CN102286132B - Method for preparing starch graft cationic type hyperbranched amide polymer - Google Patents
Method for preparing starch graft cationic type hyperbranched amide polymer Download PDFInfo
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Abstract
The invention discloses a method for preparing a starch graft cationic type hyperbranched vinyl or allyl amide polymer. The method comprises the following steps: preparing a mixed phase and a branching reagent phase, preparing a cationic monomer phase, gelatinizing the mixed phase at 25-95 DEG C for 0.1-1 hour, and adjusting the temperature to 40-80 DEG C; then adding a reversible addition-fragmentation chain transfer (RAFT) agent in the gelatinized mixed phase, adding an initiator to initiate a polymerization reaction; and finally adding the cationic monomer phase in a hyperbranched polymer system prepared from the mixed phase, and continuously reacting for 1-24 hours to obtain the starch graft copolymerization cationic type hyperbranched vinyl or allyl amide polymer. The method adopts the RAFT polymerization method and the semi-continuous polymerization technology and uses the diene monomer and the chain transfer agent with a low molar ratio to prepare the starch graft cationic type hyperbranched vinyl or allyl amide polymer in a polar solvent system with high polymerization rate and conversion rate, the polymerization reaction is easy to control and the turbidity removal effect of the product is remarkable.
Description
Technical field
The present invention relates to a kind of preparation method of flocculation agent, relate in particular to a kind ofly be applicable to disperse, stick, the preparation method of the acylamide polymer of the cationic starch graft copolymer type dissaving structure of flocculation and rheology control.
Background technology
Vinyl or propenyl amide polymer are widely used in the major areas such as water treatment, papermaking, printing and dyeing, mining, oil recovery, building materials.Now widely used vinyl or propenyl amide polymer such as polyacrylamide and multipolymer thereof are take linear structure as main, and still, the vinyl of branched structure or propenyl amide polymer are very rarely seen in the application of the 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 is also 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 with alkylamino methyl alcohol reaction preparation cationically ampholytic graft polyacrylamide flocculating agent with potassium permanganate; CN101700922A discloses a kind of compound reaction that contains quaternary ammonium salt group by starch and 2-4 kind and has prepared 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, then carry out compositely according to mass ratio at 1: 2, obtain the method for combined type modified starch flocculant.
But from the angle of practical application, on the one hand, the polymkeric substance of branched structure effect aspect the utilizations such as flocculation is better; On the other hand, the viscosity of branched polymer can dissolve fast lower than the linear polymer with molecular weight, and is easy to use.In addition, cationic-type polyacrylamide namely has bridging action, positively charged ion again can with suspended particle generation charge neutrality effect, reduce the Coulomb repulsion between particle, more be conducive to flocculation.
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 is connected on the main body of polymer chain, usually uses the special direct one-step polycondensation of ABx type monomer to make.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 by traditional radical polymerization preparation, but under high-conversion rate, the polymkeric substance generation is crosslinked, can not get branched polymer.(the Chemical Communication such as Sherrington, 2004:1138-1139) report adopts the atom transfer radical polymerization method of controlled activity, by with the copolymerization of Ethylene glycol dimethacrylate, prepare the methyl methacrylate of branching under low-conversion.(the Macromolecules such as Perrier, 2005,38:2131-2136) report adopts reversible addition-fracture to shift (RAFT) polymerization process, by using Ethylene glycol dimethacrylate to prepare the hyperbranched poly methyl methacrylate, but need to use a large amount of chain-transfer agents in polymerization process and reach the reaction of tens hours to obtain hyperbranched polymkeric substance.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, a kind of method for preparing starch graft copolymer type dissaving vinyl or propenyl amide polymer is provided.
Purpose of the present invention is achieved through the following technical solutions: a kind of method for preparing starch graft copolymer type dissaving vinyl or propenyl amide polymer, and the method comprises the following 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 respectively 0.25 ~ 5% and 2 ~ 20% of polar solvent quality;
(2) preparation branching reagent phase: branching reagent comprises polar solvent and branching reagent mutually, and wherein, branching reagent is dienes compound or Polyenes, and polar solvent is water or acidic buffer solvent, and the branching reagent quality is 0.1 ~ 5% of polar solvent quality;
(3) preparation cationic monomer phase: cationic monomer comprises polar solvent and cationic monomer mutually, and wherein, polar solvent is water or acidic buffer solvent, and the cationic monomer mass concentration is 10 ~ 100%;
(4) 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 ℃;
(5) the RAFT chain-transfer agent is joined in the mixed phase that gelatinization completes, then add the initiator initiated polymerization; In polymerization process, branching reagent joined mixed phase in 1 ~ 10 hour, dropwise rear continuation reaction 0 ~ 4 hour, final high preparation starch graft copolymer dissaving vinyl or the propenyl amide polymer of transforming; 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 mixed phase quality;
(6) cationic monomer is added in the hyperbranched polymer system that mixed phase prepares, continues reaction 1 ~ 24 hour, obtain cationic starch graft copolymer type hyperbranched amide polymer; Wherein, cationic monomer phase quality is 10 ~ 50% of mixed phase quality.
The invention has the beneficial effects as follows, the inventive method shifts (RAFT) polymerization process by reversible addition-fracture, adopt semi-continuous polymerzation technique, use the chain-transfer agent of dienes monomer and low proportioning, high rate of polymerization, high vinyl or the propenyl amide polymer polymkeric substance that transforms the starch-grafted cation type hyperbranched of preparation in the polar solvent system, polyreaction is easily controlled, and the product turbidity removal effect is remarkable.
Embodiment
the method that the present invention prepares starch graft copolymer type hyperbranched amide polymer shifts (RAFT) polymerization process by reversible addition-fracture chain, because used the high special chain transfer agent of chain transfer constant in the RAFT polymerization process, the regeneration of reversible addition-fracture occurs for this chain-transfer agent and Propagating Radical shifts, 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 technique, use the chain-transfer agent of low proportioning, the dienes compound is joined in vinyl or propenyl amide monomer system gradually, polymerization temperature is controlled between 40 ~ 80 ℃, the dienes compound joining day is controlled at 1 ~ 10 hour, the second monomer adds rear continuation reaction 1 ~ 24 hour, obtain the high starch graft copolymer hyperbranched polymer of final transformation efficiency.
The present invention prepares the method for starch graft copolymer type dissaving vinyl or propenyl amide polymer, comprises the following 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 respectively 0.25 ~ 5% and 2 ~ 20% of polar solvent quality.
Starch for the preparation of the starch graft copolymer hyperbranched amide polymer can be various cereal starchs, potato starch, legume starch and various treated starch.Cereal starch comprises glutinous rice starch, polished rice starch, Indica Rice Starch, W-Gum, wheat starch; Potato starch tapioca (flour), sweet potato starch, yam starch, yam bean starch, arrowroot starch, Rhizoma Dioscoreae starch, banana lily starch etc.; Legume starch comprises green starch, Faba bean starch, pea starch, cowpea starch; Treated starch comprises cationic starch, carboxymethyl starch, methyl starch, hydroxyalkyl starch, Sumstar 190; The amides monomer comprises the two substituted acrylamides of acrylamide, Methacrylamide, N-, N methacrylamide, NIPA, N-acryloyl morpholine, N-(2-hydroxypropyl) acrylamide, N-acryloyl tetramethyleneimine, N-vinyl formamide, NVP, 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; The branching reagent quality is 0.1 ~ 5% of polar solvent quality.
Dienes compound or Polyenes comprise N, N '-methylene-bisacrylamide, diacrylate macrogol ester, PEGDMA-400, (methyl) vinylformic acid vinyloxy group macrogol ester etc.
3, preparation cationic monomer phase, cationic monomer comprises polar solvent and cationic monomer mutually; Wherein, polar solvent is water or acidic buffer solvent; The cationic monomer mass concentration is 10 ~ 100%.
Cationic monomer for the preparation of starch graft copolymer dissaving vinyl or propenyl amide polymer comprises dimethyl diallyl ammonium chloride, dimethylaminoethyl methacrylate, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, diethylaminoethyl methacrylate, ethylacrylate-trimethylammonium chloride, dimethylaminoethyl acrylate, N, N-dimethyl ethenylphenyl ammonia and quaternary ammonium salt thereof, 2-vinyl pyridine, 4-vinylpridine.
4, 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 ℃.
5, the RAFT chain-transfer agent is joined in the mixed phase that gelatinization completes, then add the initiator initiated polymerization.In polymerization process, branching reagent joined mixed phase in 1 ~ 10 hour, dropwise rear continuation reaction 0 ~ 4 hour, final high preparation starch graft copolymer dissaving vinyl or the propenyl amide polymer of transforming; 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 mixed phase quality.
RAFT chain-transfer agent for the preparation of starch graft copolymer dissaving vinyl or propenyl amide polymer is dithio or trithio compound, comprising dithiobenzoic acid ester class, trithiocarbonic acid salt, dithiocarbamate(s), xanthate class etc.dithioesters class chain-transfer agent such as 4-cyanopentanoic acid dithiobenzoic acid ester commonly used, 2-cyano group sec.-propyl dithiobenzoic acid ester, 2-(2-propyloic dithio carbonylsulfide) propionic acid, 4-cyano group-4-(diethyl thiocarbamyl sulphur) valeric acid, 2-methoxyethyl 2-phenyl-2-(amyl group thio-carbonyl sulfide) acetic ester etc., the trithiocarbonic acid salt is as (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 (sulfanyl) two (2 Methylpropionic acid) etc., xanthate class such as xanthogenic acid guanidine-acetic acid, (2-(acetoxyl group) methyl) xanthogen phenylformic acid.
Initiator for the preparation of the starch graft copolymer hyperbranched amide polymer can be the various initiators that are applicable to the polar solvent system, as 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 (as S-WAT, sodium bisulfite, sodium formaldehyde sulphoxylate).Photochemical initiators is as (2-hydroxyl-1-[4-(hydroxyl) phenyl]-2-methyl isophthalic acid-acetone).
6, cationic monomer is added in the hyperbranched polymer system that mixed phase prepares, continues reaction and obtained cationic starch graft copolymer type hyperbranched amide polymer in 1 ~ 24 hour; Wherein, cationic monomer phase quality is 10 ~ 50% of mixed phase quality.
Further illustrate the present invention program and result below by specific embodiment, but can not think that the present invention only limits in these embodiment.In an embodiment, except specified otherwise, all marks and percentage ratio are all weight ratios.
Embodiment 1
(1) add 1.0 parts of carboxymethyl starch (CMS), 100 parts of NaAc_HAc buffer solutions (pH=5), 0.0453 part of 3-benzene first sulfydryl thiocarbonyl propionic acid (BCPA) in the 250ml there-necked flask, mechanical stirring, be warming up to 60 ℃ after letting nitrogen in and deoxidizing, gelatinization 30 minutes;
(2) 7.1 parts of acrylamides are joined in above-mentioned amidin;
(3) with 0.59 part of N, N '-methylene-bisacrylamide is dissolved in 50 parts of water, is contained on micro-injection pump;
(4) take 0.020 part of ammonium persulphate (APS), be dissolved in initiated polymerization in the mixing solutions that adds starch and acrylamide in a small amount of water;
(5) start micro-injection pump, set drop rate, with N, N '-methylene-bisacrylamide aqueous solution dropwised in 3 hours and obtains the hyperbranched poly acrylamide;
(6) aqueous solution (80wt.%) that takes 8.66 parts of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides is dissolved in 15 parts of water, adds after letting nitrogen in and deoxidizing to continue reaction 180 minutes in above-mentioned hyperbranched poly acrylamide soln.
The result demonstration, transformation efficiency is 96.7%, and the limiting viscosity number of polymerisate is 110.8 ml/g, adds the dienes monomer to increase as branching reagent post polymerization product viscosity, and molecular weight increases, and the turbidity removal rate of flocculating experiment 3ppm is 74.5 %.
Comparative Examples: do not add dienes branching reagent
(1) add 1.0 parts of carboxymethyl starch (CMS), 100 parts of NaAc_HAc buffer solutions (pH=5), 0.0453 part of 3-benzene first sulfydryl thiocarbonyl propionic acid (BCPA) in the 250ml there-necked flask, mechanical stirring, be warming up to 60 ℃ after letting nitrogen in and deoxidizing, gelatinization 30 minutes;
(2) 7.1 parts of acrylamides are joined in above-mentioned amidin;
(3) take 0.020 part of ammonium persulphate (APS), be dissolved in initiated polymerization in the mixing solutions that adds starch and acrylamide in a small amount of water;
(4) take the aqueous solution (80wt.%) of 8.66 parts of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, add after letting nitrogen in and deoxidizing and continue reaction 240 minutes in above-mentioned hyperbranched poly acrylamide soln.
The result demonstration, transformation efficiency is 97.7%, the limiting viscosity number of polymerisate is 55.29 ml/g, without obvious turbidity removal effect.
Embodiment 2
(1) add 0.6 part of carboxymethyl starch (CMS), 100 parts of NaAc_HAc buffer solutions (pH=5), 0.0272 part of 3-benzene first sulfydryl thiocarbonyl propionic acid (BCPA) in the 250ml there-necked flask, mechanical stirring, be warming up to 60 ℃ after letting nitrogen in and deoxidizing, gelatinization 30 minutes;
(2) 7.1 parts of acrylamides are joined in above-mentioned amidin;
(3) with 0.45 part of N, N '-methylene-bisacrylamide is dissolved in 50 parts of water, is contained on micro-injection pump;
(4) take 0.020 part of ammonium persulphate (APS), be dissolved in initiated polymerization in the mixing solutions that adds starch and acrylamide in a small amount of water;
(5) start micro-injection pump, set drop rate, with N, N '-methylene-bisacrylamide aqueous solution dropwised in 3 hours and obtains the hyperbranched poly acrylamide;
(6) aqueous solution (80wt.%) that takes 8.66 parts of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides is dissolved in 40 parts of water, adds after letting nitrogen in and deoxidizing to continue reaction 180 minutes in above-mentioned hyperbranched poly acrylamide soln.
The result demonstration, transformation efficiency is 97.2%, and the limiting viscosity number of polymerisate is 153.0 ml/g, and the turbidity removal rate of flocculating experiment 4ppm is 67.5 %; Improve the first monomer concentration, can effectively improve molecular weight product.
Embodiment 3
(1) add 1.0 parts of W-Gums (Maize), 100 parts of NaAc_HAc buffer solutions (pH=5), 0.0453 part of 3-benzene first sulfydryl thiocarbonyl propionic acid (BCPA) in the 250ml there-necked flask, mechanical stirring, be warming up to 95 ℃ after letting nitrogen in and deoxidizing, gelatinization 30 minutes;
(2) 7.1 parts of acrylamides are joined in above-mentioned amidin;
(3) with 0.45 part of N, N '-methylene-bisacrylamide is dissolved in 50 parts of water, is contained on micro-injection pump;
(4) take 0.020 part of ammonium persulphate (APS), be dissolved in initiated polymerization in the mixing solutions that adds starch and acrylamide in a small amount of water;
(5) start micro-injection pump, set drop rate, with N, N '-methylene-bisacrylamide aqueous solution dropwised in 3 hours and obtains the hyperbranched poly acrylamide;
(6) aqueous solution (80wt.%) that takes 8.66 parts of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides is dissolved in 15 parts of water, adds after letting nitrogen in and deoxidizing to continue reaction 240 minutes in above-mentioned hyperbranched poly acrylamide soln.
The result demonstration, transformation efficiency is 98.7%, and the limiting viscosity number of polymerisate is 90.3 ml/g, and the turbidity removal rate of flocculating experiment 3ppm is 44.9 %; Changing the total class of starch can affect molecular weight and the flocculating effect of product.
Embodiment 4
(1) add 1.0 parts of carboxymethyl starch (CMS), 100 parts of NaAc_HAc buffer solutions (pH=5), 0.0453 part of 3-benzene first sulfydryl thiocarbonyl propionic acid (BCPA) in the 250ml there-necked flask, mechanical stirring, be warming up to 60 ℃ after letting nitrogen in and deoxidizing, gelatinization 30 minutes;
(2) 7.1 parts of acrylamides are joined in above-mentioned amidin;
(3) with 0.55 part of N, N '-methylene-bisacrylamide is dissolved in 50 parts of water, is contained on micro-injection pump;
(4) take 0.020 part of ammonium persulphate (APS), be dissolved in initiated polymerization in the mixing solutions that adds starch and acrylamide in a small amount of water;
(5) start micro-injection pump, set drop rate, with N, N '-methylene-bisacrylamide aqueous solution dropwised in 3 hours and obtains the hyperbranched poly acrylamide;
(6) take the aqueous solution (80wt.%) of 13 parts of acrylyl oxy-ethyl-trimethyl salmiacs, add after letting nitrogen in and deoxidizing and continue reaction 240 minutes in above-mentioned hyperbranched poly acrylamide soln.
Turn result and show, rate is 95.2%, and the limiting viscosity number of polymerisate is 113.2 ml/g, and the turbidity removal rate of flocculating experiment 3ppm is 70.6 %; Use different cationic monomers little on molecular weight and the flocculating effect impact of product.
As fully visible, the inventive method shifts (RAFT) polymerization process by reversible addition-fracture, adopt semi-continuous polymerzation technique, use the chain-transfer agent of dienes monomer and low proportioning, high rate of polymerization, the high preparation starch graft cationic type hyperbranched amide polymer polymkeric substance that transforms in the polar solvent system, polyreaction is easily controlled, and the product turbidity removal effect is remarkable.
Above-described embodiment 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 (6)
1. a method for preparing starch graft copolymer type dissaving vinyl or propenyl amide polymer, is characterized in that, the method comprises the following steps:
(1) preparation mixed phase: mixed phase comprises polar solvent, starch and propenyl amide monomer, and wherein, polar solvent is water or acidic buffer solvent, and starch and propenyl amide monomer account for respectively 0.25 ~ 5% and 2 ~ 20% of polar solvent quality;
(2) preparation branching reagent phase: branching reagent comprises polar solvent and branching reagent mutually, and wherein, branching reagent is dienes compound or Polyenes, and polar solvent is water or acidic buffer solvent, and the branching reagent quality is 0.1 ~ 5% of polar solvent quality;
(3) preparation cationic monomer phase: cationic monomer comprises polar solvent and cationic monomer mutually, and wherein, polar solvent is water or acidic buffer solvent, and the cationic monomer mass concentration is 10 ~ 100%;
(4) 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 ℃;
(5) the RAFT chain-transfer agent is joined in the mixed phase that gelatinization completes, then add the initiator initiated polymerization; In polymerization process, branching reagent joined mixed phase in 1 ~ 10 hour, dropwise rear continuation reaction 0 ~ 4 hour, final high preparation starch graft copolymer dissaving vinyl or the propenyl amide polymer of transforming; Wherein, RAFT chain-transfer agent and propenyl amide 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 mixed phase quality;
(6) cationic monomer is added in the hyperbranched polymer system that mixed phase prepares, continues reaction 1 ~ 24 hour, obtain cationic starch graft copolymer type hyperbranched amide polymer; Wherein, cationic monomer phase quality is 10 ~ 50% of mixed phase quality.
2. prepare according to claim 1 the method for starch graft copolymer type dissaving vinyl or propenyl amide polymer, it is characterized in that, in described step (1), described starch is various cereal starchs, potato starch, legume starch or various treated starch; Wherein, described cereal starch is glutinous rice starch, polished rice starch, Indica Rice Starch, W-Gum or wheat starch; Potato starch is tapioca (flour), sweet potato starch, yam starch, yam bean starch, arrowroot starch, Rhizoma Dioscoreae starch or banana lily starch; Legume starch is green starch, Faba bean starch, pea starch or cowpea starch; Treated starch is cationic starch, carboxymethyl starch, methyl starch, hydroxyalkyl starch or Sumstar 190; The propenyl amide monomer is acrylamide, Methacrylamide, the two substituted acrylamides of N-, N methacrylamide, NIPA, N-acryloyl morpholine, N-(2-hydroxypropyl) acrylamide or N-vinyl formamide.
3. prepare according to claim 1 the method for starch graft copolymer type dissaving vinyl or propenyl amide polymer, it is characterized in that, in described step (2), described dienes compound or Polyenes are N, N '-methylene-bisacrylamide, diacrylate macrogol ester, PEGDMA-400, (methyl) vinylformic acid vinyloxy group macrogol ester.
4. prepare according to claim 1 the method for starch graft copolymer type dissaving vinyl or propenyl amide polymer, it is characterized in that, in described step (3), described cationic monomer is dimethyl diallyl ammonium chloride, dimethylaminoethyl methacrylate, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, diethylaminoethyl methacrylate, ethylacrylate-trimethylammonium chloride, dimethylaminoethyl acrylate, N, N-dimethyl ethenylphenyl ammonia and quaternary ammonium salt thereof, 2-vinyl pyridine, 4-vinylpridine.
5. prepare according to claim 1 the method for starch graft copolymer type dissaving vinyl or propenyl amide polymer, it is characterized in that, in described step (5), described RAFT chain-transfer agent is dithiobenzoic acid ester class chain-transfer agent, trithiocarbonic acid salt chain-transfer agent, dithiocarbamate(s) chain-transfer agent or xanthate class chain-transfer agent; Dithiobenzoic acid ester class chain-transfer agent is 4-cyanopentanoic acid dithiobenzoic acid ester, 2-cyano group sec.-propyl dithiobenzoic acid ester, 2-(2-propyloic dithio carbonylsulfide) propionic acid, 4-cyano group-4-(diethyl thiocarbamyl sulphur) valeric acid or 2-methoxyethyl 2-phenyl-2-(amyl group thio-carbonyl sulfide) acetic ester; Trithiocarbonic acid salt chain-transfer agent is (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 or 2,2 '-thiocarbonyl two (sulfanyl) two (2 Methylpropionic acid); Xanthate class chain-transfer agent is xanthogenic acid guanidine-acetic acid, (2-(acetoxyl group) methyl) the xanthogen phenylformic acid.
6. prepare according to claim 1 the method for starch graft copolymer type dissaving vinyl or propenyl amide polymer, it is characterized in that, in described step (5), described initiator comprises chemical initiator and radiation initiators; Wherein, chemical initiator comprises photochemical initiators, peroxide initiator, azo-initiator and oxidation-reduction initiator; The peroxide initiator is ammonium persulphate, Potassium Persulphate, azo-initiator is 4,4 '-azo two (4-cyanopentanoic acid), azo diisobutyl amidine hydrochlorides, azo di-isopropyl imidazoline salt hydrochlorate, azo di-isopropyl tetrahydroglyoxaline, oxidation-reduction initiator is the compound system of superoxide and reductive agent, superoxide is Potassium Persulphate, ammonium persulphate, and reductive agent is S-WAT, sodium bisulfite, sodium formaldehyde sulphoxylate; Photochemical initiators is 2-hydroxyl-1-[4-(hydroxyl) phenyl]-2-methyl isophthalic acid-acetone.
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