JPS6123805B2 - - Google Patents
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- Publication number
- JPS6123805B2 JPS6123805B2 JP54008438A JP843879A JPS6123805B2 JP S6123805 B2 JPS6123805 B2 JP S6123805B2 JP 54008438 A JP54008438 A JP 54008438A JP 843879 A JP843879 A JP 843879A JP S6123805 B2 JPS6123805 B2 JP S6123805B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- water
- polymerization
- chloroprene
- 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
- 239000000178 monomer Substances 0.000 claims description 30
- 150000002825 nitriles Chemical class 0.000 claims description 14
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 claims description 12
- 239000003995 emulsifying agent Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000839 emulsion Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 5
- -1 Fatty acid salt Chemical class 0.000 claims description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 4
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 claims description 4
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 description 21
- 239000004816 latex Substances 0.000 description 15
- 229920000126 latex Polymers 0.000 description 15
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 4
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- PCPYTNCQOSFKGG-ONEGZZNKSA-N (1e)-1-chlorobuta-1,3-diene Chemical compound Cl\C=C\C=C PCPYTNCQOSFKGG-ONEGZZNKSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical class C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- LIFLRQVHKGGNSG-UHFFFAOYSA-N 2,3-dichlorobuta-1,3-diene Chemical compound ClC(=C)C(Cl)=C LIFLRQVHKGGNSG-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000710 polymer precipitation Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明はクロロプレンと不飽和ニトリルとの単
量体混合物を乳化重合する方法の改良に関するも
のである。
従来、クロロプレンと不飽和ニトリルとをラジ
カル触媒を用いて乳化重合させ耐油性のクロロプ
レンゴムを製造する方法は公知である。
例えば米国特許第2066331号、同第2395649号、
同第2399407号、英国特許第858444号および特公
昭36−15043号などがある。しかし、これらの重
合方法において乳化剤として不均化ロジン酸を用
いることが開示されているが、不均化ロジン酸の
み用いると、全単量体中の不飽和ニトリルの含量
を増加させるに従つて油滴が大粒子のまま分散し
たり、系が油層と水層とに分離したままの状態と
なつて重合中のエマルジヨンの安定性が悪くな
り、重合速度が遅くなつたり、重合途中ポリマー
が析出するという欠点がある。
そのため、脂肪酸とナフタレンスルホン酸のホ
ルムアルデヒド縮合物（USP3190865）、ロジン酸
−脂肪酸−芳香族スルホン酸ソーダ
（USP3317451）及びロジン酸−不飽和脂肪酸−ナ
フタレスルホン酸ホルマリン縮合物（特公昭51−
21834）を乳化剤として使用する方法が提案され
ている。
しかし、これらの乳化剤を用いても、乳化系は
クロロプレンホモポリマーの乳化系に比べて不安
定であり、例えば５〜10℃の低温でラテツクスを
長期貯蔵すると凝集物の生成が認められたり、或
いは重合に使用する水が単量体100重量部に対し
て150〜250重量部程度の比較的多量に必要なた
め、高濃度のラテツクスが得られないので出産性
が上らない欠点がある。
本発明者はクロロプレンと不飽和ニトリルとの
乳化共重合について研究した結果、更に安定な乳
化剤を見出し、この乳化剤系は重合における水対
単量体比を減少させ、且つ低温においても乳化性
が安定であることを認め、本発明に至つた。
本発明は少なくとも50重量％以上のクロロプレ
ンと不飽和ニトリルとの単量体混合物を乳化重合
する方法において、全単量体混合物100重量部に
対し水100重量部以上と乳化剤として不均化ロジ
ン酸２〜５重量部、ナフタレンスルホン酸ホルマ
リン縮合物の水溶性塩１〜３重量部および脂肪族
炭化水素残基の炭素数12〜20の不飽和脂肪酸塩
0.5〜３重量部と更に補助乳化剤として、水溶性
のポリビニルアルコールを0.2〜1.0重量部を用い
ることを特徴とするクロロプレンと不飽和ニトリ
ルとの単量体混合物の乳化重合方法である。
クロロプレン単量体は少なくとも単量体混合物
中に50重量％以上である必要がある。この理由は
クロロプレンゴムの特性を保持するために必要な
限界である。クロロプレン単量体は重合前全量を
系内に存在させる方法または分割添加する方法を
採用してもよい。
不飽和ニトリルとしてはアクリロニトリルおよ
びメタアクリロニトリルが好ましいい単量体であ
る。本発明はこれらの不飽和ニトリルだけをクロ
ロプレンに共重合させてもよいが、この他不飽和
ニトリルの一部をこれらの単量と共重合可能な他
の単量体の１種以上に置き換えても差支えはな
い。該共重合可能な単量体は全単量体の20重量％
以下が好ましい。
ここの共重合可能な単量体として好ましいもの
はスチレン、アクリル酸、もしくはメタアクリル
酸またはこれらのエステル、１・３−ブタジエ
ン、イソプレン、１−クロロブタジエン、２・３
−ジクロロ−１・３−ブタジエンなどの共役ジオ
レフインである。このようにクロロプレンおよび
不飽和ニトリル以外に他の単量体を含む単量体混
合物を重合させる場合も本発明の範囲に含まれる
ものである。
以上説明した全単量体混合物100重量部に対
し、乳化剤として不均化ロジン酸２〜５重量部、
ナフタレンスルホン酸ホルマリン縮合物の水溶性
の塩１〜３の重量部、および脂肪族炭化水素残基
の炭素数12〜20の不飽和脂肪酸塩0.5〜３重量部
及び水溶性のポリビニルアルコール0.2〜1.0重量
部を用いる。水溶性のポリビニルアルコールとし
ては、重合度200〜2400、ケン化度70〜98％のポ
リビニルアルコールが好ましく、特に重合度300
〜2000、ケン化度80〜90％のものが最適である。
ポリビニルアルコールは全単量体混合物100重量
部に対し0.2〜1.0重量部の範囲で使用するが、量
が多いと重合系の粘度が上昇し、取扱いが不便と
なり、好ましい使用量は0.2〜0.7重量部である。
その他の乳化剤については、前記範囲より少ない
量使用すると、重合後の生成したラテツクスの貯
蔵安定性が悪く、また重合時油層と水層とが分離
する。また逆に多く用いるとラテツクスの粘度の
上昇発泡などするので好ましくない。また多量の
乳化剤の使用量は、重合体を水洗する場合流出し
排水処理も困難になる。ナフタレンスルホン酸ホ
ルマリン縮合物の水溶性の塩としてはナトリウ
ム、カリウム、アンモニウムの塩が好ましい。
不飽和脂肪酸塩としてはオレイン酸、リノール
酸、リノレイン酸のナトリウム塩、カリウム塩な
どが好ましく、これらを単独または併用で用いて
もよい。
重合に用いる水の量は単量体100重量部当り100
重量部以上必要であり、250重量部以下が好まし
く、100重量部未満ではラテツクスが不安定とな
り、250重量部をこえると不飽和ニトリルが単量
体油滴より水相に溶解する量が多くなつて生成す
る重合体中のニトリル濃度が小さくなり、更に通
常の仕上げ方法を採用できないことがある。本発
明の利点の一つとしてポリビニルアルコールを用
いることにより、重合に用いる水量を低減するこ
とができる。単量体100重量部当り100〜200重量
部の水で良好なエマルジヨンがつくられるので、
経済的でもある。
連鎖移動剤としては特に制限はないが、アルキ
ルザントゲンジスルフイドのアルキル基としてイ
ソプロピル基のものが好ましい。またメルカプタ
ン類も比較的多量使用によつて分子量調節するこ
とができる。
触媒としては過硫酸カリウム、ベンゾイルパー
オキシド、クメンヒドロパーオキシドおよび過酸
化水素などが好ましい。
重合温度は10〜60℃、好ましくは30〜50℃であ
る。この他硫黄は全単量体に対して２重量％まで
添加することができる。
本発明の乳化剤を使用することによつて特に製
造上の支障はなく、重合停止にはフエノチアジン
やタシヤリープチルカテコールなどの重合禁止剤
の使用で所望の重合率とすることができ、製造さ
れたエラストマーも公知の方法によつて乾燥固形
ゴムとすることができる。また、所望によつては
ラテツクスのまま濃縮して、あるいは未濃縮でラ
テツクスタイプとして利用することができる。
その加硫物は耐油性、耐熱性および耐ゾン性な
どに優れたものである。
以下実施例によりさらに本発明を詳しく説明す
る。
実施例 １
単量体全量５Kgを使用して、内容積30の重合
缶に第１表の重合処方により乳化重合材料を仕込
み、乳化液をつくり、触媒として過硫酸カリウム
とアンスラキノン−β−スルホン酸ソーダの水溶
液を少量ずつ添加し、窒素気流中40℃で重合を行
なつた。生成したラテツクスからストリツピング
により未反応の単量体を除去した。
得られたラテツクスについて、下記の試験を行
ない、結果を第２表に記載した。
(1) 凝固物
ラテツクスを５℃の定温器に５日間放置した
後、凝固物を80メツシユの金網で濾過し、乾燥
後ラテツクス中の全固形分に対する割合（重量
％）を求めた。
(2) 酸に対する安定性
ラテツクスに５％酢酸水溶液を加え、PHを
7.0に調整したときのラテツクスの状況を調ら
べた。
(3) ムーニー粘度
凝固乾燥したエラストマーのムーニー粘度
（ML1+4100℃）を測定した。
The present invention relates to an improvement in a method for emulsion polymerization of a monomer mixture of chloroprene and unsaturated nitrile. Conventionally, a method for producing oil-resistant chloroprene rubber by emulsion polymerizing chloroprene and unsaturated nitrile using a radical catalyst is known. For example, US Patent No. 2066331, US Patent No. 2395649,
2399407, British Patent No. 858444, and Japanese Patent Publication No. 15043/1973. However, although the use of disproportionated rosin acids as emulsifiers in these polymerization methods has been disclosed, when only disproportionated rosin acids are used, as the content of unsaturated nitriles in the total monomers is increased, Oil droplets may disperse as large particles, or the system may remain separated into an oil layer and a water layer, resulting in poor emulsion stability during polymerization, slowing down the polymerization rate, or polymer precipitation during polymerization. There is a drawback that it does. Therefore, formaldehyde condensates of fatty acids and naphthalenesulfonic acid (USP 3190865), rosin acid-fatty acids-sodium aromatic sulfonates (USP 3317451), and rosin acid-unsaturated fatty acids-naphthalesulfonic acid formalin condensates (Japanese Patent Publication No. 1989-1999-1)
21834) as an emulsifier has been proposed. However, even when these emulsifiers are used, the emulsion system is unstable compared to the emulsion system of chloroprene homopolymer, and for example, when latex is stored for a long time at a low temperature of 5 to 10°C, formation of aggregates is observed, or Since a relatively large amount of water is required for polymerization, about 150 to 250 parts by weight per 100 parts by weight of the monomer, a highly concentrated latex cannot be obtained, resulting in poor birthability. As a result of research on the emulsion copolymerization of chloroprene and unsaturated nitrile, the present inventor discovered a more stable emulsifier.This emulsifier system reduces the water to monomer ratio during polymerization and has stable emulsifying properties even at low temperatures. The present invention was developed based on this recognition. The present invention provides a method for emulsion polymerizing a monomer mixture of at least 50% by weight of chloroprene and an unsaturated nitrile, in which 100 parts by weight or more of water and disproportionated rosin acid as an emulsifier are added to 100 parts by weight of the total monomer mixture. 2 to 5 parts by weight, 1 to 3 parts by weight of a water-soluble salt of a naphthalene sulfonic acid formalin condensate, and a salt of an unsaturated fatty acid having 12 to 20 carbon atoms of an aliphatic hydrocarbon residue.
This is a method for emulsion polymerization of a monomer mixture of chloroprene and unsaturated nitrile, characterized by using 0.5 to 3 parts by weight and further 0.2 to 1.0 parts by weight of water-soluble polyvinyl alcohol as an auxiliary emulsifier. The amount of chloroprene monomer in the monomer mixture must be at least 50% by weight. The reason for this is the limit necessary to maintain the properties of chloroprene rubber. The chloroprene monomer may be present in its entirety in the system before polymerization, or may be added in portions. As unsaturated nitriles, acrylonitrile and methacrylonitrile are preferred monomers. In the present invention, only these unsaturated nitriles may be copolymerized to chloroprene, but in addition, a part of the unsaturated nitriles may be replaced with one or more types of other monomers copolymerizable with these monomers. There is no problem. The copolymerizable monomer accounts for 20% by weight of the total monomers.
The following are preferred. Preferred copolymerizable monomers include styrene, acrylic acid, methacrylic acid, or esters thereof, 1,3-butadiene, isoprene, 1-chlorobutadiene, and 2,3-butadiene.
- Conjugated diolefins such as dichloro-1,3-butadiene. In this way, the scope of the present invention also includes the case where a monomer mixture containing other monomers in addition to chloroprene and unsaturated nitrile is polymerized. Based on 100 parts by weight of the total monomer mixture explained above, 2 to 5 parts by weight of disproportionated rosin acid as an emulsifier;
1 to 3 parts by weight of a water-soluble salt of a naphthalene sulfonic acid formalin condensate, 0.5 to 3 parts by weight of an unsaturated fatty acid salt having 12 to 20 carbon atoms of an aliphatic hydrocarbon residue, and 0.2 to 1.0 parts by weight of a water-soluble polyvinyl alcohol. Use parts by weight. As water-soluble polyvinyl alcohol, polyvinyl alcohol with a degree of polymerization of 200 to 2400 and a degree of saponification of 70 to 98% is preferable, particularly a degree of polymerization of 300 to 98%.
~2000 and a degree of saponification of 80 to 90% is optimal.
Polyvinyl alcohol is used in an amount of 0.2 to 1.0 parts by weight based on 100 parts by weight of the total monomer mixture, but if the amount is too large, the viscosity of the polymerization system increases and handling becomes inconvenient, so the preferred amount is 0.2 to 0.7 parts by weight. Department.
If other emulsifiers are used in amounts less than the above range, the storage stability of the latex produced after polymerization will be poor, and the oil layer and water layer will separate during polymerization. On the other hand, if too much is used, the viscosity of the latex will increase and foaming may occur, which is not preferable. Furthermore, if a large amount of emulsifier is used, it will flow out when the polymer is washed with water, making it difficult to treat wastewater. As the water-soluble salt of the naphthalene sulfonic acid formalin condensate, sodium, potassium, and ammonium salts are preferred. Preferred unsaturated fatty acid salts include oleic acid, linoleic acid, sodium salts and potassium salts of linoleic acid, and these may be used alone or in combination. The amount of water used for polymerization is 100 parts by weight of monomer.
At least 250 parts by weight is required, and at less than 100 parts by weight, the latex becomes unstable, and at more than 250 parts by weight, more unsaturated nitrile dissolves in the water phase than monomer oil droplets. The nitrile concentration in the resulting polymer is low, and furthermore, conventional finishing methods may not be applicable. One of the advantages of the present invention is that by using polyvinyl alcohol, the amount of water used in polymerization can be reduced. A good emulsion can be made with 100 to 200 parts by weight of water per 100 parts by weight of monomer.
It's also economical. The chain transfer agent is not particularly limited, but it is preferable to use an isopropyl group as the alkyl group of the alkyl xantogen disulfide. The molecular weight of mercaptans can also be adjusted by using relatively large amounts. Preferred catalysts include potassium persulfate, benzoyl peroxide, cumene hydroperoxide, and hydrogen peroxide. The polymerization temperature is 10-60°C, preferably 30-50°C. In addition, sulfur can be added up to 2% by weight based on the total monomers. By using the emulsifier of the present invention, there is no particular problem in production, and the desired polymerization rate can be achieved by using a polymerization inhibitor such as phenothiazine or tacyalibutylcatechol to terminate the polymerization. The elastomer can also be made into a dry solid rubber by a known method. Further, if desired, the latex can be concentrated as it is, or can be used as a latex type without being concentrated. The vulcanizate has excellent oil resistance, heat resistance, and zone resistance. The present invention will be explained in more detail with reference to Examples below. Example 1 Using a total amount of 5 kg of monomers, an emulsion polymerization material was charged into a polymerization can with an internal volume of 30 according to the polymerization recipe shown in Table 1 to create an emulsion, and potassium persulfate and anthraquinone-β-sulfone were added as catalysts. An aqueous solution of sodium acid was added little by little, and polymerization was carried out at 40°C in a nitrogen stream. Unreacted monomers were removed from the resulting latex by stripping. The following tests were conducted on the obtained latex, and the results are listed in Table 2. (1) Coagulated product After the latex was left in an incubator at 5°C for 5 days, the coagulated product was filtered through an 80-mesh wire gauze, and after drying, the ratio (weight %) to the total solid content in the latex was determined. (2) Stability against acids Add 5% acetic acid aqueous solution to the latex to adjust the pH.
I investigated the latex situation when adjusting to 7.0. (3) Mooney viscosity The Mooney viscosity (ML 1+4 100°C) of the coagulated and dried elastomer was measured.
【表】【table】
【表】
実施例 ２
単量体100重量部に対する水の量を第３表の通
り変更した以外は、実施例１と同様にしてラテツ
クスを得た。実施例１と同様の方法で、５℃にお
けるラテツクスの凝固物を測定した結果を第３表
に示す。[Table] Example 2 A latex was obtained in the same manner as in Example 1, except that the amount of water relative to 100 parts by weight of monomer was changed as shown in Table 3. Table 3 shows the results of measuring the latex coagulation at 5° C. in the same manner as in Example 1.
【表】
参考例
実施例1No.3で製造したエラストマーを第４表
の配合処方によりコンパウンドをつくり、141℃
で25分間加硫した。加硫物の物性をJIS K6301に
よる伸びとASTM D471による耐油性の試験を行
なつた。また比較のために市販のホモクロロプレ
ンポリマーについても同様の試験を行なつた結果
を第５表に示す。[Table] Reference example A compound was made from the elastomer produced in Example 1 No. 3 according to the formulation shown in Table 4, and heated to 141°C.
Vulcanized for 25 minutes. The physical properties of the vulcanizate were tested for elongation according to JIS K6301 and oil resistance according to ASTM D471. For comparison, similar tests were conducted on commercially available homochloroprene polymers, and the results are shown in Table 5.
【表】【table】
Claims (1)
飽和ニトリルとの単量体混合物を乳化重合する方
法において、全単量体混合物100重量部に対し、
水100重量部以上と乳化剤として不均化ロジン酸
２〜５重量部、ナフタレンスルホン酸ホルマリン
縮合物の水溶性塩１〜３重量部、脂肪族炭化水素
残基の炭素数12〜20の不飽和脂肪酸塩0.5〜３重
量部及び水溶性のポリビニルアルコール0.2〜1.0
重量部を用いることを特徴とするクロロプレンと
不飽和ニトリルとの単量体混合物の乳化重合方
法。1. In a method of emulsion polymerizing a monomer mixture of at least 50% by weight of chloroprene and unsaturated nitrile, based on 100 parts by weight of the total monomer mixture,
100 parts by weight or more of water, 2 to 5 parts by weight of disproportionated rosin acid as an emulsifier, 1 to 3 parts by weight of a water-soluble salt of naphthalene sulfonic acid formalin condensate, unsaturated aliphatic hydrocarbon residue with 12 to 20 carbon atoms. Fatty acid salt 0.5-3 parts by weight and water-soluble polyvinyl alcohol 0.2-1.0
A method for emulsion polymerization of a monomer mixture of chloroprene and unsaturated nitrile, characterized in that parts by weight are used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP843879A JPS5599907A (en) | 1979-01-27 | 1979-01-27 | Copolymerization of chloroprene with unsaturated nitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP843879A JPS5599907A (en) | 1979-01-27 | 1979-01-27 | Copolymerization of chloroprene with unsaturated nitrile |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5599907A JPS5599907A (en) | 1980-07-30 |
| JPS6123805B2 true JPS6123805B2 (en) | 1986-06-07 |
Family
ID=11693125
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP843879A Granted JPS5599907A (en) | 1979-01-27 | 1979-01-27 | Copolymerization of chloroprene with unsaturated nitrile |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5599907A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6486902A (en) * | 1987-07-06 | 1989-03-31 | Riibotsuku Internatl Ltd | Sporting shoes and insole therefor |
| JPH07246104A (en) * | 1994-03-10 | 1995-09-26 | Joong-Taek Kwon | Multiple function shoes |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NZ330371A (en) * | 1997-06-09 | 1999-10-28 | Kuraray Co | Aqueous emulsion system having as dispersant a polyvinyl alcohol polymer and the condensate of an alkali metal salt of an aromatic sulfonic acid |
| CN110621703B (en) * | 2017-05-12 | 2022-08-26 | 电化株式会社 | Process for the production of statistical copolymers, latices and use thereof |
| JPWO2019211975A1 (en) * | 2018-05-02 | 2021-05-13 | デンカ株式会社 | Statistical copolymer latex and its uses, and method for producing statistical copolymer latex |
| ES2926815T3 (en) * | 2018-11-08 | 2022-10-28 | Denka Company Ltd | Chloroprene/Unsaturated Nitrile Copolymer Composition and Vulcanized Molded Article |
-
1979
- 1979-01-27 JP JP843879A patent/JPS5599907A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6486902A (en) * | 1987-07-06 | 1989-03-31 | Riibotsuku Internatl Ltd | Sporting shoes and insole therefor |
| JPH07246104A (en) * | 1994-03-10 | 1995-09-26 | Joong-Taek Kwon | Multiple function shoes |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5599907A (en) | 1980-07-30 |
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