CN102229690B - Method for preparing starch grafted hyperbranched amide polymer - Google Patents
Method for preparing starch grafted hyperbranched amide polymer Download PDFInfo
- Publication number
- CN102229690B CN102229690B CN 201110126696 CN201110126696A CN102229690B CN 102229690 B CN102229690 B CN 102229690B CN 201110126696 CN201110126696 CN 201110126696 CN 201110126696 A CN201110126696 A CN 201110126696A CN 102229690 B CN102229690 B CN 102229690B
- Authority
- CN
- China
- Prior art keywords
- starch
- acid
- hyperbranched
- initiator
- preparing
- 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
Landscapes
- Graft Or Block Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a method for preparing a starch grafted hyperbranched amide polymer. The method is characterized by: preparing a mixed phase and a branching reagent phase, gelatinizing the mixed phase for 0.1-1 hour at a temperature of 25-95 DEG C, then adjusting the temperature to 40-80 DEG C, adding a RAFT chain transfer agent to the gelatinized mixed phase, then adding a initiator to initiate a polymerization; during the polymerization, adding the branching reagent phase to the mixed phase in a dropwise manner within 1-10 hours, and sequentially carrying out the reaction for 0.5-4 hours after completing the adding, finally, carrying out a high-conversion preparation to prepare the starch grafted hyperbranched amide polymer. With the present invention, diene monomers and the chain transfer agent with low ratio are provided for high-polymerization rate and high- conversion preparation of the starch grafted hyperbranched amide polymer in a polar solvent system by using a semi-continuous polymerization process through a reversible addition and fragmentation chain transfer polymerization; the polymerization is easy to be controlled and turbidity removal effect of the product is significant.
Description
Technical field
The present invention relates to a kind of preparation method of flocculation agent, relate in particular to and a kind ofly be applicable to dispersion, stick, the vinyl of the starch-grafted dissaving structure of flocculation and rheology control or the preparation method of propenyl amide polymer.
Background technology
Vinyl or propenyl amide polymer are widely used in great fields such as water treatment, papermaking, printing and dyeing, mining, oil recovery, building materials.Present widely used vinyl or propenyl amide polymer such as SEPIGEL 305 and multipolymer thereof are main with linear structure, and still, the vinyl of branched structure or propenyl amide polymer are very rarely seen in the application of aspects such as water treatment.Starch all is widely used in various fields as a kind of aboundresources, low-cost natural high moleculer eompound, and water treatment also is one of them.CN1196334A discloses and has a kind ofly caused starch or Microcrystalline Cellulose skeleton grafted polyacrylamide and through the preparation method of hydrolysis and alkylamino methyl alcohol prepared in reaction cationically ampholytic graft polyacrylamide flocculating agent with potassium permanganate; CN101700922A discloses a kind of compound prepared in reaction that contains quaternary ammonium salt group by starch and 2-4 kind and has obtained the cationic starch flocculation agent; CN1990392 discloses a kind of with 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride or N-(2; 3-epoxy chloropropionate base) trimethyl ammonium chloride is made positively charged ion as etherifying agent; Under sodium hydroxide/catalyst promoter composite catalytic system katalysis, adopt the method for the synthetic high degree of substitution quaternary ammonium cationic starch flocculating agent of dry method; CN1792854 disclose a kind of with W-Gum respectively with dimethylaminoethyl methacrylate and dimethylaminoethyl methacrylate hydrochloride generation graft reaction; Obtain starch-grafted dimethylaminoethyl methacrylate and starch-grafted dimethylaminoethyl methacrylate hydrochloride; Carry out compositely then according to mass ratio at 1: 2, obtain the method for combined type modified starch flocculant.
Hyperbranched polymer is dendroid, and there is distribution in functional group in polymkeric substance, and part functional group is positioned at the end of polymer chain, and part functional group then is connected on the main body of polymer chain, uses the special direct one-step polycondensation of ABx type monomer to make usually.Yet WO 99/46301 discloses the mercaptan that uses polyenoid class monomer and suitable proportion and has been chain-transfer agent, obtain the branching polymethylmethacrylate through traditional radical polymerization preparation, but the polymkeric substance generation is crosslinked under the high-conversion rate, can not get branched polymer.(Chemical Communication such as Sherrington; 2004:1138-1139) report adopts controlled active atom transfer radical polymerization method; Through with the copolymerization of TGM 1, under low-conversion, prepare the TEB 3K of branching.(Macromolecules such as Perrier; 2005; 38:2131-2136) report adopts reversible addition-fracture to shift (RAFT) polymerization method; Through using TGM 1 to prepare the hyperbranched poly TEB 3K, but need to use a large amount of chain-transfer agents in the polymerization process and reach tens hours reaction to obtain hyperbranched polymers.
Summary of the invention
The objective of the invention is to deficiency, a kind of method for preparing the hyperbranched acylamide polymer of starch graft copolymer type is provided to prior art.
The object of the invention is realized through following technical scheme: a kind of method for preparing the hyperbranched acylamide polymer of starch graft copolymer type, and this method may further comprise the steps:
(1) preparation mixed phase, mixed phase comprises polar solvent, starch and amides monomer, and wherein, polar solvent is water or acidic buffer solvent, and starch and amides monomer account for 0.25 ~ 5% and 2 ~ 20% of polar solvent quality respectively;
(2) preparation branching reagent phase, branching reagent comprises polar solvent and branching reagent mutually; Wherein, branching reagent is dienes compound or Polyenes; Polar solvent is water or acidic buffer solvent; Branching reagent accounts for 0.1 ~ 5% of polar solvent quality;
(3) with mixed phase 25 ~ 95 ℃ of gelatinizations 0.1 ~ 1 hour, subsequently with temperature regulation to temperature of reaction, temperature of reaction is at 40 ~ 80 ℃;
(4) the RAFT chain-transfer agent is joined in the mixed phase of gelatinization completion, add the initiator initiated polymerization then; In the polymerization process, branching reagent was joined in the mixed phase in 1 ~ 10 hour, dropwise continued reaction 0.5 ~ 4 hour, the final high hyperbranched acylamide polymer of preparation starch graft copolymer that transforms; Wherein, RAFT chain-transfer agent and amides monomer mole ratio are 1/1000 ~ 1/100, and the mol ratio of initiator and RAFT chain-transfer agent is 1/10 ~ 1/1, and the quality of branching reagent phase is 10 ~ 50% of a mixed phase quality.
The invention has the beneficial effects as follows; The inventive method shifts (RAFT) polymerization method through reversible addition-fracture; Adopt semi-continuous polymerzation technology, use the chain-transfer agent of dienes monomer and low proportioning, high rate of polymerization, the high starch-grafted hyperbranched acylamide polymer polymkeric substance of preparation that transforms in the polar solvent system; Polyreaction is controlled easily, and the product turbidity removal effect is remarkable.
Embodiment
The present invention prepares the method for the hyperbranched acylamide polymer of starch graft copolymer type through reversible addition-fracture chain transfer (RAFT) polymerization method, and because of in the RAFT polymerization process, having used the high special chain transfer agent of chain transfer constant, this chain-transfer agent shifts with the regeneration that reversible addition-fracture takes place the growth radical; Keep free radical activity; Realize controlled and radical polymerization " activity ", and can regulate and control the structure of polymkeric substance, simultaneously; Adopt semi continuous operation technology; Use the chain-transfer agent of low proportioning, the dienes compound is joined in the amides monomer system gradually, polymerization temperature is controlled between 40 ~ 80 ℃; The dienes compound joining day was controlled at 1 ~ 10 hour, obtained the high starch graft copolymer hyperbranched polymer of final transformation efficiency.
The present invention prepares the method for the hyperbranched acylamide polymer of starch graft copolymer type, may further comprise the steps:
1, preparation mixed phase, mixed phase comprises polar solvent, starch and amides monomer, and wherein, polar solvent is water or acidic buffer solvent, and starch and amides monomer account for 0.25 ~ 5% and 2 ~ 20% of polar solvent quality respectively.
The starch that is used to prepare starch graft copolymer dissaving vinyl or propenyl amide polymer can be various cereal starchs, potato starch, legume starch and various treated starch.Cereal starch comprises glutinous rice starch, polished rice starch, long-grained nonglutinous rice starch, W-Gum, wheat starch; Potato starch comprises tapioca(flour), sweet potato starch, yam starch, yam bean starch, arrowroot starch, Rhizoma Dioscoreae starch, banana lily starch etc.; Legume starch comprises green starch, broad bean starch, pea starch, cowpea starch; Treated starch comprises cationic starch, CMS, methyl starch, hydroxyalkyl starch, Sumstar 190; The amides monomer comprises acrylic amide, USAF RH-1, the two substituted acrylamides of N-, N methacrylamide, N-NSC 11448, N-acryloyl morpholine, N-(2-hydroxypropyl) acrylic amide, N-acryloyl tetramethyleneimine, N-vinyl formamide, N-vinyl pyrrolidone, N-(3-sulfonic acid propyl group) 2-vinyl pyridine, 2-acrylyl oxy-ethyl phosphorylcholine.
2, preparation branching reagent phase, branching reagent comprises polar solvent and branching reagent mutually; Wherein, branching reagent is dienes compound or Polyenes; Polar solvent is water or acidic buffer solvent; Branching reagent accounts for 0.1 ~ 5% of polar solvent quality.
Dienes compound or Polyenes comprise N, N '-methylene-bisacrylamide, diacrylate macrogol ester, dimethacrylate macrogol ester, (methyl) vinylformic acid vinyloxy group macrogol ester etc.
3, with mixed phase 25 ~ 95 ℃ of gelatinizations 0.1 ~ 1 hour, subsequently with temperature regulation to temperature of reaction, temperature of reaction is at 40 ~ 80 ℃.
4, the RAFT chain-transfer agent is joined in the mixed phase of gelatinization completion, add the initiator initiated polymerization then.In the polymerization process, branching reagent was joined in the mixed phase in 1 ~ 10 hour, dropwise continued reaction 0.5 ~ 4 hour, the final high hyperbranched acylamide polymer of preparation starch graft copolymer that transforms; Wherein, RAFT chain-transfer agent and amides monomer mole ratio are 1/1000 ~ 1/100, and the mol ratio of initiator and RAFT chain-transfer agent is 1/10 ~ 1/1, and the quality of branching reagent phase is 10 ~ 50% of a mixed phase quality.
The RAFT chain-transfer agent that is used to prepare the hyperbranched acylamide polymer of starch graft copolymer is dithio or trithio compound, comprising dithiobenzoic acid ester class, trithiocarbonic acid salt, dithiocarbamate(s), xanthate class etc.Dithiobenzoic acid ester class chain-transfer agent commonly used such as 4-cyanopentanoic acid dithiobenzoic acid ester, 2-cyanic acid sec.-propyl dithiobenzoic acid ester, 2-(2-propyloic dithio carbonylsulfide) propionic acid, 4-cyanic acid-4-(diethylammonium thiocarbamyl sulphur) valeric acid, 2-methoxyethyl 2-phenyl-2-(amyl group thio-carbonyl sulfide) acetic ester etc.; The trithiocarbonic acid salt is like (3-benzene first sulfydryl thio-carbonyl sulfide) propionic acid, 2-(second sulfydryl thio-carbonyl sulfide)-2 Methylpropionic acid, 3-((1-carboxyl second sulfydryl) thio-carbonyl sulfide) propionic acid, 2; 2 '-thiocarbonyl two (sulfane base), two (2 Methylpropionic acids) etc., xanthate class such as xanthogenic acid guanidine-acetic acid, (2-(acetoxyl group) methyl) xanthogen phenylformic acid.
The initiator that is used to prepare the hyperbranched acylamide polymer of starch graft copolymer can be the various initiators that are applicable to the polar solvent system; Like chemical initiator; Photochemical initiators; Radiation initiators, suitable chemical initiator had peroxide initiator, azo-initiator, oxidation-reduction initiator.Peroxide initiator commonly used comprises ammonium persulphate, Potassium Persulphate; Azo-initiator comprises 4; 4 '-azo two (4-cyanopentanoic acid), azo diisobutyl amidine hydrochlorides, azo di-isopropyl imidazoline salt hydrochlorate, azo di-isopropyl tetrahydroglyoxaline, oxidation-reduction initiator comprises the compound system of superoxide (for example Potassium Persulphate, ammonium persulphate) and a kind of reductive agent (like S-WAT, sodium sulfite anhy 96, sodium formaldehyde sulphoxylate).Photochemical initiators is like (2-hydroxyl-1-[4-(hydroxyl) phenyl]-2-methyl isophthalic acid-acetone).
Further specify the present invention program and result through specific embodiment below, but can not think that the present invention only limits among these embodiment.In an embodiment, remove specified otherwise, all marks and percentage ratio all are weight ratios.
Embodiment 1
(1) in the 250ml there-necked flask, adds 1.0 parts of CMSs (CMS), 100 parts of acetic acid-sodium acetate buffer solution (pH=5), 0.0453 part of 3-benzene first sulfydryl thiocarbonyl propionic acid (BCPA); Mechanical stirring; Be warming up to 60 ℃ behind the letting nitrogen in and deoxidizing, gelatinization 0.5 hour;
(2) 7.1 parts of acrylic amides are joined in the above-mentioned amidin;
(3) with 0.59 part of N, N '-methylene-bisacrylamide is dissolved in 50 parts of water, is contained on the micro-injection pump;
(4) take by weighing 0.020 part of ammonium persulphate (APS), be dissolved in initiated polymerization in the mixing solutions that adds starch and acrylic amide in the less water;
(5) start micro-injection pump, set drop rate, with N, N '-methylene-bisacrylamide aqueous solution dropwised in 3 hours, continued reaction afterwards and obtained the hyperbranched poly acrylic amide in 0.5 hour.
The result shows that transformation efficiency is 98.6%, and the limiting viscosity number of polymerisate is 86.8 ml/g, adds the dienes monomer and increases as branching reagent post polymerization product viscosity, and molecular weight increases, and the turbidity removal rate of flocculating experiment 3ppm is 30.1 %.
Comparative Examples: do not add dienes branching reagent
(1) in the 250ml there-necked flask, adds 1.0 parts of CMSs (CMS), 100 parts of acetic acid-sodium acetate buffer solution (pH=5), 0.0453 part of 3-benzene first sulfydryl thiocarbonyl propionic acid (BCPA); Mechanical stirring; Be warming up to 60 ℃ behind the letting nitrogen in and deoxidizing, gelatinization 30 minutes;
(2) 7.1 parts of acrylic amides are joined in the above-mentioned amidin;
(3) take by weighing 0.020 part of ammonium persulphate (APS), be dissolved in initiated polymerization in the mixing solutions that adds starch and acrylic amide in the less water;
(4) take by weighing the aqueous solution (80wt.%) of 8.66 parts of methylacryoyloxyethyl trimethyl ammonium chlorides, add after the letting nitrogen in and deoxidizing and continue reaction 240 minutes in the above-mentioned hyperbranched poly acrylamide soln.
Transformation efficiency is 97.7%, and the limiting viscosity number of polymerisate is 55.29 ml/g, does not have obvious turbidity removal effect.
Embodiment 2
(1) in the 250ml there-necked flask, adds 0.6 part of CMS (CMS), 100 parts of acetic acid-sodium acetate buffer solution (pH=5), 0.0272 part of 3-benzene first sulfydryl thiocarbonyl propionic acid (BCPA); Mechanical stirring; Be warming up to 60 ℃ behind the letting nitrogen in and deoxidizing, gelatinization 30 minutes;
(2) 7.1 parts of acrylic amides are joined in the above-mentioned amidin;
(3) with 0.45 part of N, N '-methylene-bisacrylamide is dissolved in 50 parts of water, is contained on the micro-injection pump;
(4) take by weighing 0.020 part of ammonium persulphate (APS), be dissolved in initiated polymerization in the mixing solutions that adds starch and acrylic amide in the less water;
(5) start micro-injection pump, set drop rate, with N, N '-methylene-bisacrylamide aqueous solution dropwised in 3 hours, continued reaction afterwards and obtained the hyperbranched poly acrylic amide in 1 hour;
The result shows that transformation efficiency is 99.2%, and the limiting viscosity number of polymerisate is 93.8 ml/g, and the turbidity removal rate of flocculating experiment 4ppm is 26.4 %; Improve first monomer concentration, can effectively improve molecular weight product.
Embodiment 3
(1) in the 250ml there-necked flask, adds 1.0 parts of W-Gums (Maize), 100 parts of acetic acid-sodium acetate buffer solution (pH=5), 0.0453 part of 3-benzene first sulfydryl thiocarbonyl propionic acid (BCPA); Mechanical stirring; Be warming up to 95 ℃ behind the letting nitrogen in and deoxidizing, gelatinization 30 minutes;
(2) 7.1 parts of acrylic amides are joined in the above-mentioned amidin;
(3) with 0.45 part of N, N '-methylene-bisacrylamide is dissolved in 50 parts of water, is contained on the micro-injection pump;
(4) take by weighing 0.020 part of ammonium persulphate (APS), be dissolved in initiated polymerization in the mixing solutions that adds starch and acrylic amide in the less water;
(5) start micro-injection pump, set drop rate, with N, N '-methylene-bisacrylamide aqueous solution dropwised in 3 hours, continued reaction afterwards and obtained the hyperbranched poly acrylic amide in 1 hour;
The result shows that transformation efficiency is 98.7%, and the limiting viscosity number of polymerisate is 63.6 ml/g, and the turbidity removal rate of flocculating experiment 3ppm is 12.7 %; Change the total type of molecular weight and flocculating effect that can influence product of starch.
Embodiment 4
(1) in the 250ml there-necked flask, adds 1.0 parts of CMSs (CMS), 100 parts of acetic acid-sodium acetate buffer solution (pH=5), 0.0453 part of 3-benzene first sulfydryl thiocarbonyl propionic acid (BCPA); Mechanical stirring; Be warming up to 60 ℃ behind the letting nitrogen in and deoxidizing, gelatinization 30 minutes;
(2) 7.1 parts of acrylic amides are joined in the above-mentioned amidin;
(3) with 0.55 part of N, N '-methylene-bisacrylamide is dissolved in 50 parts of water, is contained on the micro-injection pump;
(4) take by weighing 0.020 part of ammonium persulphate (APS), be dissolved in initiated polymerization in the mixing solutions that adds starch and acrylic amide in the less water;
(5) start micro-injection pump, set drop rate, with N, N '-methylene-bisacrylamide aqueous solution dropwised in 3 hours, continued reaction afterwards and obtained the hyperbranched poly acrylic amide in 0.5 hour;
The result shows that transformation efficiency is 98.0%, and limiting viscosity number is 90.8ml/g, and the turbidity removal rate of flocculating experiment 3ppm is 28.4 %; Use different cationic monomers little to the molecular weight and the flocculating effect influence of product.
To sum up visible; The inventive method shifts (RAFT) polymerization method through reversible addition-fracture; Adopt semi-continuous polymerzation technology, use the chain-transfer agent of dienes monomer and low proportioning, high rate of polymerization, high starch-grafted hyperbranched vinyl of preparation or the propenyl amide polymer polymkeric substance of transforming in the polar solvent system; Polyreaction is controlled easily, and the product turbidity removal effect is remarkable.
The foregoing description is used for the present invention that explains, rather than limits the invention, and in the protection domain of spirit of the present invention and claim, any modification and change to the present invention makes all fall into protection scope of the present invention.
Claims (8)
1. a method for preparing the hyperbranched acylamide polymer of starch graft copolymer type is characterized in that, this method may further comprise the steps:
(1) preparation mixed phase, mixed phase comprises polar solvent, starch and amides monomer, and wherein, polar solvent is water or acidic buffer solvent, and starch and amides monomer account for 0.25～5% and 2～20% of polar solvent quality respectively;
(2) preparation branching reagent phase, branching reagent comprises polar solvent and branching reagent mutually; Wherein, branching reagent is dienes compound or Polyenes; Polar solvent is water or acidic buffer solvent; Branching reagent accounts for 0.1～5% of polar solvent quality;
(3) with mixed phase 25～95 ℃ of gelatinizations 0.1～1 hour, subsequently with temperature regulation to temperature of reaction, temperature of reaction is at 40～80 ℃;
(4) the RAFT chain-transfer agent is joined in the mixed phase of gelatinization completion, add the initiator initiated polymerization then; In the polymerization process, branching reagent was joined in the mixed phase in 1～10 hour, dropwise continued reaction 0.5～4 hour, the final high hyperbranched acylamide polymer of preparation starch graft copolymer that transforms; Wherein, RAFT chain-transfer agent and amides monomer mole ratio are 1/1000～1/100, and the mol ratio of initiator and RAFT chain-transfer agent is 1/10～1/1, and the quality of branching reagent phase is 10～50% of a mixed phase quality.
2. according to the said method for preparing the hyperbranched acylamide polymer of starch graft copolymer type of claim 1, it is characterized in that in the said step (1), said starch is various cereal starchs, potato starch, legume starch and various treated starch; Wherein, said cereal starch comprises glutinous rice starch, polished rice starch, long-grained nonglutinous rice starch, W-Gum and wheat starch; Potato starch comprises tapioca(flour), sweet potato starch, yam starch, yam bean starch, arrowroot starch, Rhizoma Dioscoreae starch and banana lily starch; Legume starch comprises green starch, broad bean starch, pea starch and cowpea starch; Treated starch comprises cationic starch, CMS, methyl starch, hydroxyalkyl starch and Sumstar 190; Said amides monomer comprises acrylic amide, USAF RH-1, the two substituted acrylamides of N-, N methacrylamide, N-NSC 11448, N-acryloyl morpholine, N-(2-hydroxypropyl) acrylic amide, N-vinyl formamide.
3. according to the said method for preparing the hyperbranched acylamide polymer of starch graft copolymer type of claim 1; It is characterized in that; In the said step (2); Said dienes compound or Polyenes comprise N, N '-methylene-bisacrylamide, diacrylate macrogol ester, dimethacrylate macrogol ester and (methyl) vinylformic acid vinyloxy group macrogol ester.
4. according to the said method for preparing the hyperbranched acylamide polymer of starch graft copolymer type of claim 1; It is characterized in that; In the said step (4); Said RAFT chain-transfer agent is dithio or trithio compound, comprises dithiobenzoic acid ester class, trithiocarbonic acid salt, dithiocarbamate(s) and xanthate class; Dithio trityl ester chain-transfer agent comprises 4-cyanopentanoic acid dithiobenzoic acid ester, 2-cyanic acid sec.-propyl dithiobenzoic acid ester, 2-(2-propyloic dithio carbonylsulfide) propionic acid, 4-cyanic acid-4-(diethylammonium thiocarbamyl sulphur) valeric acid and 2-methoxyethyl 2-phenyl-2-(amyl group thio-carbonyl sulfide) acetic ester; Trithiocarbonic acid salt chain-transfer agent comprises (3-benzene first sulfydryl thio-carbonyl sulfide) propionic acid, 2-(second sulfydryl thio-carbonyl sulfide)-2 Methylpropionic acid, 3-((1-carboxyl second sulfydryl) thio-carbonyl sulfide) propionic acid and 2; 2 '-thiocarbonyl two (sulfane base), two (2 Methylpropionic acids), xanthate class comprise xanthogenic acid guanidine-acetic acid and (2-(acetoxyl group) methyl) xanthogen phenylformic acid.
5. according to the said method for preparing the hyperbranched acylamide polymer of starch graft copolymer type of claim 1; It is characterized in that; In the said step (4); Said initiator comprises chemical initiator and radiation initiators, and chemical initiator comprises photochemical initiators, peroxide initiator, azo-initiator and oxidation-reduction initiator.
6. according to the said method for preparing the hyperbranched acylamide polymer of starch graft copolymer type of claim 5; It is characterized in that; Said peroxide initiator comprises ammonium persulphate, Potassium Persulphate; Azo-initiator comprises 4,4 '-azo two (4-cyanopentanoic acid), azo diisobutyl amidine hydrochlorides, azo di-isopropyl imidazoline salt hydrochlorate and azo di-isopropyl tetrahydroglyoxaline.
7. according to the said method for preparing the hyperbranched acylamide polymer of starch graft copolymer type of claim 5, it is characterized in that said oxidation-reduction initiator comprises the compound system of superoxide and reductive agent; Superoxide is Potassium Persulphate or ammonium persulphate, and reductive agent is S-WAT, sodium sulfite anhy 96 or sodium formaldehyde sulphoxylate.
8. according to the said method for preparing the hyperbranched acylamide polymer of starch graft copolymer type of claim 5, it is characterized in that said photochemical initiators is 2-hydroxyl-1-[4-(hydroxyl) phenyl]-2-methyl isophthalic acid-acetone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110126696 CN102229690B (en) | 2011-05-17 | 2011-05-17 | Method for preparing starch grafted hyperbranched amide polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110126696 CN102229690B (en) | 2011-05-17 | 2011-05-17 | Method for preparing starch grafted hyperbranched amide polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102229690A CN102229690A (en) | 2011-11-02 |
| CN102229690B true CN102229690B (en) | 2012-12-19 |
Family
ID=44842302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110126696 Active CN102229690B (en) | 2011-05-17 | 2011-05-17 | Method for preparing starch grafted hyperbranched amide polymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102229690B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102936318B (en) * | 2012-11-20 | 2014-11-26 | 孙安顺 | Multi-functional efficient oil scavenge polymer and preparation method of raw material graft modification starch thereof |
| CN104250381B (en) * | 2013-06-26 | 2017-09-12 | 通用电气公司 | Polymer available for water process |
| CN106006903B (en) * | 2016-05-27 | 2018-12-18 | 浙江理工大学 | A kind of preparation method of bamboo pulp fiber element & polyvinylformamide composite flocculation decoloring material |
| FR3090617B1 (en) * | 2018-12-20 | 2021-01-08 | S N F Sa | process for the treatment of suspensions of solid particles in water using amphoteric polymers |
| CN113072215B (en) * | 2021-04-15 | 2022-06-14 | 浙江德正建设有限公司 | Energy-saving emission-reducing town sewage treatment system |
| CN116162290B (en) * | 2023-03-09 | 2024-05-28 | 深圳丹伦基因科技有限公司 | Porous microcarrier, preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1196334A (en) * | 1997-04-11 | 1998-10-21 | 广州市环境保护科学研究所 | Method for preparing cation/amphoteric graft polyacrylamide flocculating agent |
| CN101693749A (en) * | 2009-10-22 | 2010-04-14 | 浙江大学 | Method for preparing dissaving vinyl or propenyl amide polymer |
-
2011
- 2011-05-17 CN CN 201110126696 patent/CN102229690B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1196334A (en) * | 1997-04-11 | 1998-10-21 | 广州市环境保护科学研究所 | Method for preparing cation/amphoteric graft polyacrylamide flocculating agent |
| CN101693749A (en) * | 2009-10-22 | 2010-04-14 | 浙江大学 | Method for preparing dissaving vinyl or propenyl amide polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102229690A (en) | 2011-11-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102286132B (en) | Method for preparing starch graft cationic type hyperbranched amide polymer | |
| CN101693749B (en) | Method for preparing dissaving vinyl or propenyl amide polymer | |
| CN102229690B (en) | Method for preparing starch grafted hyperbranched amide polymer | |
| CN104448128B (en) | Polymer mobility control agent suitable for high-temperature and high-salinity harsh reservoir and preparation method of polymer mobility control agent | |
| CN103059828B (en) | For viscosifying agent and the synthetic method thereof of aqueous fracturing fluid | |
| CN102050926B (en) | Heat-resistant salt-tolerate graft polyacrylamide and preparation method thereof | |
| CN102050913B (en) | Temperature and salt resistant grafted polyacrylamide and preparation method thereof | |
| CN105062455B (en) | A kind of water-based fracturing fluid gelatinizer and its synthetic method | |
| CN102492092B (en) | Method for preparing hyperbranched ionic amide type polymer by inverse emulsion polymerization | |
| JP2011252163A (en) | High molecular weight cationic polymer obtained by post-polymerization crosslinking reaction | |
| CN102153714B (en) | Method for preparing cation type hyperbranched ethylene or acrylamide polymer | |
| CN103987746A (en) | Preparation of polyvinylamide cellulose reactive adducts | |
| AU9052898A (en) | Aqueous stable dispersions based on water-soluble polymers containing a cationic dispersant comprising hydrophobic units | |
| JP2013543066A5 (en) | ||
| CN104119480A (en) | High-branch type polyvinyl alcohol-acrylamide graft copolymer, preparing method thereof and applications of the copolymer | |
| CN105037644A (en) | Polymer cationic surfactant, preparation method and applications thereof | |
| CN101220263B (en) | Water-based fracturing fluid gelatinizer and producing method thereof | |
| CA2524205A1 (en) | Use of water-soluble crosslinked cationic polymers for controlling deposition of pitch and stickies in papermaking | |
| CN108912288B (en) | Thermoplastic elastomer with high melt index and preparation method thereof | |
| CN103408701B (en) | The method that uv-light polymerization prepares drying strengthening agent | |
| CN103408702B (en) | Preparation method of graft-polymer cationic dry strength agent | |
| US20150112033A1 (en) | Method for synthesizing polymers from acrylic acid, one of the salts of same or the mixture thereof | |
| CN103408700A (en) | Preparation method of amphoteric dry strength agent | |
| CN105385433A (en) | Quick-dissolving thickening agent used for water-based fracture and synthesizing method thereof | |
| CN106608976B (en) | A kind of starch-containing tackifier copolymerization associated matter and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |