JPH0215568B2 - - Google Patents
Info
- Publication number
- JPH0215568B2 JPH0215568B2 JP59068562A JP6856284A JPH0215568B2 JP H0215568 B2 JPH0215568 B2 JP H0215568B2 JP 59068562 A JP59068562 A JP 59068562A JP 6856284 A JP6856284 A JP 6856284A JP H0215568 B2 JPH0215568 B2 JP H0215568B2
- Authority
- JP
- Japan
- Prior art keywords
- maleate
- acid
- copolymer
- added
- producing
- 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 - Lifetime
Links
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 23
- 229920001577 copolymer Polymers 0.000 claims description 16
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 14
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 9
- 239000011976 maleic acid Substances 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000003125 aqueous solvent Substances 0.000 claims description 6
- NLVWBYNKMPGKRG-ODZAUARKSA-N azane;(z)-but-2-enedioic acid Chemical compound N.OC(=O)\C=C/C(O)=O NLVWBYNKMPGKRG-ODZAUARKSA-N 0.000 claims description 6
- 239000003505 polymerization initiator Substances 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920001444 polymaleic acid Polymers 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002455 scale inhibitor Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-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
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-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
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- -1 alkali metal salts Chemical class 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】
本発明はマレイン酸塩共重合体の製造法に関す
る。更に詳しくは、水溶媒系中である特定範囲の
平均分子量を有するマレイン酸塩共重合体を効率
よく製造する方法に関する。
従来より、ポリマレイン酸及びマレイン酸と他
のモノマーの共重合体は分散剤、スケール防止剤
等の用途に使用されている。ポリマレイン酸はト
ルエン、キシレン等の有機溶媒中で、ベンゾイル
パーオキサイドの如き過酸化物を重合開始剤とし
て用いて製造されているのが現状である。しか
し、工業的見地からは、有機溶媒中よりも水溶媒
中で製造を行なつた方が、製造工程の簡易化、コ
ストの低下、火炎防止等の観点よりみて、はるか
に望ましい。しかるに、ポリマレイン酸塩の水溶
媒系での重合に関する研究例はほとんどなく、わ
ずかに、マレイン酸とアクリル酸又は酢酸ビニル
等との共重合体に関する例を見るのみである。
本発明者らは、ポリマレイン酸及びマレイン酸
と他のモノマーの共重合体の重合に関するかかる
現状を認識し、水溶媒系中におけるマレイン酸塩
の重合反応について鋭意研究の結果、モノマーと
してマレイン酸モノアルカリ金属塩又はマレイン
酸モノアンモニウム塩を用いると、平均分子量
300〜5000のマレイン酸塩共重合体が効率よく製
造されることを見い出し本発明を完成させた。即
ち本発明は、マレイン酸100モルとアクリル酸、
メタクリル酸、イタコン酸、アクリルアミド、
（メタ）アクリル酸エステル、ヒドロキシ（メタ）
アクリレート、スチレンスルホン酸及びアリルス
ルホン酸から選ばれるモノマー５モル未満から平
均分子量300〜5000のマレイン酸塩共重合体を製
造するに際し、マレイン酸モノアルカリ金属塩又
はマレイン酸モノアンモニウム塩に前記モノマー
を添加し、水溶媒系中で重合開始剤の存在下、80
〜180℃にて重合させることを特徴とするマレイ
ン酸塩共重合体の製造法を提供するものである。
本発明の製造法を具体的に述べると、先ずマレ
イン酸又は無水マレイン酸の水溶液を調製し、そ
れにアルカリ金属水酸化物（例えば水酸化ナトリ
ウム、水酸化カリウム等）又はアンモニア水を、
マレイン酸又は無水マレイン酸と等モル量〜10モ
ル％過剰量加えることによりマレイン酸モノアル
カリ金属塩又はマレイン酸モノアンモニウム塩の
水溶液を得る。更にこの水溶液に上記他のモノマ
ーを添加する。この時の液のPHは3.5〜5.0であ
る。該水溶液に重合開始剤を、モノマー１モルに
対し好ましくは0.02〜0.6モル、より好ましくは
0.05〜0.4モルを一括添加又は分割添加して、80
〜180℃、好ましくは100〜150℃にて重合せしめ
る。
本製造法に関するマレイン酸モノアルカリ金属
塩又はマレイン酸モノアンモニウム塩の水溶液濃
度については特に制限はないが、固型分濃度30重
量％以上60重量％以下が実用的である。重合反応
時間についても特に制限はないが、３時間以上、
特に４時間以上10時間以下が適当である。
重合反応に用いることができる重合開始剤とし
ては、ｔ―ブチルヒドロパーオキサイド、クメン
ヒドロパーオキサイドの如き、ヒドロパーオキサ
イド類、ジ―ｔ―ブチルパーオキサイドの如き、
ジ―アルキルパーオキサイド類、又は過硫酸アン
モニウムの如き、過硫酸塩類、間硫酸塩―亜硫酸
塩のレドツクス系及び水溶性アゾビス系等の開始
剤を挙げることができる。
本発明の製造法により、平均分子量300〜5000
のマレイン酸塩共重合体を効率よく容易に得るこ
とができる。その理由については明白でないが、
マレイン酸モノアルカリ金属塩又はマレイン酸モ
ノアンモニウム塩は水溶液中で分子内水素結合を
形成し平面構造を取るため、ラジカル共嗚安定化
が増大し、その重合性が増すためであると考えら
れる。
本発明の方法により製造されたマレイン酸塩共
重合体は、特に分散能、カルシウムイオン捕捉能
に優れ、スケール防止剤、顔料分散剤、洗剤ビル
ダー等の用途に供することができる。
以下、実施例をもつて本発明を更に詳しく説明
するが、本発明はこれら実施例に限定されるもの
ではない。
実施例 １
温度計、撹拌機、滴下ロート、窒素導入管及び
還流コンデンサーを備えたフラスコに無水マレイ
ン酸294ｇ（3.0モル）、水228ｇを加え、撹拌下、
40％苛性ソーダ水溶液315ｇ（NaOHとして3.15
モル）を加えた。更にアクリル酸5.4ｇ（0.075モ
ル）を添加し、系が均一となつた後、溶液を少量
取り、水で希釈し、３％水溶液とした後、PHを測
定したところ、4.09（測定温度35℃）であつた。
次いで窒素を導入しつつ系を100℃に昇温した後、
重合開始剤として過硫酸ソーダ25ｇと35％過酸化
水素水233ｇの混合液を６時間かけて滴下した。
滴下終了後100℃で２時間加熱した後、系を40℃
以下に冷却した。この溶液を少量とり、PHを測定
したところ5.02であつた。このようにして38％固
型分のマレイン酸／アクリル酸共重合体が得られ
た。
実施例 ２
アクリル酸のかわりにスチレンスルホン酸ソー
ダ12.4ｇ（0.06モル）を添加する以外は実施例１
と全く同様にしてマレイン酸／スチレンスルホン
酸ソーダ共重合体を合成した。得られた共重合体
の重合率、平均分子量を次の表１に示す。尚プロ
ミン―ブロマイド法による残存単量体の定量によ
り重合率を求めた。又ゲル・パーミエーシヨンク
ロマトグラフイーで該共重合体の平均分子量を測
定した。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing maleate copolymers. More specifically, the present invention relates to a method for efficiently producing a maleate copolymer having an average molecular weight within a certain range in an aqueous solvent system. Conventionally, polymaleic acid and copolymers of maleic acid and other monomers have been used as dispersants, scale inhibitors, and the like. Currently, polymaleic acid is produced in an organic solvent such as toluene or xylene using a peroxide such as benzoyl peroxide as a polymerization initiator. However, from an industrial standpoint, it is much more desirable to carry out the production in an aqueous solvent than in an organic solvent from the viewpoints of simplifying the production process, reducing costs, preventing flames, etc. However, there are almost no examples of research on the polymerization of polymaleate in an aqueous solvent system, and there are only a few examples of copolymers of maleic acid and acrylic acid, vinyl acetate, or the like. The present inventors recognized the current situation regarding the polymerization of polymaleic acid and copolymers of maleic acid and other monomers, and as a result of intensive research on the polymerization reaction of maleic acid salts in an aqueous solvent system, they found that When using alkali metal salts or monoammonium maleate salts, the average molecular weight
The present invention was completed by discovering that a maleate copolymer having a molecular weight of 300 to 5,000 can be efficiently produced. That is, the present invention provides 100 moles of maleic acid and acrylic acid,
methacrylic acid, itaconic acid, acrylamide,
(meth)acrylic acid ester, hydroxy (meth)
When producing a maleate copolymer having an average molecular weight of 300 to 5000 from less than 5 moles of a monomer selected from acrylate, styrene sulfonic acid, and allyl sulfonic acid, the monomer is added to a monoalkali metal maleate or a monoammonium maleate. and in the presence of a polymerization initiator in an aqueous solvent system, 80
The present invention provides a method for producing a maleate copolymer, which is characterized by polymerizing at a temperature of 180°C to 180°C. Specifically describing the production method of the present invention, first, an aqueous solution of maleic acid or maleic anhydride is prepared, and an alkali metal hydroxide (for example, sodium hydroxide, potassium hydroxide, etc.) or aqueous ammonia is added to it.
An aqueous solution of monoalkali metal maleate or monoammonium maleate is obtained by adding an equimolar amount to 10 mol% excess of maleic acid or maleic anhydride. Furthermore, the other monomers mentioned above are added to this aqueous solution. The pH of the liquid at this time is 3.5 to 5.0. A polymerization initiator is added to the aqueous solution, preferably 0.02 to 0.6 mol, more preferably 0.02 to 0.6 mol per mol of monomer.
Add 0.05 to 0.4 mol all at once or in portions to make 80
Polymerization is carried out at ~180°C, preferably 100-150°C. There is no particular restriction on the concentration of the aqueous solution of monoalkali metal maleate or monoammonium maleate in this production method, but a practical solid content concentration is 30% by weight or more and 60% by weight or less. There are no particular restrictions on the polymerization reaction time, but 3 hours or more,
In particular, a period of 4 hours or more and 10 hours or less is suitable. Examples of polymerization initiators that can be used in the polymerization reaction include hydroperoxides such as t-butyl hydroperoxide and cumene hydroperoxide, and di-t-butyl peroxide.
Mention may be made of initiators such as di-alkyl peroxides, or redox systems of persulfates, intersulfate-sulfites, such as ammonium persulfate, and water-soluble azobis systems. By the production method of the present invention, the average molecular weight is 300 to 5000.
maleate copolymers can be obtained easily and efficiently. Although the reason is not clear,
This is thought to be due to the fact that monoalkali metal maleate or monoammonium maleate forms intramolecular hydrogen bonds in an aqueous solution and takes a planar structure, which increases radical coherence stabilization and increases its polymerizability. The maleate copolymer produced by the method of the present invention has particularly excellent dispersibility and calcium ion trapping ability, and can be used as a scale inhibitor, a pigment dispersant, a detergent builder, and the like. EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. Example 1 294 g (3.0 mol) of maleic anhydride and 228 g of water were added to a flask equipped with a thermometer, stirrer, dropping funnel, nitrogen inlet tube, and reflux condenser, and while stirring,
315 g of 40% caustic soda aqueous solution (3.15 g as NaOH)
mol) was added. Furthermore, 5.4 g (0.075 mol) of acrylic acid was added, and after the system became homogeneous, a small amount of the solution was taken and diluted with water to make a 3% aqueous solution.The pH was measured, and it was found to be 4.09 (measurement temperature: 35°C). ).
Next, after increasing the temperature of the system to 100°C while introducing nitrogen,
As a polymerization initiator, a mixed solution of 25 g of sodium persulfate and 233 g of 35% hydrogen peroxide solution was added dropwise over 6 hours.
After the dropping was completed, the system was heated at 100℃ for 2 hours, and then heated to 40℃.
Cooled below. When a small amount of this solution was taken and the pH was measured, it was 5.02. A maleic acid/acrylic acid copolymer with a solids content of 38% was thus obtained. Example 2 Example 1 except that 12.4 g (0.06 mol) of sodium styrene sulfonate was added instead of acrylic acid.
A maleic acid/sodium styrene sulfonate copolymer was synthesized in exactly the same manner. The polymerization rate and average molecular weight of the obtained copolymer are shown in Table 1 below. The polymerization rate was determined by quantifying the residual monomer by the promine-bromide method. The average molecular weight of the copolymer was also measured by gel permeation chromatography. 【table】
Claims (1)
ル酸、イタコン酸、アクリルアミド、（メタ）ア
クリル酸エステル、ヒドロキシ（メタ）アクリレ
ート、スチレンスルホン酸及びアリルスルホン酸
から選ばれるモノマー５モル未満から平均分子量
300〜5000のマレイン酸塩共重合体を製造するに
際し、マレイン酸モノアルカリ金属塩又はマレイ
ン酸モノアンモニウム塩に前記モノマーを添加
し、水溶媒系中で重合開始剤の存在下、80〜180
℃にて重合させることを特徴とするマレイン酸塩
共重合体の製造法。1 Average molecular weight from 100 moles of maleic acid and less than 5 moles of a monomer selected from acrylic acid, methacrylic acid, itaconic acid, acrylamide, (meth)acrylic acid ester, hydroxy (meth)acrylate, styrene sulfonic acid, and allyl sulfonic acid.
When producing a maleate copolymer of 300 to 5,000, the monomer is added to a monoalkali metal maleate or monoammonium maleate, and in the presence of a polymerization initiator in an aqueous solvent system, a copolymer of 80 to 180
A method for producing a maleate copolymer, which comprises polymerizing at ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6856284A JPS59210913A (en) | 1984-04-06 | 1984-04-06 | Production of maleate copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6856284A JPS59210913A (en) | 1984-04-06 | 1984-04-06 | Production of maleate copolymer |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57175903A Division JPS5964615A (en) | 1982-10-06 | 1982-10-06 | Production of polymaleate salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59210913A JPS59210913A (en) | 1984-11-29 |
| JPH0215568B2 true JPH0215568B2 (en) | 1990-04-12 |
Family
ID=13377321
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6856284A Granted JPS59210913A (en) | 1984-04-06 | 1984-04-06 | Production of maleate copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59210913A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69015424T2 (en) * | 1989-04-28 | 1995-08-17 | Nippon Catalytic Chem Ind | Process for the preparation and use of salts of polymers of maleic acid with improved biodegradability. |
| US20050202996A1 (en) * | 2004-03-15 | 2005-09-15 | The Procter & Gamble Company | Surface-treating compositions containing sulfonated/carboxylated polymers |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55127415A (en) * | 1977-03-23 | 1980-10-02 | Pfizer | Copolymer of maleic acid anhydride and its use as scale preventing agent |
| JPS57175903A (en) * | 1981-03-31 | 1982-10-29 | Philips Nv | Object inspecter |
-
1984
- 1984-04-06 JP JP6856284A patent/JPS59210913A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55127415A (en) * | 1977-03-23 | 1980-10-02 | Pfizer | Copolymer of maleic acid anhydride and its use as scale preventing agent |
| JPS57175903A (en) * | 1981-03-31 | 1982-10-29 | Philips Nv | Object inspecter |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59210913A (en) | 1984-11-29 |
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