JP2002308926A - Method for hydrogenating olefinic unsaturated polymer - Google Patents
Method for hydrogenating olefinic unsaturated polymerInfo
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- JP2002308926A JP2002308926A JP2001113246A JP2001113246A JP2002308926A JP 2002308926 A JP2002308926 A JP 2002308926A JP 2001113246 A JP2001113246 A JP 2001113246A JP 2001113246 A JP2001113246 A JP 2001113246A JP 2002308926 A JP2002308926 A JP 2002308926A
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- stirred tank
- hydrogenation
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はオレフィン性不飽和
ポリマーの水素添加方法に関する。詳しくは、均一系触
媒を用いて水素添加率の高いオレフィン性不飽和ポリマ
ーを安定して製造するための水素添加方法に関する。The present invention relates to a method for hydrogenating an olefinically unsaturated polymer. More specifically, the present invention relates to a hydrogenation method for stably producing an olefinically unsaturated polymer having a high hydrogenation rate using a homogeneous catalyst.
【０００２】[0002]
【従来の技術】〔１〕背景：オレフィン性不飽和ポリマ
ー（代表例：共役ジエン系ポリマー）は、熱可塑性エラ
ストマー等として工業的に広く利用されている。オレフ
ィン性不飽和ポリマーの不飽和結合は、加硫等に利用で
きる反面、耐候性や耐熱性を損なうという不具合があ
る。このため、オレフィン性不飽和ポリマーの用途は限
定されている。しかしながら、上記の耐候性や耐熱性
は、オレフィン性不飽和ポリマーの不飽和結合を水素添
加してポリマー鎖を飽和化することで改善できるという
事情がある。2. Description of the Related Art [1] Background: Olefinically unsaturated polymers (representative examples: conjugated diene polymers) are widely used industrially as thermoplastic elastomers and the like. The unsaturated bond of the olefinically unsaturated polymer can be used for vulcanization or the like, but has a disadvantage of impairing weather resistance and heat resistance. For this reason, applications of olefinically unsaturated polymers are limited. However, the above-mentioned weather resistance and heat resistance can be improved by hydrogenating unsaturated bonds of the olefinically unsaturated polymer to saturate the polymer chain.
【０００３】〔２〕不均一系触媒と均一系触媒：オレフ
ィン性不飽和ポリマーの不飽和結合を水素添加する方法
としては、不均一系触媒を用いる方法と、均一系触媒を
用いる方法がある。 [2-1] 不均一系触媒：不均一系触媒は触媒活性が低いた
め、オレフィン性不飽和ポリマーの水素添加には、高温
・高圧の厳しい条件が必須となる。このため、ポリマー
の分解やゲル化を生じ易く、エネルギーコストも高いと
いう欠点がある。また、ＳＢＲのような共役ジエンとビ
ニル芳香族化合物との共重合体では、芳香族の不飽和結
合も水素添加されてしまうという問題もある。つまり、
共役ジエン部分のみを選択的に水素添加することが困難
である。また、不均一系触媒を用いた水素添加では、水
素添加の対象化合物と不均一系触媒との接触が必須であ
るが、オレフィン性不飽和ポリマー等のポリマーの水素
添加では、低分子の水素添加の場合よりも反応系の粘度
やポリマー鎖中の立体障害等の影響が大であるため、接
触が困難である。このため、不均一系触媒を用いて効率
良くオレフィン性不飽和ポリマー等のポリマーを水素添
加するためには多量の不均一系触媒が必要となり、コス
ト的な問題が生ずる。さらに、水素添加対象であるオレ
フィン性不飽和ポリマー等のポリマーを含有する溶液の
粘度が高いと、触媒担体等の金属が反応後の製品に同伴
して品質に問題を生ずる。このため、ポリマーを含有す
る溶液の粘度を低下させておく必要があるが、そのため
には不活性溶媒が多量に必要となり、その結果、溶媒除
去に要する設備や用役コストが高くなるという問題が生
ずる。[2] Heterogeneous Catalyst and Homogeneous Catalyst: Methods for hydrogenating unsaturated bonds of an olefinically unsaturated polymer include a method using a heterogeneous catalyst and a method using a homogeneous catalyst. [2-1] Heterogeneous catalyst: Heterogeneous catalysts have low catalytic activity, so that high-temperature and high-pressure strict conditions are essential for hydrogenation of olefinically unsaturated polymers. Therefore, there are disadvantages that the polymer is easily decomposed or gelled, and the energy cost is high. Further, in a copolymer of a conjugated diene and a vinyl aromatic compound such as SBR, there is also a problem that an aromatic unsaturated bond is hydrogenated. That is,
It is difficult to selectively hydrogenate only the conjugated diene portion. In addition, in the case of hydrogenation using a heterogeneous catalyst, contact between the target compound to be hydrogenated and the heterogeneous catalyst is indispensable. However, in the hydrogenation of polymers such as olefinically unsaturated polymers, low-molecular hydrogenation is required. Since the influence of the viscosity of the reaction system and steric hindrance in the polymer chain is greater than in the case of the above, contact is more difficult. For this reason, in order to efficiently hydrogenate a polymer such as an olefinically unsaturated polymer using a heterogeneous catalyst, a large amount of a heterogeneous catalyst is required, which causes a cost problem. Furthermore, if the viscosity of a solution containing a polymer such as an olefinically unsaturated polymer to be hydrogenated is high, a metal such as a catalyst carrier accompanies the product after the reaction, causing a quality problem. For this reason, it is necessary to reduce the viscosity of the solution containing the polymer, but this requires a large amount of an inert solvent, and as a result, there is a problem that equipment and utility costs required for removing the solvent are increased. Occurs.
【０００４】[2-2] 均一系触媒：均一系触媒は、触媒活
性が高いため穏やかな条件での反応も可能であり、触媒
量も少量で足りるという利点がある。また、条件を適切
に選択すれば、共役ジエンとビニル芳香族化合物との共
重合体に於いて、共役ジエン部分の不飽和結合を優先的
に水素添加できるという利点もある。しかし、均一系触
媒は、触媒の還元状態によって触媒活性が大きく変化す
るため、水素添加の再現性が低いという問題がある。ま
た、共存している不純物等により触媒成分が不活性化さ
れ易く、この理由からも、水素添加の再現性が低いとい
う問題が生ずる。したがって、均一系触媒では、水素添
加率の高いオレフィン性不飽和ポリマー等のポリマーを
安定的に得ることは困難である。また、元々十分に速く
ない反応速度が、触媒の還元状態や不純物に起因する触
媒活性の低下によって更に遅くなるという問題もある。
上記は均一系触媒を回分式の攪拌槽型反応器で用いて水
素添加する場合の問題点であるが、均一系触媒を連続式
の反応器（連続式ループリアクタ）で用いて水素添加す
る場合には、反応熱の除去や気液接触の効率化の観点か
ら高粘度のポリマー溶液での水素添加反応ができず、設
備的にも高価であるため、オレフィン性不飽和ポリマー
の水素添加に用いることは困難という問題がある。これ
までに、回分式の攪拌槽型反応器や、連続式の攪拌槽型
反応器を用いて水素添加していることは既に知られてお
り、例えば、特開平１１−２８６５１３号公報に記載さ
れている。しかし、通常、攪拌槽型反応器を用いて水素
添加を行う場合は、槽内の上部位置は気相部とされてい
る。このため、たとえ水素ガスを液中下部より供給して
も水素ガスの吹き抜けが生じ、気液分散は結果として上
部気相部からの巻き込みと吹き込みによるものとから成
る。しかし、上部気相部からの巻き込みによる吸収速度
は、液中での気液接触による吸収速度に比べて格段に遅
いという事情があり、このため、吸収速度が全体的に遅
くなるという欠点があった。[2-2] Homogeneous catalysts: Homogeneous catalysts have the advantage of being capable of reacting under mild conditions because of their high catalytic activity, and having the advantage of requiring a small amount of catalyst. Further, if the conditions are appropriately selected, there is an advantage that in a copolymer of a conjugated diene and a vinyl aromatic compound, the unsaturated bond in the conjugated diene portion can be preferentially hydrogenated. However, a homogeneous catalyst has a problem that reproducibility of hydrogenation is low because the catalytic activity greatly changes depending on the reduction state of the catalyst. Further, the catalyst component is easily deactivated by coexisting impurities and the like, and for this reason, there is a problem that reproducibility of hydrogenation is low. Therefore, it is difficult to obtain a polymer such as an olefinically unsaturated polymer having a high hydrogenation rate stably with a homogeneous catalyst. There is also a problem that the reaction rate, which is not originally sufficiently fast, is further reduced due to a reduction in the catalyst activity due to the reduced state of the catalyst or impurities.
The above is a problem in the case of hydrogenation using a homogeneous catalyst in a batch type stirred tank reactor, but in the case of hydrogenation using a homogeneous catalyst in a continuous reactor (continuous loop reactor). Is not suitable for hydrogenation of olefinically unsaturated polymers because it cannot perform a hydrogenation reaction with a high-viscosity polymer solution from the viewpoint of removing heat of reaction and increasing the efficiency of gas-liquid contact, and is expensive in terms of equipment. There is a problem that it is difficult. It has been known that hydrogenation has been performed using a batch-type stirred tank reactor or a continuous stirred tank reactor, and is described in, for example, JP-A-11-286513. ing. However, when hydrogen is added using a stirred tank reactor, the upper position in the tank is usually a gas phase. For this reason, even if hydrogen gas is supplied from the lower part of the liquid, blow-through of the hydrogen gas occurs, and gas-liquid dispersion results from entrainment and blowing from the upper gas phase. However, the absorption rate due to entrainment from the upper gas phase part is significantly slower than the absorption rate due to gas-liquid contact in liquid, which has the disadvantage that the absorption rate is slow overall. Was.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、均一系触媒
を用いる場合の問題点を解決することで、均一系触媒を
用いる場合の利点を生かしつつ、安定した高い水素添加
率のオレフィン性ポリマーを効率良く連続的に製造し得
る水素添加方法を提供することを目的とする。換言すれ
ば、広範囲の粘度領域のオレフィン性不飽和ポリマー
を、均一系水素添加触媒を用いて、安定した高い水素添
加率で水素添加することができる水素添加方法を提供す
ることを目的とする。SUMMARY OF THE INVENTION The present invention solves the problems of using a homogeneous catalyst, thereby making use of the advantages of using a homogeneous catalyst, while maintaining a stable and high hydrogenation rate of an olefinic polymer. It is an object of the present invention to provide a hydrogenation method capable of efficiently and continuously producing a hydrogen. In other words, an object of the present invention is to provide a hydrogenation method capable of hydrogenating an olefinically unsaturated polymer in a wide range of viscosity at a stable and high hydrogenation rate using a homogeneous hydrogenation catalyst.
【０００６】[0006]
【課題を解決するための手段】本発明は、オレフィン性
不飽和ポリマーを含有する不活性有機溶媒溶液と均一系
の水素添加触媒及び水素とを攪拌槽型反応器へ連続的に
供給するとともに該攪拌槽型反応器から反応物を連続的
に押し出すことでオレフィン性不飽和ポリマーを水素化
することを特徴とする水素添加方法である。上記に於い
て『攪拌槽型反応器から押し出す』とは、オレフィン性
不飽和ポリマーを含有する不活性有機溶媒溶液と均一系
の水素添加触媒と水素とを攪拌槽型反応器へ連続的に供
給することで、該攪拌槽型反応器内に満たされているオ
レフィン性不飽和ポリマーを含有する不活性有機溶媒溶
液と均一系の水素添加触媒及び水素と水素添加されたオ
レフィン性ポリマーとを該攪拌槽型反応器から押し出す
ことをいう。According to the present invention, an inert organic solvent solution containing an olefinically unsaturated polymer, a homogeneous hydrogenation catalyst and hydrogen are continuously supplied to a stirred tank reactor. A hydrogenation method characterized by continuously extruding a reactant from a stirred tank reactor to hydrogenate an olefinically unsaturated polymer. In the above, "extruding from a stirred tank reactor" means that an inert organic solvent solution containing an olefinically unsaturated polymer, a homogeneous hydrogenation catalyst, and hydrogen are continuously supplied to a stirred tank reactor. In this way, the inert organic solvent solution containing the olefinically unsaturated polymer and the homogeneous hydrogenation catalyst and the hydrogenated olefinic polymer filled with the olefinically unsaturated polymer are filled in the stirred tank reactor. Extrusion from a tank reactor.
【０００７】上記の如く押し出すことは、攪拌槽型反応
器の内部を満液又は満液に近い状態とすることで可能と
なる。そのため、本発明では、水素ガスを槽底部より供
給したとしても水素ガスの吹き抜けが生じにくく、槽内
上部の気液界面からの水素ガスの巻き込みも生じない
か、生じたとしても無視できる程度である。このため、
槽全体で水素ガスを吸収することができ、吸収速度の低
下という不具合も無く、高い反応速度を確保することが
可能となる。Extrusion as described above is made possible by bringing the inside of the stirred tank reactor into a state of being full or almost full. Therefore, in the present invention, even if hydrogen gas is supplied from the bottom of the tank, blow-through of the hydrogen gas is unlikely to occur, and entrainment of the hydrogen gas from the gas-liquid interface in the upper part of the tank does not occur, or even if it occurs, it is negligible. is there. For this reason,
Hydrogen gas can be absorbed in the entire tank, and a high reaction rate can be ensured without the problem of a decrease in the absorption rate.
【０００８】オレフィン性不飽和ポリマーを含有する不
活性有機溶媒溶液と均一系の水素添加触媒とは、攪拌槽
型反応器への供給前に予め混合しておき共通の管を通し
て攪拌槽型反応器へ供給してもよく、また、攪拌槽型反
応器への供給前には混合せず別々の管を通して攪拌槽型
反応器へ供給してもよい。オレフィン性不飽和ポリマー
を含有する不活性有機溶媒溶液は、ポリマー分子量等に
より広範囲な粘度領域を示す。本発明では、オレフィン
性不飽和ポリマーを含有する不活性有機溶媒溶液の粘度
は、１００００ｃＰ以下、好ましくは５０００ｃＰ以下
である。攪拌翼の形状としては、オレフィン性不飽和ポ
リマーを含有する不活性有機溶媒溶液の粘度が１０００
ｃＰ以下では、一般的な低粘度攪拌翼（代表例：パドル
翼）を用いる。好ましくは、ディスクタービン翼のよう
に攪拌槽上部からの投影面積が大きい翼形状を成し、槽
径に対する翼径の比が０．２〜０．８の範囲、好ましく
は０．３〜０．６の範囲にある攪拌翼を用いる。なお、
槽高に応じて攪拌翼を多段階に設置するようにしてもよ
い。また、オレフィン性不飽和ポリマーを含有する不活
性有機溶媒溶液の粘度が１０００ｃＰを越える場合に
は、中高粘度大型攪拌翼（代表例：マックスブレンド
翼，リボン翼）を用いる。好ましくはマックスブレンド
翼のように攪拌槽側部からの投影面積が大きい翼形状を
成し、槽径に対する翼径の比が０．２〜０．８の範囲、
好ましくは０．３〜０．６の範囲にある攪拌翼を用い
る。反応温度は、均一系触媒の活性に応じて、０〜２０
０℃の範囲、好ましくは４０〜１５０℃の範囲、更に好
ましくは９０〜１２０℃の範囲である。後述のように２
基以上の攪拌槽型反応器を用いる場合には、各攪拌槽型
反応器毎に反応温度を変えてもよい。また、後述のよう
に、攪拌槽型反応器の後段に管型反応器を設ける場合、
攪拌槽型反応器は等温反応であり、管型反応器は等温反
応と断熱反応の何れでもよい。水素の供給は、攪拌槽型
反応器に直接水素を導入してもよいし、オレフィン性不
飽和ポリマーを含有する不活性有機溶媒溶液と共通の管
を通して攪拌槽型反応器へ供給してもよい。攪拌槽型反
応器に直接水素を導入する場合には、単孔ノズル、スパ
ージャーリング等の他孔ノズルを用いることができる。
水素を効率的に吸収できる点から、更に好ましいノズル
はスパージャーリングである。An inert organic solvent solution containing an olefinically unsaturated polymer and a homogeneous hydrogenation catalyst are mixed in advance before being supplied to a stirred tank reactor, and are mixed through a common pipe. The mixture may be supplied to the stirred tank reactor through a separate tube without mixing before being supplied to the stirred tank reactor. The inert organic solvent solution containing the olefinically unsaturated polymer shows a wide viscosity range depending on the polymer molecular weight and the like. In the present invention, the viscosity of the inert organic solvent solution containing the olefinically unsaturated polymer is 10,000 cP or less, preferably 5000 cP or less. As the shape of the stirring blade, the viscosity of the inert organic solvent solution containing the olefinically unsaturated polymer is 1000.
Below cP, a general low-viscosity stirring blade (representative example: paddle blade) is used. Preferably, the blade has a blade shape having a large projected area from the upper part of the stirring tank like a disk turbine blade, and the ratio of the blade diameter to the tank diameter is in the range of 0.2 to 0.8, preferably 0.3 to 0.1. A stirring blade in the range of 6 is used. In addition,
The stirring blades may be installed in multiple stages according to the tank height. When the viscosity of the inert organic solvent solution containing the olefinically unsaturated polymer exceeds 1000 cP, a medium-high-viscosity large-size stirring blade (typical example: Max blend blade, ribbon blade) is used. Preferably, a blade shape having a large projected area from the stirring tank side like a Max Blend blade is formed, and the ratio of the blade diameter to the tank diameter is in the range of 0.2 to 0.8,
Preferably, a stirring blade in the range of 0.3 to 0.6 is used. The reaction temperature ranges from 0 to 20 depending on the activity of the homogeneous catalyst.
It is in the range of 0 ° C, preferably in the range of 40 to 150 ° C, and more preferably in the range of 90 to 120 ° C. 2 as described below
When using more than one stirred tank reactor, the reaction temperature may be changed for each stirred tank reactor. Further, as described later, when a tubular reactor is provided at the subsequent stage of the stirred tank reactor,
The stirred tank reactor is an isothermal reaction, and the tubular reactor may be either an isothermal reaction or an adiabatic reaction. Hydrogen may be supplied directly to the stirred tank reactor or may be supplied to the stirred tank reactor through a common pipe with an inert organic solvent solution containing an olefinically unsaturated polymer. . When hydrogen is directly introduced into the stirred tank reactor, other holes such as a single hole nozzle and sparger ring can be used.
A more preferable nozzle is a sparger ring because it can efficiently absorb hydrogen.
【０００９】また、本発明は、上記構成に於いて、オレ
フィン性不飽和ポリマーを含有する不活性有機溶媒溶液
と均一系の水素添加触媒と水素とを攪拌槽型反応器の槽
底部から流入させて槽上部から排出させることを特徴と
する水素添加方法である。槽底部からの流入が連続的で
あること、及び、槽上部からの排出が連続的な押し出し
によるものであることは、前述の通りである。槽底部か
ら流入させて槽上部から排出させるため、攪拌槽型反応
器内での気液接触がより十分に行われて、反応がより速
やかとなる。このため、達成される水素添加率が同じで
あれば、そのための所要時間が短縮される。Further, according to the present invention, in the above constitution, an inert organic solvent solution containing an olefinically unsaturated polymer, a homogeneous hydrogenation catalyst and hydrogen are introduced from the bottom of a stirred tank reactor. This is a hydrogenation method characterized in that the hydrogen is discharged from the upper part of the tank. As described above, the inflow from the bottom of the tank is continuous, and the discharge from the top of the tank is due to continuous extrusion. Since the gas flows from the bottom of the tank and is discharged from the top of the tank, gas-liquid contact in the stirred tank reactor is more sufficiently performed, and the reaction is more rapid. For this reason, if the achieved hydrogenation rates are the same, the time required for that is reduced.
【００１０】また、本発明は、前記の何れかの構成に於
いて、攪拌槽型反応器から押し出した後、該攪拌槽型反
応器の後段に少なくとも１段設けた攪拌槽型反応器へ連
続的に供給して、該後段の攪拌槽型反応器から連続的に
押し出すことを特徴とする水素添加方法である。当然な
がら、先頭の攪拌槽型反応器の後段に２段以上に攪拌槽
型反応器を設けた場合には、該先頭の攪拌槽型反応器か
ら押し出した後、後段の攪拌槽型反応器へ連続的に供給
して該後段の攪拌槽型反応器から連続的に押し出す過程
を、後段の各攪拌槽型反応器についてそれぞれ行うこと
を特徴とする水素添加方法である。先頭の攪拌槽型反応
器の後段に少なくとも１段設けた（各）攪拌槽型反応器
への供給を槽底部から行うとともに、該（各）攪拌槽型
反応器からの押し出しを槽上部から行うようにすると、
前述と同様の効果を後段の（各）攪拌槽型反応器でも享
受することができる。攪拌槽型反応器（＝先頭の攪拌槽
型反応器）の後段に更に少なくとも一段の攪拌槽型反応
器を設けたことで、水素添加反応による発熱を各攪拌槽
型反応器へ分散させることができる。その結果、各攪拌
槽型反応器の容積を総計した容積を持つ単一の攪拌槽型
反応器を用いる場合よりも、除熱を行い易くなる。ま
た、本発明は、上記構成に於いて、各攪拌槽型反応器の
各々へ水素を連続的に供給することを特徴とする水素添
加方法である。水素の供給先を分散させることで、水素
添加反応による発熱を各攪拌槽型反応器へ分散させるこ
とができる。その結果、攪拌槽型反応器の何れかへ水素
を供給する場合や、各攪拌槽型反応器の容積を総計した
容積を持つ単一の攪拌槽型反応器へ水素を供給する場合
よりも、水素添加反応を制御し易くなり、除熱も容易と
なる。Further, according to the present invention, in any one of the above constitutions, after extruding from the stirred tank reactor, it is continuously connected to at least one stirred tank reactor provided after the stirred tank reactor. And continuously extruding it from the subsequent stirred tank reactor. Of course, when two or more stirred tank reactors are provided after the first stirred tank reactor, after being extruded from the first stirred tank reactor, the mixture is transferred to the second stirred tank reactor. The hydrogenation method is characterized in that the step of continuously supplying and continuously extruding from the subsequent stirred tank reactor is performed for each of the subsequent stirred tank reactors. At least one stage is provided at the subsequent stage of the leading stirred tank reactor, and the (each) stirred tank reactor is supplied from the bottom of the tank, and the (each) stirred tank reactor is extruded from the top of the tank. If you do
The same effects as described above can be enjoyed in the subsequent (each) stirred tank reactor. By providing at least one more stirred tank reactor after the stirred tank reactor (= the first stirred tank reactor), heat generated by the hydrogenation reaction can be dispersed to each stirred tank reactor. it can. As a result, it becomes easier to remove heat than in the case of using a single stirred tank reactor having a total volume of the respective stirred tank reactors. Further, the present invention is the hydrogenation method as described above, wherein hydrogen is continuously supplied to each of the stirred tank reactors. By dispersing the hydrogen supply destination, the heat generated by the hydrogenation reaction can be dispersed to each stirred tank reactor. As a result, when supplying hydrogen to any of the stirred tank reactors, or when supplying hydrogen to a single stirred tank reactor having the total volume of the respective stirred tank reactors, The hydrogenation reaction becomes easier to control and the heat removal becomes easier.
【００１１】また、本発明は、前記の何れかの構成に於
いて、攪拌槽型反応器から押し出した後に連続流通式の
管型反応器へ連続的に供給することで更に水素化させる
ことを特徴とする水素添加方法である。管型反応器へ供
給してその中で更に反応させるため、攪拌槽型反応器内
で水素添加されることなく排出されたオレフィン性不飽
和ポリマーを水素添加することが可能となり、より高い
水素添加率を達成することができる。また、本発明は、
前記の何れかの構成に於いて、水素添加率が９０％以上
であることを特徴とする水素添加方法である。また、本
発明は、前記の何れかの構成に於いて、不活性有機溶媒
が、イソペンタン、シクロペンタン、シクロヘキサン、
シクロヘプタン、シクロオクタン、ｎ−ペンタン、ｎ−
ヘキサン、ｎ−ヘプタン、ｎ−オクタン、ｎ−ノナン、
ｎ−デカン、ベンゼン、トルエン、及びキシレンから選
ばれた少なくとも１種を含むことを特徴とする水素添加
方法である。また、本発明で使用される触媒としては、
均一系水素添加触媒であれば使用できる。例えば、Ｔ
ｉ、Ｚｒ、Ｈｆのいずれかを含むメタロセン化合物が使
用できる。この中でも、チタノセン化合物とアルコキシ
リチウムとを反応させた水素添加触媒は安価で工業的に
特に有用な触媒である。具体的な例を挙げると、特開平
１−２７５６０５号公報、特開平５−２７１３２６号公
報、特開平５−２７１３２５号公報、特開平５−２２２
１１５号公報、特開平１１−２９２９２４号公報、特開
２０００−３７６３２号公報、特開昭５９−１３３２０
３号公報、特開昭６３−５４０１号公報、特開昭６２−
２１８４０３号公報、特開平７−９００１７号公報、特
公昭４３−１９９６０号公報、特公昭４７−４０４７３
号公報に記載の水素添加触媒である。これらの各種の水
素添加触媒は１種のみを用いて良いし、２種以上を併用
することもできる。より好ましくは、下記一般式（１）
で表される化合物から選ばれた少なくとも１種（以下、
遷移金属化合物（１）という）を含有することを特徴と
する水素添加方法である。[0011] The present invention also relates to any one of the above-mentioned structures, wherein the hydrogenation is further performed by extruding from a stirred tank reactor and then continuously supplying it to a continuous flow type tubular reactor. This is a characteristic hydrogenation method. The olefinically unsaturated polymer discharged without being hydrogenated in the stirred tank reactor can be hydrogenated in the stirred tank reactor because it is supplied to the tubular reactor and further reacted therein. Rate can be achieved. Also, the present invention
In any one of the above structures, a hydrogenation rate is 90% or more. Further, the present invention, in any one of the above constitutions, wherein the inert organic solvent is isopentane, cyclopentane, cyclohexane,
Cycloheptane, cyclooctane, n-pentane, n-
Hexane, n-heptane, n-octane, n-nonane,
A hydrogenation method comprising at least one selected from n-decane, benzene, toluene, and xylene. Further, as the catalyst used in the present invention,
Any homogeneous hydrogenation catalyst can be used. For example, T
A metallocene compound containing any of i, Zr, and Hf can be used. Among them, a hydrogenation catalyst obtained by reacting a titanocene compound with alkoxylithium is an inexpensive and industrially particularly useful catalyst. Specific examples include JP-A-1-275605, JP-A-5-271326, JP-A-5-271325, and JP-A-5-222.
No. 115, JP-A-11-292924, JP-A-2000-37632, JP-A-59-13320
No. 3, JP-A-63-5401, JP-A-62-2
218403, JP-A-7-90017, JP-B-43-19960, JP-B-47-40473.
The hydrogenation catalyst described in Japanese Patent Application Laid-Open Publication No. H10-209,873. One of these various hydrogenation catalysts may be used alone, or two or more thereof may be used in combination. More preferably, the following general formula (1)
At least one selected from the compounds represented by
Transition metal compound (1)).
【化２】 ここで、一般式（１）において、Ｍ1はチタニウム原
子、ジルコニウム原子またはハフニウム原子を示し、Ｘ
1およびＸ2は相互に独立にシクロペンタジエン骨格を有
する炭素数５〜２０の１価の炭化水素基を示し、Ｙ1は
複素環骨格を有する基が酸素原子または窒素原子を介し
てＭ1に結合している炭素数３〜２０の１価の有機基ま
たは炭素数１〜２０のアルコキシ基または炭素数１〜２
０のアリロキシ基またはハロゲン原子を示し、Ｙ2は 複
素環骨格を有する基が酸素原子または窒素原子を介して
Ｍ1に結合している炭素数３〜２０の１価の有機基を示
す。遷移金属化合物（１）の好ましい具体例としては、
下記式（７−１）〜（７−１６）等のチタニウム化合物
を挙げることができる。下記各式において[CP]はシクロ
ペンタジエニル基を示す。Embedded image Here, in the general formula (1), M 1 represents a titanium atom, a zirconium atom or a hafnium atom;
1 and X 2 each independently represent a monovalent hydrocarbon group having 5 to 20 carbon atoms having a cyclopentadiene skeleton, and Y 1 represents a group having a heterocyclic skeleton being converted to M 1 via an oxygen atom or a nitrogen atom. A monovalent organic group having 3 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms or a carbon atom having 1 to 2 carbon atoms
Y represents an allyloxy group or a halogen atom, and Y 2 represents a monovalent organic group having 3 to 20 carbon atoms in which a group having a heterocyclic skeleton is bonded to M 1 via an oxygen atom or a nitrogen atom. Preferred specific examples of the transition metal compound (1) include:
Titanium compounds represented by the following formulas (7-1) to (7-16) can be exemplified. In the following formulas, [CP] represents a cyclopentadienyl group.
【化３】 Embedded image
【化４】 これらの遷移金属化合物（１）のうち、特に（７−
１）、（７−２）、（７−５）、（７−１１）、（７−
１２）等が好ましい。Embedded image Among these transition metal compounds (1), (7-
1), (7-2), (7-5), (7-11), (7-
12) and the like are preferable.
【００１２】また、本発明は、前記何れかの構成に於い
て、攪拌槽型反応器の攪拌の所要動力が０．１〜５．０
ｋＷ／ｍ3 であることを特徴とする水素添加方法であ
る。この所要動力は、オレフィン性不飽和ポリマーを含
有する不活性有機溶媒溶液の粘度に応じて適宜に調整す
るものとする。所要動力が大きいほど水素の拡散状態は
良好となるが、最終的には飽和する。攪拌槽型反応器を
２基以上用いる場合には、前段の攪拌槽型反応器の攪拌
の所要動力を、後段の攪拌槽型反応器の所要動力よりも
小さくすると、前段での発熱を抑えることができる。ま
た、本発明は、前記の何れかの構成に於いて、オレフィ
ン性不飽和ポリマーが共役ジエン系ポリマーであること
を特徴とする水素添加方法である。Further, according to the present invention, in any one of the above constitutions, the power required for stirring of the stirred tank reactor is 0.1 to 5.0.
kW / m 3 . The required power is appropriately adjusted according to the viscosity of the inert organic solvent solution containing the olefinically unsaturated polymer. The larger the required power is, the better the hydrogen diffusion state is, but it eventually saturates. When two or more stirred tank reactors are used, if the required power for stirring in the former stirred tank reactor is smaller than the required power in the latter stirred tank reactor, heat generation in the former stage can be suppressed. Can be. Further, the present invention is the hydrogenation method according to any one of the above constitutions, wherein the olefinically unsaturated polymer is a conjugated diene-based polymer.
【００１３】[0013]
【発明の実施の形態】以下、本発明の実施の形態を説明
する。図１と図２は、実施の形態の水素添加方法で用い
る反応器システムの構成を示し、図３は、従来の水素添
加方法で用いる反応器システムの構成を示す。図１の反
応器システムは、２基の攪拌槽型反応器を連結したもの
であり、第１の攪拌槽型反応器（図内左側の反応器）で
は、重合体溶液（オレフィン性不飽和ポリマーを含有す
る不活性有機溶媒溶液）と触媒（均一系の水素添加触
媒）と水素とが該第１の攪拌槽型反応器の槽底部から流
入されて槽上部から排出されている。なお、図示の例で
は、重合体溶液と触媒とは別々の管を通して攪拌槽型反
応器へ流入されているが、重合体溶液と触媒とを攪拌槽
型反応器への供給前に予め混合しておき共通の管を通し
て攪拌槽型反応器へ流入させてもよい。また、図１の反
応器システムでは、第１の攪拌槽型反応器の上部から排
出された液（水素添加されたオレフィン性ポリマー溶
液．但し、水素未添加の重合体溶液と触媒と水素も含有
している）は、続いて、第２の攪拌槽型反応器（図内右
側の反応器）の槽底部から流入されて槽上部から排出さ
れている。なお、第２の攪拌槽型反応器の後段に、さら
に、連続流通式の管型反応器を設けておき、第２の攪拌
槽型反応器から排出された液（水素添加されたオレフィ
ン性ポリマー溶液．但し、ごく微量の水素未添加の重合
体溶液と触媒と水素も含有している）を送り込むこと
で、第１及び第２の攪拌槽型反応器中を短い経路で通っ
たために水素未添加のままである重合体溶液（オレフィ
ン性不飽和ポリマーを含有する不活性有機溶媒溶液）を
水素添加するようにしてもよい。図１の反応器システム
内の第１及び第２の攪拌槽型反応器では、重合体溶液と
触媒と水素を槽底部から流入させて槽上部から押し出す
ため、攪拌槽型反応器内での気液接触がより十分に行わ
れて、反応がより速やかとなる。したがって、達成され
る水素添加率が同じであれば所要時間が短縮される。ま
た、図１の反応器システムでは、第１と第２の攪拌槽型
反応器を設けているため、水素添加反応による発熱を各
攪拌槽型反応器へ分散させることができ、その結果、第
１と第２の攪拌槽型反応器の総容積を持つ単一の攪拌槽
型反応器を用いる場合よりも、除熱を行い易くなる。ま
た、図１の反応器システムに於いて、第２の攪拌槽型反
応器へも、その槽底部から水素を供給するようにする
と、水素添加反応による発熱を各攪拌槽型反応器へ分散
させる効果を更に高めることができる。その結果、第１
又は第２の攪拌槽型反応器の何れか一方へ水素を供給す
る場合や、第１と第２の攪拌槽型反応器の総容積を持つ
単一の攪拌槽型反応器へ水素を供給する場合よりも、水
素添加反応を更に制御し易くなり、除熱も容易となる。
一方、図２に示す反応器システムは、３基の攪拌槽型反
応器を連結したものである。即ち、図１の反応器システ
ムに於いて、第２の攪拌槽型反応器の後段に第３の攪拌
槽型反応器を設け、更に、該第３の攪拌槽型反応器の後
段に、連続流通式の管型反応器を設けたシステムであ
る。他の構成については、図１の反応器システムと同様
である。図２の反応器システムでは、図１の反応器シス
テムが奏する上述の各作用効果を、更に十分に達成する
ことができる。なお、図２の構成では、攪拌槽型反応器
を３段に設けているが、４段以上に設けて、上述の各作
用効果を更に一層十分に得られるようにしてもよい。Embodiments of the present invention will be described below. 1 and 2 show the configuration of a reactor system used in the hydrogenation method of the embodiment, and FIG. 3 shows the configuration of a reactor system used in a conventional hydrogenation method. The reactor system of FIG. 1 is a system in which two stirred tank reactors are connected, and the first stirred tank reactor (reactor on the left side in the figure) includes a polymer solution (olefinically unsaturated polymer). , A catalyst (homogeneous hydrogenation catalyst) and hydrogen are introduced from the bottom of the first stirred tank reactor and discharged from the top of the tank. In the illustrated example, the polymer solution and the catalyst are introduced into the stirred tank reactor through separate pipes. However, the polymer solution and the catalyst are mixed in advance before being supplied to the stirred tank reactor. Alternatively, it may flow into a stirred tank reactor through a common pipe. Further, in the reactor system of FIG. 1, the liquid discharged from the upper part of the first stirred tank type reactor (hydrogenated olefinic polymer solution, but also containing hydrogen-free polymer solution, catalyst and hydrogen) ) Subsequently flows in from the bottom of the second stirred tank reactor (reactor on the right side in the figure) and is discharged from the top of the tank. In addition, a continuous flow type tubular reactor is further provided at the subsequent stage of the second stirred tank reactor, and the liquid discharged from the second stirred tank reactor (hydrogenated olefin polymer Solution, which also contains a very small amount of a non-hydrogenated polymer solution, a catalyst, and hydrogen), so that it passes through the first and second stirred tank reactors in a short path, so that the hydrogen The polymer solution which is still added (an inert organic solvent solution containing an olefinically unsaturated polymer) may be hydrogenated. In the first and second stirred tank reactors in the reactor system of FIG. 1, the polymer solution, catalyst and hydrogen flow from the bottom of the tank and are pushed out from the top of the tank. The liquid contact is performed more sufficiently, and the reaction becomes faster. Therefore, the required time is reduced if the achieved hydrogenation rates are the same. In addition, in the reactor system of FIG. 1, since the first and second stirred tank reactors are provided, the heat generated by the hydrogenation reaction can be dispersed to each stirred tank reactor. It becomes easier to remove heat than when using a single stirred tank reactor having the total volume of the first and second stirred tank reactors. Further, in the reactor system of FIG. 1, when hydrogen is also supplied to the second stirred tank reactor from the bottom of the tank, heat generated by the hydrogenation reaction is dispersed to each stirred tank reactor. The effect can be further enhanced. As a result, the first
Alternatively, when supplying hydrogen to one of the second stirred tank reactors, or supplying hydrogen to a single stirred tank reactor having the total volume of the first and second stirred tank reactors As compared with the case, the hydrogenation reaction is more easily controlled, and the heat removal is also easier.
On the other hand, the reactor system shown in FIG. 2 connects three stirred tank reactors. That is, in the reactor system of FIG. 1, a third stirred tank reactor is provided at a stage subsequent to the second stirred tank reactor, and further, a continuous stirred tank reactor is provided at a stage subsequent to the third stirred tank reactor. This is a system provided with a flow-through tubular reactor. Other configurations are the same as those of the reactor system of FIG. In the reactor system shown in FIG. 2, each of the above-described effects achieved by the reactor system shown in FIG. 1 can be more sufficiently achieved. In the configuration of FIG. 2, the stirred tank reactor is provided in three stages, but may be provided in four or more stages so that the above-described respective effects can be obtained even more sufficiently.
【００１４】図３に示す従来の反応器システムでも２基
の攪拌槽型反応器が連結されているが、重合体溶液と触
媒を第１の攪拌槽型反応器へ槽上部より供給するととも
に槽底部から排出している点、第１の攪拌槽型反応器の
槽上部に気相部のガスを抜くための管が設けられている
点、第１の攪拌槽型反応器の槽底部から排出された液を
第２の攪拌槽型反応器へ槽上部より供給するとともに槽
底部から排出している点、及び、第２の攪拌槽型反応器
の槽上部から排出した水素を第１の攪拌槽型反応器へ供
給している点に於いて、図１や図２の反応器システムと
異なる。なお、図１〜図３のシステムの各攪拌槽型反応
器内の攪拌翼は、何れもディスクタービン翼であり、所
要動力は１．０ｋＷ／ｍ3 である。In the conventional reactor system shown in FIG. 3, two stirred tank reactors are connected. The polymer solution and the catalyst are supplied to the first stirred tank reactor from the top of the tank and the tank is supplied to the tank. Discharged from the bottom, Disposed from the bottom of the first stirred tank reactor, a pipe for removing gas from the gas phase is provided above the tank of the first stirred tank reactor, Discharged from the bottom of the tank of the first stirred tank reactor The point where the separated liquid is supplied to the second stirred tank reactor from the tank top and discharged from the tank bottom, and the hydrogen discharged from the tank top of the second stirred tank reactor is subjected to the first stirring. It differs from the reactor system of FIGS. 1 and 2 in that it is fed to a tank reactor. The stirring blades in each of the stirred tank reactors in the systems shown in FIGS. 1 to 3 are disk turbine blades, and the required power is 1.0 kW / m 3 .
【００１５】以下、実施例と比較例を説明するが、本発
明は以下の実施例に限定されるものではなく、前述した
各種の態様を包含する。なお、実施例１及び２と比較例
中の％は重量％を意味し、圧力はゲージ圧力を意味す
る。また、水素添加率は、 1Ｈ−ＮＭＲスペクトル（１
００ＭＨｚ）により測定した。 〔１〕実施例１：図１の反応器システムを用いて、スチ
レン−ブタジエン−スチレンブロック共重合体の水素化
物を、下記のように製造した。即ち、ビス（η5 −シク
ロペンタジエニル）チタニウム（テトラヒドロフルフリ
ルオキシ）クロリドと、ジエチルアルミニウムクロリド
と、から成る水素化触媒１％トルエン溶液を、２００ｇ
／ｈｒで；スチレン−ブタジエン−スチレンブロック共
重合体を１７％含有しており、シクロヘキサン溶媒を用
いて調整した重合体溶液を２０ｋｇ／ｈｒで；水素を１
４００ＮＬ／ｈｒで；それぞれ第１の攪拌槽型反応器
（内容積４０Ｌ）の槽底部から供給した。また、第１の
攪拌槽型反応器と第２の攪拌槽型反応器（内容積４０
Ｌ）の槽内の温度を１１０℃に維持するとともに、第１
と第２の各攪拌槽型反応器の槽内圧力が０．８ＭＰａと
なるように第２の攪拌槽型反応器の槽上部から排出され
る液量を調整した。第１の攪拌槽型反応器から排出され
る重合体の水素添加率は８０％、第２の攪拌槽型反応器
から排出される重合体の水素添加率は９７％であった。Hereinafter, examples and comparative examples will be described. However, the present invention is not limited to the following examples, but includes the various embodiments described above. It should be noted that% in Examples 1 and 2 and Comparative Example means% by weight, and pressure means gauge pressure. In addition, the hydrogenation rate was determined by 1H-NMR spectrum (1
00 MHz). [1] Example 1: Using the reactor system of FIG. 1, a hydride of a styrene-butadiene-styrene block copolymer was produced as follows. That is, 200 g of a 1% toluene solution of a hydrogenation catalyst composed of bis (η 5 -cyclopentadienyl) titanium (tetrahydrofurfuryloxy) chloride and diethylaluminum chloride was used.
/ Hr; 20 kg / hr of a polymer solution containing 17% of a styrene-butadiene-styrene block copolymer and prepared using a cyclohexane solvent;
400 NL / hr; each was fed from the bottom of the first stirred tank reactor (40 L internal volume). In addition, a first stirred tank reactor and a second stirred tank reactor (with an internal volume of 40
While maintaining the temperature in the tank of L) at 110 ° C.,
And the amount of liquid discharged from the upper portion of the second stirred tank reactor was adjusted such that the pressure in the tank of each of the second stirred tank reactors was 0.8 MPa. The hydrogenation rate of the polymer discharged from the first stirred tank reactor was 80%, and the hydrogenation rate of the polymer discharged from the second stirred tank reactor was 97%.
【００１６】〔２〕実施例２：実施例１と実施例２との
差異は、図１のシステムに代えて図２のシステムを用い
た点、水素添加触媒の供給速度が４００ｇ／ｈｒである
点、重合体溶液の供給速度が４０ｋｇ／ｈｒである点、
及び水素の供給速度が２８００ＮＬ／ｈｒである点であ
る。以下、詳述する。図２の反応器システムを用いて、
スチレン−ブタジエン−スチレンブロック共重合体の水
素添加物を、下記のように製造した。即ち、ビス（η5
−シクロペンタジエニル）チタニウム（テトラヒドロフ
ルフリルオキシ）クロリドと、ジエチルアルミニウムク
ロリドと、から成る水素添加触媒１％トルエン溶液を、
４００ｇ／ｈｒで；スチレン−ブタジエン−スチレンブ
ロック共重合体を１７％含有しており、シクロヘキサン
溶媒を用いて調整した重合体溶液を４０ｋｇ／ｈｒで；
水素を２８００ＮＬ／ｈｒで；それぞれ第１の攪拌槽型
反応器（内容積４０Ｌ）の槽底部から供給した。また、
第１と第２と第３の各攪拌槽型反応器（各々内容積４０
Ｌ）と管型反応器（内容積２０Ｌ）の槽内の温度を１１
０℃に維持するとともに、各攪拌槽型反応器の槽内圧力
が０．８ＭＰａとなるように管型反応器の出口から排出
される液量を調整した。第１の攪拌槽型反応器から排出
される重合体の水素添加率は５０％、第２の攪拌槽型反
応器から排出される重合体の水素添加率は８０％、第３
の攪拌槽型反応器から排出される重合体の水素添加率は
９５％、管型反応器から排出される重合体の水素添加率
は９９％であった。[2] Embodiment 2: The difference between Embodiment 1 and Embodiment 2 is that the system of FIG. 2 is used instead of the system of FIG. 1, and the supply rate of the hydrogenation catalyst is 400 g / hr. The point that the feed rate of the polymer solution is 40 kg / hr,
And the supply rate of hydrogen is 2800 NL / hr. The details will be described below. Using the reactor system of FIG.
A hydrogenated styrene-butadiene-styrene block copolymer was prepared as follows. That is, the screw (η 5
-Cyclopentadienyl) titanium (tetrahydrofurfuryloxy) chloride and diethylaluminum chloride in a 1% toluene solution of a hydrogenation catalyst.
400 g / hr; 40 kg / hr of a polymer solution containing 17% of a styrene-butadiene-styrene block copolymer and prepared using a cyclohexane solvent;
Hydrogen was fed at 2800 NL / hr from the bottom of each of the first stirred tank reactors (40 L internal volume). Also,
First, second and third stirred tank reactors (each having an internal volume of 40
L) and the temperature in the vessel of the tubular reactor (internal volume 20 L) to 11
While maintaining the temperature at 0 ° C., the amount of liquid discharged from the outlet of the tubular reactor was adjusted so that the pressure in each of the stirred tank reactors was 0.8 MPa. The hydrogenation rate of the polymer discharged from the first stirred tank reactor is 50%, the hydrogenation rate of the polymer discharged from the second stirred tank reactor is 80%,
The hydrogenation rate of the polymer discharged from the stirred tank reactor was 95%, and the hydrogenation rate of the polymer discharged from the tubular reactor was 99%.
【００１７】〔３〕比較例：比較例と実施例１との差異
は、図１のシステムに代えて図３のシステムを用いた
点、水素添加触媒の供給速度が１００ｇ／ｈｒである
点、重合体溶液の供給速度が１０ｋｇ／ｈｒである点、
第１の攪拌槽型反応器の槽内圧力が０．８ＭＰａとなる
ように第２の攪拌槽型反応器の槽上部から排出される水
素を第１の攪拌槽型反応器へ槽底部より供給した点、及
び第２の攪拌槽型反応器の槽内圧力が１．０ＭＰａとな
るように第２の攪拌槽型反応器へ槽底部より水素を供給
した点である。以下、詳述する。図２の反応器システム
を用いて、スチレン−ブタジエン−スチレンブロック共
重合体の水素化物を、下記のように製造した。即ち、ビ
ス（η5 −シクロペンタジエニル）チタニウム（テトラ
ヒドロフルフリルオキシ）クロリドと、ジエチルアルミ
ニウムクロリドと、から成る水素添加触媒１％トルエン
溶液を、１００ｇ／ｈｒで；スチレン−ブタジエン−ス
チレンブロック共重合体を１７％含有しており、シクロ
ヘキサン溶媒を用いて調整した重合体溶液を１０ｋｇ／
ｈｒで；それぞれ第１の攪拌槽型反応器（内容積４０
Ｌ）の槽上部から供給した。また、第１の攪拌槽型反応
器の槽内圧力が０．８ＭＰａとなるように、第２の攪拌
槽型反応器（内容積４０Ｌ）の槽上部から排出される水
素を、第１の攪拌槽型反応器へ、その槽底部より供給す
るとともに、第２の攪拌槽型反応器の槽内圧力が１．０
ＭＰａとなるように、第２の攪拌槽型反応器へ、その槽
底部より水素を供給した。また、第１と第２の各攪拌槽
型反応器の槽内の温度を１１０℃に維持した。第１の攪
拌槽型反応器から排出される重合体の水素添加率は６５
％、第２の攪拌槽型反応器から排出される重合体の水素
添加率は８７％であった。なお、平均滞留時間を第１及
び第２の実施例より長くしても、高水素添加率を得るこ
とはできなかった。[3] Comparative Example: The difference between the comparative example and the embodiment 1 is that the system of FIG. 3 is used instead of the system of FIG. 1, that the supply rate of the hydrogenation catalyst is 100 g / hr, The feed rate of the polymer solution is 10 kg / hr,
Hydrogen discharged from the upper part of the tank of the second stirred tank reactor is supplied from the bottom of the tank to the first stirred tank reactor so that the pressure in the tank of the first stirred tank reactor becomes 0.8 MPa. And hydrogen was supplied from the bottom of the second stirred tank reactor to the second stirred tank reactor so that the pressure in the tank of the second stirred tank reactor became 1.0 MPa. The details will be described below. Using the reactor system of FIG. 2, a hydride of a styrene-butadiene-styrene block copolymer was produced as follows. That is, a 1% toluene solution of a hydrogenation catalyst composed of bis (η 5 -cyclopentadienyl) titanium (tetrahydrofurfuryloxy) chloride and diethylaluminum chloride at 100 g / hr; styrene-butadiene-styrene block copolymer It contains 17% of a polymer, and a polymer solution prepared using a cyclohexane solvent is 10 kg /
hr; the first stirred tank reactor (internal volume 40
L). Hydrogen discharged from the upper part of the tank of the second stirred tank type reactor (internal volume 40 L) is subjected to the first stirring so that the pressure in the tank of the first stirred tank type reactor becomes 0.8 MPa. The reactor was supplied to the tank reactor from the bottom of the tank, and the pressure in the tank of the second stirred tank reactor was 1.0.
Hydrogen was supplied to the second stirred tank reactor from the bottom of the tank so that the pressure became MPa. The temperature in the tank of each of the first and second stirred tank reactors was maintained at 110 ° C. The hydrogenation rate of the polymer discharged from the first stirred tank reactor is 65
%, And the hydrogenation rate of the polymer discharged from the second stirred tank reactor was 87%. Even if the average residence time was longer than in the first and second examples, a high hydrogenation rate could not be obtained.
【００１８】[0018]
【発明の効果】本発明の方法では、オレフィン性不飽和
ポリマーを含有する不活性有機溶媒溶液と均一系の水素
添加触媒と水素とを連続流通式の攪拌槽型反応器へ連続
的に供給するとともに該連続的な供給により該攪拌槽型
反応器から押し出すことでオレフィン性不飽和ポリマー
を水素化するため、広範囲の粘度領域のオレフィン性不
飽和ポリマーを、連続した工程で、安定した高い水素添
加率に水素添加することができる。According to the method of the present invention, an inert organic solvent solution containing an olefinically unsaturated polymer, a homogeneous hydrogenation catalyst, and hydrogen are continuously supplied to a continuous flow stirred tank reactor. In addition, the olefinically unsaturated polymer is hydrogenated by extruding the olefinically unsaturated polymer from the stirred tank reactor by the continuous supply. Rate can be hydrogenated.
【図１】実施の形態の水素添加方法で用いる反応器シス
テムの構成を示す説明図。実施例１の水素添加反応で用
いたシステム。FIG. 1 is an explanatory diagram showing a configuration of a reactor system used in a hydrogenation method according to an embodiment. 2 shows a system used in the hydrogenation reaction of Example 1.
【図２】実施の形態の水素添加方法で用いる反応器シス
テムの構成を示す説明図。実施例１の水素添加反応で用
いたシステム。FIG. 2 is an explanatory diagram showing a configuration of a reactor system used in the hydrogenation method of the embodiment. 2 shows a system used in the hydrogenation reaction of Example 1.
【図３】従来の水素添加方法で用いる反応器システムの
構成を例示する説明図。比較例１の水素添加反応で用い
たシステム。FIG. 3 is an explanatory diagram illustrating the configuration of a reactor system used in a conventional hydrogenation method. The system used in the hydrogenation reaction of Comparative Example 1.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 森 好弘 東京都中央区築地二丁目11番24号 ジェイ エスアール株式会社内 (72)発明者 中沢 和美 東京都中央区築地二丁目11番24号 ジェイ エスアール株式会社内 Ｆターム(参考） 4J100 AB02P AS02Q CA04 HA04 HB02 HD22 HE14 HE41 HF01 HG03 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yoshihiro Mori 2-11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Co., Ltd. (72) Inventor Kazumi Nakazawa 2-11-24 Tsukiji, Chuo-ku Tokyo F term (reference) 4J100 AB02P AS02Q CA04 HA04 HB02 HD22 HE14 HE41 HF01 HG03
Claims (10)
不活性有機溶媒溶液と均一系の水素添加触媒及び水素と
を攪拌槽型反応器へ連続的に供給するとともに該攪拌槽
型反応器から反応物を連続的に押し出すことでオレフィ
ン性不飽和ポリマーを水素化することを特徴とする水素
添加方法。1. An inert organic solvent solution containing an olefinically unsaturated polymer, a homogeneous hydrogenation catalyst and hydrogen are continuously supplied to a stirred tank reactor, and reactants are supplied from the stirred tank reactor. Wherein the olefinically unsaturated polymer is hydrogenated by continuously extruding olefins.
溶液と均一系の水素添加触媒と水素とを攪拌槽型反応器
の槽底部から供給して槽上部から排出させることを特徴
とする水素添加方法。2. The tank according to claim 1, wherein an inert organic solvent solution containing an olefinically unsaturated polymer, a homogeneous hydrogenation catalyst, and hydrogen are supplied from the tank bottom of the stirred tank reactor. A hydrogenation method characterized in that the hydrogenation is carried out.
順に設けた複数基の攪拌槽型反応器へ連続的に供給する
とともに各攪拌槽型反応器から反応物を連続的に押し出
すことを特徴とする水素添加方法。3. The method according to claim 1 or 2, wherein after being extruded from the stirred tank reactor, the mixture is continuously supplied to one or a plurality of stirred tank reactors provided in a subsequent stage. A hydrogenation method comprising continuously extruding a reactant from a stirred tank reactor.
を特徴とする水素添加方法。4. The hydrogenation method according to claim 3, wherein hydrogen is continuously supplied to each of the stirred tank reactors.
応器へ連続的に供給することで更に水素化させることを
特徴とする水素添加方法。5. The method according to claim 1, wherein the mixture is extruded from a stirred tank reactor and then continuously supplied to a continuous flow tubular reactor to further hydrogenate. Characterized hydrogenation method.
ことを特徴とする水素添加方法。6. The hydrogenation method according to claim 1, wherein the hydrogenation rate of the obtained hydrogenated polymer is 90% or more.
クロヘキサン、シクロヘプタン、シクロオクタン、ｎ−
ペンタン、ｎ−ヘキサン、ｎ−ヘプタン、ｎ−オクタ
ン、ｎ−ノナン、ｎ−デカン、ベンゼン、トルエン、及
びキシレンのうちから選ばれた少なくとも１種を含むこ
とを特徴とする水素添加方法。7. The method according to claim 1, wherein the inert organic solvent is isopentane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, n-
A hydrogenation method comprising at least one selected from pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, benzene, toluene, and xylene.
合物から選ばれた少なくとも１種を含有することを特徴
とする水素添加方法。 【化１】 ここで、一般式（１）において、Ｍ1はチタニウム原
子、ジルコニウム原子またはハフニウム原子を示し、Ｘ
1およびＸ2は相互に独立にシクロペンタジエン骨格を有
する炭素数５〜２０の１価の炭化水素基を示し、Ｙ1は
複素環骨格を有する基が酸素原子または窒素原子を介し
てＭ1に結合している炭素数３〜２０の１価の有機基ま
たは炭素数１〜２０のアルコキシ基または炭素数１〜２
０のアリロキシ基またはハロゲン原子を示し、Ｙ2は 複
素環骨格を有する基が酸素原子または窒素原子を介して
Ｍ1に結合している炭素数３〜２０の１価の有機基を示
す。8. The method according to claim 1, wherein the homogeneous hydrogenation catalyst contains at least one compound selected from the compounds represented by the following general formula (1). Hydrogenation method. Embedded image Here, in the general formula (1), M 1 represents a titanium atom, a zirconium atom or a hafnium atom;
1 and X 2 each independently represent a monovalent hydrocarbon group having 5 to 20 carbon atoms having a cyclopentadiene skeleton, and Y 1 represents a group having a heterocyclic skeleton being converted to M 1 via an oxygen atom or a nitrogen atom. A monovalent organic group having 3 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms or a carbon atom having 1 to 2 carbon atoms
Y represents an allyloxy group or a halogen atom, and Y 2 represents a monovalent organic group having 3 to 20 carbon atoms in which a group having a heterocyclic skeleton is bonded to M 1 via an oxygen atom or a nitrogen atom.
攪拌槽型反応器の攪拌の所要動力が０．１〜５．０ｋ
Ｗ／ｍ3 であることを特徴とする水素添加方法。9. The method according to claim 1, wherein
The required power for stirring of the stirred tank reactor is 0.1 to 5.0 k.
A hydrogenation method, wherein the hydrogenation rate is W / m 3 .
て、 オレフィン性不飽和ポリマーが共役ジエン系ポリ
マーであることを特徴とする水素添加方法。10. The hydrogenation method according to claim 1, wherein the olefinically unsaturated polymer is a conjugated diene-based polymer.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010031277A (en) * | 2008-07-24 | 2010-02-12 | Lanxess Inc | Method for continuous hydrogenation of carbon-carbon double bond in unsaturated polymer to produce hydrogenated polymer |
| CN103102432A (en) * | 2011-11-11 | 2013-05-15 | 中国石油化工股份有限公司 | Hydrogenation method of polymer |
| CN103788272A (en) * | 2012-10-31 | 2014-05-14 | 中国石油化工股份有限公司 | Hydrogenation method of polymer containing olefin unsaturated bonds |
| JPWO2017010562A1 (en) * | 2015-07-16 | 2018-04-05 | 旭化成株式会社 | Partially hydrogenated block copolymer, adhesive composition, adhesive tape, label, modified asphalt composition, modified asphalt mixture, and paving binder composition |
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| JPH08301928A (en) * | 1995-03-08 | 1996-11-19 | Asahi Chem Ind Co Ltd | Production of selectively and partially hydrogenated rubber containing bonded tin |
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| JP2000037632A (en) * | 1998-07-24 | 2000-02-08 | Jsr Corp | Hydrogen adding catalyst for olefinic unsaturated compound and its hydrogen adding method |
| WO2002002650A1 (en) * | 2000-06-30 | 2002-01-10 | Asahi Kasei Kabushiki Kaisha | Method for hydrogenation of polymer |
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2001
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| JPH08301928A (en) * | 1995-03-08 | 1996-11-19 | Asahi Chem Ind Co Ltd | Production of selectively and partially hydrogenated rubber containing bonded tin |
| JPH11286513A (en) * | 1998-03-31 | 1999-10-19 | Jsr Corp | Continuous production of hydrogenated olefinic unsaturated group-containing polymer |
| JP2000037632A (en) * | 1998-07-24 | 2000-02-08 | Jsr Corp | Hydrogen adding catalyst for olefinic unsaturated compound and its hydrogen adding method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010031277A (en) * | 2008-07-24 | 2010-02-12 | Lanxess Inc | Method for continuous hydrogenation of carbon-carbon double bond in unsaturated polymer to produce hydrogenated polymer |
| CN103102432A (en) * | 2011-11-11 | 2013-05-15 | 中国石油化工股份有限公司 | Hydrogenation method of polymer |
| CN103788272A (en) * | 2012-10-31 | 2014-05-14 | 中国石油化工股份有限公司 | Hydrogenation method of polymer containing olefin unsaturated bonds |
| JPWO2017010562A1 (en) * | 2015-07-16 | 2018-04-05 | 旭化成株式会社 | Partially hydrogenated block copolymer, adhesive composition, adhesive tape, label, modified asphalt composition, modified asphalt mixture, and paving binder composition |
| US10414849B2 (en) | 2015-07-16 | 2019-09-17 | Asahi Kasei Kabushiki Kaisha | Partially hydrogenated block copolymer, viscous adhesive composition, viscous adhesive tape, label, modified asphalt composition, modified asphalt mixture, and paving binder composition |
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|---|---|
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