JPS6361325B2 - - Google Patents
Info
- Publication number
- JPS6361325B2 JPS6361325B2 JP59130850A JP13085084A JPS6361325B2 JP S6361325 B2 JPS6361325 B2 JP S6361325B2 JP 59130850 A JP59130850 A JP 59130850A JP 13085084 A JP13085084 A JP 13085084A JP S6361325 B2 JPS6361325 B2 JP S6361325B2
- Authority
- JP
- Japan
- Prior art keywords
- conjugated diene
- hydroxyl group
- hydrogen peroxide
- manufacturing
- 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
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 35
- 150000001993 dienes Chemical class 0.000 claims description 33
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- 239000000178 monomer Substances 0.000 claims description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 20
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 18
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 11
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 9
- 235000019253 formic acid Nutrition 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 235000011054 acetic acid Nutrition 0.000 claims description 8
- 235000019260 propionic acid Nutrition 0.000 claims description 8
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 4
- 239000012429 reaction media Substances 0.000 claims description 4
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 7
- 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
- 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
- 239000000203 mixture Substances 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-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
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-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
- 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
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 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
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 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
- 125000000524 functional group Chemical group 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
- 239000000463 material Substances 0.000 description 1
- 150000005673 monoalkenes Chemical class 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
- 239000003973 paint 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
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 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
- 239000000126 substance Substances 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymerization Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Description
【発明の詳細な説明】
本発明は水酸基含有液状ジエン系重合体の製造
方法に関し、詳しくは比較的少量の過酸化水素を
用いて、特定の触媒の存在下にて、効率良く低粘
度の水酸基含有液状ジエン系重合体を製造する方
法に関する。
従来より、共役ジエン系単量体と過酸化水素を
反応させて水酸基含有液状ジエン系重合体を製造
する方法が知られている。この方法によれば、所
定量の水酸基を含有する液状ジエン系重合体を効
率良く製造するためには比較的多量の過酸化水素
を使用する必要がある。しかしながら、過酸化水
素は取扱い上危険が伴なう物質であり、その使用
量の低減が望まれるものである。
そこで、本発明者は過酸化水素の使用量を低減
し、かつ低粘度の水酸基含有液状ジエン系重合体
を効率良く製造する方法について鋭意検討した結
果、特定の酸の存在下に過酸化水素と共役ジエン
系単量体を反応させることにより、上記目的を達
成できることを見出し、この知見に基づいて本発
明を完成した。
すなわち本発明は、共役ジエン系単量体を反応
媒体中で蟻酸、酢酸あるいはプロピオン酸の存在
下、過酸化水素と反応させることを特徴とする水
酸基含有液状ジエン系重合体の製造方法を提供す
るものである。
本発明に用いられる共役ジエン系単量体として
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−ジエンなどがある。ここで、置換基としては
種々のものが挙げられるが、具体的にはアルキル
基、アリール基、ハロゲン、シアノ基、ニトロ基
などがある。共役ジエン系単量体としては、例え
ば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−ブタジエンなどが挙げられ
る。
本発明では、基本的には上記共役ジエン系単量
体を単独もしくは２種以上組合せて用いるが、必
要に応じて共役ジエン系単量体の一部をエチレン
性不飽和単量体で置き換えることができ、該単量
体として炭素数２〜22個のα−オレフイン性付加
重合性単量体が用いられる。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単量体は好まし
くは０〜75重量％の範囲で共役ジエン系単量体と
併用できる。
次に、共役ジエン系単量体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系単量体と過
酸化水素等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
（共役ジエン系単量体、過酸化水素、蟻酸、酢酸
あるいはプロピオン酸および溶媒）の５〜90重量
％、好ましくは30〜70重量％である。
本発明に用いられる蟻酸、酢酸あるいはプロピ
オン酸は、過酸化水素をより効率良く反応に消費
させる役割を果すもので、いわば本発明において
触媒的作用をしている。本発明においては、蟻
酸、酢酸あるいはプロピオン酸を使用することに
より比較的少量の過酸化水素の使用で十分な水酸
基含量を有する低粘度の重合体が得られるのであ
る。
本発明において蟻酸、酢酸あるいはプロピオン
酸の使用量は共役ジエン系単量体に対して0.10〜
10.0重量％、好ましくは0.15〜8.0重量％程度が好
適である。
次に、過酸化水素は共役ジエン系単量体および
共役ジエン系重合体に対し水酸基を付加するとと
もに、重合反応の触媒としての役割を果すもので
ある。過酸化水素は通常30〜80％水溶液として用
いられる。過酸化水素の使用量は目的とする水酸
基含有量により異なり一義的に決定されないが、
通常、共役ジエン系単量体の５〜20重量％、好ま
しくは８〜18重量％で十分である。使用量が５重
量％未満であると、水酸基を効率良く共役ジエン
系単量体および共役ジエン系重合体に導入するこ
とができず、また20重量％を越えても、得られる
重合体の粘度の低下に寄与しない。
本発明の反応条件は特に制限なく、原料の種
類、使用量等により適宜定めれば良く、通常は共
役ジエン系単量体に対して蟻酸、酢酸あるいはプ
ロピオン酸0.10〜10.0重量％および過酸化水素５
〜20重量％の配合量で行なう場合、反応時間50〜
200℃、好ましくは100〜150℃、反応圧力５〜100
気圧、好ましくは10〜50気圧であり、反応時間は
通常10分から24時間あるいはそれ以上、好ましく
は30分から５時間である。反応終了後、常法に従
つて処理することにより水酸基含有液状ジエン系
重合体が得られる。上述の条件にて反応させて得
られる水酸基含有液状ジエン系重合体は、平均分
子量が1000〜3000程度、水酸基含量1.00〜
2.00meq／ｇ、粘度15〜25ポイズ／30℃程度のも
のであり、各種用途、例えば舗装材、接着剤、塗
料、樹脂添加剤等に有効に用いられるものであ
る。
以上の如く、本発明によれば低粘度の水酸基含
有液状ジエン系重合体が従来法と比較してかなり
少量の過酸化水素の使用により、効率良く製造す
ることができる。
次に、本発明を実施例により詳しく説明する。
実施例 １〜４
ステンレス（SUS316）製撹拌式１オートク
レーブにイソプロパノール、60％過酸化水素水お
よびカルボン酸として蟻酸または酢酸を第１表に
示す所定量を仕込み、冷却しながら脱気した。次
いで、１，３−ブタジエンを第１表に示す所定量
送入した後、第１表に示す所定温度まで昇温し、
所定時間撹拌反応を行なつた。
反応終了後、イソプロパノールとトルエンを加
え分液ロートに移した後、800mlの水を加えて振
とう後、油層と水層に分離した。
得られた油層をエバポレーターによつて予備蒸
発させ、さらに85℃、１mmHgで2.5時間蒸発させ
て揮発分を除去し、水酸基含有ポリブタジエンを
得た。このものの収率、粘度、水酸基含量、数平
均分子量および平均官能基数を第１表に示す。
比較例 １〜２
実施例１において、カルボン酸を使用しなかつ
たこと以外は実施例１と同様にして水酸基含有ポ
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 liquid diene polymer, and more specifically, the present invention relates to a method for producing a hydroxyl group-containing liquid diene polymer. The present invention relates to a method for producing a liquid diene-based polymer. BACKGROUND ART Conventionally, a method for producing a hydroxyl group-containing liquid diene polymer by reacting a conjugated diene monomer with hydrogen peroxide has been known. According to this method, in order to efficiently produce a liquid diene polymer containing a predetermined amount of hydroxyl groups, it is necessary to use a relatively large amount of hydrogen peroxide. However, hydrogen peroxide is a substance that is dangerous to handle, and it is desired to reduce the amount of hydrogen peroxide used. Therefore, the inventor of the present invention conducted intensive studies on a method for efficiently producing a low-viscosity liquid diene polymer containing hydroxyl groups while reducing the amount of hydrogen peroxide used. The inventors have discovered that the above object can be achieved by reacting conjugated diene monomers, and have completed the present invention based on this knowledge. That is, the present invention provides a method for producing a hydroxyl group-containing liquid diene polymer, which comprises reacting a conjugated diene monomer with hydrogen peroxide in the presence of formic acid, acetic acid, or propionic acid in a reaction medium. It is something. Conjugated diene monomers used in the present invention include diolefin-type unsaturated unsubstituted-, 2-substituted- or 2,3-substituted-1, having 4 to 12 carbon atoms,
Examples include 3-diene. Here, various substituents can be mentioned, and specific examples include an alkyl group, an aryl group, a halogen, a cyano group, and a nitro group. Examples of conjugated diene monomers include 1,3-butadiene, isoprene, chloroprene, 2-cyano-1,3-butadiene, and 2,3-butadiene.
Examples include dimethyl-1,3-butadiene. 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 may be replaced with an ethylenically unsaturated monomer. As the monomer, an α-olefinic addition polymerizable monomer having 2 to 22 carbon atoms is 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. This monoolefin unsaturated monomer can be used in combination with a conjugated diene monomer, preferably in a range of 0 to 75% by weight. Next, as the liquid reaction medium for carrying out the polymerization reaction of the conjugated diene monomer, a solvent having good compatibility with the diene monomer and hydrogen peroxide, etc. is preferable. Examples of such solvents include isopropanol, ethanol, propyl ether, tetrahydrofuran, ethyl acetate, cellosolve, cellosolve acetate, ethyl cellosolve, N,N-dimethylformamide, acetone, methanol, n-propanol, butanol, and mixtures thereof. can. The amount of the solvent used is 5 to 90% by weight, preferably 30 to 70% by weight of the total charge (conjugated diene monomer, hydrogen peroxide, formic acid, acetic acid or propionic acid, and solvent). Formic acid, acetic acid, or propionic acid used in the present invention plays a role in consuming hydrogen peroxide more efficiently in the reaction, and acts as a catalyst in the present invention. In the present invention, by using formic acid, acetic acid or propionic acid, a low viscosity polymer having a sufficient hydroxyl group content can be obtained with the use of a relatively small amount of hydrogen peroxide. In the present invention, the amount of formic acid, acetic acid, or propionic acid used is 0.10 to
A suitable amount is about 10.0% by weight, preferably about 0.15 to 8.0% by weight. Next, hydrogen peroxide adds a hydroxyl group to the conjugated diene monomer and conjugated diene polymer, and also serves as a catalyst for the polymerization reaction. Hydrogen peroxide is usually used as a 30-80% aqueous solution. The amount of hydrogen peroxide used varies depending on the desired hydroxyl group content and cannot be determined unambiguously.
Usually, 5 to 20% by weight, preferably 8 to 18% by weight of the conjugated diene monomer is sufficient. If the amount used is less than 5% by weight, hydroxyl groups cannot be efficiently introduced into the conjugated diene monomer and conjugated diene polymer, and even if the amount exceeds 20% by weight, the viscosity of the resulting polymer will decrease. does not contribute to a decline in The reaction conditions of the present invention are not particularly limited and may be determined as appropriate depending on the type of raw materials, amount used, etc., and usually 0.10 to 10.0% by weight of formic acid, acetic acid, or propionic acid and hydrogen peroxide based on the conjugated diene monomer. 5
When using a compounding amount of ~20% by weight, the reaction time is ~50~
200℃, preferably 100-150℃, reaction pressure 5-100℃
The atmospheric pressure is preferably 10 to 50 atmospheres, and the reaction time is usually 10 minutes to 24 hours or more, preferably 30 minutes to 5 hours. After the reaction is completed, a hydroxyl group-containing liquid diene polymer is obtained by processing according to a conventional method. The hydroxyl group-containing liquid diene polymer obtained by the reaction under the above conditions has an average molecular weight of about 1000 to 3000 and a hydroxyl group content of 1.00 to 3000.
It has a viscosity of about 2.00 meq/g and a viscosity of 15 to 25 poise/30°C, and is effectively used in various applications such as paving materials, adhesives, paints, and resin additives. As described above, according to the present invention, a low viscosity hydroxyl group-containing liquid diene polymer can be efficiently produced by using a considerably smaller amount of hydrogen peroxide than in conventional methods. Next, the present invention will be explained in detail with reference to examples. Examples 1 to 4 Isopropanol, 60% hydrogen peroxide solution, and formic acid or acetic acid as a carboxylic acid in the predetermined amounts shown in Table 1 were charged into a stirring type autoclave made of stainless steel (SUS316), and degassed while cooling. Next, after feeding the predetermined amount of 1,3-butadiene shown in Table 1, the temperature was raised to the predetermined temperature shown in Table 1,
The reaction was stirred for a predetermined period of time. After the reaction was completed, isopropanol and toluene were added and the mixture was transferred to a separatory funnel. After adding 800 ml of water and shaking, the mixture was separated into an oil layer and an aqueous layer. The obtained oil layer was pre-evaporated using an evaporator and further evaporated at 85° C. and 1 mmHg for 2.5 hours to remove volatile components to obtain hydroxyl group-containing polybutadiene. The yield, viscosity, hydroxyl group content, number average molecular weight and average number of functional groups of this product are shown in Table 1. Comparative Examples 1-2 Hydroxyl group-containing polybutadiene was obtained in the same manner as in Example 1, except that no carboxylic acid was used. The results are shown in Table 1. 【table】
Claims (1)
酸あるいはプロピオン酸の存在下、過酸化水素と
反応させることを特徴とする水酸基含有液状ジエ
ン系重合体の製造方法。 ２ 共役ジエン系単量体が、ブタジエン、イソプ
レンあるいはクロロプレンである特許請求の範囲
第１項記載の製造方法。 ３ 反応媒体がイソプロパノール、メチルアルコ
ールあるいはエチルアルコールである特許請求の
範囲第１項記載の製造方法。 ４ 蟻酸、酢酸あるいはプロピオン酸の使用量が
共役ジエン系単量体の0.10〜10.0重量％である特
許請求の範囲第１項記載の製造方法。 ５ 過酸化水素の使用量が共役ジエン系単量体の
５〜20重量％である特許請求の範囲第１項記載の
製造方法。 ６ 水酸基含有液状ジエン系重合体が、平均分子
量1000〜3000、水酸基含量1.00〜2.00meq／ｇ、
粘度15〜25ポイズ／30℃のものである特許請求の
範囲第１項記載の製造方法。[Scope of Claims] 1. A method for producing a hydroxyl group-containing liquid diene polymer, which comprises reacting a conjugated diene monomer with hydrogen peroxide in the presence of formic acid, acetic acid, or propionic acid in a reaction medium. 2. The manufacturing method according to claim 1, wherein the conjugated diene monomer is butadiene, isoprene, or chloroprene. 3. The manufacturing method according to claim 1, wherein the reaction medium is isopropanol, methyl alcohol, or ethyl alcohol. 4. The manufacturing method according to claim 1, wherein the amount of formic acid, acetic acid, or propionic acid used is 0.10 to 10.0% by weight of the conjugated diene monomer. 5. The manufacturing method according to claim 1, wherein the amount of hydrogen peroxide used is 5 to 20% by weight of the conjugated diene monomer. 6 The hydroxyl group-containing liquid diene polymer has an average molecular weight of 1000 to 3000, a hydroxyl group content of 1.00 to 2.00meq/g,
The manufacturing method according to claim 1, which has a viscosity of 15 to 25 poise/30°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13085084A JPS6112707A (en) | 1984-06-27 | 1984-06-27 | Production of hydroxyl-containing liquid diene polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13085084A JPS6112707A (en) | 1984-06-27 | 1984-06-27 | Production of hydroxyl-containing liquid diene polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6112707A JPS6112707A (en) | 1986-01-21 |
| JPS6361325B2 true JPS6361325B2 (en) | 1988-11-29 |
Family
ID=15044151
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13085084A Granted JPS6112707A (en) | 1984-06-27 | 1984-06-27 | Production of hydroxyl-containing liquid diene polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6112707A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5043484A (en) * | 1990-02-09 | 1991-08-27 | Texaco Chemical Company | Synthesis of hydroxyl-terminated polybutadienes using glycol ether solvents |
| JPH06239912A (en) * | 1993-02-18 | 1994-08-30 | Nippon Shokubai Co Ltd | Production of polymer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5018583A (en) * | 1973-06-01 | 1975-02-27 | ||
| JPS6228964A (en) * | 1985-07-30 | 1987-02-06 | Matsushita Electric Ind Co Ltd | Recording disk reproducing device |
-
1984
- 1984-06-27 JP JP13085084A patent/JPS6112707A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5018583A (en) * | 1973-06-01 | 1975-02-27 | ||
| JPS6228964A (en) * | 1985-07-30 | 1987-02-06 | Matsushita Electric Ind Co Ltd | Recording disk reproducing device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6112707A (en) | 1986-01-21 |
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