JPS59136303A - Production of vulcanizable acrylic rubber - Google Patents
Production of vulcanizable acrylic rubberInfo
- Publication number
- JPS59136303A JPS59136303A JP1091183A JP1091183A JPS59136303A JP S59136303 A JPS59136303 A JP S59136303A JP 1091183 A JP1091183 A JP 1091183A JP 1091183 A JP1091183 A JP 1091183A JP S59136303 A JPS59136303 A JP S59136303A
- Authority
- JP
- Japan
- Prior art keywords
- monomer
- rubber
- resistance
- acrylic rubber
- acrylic
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229920000800 acrylic rubber Polymers 0.000 title abstract description 26
- 229920000058 polyacrylate Polymers 0.000 title abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 238000004073 vulcanization Methods 0.000 claims abstract description 12
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Natural products CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 229920001971 elastomer Polymers 0.000 claims abstract description 7
- 229920001577 copolymer Polymers 0.000 claims abstract description 6
- 239000005060 rubber Substances 0.000 claims abstract description 6
- 125000005396 acrylic acid ester group Chemical group 0.000 claims abstract description 5
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229960002447 thiram Drugs 0.000 claims abstract description 4
- WOWBFOBYOAGEEA-UHFFFAOYSA-N diafenthiuron Chemical compound CC(C)C1=C(NC(=S)NC(C)(C)C)C(C(C)C)=CC(OC=2C=CC=CC=2)=C1 WOWBFOBYOAGEEA-UHFFFAOYSA-N 0.000 abstract description 5
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 abstract description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- AXLMPTNTPOWPLT-UHFFFAOYSA-N prop-2-enyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCC=C AXLMPTNTPOWPLT-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005336 cracking Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 13
- 238000009472 formulation Methods 0.000 description 7
- -1 acrylic ester Chemical class 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 2
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 2
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- REEBWSYYNPPSKV-UHFFFAOYSA-N 3-[(4-formylphenoxy)methyl]thiophene-2-carbonitrile Chemical compound C1=CC(C=O)=CC=C1OCC1=C(C#N)SC=C1 REEBWSYYNPPSKV-UHFFFAOYSA-N 0.000 description 1
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- XJELOQYISYPGDX-UHFFFAOYSA-N ethenyl 2-chloroacetate Chemical compound ClCC(=O)OC=C XJELOQYISYPGDX-UHFFFAOYSA-N 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229940079826 hydrogen sulfite Drugs 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010059 sulfur vulcanization Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
硫
本発明は加温可能なアクリルゴムの製造法に係り、詳し
くはアクリル酸エステル単量体に対して、２〜１０重量
％の活性メチレン基を有するアセト酢酸系単量体を加え
て重合せしめることを特徴とするものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing heatable acrylic rubber, and more specifically, an acetoacetate monomer having an active methylene group of 2 to 10% by weight based on an acrylate monomer. It is characterized by adding polymers and polymerizing them.
従来のアクリルゴムは熱に対して安定であり、また耐油
性もエステル構造の極性のために長所の一つとして挙げ
られているが、ゴム分子中に不飽和基、即ち二重結合を
有していないので硫黄加硫が不可能であった。Conventional acrylic rubber is stable against heat and oil resistance is also cited as one of its advantages due to the polarity of its ester structure, but it has an unsaturated group, that is, a double bond, in the rubber molecule. sulfur vulcanization was impossible.
そこでこれまでのアクリルゴムにおいては脂肪酸石ケン
やエチルテトラミン、テトラエチルペンタミンなどのア
ミン類の加硫剤と反応する、例えば２−クロロエチルビ
ニルエーテル、ビニルクロロアセテートなどのハロゲン
系、或いはアリルグリシジルエーテル、グリシジルアク
リレート、グリシジルメタクリレートなどのエポキシ系
の架橋用単量体を適当量、アクリル酸エステルと共重合
させてアクリルゴムを得、加硫を行っていたものである
。Therefore, in conventional acrylic rubber, halogen-based vulcanizing agents such as 2-chloroethyl vinyl ether and vinyl chloroacetate, or allyl glycidyl ether, which react with vulcanizing agents such as fatty acid soap and amines such as ethyltetramine and tetraethylpentamine, have been used. Acrylic rubber was obtained by copolymerizing an appropriate amount of an epoxy crosslinking monomer such as glycidyl acrylate or glycidyl methacrylate with an acrylic ester, and vulcanization was performed.
しかしながらこの様な加硫系においては水分に対して不
安定で、練りゴムの生地やけを起こす欠点があった。However, such a vulcanization system has the disadvantage that it is unstable against moisture and causes the dough of the kneaded rubber to burn.
また、このほか従来の上記せるアクリルゴムでは耐寒性
、加工性に劣り、さらに加硫系に液状ポリアミンを用い
てなるものにあってはロール粘着性、貯蔵安定性、腐蝕
性やアミンの異臭、毒性が欠陥とされていた。In addition, the conventional acrylic rubbers mentioned above have poor cold resistance and processability, and those that use liquid polyamines in the vulcanization system have problems such as roll tackiness, storage stability, corrosivity, and amine odor. Toxicity was considered a defect.
本発明は上記のアクリルゴムの欠陥に鑑み、これらの欠
陥を解消した加硫アクリルゴムの製造法について鋭意研
究の結果本発明に至ったものである。In view of the above-mentioned defects of acrylic rubber, the present invention was developed as a result of intensive research into a method for producing vulcanized acrylic rubber that eliminates these defects.
即ち本発明は、活性メチレン基を有するアセ）・酢酸系
単量体をアクリルゴムの素材であるアクリル酸エステル
単量体に加えて重合せしめることにより、アクリルゴム
とすることができ、これをチウラム系の加硫剤を用いて
ゴム間架橋を行なわせることに成功したものである。That is, in the present invention, acrylic rubber can be obtained by adding an acetic acid monomer having an active methylene group to an acrylic acid ester monomer, which is a raw material for acrylic rubber, and polymerizing it. We succeeded in crosslinking rubber using a vulcanizing agent of this type.
本発明において用いる活性メチレン基を有するアセト酢
酸系単量体としてはアセト酢酸アリル、アセト酢酸メタ
リルのようなケテンダイマーと不飽和アルコールとのエ
ステル類がある。The acetoacetic acid monomer having an active methylene group used in the present invention includes esters of ketene dimer and unsaturated alcohol, such as allyl acetoacetate and methallyl acetoacetate.
これらのアセト酢酸系単量体の製法の一例を示すと、ア
リルアルコール６２重量部に酢酸ナトリウム０．４重量
部を触媒として加えて還流させながら１１０〜１１５℃
で約２時間に渡ってケテンダイマー９６重量部を分液口
斗で分割添加して反応を行い、反応終了後生成物を減圧
蒸留することによって得られるものである。An example of a method for manufacturing these acetoacetic acid monomers is to add 0.4 parts by weight of sodium acetate as a catalyst to 62 parts by weight of allyl alcohol and heat at 110 to 115°C while refluxing.
The reaction is carried out by adding 96 parts by weight of ketene dimer in portions using a separating funnel over a period of about 2 hours, and after the reaction is completed, the product is distilled under reduced pressure.
本発明でアクリル酸エステル単量体に対するアセト酢酸
系単量体の量比は２〜１０重量％好ましくは２〜６重量
％である。In the present invention, the ratio of acetoacetic acid monomer to acrylic ester monomer is 2 to 10% by weight, preferably 2 to 6% by weight.
この量が２重量％以下ではアセト酢酸基を導入する効果
がなく、また１０重量％以上を用いた場合は加硫時間は
早くなり硬化による力は増大するか硬さが増し、その結
果として伸びや屈撓性か低下するために好ましくない。If this amount is less than 2% by weight, there will be no effect of introducing acetoacetate groups, and if it is more than 10% by weight, the vulcanization time will be faster, the curing force will increase, or the hardness will increase, resulting in elongation. This is undesirable because it reduces flexibility and flexibility.
本発明においてアクリル酸エステル単量体とアセト酢酸
基を有する単量体との乳化重合により得られる共重合を
加硫するに用いる加硫剤としてはテトラメチルチウラム
ジスルフィド、またはテトラエチルチウラムジスルフィ
ドが最適であり、また促進剤としてはテトラメチルチウ
ラムモノスルフィド、或いはチアゾールが用いられる。In the present invention, tetramethylthiuram disulfide or tetraethylthiuram disulfide is most suitable as the vulcanizing agent used to vulcanize the copolymer obtained by emulsion polymerization of an acrylic acid ester monomer and a monomer having an acetoacetate group. In addition, tetramethylthiuram monosulfide or thiazole is used as a promoter.
かくして得られる本発明のアクリルゴムは、従来のアク
リルゴムに比べ著しい加硫の立」ユリの速さと加硫平担
性を有しており、このことは図面に示す１５０℃におけ
る両者の加硫曲線から明らかである。The acrylic rubber of the present invention thus obtained has remarkable vulcanization speed and flatness compared to conventional acrylic rubber. It is clear from the curve.
このほか本発明のアクリルゴムは、物性面において他の
アクリルゴムが有する耐熱性、耐油性、耐候性、耐オゾ
ン性、及び耐屈曲亀裂性などの性質を保持するばかりで
なく、その他に■低温での加硫が可能であること、■加
硫が早いこと、■ロール加工性が良いことなど、他のア
クリルゴムには見られないすぐれた利点を有している。In addition, the acrylic rubber of the present invention not only maintains the properties of other acrylic rubbers such as heat resistance, oil resistance, weather resistance, ozone resistance, and flex crack resistance, but also has the following properties: It has excellent advantages not found in other acrylic rubbers, such as: (1) rapid vulcanization; and (2) good roll processability.
このような本発明のアクリルゴムはシール、ガスケット
、Ｏ−リング、ホース、或いはロールなどの成型用とし
て活用される。The acrylic rubber of the present invention is used for molding seals, gaskets, O-rings, hoses, rolls, and the like.
次に本発明を更に具体的に説明するために実施例を示す
。なお、この実施例は本発明に何ら限定を加えるもので
はない。Next, Examples will be shown to further specifically explain the present invention. Note that this example does not limit the present invention in any way.
部数は全て重量部である。All parts are by weight.
実施例 １
次の単量体組成（重量部）単量体混合物Ａ−Ｂ・Ｃ−Ｄ
をそれぞれ共重合させ、アクリルエラストマーＡ・Ｂ−
Ｃ−Ｄを合成した。Example 1 The following monomer composition (parts by weight) Monomer mixture A-B/C-D
were copolymerized to form acrylic elastomers A and B-
CD was synthesized.
表 １ 共重合反応は次の様にして行なわれた。Table 1 The copolymerization reaction was carried out as follows.
まず、単量体混合物１００部、水２００部及び乳化剤と
してラウリルスルホン酸ナトリウム（カオーエマール１
０、花王石鹸製）０８部、ポリオキシエチレンラウリル
エーテル（カオーエマルゲン１２０花王石鹸製）２部を
反応容器に仕込み、液温を約５０℃に保ちながら十分窒
素置換した。First, 100 parts of a monomer mixture, 200 parts of water, and sodium lauryl sulfonate (Kaoh emal 1
0, manufactured by Kao Soap Co., Ltd.) and 2 parts of polyoxyethylene lauryl ether (Kaoh Emulgen 120 manufactured by Kao Soap Co., Ltd.) were charged into a reaction vessel, and the mixture was sufficiently purged with nitrogen while maintaining the liquid temperature at about 50°C.
次いで、過硫酸アンモニウム０．２部、および亜硫酸水
素ナトリウム０．２部を添加すると重合反応が開始され
、温度が上昇しはじめるが、この温度を約６０℃に保ち
ながら約１時間撹拌して重合反応を完結させ、得られた
共重合体ラテックスを約６０℃の１０％食塩水中に投入
し、凝析物を水洗した後乾燥させてアクリルエラストマ
ーを得た。重合率はいずれも９８％以上であった。Next, when 0.2 parts of ammonium persulfate and 0.2 parts of sodium hydrogen sulfite are added, the polymerization reaction starts and the temperature begins to rise, but the polymerization reaction is continued by stirring for about 1 hour while maintaining this temperature at about 60°C. The copolymer latex thus obtained was poured into 10% saline solution at about 60° C., and the coagulated product was washed with water and dried to obtain an acrylic elastomer. The polymerization rate was 98% or more in all cases.
得られたそれぞれのエラストマーについて、アクリルエ
ラストマー１００部、ステアリン酸１部、クレー９０部
、テトラメチルチウラムジスルフィド２部、およびジベ
ンゾチアジルジスルフィド２部よりなる配合処方に従っ
て８インチロールで混練し、アクリルエラストマーＡ、
Ｂ、Ｃ１およびＤからそれぞれ対応する配合物１，１．
Ｉｌｌ、および■を調製した。Each of the obtained elastomers was kneaded using an 8-inch roll according to a formulation consisting of 100 parts of acrylic elastomer, 1 part of stearic acid, 90 parts of clay, 2 parts of tetramethylthiuram disulfide, and 2 parts of dibenzothiazyl disulfide. A,
B, C1 and D respectively corresponding formulations 1,1.
Ill, and ■ were prepared.
各配合物は１５０℃の加硫温度で４分間プレス加硫され
、更に１５０℃で３時間後加硫した。次いで各加硫物の
諸物性値を測定し、その値を表２１表３、表４、および
表５に示す。Each formulation was press cured at a vulcanization temperature of 150°C for 4 minutes and then post-vulcanized at 150°C for 3 hours. Next, various physical property values of each vulcanizate were measured, and the values are shown in Table 21, Table 3, Table 4, and Table 5.
以上の結果から、従来は１８０℃、８分間プレス加硫後
、１８０℃、４時間以上後加硫が必要であったが、本発
明に係るアセト酢酸基を有する単量体を共重合させたア
クリルエラストマーでは、低温・短時間の加硫にもかか
わらず良好な物性値を示表 ２（配合物１）
表 ３（配合物１）
表 ４（配合物ＩＩＩ ）
表 ５ （配合物■）
すことが判る。From the above results, conventionally it was necessary to press vulcanize at 180°C for 8 minutes and then post-vulcanize at 180°C for 4 hours or more, but by copolymerizing the monomer having an acetoacetate group according to the present invention. Acrylic elastomers show good physical properties despite vulcanization at low temperatures and short times. I understand that.
図面は１５０℃における本発明のアクリルゴムと従来の
アクリルゴムの加硫状態を示すグラフである。
Ａ・・・従来のアクリルゴム
Ｂ・・・本発明アクリルゴム
特許出願人
内山工業株式会社
加硫時間（分）
手続補正書（方式）
１、事件の表示 昭和５８年特許願第１０９１１号２
、発明の名称 加硫可能なアクリルゴムの製造法６
補正をする者
事件との関係 特許出願人
住 所 岡山市江並６５Ｂ番地４、補正命令の
日付 昭和５８年４月２６日付拒絶理由通知書による
補正。
５、補正の対象 １明細書の表の１１ｔ＋６、補正の
内容 ′明細書第６．８．９ページの浄Ｉｆ１表
１
共重合反応は次の様にして行なわれた。
まず、単量体混合物１００部、水２００部及び乳化剤と
してラウリルスルホン酸ナトリウム（カオーエマール１
０、花王石鹸製）０．８部、ポリオキシエチレンラウリ
ルエーテル（カオーエマルゲン１２０花王石鹸製）２部
を反応容器に仕込み、液温を約５０℃に保ちながら十分
窒素置換した。
次いで、過硫酸アンモニウム０．２部、および亜硫酸水
素す） ＩＪウム０．２部を添加すると重合反応が開始
され、温度が上昇しはじめるが、この温度を約６０℃に
保ちながら約１時間撹拌して重合反応を完結させ、得ら
れた共重合体ラテックスを約６０表 ２（配合物Ｉ）
表 ３（配合物ｌ）
表 ４（配合物１ｉｔ）
表 ５（配合物■）
２５−The drawing is a graph showing the vulcanization state of the acrylic rubber of the present invention and the conventional acrylic rubber at 150°C. A... Conventional acrylic rubber B... Patent applicant for the acrylic rubber of the present invention Uchiyama Kogyo Co., Ltd. Vulcanization time (minutes) Procedural amendment (method) 1. Indication of the case Patent application No. 10911 of 1988 2
, Title of the invention Method for producing vulcanizable acrylic rubber 6
Relationship with the case of the person making the amendment Patent applicant Address: 65B-4 Enami, Okayama City, Date of amendment order: Amendment based on the notice of reasons for refusal dated April 26, 1981. 5. Target of amendment 1 Table 11t+6 of the specification, Contents of amendment 'Table If1 of page 6.8.9 of the specification
1. The copolymerization reaction was carried out as follows. First, 100 parts of a monomer mixture, 200 parts of water, and sodium lauryl sulfonate (Kaoh emal 1
0.0, manufactured by Kao Soap Co., Ltd.) and 2 parts of polyoxyethylene lauryl ether (Kaoh Emulgen 120 manufactured by Kao Soap Co., Ltd.) were charged into a reaction vessel, and the mixture was sufficiently purged with nitrogen while maintaining the liquid temperature at about 50°C. Next, when 0.2 parts of ammonium persulfate and 0.2 parts of hydrogen sulfite were added, the polymerization reaction started and the temperature started to rise, but the temperature was kept at about 60°C and stirred for about 1 hour. to complete the polymerization reaction, and the obtained copolymer latex was mixed with about 60 Table 2 (Formulation I) Table 3 (Formulation I) Table 4 (Formulation 1 it) Table 5 (Formulation ■) 25-
Claims (1)
セト酢酸基を有する単量体２〜１０重量％を加えて共重
合させ、得られた共重合物にチウラム系の加硫剤を加え
て加硫することを特徴とする加硫アクＩＪ ノ、Ｌｚゴ
ムの製造法。Copolymerize by adding 2 to 10% by weight of a monomer having an acetoacetate group to 98 to 90% by weight of an acrylic acid ester monomer, and add a thiuram-based vulcanizing agent to the resulting copolymer. A method for producing vulcanized IJ-Lz rubber characterized by vulcanization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1091183A JPS59136303A (en) | 1983-01-25 | 1983-01-25 | Production of vulcanizable acrylic rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1091183A JPS59136303A (en) | 1983-01-25 | 1983-01-25 | Production of vulcanizable acrylic rubber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59136303A true JPS59136303A (en) | 1984-08-04 |
| JPH0471083B2 JPH0471083B2 (en) | 1992-11-12 |
Family
ID=11763459
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1091183A Granted JPS59136303A (en) | 1983-01-25 | 1983-01-25 | Production of vulcanizable acrylic rubber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59136303A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005330456A (en) * | 2004-04-21 | 2005-12-02 | Yunimatekku Kk | Acrylic type elastomer composition |
| CN106749870A (en) * | 2016-12-16 | 2017-05-31 | 广州熵能创新材料股份有限公司 | A kind of acetoacetate type ACM and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012205726A (en) * | 2011-03-29 | 2012-10-25 | Toshiba Corp | Ultrasonic probe and ultrasonic probe manufacturing method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS543770A (en) * | 1977-06-08 | 1979-01-12 | Anritsu Electric Co Ltd | Mechanism of carrying long article |
| JPS5428437A (en) * | 1977-08-05 | 1979-03-03 | Mitsubishi Electric Corp | Hot wind heating apparatus |
-
1983
- 1983-01-25 JP JP1091183A patent/JPS59136303A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS543770A (en) * | 1977-06-08 | 1979-01-12 | Anritsu Electric Co Ltd | Mechanism of carrying long article |
| JPS5428437A (en) * | 1977-08-05 | 1979-03-03 | Mitsubishi Electric Corp | Hot wind heating apparatus |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005330456A (en) * | 2004-04-21 | 2005-12-02 | Yunimatekku Kk | Acrylic type elastomer composition |
| CN106749870A (en) * | 2016-12-16 | 2017-05-31 | 广州熵能创新材料股份有限公司 | A kind of acetoacetate type ACM and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0471083B2 (en) | 1992-11-12 |
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