JPH01129045A - Butadiene rubber composition - Google Patents
Butadiene rubber compositionInfo
- Publication number
- JPH01129045A JPH01129045A JP28655487A JP28655487A JPH01129045A JP H01129045 A JPH01129045 A JP H01129045A JP 28655487 A JP28655487 A JP 28655487A JP 28655487 A JP28655487 A JP 28655487A JP H01129045 A JPH01129045 A JP H01129045A
- Authority
- JP
- Japan
- Prior art keywords
- styrene
- rubber
- weight
- butadiene
- butadiene 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 14
- 229920002857 polybutadiene Polymers 0.000 title claims description 7
- 239000005062 Polybutadiene Substances 0.000 title description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229920001971 elastomer Polymers 0.000 claims abstract description 29
- 239000005060 rubber Substances 0.000 claims abstract description 29
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 29
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims abstract description 12
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 10
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 6
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 6
- 229920001194 natural rubber Polymers 0.000 claims abstract description 6
- 229920001195 polyisoprene Polymers 0.000 claims abstract description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 4
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 4
- 229920001577 copolymer Polymers 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims 1
- 238000005299 abrasion Methods 0.000 abstract description 15
- 150000002900 organolithium compounds Chemical class 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 19
- 229920000642 polymer Polymers 0.000 description 18
- 238000000034 method Methods 0.000 description 12
- 230000000704 physical effect Effects 0.000 description 11
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 9
- -1 metal halide compound Chemical class 0.000 description 8
- 239000002174 Styrene-butadiene Substances 0.000 description 7
- HSJXWMZKBLUOLQ-UHFFFAOYSA-M potassium;2-dodecylbenzenesulfonate Chemical compound [K+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HSJXWMZKBLUOLQ-UHFFFAOYSA-M 0.000 description 5
- 239000000446 fuel Substances 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 125000001979 organolithium group Chemical group 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- MAOBFOXLCJIFLV-UHFFFAOYSA-N (2-aminophenyl)-phenylmethanone Chemical class NC1=CC=CC=C1C(=O)C1=CC=CC=C1 MAOBFOXLCJIFLV-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- QWFRFVPEFDDMQD-UHFFFAOYSA-N [Li]CCCCCCCCCC[Li] Chemical compound [Li]CCCCCCCCCC[Li] QWFRFVPEFDDMQD-UHFFFAOYSA-N 0.000 description 1
- ICKXMDGNIZPYRS-UHFFFAOYSA-N [Li]CCCCCC[Li] Chemical compound [Li]CCCCCC[Li] ICKXMDGNIZPYRS-UHFFFAOYSA-N 0.000 description 1
- QQDSVXYDUMVTSQ-UHFFFAOYSA-N [Li]CCCCC[Li] Chemical compound [Li]CCCCC[Li] QQDSVXYDUMVTSQ-UHFFFAOYSA-N 0.000 description 1
- BZEZSORUWZUMNU-UHFFFAOYSA-N [Li]CCCC[Li] Chemical compound [Li]CCCC[Li] BZEZSORUWZUMNU-UHFFFAOYSA-N 0.000 description 1
- MXFRWBNCSXHXRE-UHFFFAOYSA-N [Li]\C=C\C Chemical compound [Li]\C=C\C MXFRWBNCSXHXRE-UHFFFAOYSA-N 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000001599 direct drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- VCPPTNDHEILJHD-UHFFFAOYSA-N lithium;prop-1-ene Chemical compound [Li+].[CH2-]C=C VCPPTNDHEILJHD-UHFFFAOYSA-N 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- SVMNBAVEQLDZNO-UHFFFAOYSA-M potassium;2-hexadecylbenzenesulfonate Chemical compound [K+].CCCCCCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O SVMNBAVEQLDZNO-UHFFFAOYSA-M 0.000 description 1
- LNIAEVLCVIKUGU-UHFFFAOYSA-M potassium;octadecane-1-sulfonate Chemical compound [K+].CCCCCCCCCCCCCCCCCCS([O-])(=O)=O LNIAEVLCVIKUGU-UHFFFAOYSA-M 0.000 description 1
- WIBVOBURKHLIQM-UHFFFAOYSA-N potassium;tetradecyl benzenesulfonate Chemical compound [K].CCCCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 WIBVOBURKHLIQM-UHFFFAOYSA-N 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 238000011191 terminal modification Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- PGOLTJPQCISRTO-UHFFFAOYSA-N vinyllithium Chemical compound [Li]C=C PGOLTJPQCISRTO-UHFFFAOYSA-N 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
ａ、産業上の利用分野
本発明は低燃費性を維持し、耐摩耗性、引裂き強度に優
れた特定のスチレン結合様式を持つスチレン−ブタジエ
ン共重合ゴムよりなるジエン系ゴム組成物に関する。Detailed description of the invention: a. Industrial application field The present invention provides a diene-based rubber made of styrene-butadiene copolymer rubber having a specific styrene bonding pattern that maintains low fuel consumption and has excellent abrasion resistance and tear strength. The present invention relates to a rubber composition.
ｂ、従来の技術
従来から乳化重合法で得られるスチレン−ブタジエン共
重合体ゴム（Ｅ−５ＢＲ）は、湿潤路面における耐ウエ
ツトスキツド性に優れかつ耐摩耗性も良好なため、タイ
ヤのトレッド用ゴムとして広く使用されている。しかし
ながら、このＥ−９ＢＲはエネルギーロスが大きく発熱
し易いため、大型タイヤあるいは低燃費性を志向したタ
イヤ用のゴムとしては不適当なものであった。b. Conventional technology Styrene-butadiene copolymer rubber (E-5BR) obtained by emulsion polymerization has been used as tire tread rubber because it has excellent wet skid resistance on wet road surfaces and good abrasion resistance. Widely used. However, this E-9BR was unsuitable as a rubber for large tires or tires intended for low fuel consumption because of its large energy loss and tendency to generate heat.
近年これらの欠点を改良すべく、溶液重合法にてスチレ
ン−ブタジエン共重合体ゴムが開発されてきている。In recent years, in order to improve these drawbacks, styrene-butadiene copolymer rubber has been developed using a solution polymerization method.
溶液重合法にて得られたスチレン−ブタジエン共重合体
ゴム（Ｓ−ＳＢＲ）は、Ｅ−５ＢＨに比べ、乳化剤など
の非ゴム分を含まず、また低分子量成分も一定程度少な
くすることができるため、燃費性は改良されるが、耐摩
耗性、引裂き強度は、Ｅ−ＳＢＲより劣り、タイヤ用と
して使用するには限界があった。このため、近年、カッ
プリング反応を含む末端変性に代表される共重合体を変
性することによって、ＳＢＨの諸物性を改良することが
提案されている。Styrene-butadiene copolymer rubber (S-SBR) obtained by solution polymerization method does not contain non-rubber components such as emulsifiers and can also reduce low molecular weight components to a certain extent compared to E-5BH. Therefore, although the fuel efficiency is improved, the abrasion resistance and tear strength are inferior to E-SBR, and there is a limit to its use as a tire. Therefore, in recent years, it has been proposed to improve the physical properties of SBH by modifying the copolymer, typified by terminal modification involving a coupling reaction.
例えば、特開昭５７−５５９１２号には、特定のハロゲ
ン化金属化合物による変性が、また特開昭５９−１１７
５１４号にはアミノベンゾフェノンタイプの化合物で共
重合体の末端を変性する方法が、さらち特開昭６１−２
６８７０２号には環状尿素化合物で変性する方法が提案
されている。しかしながらこれらの方法によって得られ
る変性ＳＢＲは、いずれも反撥弾性は良好であるがＥ−
５ＢＲ並の耐摩耗性、引裂き強度が得られず、また加工
性も際立ったものではないことがわかった。For example, Japanese Patent Application Laid-Open No. 57-55912 describes modification with a specific metal halide compound, and Japanese Patent Application Laid-Open No. 59-117
No. 514 describes a method of modifying the ends of a copolymer with an aminobenzophenone type compound, as disclosed in Sarachi JP-A-61-2.
No. 68702 proposes a method of modifying with a cyclic urea compound. However, although the modified SBR obtained by these methods has good rebound properties, it has poor E-
It was found that the wear resistance and tear strength comparable to that of 5BR could not be obtained, and the workability was also not outstanding.
特開昭６１−２６８７１０においては、有機リチウム化
合物重合開始剤を用いて得られるスチレン−ブタジエン
共重合体の加工性、物性を改良するため、分子量分布を
広くしさらに末端を変性することが試みられている。し
かしながらこの方法で得られた共重合体も、耐摩耗性、
引裂き強度が劣りタイヤ用途として使用するには限界が
あった。In JP-A-61-268710, an attempt was made to widen the molecular weight distribution and further modify the terminals in order to improve the processability and physical properties of a styrene-butadiene copolymer obtained using an organolithium compound polymerization initiator. ing. However, the copolymers obtained by this method also have wear resistance,
Due to its poor tear strength, there was a limit to its use in tires.
溶液重合法で得られ４ ＳＢＨのかかる問題点を解決°
するため、有機リチウム化合物重合開始剤を用いて得ら
れるスチレン−ブタジエン共重合体にて、結合スチレン
の組成分布に注目した検討が行なわれている。特開昭５
５−４０７１２号ではＳＢＨの分子量分布に沿って結合
スチレンの組成分布を有したポリマーにて加工性、物性
のバランスを改良することが提案されている。しかし耐
摩耗性、引裂強度の点で満足するレベルにない。Solved the problems of 4 SBH obtained by solution polymerization.
Therefore, studies have been conducted focusing on the compositional distribution of bound styrene in styrene-butadiene copolymers obtained using organolithium compound polymerization initiators. Japanese Patent Application Publication No. 5
No. 5-40712 proposes improving the balance between processability and physical properties using a polymer having a composition distribution of bound styrene along the molecular weight distribution of SBH. However, it is not at a satisfactory level in terms of wear resistance and tear strength.
特開昭５７−１０２９１２号、同５７−１０９８１７号
、同５７−２００４３９号では異なったブタジェン部の
ミクロ構造、および異なった結合スチレン含量を有する
二つのブロック（または二つ以上）よりなるブロックタ
イプのスチレン−ブタジエン共重合体ゴムにて物性、加
工性が改良されることが提案されている。ｉかに耐摩耗
性はよくなっているが、引裂き強度が劣りタイヤ用材料
としては今−歩不満足である。JP-A-57-102912, JP-A 57-109817 and JP-A 57-200439 disclose a block type consisting of two blocks (or two or more) with different butadiene moiety microstructures and different bound styrene contents. It has been proposed that styrene-butadiene copolymer rubber has improved physical properties and processability. Although its abrasion resistance has improved, its tear strength is poor and it is currently unsatisfactory as a tire material.
Ｃ８発明が解決しようとする問題点
本発明者らはかかる状況に鑑み、加工性、物性、とくに
Ｓ−５ＢＲで劣っている耐摩耗性、引裂強度の優れたス
チレン−ブタジエン共重合体を得るべく鋭意研究した結
果、本発明に到った。Problems to be Solved by the C8 Invention In view of this situation, the present inventors aimed to obtain a styrene-butadiene copolymer with excellent processability and physical properties, especially abrasion resistance and tear strength, which are inferior to S-5BR. As a result of intensive research, we have arrived at the present invention.
ｄ０問題点を解決するための手段
すなわち、本発明の要旨は、リチウム系開始剤によりス
チレンとブタジェンを共重合して得られｉ）結合スチレ
ンが５〜５０重量％、
ｉｉ）ブタジェン部のビニル含量が２５％以下、ｉｉｉ
）スチレン単位が１個の単連鎖が全結合スチレンの４
０重量％未満であり、かつスチレン単位が８個以上連な
ったスチレン長連鎖が全結合スチレンの１０重量％以下
、かつ
ｉｖ）ムーニー粘度（ＭＬ１＋ｎ、＋’ｏ。℃）が２０
〜２００であるスチレン−ブタジエン共重合体（Ａ）を
全ゴム中に２０〜９０重量％含み、他のジエン系ゴム（
Ｂ）として天然ゴム、ポリイソプレンゴム、スチレン−
ブタジエン共重合ゴム（ただしスチレン−ブタジエン共
重合体（１）を除＜）、ポリブタジェンゴムの中から選
ばれた一種以上を８０〜１０重量％含むジエン系ゴム組
成物にある。A means for solving the d0 problem, that is, the gist of the present invention is to copolymerize styrene and butadiene using a lithium-based initiator to obtain i) a bound styrene content of 5 to 50% by weight, and ii) a vinyl content in the butadiene moiety. is 25% or less, iii
) Single chain with one styrene unit is fully bonded styrene 4
less than 0% by weight, and styrene long chains consisting of 8 or more styrene units are 10% by weight or less of the total bonded styrene, and iv) Mooney viscosity (ML1+n, +'o.℃) is 20
The total rubber contains 20 to 90% by weight of the styrene-butadiene copolymer (A) having a
B) Natural rubber, polyisoprene rubber, styrene
A diene rubber composition containing 80 to 10% by weight of one or more selected from butadiene copolymer rubber (excluding styrene-butadiene copolymer (1)) and polybutadiene rubber.
本発明の共重合体（Ａ）は、リチウム系重合開始剤を用
いてスチレンとブタジェンを共重合して得られるが、よ
り好ましい態様としては、有機リチウム化合物および特
定の有機金属カリウムからなる共触媒を使用するもので
ある。この共触媒を使用することによって、本発明方法
は最適の性質を有する共重合体を製造するための重合反
応の制御が可能となる。The copolymer (A) of the present invention is obtained by copolymerizing styrene and butadiene using a lithium-based polymerization initiator, but in a more preferred embodiment, a cocatalyst consisting of an organolithium compound and a specific organometallic potassium is used. By using this cocatalyst, the process of the invention allows control of the polymerization reaction to produce copolymers with optimal properties.
本発明のスチレン−ブタジエン共重合体（Ａ）中の結合
スチレン含有量は、５〜５０重量％好ましくは１０〜４
５重量％である。結合スチレンが５重量％未満では破壊
強力引裂強力が劣り目的とするゴム組成物を得ることが
できない、結合スチレンが５０重量％を越えると耐摩耗
性、反撥弾性が劣り好ましくない。The bound styrene content in the styrene-butadiene copolymer (A) of the present invention is 5 to 50% by weight, preferably 10 to 4% by weight.
It is 5% by weight. If the bound styrene content is less than 5% by weight, the breaking strength and tear strength will be poor and the desired rubber composition cannot be obtained. If the bound styrene content exceeds 50% by weight, the abrasion resistance and rebound properties will be poor, which is not preferred.
ブタジェン部のビニル含量は２５％以下好ましくは１５
〜２３％の範囲である。２５％を越えると耐摩耗性、引
裂強度が劣って来るため好ましくない。The vinyl content of the butadiene moiety is 25% or less, preferably 15%.
It is in the range of ~23%. If it exceeds 25%, the abrasion resistance and tear strength will deteriorate, which is not preferable.
本発明の優れた耐摩耗性、引裂強度を有するゴム組成物
を得るためには、スチレン−ブタジエン共重合体（Ａ）
中の結合スチレンの連鎖を一定の範囲にすることが重要
である。上記ＳＢＲ（Ａ）中のスチレンの連鎖分布は試
料をオゾンによって分解した後、ゲルパーミェーション
クロマトグラムによって分析される（国中ら、Ｒｕｂｂ
ｅｒ Ｃｈｅｍｉｓｔｒｙ ａｎｄ Ｔｅｃｈｎｏｌｏ
ｇｙＶｏｌ ５９． Ｎｏ１．１６〜２６（１９８６）
）−スチレン−ブタジエン共重合体（Ａ）のスチレン単
位が１個の単連鎖は４０％未満好ましくは３５％以下で
あり、かつスチレン単位が８個以上連なったスチレン長
連鎖が全結合スチレンの１０重量％以下好ましくは５重
量％以下である。スチレン単連鎖が４０％以上では耐摩
耗性、引裂強度が劣り、またスチレン長連鎖が１０％を
越えると耐摩耗性、反撥弾性が劣り、タイヤ用途として
使用するには好ましくない。In order to obtain the rubber composition of the present invention having excellent abrasion resistance and tear strength, styrene-butadiene copolymer (A)
It is important to keep the bonded styrene chains within a certain range. The chain distribution of styrene in the above SBR (A) is analyzed by gel permeation chromatogram after decomposing the sample with ozone (Kuninaka et al., Rubb.
er Chemistry and Technology
gyVol 59. No.1.16-26 (1986)
)-Styrene-butadiene copolymer (A) has a single chain of one styrene unit of less than 40%, preferably 35% or less, and a long styrene chain of 8 or more styrene units of 10% of the total bonded styrene. It is less than 5% by weight, preferably less than 5% by weight. If the styrene single chain content is 40% or more, the abrasion resistance and tear strength will be poor, and if the styrene long chain content is more than 10%, the abrasion resistance and rebound properties will be poor, making it undesirable for use in tire applications.
本発明の共重合体（Ａ）の分子量はムーニー粘度（ＭＬ
Ｉ＋４．１゜。℃）が２０〜２００である。ムーニー粘
度が２０未満であると耐摩耗性、反撥弾性が劣り、また
２００を越えると加工性が劣り、通常の加工機では加工
するのが困難で好ましくない。The molecular weight of the copolymer (A) of the present invention is Mooney viscosity (ML
I+4.1°. °C) is 20 to 200. If the Mooney viscosity is less than 20, the abrasion resistance and rebound properties will be poor, and if it exceeds 200, the workability will be poor and it will be difficult to process with a normal processing machine, which is not preferred.
本発明のスチレン−ブタジエン共重合体（Ａ）は、他の
ジエン系ゴム（Ｂ）すなわち天然ゴム、ポリイソプレン
ゴム、（Ａ）を除＜ ＳＢＲ５Ｓ−ＳＢＲ、ポリブタジ
ェンゴムとブレンドして用いる。The styrene-butadiene copolymer (A) of the present invention is used in a blend with other diene rubbers (B), namely natural rubber, polyisoprene rubber, SBR5S-SBR, and polybutadiene rubber excluding (A).
ジエン系ゴム組成物１００重量部に対して、スチレン−
ブタジエン共重合体（Ａ）は２０〜９０重量部、天然ゴ
ム、ポリイソプレンゴム、（Ａ）を除（ＳＢＲ，ポリブ
タジェンゴムのうちの一種以上のジエン系ゴム（Ｂ）は
、８０〜１０重量部用いる。ポリブタジェンは４０重量
部以下の範囲で用いるのが好ましい。Styrene based on 100 parts by weight of the diene rubber composition
Butadiene copolymer (A) is 20 to 90 parts by weight, natural rubber, polyisoprene rubber, excluding (A) (SBR, one or more diene rubbers (B) of polybutadiene rubber are 80 to 10 parts by weight) The amount of polybutadiene used is preferably 40 parts by weight or less.
本発明のスチレン−ブタジエン共重合体（Ａ）が２０重
量部未満ではグリップ力、低燃費性を維持しつつ、良好
な耐摩耗性、引裂き強度を得ることができない。If the styrene-butadiene copolymer (A) of the present invention is less than 20 parts by weight, good abrasion resistance and tear strength cannot be obtained while maintaining grip and fuel efficiency.
９０重量部を越えると耐寒性、グリップ力、耐摩耗性、
破壊強度といった諸物性のバランスが劣ってくるので、
他のジエンゴム（Ｂ）を少なくとも１０重量部はブレン
ドすることが必要である。If it exceeds 90 parts by weight, cold resistance, grip strength, abrasion resistance,
Because the balance of physical properties such as breaking strength becomes poor,
It is necessary to blend at least 10 parts by weight of another diene rubber (B).
天然ゴム、ポリイソプレンゴム、乳化重合によるＳＢＲ
は、該ゴム組成物の破壊強度、加工性を改良するために
使用される。これらのジエンゴムはその使用量が多過ぎ
ても少な過ぎても目的とする物性を得ることができない
、ポリブタジェンゴムはガラス転移温度が低く耐摩耗性
、低温特性が優れており、これらの改良のため用いられ
る。しかし使用量が増えると、加工性破壊強度か低下す
るので４０重量％までに限られる。SBR made from natural rubber, polyisoprene rubber, and emulsion polymerization
is used to improve the breaking strength and processability of the rubber composition. If these diene rubbers are used in too much or too little amount, the desired physical properties cannot be obtained.Polybutadiene rubber has a low glass transition temperature, excellent wear resistance, and low-temperature properties, and these improvements are needed. used for However, as the amount used increases, the workability and fracture strength decreases, so the amount is limited to 40% by weight.
本発明に使用される有機リチウム重合開始剤のうち代表
的なものを挙げると次の通りである。Representative examples of the organolithium polymerization initiators used in the present invention are as follows.
エチルリチウム、プロピルリチウム、ｎ−ブチルリチウ
ム、５ｅｃ−ブチルリチウム、ｔｅｒｔ−ブチルリチウ
ムなどのアルキルリチウム；フェニルリチウム、トリル
リチウムなどのアリルリチウム；ビニルリチウム、プロ
ペニルリチウムなどのアルケニルリチウム；テトラメチ
レンジリチウム、ペンタメチレンジリチウム、ヘキサメ
チレンジリチウム、デカメチレンジリチウムなどのアル
キレンジリチウムである。Alkyl lithium such as ethyllithium, propyl lithium, n-butyl lithium, 5ec-butyl lithium, tert-butyl lithium; allyl lithium such as phenyl lithium, tolyll lithium; alkenyl lithium such as vinyl lithium, propenyl lithium; tetramethylene dilithium, These are alkylene dilithiums such as pentamethylene dilithium, hexamethylene dilithium, and decamethylene dilithium.
また、有機リチウムと共触媒として使用する有機金属カ
リウムとしてはドデシルベンゼンスルホン酸カリウム、
テトラデシルベンゼンスルホン酸カリウム、ヘキサデシ
ルベンゼンスルホン酸力、リウム、オクタデシルスルホ
ン酸カリウムなど特公昭５４−４４３１５号に記載の化
合物がある。In addition, as organometallic potassium used as a cocatalyst with organolithium, potassium dodecylbenzenesulfonate,
There are compounds described in Japanese Patent Publication No. 54-44315, such as potassium tetradecylbenzenesulfonate, potassium hexadecylbenzenesulfonate, lium, and potassium octadecylsulfonate.
また、これらの化合物にアルコール、第２級アミンを少
量添加して用いてもよい。Further, a small amount of alcohol or secondary amine may be added to these compounds for use.
有機金属カリウムはリチウム１グラム原子当量当り０．
０１〜０．５モル用いることができる。Organometallic potassium is 0.0% per gram atom equivalent of lithium.
01 to 0.5 mol can be used.
重合溶媒にはｎ−ヘキサン、シクロヘキサン、ヘプタン
、ベンゼンなどを用いることができる。N-hexane, cyclohexane, heptane, benzene, etc. can be used as the polymerization solvent.
本発明のポリマーを得るための重合反応はバッチ重合方
式、連続重合方式のいずれの方式によっても行うことが
できる。The polymerization reaction for obtaining the polymer of the present invention can be carried out by either a batch polymerization method or a continuous polymerization method.
重合温度は０℃〜１３０℃の範囲が用いられる。The polymerization temperature used is a range of 0°C to 130°C.
また等温重合、昇温重合、あるいは断熱重合のいずれの
重合形式によっても行うことができる。Further, any polymerization method such as isothermal polymerization, temperature-programmed polymerization, or adiabatic polymerization can be used.
さらにまた、重合時に反応容器内にゲルが生成するのを
防止するため、１，２−ブタジェンなどのアレン化合物
を添加することもできる。Furthermore, an allene compound such as 1,2-butadiene may be added to prevent gel formation in the reaction vessel during polymerization.
本発明のスチレン−ブタジエン共重合体は必要に応じて
ナフテンオイル、高芳香族オイルあるいは軟化剤、また
は液状ポリマーを添加し、直接乾燥法やスチームストリ
ッピング法によってゴムと溶剤を分離して洗浄し、乾燥
することができる。The styrene-butadiene copolymer of the present invention can be washed by adding naphthenic oil, highly aromatic oil, softener, or liquid polymer as necessary, and separating the rubber and solvent by direct drying or steam stripping. , can be dried.
カーボンブラックまたはシリカなどの補強剤および各種
配合剤とロール、バンバリーミキサ−によって混錬りし
た後、硫黄、加硫促進剤などを添加して加硫しトレンド
、サイドウオール、カーカスなどのタイヤ用ゴムをはじ
めベルト、防振ゴム、その他の工業用品に用いられる。After kneading reinforcing agents such as carbon black or silica and various compounding agents on a roll or Banbury mixer, sulfur, vulcanization accelerators, etc. are added and vulcanized to produce rubber for tires such as tires, sidewalls, and carcass. Used for belts, anti-vibration rubber, and other industrial products.
ｅ、実施例
以下、実施例によって本発明をさらに詳しく説明するが
、これらの実施例は本発明の範囲を制限するものではな
い。e. Examples Hereinafter, the present invention will be explained in more detail with reference to Examples, but these Examples are not intended to limit the scope of the present invention.
くポリマーＡ〉
リボン型攪拌機を有する内容積１１の第１の種型反応器
に１，２−ブタジェン３００ｐｐ−を含む１．３ブタジ
ェン２．２５ｋｇ／ｈｒ、スチレン０．７５に＋ｒ／ｈ
ｒ、シクロヘキサン１３．５ｋｇ／ｈｒ、 ｎ−ブチル
リチウム１．８０ｇ／ｈｒ、 ドデシルベンゼンスル
ホン酸カリウム０．８２０ｇ／ｈｒで連続的に供給し、
９０℃で重合を行なった。第１の反応器と同じ大きさの
第２の反応器に重合溶液を導入し、９０℃でさらに重合
を行なった。反応器の出口において流出して（る重合溶
液中に２．６−ジーｔｅｒ ｔ−ブチルクレゾールを重
合体１００重量部当り０．６重量部加えて重合を停止さ
せた。Polymer A> 2.25 kg/hr of 1.3 butadiene containing 300 pp- of 1,2-butadiene in a first seed reactor with an internal volume of 11 and equipped with a ribbon-type stirrer, +r/h of styrene 0.75
r, cyclohexane 13.5 kg/hr, n-butyl lithium 1.80 g/hr, potassium dodecylbenzenesulfonate 0.820 g/hr continuously supplied,
Polymerization was carried out at 90°C. The polymerization solution was introduced into a second reactor of the same size as the first reactor, and further polymerization was carried out at 90°C. The polymerization was stopped by adding 0.6 parts by weight of 2,6-di-tert-butylcresol per 100 parts by weight of the polymer into the polymerization solution flowing out at the outlet of the reactor.
次いでスチームストリッピングにより重合体から溶剤を
分離し、１１０℃熱ロールで乾燥することにより試料を
得た０表−１にポリマーの分子特性測定結果を記した。Next, the solvent was separated from the polymer by steam stripping, and a sample was obtained by drying with a hot roll at 110° C. Table 1 shows the results of measuring the molecular characteristics of the polymer.
くポリマーＢ〉
脱水脱気したシクロヘキサン２０００ｇ 、１． ３−
ブタジェン３５０ｇ 、スチレン１５０ｇ、テトラヒド
ロフラン０．１ｇ、 ドデシルベンゼンスルホン酸カ
リウムを０．４ミリモル、ｎ−ブチルリチウム４ミリモ
ルを加え５０〜１００℃の上昇温度下で重合を行った。Polymer B> 2000 g of dehydrated and degassed cyclohexane, 1. 3-
350 g of butadiene, 150 g of styrene, 0.1 g of tetrahydrofuran, 0.4 mmol of potassium dodecylbenzenesulfonate, and 4 mmol of n-butyllithium were added, and polymerization was carried out at an elevated temperature of 50 to 100°C.
得られたスチレン−ブタジエン共重合体の物性の分析結
果を表−１に示す。Table 1 shows the analysis results of the physical properties of the obtained styrene-butadiene copolymer.
くポリマーＣ〉
ｎ−ブチルリチウムを１．２０ｇ／ｈｒ、ドデシルベン
ゼンスルホン酸カリウムを０．５４６ｇ／ｈｒにする以
外はポリマーＡと同一の重合方法でポリマーを得た。重
合体溶液にポリマー１００重量部当り高芳香族プロセス
オイル（ＪＳＲＡＲＯＭＡ） ３７．５重量部を添加し
た後、スチームストリフピングにより溶剤を分離し、１
１０℃の熱ロールで乾燥することによって得た。分析結
果を表−１に示す。Polymer C> A polymer was obtained by the same polymerization method as Polymer A except that n-butyllithium was used at 1.20 g/hr and potassium dodecylbenzenesulfonate was used at 0.546 g/hr. After adding 37.5 parts by weight of highly aromatic process oil (JSRAROMA) per 100 parts by weight of polymer to the polymer solution, the solvent was separated by steam stripping, and 1
It was obtained by drying with a hot roll at 10°C. The analysis results are shown in Table-1.
くポリマーＥ−Ｍ＞
ドデシルベンゼンスルホン酸カリウムの使用量を変え、
連続重合処方でポリマーＥ−Ｍを作成した。Polymer E-M> By changing the amount of potassium dodecylbenzenesulfonate used,
Polymer E-M was prepared using a continuous polymerization recipe.
表−１に分析結果を示した。Table 1 shows the analysis results.
実施例１〜１０、比較例１〜７
以上の通りに得られたポリマーＡ−Ｍを表−２の配合処
方で２５０ｃｃプラストミルにて混錬りし、１４５℃−
３０分加硫を行なった。物性の評価結果を表−３に示す
。Examples 1 to 10, Comparative Examples 1 to 7 Polymers A-M obtained as above were kneaded in a 250cc plastomill according to the formulation shown in Table 2, and the mixture was mixed at 145°C.
Vulcanization was performed for 30 minutes. The evaluation results of physical properties are shown in Table-3.
その結果実施例−１〜９は比較例−１〜４．６．７と対
比して物性が良好であることがわかる。As a result, it can be seen that Examples-1 to 9 have better physical properties than Comparative Examples-1 to 4.6.7.
また油展ポリマーである実施例−１０，１１の物性も比
較例−５と対比して優れている。Furthermore, the physical properties of Examples 10 and 11, which are oil extended polymers, are also excellent compared to Comparative Example 5.
−２配人几
重量部
ポリマー １００ＲＡＰカーボ
ン ５０ステアリン酸
２亜鉛華
３老化防止剤８１ＯＮＡ ” １促進
剤 ＣＺ ” Ｑ、５Ｍ ”
０．６
Ｄ 傘４ ０．４イ
オウ １．５傘Ｉ Ｎ−フ
ェニル−Ｎ′ −イソプロピル−ｐ−フ二ユニンジアミ
ン
＊２ Ｎ−シクロヘキシル−２−ベンゾチアゾリルスル
フェンアミド
＄３２−メｌレカブトベンソ゛チアゾール＄４１．３−
ジフェニルグアニジン
１０発明の効果
本発明のゴム組成物は反撥弾性を損なうことなく耐摩耗
性、および引裂強度に優れており、この特性を生かして
タイヤ用およびベルト、防振ゴム、その他工業用品用に
用いることができる。-2 parts by weight Polymer 100 RAP carbon 50 stearic acid
2 Zinc white
3 Anti-aging agent 81ONA ” 1 Accelerator CZ ” Q, 5M ”
0.6 D Umbrella 4 0.4 Sulfur 1.5 Umbrella I N-phenyl-N'-isopropyl-p-phunidinediamine*2 N-cyclohexyl-2-benzothiazolylsulfenamide $32-Melrekabut Benzothiazole $41.3-
Diphenylguanidine 10 Effects of the Invention The rubber composition of the present invention has excellent abrasion resistance and tear strength without impairing rebound properties, and by taking advantage of these properties, it can be used for tires, belts, vibration-proof rubber, and other industrial products. Can be used.
特許出願人 日本合成ゴム株式会社（ほか２名）Patent applicant: Japan Synthetic Rubber Co., Ltd. (and 2 others)
Claims (1)
共重合して得られ ｉ）結合スチレンが５〜５０重量％、 ｉｉ）ブタジエン部のビニル含量が２５％以下、ｉｉｉ
）スチレン単位が１個の単連鎖が全結合スチレンの４０
重量％未満であり、かつスチレン単位が８個以上連なっ
たスチレン長連鎖が全結合スチレンの１０重量％以下、
かつ ｉｖ）ムーニー粘度（ＭＬ＿１＿＋＿４＿，＿１＿０＿
０℃）が２０〜２００であるスチレン−ブタジエン共重
合体（Ａ）を全ゴム中に２０〜９０重量％含み、他のジ
エン系ゴム（Ｂ）として天然ゴム、ポリイソプレンゴム
、乳化重合スチレン−ブタジエン共重合ゴム（ただしス
チレン−ブタジエン共重合体（Ａ）を除く）、ポリブタ
ジエンゴムの中から選ばれた一種以上を８０〜１０重量
％含むジエン系ゴム組成物。(1) Obtained by copolymerizing styrene and butadiene with a lithium-based initiator i) 5 to 50% by weight of bound styrene, ii) Vinyl content in the butadiene moiety is 25% or less, iii
) 40 of single-chain fully bonded styrene with one styrene unit
% by weight, and long styrene chains consisting of 8 or more styrene units are 10% by weight or less of the total combined styrene;
and iv) Mooney viscosity (ML_1_+_4_,_1_0_
The total rubber contains 20 to 90% by weight of a styrene-butadiene copolymer (A) having a temperature of 0°C) of 20 to 200, and other diene rubbers (B) include natural rubber, polyisoprene rubber, and emulsion polymerized styrene. A diene rubber composition containing 80 to 10% by weight of one or more selected from butadiene copolymer rubber (excluding styrene-butadiene copolymer (A)) and polybutadiene rubber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62286554A JPH07110911B2 (en) | 1987-11-13 | 1987-11-13 | Butadiene rubber composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62286554A JPH07110911B2 (en) | 1987-11-13 | 1987-11-13 | Butadiene rubber composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01129045A true JPH01129045A (en) | 1989-05-22 |
| JPH07110911B2 JPH07110911B2 (en) | 1995-11-29 |
Family
ID=17705913
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62286554A Expired - Lifetime JPH07110911B2 (en) | 1987-11-13 | 1987-11-13 | Butadiene rubber composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07110911B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5550200A (en) * | 1992-12-24 | 1996-08-27 | Bridgestone Corporation | Method of producing conjugated diene-aromatic vinyl hydrocarbon copolymers |
| EP0447066B2 (en) † | 1990-03-02 | 2000-08-16 | Bridgestone Corporation | Pneumatic tyres |
| JP2004067987A (en) * | 2002-06-14 | 2004-03-04 | Jsr Corp | Conjugated diolefin copolymer rubber, method for producing the copolymer rubber, rubber composition, and tire |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59197443A (en) * | 1983-04-26 | 1984-11-09 | Nippon Zeon Co Ltd | Tire tread rubber composition |
| JPS61271338A (en) * | 1985-05-25 | 1986-12-01 | Nippon Erasutomaa Kk | Styrene/butadiene random copolymer composition |
| JPS6243439A (en) * | 1985-08-22 | 1987-02-25 | Nippon Erasutomaa Kk | Random styrene-butadiene copolymer composition |
| JPS62161844A (en) * | 1986-01-10 | 1987-07-17 | Asahi Chem Ind Co Ltd | Rubber composition for tire tread |
-
1987
- 1987-11-13 JP JP62286554A patent/JPH07110911B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59197443A (en) * | 1983-04-26 | 1984-11-09 | Nippon Zeon Co Ltd | Tire tread rubber composition |
| JPS61271338A (en) * | 1985-05-25 | 1986-12-01 | Nippon Erasutomaa Kk | Styrene/butadiene random copolymer composition |
| JPS6243439A (en) * | 1985-08-22 | 1987-02-25 | Nippon Erasutomaa Kk | Random styrene-butadiene copolymer composition |
| JPS62161844A (en) * | 1986-01-10 | 1987-07-17 | Asahi Chem Ind Co Ltd | Rubber composition for tire tread |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0447066B2 (en) † | 1990-03-02 | 2000-08-16 | Bridgestone Corporation | Pneumatic tyres |
| US5550200A (en) * | 1992-12-24 | 1996-08-27 | Bridgestone Corporation | Method of producing conjugated diene-aromatic vinyl hydrocarbon copolymers |
| US5916962A (en) * | 1992-12-24 | 1999-06-29 | Bridgestone Corporation | Rubber composition including a diene copolymer |
| JP2004067987A (en) * | 2002-06-14 | 2004-03-04 | Jsr Corp | Conjugated diolefin copolymer rubber, method for producing the copolymer rubber, rubber composition, and tire |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07110911B2 (en) | 1995-11-29 |
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