JPS60110708A - Production of hydroxy group-containing diene polymer - Google Patents
Production of hydroxy group-containing diene polymerInfo
- Publication number
- JPS60110708A JPS60110708A JP21779783A JP21779783A JPS60110708A JP S60110708 A JPS60110708 A JP S60110708A JP 21779783 A JP21779783 A JP 21779783A JP 21779783 A JP21779783 A JP 21779783A JP S60110708 A JPS60110708 A JP S60110708A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- hydrogen peroxide
- polymer
- conjugated diene
- acidic substance
- 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.)
- Granted
Links
Landscapes
- Polymerization Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
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、
詳しくは比較的緩やかな反応条件での低分子量の水酸基
含有ジエツ系重合体の効率の良い製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a hydroxyl group-containing diene polymer,
Specifically, the present invention relates to an efficient method for producing a low molecular weight hydroxyl group-containing diet polymer under relatively mild reaction conditions.
従来より、過酸化水素を用いて共役ジエンモノマーを重
合する方法が知られている。この従来法によれば、反応
温度１３０℃前後の比較的高温で重合が行なわれ、また
ポリウレタンの原料として用いる場合に好ましい低分子
量ジエン系重合体、すなわち平均分子量１０００程度の
重合体を多く得るためには、開始剤である過酸化水素を
大量に用いる必要があった。しかし、この場合は未反応
の過酸化水素を回収することができず、経済的に極めて
不利なものであった。BACKGROUND ART A method of polymerizing a conjugated diene monomer using hydrogen peroxide has been conventionally known. According to this conventional method, polymerization is carried out at a relatively high reaction temperature of around 130°C, and a large amount of low molecular weight diene polymer, that is, a polymer with an average molecular weight of about 1000, which is preferable when used as a raw material for polyurethane, can be obtained. It was necessary to use large amounts of hydrogen peroxide as an initiator. However, in this case, unreacted hydrogen peroxide could not be recovered, which was extremely disadvantageous economically.
そこで、本発明者はより緩やかな条件で反応を行ない、
しかも過酸化水素の使用量を低減させて低分子量ジエン
系重合体を多量に効率良（得る方法について鋭意研究し
た結果、過酸化水素とともに特定の物質を用いることに
より、目的が達成されることを見い出し、その知見に基
づき本発明を完成した。Therefore, the inventor conducted the reaction under milder conditions,
Moreover, by reducing the amount of hydrogen peroxide used and efficiently producing large amounts of low-molecular-weight diene polymers (as a result of extensive research into methods for obtaining them, we have found that by using a specific substance along with hydrogen peroxide, the objective can be achieved). Based on this finding, the present invention was completed.
すなわち、本発明は共役ジエンモノマーを重合して水酸
基含有ジエン系重合体を製造する方法において、過酸化
水素および酸性物質の存在下に重合せしめることを特徴
とする水酸基含有ジエン系重合体の製造方法に関する。That is, the present invention provides a method for producing a hydroxyl group-containing diene polymer by polymerizing a conjugated diene monomer, which is characterized in that the polymerization is carried out in the presence of hydrogen peroxide and an acidic substance. Regarding.
本発明の原料である共役ジエンモノマー・とじては、特
に制限なく種々のものが用いられるが、通常は炭素数４
〜１２個のジオレフィン形不飽和の非置換−１２−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、１．３−７”クジエン。インプレン、クロロ
クレン。The conjugated diene monomer that is the raw material of the present invention can be used without any particular limitation, but usually has 4 carbon atoms.
There are ~12 diolefinically unsaturated unsubstituted-12-substituted- or 2,3-substituted ~1°3-dienes. Here, substituents include alkyl groups, aryl groups, halogen,
These include cyano groups and nitro groups. Examples of specific monomers include 1.3-7" kudiene, imprene, and chlorocrene.
２−シアノ−１，３−ブタジェン、２．３−ジメチル−
１，３−ブタジェンなどがある。2-cyano-1,3-butadiene, 2,3-dimethyl-
Examples include 1,3-butadiene.
前記重合体の製造においては、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−オレフィ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。In the production of the above polymer, 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 monomer can be replaced with an ethylenically unsaturated monomer, and the conjugated diene monomer has 2 to 22 carbon atoms.
α-olefinic addition polymerizable monomers are used. Specifically, styrene, α-methylstyrene, and vinyltoluene.
メタアクリル酸メチ〃、アクリル酸、塩化ビニル。Methyl methacrylate, acrylic acid, vinyl chloride.
塩化ビニリデン、アクリロニトリル、アクリルアミド、
２−エチルへ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。このモノオレフィン
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。vinylidene chloride, acrylonitrile, acrylamide,
Examples include 2-ethylhexyl acrylate, n-octadecyl acrylate, maleic anhydride, butene, and 2-hydroxyethyl methacrylate. This monoolefinically unsaturated monomer can be used in combination with the conjugated diene monomer, preferably in a range of 0 to 75% by weight.
本発明の重合反応は通常、反応媒体中で行なわれ、その
反応媒体としては共役ジエンモノマーと過酸化水素の両
方に対して相溶性の良好な溶媒が好ましい。このような
溶媒としてメタノール、エタノール、ｎ′−プロパツー
ル、イソプロパツール。The polymerization reaction of the present invention is usually carried out in a reaction medium, and the reaction medium is preferably a solvent having good compatibility with both the conjugated diene monomer and hydrogen peroxide. Such solvents include methanol, ethanol, n'-propanol, and isopropanol.
ブタノール、プロピルエーテル、ナト２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
チルセロンルブ、Ｎ、Ｎ−ジメチルホルムアミド、アセ
トンなどや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量（モノマー、溶媒、過酸化水素お
よび酸性物質）の５〜９０重量％、好ましくは３０〜７
０重量％である。butanol, propyl ether, nathydrofuran,
Examples include acetic acid, ethyl, cellosolve, cellosolve acetate, ethyl cellonolub, N,N-dimethylformamide, acetone, and mixtures thereof. The amount of solvent used is 5 to 90% by weight of the total charge (monomer, solvent, hydrogen peroxide, and acidic substance), preferably 30 to 7% by weight.
It is 0% by weight.
また、触媒として作用する過酸化水素は通常、３０〜８
０％水溶液、好ましくは約５０％水溶液が用いられ、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ｏ
ｓＨ％以上である。一般的には過酸化水素として共役ジ
エンモノマーの２０重量％を著しく超えて添加すること
なく、好ましくは１〜１２重量％添加する。In addition, hydrogen peroxide, which acts as a catalyst, is usually 30 to 8
A 0% aqueous solution, preferably about 50% aqueous solution is used, in any case containing the conjugated diene monomer as hydrogen peroxide.
sH% or more. Generally, hydrogen peroxide is added in an amount not significantly exceeding 20% by weight of the conjugated diene monomer, preferably from 1 to 12% by weight.
さらに、本発明においては酸性物質を用いる。Furthermore, an acidic substance is used in the present invention.
これは、主に過酸化水素の触媒効果を促進する助触媒と
しての役割を果している。本発明の重合反応に際して酸
性物質を加えることにより、比較的少量の過酸化水素を
用いて目的とする低分子量ジエン系重合体を収率良く得
られるのである。これは過酸化水素からのヒドロキ高ジ
カルの発生が熱による以外に酸性物質により促進される
ためであると考えられる。It mainly plays the role of a co-catalyst that promotes the catalytic effect of hydrogen peroxide. By adding an acidic substance during the polymerization reaction of the present invention, the desired low molecular weight diene polymer can be obtained in good yield using a relatively small amount of hydrogen peroxide. This is thought to be because the generation of hydroxy radicals from hydrogen peroxide is promoted not only by heat but also by acidic substances.
ここで、酸性物質としては様々の無機酸あるいは有機酸
を用いることができる。具体的には無機酸として過塩素
酸、硫酸、リン酸、硝酸等があげられ、有機酸としては
スルホン酸類、例えばメタンスルホン酸、エタンスルホ
ン酸、ベンゼンスルホンＭ１．．ｐ−トルエンスルホン
酸、ナフタリンスルホン酸等やスルフィン酸類、例えば
メタンスルフィン酸、エタンスルフィン酸、ベンゼンス
ルフィン酸、ｐ−トルエンスルフィン酸、ナフタレンス
ルフィン酸等、その他チオフェノール類、例えばチオフ
ェノール、チオクレゾール、ジメチルチオフェノール等
やメルカプタン類、例えばメルカプト安息香酸、ｎ−ブ
チルメルカプタン、ラウリルメルカプタン等および酢酸
などが挙げられる。Here, various inorganic acids or organic acids can be used as the acidic substance. Specifically, inorganic acids include perchloric acid, sulfuric acid, phosphoric acid, nitric acid, etc., and organic acids include sulfonic acids, such as methanesulfonic acid, ethanesulfonic acid, benzenesulfone M1. ．． p-Toluenesulfonic acid, naphthalenesulfonic acid, etc., sulfinic acids such as methanesulfinic acid, ethanesulfinic acid, benzenesulfinic acid, p-toluenesulfinic acid, naphthalenesulfinic acid, etc., and other thiophenols such as thiophenol, thiocresol, Examples include dimethylthiophenol, mercaptans such as mercaptobenzoic acid, n-butyl mercaptan, lauryl mercaptan, and acetic acid.
酸性物質の添加量は共役ジエンモノマーに対して０・０
１〜１０重量％、好ましくは０．０５〜５重景％である
。添加量が０．０１重量％未満であると、実質的効果が
得られず、また１０重量％を超えて加えても、それ以上
効果を期待できないばかりか、かえって過酸化水素を分
解するので好ましくない。The amount of acidic substance added is 0.0 relative to the conjugated diene monomer.
It is 1 to 10% by weight, preferably 0.05 to 5% by weight. If the amount added is less than 0.01% by weight, no substantial effect will be obtained, and if it is added in excess of 10% by weight, not only no further effect can be expected, but also hydrogen peroxide will be decomposed, so it is preferable. do not have.
本発明による共役ジエンモノマー９重合反応条件は使用
する共役ジエンモノマー等の種類、使用量などにより異
なり一義的に決定することはできないが、通常は攪拌上
反応温度８０〜１５０℃、反応圧力５〜１００気圧、好
ましくは１０〜５０気圧で１０分間から５時間、好まし
くは０．５〜３時間反応させることによってジエン系重
合体を製造することができる。Conjugated diene monomer 9 polymerization reaction conditions according to the present invention vary depending on the type of conjugated diene monomer used, the amount used, etc., and cannot be unambiguously determined, but usually the reaction temperature is 80 to 150°C with stirring, and the reaction pressure is 5 to 50°C. The diene polymer can be produced by reacting at 100 atm, preferably 10 to 50 atm for 10 minutes to 5 hours, preferably 0.5 to 3 hours.
このようにして得られた重合体は平均分子量１０００程
度の重合体を多く含み、ポリウレタンの原料として極め
て好適なものである。The polymer thus obtained contains a large amount of polymer having an average molecular weight of about 1000, and is extremely suitable as a raw material for polyurethane.
本発明の方法によれば、従来法よりも低い温度で、しか
も短時間で低分子量の水酸基含有ジエン系重合体を得る
ことができる。また、この重合反応において触媒として
用いられる過酸化水素の使用量を低減できるため、本発
明は実用性に富むものである。According to the method of the present invention, a low molecular weight hydroxyl group-containing diene polymer can be obtained at a lower temperature and in a shorter time than conventional methods. Further, since the amount of hydrogen peroxide used as a catalyst in this polymerization reaction can be reduced, the present invention is highly practical.
次に、本発明を実施例により説明する。Next, the present invention will be explained by examples.
実施例１〜１４
ステンレス製３（ＨＪ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、過酸化水素酸性物質を所
定量仕込み、冷却しながらオートクレーフ内部の空気を
真空脱気した。次いで、１，３−ブタジェンを１ｏｏｋ
量部装入した後、］、 ００℃に昇温した。その後、６
０分間、５５ストロ一ク／分の振盪攪拌を行ない反応さ
せた。Examples 1 to 14 A stainless steel 3 (HJ) shaking autoclave was charged with 100 parts by weight of isopropyl alcohol and a predetermined amount of hydrogen peroxide acidic substance, and the air inside the autoclave was vacuum degassed while cooling. 1ook
After charging a certain amount, the temperature was raised to 00°C. After that, 6
The reaction was carried out by shaking and stirring at 55 strokes/minute for 0 minutes.
反応終了後、反応液にイングロビルアルコール約３０Ｍ
、）ルエン約６ｏゴおよび水約１５０ｄを加えて油層を
分離した。さらに、油層をエバポレーターにて予備脱気
したのちさらに１ ｍｍ１１ｇで８０°Ｃにて３０分間
脱気して蒸発分を除去した。After the reaction is complete, add about 30M of Inglovil alcohol to the reaction solution.
,) About 6 g of toluene and about 150 g of water were added to separate the oil layer. Furthermore, the oil layer was preliminarily degassed using an evaporator, and then further degassed using 1 mm and 11 g at 80°C for 30 minutes to remove evaporated components.
得られた重合体の諸性質について測定した結果を第１表
に示す。Table 1 shows the results of measuring various properties of the obtained polymer.
比較例１
実施例１において、酸性物質を用いなかったこと以外は
、実施例１と同様に反応を行ない重合体を得た。結果を
第１表に示す。Comparative Example 1 A polymer was obtained by carrying out the reaction in the same manner as in Example 1, except that no acidic substance was used. The results are shown in Table 1.
Claims (4)
系重合体を製造する方法において、過酸化水素および酸
性物質の存在下に重合せしめる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。(1) A method for producing a hydroxyl group-containing diene polymer by polymerizing a conjugated diene monomer, the method comprising polymerizing in the presence of hydrogen peroxide and an acidic substance.
求の範囲第１項記載の製造方法。(2) The manufacturing method according to claim 1, wherein the acidic substance is an inorganic acid or an organic acid.
いずれかである特許請求の範囲第２項記載の製造方法。(3) The manufacturing method according to claim 2, wherein the inorganic acid is any one of perchloric acid, sulfuric acid, phosphoric acid, and nitric acid.
の範囲第２項記載の製造方法。(4) The organic acids are sulfonic acids and sulfinic acids. The manufacturing method according to claim 2, which is either thiophenols or acetic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21779783A JPS60110708A (en) | 1983-11-21 | 1983-11-21 | Production of hydroxy group-containing diene polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21779783A JPS60110708A (en) | 1983-11-21 | 1983-11-21 | Production of hydroxy group-containing diene polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60110708A true JPS60110708A (en) | 1985-06-17 |
| JPS6258614B2 JPS6258614B2 (en) | 1987-12-07 |
Family
ID=16709879
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21779783A Granted JPS60110708A (en) | 1983-11-21 | 1983-11-21 | Production of hydroxy group-containing diene polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60110708A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5153287A (en) * | 1990-10-12 | 1992-10-06 | Texaco Chemical Company | Preparation of hydroxylated low molecular weight polymodal butadiene polymers |
| WO1994005705A1 (en) * | 1992-09-03 | 1994-03-17 | Nippon Shokubai Co., Ltd. | Process for producing polymer |
| WO1994019378A1 (en) * | 1993-02-18 | 1994-09-01 | Nippon Shokubai Co., Ltd. | Process for producing polymer |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0479613U (en) * | 1990-11-21 | 1992-07-10 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58127711A (en) * | 1982-01-25 | 1983-07-29 | Idemitsu Kosan Co Ltd | Hydroxyl group-containing diene polymer and its production |
-
1983
- 1983-11-21 JP JP21779783A patent/JPS60110708A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58127711A (en) * | 1982-01-25 | 1983-07-29 | Idemitsu Kosan Co Ltd | Hydroxyl group-containing diene polymer and its production |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5153287A (en) * | 1990-10-12 | 1992-10-06 | Texaco Chemical Company | Preparation of hydroxylated low molecular weight polymodal butadiene polymers |
| WO1994005705A1 (en) * | 1992-09-03 | 1994-03-17 | Nippon Shokubai Co., Ltd. | Process for producing polymer |
| EP0610515A1 (en) * | 1992-09-03 | 1994-08-17 | Nippon Shokubai Co., Ltd. | Process for producing polymer |
| US5391664A (en) * | 1992-09-03 | 1995-02-21 | Nippon Shokubai Co., Ltd. | Process for producing polymer |
| EP0610515B1 (en) * | 1992-09-03 | 1997-10-01 | Nippon Shokubai Co., Ltd. | Process for producing polymer |
| WO1994019378A1 (en) * | 1993-02-18 | 1994-09-01 | Nippon Shokubai Co., Ltd. | Process for producing polymer |
| US5470930A (en) * | 1993-02-18 | 1995-11-28 | Nippon Shokubai Co., Ltd. | Process for producing polymer having hydroxyl group at both terminals |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6258614B2 (en) | 1987-12-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR0178988B1 (en) | Solid state hydroxylation of rubbers | |
| GB1013205A (en) | Polymerization processes | |
| JPS60110708A (en) | Production of hydroxy group-containing diene polymer | |
| EP0000419A1 (en) | Process for preparing copolymers, and products fully or partly made of these copolymers. | |
| MXPA05011015A (en) | Dosing of peroxide to a suspension process wherein styrene is polymerized. | |
| US4064337A (en) | Mixing of organosulfur molecular weight modifier with emulsifier for emulsion polymerization systems | |
| JPS6261048B2 (en) | ||
| US2911391A (en) | Polymer hydroperoxides | |
| US4478986A (en) | Tri-N-substituted-s-triazine-trione chain terminator for polyvinyl chloride polymerization | |
| US2753385A (en) | Modified synthetic drying oil | |
| US4477638A (en) | Hindered phenolic esters of oligomeric glycols as chain terminators for polyvinyl chloride polymerization | |
| JPH02265908A (en) | Production of conjugated diene copolymer | |
| JPS60112808A (en) | Preparation of hydroxyl group-containing diene polymer | |
| US4619978A (en) | Substituted phenol chain terminator for polyvinyl chloride polymerization | |
| GB1484034A (en) | Process for the manufacture of an acrylate or styrene polymer dispersion which is substantially free from the odour of mercapto compounds | |
| JPS60233112A (en) | Production of diene polymer containing hydroxyls | |
| JPS58118807A (en) | Manufacture of poly(p-methylstyrene) | |
| JPH06298862A (en) | Production of para-hydroxystyrene polymer | |
| JP3247193B2 (en) | Method for producing pt-butoxystyrene polymer | |
| JPS5817106A (en) | Polyvinyl chloride polymerization chain stopping method | |
| US2555665A (en) | Use of a mono-ether of ethylene glycol to activate emulsion polymerization in the presence of a heavy mercaptan | |
| US3137681A (en) | Polymerization process and product | |
| JPS6361325B2 (en) | ||
| JPS6131409A (en) | Novel episulfide compound and preparation thereof | |
| US2501693A (en) | Homogeneous bulk polymerization of ethylenic unsaturates in the presence of diazo-thio-ethers |