CN1161347A - Co-polymer of sulfonate, the prepn. method and use thereof - Google Patents
Co-polymer of sulfonate, the prepn. method and use thereof Download PDFInfo
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- CN1161347A CN1161347A CN97103642A CN97103642A CN1161347A CN 1161347 A CN1161347 A CN 1161347A CN 97103642 A CN97103642 A CN 97103642A CN 97103642 A CN97103642 A CN 97103642A CN 1161347 A CN1161347 A CN 1161347A
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- sulfonate
- polymer
- initiator
- monomer
- monomers
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Classifications
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
- C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
Abstract
A phosphorus free sulfonate copolymer water treating agent is prepd as follows: monomer AMPS and monomer B, monomer C with water as solvent, in the presence of initiator are polymerized in a reactor under 20-125 deg.C for 30 to 300 min. to form polysulfonates copolymer. This product is used as dispersion scale inhibitor, corrosion inhibitor, flocculating agent for water treatment, the scale inhibiting efficiency can be up to 85%. The prepn. technology is simple and cost can be lowered greatly.
Description
The present invention relates to a kind of water conditioner and preparation method, particularly use co-polymer of sulfonate as water conditioner and its production and use.
At present industrial with containing co-polymer of sulfonate as dirt dispersion agent, as document 1, (the Treatment of Industrial Water that " contains the state of the art of co-polymer of sulfonate " as dirt dispersion agent, 1993, V01.13. № 4) described in, this class contains the influence that the co-polymer of sulfonate scale effect is not subjected to whether to exist in the water metal ion, especially to P, S, Ca, Ba, Mg, (OH)
2, CaCO
3Deng salt crust good restraining effect is arranged, the efficacy of a drug is lasting, is difficult for advantages such as gum deposit, and it can be divided into five big classes;
Wherein: AA: vinylformic acid, MA toxilic acid (acid anhydride); SS: styrene sulfonic acid
| Class-mark | Sulfonic acid (salt) | Multipolymer |
| ????1 | The monoene hydrocarbon sulfonate | The AA/ vinyl sulfonic acid, AA/ allyloxy sulfonic acid, MA/SS, AA/SS, AA/ vinyl sulfonic acid/ethene acetate |
| ????2 | Acrylic amide sulfonate | AA/AMPS, AA/AM/AMPS, AA/AMPS/ vinyl alcohol, AA/AMPS/AMPP, AA/AMPS/SS |
| ????3 | Allyloxy class sulfonate | AA/HAPSE/MA，AA/HSPSE， AA/ABS |
| ????4 | Acrylic acid or the like sulfonate | The AA/ methyl, ethylacrylic acid sulfonic acid |
| ????5 | The diene hydrocarbon sulfonate | AA/MBSN/HPAAA/ cyclopentadiene sulfonic acid/pair key component |
AMPS:2-acrylamido-2-methyl propane sulfonic acid-1; AM: acrylic amine
AMPP:2-acrylamido-2-methylpropane phosphoric acid
HAPS:2-hydroxyl-3-allyloxy-1-propyl sulfonic acid
ABS: allyloxy Phenylsulfonic acid; MBSN isoprene sulfonate
HPA: Propylene glycol monoacrylate
In the five class sulfonate monomers, except that the diene hydro carbons, abroad all produce by batch.Wherein, vinyl sulfonic acid, propene sulfonic acid, owing to itself be difficult for carrying out radical polymerization, thereby the use in water treatment industry is restricted; Styrene sulfonic acid makes it to be in higher activity because of its sulfonic acid has inducing action to the ethene of contraposition, thus than the easy polymerization of other monomer, and Heat stability is good, but complicate fabrication process, price height, the contained sulfo group of unit weight is few; Sulfonation methyl, ethylacrylic acid are compared with vinylbenzene, though cost is lower, are easy to hydrolysis, instability, thus also limited its use; The AMPS moderate cost, being easy to make is most popular monomer.HAPS, ABS and MBSN are sulfonic acid (salt) newly developed, but its scale inhibition is also undesirable.
Develop sulfonated phenylethylene-maleic anhydride copolymers (SSMA) subsequently in the world as water conditioner, scale inhibition effect is from document 2, show in " the synthetic and scale-inhibiting properties research of sulfonated phenylethylene-maleic anhydride copolymers " (Treatment of Industrial Water, 1994, V01.14. № 5) literary composition: at Ca
+ 2Concentration 300 * 10
-6Below, have CaCO preferably below the PH=8.5
3The scale-inhibiting properties of dirt perhaps needs with the common scale inhibition effect that uses such as organic phosphoric acid, zinc salt better.SSMA synthetic has two kinds of methods, and a kind of is vinylbenzene (ST) monomer earlier sulfonation, uses sulfonated phenylethylene and maleic anhydride (MA) to carry out copolymerization then.Another kind method is to produce vinylbenzene-maleic anhydride copolymers (SMA) earlier, then with the multipolymer sulfonation.Concrete technology is as follows: it is initiator that earlier synthetic SMA (vinylbenzene-maleic anhydride copolymers) adopts BPO, butanone is a solvent, under reflux temperature, carry out copolyreaction and prepare vinylbenzene: maleic anhydride=1: 1 (molecular ratio) multipolymer, 80 ℃ of its polymerization---temperature of reaction, monomer concentration 20%, two monomer molecules ratio is 1: 1, BPO consumption 5%, 4 hours reaction times.After carrying out the sulfonation and copolymerization reaction end of SMA then, in copolymer solution, drip SO
3-HCCI
3Mixed solution adds HCCI
3Be in order to dilute SO
3, 10 ℃ of CO of its sulfonation---temperature of reaction
3: ST=1: 1 (molecular ratio) reaction times was 1.5 hours.Sulfonation end back adds precipitation agent, and product is separated out, and filters, and filter cake is dry in vacuum drying oven, gets powder agglomates shape SSMA.
Before a kind of method can not use the vinylbenzene Direct Sulfonation, will use the alkali dehydrohalogenation again after the sulfonation of 2-halo ethylbenzene normally earlier, make styrene sulfonate again with maleic anhydride copolymerization, thereby process complexity, cost height.
Expensive among a kind of preparation method in back owing to having adopted butanone to make the solvent cost of material, and increase cost, also adopt the esters of acrylic acid raw material that the intense stimulus smell is arranged in addition in process of production, so to direct labor and surrounding environment all effected; And production also will be discharged waste liquid and be caused environmental pollution.
In addition at＜Speciality Petrochemicals〉among 1991 (6) 33-38 in report " acid/maleic acid copolymers barium strontium ion stablizer " article report be that the synthetic ion stabilizer of main raw material is used for oil-field water and handles with the cis-butenedioic anhydride, but the AMPS of employing raw material is not arranged.
The objective of the invention is to overcome the shortcoming and defect of above-mentioned prior art, a kind of novel not phosphorated co-polymer of sulfonate water conditioner is provided, be used in dispersing and antisludging under the abominable water quality situation of high rigidity, high basicity, high pH value and inhibition, flocculation.
Two of purpose is to solve prior art and causes " three wastes " problem.
Three of purpose is to reduce cost, and reaction does not need enrichment process, reaches one step of reaction to finish, and improve the rate of recovery of polymkeric substance, and the preparation method is simple.
The object of the present invention is achieved like this:
Its structure of polybasic sulfoacid salt copolymer provided by the invention is:
M=10-100 wherein; P=10-100; K=0-3;
Molecular weight is 1000-10000;
The invention provides a kind of by monomer A: 2-acrylamido-2-methyl propane sulfonic acid (AMPS) and monomers B, also can add monomer C, it is solvent with water, is adding polymerization generation polybasic sulfoacid salt copolymer under the initiator situation.
Monomers B wherein: organic acid anhydride, monomer C can be vinylformic acid, vinyl cyanide, acrylate, and initiator can be potassium permanganate, clorox, hydrogen peroxide, persulphate; Organic acid anhydride is preferably: MALEIC ANHYDRIDE; Monomer A (AMPS) can with a monomers B polymerization, can also and one or more monomers C polymerization generate the polybasic sulfoacid salt copolymer.
The invention provides the method for preparing the dibasic sulfoacid salt copolymer is to select monomer A and monomers B and initiator for use, presses A: B: initiator (weight ratio)=5-50: 10-90: 1-6 batching, and its reaction is:
It generates the ternary co-polymer of sulfonate is monomer A and monomers B, C and initiator, presses A: B: C: initiator (weight ratio)=5-30: 10-80: 50: 1-10 batching, and its reaction formula is:
N=10-100 wherein, m=10-100, p=10-100, molecular weight are 1000-10000;
Above-mentioned raw materials solution to be mixed preparing, send in the reactor, carry out polyreaction, its temperature of reaction is-20-125 ℃ polymerization reaction time 30-300 minute, undertaken by common polymerization procedure, can prepare the polybasic co-polymer of sulfonate.
Co-polymer of sulfonate provided by the invention is applicable to and comprises: process waters such as chemical industry, oil, weaving, electric power, papermaking, as: dispersing and antisludging, inhibition, the flocculation treatment of recirculated cooling water, air conditioner water, feedwater, oil-field flooding, tap water, middle water and waste water etc.Advantage of the present invention:
Co-polymer of sulfonate provided by the invention is light yellow or amber thick liquid, and solid content 〉=30%, molecular weight are 1000-10000, pH value=1-2, free monomer content≤1.0-240.It does dispersing and antisludging agent, inhibiter, flocculation agent, is used to handle process waters such as chemical industry, oil, weaving, electric power, papermaking, and the recirculated cooling water of the high-alkali high rigidity of high pH value, middle water and waste water, and scale removal efficient reaches more than 85%.
Preparation method of the present invention is simple, and it is cheap to do the solvent cost of material with water, does not need enrichment step, reaction is once finished, and reduces intermediate steps and improves production repeatability, ensures the quality of products, shorten the production cycle, reduce cost of labor and reduce greatly, the thick yield of this method product reaches more than 95%.
The present invention is described in detail below in conjunction with drawings and Examples:
Fig. 1 is a process flow sheet of the present invention
Embodiment 1: at first get monomer A: AMPS; Monomers B: C
4H
2O
3(MALEIC ANHYDRIDE), initiator: hydrogen peroxide, A: B: initiator (weight ratio) weighing in 20: 75: 5 is a solvent with water, prepares burden separately in the still by the suction of material pipeline, the required water of preparing burden is provided by the water header tank.Monomer for preparing and initiator are evacuated in mix monomer header tank and the initiator header tank by pipeline.Carry out polyreaction, its initiator solution and mix monomer through flow control valve and visor by filling tube adding reaction kettle for reaction formula are:
Temperature remains under 80 ℃ during reaction, reacts 125 minutes.Reactor is provided with the gangway of steam and recirculated cooling water, and steam enters chuck by the reactor side, enters trench by the reactor side-lower through trap etc.; Recirculated cooling water then from the bottom to top, flow to opposite with steam, through entering return piping behind the chuck.In the reaction process, the reaction vapor in the reactor enters its tube side by condenser top, and lime set is back in the reactor through pipeline by its underpart.Water coolant is walked shell side, goes out on advancing down, and the dibasic sulfoacid salt copolymer of generation is exported from reactor.The mass transport of this device all adopts vacuum to carry, and therefore is provided with vacuum pump.The dibasic sulfoacid salt copolymer that present embodiment generates is used to handle waste water, and its dispersing and antisludging efficient reaches 85%.Embodiment 2:
At first in the aqueous solution, dissolve with MALEIC ANHYDRIDE with vinylformic acid, monomers B with monomer C with the AMPS material by monomer A, and adding initiator persulphate, its ratio of components is pressed monomer A: monomers B: C: initiator=10: 75: 80: 6 (weight ratios), temperature of reaction was 80 ℃ of following polyreactions 100 minutes, technological process is identical with embodiment 1, its reaction formula:
The ternary co-polymer of sulfonate molecular weight product that generates is: 1000-10000 is used to handle industrial circulating cooling water, and dispersing and antisludging efficient reaches 85%.Embodiment 3:
Preparation technology presses embodiment 1 fully, and the change ratio of components is a monomer A: monomers B: initiator=10: 85: 5 (weight ratio), monomer A AMPS, the monomers B MALEIC ANHYDRIDE, initiator potassium permanganate, temperature of reaction is more than 80 ℃, reaction times is 20 minutes, and its reaction formula is
The dibasic sulfoacid salt copolymer molecular weight product that generates is: 1000-10000 is used for service water dispersing and antisludging efficient and reaches 85%.Embodiment 4:
Processing step is identical with embodiment 1, only changes the proportioning of monomer A and monomers B, monomer C, and monomer C selects acrylate for use, its A: B: C: initiator=50: 10: 1: 10, and effect is identical with embodiment 1.
Claims (10)
1. co-polymer of sulfonate, its composition comprises monomer A: AMPS; Monomers B and initiator is characterized in that: the composition proportioning that monomer A and monomers B and initiator aggregate into the dibasic sulfoacid salt copolymer is A: B: initiator=5-50: 10-90: 1-6 (weight ratio), and structure is:
The composition proportioning that aggregates into the ternary co-polymer of sulfonate is A: B: C: initiator=5-30: 10-80: 20-50: 1-6, and structure is:
M=10-100 wherein; P=10-100; N=10-100; K=0-3.
2. a kind of co-polymer of sulfonate as claimed in claim 1, but it is characterized in that described polymerization monomer A (AMPS) and a monomers B polymerization.
3. a kind of co-polymer of sulfonate as claimed in claim 1, but it is characterized in that described polymerization monomer A (AMPS) and a monomers B polymerization and one or more monomers C polymerization.
4. a kind of co-polymer of sulfonate as claimed in claim 1 is characterized in that described initiator is: potassium permanganate, clorox, hydrogen peroxide, persulphate.
5. a kind of co-polymer of sulfonate as claimed in claim 1 is characterized in that described monomer C is vinylformic acid, vinyl cyanide, acrylate.
6. a kind of co-polymer of sulfonate as claimed in claim 4 is characterized in that described monomer C is an organic acid anhydride.
7. a kind of co-polymer of sulfonate as claimed in claim 6 is characterized in that described organic acid anhydride is a MALEIC ANHYDRIDE.
8. preparation method who prepares right 1 described co-polymer of sulfonate, it is characterized in that: choose monomer A: AMPS, monomers B, with water is solvent, when adding initiator generation dibasic sulfoacid salt copolymer, press A: B: initiator=5-50: 10-90: 1-6 (weight ratio) batching, when generating the ternary co-polymer of sulfonate, press A: B: C: initiator=5-30: 10-80: 20-50: 1-10 (weight ratio) batching, the mixing of above-mentioned raw materials solution is prepared, sending in the reactor routinely, polymerization technique carries out polyreaction, 20 ℃-125 ℃ of its temperature of reaction, reaction times 30-300 minute.
9. the preparation method of a kind of co-polymer of sulfonate as claimed in claim 6 is characterized in that described initiator is potassium permanganate, clorox, hydrogen peroxide, persulphate.
10. the purposes of right 1 a described co-polymer of sulfonate is characterized in that dispersing and antisludging agent, inhibiter, the flocculation agent of co-polymer of sulfonate as treating water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97103642A CN1082058C (en) | 1997-03-25 | 1997-03-25 | Co-polymer of sulfonate, the prepn. method and use thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97103642A CN1082058C (en) | 1997-03-25 | 1997-03-25 | Co-polymer of sulfonate, the prepn. method and use thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1161347A true CN1161347A (en) | 1997-10-08 |
| CN1082058C CN1082058C (en) | 2002-04-03 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97103642A Expired - Fee Related CN1082058C (en) | 1997-03-25 | 1997-03-25 | Co-polymer of sulfonate, the prepn. method and use thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101914182A (en) * | 2010-08-24 | 2010-12-15 | 北京红芬兴业技术开发有限公司 | Method for synthesizing base underground crosslinked thickening agent |
| CN110026143A (en) * | 2019-05-24 | 2019-07-19 | 廊坊市海寰科技有限公司 | Utilize the device and its process of organic waste exploitation anti-incrustation corrosion inhibitor |
| CN114574225A (en) * | 2022-04-12 | 2022-06-03 | 浙江汉景环保化学材料科技有限公司 | Water-soluble dispersant |
| CN115322001A (en) * | 2022-09-15 | 2022-11-11 | 江阴誉球耐火材料有限公司 | High-temperature-resistant iron runner castable and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5032295A (en) * | 1989-04-25 | 1991-07-16 | National Starch And Chemical Investment Holding Corporation | Polymers for use in drilling muds |
| FR2677376B1 (en) * | 1991-06-07 | 1994-04-01 | Rhone Poulenc Fibres | PROCESS FOR OBTAINING POLYAMIDE YARNS WITH BETTER PRODUCTIVITY. |
| CA2092492A1 (en) * | 1992-03-30 | 1993-10-01 | Ecc Specialty Chemicals Inc. | N-(2-hydroxyethyl)-n-bis (methylenephosphonic acid) and corresponding n-oxide thereof for high ph scale control |
| US5300231A (en) * | 1992-08-05 | 1994-04-05 | Calgon Corporation | Controlling silica/silicate deposition using phosphonate combinations |
| US5366637A (en) * | 1993-05-24 | 1994-11-22 | Betz Laboratories, Inc. | Method for dewatering municipal solid waste refuse |
-
1997
- 1997-03-25 CN CN97103642A patent/CN1082058C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101914182A (en) * | 2010-08-24 | 2010-12-15 | 北京红芬兴业技术开发有限公司 | Method for synthesizing base underground crosslinked thickening agent |
| CN101914182B (en) * | 2010-08-24 | 2015-10-21 | 北京红芬兴业技术开发有限公司 | The synthetic method of base underground crosslinked thickening agent |
| CN110026143A (en) * | 2019-05-24 | 2019-07-19 | 廊坊市海寰科技有限公司 | Utilize the device and its process of organic waste exploitation anti-incrustation corrosion inhibitor |
| CN110026143B (en) * | 2019-05-24 | 2023-12-29 | 南京辰翌科技有限公司 | Device for developing scale and corrosion inhibitor by utilizing organic waste and process method thereof |
| CN114574225A (en) * | 2022-04-12 | 2022-06-03 | 浙江汉景环保化学材料科技有限公司 | Water-soluble dispersant |
| CN115322001A (en) * | 2022-09-15 | 2022-11-11 | 江阴誉球耐火材料有限公司 | High-temperature-resistant iron runner castable and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1082058C (en) | 2002-04-03 |
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