JPH04154820A - Polymerization for polybutadiene - Google Patents
Polymerization for polybutadieneInfo
- Publication number
- JPH04154820A JPH04154820A JP27932990A JP27932990A JPH04154820A JP H04154820 A JPH04154820 A JP H04154820A JP 27932990 A JP27932990 A JP 27932990A JP 27932990 A JP27932990 A JP 27932990A JP H04154820 A JPH04154820 A JP H04154820A
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- butadiene
- compound
- cis
- aging
- 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
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 78
- 239000005062 Polybutadiene Substances 0.000 title description 14
- 229920002857 polybutadiene Polymers 0.000 title description 14
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 230000032683 aging Effects 0.000 claims abstract description 20
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 11
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 150000001869 cobalt compounds Chemical class 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract 1
- IZMHKHHRLNWLMK-UHFFFAOYSA-M chloridoaluminium Chemical compound Cl[Al] IZMHKHHRLNWLMK-UHFFFAOYSA-M 0.000 abstract 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 239000000499 gel Substances 0.000 description 10
- 230000005070 ripening Effects 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- -1 for example Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- BJZQPUBYOZDEHI-UHFFFAOYSA-M Cl(=O)[O-].C(C)[Al+]CC Chemical compound Cl(=O)[O-].C(C)[Al+]CC BJZQPUBYOZDEHI-UHFFFAOYSA-M 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- BKFAZDGHFACXKY-UHFFFAOYSA-N cobalt(II) bis(acetylacetonate) Chemical compound [Co+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O BKFAZDGHFACXKY-UHFFFAOYSA-N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- VJRUISVXILMZSL-UHFFFAOYSA-M dibutylalumanylium;chloride Chemical compound CCCC[Al](Cl)CCCC VJRUISVXILMZSL-UHFFFAOYSA-M 0.000 description 1
- HRGXHRPMGDCKQM-UHFFFAOYSA-L dichlorocobalt;pyridine Chemical compound Cl[Co]Cl.C1=CC=NC=C1 HRGXHRPMGDCKQM-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、シス−２−ブテンを主成分とするＣ４留分を
重合溶媒として１，３−ブタジエンを重合する、高シス
−１，４−ポリブタジエンの製造方法に関する。Detailed Description of the Invention [Industrial Field of Application] The present invention is directed to the polymerization of high cis-1,4-butadiene in which 1,3-butadiene is polymerized using a C4 fraction containing cis-2-butene as a main component as a polymerization solvent. -Regarding a method for producing polybutadiene.
１．３−ブタジエンを、チーグラー・ナツタ系触媒を用
いて高シス−１，４−重合する際の重合溶媒として、従
来はベンゼン、トルエン、ヘキサン等か一般的に用いら
れてきた。しかし、これらの溶媒を重合溶媒として用い
た場合、得られる重合溶液の粘度か高くなるので、攪拌
、伝熱、移送等か困難になるという問題があった。又、
これらの溶媒は沸点が高いため、重合溶液からの回収が
困難であった。Conventionally, benzene, toluene, hexane, etc. have been commonly used as a polymerization solvent for high cis-1,4-polymerization of 1,3-butadiene using a Ziegler-Natsuta catalyst. However, when these solvents are used as polymerization solvents, the resulting polymerization solution has a high viscosity, making stirring, heat transfer, transportation, etc. difficult. or,
Since these solvents have high boiling points, it has been difficult to recover them from the polymerization solution.
上記の問題点を解決するため、ベンゼンやトルエン、ヘ
キサンの替わりに、シス−２−ブテンを主成分とするＣ
４留分を重合溶媒として用いることが試みられた。In order to solve the above problems, instead of benzene, toluene, and hexane, C
Attempts were made to use the four fractions as polymerization solvents.
シス−２−ブテンを主成分とするＣ４留分を重合溶媒と
する重合方法としては、例えば、水とジエチルアルミニ
ウムクロライドをベンゼン中で予め反応させてクロルエ
チルアルミノキサンを得、これにコバルト化合物を添加
して触媒とし、上記のＣ４留分を溶媒として１． ３−
ブタジエンを重合するという方法（特公昭４４−５２３
８）か試みられた。As a polymerization method using a C4 fraction containing cis-2-butene as a main component as a polymerization solvent, for example, water and diethylaluminum chloride are reacted in advance in benzene to obtain chloroethylaluminoxane, and a cobalt compound is added to this. Using the above C4 fraction as a solvent, 1. 3-
A method of polymerizing butadiene (Japanese Patent Publication No. 44-523
8) was attempted.
又、沸点１５０℃以上のパラフィン系炭化水素中でコバ
ルト化合物−水一有機アルミニウム化合物触媒を調製し
、上記のＣ４留分を溶媒として１゜３−ブタジエンを重
合するという重合方法か試みられた（特公昭４７−１）
８１０）。In addition, a polymerization method was attempted in which a cobalt compound-water-organoaluminum compound catalyst was prepared in a paraffinic hydrocarbon having a boiling point of 150°C or higher, and 1°3-butadiene was polymerized using the above C4 fraction as a solvent ( Tokuko Sho 47-1)
810).
更に、１． ３−ブタジエンを精留するときに缶出液と
して得られる炭化水素か１．２−ブタジエンを含有して
いるので、これを分子量調節剤及び重合溶媒の補填剤と
して、重合溶液に添加することも試みられた（特公昭４
９−１８６３５）。Furthermore, 1. Since it contains 1,2-butadiene, a hydrocarbon obtained as the bottoms when rectifying 3-butadiene, it can also be added to the polymerization solution as a molecular weight regulator and a supplement for the polymerization solvent. Attempted (Tokuko Sho 4)
9-18635).
これらの方法においては、シス−２−ブテンを主成分と
するＣ４留分を重合溶媒に用いることにより重合溶液の
粘度が大きく低下し、攪拌、伝熱、移送等はずっと容易
になった。又、溶媒の沸点も低いので、溶媒の回収も容
易になった。In these methods, by using a C4 fraction containing cis-2-butene as a main component as a polymerization solvent, the viscosity of the polymerization solution is greatly reduced, making stirring, heat transfer, transportation, etc. much easier. Furthermore, since the boiling point of the solvent was low, recovery of the solvent was also facilitated.
しかし、ゲル含有量の低減という点ては不十分であり、
ゲル含量０．２％以上のゲル含量の高いポリブタジェン
しか得られなかった。However, the reduction in gel content is insufficient;
Only polybutadiene with a high gel content of 0.2% or more was obtained.
又、触媒をベンゼンやパラフィン中で調製してからＩ、
３−ブタジエンの重合溶媒溶液に添加する方法にお
いては、工業的実施には経済性の面で問題かあった。Alternatively, after preparing the catalyst in benzene or paraffin,
In the method of adding 3-butadiene to a polymerization solvent solution, there were problems in terms of economic efficiency for industrial implementation.
本発明は、シス−２−ブテンを主成分とするＣ４留分を
重合溶媒とする高シス−１，４−ポリブタジエンの製造
方法において、ゲル含有量の少ないポリブタジェンか得
られ、且つ経済性にも優れた製造方法を提供することを
目的とする。The present invention provides a method for producing high cis-1,4-polybutadiene using a C4 fraction containing cis-2-butene as the main component, which produces polybutadiene with a low gel content and is also economical. The purpose is to provide an excellent manufacturing method.
本発明の重合法は以下の通りである。 The polymerization method of the present invention is as follows.
即ち、シス−２−ブテンを主成分とするＣ４留分を重合
溶媒として、コバルト化合物−水一有機アルミニウム化
合物系の触媒により、ｌ、３−ブタジエンを重合し、高
シス−１，４−ポリブタジエンを製造する方法であって
、
■１．３−ブタジエンの重合溶媒溶液中、有機アルミニ
ウム化合物と水を、
θ≧１０１ｆ＋２７０／Ｔゝ−３６６Ｊθ：熟成時間（
分）
Ｔ、熟成温度（Ｋ）
て示される時間θの間熟成しくこの段階の溶液を以下「
熟成液」という）、
■次いでコバルト化合物を添加して、１． ３−ブタジ
エンを重合し、
■次いで、熟成液を追加供給して重合を継続することを
特徴とする、
シス−１，４−ポリブタジエンの重合方法である。That is, 1,3-butadiene is polymerized using a C4 fraction containing cis-2-butene as a main component as a polymerization solvent with a cobalt compound-water-organoaluminum compound catalyst to form high-cis-1,4-polybutadiene. 1. An organoaluminum compound and water in a polymerization solvent solution of 1.3-butadiene, θ≧101f+270/Tゝ-366Jθ: Aging time (
The solution at this stage is aged for a time θ given by T, aging temperature (K), and the solution at this stage is referred to as "
(referred to as "ripening liquid"); 1. Next, a cobalt compound is added, and 1. This is a method for polymerizing cis-1,4-polybutadiene, which is characterized in that 3-butadiene is polymerized, and (1) a ripening liquid is additionally supplied to continue the polymerization.
最初に、本発明の重合方法の各工程について説明する。First, each step of the polymerization method of the present invention will be explained.
先ず、熟成工程においては、熟成時間θは、θ≧ｌθ°
＋２７０／Ｔゝ−″、 ６ｇ１θ、熟成時間（分）
Ｔ：熟成温度（Ｋ）
の範囲でなくではならない。First, in the aging process, the aging time θ is θ≧lθ°
+270/Tゝ-'', 6g1θ, ripening time (minutes) T: ripening temperature (K).
熟成時間か
θ ＝ ＋ ０１＋１３７０／丁１−Ｌ６ｇ＋で示
されるθよりも短いと、Ｉ、３−ブタジエン、水、及び
有機アルミニウム化合物の接触により生じたカチオンが
充分失活しない。このため、その後の重合工程において
ゲルか発生し易（なり、本発明の効果か得られなくなる
。If the aging time is shorter than θ, which is expressed as θ=+01+1370/1−L6g+, the cations produced by contact of I, 3-butadiene, water, and the organoaluminum compound will not be sufficiently deactivated. For this reason, a gel is likely to be generated in the subsequent polymerization step (and the effects of the present invention cannot be obtained).
熟成温度は一１０〜６０°Ｃの範囲か好ましく、０〜５
０°Ｃの範囲か特に好ましい。熟成温度か一１０°Ｃよ
り低いと熟成時間θが長くなり過ぎるので好ましくない
。又、熟成温度か６０°Ｃを越えると、触媒の重合活性
か低下するので好ましくない。The ripening temperature is preferably in the range of 10 to 60°C, and 0 to 5°C.
A range of 0°C is particularly preferred. If the ripening temperature is lower than -10°C, the ripening time θ becomes too long, which is not preferable. Furthermore, if the aging temperature exceeds 60°C, the polymerization activity of the catalyst will decrease, which is not preferable.
１．３−ブタジエン、溶媒、水、及び有機アルミニウム
化合物の割合は、次の通りである。The proportions of 1.3-butadiene, solvent, water, and organoaluminum compound are as follows.
１．３−ブタジエンの割合は１０〜７０重量％の範囲か
好ましい。特に好ましい範囲は２０〜５０重量％である
。１．３−ブタジエンの割合か７０重量％より高い場合
は重合反応の制御が困難となり、又熟成段階でカチオン
ポリマーの析出か多くなるので好ましくない。又、１０
重量部より低い場合はポリブタジェンを効率良く製造で
きなくなる。The proportion of 1,3-butadiene is preferably in the range of 10 to 70% by weight. A particularly preferred range is 20 to 50% by weight. If the proportion of 1,3-butadiene is higher than 70% by weight, it is not preferable because it becomes difficult to control the polymerization reaction and more cationic polymers precipitate during the ripening stage. Also, 10
If it is lower than parts by weight, polybutadiene cannot be efficiently produced.
有機アルミニウム化合物の割合は、１．３−ブタジエン
１ｍｏｊ７に対して、０．１〜１０ｍｍｏｊ７の範囲か
好ましく、０．２〜８ｍｍｏ＃の範囲か特に好ましい。The ratio of the organoaluminum compound is preferably in the range of 0.1 to 10 mmoj7, particularly preferably in the range of 0.2 to 8 mmo#, per moj7 of 1.3-butadiene.
水の割合は、有機アルミニウム化合物１ｍｏｊ？当たり
好ましくは０．１〜１ｍｏｊ２．特に好ましくは０．２
〜０．７ ｍ ｏ Ｉ！の範囲である。The proportion of water is 1 moj of organoaluminum compound? Preferably 0.1 to 1 moj2. Particularly preferably 0.2
~0.7 m o I! is within the range of
次に重合工程について説明する。Next, the polymerization process will be explained.
重合は、上記の熟成液にコバルト化合物を添加して行う
。そして、重合中に少なくとも１回、熟成液を添加する
。Polymerization is performed by adding a cobalt compound to the above-mentioned aging solution. A maturing solution is then added at least once during the polymerization.
重合は単一の重合槽で行ってもよい。又、２以上の重合
槽を直列に用いて連続的に重合を行ってもよい。２槽以
上の重合槽を直列に用いて重合を行う場合は、熟成液を
２槽目以降の重合槽に添加することか好ましい。Polymerization may be carried out in a single polymerization tank. Alternatively, two or more polymerization tanks may be used in series to carry out the polymerization continuously. When polymerization is carried out using two or more polymerization tanks in series, it is preferable to add the aging liquid to the second and subsequent polymerization tanks.
重合温度は０〜８０°Ｃの範囲が好ましく、１０〜７０
°Ｃの範囲か特に好ましい。The polymerization temperature is preferably in the range of 0 to 80°C, and 10 to 70°C.
℃ range is particularly preferred.
次に、本発明で使用する重合溶媒、及び触媒等について
説明する。Next, the polymerization solvent, catalyst, etc. used in the present invention will be explained.
重合溶媒は、シス−２−ブテンを主成分とするＣ４留分
からなる。このＣ４留分はシス−２−ブテンとトランス
−２−ブテンの含有量の合計が５０重量９６以」二であ
ることか好ましい。そして、ラス−２−ブテン、トラン
ス−２−ブテンの他に、ｎ−ブタン、ブテン−１、プロ
パン、エタン等の炭化水素を含んでいてもよい。特に好
ましいのは、実質的にシス−２−ブテンとトランス−２
−ブテンからなるものである。但し、シス−２−ブテン
とトランス−２−ブテンの含有量の合計が５０重量％よ
りも少ないＣ４留分はポリブタジェンの溶解性か低いの
で、重合溶液か不均一になりやすい。The polymerization solvent consists of a C4 fraction containing cis-2-butene as a main component. It is preferable that the total content of cis-2-butene and trans-2-butene in this C4 fraction is 50% by weight or more. In addition to ras-2-butene and trans-2-butene, it may also contain hydrocarbons such as n-butane, butene-1, propane, and ethane. Particularly preferred is substantially cis-2-butene and trans-2
- It consists of butene. However, since the C4 fraction in which the total content of cis-2-butene and trans-2-butene is less than 50% by weight has a low solubility of polybutadiene, the polymerization solution tends to be non-uniform.
従って、重合溶媒としては好ましくない。重合溶液か不
均一になると、ゲルか発生しやすくなるからである。Therefore, it is not preferred as a polymerization solvent. This is because if the polymerization solution becomes non-uniform, gels tend to form.
尚、ポリブタジェン製造プラントを長期運転すると、１
．３−ブタジエンの不純物であるシス−２−ブテンが溜
まってくるか、これも、重合溶媒として好ましく用いる
ことかできる。In addition, if a polybutadiene production plant is operated for a long time, 1
．． Cis-2-butene, which is an impurity of 3-butadiene, accumulates and can also be preferably used as a polymerization solvent.
コバルト化合物としては、有機酸塩や錯化合物、或いは
塩化物か好ましく用いられる。具体的には、コバルトオ
クトエート、コバルトナフテート、コバルトドリアセチ
ルアセトネート、塩化コバルトピリジン錯体、塩化コバ
ルトｌ・リフェニルホスフィン錯体、等の化合物が特に
好ましい。As the cobalt compound, an organic acid salt, a complex compound, or a chloride is preferably used. Specifically, compounds such as cobalt octoate, cobalt naphtate, cobalt diacetylacetonate, cobalt chloride pyridine complex, and cobalt chloride/liphenylphosphine complex are particularly preferred.
有機アルミニウム化合物としては、
Ａ Ａ Ｒ、、ＣＡ’ ５−０
（Ｒはアルキル、シクロアルキル、又はアリール基、ｎ
は１．５〜２）、
なる−紋穴で表されるものが特に好ましい。As the organoaluminum compound, A A R,, CA' 5-0 (R is an alkyl, cycloalkyl, or aryl group, n
is 1.5 to 2), and those represented by the following symbol are particularly preferable.
このようなものとしては、具体的にはジエチルアルミニ
ウムモノクロライト、ジ−ｎ−ブチルアルミニウムモノ
クロライド、ジ−イソブチルアルミニウムモノクロライ
ド、エチルアルミニウムセスキクロライド、等の化合物
かある。Specific examples of such compounds include compounds such as diethylaluminum monochlorite, di-n-butylaluminum monochloride, di-isobutylaluminum monochloride, and ethylaluminum sesquichloride.
このほか、重合溶液には、必要に応じて、ｌ。In addition, l may be added to the polymerization solution as needed.
５−シクロオクタジエンや１，２−ブタジエン等の既知
の分子量調節剤、及び／又はゲル防止剤を添加してもよ
い。Known molecular weight regulators such as 5-cyclooctadiene and 1,2-butadiene and/or anti-gelling agents may be added.
以下、実施例により、本発明を具体的に説明する。Hereinafter, the present invention will be specifically explained with reference to Examples.
以下に本発明の実施例を示す。 Examples of the present invention are shown below.
実施例１
水分を４５ｍｇ（２，５ｍｍｏｊ？）／ｊ？の割合で含
み、且つ１．３−ブタジエン３０重量９６、シス−２−
ブテン５６重量９６、トランス−２−ブテン１３重量％
、残りがｎ−ブタン、プロパン、エタン等からなる１、
３−ブタジエンの重合溶媒溶液を、内容積３．Ｏｐの攪
拌機付熟成槽に毎時８，５１の割合で供給し、ジエチル
アルミニウムモノクロライドを毎時３．９１ ｇ （３
２，４ｍｍｏＡ）の割合で供給し、この混合液を３５°
Ｃで２１分間（平均滞留時間）熟成した。Example 1 45 mg (2.5 mmoj?)/j? of water and 1,3-butadiene 30% by weight, 96% by weight, cis-2-
Butene 56% by weight, 96% by weight, trans-2-butene 13% by weight
, the remainder consists of n-butane, propane, ethane, etc. 1,
A polymerization solvent solution of 3-butadiene was added to an internal volume of 3. Diethylaluminum monochloride was fed to the ripening tank with a stirrer at a rate of 8.51 g/hr, and 3.91 g (3.91 g/hr) of diethylaluminum monochloride was
2.4 mmoA), and the mixture was heated at 35°
Aged for 21 minutes (average residence time) at C.
得られた熟成液を内容積５１の攪拌機付第１重合槽に毎
時７，５βの割合で供給し、１，２−ブタジエンを毎時
２．４４ ｇ （４５，１ｍｍｏｊ７） 、コバルトオ
クトエートを毎時３０■（０，０８７ｒｎｍ。The obtained aged liquid was supplied to a first polymerization tank with an internal volume of 51 and equipped with a stirrer at a rate of 7.5β per hour, and 1,2-butadiene was supplied at a rate of 2.44 g (45.1 mmoj7) per hour, and cobalt octoate was supplied at a rate of 30 g per hour. ■(0,087rnm.
Ｉりの速度で供給し、重合温度４０°Ｃ１平均滞留時間
４０分の条件で、１，３−ブタジエンを重合した。この
重合液のポリマー濃度は１４重量％てあった。1,3-butadiene was polymerized at a polymerization temperature of 40 DEG C. and an average residence time of 40 minutes. The polymer concentration of this polymerization solution was 14% by weight.
第１重合槽で得られた重合溶液を、内容積５１の攪拌機
付の第２重合槽に毎時７．５１の割合で連続的に供給し
、熟成槽で得られた熟成液を毎時ＩＯ１，１，２−ブタ
ジエンを毎時１．４ｇ（２５，９ｍｍ０Ｉり、コバルト
オクトエートを４０■（０゜１）６ｍｍｏｊ？）供給し
、重合温度４０°Ｃ１平均滞留時間３５分間の条件で、
重合を継続した。この重合溶液のポリマー濃度は２３重
量％であった。The polymerization solution obtained in the first polymerization tank is continuously supplied to a second polymerization tank with an internal volume of 51 and equipped with a stirrer at a rate of 7.51 mL per hour, and the aged solution obtained in the aging tank is fed at a rate of 1.1 IO per hour. , 2-butadiene was fed at 1.4 g (25.9 mmOl) per hour, cobalt octoate was fed at 40 mm (0°1) 6 mmoj?, and the polymerization temperature was 40° C., and the average residence time was 35 minutes.
Polymerization was continued. The polymer concentration of this polymerization solution was 23% by weight.
この重合溶液を攪拌機付混合槽に連続的に供給し、これ
に２．６−ジーｔ−ブチルフェノール７゜５重量％のヘ
キサン溶液を毎時＋００ｉ＃０及び少量のメタノールを
混入して重合を呈した。この混合物に、３０容量％の水
を加えて攪拌、水洗して、水を分離した後、溶媒及びモ
ノマーを脱揮して、得られたポリマーを４０°Ｃで真空
乾燥し、ポリブタジェンを得た。This polymerization solution was continuously supplied to a mixing tank equipped with a stirrer, and a hexane solution of 7.5% by weight of 2.6-di-t-butylphenol was added every hour to +00i#0 and a small amount of methanol to effect polymerization. . After adding 30% by volume of water to this mixture, stirring and washing with water to separate the water, the solvent and monomer were devolatilized, and the resulting polymer was vacuum-dried at 40°C to obtain polybutadiene. .
２４時間連続運転して１時間当たりのポリブタジェンの
生成量は１．２１ ｋｇてあった。このポリブタジェン
のムーニー粘度ＭＬ＋＋＋ （１ｏｏ°Ｃ）は４３で
あり、シス−１，４−構造の含有量は９８゜３重量％で
あり、ゲル含有量は２■／ポリブタジ工ンＩＯｇ（０，
０２重量９６）であった。During continuous operation for 24 hours, the amount of polybutadiene produced per hour was 1.21 kg. The Mooney viscosity ML+++ (1oo°C) of this polybutadiene is 43, the content of cis-1,4-structure is 98°3% by weight, and the gel content is 2■/polybutadiene IOg (0,
02 weight 96).
本発明の重合法においては、１． ３−ブタジエンの重
合溶媒溶液に触媒成分である水と有機金属化合物を予め
添加して所定時間熟成し、熟成液とした後、遷移金属化
合物を加えて重合を行っている。これにより、ゲル化の
大きな因子の一つであるカチオンが失活し、重合時のゲ
ルの生成、及び重合槽内へのゲルの付着を防止できる。In the polymerization method of the present invention, 1. Water and an organometallic compound as catalyst components are added in advance to a polymerization solvent solution of 3-butadiene, and the solution is aged for a predetermined period of time to obtain a ripening liquid. After that, a transition metal compound is added and polymerization is performed. This deactivates cations, which are one of the major factors in gelation, and prevents the formation of gel during polymerization and the adhesion of gel into the polymerization tank.
又、重合中に上記の熟成液を添加し重合を継続するので
、重合溶液中のポリブタジェン濃度を従来の０４溶媒で
の重合の場合よりも高くしても、重合液中のゲルの発生
が殆どない。In addition, since the above-mentioned aging solution is added during polymerization to continue polymerization, even if the polybutadiene concentration in the polymerization solution is higher than that in conventional 04 solvent polymerization, gel generation in the polymerization solution is almost non-existent. do not have.
このため、ゲル含有量の極めて少ないポリブタジェンが
得られるだけでなく、重合溶液中のポリブタジェン濃度
を従来よりも高くできるので、経済性にも優れている。Therefore, not only can polybutadiene with an extremely low gel content be obtained, but also the polybutadiene concentration in the polymerization solution can be made higher than before, which is excellent in economical efficiency.
Claims (2)
合溶媒として、コバルト化合物−水−有機アルミニウム
化合物系の触媒により１，３−ブタジエンを重合し、高
シス−１，４−ポリブタジエンを製造する方法において
、 ［１］１，３−ブタジエンの重合溶媒溶液中、有機アル
ミニウム化合物と水を、 θ≧１０＾［＾（＾１＾３＾７＾０＾／＾Ｔ＾）＾−＾
３＾．＾６＾６＾］θ：熟成時間（分） Ｔ：熟成温度（Ｋ） で示される時間θの間熟成し、熟成液とし、 ［２］次いでコバルト化合物を添加して、１，３−ブタ
ジエンを重合し、 ［３］次いで、上記熟成液を追加供給して重合を継続す
ることを特徴とする、 シス−１，４−ポリブタジエンの重合方法。(1) Using the C_4 fraction containing cis-2-butene as a main component as a polymerization solvent, 1,3-butadiene is polymerized using a cobalt compound-water-organoaluminum compound catalyst, resulting in high-cis-1,4-polybutadiene. [1] In a polymerization solvent solution of 1,3-butadiene, an organoaluminum compound and water are mixed, θ≧10^[^(^1^3^7^0^/^T^)^- ^
3^. ^6^6^] θ: Aging time (minutes) T: Aging temperature (K) Aging is performed for a period of time θ, which is indicated by [3] A method for polymerizing cis-1,4-polybutadiene, comprising: [3] Then, the above-mentioned aging liquid is additionally supplied to continue the polymerization.
合溶媒として、コバルト化合物−水−有機アルミニウム
化合物系の触媒により１，３−ブタジエンを重合し、高
シス−１，４−ポリブタジエンを製造する方法において
、 ［１］（ａ）１，３−ブタジエンの重合溶媒溶液中、上
記有機アルミニウム化合物と水を、 θ≧１０＾［＾（＾１＾３＾７＾０＾／＾Ｔ＾）＾−＾
３＾．＾６＾６＾］θ：熟成時間（分） Ｔ：熟成温度（Ｋ） で示される時間θの間熟成し熟成液を得、 ［２］（ａ）次いでコバルト化合物を添加して、 （ｂ）重合槽を２槽以上直列に用い、連続運転を行い、
且つ、 ［３］２槽目以降の重合槽に、上記の熟成液をその重合
槽温度以下の温度に冷却して追加供給することを特徴と
する、 シス−１，４−ポリブタジエンの重合方法。(2) Polymerize 1,3-butadiene with a cobalt compound-water-organoaluminium compound catalyst using the C_4 fraction containing cis-2-butene as the main component as a polymerization solvent to produce high-cis-1,4-polybutadiene. [1] (a) In a polymerization solvent solution of 1,3-butadiene, the organoaluminum compound and water are mixed, θ≧10^[^(^1^3^7^0^/^T ^) ^-^
3^. ＾6＾6＾] θ: Aging time (minutes) T: Aging temperature (K) Aging is performed for the time θ shown by [2] (a) Next, a cobalt compound is added, and (b ) Two or more polymerization tanks are used in series, and continuous operation is carried out.
[3] A method for polymerizing cis-1,4-polybutadiene, characterized in that the above-mentioned aging liquid is cooled to a temperature equal to or lower than the temperature of the polymerization tank and is additionally supplied to the second and subsequent polymerization tanks.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27932990A JPH04154820A (en) | 1990-10-19 | 1990-10-19 | Polymerization for polybutadiene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27932990A JPH04154820A (en) | 1990-10-19 | 1990-10-19 | Polymerization for polybutadiene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04154820A true JPH04154820A (en) | 1992-05-27 |
Family
ID=17609663
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27932990A Pending JPH04154820A (en) | 1990-10-19 | 1990-10-19 | Polymerization for polybutadiene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04154820A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016158084A1 (en) * | 2015-03-30 | 2016-10-06 | 宇部興産株式会社 | Process for producing diene-based polymer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4918635A (en) * | 1972-06-14 | 1974-02-19 | ||
| JPS5417989A (en) * | 1977-07-09 | 1979-02-09 | Bunawerke Huels Gmbh | Preparation of polybutadiene of ciss1*4 high content |
-
1990
- 1990-10-19 JP JP27932990A patent/JPH04154820A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4918635A (en) * | 1972-06-14 | 1974-02-19 | ||
| JPS5417989A (en) * | 1977-07-09 | 1979-02-09 | Bunawerke Huels Gmbh | Preparation of polybutadiene of ciss1*4 high content |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016158084A1 (en) * | 2015-03-30 | 2016-10-06 | 宇部興産株式会社 | Process for producing diene-based polymer |
| JP6098859B2 (en) * | 2015-03-30 | 2017-03-22 | 宇部興産株式会社 | Method for producing diene polymer |
| JPWO2016158084A1 (en) * | 2015-03-30 | 2017-04-27 | 宇部興産株式会社 | Method for producing diene polymer |
| JP2017088905A (en) * | 2015-03-30 | 2017-05-25 | 宇部興産株式会社 | Manufacturing method of diene polymer |
| KR20170124434A (en) * | 2015-03-30 | 2017-11-10 | 우베 고산 가부시키가이샤 | Diene-based polymer production method |
| CN107428853A (en) * | 2015-03-30 | 2017-12-01 | 宇部兴产株式会社 | The manufacture method of diolefinic polymer |
| KR101855605B1 (en) * | 2015-03-30 | 2018-06-08 | 우베 고산 가부시키가이샤 | Diene-based polymer production method |
| CN107428853B (en) * | 2015-03-30 | 2018-11-30 | 宇部兴产株式会社 | The manufacturing method of diolefinic polymer |
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