CN109160973B - Aqueous phase ultrasonic synthesis method of maleic anhydride/alpha-arene copolymer - Google Patents
Aqueous phase ultrasonic synthesis method of maleic anhydride/alpha-arene copolymer Download PDFInfo
- Publication number
- CN109160973B CN109160973B CN201810848086.1A CN201810848086A CN109160973B CN 109160973 B CN109160973 B CN 109160973B CN 201810848086 A CN201810848086 A CN 201810848086A CN 109160973 B CN109160973 B CN 109160973B
- Authority
- CN
- China
- Prior art keywords
- maleic anhydride
- arene
- alpha
- aqueous phase
- synthesis method
- 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.)
- Active
Links
Classifications
-
- 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
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/10—Aqueous solvent
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/28—Oxygen or compounds releasing free oxygen
- C08F4/32—Organic compounds
- C08F4/34—Per-compounds with one peroxy-radical
Abstract
The invention provides a water-phase ultrasonic synthesis method of maleic anhydride/alpha-arene copolymer, which comprises the steps of carrying out ultrasonic activation treatment on deionized water, maleic anhydride, an RAFT reagent, an initiator and a cross-linking agent, then adding alpha-arene for polymerization reaction, adding proper alkali, and adjusting the pH value to be 7 to obtain a maleic anhydride-alpha-arene copolymer aqueous solution. The aqueous phase ultrasonic synthesis method of the maleic anhydride/alpha-arene copolymer provided by the invention has the advantages that the microwave technology is utilized to accelerate the activity and reaction rate of aqueous phase polymerization of the maleic anhydride/alpha-arene, and the polymerization temperature is reduced, so that the polymerization reaction is carried out under a milder condition.
Description
Technical Field
The invention belongs to the field of organic polymer synthesis, and particularly relates to an aqueous phase ultrasonic synthesis method of maleic anhydride/alpha-arene copolymer.
Background
The maleic anhydride/alpha-arene copolymer is alpha-methyl styrene (AMS) and maleic acid liver (MAn) copolymer, is a novel high polymer material with low price and high potential value, is widely applied to the fields of various paint pigment additives, plastic product modifiers, material processability improvement and the like, and has high economic value.
At present, the usual methods for preparing maleic anhydride/α -arene copolymers are mainly solution polymerization and precipitation polymerization.
In CN201110051524.X, benzene, toluene or xylene is used as solvent, organic peroxide is used as initiator, and thiol compounds are used as polymerization inhibitor, and low molecular weight styrene-maleic anhydride polymer (molecular weight is 5000-10000) is synthesized by precipitation method at 60-80 deg.C.
CN200910216692.2, toluene is used as solvent, benzoyl peroxide is used as initiator, and the styrene-maleic anhydride polymer is synthesized by precipitation method at 80 ℃.
In CN201310012012.1, butanone is used as a solvent, azobisisobutyronitrile is used as an initiator, solution polymerization is carried out at 80 ℃, and a styrene-maleic anhydride polymer is obtained by discharging in a melting method.
In CN200910079490.8, a mixture of alkyl ester and alkane is used as a solvent, azobisisobutyronitrile is used as an initiator, and AMS is used as a molecular weight regulator to synthesize a styrene-maleic anhydride polymer (with a molecular weight of 3000-12000 and a molecular weight distribution of 1.36-2.0) by a precipitation method.
Javni, I.; Fles, D.et al, in "the polymerization of alpha-methyl and maleic anhydride" (Polymer chemistry edition (1982), 20 (4), 977-86), using a radical polymerization method, either in bulk or in solution in benzene (C6H 6) or Methylethyl (MEK), can produce copolymers of either methylstyrene and maleic acid having an alternating structure.
In CN200910087181.5, a mixture of alkyl ester and alkane is used as a solvent, azobisisobutyronitrile is used as an initiator, and a styrene-maleic anhydride polymer is synthesized by a precipitation method.
The methods have the defects of high organic solvent pollution, low reaction rate, high reaction temperature and the like, and even some methods need nitrogen protection to ensure the activity of the organic initiator.
Disclosure of Invention
In view of the above, the present invention aims to provide an aqueous phase ultrasonic synthesis method of maleic anhydride/α -arene copolymer, so as to overcome the defects of the prior art, wherein deionized water, maleic anhydride, a RAFT reagent, an initiator and a crosslinking agent are subjected to ultrasonic activation treatment, then α -arene is added for polymerization reaction, the activity and reaction rate of maleic anhydride/α -arene aqueous phase polymerization are accelerated by using a microwave technology, and the polymerization temperature is reduced so that the polymerization reaction is performed under a milder condition.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a water phase ultrasonic synthesis method of maleic anhydride/alpha-arene copolymer is characterized in that deionized water, maleic anhydride, RAFT reagent, initiator and cross-linking agent are subjected to ultrasonic activation treatment, and then alpha-arene is added for polymerization reaction; the structure of the prepared maleic anhydride/alpha-arene copolymer is as follows:
wherein R is1Is an aliphatic alkyl radical, R2Is aliphatic alkyl or aryl, and Ar is aryl.
Preferably, the aqueous phase ultrasonic synthesis method of the maleic anhydride/alpha-arene copolymer comprises the following steps:
(1) adding deionized water, maleic anhydride, RAFT reagent, initiator and cross-linking agent into a polymerization reactor, and performing ultrasonic activation treatment at 20-90 ℃ for 0.5-5 min to obtain a mixed solution;
(2) slowly adding alpha-arene into the mixed solution, and continuing to react for 5-30 min after the addition is finished; the slow adding mode can adopt a peristaltic pump;
(3) and (3) after the reaction in the step (2) is finished, adding a proper amount of alkali, and adjusting the pH =7 to obtain the maleic anhydride-alpha-arene copolymer aqueous solution.
Preferably, the α -arene structure is:
wherein R is1Is an aliphatic alkyl radical, R2Is aliphatic alkyl or aryl, and Ar is aryl.
Preferably, R1H or straight-chain alkane of C1-C5; r2Is straight-chain alkane of C1-C5; ar is phenyl.
Preferably, the RAFT agent is a water soluble dithioester or trithioester of the structure:
preferably, the RAFT agent is RAFT-1 or RAFT-3.
Preferably, the dosage of the RAFT reagent is 0.1-8.0% of the total mass of the maleic anhydride monomer and the alpha-arene monomer; preferably, the dosage of the RAFT reagent is 2-5% of the total mass of the maleic anhydride monomer and the alpha-arene monomer.
Preferably, the dosage of the cross-linking agent is 0.1-5.0% of the mass of the alpha-arene monomer; the cross-linking agent is one of methylene bisacrylamide, ethylene glycol diacrylate, m-phenylene bismaleimide and pentaerythritol triacrylate; preferably, the crosslinking agent is N, N-dimethylethanolamine or pentaerythritol triacrylate.
Preferably, the using amount of the initiator is 0.1-5.0% of the total mass of the maleic anhydride monomer and the alpha-arene monomer; the initiator is a peroxide initiator; preferably, the initiator is hydrogen peroxide, ammonium persulfate, potassium persulfate or sodium persulfate; preferably, the initiator is ammonium sulfate or sodium persulfate.
Preferably, the base is sodium hydroxide, potassium hydroxide or ammonia water; the molar ratio of the use amount of the alkali to the use amount of the maleic anhydride is 1: 5-5: 1.
Preferably, the molar ratio of the maleic anhydride monomer to the alpha-arene monomer is 1: 5-5: 1; the weight average molecular weight of the maleic anhydride/alpha-arene copolymer is 1000-80000, and the molecular weight distribution is 1.0-3.0.
Compared with the prior art, the aqueous phase ultrasonic synthesis method of the maleic anhydride/alpha-arene copolymer has the following advantages:
(1) different from the traditional preparation method of maleic anhydride/alpha-arene copolymer, the invention adopts green and environment-friendly water as a solvent, avoids the pollution problem caused by organic solvents, and improves polymerization activity and polymerization rate by combining an ultrasonic technology.
(2) According to the invention, an aqueous RAFT active polymerization method is adopted, and a water-soluble RAFT chain transfer agent is added into a reaction system, so that the molecular weight of the polymer can be better regulated and controlled compared with the traditional free radical polymerization. The RAFT chain transfer agent is preferably of the structure:
(3) in the invention, a hydrophilic cross-linking agent, such as diethanolamine, N-dimethylethanolamine, methylene bisacrylamide, ethylene glycol diacrylate, m-phenylene bismaleimide or pentaerythritol triacrylate, is added into a reaction system, alpha-arene is dispersed in water in the form of micro-droplets, and the dispersibility of the alpha-arene in the water is improved by combining an ultrasonic technology, thereby improving the reaction efficiency of polymerization.
(4) The invention selects peroxide such as hydrogen peroxide, ammonium persulfate, potassium persulfate or sodium persulfate and the like as an initiator, can be dissolved in water to form homogeneous solution with maleic anhydride aqueous solution, and improves the initiation efficiency of polymerization.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to examples.
Comparative example 1:
adding 40.000 g of deionized water, 9.806 g of maleic anhydride, 0.101 g of RAFT-1 reagent, 0.101 g of sodium persulfate and 0.049 g of diethanolamine into a polymerization reactor, slowly adding 10.415 g of styrene at 25 ℃, and continuing the reaction for 10 min after the addition is finished; adding proper alkali, adjusting pH =7, and obtaining turbid maleic anhydride/styrene copolymer aqueous solution. The viscosity average molecular weight of the polymer was 1000, and the molecular weight distribution was 2.4.
Comparative example 2
Adding 40.000 g of deionized water, 9.806 g of maleic anhydride, 0.101 g of RAFT-1 reagent, 0.101 g of sodium persulfate and 0.049 g of diethanolamine into a polymerization reactor, slowly adding 10.415 g of styrene at 80 ℃, and continuing the reaction for 30 min after the addition is finished; adding proper alkali, adjusting pH =7, and obtaining turbid maleic anhydride/styrene copolymer aqueous solution. The viscosity average molecular weight of the polymer was 3000, and the molecular weight distribution was 2.8.
The first embodiment is as follows:
40.000 g of deionized water, 9.806 g of maleic anhydride, 0.101 g of RAFT-1 reagent, 0.101 g of sodium persulfate and 0.049 g of diethanolamine are added into a polymerization reactor, and ultrasonic activation treatment is carried out for 0.5-5 min, wherein the temperature is controlled at 25 ℃. Slowly adding 10.415 g of styrene, and continuing to react for 10 min after the addition is finished; adding proper alkali, adjusting pH =7, and obtaining clear maleic anhydride/styrene polymer water solution. The viscosity average molecular weight of the polymer is 18000, and the molecular weight distribution is 2.1.
Example two:
40.000 g of deionized water, 9.806 g of maleic anhydride, 0.202 g of RAFT-1 reagent, 0.202 g of sodium persulfate and 0.049 g of diethanolamine were charged into a polymerization reactor, and ultrasonic activation treatment was carried out for 1min while the temperature was controlled at 27 ℃. Slowly adding 10.415 g of styrene, and continuing to react for 14 min after the addition is finished; adding proper alkali, adjusting pH =7, and obtaining clear maleic anhydride/styrene copolymer water solution. The viscosity average molecular weight of the polymer is 18000, and the molecular weight distribution is 1.8.
Example three:
40.000 g of deionized water, 9.806 g of maleic anhydride, 0.202 g of gRAFT-3 reagent, 0.202 g of sodium persulfate and 0.049 g of diethanolamine were charged into a polymerization reactor, and ultrasonic activation treatment was carried out for 2 minutes while the temperature was controlled at 30 ℃. Slowly adding 10.415 g of styrene, and continuing to react for 18min after the addition is finished; adding proper alkali, adjusting pH =7, and obtaining clear maleic anhydride/styrene copolymer water solution. The viscosity average molecular weight of the polymer is 10000, and the molecular weight distribution is 2.0.
Example four:
40.000 g of deionized water, 9.806 g of maleic anhydride, 0.202 g of gRAFT-3 reagent, 0.202 g of sodium persulfate and 0.049 g N, N-dimethylethanolamine were charged into a polymerization reactor and subjected to ultrasonic activation treatment for 1min while the temperature was controlled at 40 ℃. Slowly adding 10.415 g of styrene, and continuing to react for 20 min after the addition is finished; adding proper alkali, adjusting pH =7, and obtaining clear maleic anhydride/styrene copolymer water solution. The viscosity average molecular weight of the polymer is 10000, and the molecular weight distribution is 2.0.
Example five:
40.000 g of deionized water, 19.612 g of maleic anhydride, 0.300 g of gRAFT-3 reagent, 0.300 g of sodium persulfate and 0.049 g N, N-dimethylethanolamine were charged into a polymerization reactor, and ultrasonic activation treatment was carried out for 3 minutes while the temperature was controlled at 50 ℃. Slowly adding 10.415 g of styrene, and continuing to react for 25 min after the addition is finished; adding proper alkali, adjusting pH =7, and obtaining clear maleic anhydride/styrene copolymer water solution. The viscosity average molecular weight of the polymer was 25000, and the molecular weight distribution was 1.5.
Example six:
40.000 g of deionized water, 19.612 g of maleic anhydride, 0.300 g of gRAFT-3 reagent, 0.300 g of ammonium persulfate and 0.049 g N, N-dimethylethanolamine were charged into a polymerization reactor and subjected to ultrasonic activation treatment for 4 minutes while the temperature was controlled at 63 ℃. Slowly adding 10.415 g of styrene, and continuing to react for 24 min after the addition is finished; adding proper alkali, adjusting pH =7, and obtaining clear maleic anhydride/styrene copolymer water solution. The viscosity average molecular weight of the polymer was 23000, and the molecular weight distribution was 1.7.
Example seven:
40.000 g of deionized water, 9.806 g of maleic anhydride, 0.216 g of gRAFT-3 reagent, 0.216 g of sodium persulfate and 0.049 g N, N-dimethylethanolamine were charged into a polymerization reactor and subjected to ultrasonic activation treatment for 4 minutes while the temperature was controlled at 70 ℃. Slowly adding 11.818 g of alpha-methyl styrene, and continuing to react for 26 min after the addition is finished; adding proper alkali, adjusting pH =7, and obtaining clear maleic anhydride/alpha-methyl styrene copolymer water solution. The viscosity average molecular weight of the polymer is 22000, and the molecular weight distribution is 1.6.
Example eight:
40.000 g of deionized water, 9.806 g of maleic anhydride, 0.278 g of gRAFT-3 reagent, 0.278 g of sodium persulfate and 0.049 g N, N-dimethylethanolamine were charged into a polymerization reactor, and ultrasonic activation treatment was carried out for 5 minutes while the temperature was controlled at 85 ℃. 18.025 g of 1, 1-diphenylethylene is slowly added, and the reaction is continued for 28 min after the addition is finished; adding proper alkali, adjusting pH =7, and obtaining clear maleic anhydride/1, 1-diphenyl ethylene copolymer water solution. The viscosity average molecular weight of the polymer was 15000 and the molecular weight distribution was 1.9.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (15)
1. An aqueous phase ultrasonic synthesis method of maleic anhydride/alpha-arene copolymer is characterized in that: performing ultrasonic activation treatment on deionized water, maleic anhydride, an RAFT reagent, an initiator and a crosslinking agent, and then adding alpha-arene for polymerization reaction; the structure of the prepared maleic anhydride/alpha-arene copolymer is as follows:
wherein R is1Is an aliphatic alkyl radical, R2Is aliphatic alkyl or aryl, and Ar is aryl.
2. The aqueous phase ultrasonic synthesis method of maleic anhydride/α -arene copolymer according to claim 1, wherein: the method comprises the following steps:
(1) adding deionized water, maleic anhydride, RAFT reagent, initiator and cross-linking agent into a polymerization reactor, and performing ultrasonic activation treatment at 20-90 ℃ for 0.5-5 min to obtain a mixed solution;
(2) slowly adding alpha-arene into the mixed solution, and continuing to react for 5-30 min after the addition is finished;
(3) and (3) after the reaction in the step (2) is finished, adding a proper amount of alkali, and adjusting the pH =7 to obtain the maleic anhydride-alpha-arene copolymer aqueous solution.
3. The aqueous phase ultrasonic synthesis method of maleic anhydride/α -arene copolymer according to claim 1 or 2, wherein: the alpha-arene structure is as follows:
wherein R is1Is an aliphatic alkyl radical, R2Is aliphatic alkyl or aryl, and Ar is aryl.
4. The aqueous phase ultrasonic synthesis method of maleic anhydride/α -arene copolymer according to claim 3, wherein: r1H or straight-chain alkane of C1-C5; r2Is straight-chain alkane of C1-C5; ar is phenyl.
5. The aqueous phase ultrasonic synthesis method of maleic anhydride/α -arene copolymer according to claim 1 or 2, wherein: the RAFT agent is a water soluble dithioester or trithioester of the structure:
6. the method for the aqueous phase ultrasonic synthesis of maleic anhydride/α -arylalkene copolymer according to claim 5, wherein: the RAFT agent is RAFT-1 or RAFT-3.
7. The aqueous phase ultrasonic synthesis method of maleic anhydride/α -arene copolymer according to claim 1 or 2, wherein: the dosage of the RAFT reagent is 0.1-8.0% of the total mass of the maleic anhydride monomer and the alpha-arene monomer.
8. The aqueous phase ultrasonic synthesis method of maleic anhydride/alpha-arene copolymer according to claim 7
The method is characterized in that: the dosage of the RAFT reagent is 2-5% of the total mass of the maleic anhydride monomer and the alpha-arene monomer.
9. The aqueous phase ultrasonic synthesis method of maleic anhydride/α -arene copolymer according to claim 1 or 2, wherein: the dosage of the cross-linking agent is 0.1 to 5.0 percent of the mass of the alpha-arene monomer; the cross-linking agent is one of methylene bisacrylamide, ethylene glycol diacrylate, m-phenylene bismaleimide and pentaerythritol triacrylate.
10. The aqueous phase ultrasonic synthesis method of maleic anhydride/α -arene copolymer according to claim 9, wherein: the cross-linking agent is N, N-dimethylethanolamine or pentaerythritol triacrylate.
11. The aqueous phase ultrasonic synthesis method of maleic anhydride/α -arene copolymer according to claim 1 or 2, wherein: the dosage of the initiator is 0.1 to 5.0 percent of the total mass of the maleic anhydride monomer and the alpha-arene monomer; the initiator is a peroxide initiator.
12. The aqueous phase ultrasonic synthesis method of maleic anhydride/alpha-arene copolymer according to claim 11
The method is characterized in that: the initiator is hydrogen peroxide, ammonium persulfate, potassium persulfate or sodium persulfate.
13. The method for the aqueous phase ultrasonic synthesis of maleic anhydride/α -arylalkene copolymer according to claim 12, wherein: the initiator is ammonium persulfate or sodium persulfate.
14. The aqueous phase ultrasonic synthesis method of maleic anhydride/α -arene copolymer according to claim 2, wherein: the alkali is sodium hydroxide, potassium hydroxide or ammonia water; the molar ratio of the use amount of the alkali to the use amount of the maleic anhydride is 1: 5-5: 1.
15. The aqueous phase ultrasonic synthesis method of maleic anhydride/α -arene copolymer according to claim 1, wherein: the molar ratio of the maleic anhydride monomer to the alpha-arene monomer is 1: 5-5: 1; the weight average molecular weight of the maleic anhydride/alpha-arene copolymer is 1000-80000, and the molecular weight distribution is 1.0-3.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810848086.1A CN109160973B (en) | 2018-07-27 | 2018-07-27 | Aqueous phase ultrasonic synthesis method of maleic anhydride/alpha-arene copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810848086.1A CN109160973B (en) | 2018-07-27 | 2018-07-27 | Aqueous phase ultrasonic synthesis method of maleic anhydride/alpha-arene copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109160973A CN109160973A (en) | 2019-01-08 |
| CN109160973B true CN109160973B (en) | 2021-01-12 |
Family
ID=64898498
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810848086.1A Active CN109160973B (en) | 2018-07-27 | 2018-07-27 | Aqueous phase ultrasonic synthesis method of maleic anhydride/alpha-arene copolymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109160973B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1631923A (en) * | 2004-11-09 | 2005-06-29 | 四川大学 | High purity copolymer nano emulsion and method for preparing same |
| WO2008064973A1 (en) * | 2006-11-27 | 2008-06-05 | Unilever Plc | Composition comprising brush copolymer for treating hair |
| CN102070742A (en) * | 2010-12-22 | 2011-05-25 | 广州立白企业集团有限公司 | Method for synthesizing acrylic acid-maleic anhydride copolymer in aqueous phase by RAFT method |
| CN102177183A (en) * | 2008-08-12 | 2011-09-07 | 阿肯马法国公司 | Method for synthesizing amphiphilic gradient copolymers soluble in an alkaline medium |
| CN106492705A (en) * | 2016-08-31 | 2017-03-15 | 南京工业大学 | A kind of block macromolecular dispersant and preparation method and application |
-
2018
- 2018-07-27 CN CN201810848086.1A patent/CN109160973B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1631923A (en) * | 2004-11-09 | 2005-06-29 | 四川大学 | High purity copolymer nano emulsion and method for preparing same |
| WO2008064973A1 (en) * | 2006-11-27 | 2008-06-05 | Unilever Plc | Composition comprising brush copolymer for treating hair |
| CN102177183A (en) * | 2008-08-12 | 2011-09-07 | 阿肯马法国公司 | Method for synthesizing amphiphilic gradient copolymers soluble in an alkaline medium |
| CN102070742A (en) * | 2010-12-22 | 2011-05-25 | 广州立白企业集团有限公司 | Method for synthesizing acrylic acid-maleic anhydride copolymer in aqueous phase by RAFT method |
| CN106492705A (en) * | 2016-08-31 | 2017-03-15 | 南京工业大学 | A kind of block macromolecular dispersant and preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109160973A (en) | 2019-01-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5669327B2 (en) | Aqueous emulsion | |
| CN103554325B (en) | A kind of preparation method of functional hollow polymer microballoon | |
| KR102014744B1 (en) | Dispersion of adsorbing emulsion polymer particles | |
| CN110577614B (en) | Preparation of high-solid-content hydroxy acrylic acid dispersion | |
| WO2013134965A1 (en) | Poly((meth)acrylic acid-b-styrene-b-butadiene-b-styrene) block copolymer latex and preparation method therefor | |
| JP2002533481A (en) | Method for producing high molecular weight reaction product | |
| CN1908023A (en) | Acrylic acid bulk hybridization emulsion composition | |
| CN102070742A (en) | Method for synthesizing acrylic acid-maleic anhydride copolymer in aqueous phase by RAFT method | |
| CN106928440A (en) | A kind of polyetheramides, water reducer and preparation method as obtained in the polyetheramides | |
| NZ754070A (en) | Aqueous polymer composition | |
| KR20190101394A (en) | Aqueous polymer composition | |
| CN109160973B (en) | Aqueous phase ultrasonic synthesis method of maleic anhydride/alpha-arene copolymer | |
| CN112094378B (en) | Hyperbranched polyester, preparation method thereof and water-based paint prepared from hyperbranched polyester | |
| CN110878131B (en) | Method for preparing monodisperse polymer microspheres by redox-initiated dispersion polymerization | |
| CN102408512B (en) | Preparation method of water-soluble acrylic resin | |
| CN109160974B (en) | Aqueous phase preparation method of maleic anhydride-conjugated diene copolymer | |
| CN111978461A (en) | Water-based functional acrylic resin and preparation method thereof | |
| JPH0651733B2 (en) | Method for producing resin-reinforced emulsion polymer | |
| CN111171220A (en) | Preparation method of water-based pigment dispersion and water-based ink | |
| CN110483707B (en) | Vinyl monomer RAFT cation soap-free emulsion polymerization method with good controllability | |
| CN109206549B (en) | Cationic free radical polymerization emulsion for metal surface treatment field and preparation method thereof | |
| CN112608426A (en) | Polycarboxylate superplasticizer and preparation method thereof | |
| JPS63258913A (en) | Hardening water-based resin dispersion | |
| CN108912256B (en) | Synthesis method of low-molecular-weight cationic polymer for template polymerization | |
| CN109021157A (en) | A kind of chlorinated polyether resin of Narrow Molecular Weight Distribution and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |