20重量％から
なるゴム組成物。 ２ (A)成分がトランス―１，４結合70ないし90モ
ル％の重合体である特許請求の範囲第１項記載の
ゴム組成物。 ３ (A)成分が不活性希釈剤中においてＡ族金属
の化合物と有機リチウム化合物及び／又は有機マ
グネシウム化合物を主成分とする複合開始剤の存
在下、対応する単量体を重合又は共重合すること
によつて得られる重合体である特許請求の範囲第
１項又は第２項記載のゴム組成物。 ４ ムーニー粘度が30〜150、重量平均分子量と
数平均分子量の比で表わされる分子量分布が1.2
〜5.0である特許請求の範囲第１項、第２項又は
第３項記載のゴム組成物。 ５ (A)成分と(B)成分に加え、さらにカーボンブラ
ツク及び加硫剤を含む特許請求の範囲第１項記載
のゴム組成物。[Scope of Claims] 1 (A) Butadiene polymer, isoprene-butadiene copolymer, or styrene-butadiene copolymer containing 60 to 95 mol% of trans-1,4 bonds in the diene moiety obtained by solution polymerization. 80% by weight
and (B) a rubber composition comprising 80 to 20% by weight of a butadiene polymer, styrene-butadiene copolymer, or isoprene polymer having a glass transition temperature of -60°C to -10°C. 2. The rubber composition according to claim 1, wherein component (A) is a polymer containing 70 to 90 mol% of trans-1,4 bonds. 3 Component (A) polymerizes or copolymerizes the corresponding monomer in an inert diluent in the presence of a composite initiator whose main components are a group A metal compound and an organolithium compound and/or an organomagnesium compound. A rubber composition according to claim 1 or 2, which is a polymer obtained by: 4 Mooney viscosity is 30 to 150, and molecular weight distribution expressed as the ratio of weight average molecular weight to number average molecular weight is 1.2.
5.0~5.0. 5. The rubber composition according to claim 1, which further contains carbon black and a vulcanizing agent in addition to components (A) and (B).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17769780A JPS57100146A (en) | 1980-12-16 | 1980-12-16 | Novel rubber composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17769780A JPS57100146A (en) | 1980-12-16 | 1980-12-16 | Novel rubber composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57100146A JPS57100146A (en) | 1982-06-22 |
| JPS634579B2 true JPS634579B2 (en) | 1988-01-29 |
Family
ID=16035518
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17769780A Granted JPS57100146A (en) | 1980-12-16 | 1980-12-16 | Novel rubber composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57100146A (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5945341A (en) * | 1982-09-09 | 1984-03-14 | Yokohama Rubber Co Ltd:The | Rubber composition for tire tread |
| JPS5945342A (en) * | 1982-09-09 | 1984-03-14 | Yokohama Rubber Co Ltd:The | Rubber composition for tire tread |
| JPH0618931B2 (en) * | 1984-04-23 | 1994-03-16 | 旭化成工業株式会社 | Rubber composition |
| JPH0621186B2 (en) * | 1984-06-08 | 1994-03-23 | 旭化成工業株式会社 | Improved rubber composition for tires |
| JPH0739510B2 (en) * | 1984-10-05 | 1995-05-01 | 株式会社ブリヂストン | Tire tread rubber composition |
| JPH0621192B2 (en) * | 1984-11-17 | 1994-03-23 | 旭化成工業株式会社 | Vulcanized rubber composition for tire tread |
| US4616065A (en) * | 1985-04-15 | 1986-10-07 | Gencorp Inc. | High trans butadiene based elastomeric block copolymers and blends |
| JPH0699598B2 (en) * | 1986-04-10 | 1994-12-07 | 住友化学工業株式会社 | Rubber composition for tire tread |
| JPS6354455A (en) * | 1986-08-23 | 1988-03-08 | Kurashiki Kako Kk | Temperature-sensitive rubber composition |
| JPH0627219B2 (en) * | 1986-09-08 | 1994-04-13 | 日本合成ゴム株式会社 | Polybutadiene rubber composition |
| JPS63291932A (en) * | 1987-05-25 | 1988-11-29 | Yokohama Rubber Co Ltd:The | Rubber composition for tire |
| JPH0643520B2 (en) * | 1987-10-09 | 1994-06-08 | 日本合成ゴム株式会社 | Rubber composition for tires |
| JPH0784540B2 (en) * | 1987-11-21 | 1995-09-13 | 日本合成ゴム株式会社 | Rubber composition for tires |
| JPH0653830B2 (en) * | 1988-06-10 | 1994-07-20 | 株式会社ブリヂストン | Pneumatic tire |
| JPH02308834A (en) * | 1989-05-23 | 1990-12-21 | Bridgestone Corp | Pneumatic tire |
| JP2811484B2 (en) * | 1989-12-20 | 1998-10-15 | 日本ゼオン株式会社 | Rubber composition |
| US5844044A (en) * | 1997-07-18 | 1998-12-01 | The Goodyear Tire & Rubber Company | Trans 1,4-butadiene/isoprene copolymers and tire with tread thereof |
| KR100445829B1 (en) * | 2001-11-26 | 2004-08-30 | 한국타이어 주식회사 | Tire tread rubber composition |
| US20050061418A1 (en) * | 2003-08-25 | 2005-03-24 | Bates Kenneth Allen | Pneumatic tire having a component containing high trans isoprene-butadiene rubber |
| US20150096654A1 (en) * | 2013-10-08 | 2015-04-09 | The Goodyear Tire & Rubber Company | Rubbery blend containing trans isoprene-butadiene copolymer |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS529090A (en) * | 1975-07-07 | 1977-01-24 | Gen Tire & Rubber Co | Preparation of liquid polymer |
| GB1519697A (en) * | 1975-04-14 | 1978-08-02 | Phillips Petroleum Co | Blended elastomer compositions |
| JPS5450545A (en) * | 1977-09-09 | 1979-04-20 | Dunlop Co Ltd | Elastomer composition vulcanizable composition and tire |
| JPS5512133A (en) * | 1978-07-11 | 1980-01-28 | Nippon Zeon Co Ltd | Rubber composition for tire tread |
| JPS5527337A (en) * | 1978-08-18 | 1980-02-27 | Asahi Chem Ind Co Ltd | Isoprene-butadiene copolymer rubber having improved processability |
-
1980
- 1980-12-16 JP JP17769780A patent/JPS57100146A/en active Granted
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1519697A (en) * | 1975-04-14 | 1978-08-02 | Phillips Petroleum Co | Blended elastomer compositions |
| JPS529090A (en) * | 1975-07-07 | 1977-01-24 | Gen Tire & Rubber Co | Preparation of liquid polymer |
| JPS5488986A (en) * | 1975-07-07 | 1979-07-14 | Gen Tire & Rubber Co | Solution polymer |
| JPS5450545A (en) * | 1977-09-09 | 1979-04-20 | Dunlop Co Ltd | Elastomer composition vulcanizable composition and tire |
| JPS5512133A (en) * | 1978-07-11 | 1980-01-28 | Nippon Zeon Co Ltd | Rubber composition for tire tread |
| JPS5527337A (en) * | 1978-08-18 | 1980-02-27 | Asahi Chem Ind Co Ltd | Isoprene-butadiene copolymer rubber having improved processability |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57100146A (en) | 1982-06-22 |
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