JPH0291105A - Polybutadiene - Google Patents
PolybutadieneInfo
- Publication number
- JPH0291105A JPH0291105A JP24352488A JP24352488A JPH0291105A JP H0291105 A JPH0291105 A JP H0291105A JP 24352488 A JP24352488 A JP 24352488A JP 24352488 A JP24352488 A JP 24352488A JP H0291105 A JPH0291105 A JP H0291105A
- Authority
- JP
- Japan
- Prior art keywords
- polybutadiene
- molecular weight
- mooney viscosity
- average molecular
- ratio
- 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.)
- Pending
Links
- 229920002857 polybutadiene Polymers 0.000 title claims abstract description 46
- 239000005062 Polybutadiene Substances 0.000 title claims abstract description 44
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000009826 distribution Methods 0.000 claims abstract description 8
- 150000002816 nickel compounds Chemical class 0.000 claims abstract description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 abstract description 14
- 238000006116 polymerization reaction Methods 0.000 abstract description 12
- 239000002904 solvent Substances 0.000 abstract description 7
- 238000001125 extrusion Methods 0.000 abstract description 6
- 230000032683 aging Effects 0.000 abstract description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 229930195733 hydrocarbon Natural products 0.000 abstract description 2
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 2
- 238000005096 rolling process Methods 0.000 abstract 1
- 239000011877 solvent mixture Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000203 mixture Substances 0.000 description 8
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KZMAWJRXKGLWGS-UHFFFAOYSA-N 2-chloro-n-[4-(4-methoxyphenyl)-1,3-thiazol-2-yl]-n-(3-methoxypropyl)acetamide Chemical compound S1C(N(C(=O)CCl)CCCOC)=NC(C=2C=CC(OC)=CC=2)=C1 KZMAWJRXKGLWGS-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 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
- 239000005063 High cis polybutadiene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NBICYCZLCAMSBG-UHFFFAOYSA-L [Co+2].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O Chemical compound [Co+2].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O NBICYCZLCAMSBG-UHFFFAOYSA-L 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- -1 ethylaluminum toluene Chemical compound 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- UIEKYBOPAVTZKW-UHFFFAOYSA-L naphthalene-2-carboxylate;nickel(2+) Chemical compound [Ni+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 UIEKYBOPAVTZKW-UHFFFAOYSA-L 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はポリブタジェンに関し、詳しくは、特にタイヤ
等で押出加工性（シャープエッヂ性能）を要求される部
分に好適に利用し得る他、ロール加工性に優れゴルフボ
ール等の単味配合時に好適に利用し得るポリブタジェン
に関する。さらには耐衝撃性ポリスチレン系樹脂組成物
のゴム成分や医薬用途にも好適に利用し得るポリブタジ
ェンに関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to polybutadiene, and more specifically, it can be suitably used in parts of tires etc. that require extrusion processability (sharp edge performance), as well as roll processing. The present invention relates to polybutadiene which has excellent properties and can be suitably used when compounding single ingredients such as golf balls. Furthermore, the present invention relates to polybutadiene which can be suitably used as a rubber component of impact-resistant polystyrene resin compositions and for pharmaceutical applications.
ポリブタジェンは、有機アルミニウム化合物とコバルト
またはニッケル化合物とを含む触媒を用いる等の公知の
製造法で１，３−ブタジェンを重合させることにより、
シス−１，４構造体、トランス−１，４構造体および１
，２−ビニル構造体の繰返し単位の混合物として得られ
る。ポリブタジェンは種々の用途、例えば各種工業用品
、スポーツ用品、玩具、樹脂改質剤等に広く利用されて
いる。とりわけ工業用品やスポーツ用品等においては、
その用途の拡大および該組成物から得られる製品の品質
向上および生産性向上を図る上から優れた加工性、特に
押出加工性やロール加工性が要望されている。Polybutadiene is produced by polymerizing 1,3-butadiene using a known production method such as using a catalyst containing an organoaluminum compound and a cobalt or nickel compound.
Cis-1,4 structure, trans-1,4 structure and 1
, 2-vinyl structure repeating units. Polybutadiene is widely used for various purposes, such as various industrial products, sporting goods, toys, and resin modifiers. Especially in industrial goods and sporting goods, etc.
Excellent processability, particularly extrusion processability and roll processability, is desired in order to expand the use of the composition and to improve the quality and productivity of products obtained from the composition.
しかしながら、従来のポリブタジェンは、十分な加工性
を有するものではなかった。However, conventional polybutadiene did not have sufficient processability.
本発明の目的は、上記従来技術の欠点を解決し、優れた
加工性を有するポリブタジェンを提供することにある。An object of the present invention is to solve the above-mentioned drawbacks of the prior art and to provide a polybutadiene having excellent processability.
本発明者らは、鋭意検討した結果、分子量分布曲線が単
一のピークをもち、かつＺ平均分子量とムーニー粘度の
比が特定範囲内にある高シスポリブタジェンが上記目的
を達成し得ることを見出し、本発明に到達した。As a result of intensive studies, the present inventors have found that a high-cis polybutadiene whose molecular weight distribution curve has a single peak and whose ratio of Z average molecular weight to Mooney viscosity is within a specific range can achieve the above object. They discovered this and arrived at the present invention.
すなわち、本発明は、シス１．４構造含有率が８５〜９
９％、トランス１．４構造含有率が０．５〜７．５％、
Ｌ、２構造含有率が０．５〜７．５％であり、ムーニー
粘度（Ｍ Ｌ Ｉ−ａ （１００℃）〕が２０〜１００
で、かつ分子量分布曲線が単一のピークをもち、Ｚ平均
分子１（ＭＺ）とムーニー粘度の比（Ｍｚ／ムーニー粘
度）が３．０×１０４以上であるポリブタジェンである
。That is, in the present invention, the cis 1.4 structure content is 85 to 9
9%, trans 1.4 structure content 0.5-7.5%,
The L, 2 structure content is 0.5 to 7.5%, and the Mooney viscosity (M L I-a (100°C)) is 20 to 100.
It is a polybutadiene whose molecular weight distribution curve has a single peak and whose ratio of Z average molecule 1 (MZ) to Mooney viscosity (Mz/Mooney viscosity) is 3.0×10 4 or more.
本発明のポリブタジェンのムーニー粘度〔ＭＬＩや、
（１００℃）〕は２０〜１００であり、好ましくは２３
〜６５である。ムーニー粘度が２０未満ではポリブタジ
ェンとしての強度が得られず、また１００を超えると加
工性が極めて悪い。Mooney viscosity of the polybutadiene of the present invention [MLI,
(100℃)] is 20 to 100, preferably 23
~65. If the Mooney viscosity is less than 20, strength as polybutadiene cannot be obtained, and if it exceeds 100, processability is extremely poor.
本発明におけるポリブタジェンのシス−１，４構造含有
率は８５〜９９％、好ましくは９０〜９９％であり、ト
ランス−１，４構造含有率０．５〜７．５％、１．２構
造含有率０．５〜７．５％である。The polybutadiene in the present invention has a cis-1,4 structure content of 85 to 99%, preferably 90 to 99%, a trans-1,4 structure content of 0.5 to 7.5%, and a 1.2 structure content. The percentage is 0.5-7.5%.
また、本発明のポリブタジェンは、分子量分布曲線が単
一のピークをもち、かつＺ平均分子量（Ｍｚ）とムーニ
ー粘度との比（Ｍｚ／ムーニー粘度）が３．０×１０４
以上であり、好ましくは３゜０ＸＩＯ’〜６．０Ｘ１０
’である。Ｚ平均分子量（Ｍｚ）とムーニー粘度との比
（Ｍｚ／ムーニー粘度）が３．０Ｘ１０’未満のポリブ
タジェンを用いた場合は、加工性は著しく劣り、大きす
ぎる場合、例えば１０．０Ｘ１０’を超えるようなポリ
ブタジェンは、製造することも難しく、製造できたとし
ても実用に供することができない。Furthermore, the polybutadiene of the present invention has a molecular weight distribution curve with a single peak, and a ratio of Z average molecular weight (Mz) to Mooney viscosity (Mz/Mooney viscosity) of 3.0×104
or more, preferably 3°0XIO' to 6.0X10
'is. If polybutadiene with a ratio of Z average molecular weight (Mz) to Mooney viscosity (Mz/Mooney viscosity) of less than 3.0X10' is used, processability will be significantly poor; Polybutadiene is also difficult to produce, and even if it can be produced, it cannot be put to practical use.
また、Ｍｚとムーニー粘度の比がたとえ本発明の範囲に
あっても、分子量分布曲線が複数のピークを有するもの
は意外にもロール加工性が劣る。Moreover, even if the ratio of Mz to Mooney viscosity is within the range of the present invention, those whose molecular weight distribution curve has multiple peaks have unexpectedly poor roll processability.
この理由は必ずしも明らかではないが、分子量分布曲線
が複数のピークを有するポリブタジェンは、加工性に敏
感なムーニー粘度に影響を与えるために、ロール加工性
が劣るものと推定される。Although the reason for this is not necessarily clear, it is presumed that polybutadiene whose molecular weight distribution curve has multiple peaks has poor roll processability because it affects Mooney viscosity, which is sensitive to processability.
本発明のポリブタジェンは、有機アルミニウム化合物と
ニッケル化合物とを含む触媒を用いる等の従来公知の製
造法において、トルエン等の芳香族系炭化水素溶剤単独
、または芳香族系炭化水素溶剤と最大２０重量％までの
他の炭化水素溶剤との混合物を使用することによって製
造されることを特徴とし、さらには有機アルミニウム化
合物とニッケル化合物との比が５．０以上、触媒熟成温
度が７０°Ｃ以下、好ましくは１０〜５０℃で、重合温
度が１００°Ｃ以下、好ましくは３０〜８０°Ｃにおい
て、本発明のポリブタジェンを得ることを特徴とする。The polybutadiene of the present invention can be produced using an aromatic hydrocarbon solvent such as toluene alone or together with an aromatic hydrocarbon solvent up to 20% by weight in a conventionally known production method such as using a catalyst containing an organoaluminum compound and a nickel compound. It is characterized in that it is produced by using a mixture with other hydrocarbon solvents up to is characterized in that the polybutadiene of the present invention is obtained at a temperature of 10 to 50°C and a polymerization temperature of 100°C or less, preferably 30 to 80°C.
本発明のポリブタジェンを用いて製品を得る際には、必
要に応じて本発明のポリブタジェンの他に、例えば、ス
チレン−ブタジェン共重合体、天然ゴム（ＮＲ）、アク
リル系ゴム等を併用できる。When obtaining a product using the polybutadiene of the present invention, for example, a styrene-butadiene copolymer, natural rubber (NR), acrylic rubber, etc. may be used in combination with the polybutadiene of the present invention, if necessary.
また、本発明のポリブタジェンを単独または上述の如（
併用した場合においても、加工する際に必要に応じ種々
の添加剤、例えばカーボン、オイル、安定剤、充填剤、
着色剤、加硫剤等を適宜添加してもよい。なお、本発明
のポリブタジェンは５、従来のポリブタジェンと同様な
種々の用途に用いることがき、その用途が制限されるも
のではない。In addition, the polybutadiene of the present invention may be used alone or as described above (
Even when used together, various additives such as carbon, oil, stabilizers, fillers, etc. may be added as necessary during processing.
A coloring agent, a vulcanizing agent, etc. may be added as appropriate. Note that the polybutadiene of the present invention can be used for various purposes similar to those of conventional polybutadiene, and its uses are not limited.
以下に本発明の実施例を述べるが、実施例中、重合体１
００重量部に対する割合（重量部）はｐｈｒで、またモ
ノマー１００重量部に対する割合（重量部）をｐｈｍで
示す。なお、以下の実施例で用いられる２平均分子量お
よびムーニー粘度の測定は次のように行った。Examples of the present invention will be described below. In the examples, polymer 1
The ratio (parts by weight) to 100 parts by weight of the monomer is expressed as phr, and the ratio (parts by weight) to 100 parts by weight of the monomer is expressed as phm. The two-average molecular weight and Mooney viscosity used in the following examples were measured as follows.
（１）Ｚ平均分子ｆｉ（Ｍｚ）
武内次夫・森定雄共著（丸善株式会社）「ゲルパーミェ
ーションクロマトグラフィー」に記載のＺ平均分子量の
ゲルパーミェーションクロマトグラフ（ｃｐｃ）からの
Ｚ平均分子量計算方法に依った。(1) Z average molecular weight fi (Mz) From the gel permeation chromatograph (CPC) of the Z average molecular weight described in “Gel Permeation Chromatography” co-authored by Tsuguo Takeuchi and Sadao Mori (Maruzen Co., Ltd.) Based on the Z average molecular weight calculation method.
ゲルパーミェーションクロマトグラフの測定は、溶媒と
してテトラヒドロフランを用い、温度３８゛Ｃ１東ソ一
社製、ＨＬＣ−８０２Ａ型高速ＧＰＣ（カラムＧ７００
０Ｈ６→Ｇ６０００Ｈ６→Ｇ５０００Ｈ６→Ｇ４０００
Ｈ８）で流速１．０ ｍｅ／ｓｉｎにて測定した。得ら
れたＺ平均分子量はポリスチレン換算Ｚ平均分子量であ
る。Gel permeation chromatography measurements were performed using tetrahydrofuran as a solvent and a high-speed GPC (column G700) model HLC-802A manufactured by Tosoichi Co., Ltd. at a temperature of 38°C.
0H6→G6000H6→G5000H6→G4000
H8) at a flow rate of 1.0 me/sin. The obtained Z average molecular weight is a polystyrene equivalent Z average molecular weight.
（２）ムーニー粘度（ＭＬ、や４ （１００°Ｃ） ）
ＪＩＳ−に６３８３に従って測定した。(2) Mooney viscosity (ML, Ya4 (100°C))
Measured according to JIS-6383.
実施例１
トルエン７５００ｇに１．３−ブタジェン１５００ｇを
加え、一方窒素ガスで置換したガラス製３００ｄの耐圧
瓶に、ナフテン酸ニッケルトルエン溶液をニッケル換算
で０．００３４ｐｈｍ、三フッ化ホウ素エーテラートト
ルエン溶液を三フッ化ホウ素として０．０４５０ｐｈｍ
、）リエチルアルミニウムトルエン溶液を０．０５０２
ｐｈｍの各々を加え、２０℃で６０分間静置して熟成し
たものを、先に準備したトルエン／１，３−ブタジェン
に加えた後、６０ ”Ｃ下で１２０分間撹拌して１゜３
−ブタジェンの重合反応を行わせた。重合反応終了後、
重合溶液に少量の２．６−ジ第三ブチルパラクレゾール
を含むメタノールを注入して重合を停止させ、次いでス
チームストリッピングして溶媒を除去し、重合体をクラ
ムとして回収し、１２０″Ｃの熱ロールで乾燥してポリ
ブタジェンを得た。得られたポリブタジェンのＧＰＣパ
ターンを第１図に示す、得られたポリブタジェンのムー
ニー粘度、Ｚ平均分子量、シス含量およびムーニー粘度
とＺ平均分子量の比を第１表に示す。Example 1 Add 1,500 g of 1,3-butadiene to 7,500 g of toluene, and place a nickel naphthenate toluene solution at 0.0034 phm in terms of nickel and a boron trifluoride etherate toluene solution in a 300 d glass pressure bottle that was purged with nitrogen gas. 0.0450 phm as boron trifluoride
,)0.0502 ethylaluminum toluene solution
After adding each phm and leaving it for 60 minutes at 20°C to mature, add it to the previously prepared toluene/1,3-butadiene, stir at 60"C for 120 minutes, and heat to 1°3.
- A polymerization reaction of butadiene was carried out. After the polymerization reaction is completed,
The polymerization was stopped by injecting a small amount of 2,6-di-tert-butyl para-cresol in methanol into the polymerization solution, then the solvent was removed by steam stripping, the polymer was recovered as crumbs, and the polymerization was heated at 120″C. Polybutadiene was obtained by drying with a hot roll. The GPC pattern of the obtained polybutadiene is shown in Figure 1. It is shown in Table 1.
実施例２〜５
実施例１において三フッ化ホウ素エーテラート、触媒熟
成温度および重合温度を第１表に示す値に変えた以外は
、実施例１と同じ条件下で実施し、それぞれポリブタジ
ェンを得た。得られたポリブタジェンのムーニー粘度、
Ｚ平均分子量、シス含量およびムーニー粘度とＺ平均分
子量の比を第１表に示す。Examples 2 to 5 Polybutadiene was obtained under the same conditions as in Example 1, except that the boron trifluoride etherate, catalyst aging temperature, and polymerization temperature were changed to the values shown in Table 1. . Mooney viscosity of the obtained polybutadiene,
The Z average molecular weight, cis content and ratio of Mooney viscosity to Z average molecular weight are shown in Table 1.
比較例１
実施例１においてトルエン７５００ｇの代わりにトルエ
ン３７５０ｇおよびヘプタン３７５０ｇを用い、触媒系
の量、熟成温度、重合条件を第１表に示す値に変えた以
外は、実施例１と同様の条件下でポリブタジェンを得た
。得られたポリブタジェンのムーニー粘度、Ｚ平均分子
量、シス含量およびムーニー粘度とＺ平均分子量の比を
第１表に示す。Comparative Example 1 The same conditions as in Example 1 except that 3750 g of toluene and 3750 g of heptane were used instead of 7500 g of toluene in Example 1, and the amount of catalyst system, aging temperature, and polymerization conditions were changed to the values shown in Table 1. Polybutadiene was obtained below. Table 1 shows the Mooney viscosity, Z average molecular weight, cis content, and ratio of Mooney viscosity to Z average molecular weight of the polybutadiene obtained.
比較例２
実施例１において触媒系の量、熟成温度、重合条件を第
１表に示す値に変えた以外は、実施例１と同様の条件下
でポリブタジェンを得た。この例は、特に熟成温度を高
くしたものである。得られたポリブタジェンのムーニー
粘度、２平均分子量、シス含量およびムーニー粘度とＺ
平均分子量の比を第１表に示す。Comparative Example 2 Polybutadiene was obtained under the same conditions as in Example 1, except that the amount of catalyst system, aging temperature, and polymerization conditions were changed to the values shown in Table 1. In this example, the aging temperature was particularly high. Mooney viscosity, 2 average molecular weight, cis content, Mooney viscosity and Z of the obtained polybutadiene
The average molecular weight ratios are shown in Table 1.
比較例３
トルエン７５００ｇに１．３−ブタジェン１５００ｇを
加え、次いで水０．０３９ｐｈｍ、ジエチルアルミニウ
ムモノクロライド（ＤＥＡＣ））ルエン溶液０．５０ｐ
ｈｍおよびオクテン酸コバルトトルエン溶液をコバルト
換算で０．００２ｐｈｍを加えた後、６０°Ｃ下で１２
０分間攪拌して１．３−ブタジェンの重合反応を行わせ
た。重合反応終了後は実施例１と同様に処理しポリブタ
ジェンを得た。得られたポリブタジェンのムーニー粘度
、Ｚ平均分子量、シス含量およびムーニー粘度と２平均
分子量の比を第２表に示す。Comparative Example 3 Add 1,3-butadiene 1,500 g to 7,500 g of toluene, then add 0.039 phm of water and 0.50 p of diethyl aluminum monochloride (DEAC) toluene solution.
After adding 0.002 phm (calculated as cobalt) to the toluene solution of cobalt octenoate and
The mixture was stirred for 0 minutes to carry out a polymerization reaction of 1,3-butadiene. After the polymerization reaction was completed, the same treatment as in Example 1 was carried out to obtain polybutadiene. The Mooney viscosity, Z average molecular weight, cis content, and ratio of Mooney viscosity to 2 average molecular weight of the obtained polybutadiene are shown in Table 2.
比較例４および５
比較例３において水を第１表に示す値に変えた以外は、
比較例３と同じ条件下で実施して、それぞれのポリブタ
ジェンを得た。得られたポリブタジェンのムーニー粘度
、Ｚ平均分子量、シス含量およびムーニー粘度とＺ平均
分子量の比を第２表に示す。Comparative Examples 4 and 5 Except for changing the water to the values shown in Table 1 in Comparative Example 3,
It was carried out under the same conditions as in Comparative Example 3 to obtain each polybutadiene. Table 2 shows the Mooney viscosity, Z average molecular weight, cis content, and ratio of Mooney viscosity to Z average molecular weight of the obtained polybutadiene.
比較例６〜１１
市販のポリブタジェンの各種を掲げ、これらのポリブタ
ジェンのムーニー粘度、Ｚ平均分子量、シス含量および
ムーニー粘度とＺ平均分子量の比を第３表に示す。比較
例１１のポリブタジェンのＧＰＣパターンを第２図に示
す。Comparative Examples 6 to 11 Various types of commercially available polybutadiene are listed, and the Mooney viscosity, Z average molecular weight, cis content, and ratio of Mooney viscosity to Z average molecular weight of these polybutadiene are shown in Table 3. The GPC pattern of polybutadiene of Comparative Example 11 is shown in FIG.
第３表
実施例１〜５、比較例１〜１１のポリブタジェンを用い
て下記により配合物を製造し、押出加工性を評価した。Using the polybutadienes of Examples 1 to 5 and Comparative Examples 1 to 11 in Table 3, blends were produced as described below, and their extrusion processability was evaluated.
先ず、下表に示した配合処方により、ノンプロＩりはＢ
型バンバリーにて、プロ練りはＡＳＴＭ（Ｄ１５−６６
７）規定の６インチロールを用いて配合物を得た。First, according to the formulation shown in the table below, Non-Pro I is B.
Professional kneading is performed using ASTM (D15-66) at Banbury.
7) A formulation was obtained using a regular 6 inch roll.
（注） １） ： Ａ社品
２）：〃
３）：〃
評価：
４）２８社品 １
２、 ５）：〃２
３、６）：Ａ社品 ４
１、
注） （１） ： Ｎ−オキシジエチレン−２−ベンゾ
チアゾールスルフォンアミド
得られた配合物をＡＳＴＭ
Ｄ２２３０−８３に
準拠して押出加工性（形状の試験）
果を第４表に示す。(Note) 1): Company A product 2):〃 3):〃 Evaluation: 4) 28 company product 1 2, 5):〃2 3, 6): Company A product 4 1, Note) (1): N -Oxydiethylene-2-benzothiazolesulfonamide The results of the extrusion processability (shape test) of the resulting formulation are shown in Table 4 in accordance with ASTM D2230-83.
第４表
を評価した結
注”） （１） ： ３０°エツヂの鋭さと連続性を最
高１０点、最低１点で採点。Conclusion on evaluating Table 4 (1): Score the sharpness and continuity of the 30° edge with a maximum of 10 points and a minimum of 1 point.
（２）：表面肌の平滑性を最高Ａ、最低Ｅで採点。(2): Scoring the smoothness of the surface skin with a maximum of A and a minimum of E.
次に、実施例１〜５、比較例１〜１１のポリブタジェン
を用いて、生ゴムロール加工性を評価した。評価方法は
、ロール表面温度は５０±２°Ｃ３０−ル間隙は１．５
閣、ガイド幅は２５ｆｆｉＩ１１およびロール回転速度
はフロントロール １８ｒｐｍ、バックロール ２１ｒ
ｐｍの条件に設定し、６インチ型練りロール機を用いて
ポリブタジェン４００ｇを５分間巻き付かせ、巻き付き
状況を観察した。その結果を第５表に示す。Next, the raw rubber roll processability was evaluated using the polybutadienes of Examples 1 to 5 and Comparative Examples 1 to 11. The evaluation method is that the roll surface temperature is 50±2°C, and the roll gap is 1.5.
The guide width is 25ffi11 and the roll rotation speed is front roll 18 rpm, back roll 21r.
pm, 400 g of polybutadiene was wound for 5 minutes using a 6-inch kneading roll machine, and the state of the wrapping was observed. The results are shown in Table 5.
以下余白
Ｔ ； （Ｔｉｇｈｔ）ゴムがロールにぴったりと巻き
付いた状態。Below is the margin T; (Tight) The state in which the rubber is tightly wrapped around the roll.
Ｃ； （Ｃｒｕｎ＋ｂｌｉｎｇ）ゴムのシート面に穴ま
たは裂は目ができる状態。C: (Crun+bling) Holes or cracks appear on the rubber sheet surface.
Ｆ ； （Ｆｏｌｄｉｎｇ）ロールに巻き付いたゴムが
ロール間隙に入る直前でロール表面か
ら浮き上がる状態
Ｂ ； （Ｂａｇｇｙ） ロール下部にゴムシートが
ロールを離れて垂れ下がる状態。F: (Folding) A state in which the rubber wrapped around the roll lifts off the roll surface just before entering the gap between the rolls B; (Baggy) A state in which the rubber sheet leaves the roll and hangs down at the bottom of the roll.
本発明のポリブタジェンによれば、優れた加工性（押出
加工性、ロール加工性）が得られ、各種工業用品、スポ
ーツ用品等に極めて有用なポリブタジェンを提供するこ
とができる。According to the polybutadiene of the present invention, excellent processability (extrusion processability, roll processability) can be obtained, and it is possible to provide polybutadiene that is extremely useful for various industrial products, sporting goods, etc.
第１図は、実施例１で得られたＧＰＣパターン図、第２
図は比較例１１で得られたＧＰＣパターン図である。
特許出願人 日本合成ゴム株式会社
代理人 弁理士 川 北 武 長
汀） （１） ：巻き付き状況は次により評価した。Figure 1 is a GPC pattern diagram obtained in Example 1,
The figure is a GPC pattern diagram obtained in Comparative Example 11. Patent Applicant: Japan Synthetic Rubber Co., Ltd. Representative, Patent Attorney: Takeshi Kawakita) (1): The wrapping condition was evaluated as follows.
Claims (2)
１，４構造含有率が０．５〜７．５％、１，２構造含有
率が０．５〜７．５％であり、ムーニー粘度〔ＭＬ＿１
＿＋＿４（１００℃）〕が２０〜１００で、かつ分子量
分布曲線が単一のピークをもち、Ｚ平均分子量（Ｍｚ）
とムーニー粘度の比（Ｍｚ／ムーニー粘度）が３．０×
１０＾４以上であるポリブタジエン。(1) The cis 1,4 structure content is 85 to 99%, the trans 1,4 structure content is 0.5 to 7.5%, and the 1,2 structure content is 0.5 to 7.5%. , Mooney viscosity [ML_1
＿+＿4(100℃)] is 20 to 100, and the molecular weight distribution curve has a single peak, and the Z average molecular weight (Mz)
and Mooney viscosity ratio (Mz/Mooney viscosity) is 3.0×
Polybutadiene with a molecular weight of 10^4 or more.
を用いて製造される請求項（１）記載のポリブタジエン
。(2) The polybutadiene according to claim (1), which is produced using a catalyst containing an organoaluminum and a nickel compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24352488A JPH0291105A (en) | 1988-09-28 | 1988-09-28 | Polybutadiene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24352488A JPH0291105A (en) | 1988-09-28 | 1988-09-28 | Polybutadiene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0291105A true JPH0291105A (en) | 1990-03-30 |
Family
ID=17105187
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24352488A Pending JPH0291105A (en) | 1988-09-28 | 1988-09-28 | Polybutadiene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0291105A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010086972A (en) * | 2005-04-08 | 2010-04-15 | Toshiba Lighting & Technology Corp | Self-ballasted lamp |
| US7758223B2 (en) | 2005-04-08 | 2010-07-20 | Toshiba Lighting & Technology Corporation | Lamp having outer shell to radiate heat of light source |
| US8360606B2 (en) | 2009-09-14 | 2013-01-29 | Toshiba Lighting & Technology Corporation | Light-emitting device and illumination device |
| US8998457B2 (en) | 2009-09-25 | 2015-04-07 | Toshiba Lighting & Technology Corporation | Self-ballasted lamp and lighting equipment having a support portion in contact with an inner circumference of a base body |
| JP2015189971A (en) * | 2014-03-31 | 2015-11-02 | 宇部興産株式会社 | polybutadiene |
-
1988
- 1988-09-28 JP JP24352488A patent/JPH0291105A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010086972A (en) * | 2005-04-08 | 2010-04-15 | Toshiba Lighting & Technology Corp | Self-ballasted lamp |
| JP2010086973A (en) * | 2005-04-08 | 2010-04-15 | Toshiba Lighting & Technology Corp | Self-ballasted lamp |
| US7758223B2 (en) | 2005-04-08 | 2010-07-20 | Toshiba Lighting & Technology Corporation | Lamp having outer shell to radiate heat of light source |
| US8858041B2 (en) | 2005-04-08 | 2014-10-14 | Toshiba Lighting & Technology Corporation | Lamp having outer shell to radiate heat of light source |
| US9080759B2 (en) | 2005-04-08 | 2015-07-14 | Toshiba Lighting & Technology Corporation | Lamp having outer shell to radiate heat of light source |
| US9772098B2 (en) | 2005-04-08 | 2017-09-26 | Toshiba Lighting & Technology Corporation | Lamp having outer shell to radiate heat of light source |
| US8360606B2 (en) | 2009-09-14 | 2013-01-29 | Toshiba Lighting & Technology Corporation | Light-emitting device and illumination device |
| US8998457B2 (en) | 2009-09-25 | 2015-04-07 | Toshiba Lighting & Technology Corporation | Self-ballasted lamp and lighting equipment having a support portion in contact with an inner circumference of a base body |
| JP2015189971A (en) * | 2014-03-31 | 2015-11-02 | 宇部興産株式会社 | polybutadiene |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU649204B2 (en) | High performance segmented elastomer | |
| KR880004017A (en) | Rubber composition | |
| KR101511188B1 (en) | Polybutadiene grafted isoprene rubber, preparation method thereof, and vulcanizate and mixed compound therefrom | |
| JPS59187041A (en) | Styrene-butediene copolymer rubber composition | |
| JP4123019B2 (en) | Cis-1,4-polybutadiene and method for producing the same | |
| US3281389A (en) | Processing of cis polybutadiene rubber by compounding with liquid polybutadienes | |
| CN104628963A (en) | Polyisoprene, preparation method thereof and vulcanized rubber | |
| JPH0291105A (en) | Polybutadiene | |
| US4577002A (en) | Elastomeric copolymers, their preparation and their use | |
| JPH04249511A (en) | Segmented elastomer | |
| CN110536930B (en) | Shrink sleeve material with inherent non-stick properties | |
| JPH093129A (en) | Production of polybutadiene rubber | |
| JP3102930B2 (en) | Hydrogenated butadiene copolymer | |
| CN110305240B (en) | Preparation method of polybutadiene oligomer, grafting modifier and rare earth isoprene rubber | |
| CN110294869B (en) | Polybutadiene, preparation method thereof and vulcanized rubber | |
| CN112210128B (en) | Tire sidewall rubber material based on gradient block lithium BIR and preparation method thereof | |
| JPH08325330A (en) | New cis-1,4-polybutadiene rubber, its production and rubber composition | |
| JP5447709B2 (en) | Method for producing vinyl cis-polybutadiene | |
| JPH03103454A (en) | Tire having tread formed from new rubbery copolymer | |
| JPH01135844A (en) | Rubber composition for tire | |
| CN106977636A (en) | A kind of trans polycyclic amylene rubber of liquid and its preparation method and application | |
| CN113563547A (en) | SEBS (styrene-ethylene-butylene-styrene) with sandwich layered structure, preparation method thereof and application thereof in heat sealing film | |
| JPH0559925B2 (en) | ||
| DE112019003785T5 (en) | MANUFACTURING PROCESS FOR AROMATIC VINYL-DIENE COPOLYMER AND MANUFACTURING PROCESS FOR RUBBER COMPOSITION | |
| CN112646083A (en) | Preparation method of toughening agent of polystyrene |