JPH0212246B2 - - Google Patents
Info
- Publication number
- JPH0212246B2 JPH0212246B2 JP11476281A JP11476281A JPH0212246B2 JP H0212246 B2 JPH0212246 B2 JP H0212246B2 JP 11476281 A JP11476281 A JP 11476281A JP 11476281 A JP11476281 A JP 11476281A JP H0212246 B2 JPH0212246 B2 JP H0212246B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- viscosity
- acid
- polymer
- soluble polymer
- 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
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- 229920003169 water-soluble polymer Polymers 0.000 claims description 35
- 150000003839 salts Chemical class 0.000 claims description 15
- 239000003638 chemical reducing agent Substances 0.000 claims description 12
- 239000007800 oxidant agent Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 9
- 239000012966 redox initiator Substances 0.000 claims description 6
- 150000003460 sulfonic acids Chemical class 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 13
- 239000000839 emulsion Substances 0.000 description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- 239000002270 dispersing agent Substances 0.000 description 7
- 239000003995 emulsifying agent Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- -1 sulfoxy compounds Chemical class 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002455 scale inhibitor Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 description 1
- PRAMZQXXPOLCIY-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethanesulfonic acid Chemical compound CC(=C)C(=O)OCCS(O)(=O)=O PRAMZQXXPOLCIY-UHFFFAOYSA-N 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- KFNGWPXYNSJXOP-UHFFFAOYSA-N 3-(2-methylprop-2-enoyloxy)propane-1-sulfonic acid Chemical compound CC(=C)C(=O)OCCCS(O)(=O)=O KFNGWPXYNSJXOP-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical class CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229940091181 aconitic acid Drugs 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-N dithionous acid Chemical class OS(=O)S(O)=O GRWZHXKQBITJKP-UHFFFAOYSA-N 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- 125000004964 sulfoalkyl group Chemical group 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Landscapes
- Polymerization Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は水溶性重合体の製造方法に関するもの
であり、更に詳しくはエチレン系不飽和カルボン
酸またはその塩からなる単量体とエチレン系不飽
和スルホン酸またはその塩からなる単量体とをレ
ドツクス系開始剤を用いて重合するに際して、還
元剤と酸化剤との比を特定量にすることにより、
放置における安定性良好な水溶性重合体の製造方
法に関するものである。
アクリル酸またはメタクリル酸とスルホン酸含
有単量体との水溶性重合体は重合体エマルジヨン
製造における高分子乳化剤、各種分散剤、導電処
理剤、スケール防止剤、製紙用添加剤等にそれぞ
れの用途に応じて該水溶性重合体の成分組成、重
合度、粘度等を規定して巾広く使用されている。
ところが、かかる有用な前記水溶性重合体につ
いて更に検討を加えたところ、本発明者は前記水
溶性重合体の合成に際して、レドツクス系開始剤
を用いて得た水溶性重合体は常温もしくはそれ以
上の温度で放置された場合に粘度増加が生起する
ことを認めた。
このような水溶性重合体の粘度増加は品質の変
動原因となり、例えば重合後長期間放置して粘度
増加したところ水溶性重合体を用いて重合体エマ
ルジヨンを作成する場合、エマルジヨンの粒子径
および化学的、機械的安定性に変化が生じ、品質
の安定したエマルジヨンを作成することができ
ず、また各種分散剤として使用する場合、分散性
能が変化する等の問題を惹起する。
ここにおいて本発明者は上記水溶性重合体の合
成に際して、使用するレドツクス系開始剤の還元
剤と酸化剤との当量比を特定化することにより、
放置による安定性良好な水溶性重合体を製造しう
ることを見出し本発明に達した。
即ち本発明の目的は放置により実質的に変質す
ることのない安定性良好な水溶性重合体を得る方
法を提供することにある。
本発明の他の目的は水溶性重合体を重合体エマ
ルジヨン製造における高分子乳化剤、各種分散
剤、導電処理剤、スケール防止剤、製紙用添加剤
等への使用に際して時間の経過により品質が変化
することのない安定な品質の水溶性重合体を製造
することにある。
本発明の更に異なる他の目的は以下に述べる本
発明の具体的な説明によつて明らかとなろう。
かくの如き本発明の目的はエチレン系不飽和カ
ルボン酸またはその塩からなる単量体とエチレン
系不飽和スルホン酸またはその塩からなる単量体
とを還元剤が酸化剤の1.0〜1.9当量からなるレド
ツクス系開始剤を用いて重合することにより達成
することができる。
かかる本発明方法に従つて得た水溶性重合体は
常温もしくはそれ以上の温度で長期間放置した場
合にも粘度増加等の品質変動は殆ど認められな
い。
従つて本発明による水溶性重合体を用いて重合
体エマルジヨンを作成すれば、常に目的とした微
粒子径でかつ化学的、機械的に安定した品質の重
合体エマルジヨンを再現性よく製造することがで
き、また各種分散剤、添加剤等に使用する場合に
も、保存、放置等によつても変質の起らない安定
した品質を有する水溶性重合体を作成することが
できる。
ここにおいて本発明に係る水溶性重合体とは該
重合体構成単位としてエチレン系不飽和カルボン
酸またはその塩からなる単量体（Ａ成分）とエチ
レン系不飽和スルホン酸またはその塩からなる単
量体（Ｂ成分）とを、還元剤を酸化剤に対して
1.0〜1.9当量、好ましくは1.0〜1.7当量となる水
溶性レドツクス系開始剤を用いて共重合（特に、
水を重合媒体として用いる溶液重合が好適であ
る）せしめることにより製造することができる。
かかる重合において、還元剤を酸化剤に対して
1.9当量以上用いた場合、得られる水溶性重合体
は放置によつて粘度増加を起し不安定となる。一
方、1.0当量以下ではレドツクス系としての能力
が減少し重合速度低下、重合率低下、重合度上
昇、重合過程における粘度増加等の問題を惹起し
操業上支障をきたすとともに目標とする品質の水
溶性重合体が得られないので好ましくない。
また、かかる水溶性重合体のＡ成分とＢ成分と
の組成割合は該水溶性重合体の使用目的によつて
異なり一義的に限定することは困難であるが、一
般にＡ成分／Ｂ成分＝20〜90％／80〜10％の範囲
にあることが望ましい。
なお、かくの如き水溶性重合体中に導入される
Ａ成分としては、アクリル酸、メタクリル酸、ビ
ニル酢酸、クロトン酸等の不飽和一価カルボン酸
およびこれらの塩：マレイン酸、フマル酸、イタ
コン酸、アコニツト酸、シトラコン酸、メサコン
酸等の不飽和多価カルボン酸およびこれらの塩等
を挙げることができるが、特に、高分子乳化剤と
して使用する場合におけるエマルジヨンの安定
性、エマルジヨンの粒子径、或は分散剤として使
用する場合における分散性能等の見地からメタク
リル酸およびその塩からなる単量体単位の導入が
推奨される。
また、Ｂ成分としてはスチレンスルホン酸、ア
リルスルホン酸、メタリルスルホン酸等のスルホ
ン化不飽和炭化水素類およびこれらの塩；メタク
リル酸スルホエチルエステル、メタクリル酸スル
ホプロピルエステル等のアクリル酸またはメタク
リル酸のスルホアルキルエステル類およびこれら
の塩；アクリルアミドのアルキルスルホン酸誘導
体およびこれらの塩等を挙げることができるが、
特に、高分子乳化剤として使用する場合における
エマルジヨンの安定性、エマルジヨンの粒子径或
は分散剤として使用する場合における分散性能等
の見地からスチレンスルホン酸およびその塩から
なる単量体単位の導入が推奨される。
さらに該水溶性重合体の製造に使用するレドツ
クス系開始剤としては、通常使用される酸化剤と
還元剤との組合せであれば何でもよく、例えば酸
化剤として過硫酸塩、過酸化水素、過マンガン酸
塩、第二金属塩、亜硫酸塩、過酢酸などとこれら
酸化剤とレドツクスを組む還元剤として亜硫酸
塩、重亜硫酸塩、メタ亜硫酸塩、ヒドロ亜硫酸
塩、チオ硫酸塩等の還元性スルホキシ化合物；鉄
塩、蓚酸、硫酸銀などを適宜組合せて使用するこ
とができるが、特に、過硫酸塩と還元性スルホキ
シ化合物（および／または第一鉄イオン）との組
合せ、塩素酸塩と還元性スルホキシ化合物との組
合せからなるレドツクス系開始剤の使用が望まし
い。
なお、水溶性重合体の分子量を調整するため必
要に応じて重合系に四塩化炭素、メルカプタン類
等の連鎖移動剤を共存させることは何ら差支えな
い。
かくして、本発明に従つて得られた水溶性重合
体は室温もしくはそれ以上の温度で放置した場合
でも粘度増加は生起せず、放置安定性が優れてい
るため重合体エマルジヨン製造における乳化剤、
各種分散剤、スケール防止剤、製紙用添加剤等へ
の使用に対して、夫々の用途目的に合つた品質の
一定した水溶性重合体を有利に適用することがで
きる。
以下に記載する実施例は本発明をよりよく説明
するものであり本発明の範囲を何ら限定するもの
ではない。なお実施例に示される百分率および部
は特に断わりのない限り全て重量基準によるもの
である。
実施例 １
メタクリル酸（MAA）70部、ｐ−スチレンス
ルホン酸ソーダ（SPSS）30部に、塩化第一鉄
0.0015部およびイオン交換水300部を撹拌機付反
応容器に入れ、過硫酸アンモン（APS）と酸性
亜硫酸ソーダの当量比を第１表のように変化させ
て添加し、撹拌条件下に70℃で１時間重合し水溶
性共重合体７種を得た。
いずれの水溶性重合体も重合率は100％であつ
た。
この７種の重合体溶液の重合直後の粘度をV0
とし、40℃で50時間放置後の粘度をV1として放
置による粘度増加比V1／V0を測定、算出した結
果を第１表に併記した。
The present invention relates to a method for producing a water-soluble polymer, and more specifically, the present invention relates to a method for producing a water-soluble polymer, and more specifically, the present invention relates to a method for producing a water-soluble polymer. When polymerizing using a system initiator, by adjusting the ratio of reducing agent and oxidizing agent to a specific amount,
The present invention relates to a method for producing a water-soluble polymer with good stability when left standing. Water-soluble polymers of acrylic acid or methacrylic acid and sulfonic acid-containing monomers have various uses such as polymer emulsifiers in the production of polymer emulsions, various dispersants, conductive treatment agents, scale inhibitors, and paper manufacturing additives. Accordingly, the component composition, degree of polymerization, viscosity, etc. of the water-soluble polymer are specified and used widely. However, upon further investigation into such useful water-soluble polymers, the present inventor found that the water-soluble polymers obtained using a redox initiator during the synthesis of the water-soluble polymers could be heated at room temperature or higher. It was observed that viscosity increased when left at high temperatures. Such an increase in the viscosity of water-soluble polymers causes quality fluctuations. For example, when a water-soluble polymer is used to create a polymer emulsion, the viscosity increases after being left for a long period of time after polymerization. This causes changes in physical and mechanical stability, making it impossible to create emulsions with stable quality, and when used as various dispersants, causes problems such as changes in dispersion performance. Here, the present inventor specified the equivalent ratio of the reducing agent and oxidizing agent of the redox initiator used in the synthesis of the water-soluble polymer.
The present invention was accomplished by discovering that it is possible to produce a water-soluble polymer that exhibits good stability upon standing. That is, an object of the present invention is to provide a method for obtaining a highly stable water-soluble polymer that does not undergo substantial deterioration upon standing. Another object of the present invention is to prevent quality changes over time when water-soluble polymers are used as polymer emulsifiers, various dispersants, conductive treatment agents, scale inhibitors, papermaking additives, etc. in the production of polymer emulsions. Our aim is to produce water-soluble polymers of consistently stable quality. Still other objects of the present invention will become apparent from the detailed description of the invention that follows. The object of the present invention is to combine a monomer consisting of an ethylenically unsaturated carboxylic acid or a salt thereof and a monomer consisting of an ethylenically unsaturated sulfonic acid or a salt thereof, in which the reducing agent is 1.0 to 1.9 equivalents of the oxidizing agent. This can be achieved by polymerization using a redox initiator. The water-soluble polymer obtained according to the method of the present invention shows almost no change in quality such as an increase in viscosity even when it is left at room temperature or higher for a long period of time. Therefore, if a polymer emulsion is prepared using the water-soluble polymer according to the present invention, a polymer emulsion with a desired fine particle size and chemically and mechanically stable quality can be produced with good reproducibility. Furthermore, when used in various dispersants, additives, etc., water-soluble polymers with stable quality that do not undergo deterioration even when stored, left, etc. can be produced. Here, the water-soluble polymer according to the present invention refers to a monomer (component A) consisting of an ethylenically unsaturated carboxylic acid or its salt and a monomer consisting of an ethylenically unsaturated sulfonic acid or its salt as the polymer constituent units. body (component B), and the reducing agent to the oxidizing agent.
Copolymerization (especially,
Solution polymerization using water as the polymerization medium is preferred). In such polymerizations, the reducing agent is opposed to the oxidizing agent.
If more than 1.9 equivalents are used, the resulting water-soluble polymer will increase in viscosity and become unstable upon standing. On the other hand, if the amount is less than 1.0 equivalent, the ability as a redox system decreases, causing problems such as a decrease in polymerization rate, a decrease in polymerization rate, an increase in polymerization degree, and an increase in viscosity during the polymerization process. This is not preferred because a polymer cannot be obtained. In addition, the composition ratio of component A and component B of such a water-soluble polymer varies depending on the purpose of use of the water-soluble polymer and is difficult to limit, but generally, component A/component B = 20. It is desirable to be in the range of ~90%/80~10%. The A component introduced into such water-soluble polymers includes unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, vinyl acetic acid, and crotonic acid, and salts thereof: maleic acid, fumaric acid, and itacon. Acids, unsaturated polyhydric carboxylic acids such as aconitic acid, citraconic acid, mesaconic acid, and salts thereof can be mentioned, but in particular, the stability of the emulsion when used as a polymer emulsifier, the particle size of the emulsion, Alternatively, when used as a dispersant, it is recommended to introduce monomer units consisting of methacrylic acid and its salts from the viewpoint of dispersion performance. In addition, as component B, sulfonated unsaturated hydrocarbons such as styrene sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, and salts thereof; acrylic acid or methacrylic acid such as methacrylic acid sulfoethyl ester, methacrylic acid sulfopropyl ester, etc. Examples include sulfoalkyl esters of and salts thereof; alkylsulfonic acid derivatives of acrylamide and salts thereof;
In particular, it is recommended to introduce monomer units consisting of styrene sulfonic acid and its salts from the viewpoints of emulsion stability when used as a polymer emulsifier, emulsion particle size, and dispersion performance when used as a dispersant. be done. Furthermore, the redox initiator used in the production of the water-soluble polymer may be any combination of commonly used oxidizing agents and reducing agents, such as persulfate, hydrogen peroxide, permanganese, etc. Reducing sulfoxy compounds such as sulfites, bisulfites, metasulfites, hydrosulfites, thiosulfates, etc. as reducing agents that form redox with acid salts, second metal salts, sulfites, peracetic acids, etc.; Iron salts, oxalic acid, silver sulfate, etc. can be used in appropriate combinations, but in particular, combinations of persulfates and reducing sulfoxy compounds (and/or ferrous ions), chlorates and reducing sulfoxy compounds It is desirable to use a redox initiator consisting of a combination of Incidentally, in order to adjust the molecular weight of the water-soluble polymer, there is no problem in coexisting a chain transfer agent such as carbon tetrachloride or mercaptans in the polymerization system as necessary. Thus, the water-soluble polymer obtained according to the present invention does not increase in viscosity even when left at room temperature or higher temperature, and has excellent storage stability, so it can be used as an emulsifier in the production of polymer emulsions.
For use in various dispersants, scale inhibitors, paper-making additives, etc., water-soluble polymers of uniform quality suitable for each purpose can be advantageously applied. The examples described below are intended to better explain the invention and are not intended to limit the scope of the invention in any way. It should be noted that all percentages and parts shown in the examples are based on weight unless otherwise specified. Example 1 Ferrous chloride was added to 70 parts of methacrylic acid (MAA) and 30 parts of sodium p-styrene sulfonate (SPSS).
0.0015 parts and 300 parts of ion-exchanged water were placed in a reaction vessel equipped with a stirrer, and the equivalence ratios of ammonium persulfate (APS) and acidic sodium sulfite were changed as shown in Table 1, and the mixture was heated at 70°C under stirring conditions. Polymerization was carried out for 1 hour to obtain 7 types of water-soluble copolymers. The polymerization rate of all water-soluble polymers was 100%. The viscosity of these seven types of polymer solutions immediately after polymerization is V 0
The viscosity after standing at 40°C for 50 hours was V 1 , and the viscosity increase ratio V 1 /V 0 due to standing was measured and calculated. The results are also listed in Table 1.
【表】
て測定した。
この結果、酸化剤に対して還元剤を2.0当量以
上添加したａ、ｂ、ｃは40℃で50時間の放置によ
り水溶性重合体の粘度増加が著しい。酸化剤に対
して還元剤1.9〜1.7当量添加したｄ、ｅは粘度増
加は小さく、1.3〜1.0当量添加したｆ、ｇは粘度
増加はなく、放置による品質変動は起つていな
い。
酸化剤に対して還元剤を0.8当量添加して重合
した水溶性重合体ｈは放置によつては粘度は増加
しないものの、重合時の粘度はｇの２倍以上にも
なり高粘度のため操業上にも支障があつた。
実施例 ２
メタクリル酸（MAA）50部、２−アクリルア
ミド−２−メチルプロパンスルホン酸（AMPS）
50部に塩化第一鉄0.0015部、イオン交換水300部
を撹拌機付反応容器に入れ、過硫酸アンモン
（APS）と酸性亜硫酸ソーダの当量比を第２表に
示すごとく３水準変化させて添加し、撹拌条件下
に70℃で１時間重合し水溶性重合体ｉ、ｊ、ｋの
３種を得た。
いずれの水溶性重合体も重合率は100％であつ
た。
この重合性溶液を30℃で１週間放置し放置前後
の粘度（夫々V0、V1）を測定し、放置による粘
度増加比V1／V0を求めた結果を第２表に併記し
た。[Table] Measured.
As a result, the viscosity of the water-soluble polymers of a, b, and c, in which 2.0 equivalents or more of the reducing agent was added to the oxidizing agent, was left at 40° C. for 50 hours was significant. In d and e, in which 1.9 to 1.7 equivalents of reducing agent were added to the oxidizing agent, the viscosity increased little, and in f and g, in which 1.3 to 1.0 equivalents were added, there was no increase in viscosity, and no quality change occurred due to standing. Water-soluble polymer h, which was polymerized by adding 0.8 equivalents of reducing agent to oxidizing agent, did not increase in viscosity when left to stand, but the viscosity during polymerization was more than twice that of g, making it difficult to operate due to the high viscosity. There was also a problem at the top. Example 2 50 parts of methacrylic acid (MAA), 2-acrylamido-2-methylpropanesulfonic acid (AMPS)
50 parts, 0.0015 parts of ferrous chloride, and 300 parts of ion-exchanged water were placed in a reaction vessel equipped with a stirrer, and the equivalence ratio of ammonium persulfate (APS) and acidic sodium sulfite was added at three different levels as shown in Table 2. Then, polymerization was carried out at 70° C. for 1 hour under stirring conditions to obtain three types of water-soluble polymers i, j, and k. The polymerization rate of all water-soluble polymers was 100%. This polymerizable solution was left at 30°C for one week, and the viscosity (V 0 and V 1 ) before and after the standing was measured, and the viscosity increase ratio V 1 /V 0 due to standing was determined. The results are also shown in Table 2.
【表】
〓註〓 水溶性重合体の粘度測定は(株)東京計器
製造所製のB型粘度計を使用し、30℃に
て測定した。
この結果、酸化剤に対して還元剤を2.0当量添
加したｉは30℃で１週間放置によつて粘度増加は
著しいが、1.7〜1.3当量のｊ、ｋは粘度増加は小
さい。[Table] Note: The viscosity of the water-soluble polymer was measured at 30°C using a B-type viscometer manufactured by Tokyo Keiki Seisakusho.
As a result, the viscosity of i, in which 2.0 equivalents of the reducing agent was added to the oxidizing agent, increased significantly when left at 30° C. for one week, but the viscosity of i, which had 1.7 to 1.3 equivalents added, was small.
Claims (1)
らなる単量体とエチレン系不飽和スルホン酸また
はその塩からなる単量体とを、還元剤が酸化剤の
1.0〜1.9当量からなるレドツクス系開始剤で重合
することを特徴とする安定性良好な水溶性重合体
の製造方法。1 A monomer consisting of an ethylenically unsaturated carboxylic acid or its salt and a monomer consisting of an ethylenically unsaturated sulfonic acid or its salt are combined in a manner that the reducing agent is the oxidizing agent.
1. A method for producing a water-soluble polymer with good stability, which comprises polymerizing with a redox initiator containing 1.0 to 1.9 equivalents.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11476281A JPS5815512A (en) | 1981-07-22 | 1981-07-22 | Production of water-soluble polymer having good stability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11476281A JPS5815512A (en) | 1981-07-22 | 1981-07-22 | Production of water-soluble polymer having good stability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5815512A JPS5815512A (en) | 1983-01-28 |
| JPH0212246B2 true JPH0212246B2 (en) | 1990-03-19 |
Family
ID=14646042
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11476281A Granted JPS5815512A (en) | 1981-07-22 | 1981-07-22 | Production of water-soluble polymer having good stability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5815512A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61231043A (en) * | 1985-04-04 | 1986-10-15 | Japan Synthetic Rubber Co Ltd | Pluoropolymer partible having uniform particle size and production thereof |
| DE3786003T2 (en) * | 1986-12-19 | 1993-09-02 | Nat Starch Chem Invest | WATER-SOLUBLE POLYMERS CONTAINING ALLYLOXYBENZENE SULFONATE MONOMERS. |
| JP2557380B2 (en) * | 1987-04-30 | 1996-11-27 | 株式会社クラレ | Suspension polymerization dispersant |
| JP2528876B2 (en) * | 1987-04-30 | 1996-08-28 | 株式会社 クラレ | Method for producing heat-resistant methacrylic resin |
| JP4778719B2 (en) * | 2005-03-30 | 2011-09-21 | Ｊｓｒ株式会社 | Copolymer latex for can sealant |
-
1981
- 1981-07-22 JP JP11476281A patent/JPS5815512A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5815512A (en) | 1983-01-28 |
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