JPH0323084B2 - - Google Patents
Info
- Publication number
- JPH0323084B2 JPH0323084B2 JP22994683A JP22994683A JPH0323084B2 JP H0323084 B2 JPH0323084 B2 JP H0323084B2 JP 22994683 A JP22994683 A JP 22994683A JP 22994683 A JP22994683 A JP 22994683A JP H0323084 B2 JPH0323084 B2 JP H0323084B2
- Authority
- JP
- Japan
- Prior art keywords
- conjugated diene
- polymer
- water
- diene monomer
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 150000001993 dienes Chemical class 0.000 claims description 50
- 229920000642 polymer Polymers 0.000 claims description 42
- 239000000178 monomer Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000011541 reaction mixture Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 239000002685 polymerization catalyst Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 239000012071 phase Substances 0.000 description 22
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 20
- 239000008346 aqueous phase Substances 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002954 polymerization reaction product Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は共役ジエン系重合体の製造方法に関
し、詳しくは共役ジエン系重合体を、重合体の損
失をほとんど伴うことなく、効率よく製造しうる
方法に関する。
一般に常温で液状の共役ジエン系重合体は、ア
ルコールを含む溶媒中で過酸化水素などの水溶性
触媒を用いて共役ジエン系単量体を重合させるこ
とにより製造されているが、精製過程における重
合体の損失が大きいという問題がある。
そこで、この問題点を解消するために、重合反
応により得られた重合反応生成物に、水を添加し
て上層を油相、下層を水相として分離して重合体
を得る方法が提案されている（特公昭52−22395
号公報）が、この方法によつても水相中への重合
体の損失量が0.3％以上あり、未だ十分なものと
は言い難いものであつた。
また、重合反応により得られた重合反応生成物
に、トルエンのような抽出剤と水との混合物を添
加することによつて分離して重合体を得ることも
知られているが、この場合はトルエンが水相に移
行し、それに伴つて重合体の損失量をそれほど減
少させることはできなかつた。
本発明は上記従来の問題点を解消して、水相中
の重合体の濃度を大巾に減少させ、重合体の収率
を向上させることができ、これにより排水処理を
容易化しうる共役ジエン系重合体の製造方法を提
供することを目的とするものである。
すなわち本発明は、重合反応溶媒としてアルコ
ールを含む溶媒を用い、重合触媒として水溶性触
媒を用いて共役ジエン系単量体を重合させて常温
で液状の共役ジエン系重合体を製造するにあた
り、前記共役ジエン系単量体を重合反応させた
後、反応混合物中における共役ジエン系単量体と
水の量をそれぞれ共役ジエン系重合体100重量部
に対し前者は10〜150重量部、後者は50〜1000重
量部に調節し、次いで該反応混合物から共役ジエ
ン系重合体と共役ジエン系単量体を主成分とする
油相を分離し、該油相から共役ジエン系単量体を
除去することを特徴とする共役ジエン系重合体の
製造方法を提供するものである。
本発明における重合反応溶媒としてはアルコー
ルを含む溶媒が用いられ、アルコール単独の他、
水・アルコール混合溶媒などが用いられる。アル
コールとしては低級アルコールが好ましく、具体
的にはメタノール、エタノール、ｎ−プロパノー
ル、イソプロパノール等が挙げられる。なお、
水・アルコール混合溶媒を用いる場合、水に可溶
なアルコールが用いられる。
次に本発明においては、重合触媒として水溶性
触媒が用いられる。ここで水溶性触媒としては様
様なものが用いられ、例えば過酸化水素、過硫酸
塩、コハク酸過酸化物等を挙げることができる。
さらに、本発明において用いる共役ジエン系単
量体としては特に制限はなく様々なものが用いら
れる。具体的には例えば１，３−ブタジエン、イ
ソプレン、クロロプレン等が用いられ、これらを
単独で或いは２種以上を組合せて用いることがで
きる。さらに、これらの共役ジエン系単量体をア
クリロニトリル、スチレン、メチルメタクリレー
トなどと共重合させてもよい。
重合反応条件は通常、反応温度常温〜150℃、
反応時間0.5〜５時間であり、好ましくは反応温
度100〜140℃、反応時間１〜３時間である。
また、重合触媒の濃度、使用量は使用する共役
ジエン系単量体の種類や触媒の種類等の条件によ
り異なり、一義的に決定することは困難である。
例えば、重合触媒として過酸化水素を用い１，３
−ブタジエンを重合させる場合、該触媒の濃度は
通常30〜70重量％、好ましくは50〜60重量％であ
り、該触媒の使用量は通常１，３−ブタジエンの
使用量の１〜80重量％、好ましくは２〜40重量％
である。
本発明においては、このように重合反応して得
られた反応混合物中に共役ジエン系単量体が含ま
れていることが必要である。この反応混合物中に
含まれる共役ジエン系単量体は、未反応の共役ジ
エン系単量体であつてもよく、また重合反応後に
加えた共役ジエン系単量体であつてもよい。この
反応後に加える共役ジエン系単量体は前記したも
のと同一であつてもよく異なつてもよい。さら
に、未反応の共役ジエン系単量体と重合反応後に
加えた共役ジエン系単量体の混合物であつてもよ
い。
ここで反応混合物中に存在させる共役ジエン系
単量体の量は重合反応により生成した共役ジエン
系重合体100重量部に対して10〜150重量部であ
る。ここで反応混合物中における共役ジエン系単
量体の存在量が、生成重合体100重量部に対して
10重量部未満であると、水相への重合体の損失量
が多く、一方150重量部を超えると、重合体の損
失量が使用される単量体量に比例するほど低下せ
ず好ましくない。また、反応混合物中に存在させ
る水の量は生成重合体100重量部に対して50〜
1000重量部とすべきである。
次いで、このような共役ジエン系単量体を含む
反応混合物から共役ジエン系重合体と共役ジエン
系単量体を主成分とする油相を分離する。この油
相の分離は、反応混合物を撹拌後静置して該油相
と、低級アルコール、水溶性残存触媒や水などを
主成分とする水相に分液することにより行なわれ
る。また、この分離に先立ち、反応混合物に必要
に応じて水を添加することもできる。なお、水を
添加する場合、反応混合物中の水の量について
は、共役ジエン系重合体と共役ジエン系単量体を
主成分とする油相の比重ρ1と、低級アルコール、
水溶性残存触媒および水を主成分とする水相の比
重ρ2との関係がρ1＜ρ2となるように水の量を調節
すればよい。通常は前記したように生成重合体
100重量部に対して50〜1000重量部の範囲内に調
節する。
本発明において上記油相中における共役ジエン
系単量体は液化状態であるので、分離層は通常１
〜30Kg／cm3の圧力に加圧される。また分離層の温
度は通常０〜100℃とする。
次いで、このようにして分離された油相から共
役ジエン系単量体を除去し、共役ジエン系重合体
を得る。なお、油相から共役ジエン系単量体を除
去するには、加圧状態で分離された油相を常圧に
戻すことにより容易に行なうことができる。また
フラツシユ蒸留などによつても行なうことができ
る。
本発明によれば、水相中への重合体の移行を抑
えることができ、水相と油相とをほぼ完全に分離
することができる。
したがつて、水相中における重合体の濃度を大
巾に減少させ、重合体の収率を向上させることが
できる。しかも、これにより水相の排水処理を容
易化することができる。
さらに、本発明によれば油相と水相を分離する
際の水の使用量を低減化させることができる。
また、本発明においては油相から共役ジエン系
単量体を除去することも容易であり、この場合多
少該単量体に重合体が移行しても何ら問題はな
く、しかもこの除去された共役ジエン系単量体を
再使用することができる。
それ故、本発明の方法は共役ジエン系重合体の
製造に有効に用いることができる。
次に本発明を実施例により説明する。
実施例 １
ブタジエン100ｇ、イソプロパノール70ｇおよ
び過酸化水素水18ｇ（60重量％）を700mlのオー
トクレーブに仕込み、120℃，20Kg／cm2Ｇで2.5時
間反応させた。次いでオートクレーブを水中に投
入して反応系を急冷し、反応を停止させた。この
際の圧力は３Kg／cm2Ｇであつた。収率60％にて共
役ジエン系重合体が得られた。得られた反応混合
物からブタジエンの一部17.8ｇをパージすること
により抜き出した（ブタジエンの存在量22.2ｇ）。
その後、水を300ml添加し、共役ジエン系重合体
およびブタジエンを主成分とする油相（上層）
と、イソプロパノール、水および残存触媒を主成
分とする水相（下層）とに分離した。下層の水相
約380ｇ中の重合体は0.07ｇであつた。
実施例 ２〜６
実施例１において、ブタジエンの存在量を種々
変えたこと以外は実施例１と同様な操作にて、油
相と水相を分離し、下層の水相中の重合体量、す
なわち水相への重合体の損失量を測定した。結果
を第１表に示す。
比較例 １
実施例１において、ブタジエンを完全にパージ
したこと以外は実施例１と同様な操作にて、油相
と水相を分離し、下層の水相中の重合体量を測定
した。結果を第１表に示す。
実施例 ７〜９
実施例１において、水の添加量を種々変えたこ
と以外は実施例１と同様な操作にて、油相と水相
を分離し、下層の水相中の重合体量を測定した。
結果を第１表に示す。
比較例 ２
実施例１と同様な操作にて、収率60％で共役ジ
エン系重合体を得た。得られた反応混合物からブ
タジエンを完全にパージした後、トルエンを44.4
ｇ、水を300ml添加して油相と水相を分離し、下
層の水相中の重合体量を測定した。結果を第１表
に示す。
The present invention relates to a method for producing a conjugated diene polymer, and more particularly to a method for efficiently producing a conjugated diene polymer with almost no loss of polymer. Conjugated diene polymers, which are generally liquid at room temperature, are produced by polymerizing conjugated diene monomers in a solvent containing alcohol using a water-soluble catalyst such as hydrogen peroxide. There is a problem in that the loss of merging is large. Therefore, in order to solve this problem, a method has been proposed in which water is added to the polymerization reaction product obtained by the polymerization reaction to separate the upper layer as an oil phase and the lower layer as an aqueous phase to obtain a polymer. There is (Special Public Service 52-22395)
However, even with this method, the amount of polymer lost into the aqueous phase was 0.3% or more, and it was still far from being sufficient. It is also known that a mixture of an extractant such as toluene and water is added to the polymerization reaction product obtained by the polymerization reaction to separate it and obtain a polymer. It was not possible to appreciably reduce the amount of toluene transferred to the aqueous phase and the concomitant loss of polymer. The present invention solves the above-mentioned conventional problems, greatly reduces the concentration of the polymer in the aqueous phase, improves the yield of the polymer, and thereby facilitates wastewater treatment. The object of the present invention is to provide a method for producing a polymer. That is, the present invention uses a solvent containing alcohol as a polymerization reaction solvent and a water-soluble catalyst as a polymerization catalyst to polymerize a conjugated diene monomer to produce a conjugated diene polymer that is liquid at room temperature. After polymerizing the conjugated diene monomer, the amounts of the conjugated diene monomer and water in the reaction mixture are adjusted to 10 to 150 parts by weight and 50 parts by weight for the former and 100 parts by weight of the conjugated diene polymer, respectively. ~1000 parts by weight, then separating an oil phase mainly composed of a conjugated diene polymer and a conjugated diene monomer from the reaction mixture, and removing the conjugated diene monomer from the oil phase. The present invention provides a method for producing a conjugated diene polymer characterized by the following. As the polymerization reaction solvent in the present invention, a solvent containing alcohol is used, and in addition to alcohol alone,
A mixed solvent of water and alcohol is used. As the alcohol, lower alcohols are preferred, and specific examples include methanol, ethanol, n-propanol, and isopropanol. In addition,
When using a water/alcohol mixed solvent, a water-soluble alcohol is used. Next, in the present invention, a water-soluble catalyst is used as a polymerization catalyst. Various water-soluble catalysts can be used here, including hydrogen peroxide, persulfates, succinic acid peroxide, and the like. Further, the conjugated diene monomer used in the present invention is not particularly limited, and various types can be used. Specifically, for example, 1,3-butadiene, isoprene, chloroprene, etc. are used, and these can be used alone or in combination of two or more kinds. Furthermore, these conjugated diene monomers may be copolymerized with acrylonitrile, styrene, methyl methacrylate, or the like. Polymerization reaction conditions are usually a reaction temperature of room temperature to 150℃,
The reaction time is 0.5 to 5 hours, preferably the reaction temperature is 100 to 140°C, and the reaction time is 1 to 3 hours. Further, the concentration and amount of the polymerization catalyst used vary depending on conditions such as the type of conjugated diene monomer used and the type of catalyst, and are difficult to determine unambiguously.
For example, using hydrogen peroxide as a polymerization catalyst, 1,3
- When butadiene is polymerized, the concentration of the catalyst is usually 30 to 70% by weight, preferably 50 to 60% by weight, and the amount of the catalyst used is usually 1 to 80% by weight of the amount of 1,3-butadiene used. , preferably 2-40% by weight
It is. In the present invention, it is necessary that a conjugated diene monomer be contained in the reaction mixture obtained by the polymerization reaction. The conjugated diene monomer contained in this reaction mixture may be an unreacted conjugated diene monomer or a conjugated diene monomer added after the polymerization reaction. The conjugated diene monomer added after this reaction may be the same as or different from those described above. Furthermore, it may be a mixture of an unreacted conjugated diene monomer and a conjugated diene monomer added after the polymerization reaction. The amount of the conjugated diene monomer present in the reaction mixture is 10 to 150 parts by weight based on 100 parts by weight of the conjugated diene polymer produced by the polymerization reaction. Here, the amount of conjugated diene monomer in the reaction mixture is calculated based on 100 parts by weight of the produced polymer.
If it is less than 10 parts by weight, the amount of polymer lost to the aqueous phase will be large, while if it exceeds 150 parts by weight, the amount of polymer lost will not decrease proportionally to the amount of monomer used, which is undesirable. . In addition, the amount of water present in the reaction mixture is 50 to 100 parts by weight of the produced polymer.
Should be 1000 parts by weight. Next, an oil phase containing the conjugated diene polymer and the conjugated diene monomer as main components is separated from the reaction mixture containing the conjugated diene monomer. Separation of the oil phase is carried out by stirring the reaction mixture and then allowing it to stand still to separate the oil phase and an aqueous phase containing lower alcohol, water-soluble residual catalyst, water, etc. as main components. Moreover, water can also be added to the reaction mixture as necessary prior to this separation. In addition, when adding water, the amount of water in the reaction mixture is determined by the specific gravity ρ 1 of the oil phase whose main components are a conjugated diene polymer and a conjugated diene monomer, lower alcohol,
The amount of water may be adjusted so that the relationship between the water-soluble residual catalyst and the specific gravity ρ 2 of the aqueous phase mainly composed of water satisfies ρ 1 <ρ 2 . Usually, as mentioned above, the produced polymer
The amount is adjusted within the range of 50 to 1000 parts by weight per 100 parts by weight. In the present invention, since the conjugated diene monomer in the oil phase is in a liquefied state, the separation layer is usually 1
Pressurized to ~30Kg/ cm3 pressure. Further, the temperature of the separation layer is usually 0 to 100°C. Next, the conjugated diene monomer is removed from the oil phase thus separated to obtain a conjugated diene polymer. The conjugated diene monomer can be easily removed from the oil phase by returning the oil phase separated under pressure to normal pressure. It can also be carried out by flash distillation or the like. According to the present invention, migration of the polymer into the aqueous phase can be suppressed, and the aqueous phase and oil phase can be almost completely separated. Therefore, the concentration of the polymer in the aqueous phase can be significantly reduced and the yield of the polymer can be improved. Moreover, this facilitates the treatment of water phase wastewater. Furthermore, according to the present invention, the amount of water used when separating the oil phase and the aqueous phase can be reduced. In addition, in the present invention, it is easy to remove the conjugated diene monomer from the oil phase, and in this case, there is no problem even if some polymer transfers to the monomer, and the removed conjugate Diene monomers can be reused. Therefore, the method of the present invention can be effectively used for producing conjugated diene polymers. Next, the present invention will be explained by examples. Example 1 100 g of butadiene, 70 g of isopropanol, and 18 g (60% by weight) of hydrogen peroxide were placed in a 700 ml autoclave and reacted at 120° C. and 20 Kg/cm 2 G for 2.5 hours. Next, the autoclave was put into water to rapidly cool the reaction system and stop the reaction. The pressure at this time was 3 Kg/cm 2 G. A conjugated diene polymer was obtained with a yield of 60%. A portion of 17.8 g of butadiene was extracted from the resulting reaction mixture by purging (22.2 g of butadiene present).
After that, 300ml of water was added, and the oil phase (upper layer) mainly composed of conjugated diene polymer and butadiene was added.
and an aqueous phase (lower layer) containing isopropanol, water, and residual catalyst as main components. The amount of polymer in about 380 g of the lower aqueous phase was 0.07 g. Examples 2 to 6 In Example 1, the oil phase and the water phase were separated by the same operation as in Example 1 except that the amount of butadiene was varied, and the amount of polymer in the lower water phase was determined. That is, the amount of polymer lost to the aqueous phase was measured. The results are shown in Table 1. Comparative Example 1 An oil phase and an aqueous phase were separated in the same manner as in Example 1 except that butadiene was completely purged, and the amount of polymer in the lower aqueous phase was measured. The results are shown in Table 1. Examples 7 to 9 In Example 1, the oil phase and aqueous phase were separated by the same operation as in Example 1, except that the amount of water added was varied, and the amount of polymer in the lower aqueous phase was determined. It was measured.
The results are shown in Table 1. Comparative Example 2 A conjugated diene polymer was obtained in the same manner as in Example 1 with a yield of 60%. After completely purging the butadiene from the resulting reaction mixture, toluene was added to 44.4
g, 300 ml of water was added to separate the oil phase and aqueous phase, and the amount of polymer in the lower aqueous phase was measured. The results are shown in Table 1.
【表】【table】
Claims (1)
用い、重合触媒として水溶性触媒を用いて共役ジ
エン系単量体を重合させて常温で液状の共役ジエ
ン系重合体を製造するにあたり、前記共役ジエン
系単量体を重合反応させた後、反応混合物中にお
ける共役ジエン系単量体と水の量をそれぞれ共役
ジエン系重合体100重量部に対し前者は10〜150重
量部、後者は50〜1000重量部に調節し、次いで該
反応混合物から共役ジエン系重合体と共役ジエン
系単量体を主成分とする油相を分離し、該油相か
ら共役ジエン系単量体を除去することを特徴とす
る共役ジエン系重合体の製造方法。1. When producing a conjugated diene polymer that is liquid at room temperature by polymerizing a conjugated diene monomer using an alcohol-containing solvent as a polymerization reaction solvent and a water-soluble catalyst as a polymerization catalyst, the conjugated diene monomer is After the polymerization reaction, the amounts of the conjugated diene monomer and water in the reaction mixture are adjusted to 10 to 150 parts by weight for the former and 50 to 1000 parts by weight for the latter, relative to 100 parts by weight of the conjugated diene polymer. and then separating an oil phase containing a conjugated diene polymer and a conjugated diene monomer as main components from the reaction mixture, and removing the conjugated diene monomer from the oil phase. A method for producing a conjugated diene polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22994683A JPS60123512A (en) | 1983-12-07 | 1983-12-07 | Production of conjugated diene based polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22994683A JPS60123512A (en) | 1983-12-07 | 1983-12-07 | Production of conjugated diene based polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60123512A JPS60123512A (en) | 1985-07-02 |
| JPH0323084B2 true JPH0323084B2 (en) | 1991-03-28 |
Family
ID=16900193
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22994683A Granted JPS60123512A (en) | 1983-12-07 | 1983-12-07 | Production of conjugated diene based polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60123512A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01146911A (en) * | 1987-12-03 | 1989-06-08 | Idemitsu Petrochem Co Ltd | Preparation of liquid diene polymer |
-
1983
- 1983-12-07 JP JP22994683A patent/JPS60123512A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60123512A (en) | 1985-07-02 |
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