JPS6361324B2 - - Google Patents
Info
- Publication number
- JPS6361324B2 JPS6361324B2 JP59089317A JP8931784A JPS6361324B2 JP S6361324 B2 JPS6361324 B2 JP S6361324B2 JP 59089317 A JP59089317 A JP 59089317A JP 8931784 A JP8931784 A JP 8931784A JP S6361324 B2 JPS6361324 B2 JP S6361324B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen peroxide
- hydroxyl group
- conjugated diene
- weight
- diene monomer
- 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
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 33
- 150000001993 dienes Chemical class 0.000 claims description 24
- 239000000178 monomer Substances 0.000 claims description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 13
- 150000002898 organic sulfur compounds Chemical class 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000012429 reaction media Substances 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 claims 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- LEKIODFWYFCUER-UHFFFAOYSA-N 2-methylidenebut-3-enenitrile Chemical compound C=CC(=C)C#N LEKIODFWYFCUER-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-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
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- -1 anilylonitrile Chemical compound 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymerization Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】
本発明は水酸基含有ジエン系重合体の製造方法
に関し、詳しくは過酸化水素の使用量を低減せし
め、かつ収率の向上した水酸基含有ジエン系重合
体の製造方法に関する。
過酸化水素を触媒として共役ジエンモノマーを
重合せしめて水酸基末端の液状ジエン系重合体を
得ることは従来より知られている。
しかし、従来の方法では過酸化水素が重合の触
媒としておよび末端水酸基として消費される以外
にも、水と酸素に分解する副反応による消費が大
きな割合を占め、有効に利用されていなかつた。
そこで、本発明者らは比較的高価な過酸化水素を
有効に利用し、また重合体収率を向上させる方法
について鋭意研究した結果、反応系に特定の化合
物を存在させることにより、目的が達せられるこ
とを見い出し、その知見に基づいて本発明を完成
した。
すなわち本発明は、共役ジエン系モノマーを液
体反応媒体中で過酸化水素を触媒として重合反応
させて、水酸基含有ジエン系重合体を製造するに
あたり、重合反応をジフエニルスルホン、スルホ
ランおよびジチオリン酸０，0′−ジエチルから選
ばれた１種の有機硫黄化合物の存在化で行なうこ
とを特徴とする水酸基含有ジエン系重合体の製造
方法を提供するものである。
本発明の水酸基含有ジエン系重合体の製造に用
いる共役ジエン系モノマーとしては炭素数４〜12
個のジオレフイン形不飽和の非置換−、２−置換
−もしくは２，３−置換−１，３−ジエンがあ
る。ここで置換基としてはアルキル基、アリール
基、ハロゲン、シアノ基、ニトロ基などがある。
具体的なモノマーを例示すると、１，３−ブタジ
エン、イソプレン、クロロプレン、２−シアノ−
１，３−ブタジエン、２，３−ジメチル−１，３
−ブタジエンなどがある。
本発明では、基本的には上記共役ジエンモノマ
ーを単独もしくは２種以上組合せて用いるが、必
要に応じて共役ジエンモノマーの一部をエチレン
性不飽和モノマーで置き換えることができ、炭素
数２〜22個のα−オレフイン性付加重合性モノマ
ーが用いられる。具体的にはスチレン、α−メチ
ルスチレン、ビニルトルエン、メタアクリル酸メ
チル、アクリル酸、塩化ビニル、塩化ビニリデ
ン、アニリロニトリル、アクリルアミド、２−エ
チルヘキシルアクリレート、ｎ−オクタデシルア
クリレート、無水マレイン酸、ブテン、２−ヒド
ロキシエチルメタクリレートなどがある。このモ
ノオレフイン不飽和モノマーは好ましくは０〜75
重量％の範囲で共役ジエンモノマーと併用でき
る。
次に、共役ジエンモノマーの重合反応を行なう
際の液体反応媒体としては該ジエンモノマー、過
酸化水素および有機硫黄化合物に対して相溶性の
良好な溶媒が好ましい。このような溶媒としてイ
ソプロパノール、エタノール、プロピルエーテ
ル、テトラヒドロフラン、酢酸エチル、セロソル
ブ、セロソルブアセテート、エチルセロソルブ、
Ｎ，Ｎ−ジメチルホルムアミド、アセトン、メタ
ノール、ｎ−プロパノール、ブタノールなどある
いはこれらの混合物をあげることができる。溶媒
の使用量は全仕込み（モノマー、過酸化水素およ
び溶媒）の５〜90重量％、好ましくは30〜70重量
％である。
また、触媒として作用する過酸化水素は通常、
30〜80％水溶液として用い、いずれにしても過酸
化水素として共役ジエンモノマーの５重量％以
上、通常は５〜60重量％を存在させることが必要
である。
これに対して従来法では過酸化水素は共役ジエ
ンモノマーに対して10重量％以上、10〜80重量％
程度使用する必要があつたが、本発明では上記範
囲の量を用いれば充分である。
本発明においては、ジフエニルスルホン、スル
ホランおよびジチオリン酸０，0′−ジエチルから
選ばれた１種の有機硫黄化合物の存在下で重合体
の製造をすることを特徴としている。この有機硫
黄化合物は過酸化水素の助触媒としての役割を果
し、過酸化水素の副反応への消費を防止し、重合
反応を効率良く行なうものである。
この有機硫黄化合物の使用量は特に制限はない
が、通常はジエンモノマーに対して0.01〜10重量
％、好ましくは0.05〜５重量％である。0.01重量
％未満では助触媒として充分に機能せず、また10
重量％を越えて使用しても、過酸化水素の使用量
を低減させる効果は向上しない。
本発明の共役ジエン系モノマーの重合反応は上
記各成分を配合し、温度50〜200℃、好ましくは
80〜150℃、圧力５〜100気圧、好ましくは10〜50
気圧にて10分〜24時間、好ましくは30分〜５時間
反応させれば良い。
反応終了後、通常の手順に従つて反応媒体等を
除去し、水酸基含有ジエン系重合体が得られる。
本発明の方法によれば、水酸基含有ジエン系重
合体が収率良く製造でき、しかも過酸化水素の使
用量を低減することができる。
したがつて、本発明は水酸基含有ジエン系重合
体の製造方法として極めて有用である。
次に、本発明を実施例により詳しく説明する。
実施例 １〜３
ステンレス製30ml振盪式オートクレーブにイソ
プロピルアルコール100重量部、50％過酸化水素
水10重量部および第１表に掲げる有機硫黄化合物
を仕込み、冷却しながらオートクレーブ内の空気
を脱気した。次いで、１，３−ブタジエン100重
量部を添加し、130℃に昇温した。その後、60分
間55ストローク／分で振盪撹拌して重合反応を行
なつた。
反応終了後、オートクレーブから反応液を取り
出し、イソプロピルアルコール、トルエンおよび
水の混合液（混合体積比１：２：５）を加えて油
層と水層に分離した。次に、油層をエバポレータ
ーにて予備脱気し、さらに１mmHg、80℃で30分
間脱気して水酸基含有ポリブタジエンを得た。こ
の重合体の収率を第１表に示す。
比較例 １
実施例１において、有機硫黄化合物を使用しな
かつたこと以外は実施例１と同様にして行ない水
酸基含有ポリブタジエンを得た。結果を第１表に
示す。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a hydroxyl group-containing diene polymer, and more particularly to a method for producing a hydroxyl group-containing diene polymer in which the amount of hydrogen peroxide used is reduced and the yield is improved. It has been known to polymerize conjugated diene monomers using hydrogen peroxide as a catalyst to obtain a liquid diene polymer having a hydroxyl group terminal. However, in conventional methods, in addition to being consumed as a polymerization catalyst and as a terminal hydroxyl group, hydrogen peroxide was not utilized effectively because a large proportion of hydrogen peroxide was consumed through side reactions in which it decomposed into water and oxygen.
Therefore, the inventors of the present invention conducted intensive research on a method for effectively utilizing relatively expensive hydrogen peroxide and improving the polymer yield. The present invention was completed based on this finding. That is, the present invention involves polymerizing a conjugated diene monomer in a liquid reaction medium using hydrogen peroxide as a catalyst to produce a hydroxyl group-containing diene polymer. The present invention provides a method for producing a hydroxyl group-containing diene polymer, characterized in that the method is carried out in the presence of one type of organic sulfur compound selected from 0'-diethyl. The conjugated diene monomer used in the production of the hydroxyl group-containing diene polymer of the present invention has 4 to 12 carbon atoms.
There are several diolefinically unsaturated unsubstituted, 2-substituted or 2,3-substituted 1,3-dienes. Examples of the substituent here include an alkyl group, an aryl group, a halogen, a cyano group, and a nitro group.
Specific monomers include 1,3-butadiene, isoprene, chloroprene, 2-cyano-
1,3-butadiene, 2,3-dimethyl-1,3
-Butadiene, etc. In the present invention, the above conjugated diene monomers are basically used alone or in combination of two or more, but if necessary, a part of the conjugated diene monomers can be replaced with an ethylenically unsaturated monomer, and the carbon number is 2 to 22. α-olefinic addition polymerizable monomers are used. Specifically, styrene, α-methylstyrene, vinyltoluene, methyl methacrylate, acrylic acid, vinyl chloride, vinylidene chloride, anilylonitrile, acrylamide, 2-ethylhexyl acrylate, n-octadecyl acrylate, maleic anhydride, butene, Examples include 2-hydroxyethyl methacrylate. The monoolefinically unsaturated monomer is preferably 0 to 75
It can be used in combination with a conjugated diene monomer within the range of weight percent. Next, as a liquid reaction medium when carrying out a polymerization reaction of a conjugated diene monomer, a solvent having good compatibility with the diene monomer, hydrogen peroxide, and an organic sulfur compound is preferable. Such solvents include isopropanol, ethanol, propyl ether, tetrahydrofuran, ethyl acetate, cellosolve, cellosolve acetate, ethyl cellosolve,
Examples include N,N-dimethylformamide, acetone, methanol, n-propanol, butanol, and mixtures thereof. The amount of solvent used is 5 to 90% by weight, preferably 30 to 70% by weight of the total charge (monomer, hydrogen peroxide and solvent). Additionally, hydrogen peroxide, which acts as a catalyst, usually
It is used as a 30-80% aqueous solution, and in any case it is necessary to have at least 5% by weight of the conjugated diene monomer as hydrogen peroxide, usually 5-60% by weight. In contrast, in the conventional method, hydrogen peroxide is 10% by weight or more, 10 to 80% by weight based on the conjugated diene monomer.
However, in the present invention, it is sufficient to use the amount within the above range. The present invention is characterized in that the polymer is produced in the presence of one type of organic sulfur compound selected from diphenylsulfone, sulfolane, and 0,0'-diethyl dithiophosphate. This organic sulfur compound serves as a co-catalyst for hydrogen peroxide, prevents hydrogen peroxide from being consumed in side reactions, and efficiently carries out the polymerization reaction. The amount of this organic sulfur compound to be used is not particularly limited, but it is usually 0.01 to 10% by weight, preferably 0.05 to 5% by weight based on the diene monomer. If it is less than 0.01% by weight, it will not function sufficiently as a promoter;
Even if it is used in excess of this amount by weight, the effect of reducing the amount of hydrogen peroxide used will not be improved. In the polymerization reaction of the conjugated diene monomer of the present invention, the above components are blended and the temperature is 50 to 200°C, preferably
80-150℃, pressure 5-100 atm, preferably 10-50
The reaction may be carried out at atmospheric pressure for 10 minutes to 24 hours, preferably 30 minutes to 5 hours. After the reaction is completed, the reaction medium and the like are removed according to a normal procedure to obtain a hydroxyl group-containing diene polymer. According to the method of the present invention, a hydroxyl group-containing diene polymer can be produced in good yield, and the amount of hydrogen peroxide used can be reduced. Therefore, the present invention is extremely useful as a method for producing a hydroxyl group-containing diene polymer. Next, the present invention will be explained in detail with reference to examples. Examples 1 to 3 100 parts by weight of isopropyl alcohol, 10 parts by weight of 50% hydrogen peroxide solution, and the organic sulfur compounds listed in Table 1 were placed in a 30 ml stainless steel shaking autoclave, and the air inside the autoclave was degassed while cooling. . Next, 100 parts by weight of 1,3-butadiene was added, and the temperature was raised to 130°C. Thereafter, the polymerization reaction was carried out by shaking and stirring at 55 strokes/min for 60 minutes. After the reaction was completed, the reaction solution was taken out from the autoclave, and a mixed solution of isopropyl alcohol, toluene, and water (mixed volume ratio 1:2:5) was added to separate it into an oil layer and an aqueous layer. Next, the oil layer was preliminarily degassed using an evaporator, and further degassed at 1 mmHg and 80°C for 30 minutes to obtain hydroxyl group-containing polybutadiene. The yield of this polymer is shown in Table 1. Comparative Example 1 Hydroxyl group-containing polybutadiene was obtained in the same manner as in Example 1 except that the organic sulfur compound was not used. The results are shown in Table 1. 【table】
Claims (1)
酸化水素を触媒として重合反応させて水酸基含有
ジエン系重合体を製造するにあたり、重合反応を
ジフエニルスルホン、スルホランおよびジチオリ
ン酸０，0′−ジエチルから選ばれた１種の有機硫
黄化合物の存在下で行なうことを特徴とする水酸
基含有ジエン系重合体の製造方法。 ２ 有機硫黄化合物の使用量が共役ジエン系モノ
マーに対して0.01〜10重量％である特許請求の範
囲第１項記載の製造方法。[Scope of Claims] 1. In producing a hydroxyl group-containing diene polymer by polymerizing a conjugated diene monomer in a liquid reaction medium using hydrogen peroxide as a catalyst, the polymerization reaction is carried out using diphenyl sulfone, sulfolane, and dithiophosphoric acid. , 0'-diethyl. , 0'-diethyl. 2. The manufacturing method according to claim 1, wherein the amount of the organic sulfur compound used is 0.01 to 10% by weight based on the conjugated diene monomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8931784A JPS60233112A (en) | 1984-05-07 | 1984-05-07 | Production of diene polymer containing hydroxyls |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8931784A JPS60233112A (en) | 1984-05-07 | 1984-05-07 | Production of diene polymer containing hydroxyls |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60233112A JPS60233112A (en) | 1985-11-19 |
| JPS6361324B2 true JPS6361324B2 (en) | 1988-11-29 |
Family
ID=13967283
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8931784A Granted JPS60233112A (en) | 1984-05-07 | 1984-05-07 | Production of diene polymer containing hydroxyls |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60233112A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2812293B1 (en) | 2000-07-28 | 2002-12-27 | Rhodia Chimie Sa | METHOD FOR SYNTHESIS OF BLOCK POLYMERS BY CONTROLLED RADICAL POLYMERIZATION |
| US20120037223A1 (en) * | 2009-07-01 | 2012-02-16 | Isao Yamanaka | Binder resin for conductive paste, conductive paste, and solar cell element |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6228964A (en) * | 1985-07-30 | 1987-02-06 | Matsushita Electric Ind Co Ltd | Recording disk reproducing device |
| JPS6258614A (en) * | 1985-09-03 | 1987-03-14 | Daido Steel Co Ltd | Arsenide galium epitaxial wafer and manufacture thereof |
-
1984
- 1984-05-07 JP JP8931784A patent/JPS60233112A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6228964A (en) * | 1985-07-30 | 1987-02-06 | Matsushita Electric Ind Co Ltd | Recording disk reproducing device |
| JPS6258614A (en) * | 1985-09-03 | 1987-03-14 | Daido Steel Co Ltd | Arsenide galium epitaxial wafer and manufacture thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60233112A (en) | 1985-11-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100344137B1 (en) | Hydrogenated Rubber Manufacturing Method | |
| BE1006548A3 (en) | Modifier anionic polymerization. | |
| US2380473A (en) | Catalysts for the addition polymerization of unsaturated organic compounds | |
| US5070150A (en) | Process for the solid state (solventless) hydroxylation of vinyl-containing rubbers using a hydroxymercaptan | |
| JP3073509B2 (en) | Method for producing cis 1,4-polybutadiene | |
| DE969407C (en) | Process for the production of polymer hydroperoxides | |
| US5057601A (en) | Process for producing a gel-free coagulated rubber with low ethylenic unsaturation | |
| JPS6361324B2 (en) | ||
| Bonnet et al. | New divalent samarocenes for butadiene polymerisation: influence of the steric effect and the electron density on the catalytic activity | |
| JPS6338043B2 (en) | ||
| US5561197A (en) | Hydrogenation of diene copolymers | |
| JPS60110708A (en) | Production of hydroxy group-containing diene polymer | |
| Wigal et al. | Mechanism of conjugate additions of dialkylcuprates to bromonaphthoquinones | |
| US2424851A (en) | Polymeric peroxides of acetonyl acetone | |
| JP4752112B2 (en) | Method for hydrogenating carbon-carbon double bonds of unsaturated polymers | |
| JPS6228964B2 (en) | ||
| JP2013517346A (en) | High CIS polybutadiene rubber in harmless solvent and process for preparing the same | |
| JPS6361325B2 (en) | ||
| JP2007301449A (en) | Method for hydrogenating conjugated diene polymer | |
| US2588975A (en) | Reaction rate of an emulsion polymerization process | |
| US20040068068A1 (en) | Optically active polymer with epoxide functions, method for preparing same, and use thereof | |
| JPH0457650B2 (en) | ||
| CN105985382A (en) | Metal complex, preparation method thereof, metal catalyst and application thereof, and preparation method of polybutadiene | |
| JP3966175B2 (en) | Method for polymerizing butadiene | |
| Schmitz | Preparation of Tetraethylene Glycol Dimethacrylate |