JPH0365828B2 - - Google Patents
Info
- Publication number
- JPH0365828B2 JPH0365828B2 JP59052377A JP5237784A JPH0365828B2 JP H0365828 B2 JPH0365828 B2 JP H0365828B2 JP 59052377 A JP59052377 A JP 59052377A JP 5237784 A JP5237784 A JP 5237784A JP H0365828 B2 JPH0365828 B2 JP H0365828B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- present
- trans
- polybutadiene
- processability
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920001971 elastomer Polymers 0.000 claims description 31
- 239000005060 rubber Substances 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 21
- 229920002857 polybutadiene Polymers 0.000 claims description 18
- 229920003244 diene elastomer Polymers 0.000 claims description 15
- 239000005062 Polybutadiene Substances 0.000 claims description 13
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- 230000000704 physical effect Effects 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 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
- 229920001577 copolymer Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 229920001084 poly(chloroprene) Polymers 0.000 description 3
- 239000012744 reinforcing agent Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-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
- 239000006229 carbon black Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 2
- 239000004913 cyclooctene Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000012770 industrial material Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229920006027 ternary co-polymer Polymers 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229920001875 Ebonite Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 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
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 244000001591 balata Species 0.000 description 1
- 235000016302 balata Nutrition 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000002421 finishing Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 description 1
- 238000010077 mastication Methods 0.000 description 1
- 230000018984 mastication Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 150000002825 nitriles Chemical class 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
- 239000003921 oil Substances 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 150000002901 organomagnesium compounds Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 239000007965 rubber solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- -1 tackifiers Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は加工性あるいはコールドフロー性の改
良されたゴム組成物に関する。
各種ジエン系ゴムはその鎖中に存在するイオウ
架橋を可能とする炭素−炭素2重結合によつて特
徴付けられ、各種構造のものが、その特性に合
せ、ゴム用途その他に広く使用されている。
これらジエン系ゴムは一般にポリマーの分子量
が大きく、直鎖状のものほど各種ゴム物性、例え
ば強度、弾性において優れるが、逆に加工性、例
えばバンバリー作業における混合性、ロール作業
における操作性、押出作業における生産性等で劣
り、又、このように加工性の悪いゴムを使つて得
られる製品は製品の肌、エツヂ等でも劣るものと
なる例が多い。更に場合によつては、例えばジエ
ン系ゴムがポリブタジエンの場合には、コールド
フローが大きく、これが問題となることもある。
これらジエン系ゴムのコールドフローを含む加
工性の改良については多くの提案があり、その中
にはトランス系ジエンポリマーの利用も提案され
ている。例えばシクロオクテンの開環重合体であ
つてトランス構造の多いものはトランスポリオク
テナマーと呼称され、エチレン・プレピレン・ジ
エン3元共重合体ゴム、クロロプレンゴムあるい
はアクリロニトリルーブタジエン共重合ゴム等に
ブレンドして加工性を改良する効果が知られる
(ポリマーの友、1983年,8月号,507〜513頁)。
しかし、この方法は確かに加工性改良効果は認め
られるものの、一部物性、例えばゴム弾性の低下
がみられ、ポリマーの原料であるシクロオクテン
が比較的高価なものであるためかポリマーの価格
も高く、広く工業的に利用されるには至つていな
い。また、不均一触媒系でブタジエンを重合する
ことによつて得られるトランスポリブタジエンは
トランス4として知られ、これをスチレン・ブタ
ジエン共重合ゴムにブレンドして押出加工性の改
良に用いること(工業材料、第10巻,第6号,19
〜21頁,1962年刊)、あるいはミデイアムビニル
ポリブタジエンにブレンドしてコールドフローの
防止に利用すべく提案も知られた(米国特許
4310582号)。しかし、当時における不均一触媒で
得られたトランスポリブタジエンは分子量分布が
広く、場合によつて多量のゲルを含むもので、そ
の物性は天然のトランスポリマーであるバラタ
(トランスポリイソプレン)に比して劣るレベル
のものでしかなく(上述、工業材料、第10巻,第
6号,19頁表参照)、いずれのブレンドにおいて
も、各々目的とした加工性ないしはコールドフロ
ーの改良の効果は認められるものの、その物性、
特に反発弾性で代表されるゴムの動的特性の低下
が著しく、工業的に利用されるには至つていな
い。
本発明者らは、これらトランス系ジエンポリマ
ーが有する、比較的低温で結晶化することからく
るとみられる優れた加工性改良効果と、他のジエ
ン系ポリマーとの共加硫性の特長に注目し、更に
その欠点である物性低下をいかにして軽減するか
を目的に種々の検討を実施し、ある特定されたポ
リマー構造のトランスポリブタジエンを限定され
た組成でジエン系ゴムにブレンドすることによ
り、ジエン系ゴムのゴム物性と加工性が高度にバ
ランスされえることを見出し、本発明に到達し
た。
すなわち本発明は、その特許請求の範囲に示す
通り、トランス結合75〜90%、ビニル結合3〜10
%、分子量分布(w/n)1.2〜5、ムーニ
ー粘度50以下のトランスポリブタジエン3〜20重
量部とジエン系ゴム(但し、前記トランスポリブ
タジエンを除く)97〜80重量部よりなるゴム組成
物を提案するものである。
本発明のトランスポリブタジエンはその結合様
式がトランス結合75〜90%、好ましくは80〜88
%、又ビニル結合は3〜10%、好ましくは4〜9
%である。この範囲より低いトランス結合にあつ
ては加工性改良効果が不十分であり、一方これよ
り高いものであつてはゴム弾性等の物性低下が認
められる。本発明の結合様式は赤外分光計を用い
るモレロの方法により測定される。
又、ゲルパーミエーシヨンクロマトグラフ
(GPC)によつて測定される分子量分布は重量平
均分子量(w)と数平均分子量(n)の比
(w/n)で表示し、1.2〜5、好ましくは
1.5〜3.0、更に好ましくは1.8〜2.5であることを
必要とする。この範囲を超えた分子量分布のポリ
マーでは著しい物性低下を招き本発明の効果が発
現しない。
更に、Lローターを使用し100℃で測定される
ムーニー粘度は50以下、好ましくは20以下、更に
好ましくは10以下であることを必要とする。ムー
ニー粘度がこれ以上あつては本発明の加工性改良
効果が発現しない。
上述の特定されたトランスポリブタジエンはそ
の分子鎖中に少量の共重合成分、例えば30重量%
以下のスチレン、イソプレン等の単量体単位をラ
ンダム状またはブロツク状に含むものであつても
よい。
このような特定された構造を有するトランスポ
リブタジエンはブタジエンをバリウム、ストロン
チウムまたはカルシウム化合物と有機リチウム化
合物または/および有機マグネシウム化合物(場
合により更に有機アルミニウム化合物)よりなる
均一複合触媒の存在下に重合させることによつて
容易に得ることができ、その結合様式、分子量分
布、ムーニー粘度等は触媒量、組成および重合温
度等の重合条件によつて可変なものである(例え
ば特開昭55−38827号、同56−112916号を参照)。
本発明の上記トランスポリブタジエンの本発明
のゴム組成物における組成は3〜20重量部、好ま
しくは5〜18ないし20重量部であることを必要と
する。これ以下の比率では加工性改良効果が十分
発揮されえず、一方、これ以上の添加は改良すべ
くジエン系ゴムの特性を著しく減ずるものとな
る。
本発明のゴム組成物の残部を構成する改良され
るべきジエン系ゴムとしては天然ゴム、ポリイソ
プレンゴム、ポリブタジエンゴム、スチレン−ブ
タジエン共重合ゴム、アクリロニトリル−ブタジ
エン共重合ゴム、クロロプレンゴム、エチレン−
プロピレン−ジエン3元共重合ゴム等が挙げら
れ、効果が特に著しく好ましいものとして、ポリ
ブタジエンゴム(ローシス及びハイシス)、溶液
重合スチレン−ブタジエン共重合ゴム、アクリロ
ニトリル−ブタジエン共重合ゴム(特に中高ニト
リルおよび高ニトリル)およびクロロプレンゴム
がある。これらのジエン系ゴムには種々のタイ
プ、銘柄が用途に合せて市販されているが、本発
明の効果は先述したように、一般にポリマー鎖の
構造が比較的高分子量で、リニアなもの、すなわ
ち物性は優れるが加工性は劣るとされるタイプ、
銘柄に大きく発現する。
本発明のゴム組成物は組成物を構成する前述の
2成分単独またはこれと他の成分、例えば各種配
合剤、充填剤、加硫剤等とともに、公知のゴム組
成物を製造するに用いられている種々の方法で混
合することにより容易に得ることができる。これ
らの最も一般的な方法は、バンバリー、ロール等
の機械的混練による方法である。又、本発明の組
成物は、各々の成分を溶液状として、いわゆる溶
液ブレンドにより得ることもできる。この方法は
特に改良すべきジエン系ゴムが溶液重合で得られ
るゴムの場合に有用である。
本発明のゴム組成物は単独で各種プラスチツク
とブレンド又はグラフトしてその耐衝撃性改良剤
としても用いることができるが、一般にはジエン
系ゴムにおいて広く使用されている各種配合薬
品、補強剤および充填剤あるいはその他の副資材
を配合混練し、公知の加硫方法によつて加硫ゴム
とし用いられる。これら配合剤の例としては次の
ようなものが挙げられる。加硫剤、加硫促進剤、
老化防止剤、素練促進剤、軟化剤、可塑剤、粘着
付与剤、プロセス油、カーボンブラツク、無機補
強剤、有機補強剤、無機充填剤、各種繊維材料、
加工助剤、仕上剤、ゴム用溶剤等。
本発明の組成物は上述のように加硫ゴムとして
特にその優れた物性と加工性を生かし次のような
広い用途に用いられる。タイヤトレツド、カーカ
ス、サイドウオール等のタイヤ用途、ベルト、ホ
ース、ロール、防振ゴム、エボナイト、ライニン
グ、スポンジ、接着剤、はきもの、ゴム引布、カ
ツトシート製品、各種医療用ゴム、電線、各種ボ
ール及び各種分出製品、押出製品等。
本発明を更に詳細に説明するために以下に本発
明の実施例を示す。
実施例1〜6,比較例1〜6及び16
本発明のゴム組成物がトランスポリブタジエン
とポリブタジエンゴムよりなる場合の実験結果を
実施例1〜6,比較例1〜6及び16として表1お
よび表2に示す。ここで用いたトランスポリブタ
ジエンはバリウムジノニルフエノキシド、ブチル
リチウム、ジブチルマグネシウムおよびトリエチ
ルアルミニウムよりなる均一複合触媒を用いる重
合によつて作成したものである。組成物はn−ヘ
キサンの20重量パーセント溶液を用い溶液ブレン
ドした実施例4を除き、ロールにより混練した機
械的ブレンド物を用いた。
表1,表2より明らかなように本発明の組成物
は、コールドフロー性と加工性が著しく改良され
たものであることが分かる。又、その加硫物の物
性は改良前のジエン系ゴム単独の物性とほぼ同等
であり、場合により優れることもある。すなわち
ジエン系ゴムにおいて高度な加工性と物性のバラ
ンスが得られていることが示される。
また、比較例をも併せみると、本発明の上述の
効果は、トランスポリブタジエンの構造と、その
組成比が本発明の範囲にあつてはじめて発現して
いることが分かる。
The present invention relates to a rubber composition with improved processability or cold flow properties. Various diene rubbers are characterized by carbon-carbon double bonds present in their chains that enable sulfur crosslinking, and various structures are widely used for rubber and other purposes depending on their properties. . These diene rubbers generally have a larger polymer molecular weight, and the more linear they are, the better they are in various rubber physical properties, such as strength and elasticity.However, on the contrary, they have poor processability, such as mixability in Banbury work, operability in roll work, and extrusion work. In many cases, products obtained using rubber with poor processability are inferior in terms of skin, edges, etc. Furthermore, in some cases, for example, when the diene rubber is polybutadiene, the cold flow may be large, which may pose a problem. There have been many proposals for improving the processability, including cold flow, of these diene rubbers, including the use of trans diene polymers. For example, ring-opened polymers of cyclooctene with many trans structures are called transpolyoctenamers, and are blended with ethylene-prepylene-diene ternary copolymer rubber, chloroprene rubber, acrylonitrile-butadiene copolymer rubber, etc. The effect of improving processability is known (Polymer no Tomo, August issue, 1983, pp. 507-513).
However, although this method does have the effect of improving processability, some physical properties, such as rubber elasticity, are degraded, and the price of the polymer is low, perhaps because cyclooctene, the raw material for the polymer, is relatively expensive. It is expensive and has not yet been widely used industrially. In addition, trans polybutadiene obtained by polymerizing butadiene in a heterogeneous catalyst system is known as trans 4, and it is used to improve extrusion processability by blending it with styrene-butadiene copolymer rubber (industrial materials, Volume 10, No. 6, 19
~21 pages, published in 1962), or it was proposed to be blended with medium vinyl polybutadiene to prevent cold flow (U.S. patent).
No. 4310582). However, the transpolybutadiene obtained using heterogeneous catalysts at that time had a wide molecular weight distribution and sometimes contained a large amount of gel, and its physical properties were compared to balata (transpolyisoprene), a natural transpolymer. (See table above, Industrial Materials, Vol. 10, No. 6, p. 19), and although both blends have the effect of improving processability or cold flow as desired, , its physical properties,
In particular, the dynamic properties of the rubber, typified by its impact resilience, are significantly reduced, and it has not been used industrially. The present inventors focused on the excellent processability improvement effect of these trans-based diene polymers, which appears to result from crystallization at relatively low temperatures, and the co-vulcanization characteristics with other diene-based polymers. Furthermore, various studies were carried out with the aim of alleviating the deterioration in physical properties, which is a drawback of this technology. The inventors have discovered that the physical properties and processability of the rubber-based rubber can be highly balanced, and have arrived at the present invention. That is, the present invention, as shown in the claims, has trans bonds of 75 to 90% and vinyl bonds of 3 to 10%.
%, molecular weight distribution (w/n) of 1.2 to 5, Mooney viscosity of 50 or less, a rubber composition consisting of 3 to 20 parts by weight of trans polybutadiene and 97 to 80 parts by weight of diene rubber (excluding the above trans polybutadiene). It is something to do. The trans polybutadiene of the present invention has a binding mode of trans bonds of 75 to 90%, preferably 80 to 88%.
%, and the vinyl bond is 3 to 10%, preferably 4 to 9
%. If the transformer bond is lower than this range, the effect of improving processability will be insufficient, while if it is higher than this range, a decrease in physical properties such as rubber elasticity will be observed. The binding mode of the present invention is determined by Morello's method using an infrared spectrometer. In addition, the molecular weight distribution measured by gel permeation chromatography (GPC) is expressed as a ratio (w/n) of weight average molecular weight (w) to number average molecular weight (n), and is preferably 1.2 to 5.
It needs to be 1.5 to 3.0, more preferably 1.8 to 2.5. Polymers with a molecular weight distribution exceeding this range result in significant deterioration of physical properties and do not exhibit the effects of the present invention. Furthermore, the Mooney viscosity measured at 100° C. using an L rotor must be 50 or less, preferably 20 or less, and more preferably 10 or less. If the Mooney viscosity is higher than this, the processability improvement effect of the present invention will not be achieved. The transpolybutadiene specified above contains a small amount of copolymer component in its molecular chain, for example 30% by weight.
It may contain the following monomer units such as styrene and isoprene in random or block form. Trans-polybutadiene having such a specified structure can be obtained by polymerizing butadiene in the presence of a homogeneous composite catalyst consisting of a barium, strontium or calcium compound, an organolithium compound or/and an organomagnesium compound (and optionally an organoaluminum compound). The bonding mode, molecular weight distribution, Mooney viscosity, etc. are variable depending on the polymerization conditions such as the amount of catalyst, composition, and polymerization temperature (for example, Japanese Patent Application Laid-Open No. 38827/1983). (See No. 56-112916). The composition of the transpolybutadiene of the present invention in the rubber composition of the present invention needs to be 3 to 20 parts by weight, preferably 5 to 18 to 20 parts by weight. If the ratio is less than this, the effect of improving processability cannot be sufficiently exhibited, while if it is added more than this, the properties of the diene rubber to be improved will be significantly reduced. The diene rubbers to be improved which constitute the remainder of the rubber composition of the present invention include natural rubber, polyisoprene rubber, polybutadiene rubber, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, chloroprene rubber, and ethylene-based rubber.
Examples include propylene-diene ternary copolymer rubber, and those with particularly favorable effects include polybutadiene rubber (low-cis and high-cis), solution-polymerized styrene-butadiene copolymer rubber, and acrylonitrile-butadiene copolymer rubber (particularly medium-high nitrile and high- nitrile) and chloroprene rubber. Various types and brands of these diene rubbers are commercially available depending on the application, but as mentioned above, the effect of the present invention is generally achieved when the polymer chain structure is relatively high molecular weight and linear. A type that has excellent physical properties but poor processability.
It is greatly reflected in the brand. The rubber composition of the present invention can be used alone or together with other components, such as various compounding agents, fillers, vulcanizing agents, etc., to produce known rubber compositions. It can be easily obtained by mixing in various ways. The most common of these methods are mechanical kneading methods such as Banbury and roll kneading. The composition of the present invention can also be obtained by so-called solution blending, in which each component is in the form of a solution. This method is particularly useful when the diene rubber to be improved is a rubber obtained by solution polymerization. The rubber composition of the present invention can be used alone as an impact modifier by blending or grafting with various plastics, but in general, various compounded chemicals, reinforcing agents, and fillers widely used in diene rubbers are used. The mixture is mixed with additives or other auxiliary materials, and used as a vulcanized rubber using a known vulcanization method. Examples of these compounding agents include the following. Vulcanizing agent, vulcanization accelerator,
Antiaging agents, mastication accelerators, softeners, plasticizers, tackifiers, process oils, carbon black, inorganic reinforcing agents, organic reinforcing agents, inorganic fillers, various fiber materials,
Processing aids, finishing agents, rubber solvents, etc. As mentioned above, the composition of the present invention can be used as a vulcanized rubber in a wide range of applications, particularly by taking advantage of its excellent physical properties and processability. Tire applications such as tire treads, carcass, and sidewalls, belts, hoses, rolls, anti-vibration rubber, ebonite, linings, sponges, adhesives, footwear, rubberized fabrics, cut sheet products, various medical rubbers, electric wires, various balls, and Various separated products, extruded products, etc. Examples of the present invention are shown below to explain the present invention in more detail. Examples 1 to 6, Comparative Examples 1 to 6 and 16 The experimental results when the rubber composition of the present invention is composed of trans polybutadiene and polybutadiene rubber are shown in Tables 1 and 16 as Examples 1 to 6, Comparative Examples 1 to 6 and 16. Shown in 2. The transpolybutadiene used here was produced by polymerization using a homogeneous composite catalyst consisting of barium dinonyl phenoxide, butyllithium, dibutylmagnesium, and triethylaluminum. The compositions used were mechanical blends kneaded with rolls, except for Example 4, which was solution blended using a 20 weight percent solution of n-hexane. As is clear from Tables 1 and 2, it can be seen that the composition of the present invention has significantly improved cold flow properties and processability. Further, the physical properties of the vulcanizate are almost the same as those of the diene rubber alone before improvement, and may be superior in some cases. In other words, it is shown that a high balance between processability and physical properties is obtained in the diene rubber. Moreover, when comparing comparative examples as well, it can be seen that the above-mentioned effects of the present invention are only realized when the structure of trans-polybutadiene and its composition ratio are within the range of the present invention.
【表】【table】
【表】【table】
【表】【table】
【表】
表3 配合表(1)
ゴム組成物 100重量部
HAF級カーボンブラツク 45 〃
アロマ系オイル 5 〃
亜鉛華 5 〃
ステアリン酸 2 〃
イオウ 1.7 〃 促進剤CBS* 1.0 〃
計 159.7 〃
*N−シクロヘキシル−2−ベンゾチアゾール
スルフエンアミド
実施例7〜9,比較例7〜9及び17
ジエン系ゴムがミデイアムビニルポリブタジエ
ンゴムの場合の実験結果を実施例7〜9,比較例
7〜9及び17として表4および表5に示す。ここ
で用いたミデイアムビニルポリブタジエンはブチ
ルリチウムとテトラヒドロフランよりなる触媒を
用いる重合により作成したもので、その構造分析
値はムーニー粘度53、ビニル結合54%、分子量分
布(w/n)2.0であつた。又、組成物はす
べてシクロヘキサンの20重量パーセント溶液で溶
液ブレンドにより作成した。
表4,表5より明らかなように本発明の効果は
ジエン系ゴムがミデイアムビニルポリブタジエン
ゴムの場合も発現するものである。またその実施
例と比較例との対比より、コールドフローのみの
改良であればトランスポリブタジエンの構造を本
発明の範囲に限定する必要はないが、加工性の改
良、更に物性の低下をさけるためには本発明の構
造限定が必須となつていることが分かる。[Table] Table 3 Formula (1) Rubber composition 100 parts by weight HAF grade carbon black 45 Aroma oil 5 Zinc white 5 Stearic acid 2 Sulfur 1.7 Accelerator CBS * 1.0 Total 159.7 *N- Cyclohexyl-2-benzothiazolesulfenamide Examples 7-9, Comparative Examples 7-9 and 17 The experimental results when the diene rubber is medium vinyl polybutadiene rubber are shown as Examples 7-9 and Comparative Examples 7-9 and 17. It is shown in Tables 4 and 5. The medium vinyl polybutadiene used here was prepared by polymerization using a catalyst consisting of butyllithium and tetrahydrofuran, and its structural analysis values were a Mooney viscosity of 53, a vinyl bond of 54%, and a molecular weight distribution (w/n) of 2.0. All compositions were also made by solution blending with 20 weight percent solutions of cyclohexane. As is clear from Tables 4 and 5, the effects of the present invention are also exhibited when the diene rubber is medium vinyl polybutadiene rubber. Furthermore, from the comparison between the examples and comparative examples, it is clear that if only the cold flow is improved, there is no need to limit the structure of trans-polybutadiene to the scope of the present invention, but it is necessary to improve the processability and avoid deterioration of the physical properties. It can be seen that the structure limitation of the present invention is essential.
【表】
〓表1脚注と同じ。
*3[Table] = Same as Table 1 footnote.
*3
Claims (1)
%、分子量分布(w/n)1.2〜5、ムーニ
ー粘度50以下のトランスポリブタジエン3〜20重
量部とジエン系ゴム(但し前記トランスポリブタ
ジエンを除く)97〜80重量部よりなるゴム組成
物。1 Trans bond 75-90%, vinyl bond 3-10
%, molecular weight distribution (w/n) of 1.2 to 5, and a Mooney viscosity of 50 or less, a rubber composition comprising 3 to 20 parts by weight of trans polybutadiene and 97 to 80 parts by weight of a diene rubber (excluding the above trans polybutadiene).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5237784A JPS60197749A (en) | 1984-03-21 | 1984-03-21 | Rubber composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5237784A JPS60197749A (en) | 1984-03-21 | 1984-03-21 | Rubber composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS60197749A JPS60197749A (en) | 1985-10-07 |
JPH0365828B2 true JPH0365828B2 (en) | 1991-10-15 |
Family
ID=12913110
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP5237784A Granted JPS60197749A (en) | 1984-03-21 | 1984-03-21 | Rubber composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS60197749A (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH082996B2 (en) * | 1987-11-21 | 1996-01-17 | 日本合成ゴム株式会社 | Butadiene-based polymer composition for tires |
JPH03190944A (en) * | 1989-12-20 | 1991-08-20 | Nippon Zeon Co Ltd | Abrasion-resistant rubber composition |
US5174838A (en) * | 1991-03-27 | 1992-12-29 | The Goodyear Tire & Rubber Company | Tire with tread base rubber blend |
US5386865A (en) * | 1991-10-21 | 1995-02-07 | The Goodyear Tire & Rubber Company | Tire with rubber sidewall |
CA2081533A1 (en) * | 1992-09-16 | 1994-03-17 | Thomas Joseph Segatta | Tire with apex rubber blend |
US6024146A (en) * | 1994-05-02 | 2000-02-15 | The Goodyear Tire & Rubber Company | Pneumatic tire having an innerliner of a cured rubber compound containing trans 1,4-polybutadiene rubber |
US5988248A (en) * | 1997-02-25 | 1999-11-23 | The Goodyear Tire & Rubber Company | Tire with rubber sidewall |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5538827A (en) * | 1978-09-13 | 1980-03-18 | Asahi Chem Ind Co Ltd | Production of conjugated diene polymer |
JPS5945342A (en) * | 1982-09-09 | 1984-03-14 | Yokohama Rubber Co Ltd:The | Rubber composition for tire tread |
-
1984
- 1984-03-21 JP JP5237784A patent/JPS60197749A/en active Granted
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5538827A (en) * | 1978-09-13 | 1980-03-18 | Asahi Chem Ind Co Ltd | Production of conjugated diene polymer |
JPS5945342A (en) * | 1982-09-09 | 1984-03-14 | Yokohama Rubber Co Ltd:The | Rubber composition for tire tread |
Also Published As
Publication number | Publication date |
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JPS60197749A (en) | 1985-10-07 |
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