JPS61243813A - Production of chloroprene rubber - Google Patents
Production of chloroprene rubberInfo
- Publication number
- JPS61243813A JPS61243813A JP8544385A JP8544385A JPS61243813A JP S61243813 A JPS61243813 A JP S61243813A JP 8544385 A JP8544385 A JP 8544385A JP 8544385 A JP8544385 A JP 8544385A JP S61243813 A JPS61243813 A JP S61243813A
- Authority
- JP
- Japan
- Prior art keywords
- chloroprene
- weight
- hydroxyl group
- containing polymerizable
- amount
- 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
- Polymerisation Methods In General (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は貯蔵中または使用中に相分離を生じない樹脂変
成りｏａプレン接着剤に有用なりロｐプレン重合体の製
造法忙関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a polypropylene polymer useful in resin-modified OA-prene adhesives that do not undergo phase separation during storage or use. be.
醸化マグネシウムなどの金属醸化物と加熱反応性フェノ
ールホルムアルデヒド樹脂との反応生成物を含有するり
四ロプレン接着剤が種々の材質の接着剤として広く使用
されているが、この種の接着剤は製造直後は均一不透明
な分散相であるが、長時間静置しておくと透明または不
透明な部分と金属蒸化物および無機光てん剤の沈降偏在
部分とに分かれる、いわゆる相分離現象をおこす。Polytetraprene adhesives containing the reaction products of metal compounds such as magnesium ferments and heat-reactive phenol-formaldehyde resins are widely used as adhesives for various materials; Immediately after, it is a homogeneous and opaque dispersed phase, but if it is left to stand for a long time, it will separate into a transparent or opaque part and a precipitated unevenly distributed part of metal evaporates and inorganic brighteners, which is a so-called phase separation phenomenon.
この相分離の問題を克服するため、クロロプレンゴム、
加熱反応型フェノールホルムアルデヒド樹脂、添加剤等
の諸点について多くの方法が提案されている。To overcome this phase separation problem, chloroprene rubber,
Many methods have been proposed regarding various aspects such as heat-reactive phenol formaldehyde resin and additives.
例えば、クロ田プレンゴムラテックスをあらかじめ熱処
理する方法（特公昭４７−６０５８号）。For example, a method of preheat-treating Kurotaprene rubber latex (Japanese Patent Publication No. 47-6058).
りｔｘ’ａプレン乳化重合時の界面活性剤について変性
賞ジン／脂肪際併用する方法（特開昭４９−６３７７８
号）、ロジン酸／脂肪酸併用する方法（特公昭４９−５
２７８５号）、ロジン酸／非イオン界面活性剤併用する
方法（特開昭４９−５９１８６号） 、 Ｒ−／Ｃ＞０
００１１１存在下クロロプレンを乳化重合する方法（特
開昭４９−２２４５５号）、シラン化合物を添加する方
法（特開昭４９−２５０５２号）、有機カルボン酸無水
物を配合する方法（特公昭４９−１６１０４号）、Ｒ−
ｓニーＲを添加する方法（特公昭３８−１０９８５号）
。Method of using surfactant in combination with denatured gin/fat during emulsion polymerization of tx'aprene (JP-A-49-63778
No.), rosin acid/fatty acid combination method (Special Publication No. 1987-5)
2785), Method of using rosin acid/nonionic surfactant in combination (JP-A-49-59186), R-/C>0
A method of emulsion polymerization of chloroprene in the presence of 00111 (Japanese Patent Publication No. 49-22455), a method of adding a silane compound (Japanese Patent Publication No. 49-25052), a method of blending an organic carboxylic acid anhydride (Japanese Patent Publication No. 49-16104) No.), R-
Method of adding snee R (Special Publication No. 38-10985)
.
高分子量加熱反応型フェノールホルムアルデヒド樹脂を
使用する方法（特公昭４６−８１１５号）。A method using a high molecular weight heat-reactive phenol formaldehyde resin (Japanese Patent Publication No. 8115/1983).
〇−置換体を原料とした加熱反応型フェノールホルムア
ルデヒド樹脂を使用する方法（特公昭４６−２１１１３
号）等がある。A method using heat-reactive phenol formaldehyde resin made from 〇-substituted product (Japanese Patent Publication No. 46-21113)
No.) etc.
本発明は、従来の方法とは異なる方法により、貯蔵中ま
たは使用中に相分離を生じない樹脂変成りロロプレン接
着剤に有用なり四ロプレン重合体を製造することにある
。The present invention is to produce tetraloprene polymers useful in resin-modified roroprene adhesives that do not undergo phase separation during storage or use by a method different from conventional methods.
即ち、本発明はクロロプレン単独またはクロロプレンと
共重合可能な単量体との混合物１００重置部に対し、一
般式嶋＝Ｏ−０−０＋Ｒ’Ｏ＋、Ｈ（式中ｎは１〜２０
の整数で、Ｒは炭素数１〜４の炭化水素基または水素で
、Ｒ′は炭素数２または５の炭化水素基である）で示さ
れる水ｉ基含有重合性単量体１１〜２０重量部の存在下
でアルカリ性水性乳化液中で重合させることにある。That is, in the present invention, the general formula Shima=O-0-0+R'O+, H (wherein n is 1 to 20
R is a hydrocarbon group having 1 to 4 carbon atoms or hydrogen, and R' is a hydrocarbon group having 2 or 5 carbon atoms 11 to 20 by weight polymerization in an alkaline aqueous emulsion in the presence of
以下、本発明の詳細について更に説明する。The details of the present invention will be further explained below.
本発明で用いられる共重合可能な単量体としては、１−
クロロブタジェン、２．３−ジクロロブタジェン、ブタ
ジェン、スチレン、アクリロニトリル。The copolymerizable monomer used in the present invention includes 1-
Chlorobutadiene, 2,3-dichlorobutadiene, butadiene, styrene, acrylonitrile.
メタクリル醗アルキル等があり、これらは２０重量％ま
で用いることができる。Examples include methacrylic alkyl and the like, and these can be used in an amount up to 20% by weight.
液化液を形成させるために用いる界面活性剤としては、
クロロプレンの重合に通常用いられる界面活性剤、例え
ば非変性ロジン酸、不均化ロジン酸。Surfactants used to form a liquefied liquid include:
Surfactants commonly used in the polymerization of chloroprene, such as unmodified rosin acids, disproportionated rosin acids.
脂肪族カルボン醸、アルキルベンゼンスルホン酸等のア
ルカリ金属塩あるいはアンモニウム塩等が用いられる。Aliphatic carboxylic acids, alkali metal salts such as alkylbenzenesulfonic acids, ammonium salts, etc. are used.
分子量調節剤としては、通常用いられるアルキルメルカ
プタン、アルキルキサントゲンジスルフィド等が、重合
開始剤としては通常用いられる有機または無機の過酸化
物、例えば過酸化ベンゾイル。As the molecular weight modifier, commonly used alkyl mercaptans, alkyl xanthogen disulfides, etc. are used, and as the polymerization initiator, commonly used organic or inorganic peroxides, such as benzoyl peroxide.
過硫醸カリウム等が用いられる。Persulfated potassium etc. are used.
１合性単量体としては、例えばＯＨ，＝ＯＲ−００−０
０．）１．ＯＨ。As monomer monomers, for example, OH,=OR-00-0
0. )1. Oh.
ｏｙｏ（ｏ４）−ｏｏ−東＾０鳥ｏＶｏ （ＯＨＭ）−
００→へ−ＯＨ。oyo(o4)-oo-East^0bird oVo (OHM)-
00→to-OH.
０Ｈｒ−０（ＯＨａ） ０ｏ−０（％’ｋＭ’ｙ Ｃ４
閥（０％） ００−ト（ＯＨにＯｋ＊Ｈ等があり、これ
らは単独あるいは２種以上併用して用いられる。また使
用量としてはクロロプレンまたはそれと共重合可能な単
量体の混合物１００重量部に対して、１１〜２０重量部
、好ましくは１５〜１０重量部である。0Hr-0(OHa) 0o-0(%'kM'y C4
(0%) 00-t (OH includes Ok*H, etc., and these are used alone or in combination of two or more.The amount used is 100% by weight of chloroprene or a mixture of monomers copolymerizable with it. 11 to 20 parts by weight, preferably 15 to 10 parts by weight.
こ６量がα１重量部より少ないと相分離防止効果が少な
い。そして２０重量部までで効果は十分であり、それよ
り多いと不経済であるばかりでなく、接着強度の低下を
まねく。If the amount of 6 is less than 1 part by weight, the effect of preventing phase separation will be small. The effect is sufficient up to 20 parts by weight, and more than that is not only uneconomical but also leads to a decrease in adhesive strength.
重合は０〜１００℃、好ましくは５〜６０℃の温度にお
いて、アルカリ性水性乳化液中て少なくとも６０％の転
化率に達するまで行われ、ついで通常の禁止剤、例えば
ｔ−ブチルカテコール、フェノチアジン等を加えて重合
を停止させる。残存する単量体は例えば高温て減圧処理
して除去し、凍結、凝固、水洗、乾燥して固形のりｐロ
プレンゴムを得る。The polymerization is carried out in an alkaline aqueous emulsion at a temperature of 0 to 100°C, preferably 5 to 60°C, until a conversion of at least 60% is reached, and then the usual inhibitors such as tert-butylcatechol, phenothiazine, etc. are added. In addition, polymerization is stopped. The remaining monomer is removed, for example, by treatment at high temperature and reduced pressure, followed by freezing, coagulation, washing with water, and drying to obtain a solid paste proprene rubber.
本発明によると、ごく少量の一般式
０Ｈｒ−０−０＋（怖九１１ （式中ｎは１．〜２０の
整数で、Ｒは炭素数１〜４の炭化水素基または水素で、
Ｒ′は炭素数２または５の炭化水素基）で示される水酸
基含有重合性単量体を用いることＫより、貯蔵中または
使用中忙相分離を生じない樹脂変成り四ロプレン接着剤
に有用なりロｐプレン重合体が容易に得られ、産業上非
常に有用である。According to the present invention, a very small amount of the general formula 0Hr-0-0+(911 (in the formula, n is an integer of 1 to 20, R is a hydrocarbon group having 1 to 4 carbon atoms or hydrogen,
By using a hydroxyl group-containing polymerizable monomer (R' is a hydrocarbon group having 2 or 5 carbon atoms), it is useful for resin-modified tetraloprene adhesives that do not cause busy phase separation during storage or use. Loprene polymers are easily obtained and are very useful industrially.
以下実施例により本発明を具体的に説明するが、これら
実施例に限定されるものではない。The present invention will be specifically explained below with reference to Examples, but it is not limited to these Examples.
なお、本文中特に記載しない限り部および襲は重量部お
よび重量％である。In addition, unless otherwise specified in the text, parts and weights are parts by weight and weight %.
（実施例１〜３．比較例１）
表１に示した組成割合で攪拌機付きオートクレーブに仕
込み、重合触媒として過硫酸カリウムα５％及びアンス
ラキノン−β−スルホン酸ソーダ［１０５％の混合水溶
液を添加して、窒素気流下１０℃で重合を行った。フェ
ノチアジン及び１−ブチルカテコール各α０１部を含む
乳化液を加え転化率７０％て重合を停止させ、未反応の
単量体を減圧下で除去した。次いで１０％酢酸水溶液を
加えてｐＨ７，０に調節し、凍結ロール上で重合体を分
離、乾燥した。それぞれについて以下の手順でクロロプ
レン／変性樹脂系−溶剤型接着剤を調製した。(Examples 1 to 3. Comparative Example 1) The composition ratio shown in Table 1 was charged into an autoclave equipped with a stirrer, and a mixed aqueous solution of α5% potassium persulfate and 105% sodium anthraquinone-β-sulfonate was added as a polymerization catalyst. Then, polymerization was carried out at 10° C. under a nitrogen stream. An emulsion containing α01 part each of phenothiazine and 1-butylcatechol was added to terminate the polymerization at a conversion rate of 70%, and unreacted monomers were removed under reduced pressure. Next, a 10% acetic acid aqueous solution was added to adjust the pH to 7.0, and the polymer was separated and dried on a freezing roll. For each, a chloroprene/modified resin-based solvent-based adhesive was prepared according to the following procedure.
（１） 溶剤４３５重量部に変性フェノール樹脂５０
重量部、マグネシア４重量部を混合し常温で２４時間振
とうを続けた。(1) 435 parts by weight of solvent and 50 parts by weight of modified phenol resin
parts by weight and 4 parts by weight of magnesia were mixed and continued to be shaken at room temperature for 24 hours.
（Ｕ） クロロプレン重合体１００重量部をゴム用ミ
キシングロールで素練りし、これにスチレン化フェノー
ル（老化防止剤）２重量部、マグネシア４重量部、亜鉛
華５重量部を添加して充分に混合した。(U) 100 parts by weight of chloroprene polymer was masticated using a rubber mixing roll, and 2 parts by weight of styrenated phenol (antiaging agent), 4 parts by weight of magnesia, and 5 parts by weight of zinc white were added and thoroughly mixed. did.
次いで（１）Ｋ（ＩＩ）を投入し、常温で攪拌溶解した
。この接着剤を内径２０ミリ、高さ２００ミリの試験管
に採取し、２５℃で貯蔵し、透明な上相と不透明な固相
に分離する状況を観察し、上相の高さと下相の高さを計
測して沈降度を次式で表わした。Next, (1) K(II) was added and dissolved with stirring at room temperature. This adhesive was collected in a test tube with an inner diameter of 20 mm and a height of 200 mm, stored at 25°C, and the separation into a transparent upper phase and an opaque solid phase was observed. The height was measured and the degree of sedimentation was expressed by the following formula.
接着剤放置による沈降度と混合溶剤１．ｎ、ｍの３種類
との関係を表２に示した。なお、変性フェノール樹脂は
ＯＫＭＩ６３４（昭和高分子製）を使用した。Sedimentation degree of adhesive and mixed solvent 1. Table 2 shows the relationship with the three types of n and m. In addition, OKMI634 (manufactured by Showa Kobunshi) was used as the modified phenol resin.
表２ 接着剤沈降度
！＝トルエン、ｎ−へキサン、酢戯エチル等容混合物■
： トルエン、ｎ−ヘキサン、メチルエチルケトン ｒ
ｌｌ：）ルエン、ｎ−ヘキサン、アセトン ｒ（
実施例４〜７）
表３に示した組成割合で重合温度を２０℃Ｋかえ、実施
例１〜３と同様にしてクロロプレンゴムを得、それぞれ
について実施例１〜３と同様にして接着剤を調製し、沈
降度を求めた。Table 2 Adhesive sedimentation degree! = Mixture of equal volumes of toluene, n-hexane, and ethyl acetate■
: Toluene, n-hexane, methyl ethyl ketone r
ll:) Luene, n-hexane, acetone r(
Examples 4 to 7) Chloroprene rubber was obtained in the same manner as in Examples 1 to 3, except that the polymerization temperature was changed by 20°C with the composition ratio shown in Table 3, and adhesives were prepared in the same manner as in Examples 1 to 3. It was prepared and the degree of sedimentation was determined.
表４ 接着剤沈降度
■＝トルエン、ｎ−ヘキサン、酢酸エチル等容混合物■
：トルエン、ｎ−ヘキサン、メチルエチルケトン 〃■
：トルエン、ｎ−ヘキサン、アセトン １以上のご
とく表２１表４の結果より本発明の効果は明らかである
。Table 4 Adhesive sedimentation degree ■=Equivalent mixture of toluene, n-hexane, and ethyl acetate■
:Toluene, n-hexane, methyl ethyl ketone 〃■
: toluene, n-hexane, acetone As mentioned above, the effects of the present invention are clear from the results in Table 21 and Table 4.
Claims (1)
能な単量体との混合物１００重量部に対し、一般式▲数
式、化学式、表等があります▼（式中ｎは １〜２０の整数で、Ｒは炭素数１〜４の炭化水素基また
は水素で、Ｒ′は炭素数２または３の炭化水素基である
）で示される水酸基含有重合性単量体０．１〜２０重量
部の存在下でアルカリ性乳化液中で重合させることを特
徴とするクロロプレンゴムの製造法。(1) For 100 parts by weight of chloroprene alone or a mixture of chloroprene and a copolymerizable monomer, the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (in the formula, n is an integer from 1 to 20, R is alkaline in the presence of 0.1 to 20 parts by weight of a hydroxyl group-containing polymerizable monomer represented by a hydrocarbon group having 1 to 4 carbon atoms or hydrogen, where R' is a hydrocarbon group having 2 or 3 carbon atoms. A method for producing chloroprene rubber, characterized by polymerization in an emulsion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8544385A JPS61243813A (en) | 1985-04-23 | 1985-04-23 | Production of chloroprene rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8544385A JPS61243813A (en) | 1985-04-23 | 1985-04-23 | Production of chloroprene rubber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61243813A true JPS61243813A (en) | 1986-10-30 |
| JPH0576488B2 JPH0576488B2 (en) | 1993-10-22 |
Family
ID=13859012
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8544385A Granted JPS61243813A (en) | 1985-04-23 | 1985-04-23 | Production of chloroprene rubber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61243813A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008026671A1 (en) * | 2006-08-31 | 2008-03-06 | Showa Denko K. K. | Chloroprene polymer latex and process for producing the same |
| JP2009197127A (en) * | 2008-02-21 | 2009-09-03 | Denki Kagaku Kogyo Kk | Chloroprene rubber composition and chloroprene rubber molded article formed form the chloroprene rubber composition |
-
1985
- 1985-04-23 JP JP8544385A patent/JPS61243813A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008026671A1 (en) * | 2006-08-31 | 2008-03-06 | Showa Denko K. K. | Chloroprene polymer latex and process for producing the same |
| US8586670B2 (en) | 2006-08-31 | 2013-11-19 | Showa Denko K.K. | Chloroprene polymer latex and process for producing the same |
| JP2009197127A (en) * | 2008-02-21 | 2009-09-03 | Denki Kagaku Kogyo Kk | Chloroprene rubber composition and chloroprene rubber molded article formed form the chloroprene rubber composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0576488B2 (en) | 1993-10-22 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |