CN1050367C - Production of acid polymer from maleic acid - Google Patents
Production of acid polymer from maleic acid Download PDFInfo
- Publication number
- CN1050367C CN1050367C CN93115343A CN93115343A CN1050367C CN 1050367 C CN1050367 C CN 1050367C CN 93115343 A CN93115343 A CN 93115343A CN 93115343 A CN93115343 A CN 93115343A CN 1050367 C CN1050367 C CN 1050367C
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- CN
- China
- Prior art keywords
- acid
- maleic
- maleic anhydride
- hydrogen peroxide
- add
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
- C08F222/06—Maleic anhydride
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerization Catalysts (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The present invention uses water as solvents, uses maleic acid as monomers, uses peroxide as initiating agents, uses Fe, Ni as catalysts, and uses hydrochloric acid, nitric acid and sulfuric acid to regulate pH values to carry out polymerization reactions. Polymerization rates are obviously increased, and scale inhibiting performance is better than that of a solvent method. The present invention is safer than the solvent method, and can not pollute environment.
Description
The invention belongs to the manufacture method of toxilic acid polymkeric substance, is the manufacture method of acid type toxilic acid homopolymer and acid type maleic acid furtherly.
Solvent method is made acid polymer from maleic acid, and quality product is fair, but solvent method has inflammable, explosive danger, and environmental pollution is heavier, so need be improved.Europe EP337694 patent introduction be to be solvent with water, be catalyzer with iron, copper or vanadium, add the processing method that the hydrogen peroxide initiator is made acid polymer from maleic acid.Though it is solvent that this patent adopts with water, has eliminated inflammable, the explosive danger of solvent method, catalyst levels is bigger.This patent catalyst levels is when 15ppm is following, and reality has not manufactured operable toxilic acid polymkeric substance, and the product colour that the method for this patent produces is dark, and unreacted monomer is many, and productive rate is low, and scale-inhibiting properties is undesirable.So the manufacture method of acid polymer from maleic acid still need be improved.
The present invention is intended to overcome the shortcoming of aforesaid method.One strip adoption iron is proposed, nickel is catalyzer, strong acid is the PH conditioning agent, hydrogen peroxide is the operational path of initiator.
The present invention with the maleic anhydride hydrolysis after, regulate PH, add iron, nickel catalyzator and hydrogen peroxide initiator with strong acid, under insulation and whipped state, react, obtaining outward appearance is saffron heavy-gravity acid type toxilic acid homopolymer; Perhaps with the maleic anhydride hydrolysis, add other monomer again, as vinylformic acid, vinyl acetate between to for plastic, methacrylic acid, (methyl) Hydroxyethyl acrylate, (methyl) acrylamide, (methyl) propene sulfonic acid (sodium), 2-first propyl sulfonic acid (sodium), styrene sulfonic acid (sodium), monomers such as maleic sulfonic acid dicarboxylic acid, the monomeric molecular ratio of maleic anhydride and multipolymer is 6.2-15.6: 1, regulate PH with strong acid, add iron, nickel catalyzator, the hydrogen peroxide initiator, under insulation and whipped state, carried out polyreaction 2 hours, obtain the acid type maleic acid, outward appearance is a safran heavy-gravity liquid.
The monomer concentration that the present invention uses is at 30-99%.
The present invention is a catalyzer with iron, nickel, add-on 1.0-40ppm.
The pH value of polyreaction has suitable influence to catalyst activity, the pH value when the present invention adds the strong acid telo merization.The present invention uses inorganic acid example hydrochloric acid, nitric acid, the pH value when sulfuric acid is adjusted polyreaction, and the pH value when the acid amount of adding generally makes polyreaction can remain in the 0.5-1.5 scope is advisable, and can make the molecular weight distribution of polymkeric substance narrower like this.
Superoxide kind as initiators for polymerization is a lot, as persulphate, perborate, percarbonate, peroxidation acetate etc.The present invention uses hydrogen peroxide to be initiator of polyreaction, and add-on is the 1.0-90g/mol maleic anhydride.
The temperature of hydrolysis and polyreaction, the present invention is controlled at respectively in the scope of 100-110 ℃ and 90-120 ℃.
The toxilic acid polymkeric substance that the present invention makes, even molecular weight distribution, the productive rate height, method is simple, and does not have inflammable, explosive danger.Product can be used as washing agent, weaving lotion, and Scale inhibitors is injected in oil production, and the Scale inhibitors of power plant, chemical plant recirculated cooling water and Steel Plant's control of dust water, feedwater etc. have special efficacy to resistance lime carbonate, calcium sulfate dirt.
Example 1
In the reactor that reflux exchanger, agitator, thermometer Drop-adding device are housed, the maleic anhydride of the 197.2 gram purity 99.37% of packing into, the water that adds 75.1 grams, be warming up to 100-110 ℃ then, making the maleic anhydride complete hydrolysis become toxilic acid is 232 grams (2.0mol), the vitriol oil that adds 4ml proportion 1.84, add ferrous sulfate 2.5ppm again, at the uniform velocity the hydrogen peroxide 92.1 of Dropwise 5 0% restrains under 100-110 ℃ of gentle reflux state, dripping the back reacted 2 hours under insulation and whipped state, promptly obtain a heavy-gravity toxilic acid homopolymer, outward appearance is a safran.Solid part is 62.55%, relative viscosity 1.0194, and unreacted monomer 1.23%, productive rate are 99.95% (in maleic anhydride), scale inhibition performance is 67.43%.
Example 2
With the same equipment of example 1, add the ferrous sulfate of 15ppm, other is operated with example 1, and obtaining product solid part is 60.33%, relative viscosity 1.0150, unreacted monomer is 0.88%, and scale inhibition performance is 69.51%, and productive rate is 100% (in maleic anhydride).
Example 3
Conversion unit is with example 1, add 197.2 gram (2mol) maleic anhydrides, water 75.1 grams, purity is 97.6% vinylformic acid 23.8 grams, ferrous sulfate 15ppm, the sulfuric acid 4ml of proportion 1.84 is warming up to 100-105 ℃, then hydrogen peroxide 92 grams of Dropwise 5 0%, drip back insulated and stirred reaction 2 hours, obtain toxilic acid and acrylic acid multipolymer, outward appearance is the safran thick liquid, solid part 62.31%, relative viscosity 1.0200, unreacted monomer is 0.65%, and scale inhibition performance is 74.51%, productive rate 96.88% (in maleic anhydride).
Example 4
Conversion unit is with example 1.The maleic anhydride that adds 497.2 gram purity 99.37%, water 75.1 grams, 97.6% vinylformic acid 23.8 grams, ferrous sulfate 10ppm, 65% nitric acid 8ml is warming up to 100-105 ℃ then, hydrogen peroxide 92.1 grams of Dropwise 5 0%, drip back insulated and stirred reaction 2 hours, obtain the thickness toxilic acid and the acrylic copolymer of yellow transparent, solid part 62.96%, relative viscosity is 1.0199, unreacted monomer 1.37%, scale inhibition performance 77.9%.
Example 5
Conversion unit is with example 1.Add nickelous chloride 0.219 gram/100ml 6ml, sulfuric acid 4ml (proportion 1.84), vinylformic acid 40 grams, other is with example 4.Product appearance is yellowish transparent color, solid part 40%, relative viscosity 1.0172, unreacted unit 0.78%, productive rate 97% (in maleic anhydride).
Example 6
Conversion unit is with example 1.Add sodium allylsulfonate 24.8 grams, the ferrous sulfate 1ml of 0.254 gram/100ml, the sulfuric acid of 4ml 98% is warming up to 100 ℃, hydrogen peroxide 92 grams of Dropwise 5 0%, the insulated and stirred reaction is 2 hours then, temperature 100-105 ℃.Product solid part 63.4%, relative viscosity 1.0176, unreacted monomer 0.9%, productive rate 99% (in maleic anhydride), scale inhibition performance 78.2%.
Claims (3)
1. method of making acid polymer from maleic acid, be with maleic anhydride after 100-110 ℃ of hydrolysis, under catalytic condition, use the polymerization of hydrogen peroxide initiator, perhaps after the maleic anhydride hydrolysis, add and be selected from vinylformic acid, vinyl acetate between to for plastic, methacrylic acid, (methyl) Hydroxyethyl acrylate, (methyl) acrylamide, (methyl) propene sulfonic acid (sodium), 2-first propyl sulfonic acid (sodium), styrene sulfonic acid (sodium), the polymer monomers of maleic sulfonic acid, under catalytic condition, use the polymerization of hydrogen peroxide initiator, it is characterized in that maleic anhydride and multipolymer monomer molecule ratio are 6.2-15.6: 1, with mineral acid the pH value is transferred in the 0.5-1.5 scope, add the iron of 1.5-40ppm or the hydrogen peroxide initiator of nickel catalyzator and 1.0-90 gram/mol toxilic acid, the insulation polymerization is 2 hours under 90-120 ℃ of stirring.
2. the method for claim 1 is characterized in that said mineral acid can be sulfuric acid, hydrochloric acid or nitric acid.
3. the method for claim 1 is characterized in that making catalyzer with nickel ion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93115343A CN1050367C (en) | 1993-12-27 | 1993-12-27 | Production of acid polymer from maleic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93115343A CN1050367C (en) | 1993-12-27 | 1993-12-27 | Production of acid polymer from maleic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1104653A CN1104653A (en) | 1995-07-05 |
| CN1050367C true CN1050367C (en) | 2000-03-15 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93115343A Expired - Fee Related CN1050367C (en) | 1993-12-27 | 1993-12-27 | Production of acid polymer from maleic acid |
Country Status (1)
| Country | Link |
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| CN (1) | CN1050367C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106380535A (en) * | 2016-08-30 | 2017-02-08 | 句容宁武高新技术发展有限公司 | Oil field scale inhibitor and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0337694A2 (en) * | 1988-04-11 | 1989-10-18 | Nippon Shokubai Co., Ltd. | Process for producing acid-type maleic acid polymer and water-treating agent and detergent additive containing said polymer |
| JPH0360798A (en) * | 1989-07-26 | 1991-03-15 | Nippon Shokubai Kagaku Kogyo Co Ltd | Scale inhibitor for magnesium hydroxide |
-
1993
- 1993-12-27 CN CN93115343A patent/CN1050367C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0337694A2 (en) * | 1988-04-11 | 1989-10-18 | Nippon Shokubai Co., Ltd. | Process for producing acid-type maleic acid polymer and water-treating agent and detergent additive containing said polymer |
| JPH0360798A (en) * | 1989-07-26 | 1991-03-15 | Nippon Shokubai Kagaku Kogyo Co Ltd | Scale inhibitor for magnesium hydroxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1104653A (en) | 1995-07-05 |
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| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |