CN103396511A - Method for preparing novel long-time stable amphoteric polyacrylamide aqueous dispersion - Google Patents
Method for preparing novel long-time stable amphoteric polyacrylamide aqueous dispersion Download PDFInfo
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Abstract
The invention discloses a method for preparing a novel long-time stable amphoteric polyacrylamide aqueous dispersion, comprising the following step of: by using a water dispersion polymerization method, under existence of stabilizing agent poly (diallyldimethylammonium chloride) and ammonium sulfate solution, inducedly polymerizing monomer acrylamide, cation monomer dimethyl diallyl ammonium chloride and anion monomer maleic acid by a ring azo amidine initiator VA-044, to form the amphoteric polyacrylamide aqueous dispersion. The relative molecular mass can reach a maximum height of 3.87107g/mol. Compared with a current method for preparing an amphoteric polyacrylamide aqueous dispersion with high relative molecular mass, the preparation provided by the invention has beneficial effects that: the method is an environment friendly method without an organic solvent; cation monomer dimethyl diallyl ammonium chloride and anion monomer maleic acid are used in a polymerization formula, thereby raising charge density of the polymer; a ring azo amidine initiator is used as a single initiator which has advantages of small usage amount and high efficiency.
Description
Technical field
The present invention relates to a kind of preparation method of acrylamide analog copolymer, particularly a kind of preparation method of novel long-time stable amphiprotic polyacrylamide water dispersion.
Background technology
Amphiprotic polyacrylamide (Amphoteric Polyacrylamide, APAM) refer to the water-soluble polymer that contains simultaneously positive and negative two kinds of electric charge groups on the macromole chain link, with the water-soluble cationic that only contains a kind of electric charge (Cation) or negatively charged ion (Anion) polyacrylamide (PAM), compare, APAM not only has both over-all propertieies concurrently, and has significantly the characteristics such as " anti-polyelectrolyte effect " and pH be applied widely.At present, the pressed powder that mainly prepares take the aqueous solution polymerization technology of commercial amphiprotic polyacrylamide is as main.But powdery product needs to dissolve in application process, needs to consume a large amount of energy.Adopt aqueous dispersion polymerization technique to prepare the amphiprotic polyacrylamide particle tiny and even, molecular weight and water-soluble being easy to are regulated, and the dissolution rate in water is fast, and application performance is good.The quality product homogeneous, stable, cost is low and easy to use be the direction of current polyacrylamide production technology development.As the amphiprotic polyacrylamide that efficient paper making additive uses, its retention aid and filter aid performance strengthens with the increase of amphiprotic polyacrylamide negatively charged ion degree, with the increase of amphiprotic polyacrylamide molecular weight and consumption, strengthens; Relative molecular weight is large except requiring for the amphiprotic polyacrylamide of applying as efficient flocculant, dissolution rate fast, also require that its synthesis technique is simple to operation, the polymerization cost value is lower etc.The purposes of polyacrylamide depends on chemical constitution and the relative molecular mass of acrylamide series polymkeric substance to a great extent.For example the high molecular weight amphiprotic polyacrylamide uses as flocculation agent in sewage treatment process, and advantage is paid close attention to day by day widely because its consumption is few, flocculating effect is good and sedimentation and filtration speed is fast etc.
Xu Qing woodss in 2003 etc. have been synthesized novel texture amphiprotic polyacrylamide dispersion soln, and study its enhancing, retention aid and filter aid effect.Result shows, it all has good enhancing, retention and drainage effect to various paper wastes and non-wood pulp, can not only with the composite use of Tai-Ace S 150, be more suitable for the requirement of neutral papermaking.Amphiprotic polyacrylamide is except having good enhancing, retention and drainage effect, also has well auxiliary sizing efficiency, when consumption is 0.2%, can make the stuff sizing degree improve (Xu Qinglin, Hu Huiren more than 50%, Chen Fushan, the novel texture amphiprotic polyacrylamide strengthens, the research of retention aid and filter aid performance, Chinese papermaking journal, 2003,18 (1), 88-93); 20l0, Wu Yumin etc. are take acrylamide (AM), MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (DMC) and vinylformic acid (AA) as monomer, polymethyl acyl-oxygen ethyl-trimethyl salmiac (PDMC) is dispersion stabilizer, 2,2,-azo (2-amidine propane) dihydrochloride (V-50) is initiator, in ammonium sulfate solution, has successfully prepared amphiprotic polyacrylamide.Investigated the impact on aqueous dispersion of dispersion stabilizer relative molecular mass, reaction medium pH value, temperature of reaction and stirring velocity, and with infrared spectrometer and scanning electron microscope, product structure has been characterized.(Yumin Wu, Chuanxing Wang, Jun Xu, Aqueous dispersion polymerization of amphoteric polyacrylamide, Journal of Applied Polymer Science, 2010,115 (2), 1131-1137; Liu Hanlei, Wu Yumin, the preparation of amphiprotic polyacrylamide aqueous dispersion, Qingdao University of Science and Technology's journal (natural science edition), 2010,31,4,371-375); The military beautiful people in 2011 etc. are usingd homemade amphiprotic polyacrylamide dispersion system as sewage flocculant.The processing power of examination to municipal effluent.The research discovery, the flocculation ability of amphiprotic polyacrylamide is subjected to the impact of ion degree, and the more flocculation abilities of ionic group are stronger, but too much ionic group can bring negative impact.Amphiprotic polyacrylamide is wider to the subject range of the pH value of system.Amphiprotic polyacrylamide need first dissolve with 1% sodium chloride solution when application, when salt concn was too low, polymkeric substance can not fully dissolve, higher than this value, flocculation process is had no significant effect to (Wang Chuanxing, Li Xiangtao, Wu Yumin, the flocculating property of amphiprotic polyacrylamide aqueous dispersion, Chinese Marine University's journal, 2011,41 (1/2), 125-128); He Peixin etc. are take acrylamide (AM), MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (DMC) and 2-acrylamido-2 methyl propane sulfonic acid salt (AMPS) as monomer, polymethyl acyl-oxygen ethyl-trimethyl salmiac (PDMC) is dispersion stabilizer, 2,2-azo (2-amidine propane) dihydrochloride (V-50) is initiator, in ammonium sulfate solution, has prepared amphiprotic polyacrylamide.Systematic study ammonium sulfate solution concentration, amount of stabilizer, monomer concentration and the initiator concentration impact (Y.Zou on aqueous dispersion viscosity and particle diameter, Y.H.Zhang, P.X.He, Synthesis and characterization of amphoteric polyacrylamide by dispersion polymerization in aqueous salts solution, Designed Monomers and Polymers, 20l3,16 (6), 592-600.).
In sum, the loose polymerization of applied moisture prepares the water dispersion of amphiprotic polyacrylamide, and it is simple that it has use, belong to environmentally friendly polymkeric substance, the application comprehensive benefit is high, but the water dispersion molecular weight of synthetic amphiprotic polyacrylamide is lower at present, has limited its range of application.In view of dimethyl diallyl ammonium chloride (DMDAAC) polymkeric substance has high effect nontoxic, positive charge density is high, lower-price characteristic, it is longer that study emphasis acrylamide of the present invention (AM) and DMDAAC and maleic acid copolymerization obtain steady time, the amphiprotic polyacrylamide water dispersion research that relative molecular weight is higher, and optimize synthesis technique, thus impel the product better effects if of exploitation, cost is lower, applies more extensive.
Summary of the invention
The object of the invention is to: in the amphoteric polyacrylamide flocculation agent, because the DMDAAC polymkeric substance has high effect nontoxic, positive charge density is high, lower-price characteristic, so answer the polymerization studies of study emphasis AM and DMDAAC, optimize synthesis technique, thereby make the product of developing better effects if, cost is lower, applies more extensive.The amphiprotic polyacrylamide water dispersion, because products obtained therefrom does not need to carry out any separation, its water dispersion can be directly used in paper plant and produce, and this method does not have " three wastes " substantially, and investment goods is few, and production cost is low.The aqueous dispersion polymerization method is not only safety but also economical rationality aborning, becomes gradually the main production technology of polyacrylamide.In the present invention, adopting water-soluble azo compounds VA-044 is the main body initiator, and it has following features: 1. the pH value that can not change polymerization system in propagation process; 2. need only add a small amount of water-soluble azo initiator, polyreaction can obtain the transformation efficiency near 100%; 3. water-soluble azo compounds forms the free radical centered by carbon after decomposing, hydrogen-taking capacity a little less than, the side chain of resulting polymers molecule is less, macromolecular chain comparatively stretches, the hydrokinetics volume of polymer molecule is larger in the aqueous solution, and the Efficient Adhesive Promotion of polymeric articles is better.
The present invention includes following steps: in mechanical stirrer is housed, connects the four-hole round-bottomed flask of nitrogen protection device; by the monomer acrylamide of certain mol proportion, cationic monomer diallyldimethylammonChloride Chloride, anionic monomer maleic acid (sodium salt), ammonium sulfate; the dispersion stabilizer Poly Dimethyl Diallyl Ammonium Chloride together; with appropriate distilled water, dissolve fully, and guarantee required monomer concentration and ammonium sulfate concentrations.Put it in water bath with thermostatic control, open and stir, regulate pH value size, start to pass into nitrogen, after 30 minutes, add required azo-initiator (VA-044), and in the atmosphere of nitrogen sustained reaction 2～10 hours, polyreaction can obtain the water dispersion of the amphiprotic polyacrylamide of stable homogeneous and good fluidity after fully.
In the preparation method of above-mentioned ultra-high molecular weight amphiprotic polyacrylamide water dispersion, in monomer solution, the total concentration of monomer is 10～35%, and the molar ratio cationic monomer/acrylamide monomer of monomer/anionic monomer is 1/ (1～18)/1.
In the preparation method of above-mentioned ultra-high molecular weight amphiprotic polyacrylamide water dispersion, the mass percent that initiator accounts for monomer is 0.0005%～0.5%.
In the preparation method of above-mentioned ultra-high molecular weight amphiprotic polyacrylamide water dispersion, described temperature of reaction system should be controlled at 30～65 ℃, and the pH value of reaction system should be controlled at 2～10, polymerization time 2～10 hours.
The preparation method of above-mentioned ultra-high molecular weight amphiprotic polyacrylamide water dispersion, preparation method compared to existing high molecular weight amphiprotic polyacrylamide, beneficial effect of the present invention is: the amphiprotic polyacrylamide relative molecular mass is higher, can reach 3.87 * 10
7G/mol; It is that demixing phenomenon did not occur in 240 days that dispersion system steady time is the longest.The water dispersion copolymerization method, organic solvent-free, free from environmental pollution, the friendly production method of based environment; Use maleic acid (sodium salt) as anionic monomer, be conducive to improve the electric density of polymkeric substance, thereby enlarged polymkeric substance in industrial ranges of application such as papermaking; In polymerization formula, use single initiator, in whole polymerization process, not only simple to operate, and reaction temperature and, initiator amount is few, efficiency is high, the application of gained water dispersion is simple, steady time is long, has huge economic benefit.
Embodiment
EXAMPLE l
in the present embodiment, adopt the aqueous dispersion polymerization method, mechanical stirrer is being housed, in the four-hole round-bottomed flask of connection nitrogen protection device, add acrylamide monomer 5.6864g (0.08mo1), cationic monomer 1.6167g (0.01mo1), anionic monomer 1.1607g (0.01mo1), ammonium sulfate 16g (20wt%), dispersion stabilizer Poly Dimethyl Diallyl Ammonium Chloride 2.0515g (0.45g/g), add distilled water that it is dissolved fully, monomer concentration is 20wt%, connect device, put it in 50 ℃ of waters bath with thermostatic control, open and stir, with finite concentration NaOH solution and HCl solution conditioned reaction system pH=7, pass into nitrogen after 30 minutes, add azo-initiator 0.0022g (0.05wt%), and in the atmosphere of nitrogen, continued to stir 8-10 hour, react the complete water dispersion that namely obtains amphiprotic polyacrylamide amine.According to national standard " GBl2005.1-89. Molecular Weight for Polyacrylamide measuring method ", adopt " one point method " to make solvent with 1mol/L NaCl solution, in 30 ℃ of waters bath with thermostatic control, with Ubbelohde viscometer, recording the limiting viscosity η of polyacrylamide, is 2.27 * 10 by can be calculated Polymer Molecular Weight
7Gmol
-1, with SNB-1 type rotational viscosimeter, recording apparent viscosity is 335.86mpas, good fluidity, stable system not layering in 240 days.
Embodiment 2
adding amount of medicines monomer mole ratio (the cationic monomer: acrylamide monomer: anionic monomer) be 10: 80: 10 that feeds intake in experimental system, ammonium sulfate 16g (20wt%), dispersion stabilizer Poly Dimethyl Diallyl Ammonium Chloride 2.0515g (0.45g/g), add distilled water that it is dissolved fully, monomer concentration is 20wt%, connect device, put it in 50 ℃ of waters bath with thermostatic control, open and stir, conditioned reaction system pH=8, pass into nitrogen after 30 minutes, add azo-initiator 0.0022g (0.05wt%), and in the atmosphere of nitrogen, continued to stir 8-10 hour, react the complete water dispersion that namely obtains amphiprotic polyacrylamide amine.Through test, can obtain Polymer Molecular Weight is 2.69 * 10
7Gmol
-1, apparent viscosity is 17.62mpas, good fluidity.(relevant testing method is shown in embodiment 1)
Embodiment 3
adding amount of medicines monomer mole ratio (the cationic monomer: acrylamide monomer: anionic monomer) be 10: 80: 10 that feeds intake in experimental system, ammonium sulfate 16g (20wt%), dispersion stabilizer Poly Dimethyl Diallyl Ammonium Chloride 2.0515g (0.45g/g), add distilled water that it is dissolved fully, monomer concentration is 20wt%, connect device, put it in 50 ℃ of waters bath with thermostatic control, open and stir, with finite concentration NaOH solution and HCl solution conditioned reaction system pH=10, pass into nitrogen after 30 minutes, add azo-initiator 0.0022g (0.05wt%), and in the atmosphere of nitrogen, continued to stir 8-10 hour, react the complete water dispersion that namely obtains amphiprotic polyacrylamide amine.Through test, can obtain Polymer Molecular Weight is 3.19 * 1
06gmo1
-1, system viscosity is large, poor fluidity.(relevant testing method is shown in embodiment 1)
Embodiment 4
adding amount of medicines monomer mole ratio (the cationic monomer: acrylamide monomer: anionic monomer) be 10: 80: 10 that feeds intake in experimental system, ammonium sulfate 16g (20wt%), dispersion stabilizer Poly Dimethyl Diallyl Ammonium Chloride 2.0515g (0.45g/g), add distilled water that it is dissolved fully, monomer concentration is 20wt%, connect device, put it in 50 ℃ of waters bath with thermostatic control, open and stir, with finite concentration NaOH solution and HCl solution conditioned reaction system pH=5, pass into nitrogen after 30 minutes, add azo-initiator 0.0022g (0.05wt%), and in the atmosphere of nitrogen, continued to stir 8-10 hour, react the complete water dispersion that namely obtains amphiprotic polyacrylamide amine.Through test, can obtain Polymer Molecular Weight is 9.07 * 10
6Gmo1
-1, system layering after 18 days.(relevant testing method is shown in embodiment 1)
Embodiment 5
adding amount of medicines monomer mole ratio (the cationic monomer: acrylamide monomer: anionic monomer) be 10: 80: 10 that feeds intake in experimental system, ammonium sulfate 16g (20wt%), dispersion stabilizer Poly Dimethyl Diallyl Ammonium Chloride 2.0515g (0.45g/g), add distilled water that it is dissolved fully, monomer concentration is 20wt%, connect device, put it in 45 ℃ of waters bath with thermostatic control, open and stir, with finite concentration NaOH solution and HCI solution conditioned reaction system pH=7, pass into nitrogen after 30 minutes, add azo-initiator 0.0022g (0.05wt%), and in the atmosphere of nitrogen, continued to stir 8-10 hour, react the complete water dispersion that namely obtains amphiprotic polyacrylamide amine.Through test, can obtain Polymer Molecular Weight is 1.79 * 10
7Gmol
-1, system layering after 25 days.(relevant testing method is shown in embodiment 1)
Embodiment 6
adding amount of medicines monomer mole ratio (the cationic monomer: acrylamide monomer: anionic monomer) be 10: 80: 10 that feeds intake in experimental system, ammonium sulfate 16g (20wt%), dispersion stabilizer Poly Dimethyl Diallyl Ammonium Chloride 2.0515g (0.45g/g), add distilled water that it is dissolved fully, monomer concentration is 20wt%, connect device, 55 ℃ of conditioned reaction system temperatures, open and stir, with finite concentration NaOH solution and HCl solution conditioned reaction system pH=7, pass into nitrogen after 30 minutes, add azo-initiator 0.0022g (0.05wt%), and in the atmosphere of nitrogen, continued to stir 8-10 hour, react the complete water dispersion that namely obtains amphiprotic polyacrylamide amine.Through test, can obtain Polymer Molecular Weight is 2.24 * 10
7Gmol
-1, apparent viscosity is 209.50mpas, good fluidity, stable system not layering in 240 days.(relevant testing method is shown in embodiment 1)
Embodiment 7
adding amount of medicines monomer mole ratio (the cationic monomer: acrylamide monomer: anionic monomer) be 10: 80: 10 that feeds intake in experimental system, ammonium sulfate 16g (20wt%), dispersion stabilizer Poly Dimethyl Diallyl Ammonium Chloride 2.0515g (0.45g/g), add distilled water that it is dissolved fully, monomer concentration is 20wt%, connect device, 60 ℃ of conditioned reaction system temperatures, open and stir, with finite concentration NaOH solution and HCl solution conditioned reaction system pH=7, pass into nitrogen after 30 minutes, add azo-initiator 0.0022g (0.05wt%), and in the atmosphere of nitrogen, continued to stir 8-10 hour, react the complete water dispersion that namely obtains amphiprotic polyacrylamide amine.Through test, can obtain Polymer Molecular Weight is 7.34 * 10
6Gmol
-1, after 14 days, system becomes muddy, system layering after 20 days.(relevant testing method is shown in embodiment 1)
Embodiment 8
in experimental system, change the adding amount of medicines monomer mole ratio (cationic monomer: acrylamide monomer: anionic monomer) be 15: 70: 15 that feeds intake, ammonium sulfate 16g (20wt%), dispersion stabilizer Poly Dimethyl Diallyl Ammonium Chloride 2.0515g (0.45g/g), add distilled water that it is dissolved fully, monomer concentration is 20wt%, connect device, put it in 50 ℃ of waters bath with thermostatic control, open and stir, with finite concentration NaOH solution and HCl solution conditioned reaction system pH=7, pass into nitrogen after 30 minutes, add azo-initiator 0.0022g (0.05wt%), and in the atmosphere of nitrogen, continued to stir 8-10 hour, react the complete water dispersion that namely obtains amphiprotic polyacrylamide amine.Through test, can obtain Polymer Molecular Weight is 3.87 * 10
7Gmol
-1, apparent viscosity is 90.01mpas, good fluidity, stable system not layering in 240 days.(relevant testing method is shown in embodiment 1)
Embodiment 9
in experimental system, change the adding amount of medicines monomer mole ratio (cationic monomer: acrylamide monomer: anionic monomer) be 20: 60: 20 that feeds intake, ammonium sulfate 16g (20wt%), dispersion stabilizer Poly Dimethyl Diallyl Ammonium Chloride 2.0515g (0.45g/g), add distilled water that it is dissolved fully, monomer concentration is 20wt%, connect device, put it in 50 ℃ of waters bath with thermostatic control, open and stir, with finite concentration NaOH solution and HCl solution conditioned reaction system pH=7, pass into nitrogen after 30 minutes, add azo-initiator 0.0022g (0.05wt%), and in the atmosphere of nitrogen, continued to stir 8-10 hour, react the complete water dispersion that namely obtains amphiprotic polyacrylamide amine.Through test, can obtain Polymer Molecular Weight is 9.10 * 10
6Gmol
-1, system viscosity is large, poor fluidity.(relevant testing method is shown in embodiment 1)
Embodiment 10
adding amount of medicines monomer mole ratio (the cationic monomer: acrylamide monomer: anionic monomer) be 10: 80: 10 that feeds intake in experimental system, ammonium sulfate 16g (20wt%), dispersion stabilizer Poly Dimethyl Diallyl Ammonium Chloride 2.0515g (0.45g/g), add distilled water that it is dissolved fully, monomer concentration is 20wt%, connect device, put it in 50 ℃ of waters bath with thermostatic control, open and stir, with finite concentration NaOH solution and HCl solution conditioned reaction system pH=7, pass into nitrogen after 30 minutes, adding the mass percent that accounts for monomer is 0.1% initiator, and in the atmosphere of nitrogen, continued to stir 8-10 hour, react the complete water dispersion that namely obtains amphiprotic polyacrylamide amine.Through test, can obtain Polymer Molecular Weight is 1.44 * 10
6Gmol
-1, system viscosity is large, poor fluidity.(relevant testing method is shown in embodiment 1)
Embodiment 1l
adding amount of medicines monomer mole ratio (the cationic monomer: acrylamide monomer: anionic monomer) be 10: 80: 10 that feeds intake in experimental system, ammonium sulfate 16g (20wt%), dispersion stabilizer Poly Dimethyl Diallyl Ammonium Chloride 2.0515g (0.45g/g), add distilled water that it is dissolved fully, monomer concentration is 20wt%, connect device, put it in 50 ℃ of waters bath with thermostatic control, open and stir, with finite concentration NaOH solution and HCl solution conditioned reaction system pH=7, start to pass into nitrogen, after 30 minutes, adding the mass percent that accounts for monomer is 0.01% initiator, and in the atmosphere of nitrogen, continued to stir 8-10 hour, react the complete water dispersion that namely obtains amphiprotic polyacrylamide amine.Through test, can obtain Polymer Molecular Weight is 2.32 * 10
7Gmol
-1, apparent viscosity is 290.10mpas, good fluidity, stable system not layering in 240 days.(relevant testing method is shown in embodiment 1)
Embodiment 12
adding amount of medicines monomer mole ratio (the cationic monomer: acrylamide monomer: anionic monomer) be 10: 80: 10 that feeds intake in experimental system, ammonium sulfate 16g (20wt%), dispersion stabilizer Poly Dimethyl Diallyl Ammonium Chloride 2.0515g (0.45g/g), add distilled water that it is dissolved fully, monomer concentration is 20wt%, connect device, put it in 50 ℃ of waters bath with thermostatic control, open and stir, with finite concentration NaOH solution and HCl solution conditioned reaction system pH=7, pass into nitrogen after 30 minutes, adding the mass percent that accounts for monomer is 0.005% initiator, and in the atmosphere of nitrogen, continued to stir 8-10 hour, react the complete water dispersion that namely obtains amphiprotic polyacrylamide amine.Through test, can obtain Polymer Molecular Weight is 1.02 * 10
7Gmol
-1, apparent viscosity is 219.40mpas, good fluidity, stable system not layering in 240 days.(relevant testing method is shown in embodiment 1)
Embodiment 13
adding amount of medicines monomer mole ratio (the cationic monomer: acrylamide monomer: anionic monomer) be 10: 80: 10 that feeds intake in experimental system, ammonium sulfate 16g (20wt%), dispersion stabilizer Poly Dimethyl Diallyl Ammonium Chloride 2.0515g (0.45g/g), add distilled water that it is dissolved fully, monomer concentration is 20wt%, connect device, put it in 50 ℃ of waters bath with thermostatic control, open and stir, with finite concentration NaOH solution and HCl solution conditioned reaction system pH=7, pass into nitrogen after 30 minutes, adding the mass percent that accounts for monomer is 0.001% initiator, and in the atmosphere of nitrogen, continued to stir 8-10 hour, react the complete water dispersion that namely obtains amphiprotic polyacrylamide amine.Through test, can obtain Polymer Molecular Weight is 7.44 * 10
6Gmol
-l, system viscosity is large, poor fluidity.(relevant testing method is shown in embodiment 1)
Embodiment 14
adding amount of medicines monomer mole ratio (the cationic monomer: acrylamide monomer: anionic monomer) be 10: 80: 10 that feeds intake in experimental system, ammonium sulfate 16g (20wt%), dispersion stabilizer Poly Dimethyl Diallyl Ammonium Chloride 2.0515g (0.45g/g), the change monomer concentration is 25wt%, connect device, put it in 50 ℃ of waters bath with thermostatic control, open and stir, with finite concentration NaOH solution and HCl solution conditioned reaction system pH=7, pass into nitrogen after 30 minutes, add azo-initiator 0.0022g (0.05wt%), and in the atmosphere of nitrogen, continued to stir 8-10 hour, react the complete water dispersion that namely obtains amphiprotic polyacrylamide amine.Through test, can obtain Polymer Molecular Weight is 2.87 * 10
7Gmol
-1, apparent viscosity is 225.00mpas, good fluidity, stable system not layering in 240 days.(relevant testing method is shown in embodiment 1)
Embodiment 15
adding amount of medicines monomer mole ratio (the cationic monomer: acrylamide monomer: anionic monomer) be 10: 80: 10 that feeds intake in experimental system, ammonium sulfate 16g (20wt%), dispersion stabilizer Poly Dimethyl Diallyl Ammonium Chloride 2.0515g (0.45g/g), the change monomer concentration is 30wt%, connect device, put it in 50 ℃ of waters bath with thermostatic control, open and stir, with finite concentration NaOH solution and HCl solution conditioned reaction system pH=7, pass into nitrogen after 30 minutes, add azo-initiator 0.0022g (0.05wt%), and the lasting 8-10 of stirring reacted in individual hour in the atmosphere of nitrogen, the complete water dispersion that namely obtains amphiprotic polyacrylamide amine.Through test, can obtain Polymer Molecular Weight is 1.74 * 10
7Gmol
-1, system viscosity is large, poor fluidity.(relevant testing method is shown in embodiment 1)
Embodiment 16
adding amount of medicines monomer mole ratio (the cationic monomer: acrylamide monomer: anionic monomer) be 10: 80: 10 that feeds intake in experimental system, ammonium sulfate 16g (20wt%), dispersion stabilizer Poly Dimethyl Diallyl Ammonium Chloride 2.0515g (0.45g/g), the change monomer concentration is 15wt%, connect device, put it in 50 ℃ of waters bath with thermostatic control, open and stir, with finite concentration NaOH solution and HCl solution conditioned reaction system pH=7, pass into nitrogen after 30 minutes, add azo-initiator 0.0022g (0.05wt%), and in the atmosphere of nitrogen, continued to stir 8-10 hour, react the complete water dispersion that namely obtains amphiprotic polyacrylamide amine.Through test, can obtain Polymer Molecular Weight is 9.72 * 10
6Gmol
-1, it is muddy that water dispersion became afterwards at 14 days, and after 20 days, system viscosity increases.(relevant testing method is shown in embodiment 1)
Embodiment 17
adding amount of medicines monomer mole ratio (the cationic monomer: acrylamide monomer: anionic monomer) be 10: 80: 10 that feeds intake in experimental system, ammonium sulfate 16g (20wt%), dispersion stabilizer Poly Dimethyl Diallyl Ammonium Chloride 2.0515g (0.45g/g), the change monomer concentration is 10wt%, connect device, put it in 50 ℃ of waters bath with thermostatic control, open and stir, with finite concentration NaOH solution and HCl solution conditioned reaction system pH=7, pass into nitrogen after 30 minutes, add azo-initiator 0.0022g (0.05wt%), and in the atmosphere of nitrogen, continued to stir 8-10 hour, react the complete water dispersion that namely obtains amphiprotic polyacrylamide amine.Through test, can obtain Polymer Molecular Weight is 1.39 * 10
6Gmol
-1, it is muddy that water dispersion became in 10 days afterwards, layering after 25 days.(relevant testing method is shown in embodiment 1)
Embodiment 18
adding amount of medicines monomer mole ratio (the cationic monomer: acrylamide monomer: anionic monomer) be 10: 80: 10 that feeds intake in experimental system, ammoniumsulphate soln concentration is 25%, dispersion stabilizer Poly Dimethyl Diallyl Ammonium Chloride 2.0515g (0.45g/g), add distilled water that it is dissolved fully, monomer concentration is 20wt%, connect device, put it in 50 ℃ of waters bath with thermostatic control, open and stir, with finite concentration NaOH solution and HCl solution conditioned reaction system pH=7, pass into nitrogen after 30 minutes, add azo-initiator 0.0022g (0.05wt%), and in the atmosphere of nitrogen, continued to stir 8-10 hour, react the complete water dispersion that namely obtains amphiprotic polyacrylamide amine.The relative molecular mass that obtains polymkeric substance through test is 3.11 * 10
7Gmnol
-1, apparent viscosity is 328.17mpas, good fluidity, stable system not layering in 240 days.(relevant testing method is shown in embodiment 1)
Embodiment 19
adding amount of medicines monomer mole ratio (the cationic monomer: acrylamide monomer: anionic monomer) be 10: 80: 10 that feeds intake in experimental system, changing ammoniumsulphate soln concentration is 30%, dispersion stabilizer Poly Dimethyl Diallyl Ammonium Chloride 2.0515g (0.45g/g), add distilled water that it is dissolved fully, monomer concentration is 20wt%, connect device, put it in 50 ℃ of waters bath with thermostatic control, open and stir, with finite concentration NaOH solution and HCl solution conditioned reaction system pH=7, pass into nitrogen after 30 minutes, add azo-initiator 0.0022g (0.05wt%), and in the atmosphere of nitrogen, continued to stir 8-10 hour, react the complete water dispersion that namely obtains amphiprotic polyacrylamide amine.Through test, can obtain Polymer Molecular Weight is 1.65 * 10
7Gmol
-1, apparent viscosity is 286.75mpas, good fluidity, stable system not layering in 210 days.(relevant testing method is shown in embodiment 1)
Embodiment 20
adding amount of medicines monomer mole ratio (the cationic monomer: acrylamide monomer: anionic monomer) be 10: 80: 10 that feeds intake in experimental system, changing ammoniumsulphate soln concentration is 35%, dispersion stabilizer Poly Dimethyl Diallyl Ammonium Chloride 2.0515g (0.45g/g), add distilled water that it is dissolved fully, monomer concentration is 20wt%, connect device, put it in 50 ℃ of waters bath with thermostatic control, open and stir, with finite concentration NaOH solution and HCl solution conditioned reaction system pH=7, pass into nitrogen after 30 minutes, add azo-initiator 0.0022g (0.05wt%), and in the atmosphere of nitrogen, continued to stir 8-10 hour, react the complete water dispersion that namely obtains amphiprotic polyacrylamide amine.Through test, can obtain Polymer Molecular Weight for being 8.80 * 10
6Gmol
-1, after 30 days, salt out.(relevant testing method is shown in embodiment 1)
Embodiment 2l
adding amount of medicines monomer mole ratio (the cationic monomer: acrylamide monomer: anionic monomer) be 10: 80: 10 that feeds intake in experimental system, changing ammoniumsulphate soln concentration is 15%, dispersion stabilizer Poly Dimethyl Diallyl Ammonium Chloride 2.0515g (0.45g/g), add distilled water that it is dissolved fully, monomer concentration is 20wt%, connect device, put it in 50 ℃ of waters bath with thermostatic control, open and stir, with finite concentration NaOH solution and HCl solution conditioned reaction system pH=7, pass into nitrogen after 30 minutes, add azo-initiator 0.0022g (0.05wt%), and in the atmosphere of nitrogen, continued to stir 8-10 hour, react complete, result can't generate water dispersion.(relevant testing method is shown in embodiment 1)
Embodiment 22
adding amount of medicines monomer mole ratio (the cationic monomer: acrylamide monomer: anionic monomer) be 10: 80: 10 that feeds intake in experimental system, ammoniumsulphate soln concentration is 25%, changing dispersion stabilizer Poly Dimethyl Diallyl Ammonium Chloride consumption is 0.50g/g, add distilled water that it is dissolved fully, monomer concentration is 20wt%, connect device, put it in 50 ℃ of waters bath with thermostatic control, open and stir, with finite concentration NaOH solution and HCl solution conditioned reaction system pH=7, pass into nitrogen after 30 minutes, add azo-initiator 0.0022g (0.05wt%), and in the atmosphere of nitrogen, continued to stir 8-10 hour, react the complete water dispersion that namely obtains amphiprotic polyacrylamide amine.The relative molecular mass that obtains polymkeric substance through test is 9.14 * 10
6Gmol
-1, system viscosity is large, poor fluidity.(relevant testing method is shown in embodiment 1)
Embodiment 23
in experimental system, the adding amount of medicines monomer mole ratio (cationic monomer/acrylamide monomer/anionic monomer) that feeds intake is 10: 80: 10, ammoniumsulphate soln concentration is 25%, changing dispersion stabilizer Poly Dimethyl Diallyl Ammonium Chloride consumption is 0.40g/g, add distilled water that it is dissolved fully, monomer concentration is 20wt%, connect device, put it in 50 ℃ of waters bath with thermostatic control, open and stir, with finite concentration NaOH solution and HCl solution conditioned reaction system pH=7, pass into nitrogen after 30 minutes, add azo-initiator 0.0022g (0.05wt%), and in the atmosphere of nitrogen, continued to stir 8-10 hour, react the complete water dispersion that namely obtains amphiprotic polyacrylamide amine.The relative molecular mass that obtains polymkeric substance through test is 2.15 * 10
7Gmol
-1, apparent viscosity is 540.20mpas, good fluidity, stable system not layering in 240 days.(relevant testing method is shown in embodiment 1)
Embodiment 24
adding amount of medicines monomer mole ratio (the cationic monomer: acrylamide monomer: anionic monomer) be 10: 80: 10 that feeds intake in experimental system, ammoniumsulphate soln concentration is 25%, changing dispersion stabilizer Poly Dimethyl Diallyl Ammonium Chloride consumption is 0.35g/g, add distilled water that it is dissolved fully, monomer concentration is 20wt%, connect device, put it in 50 ℃ of waters bath with thermostatic control, open and stir, with finite concentration NaOH solution and HCl solution conditioned reaction system pH=7, pass into nitrogen after 30 minutes, add azo-initiator 0.0022g (0.05wt%), and in the atmosphere of nitrogen, continued to stir 8-10 hour, react the complete water dispersion that namely obtains amphiprotic polyacrylamide amine.The relative molecular mass that obtains polymkeric substance through test is for being 1.88 * 10
7Gmol
-1, became muddy, layering in 42 days in system 2l days.(relevant testing method is shown in embodiment 1)
Above-described embodiment is only preferred embodiment of the present invention, is not intended to limit scope of the present invention, when using, can to above-described embodiment, simplify according to actual needs or the equivalence variation.
Claims (8)
1. the preparation method of a super novel long-time stable amphiprotic polyacrylamide water dispersion, it is characterized in that: mechanical stirrer is being housed, connect in the four-hole round-bottomed flask of nitrogen protection device, the acrylamide monomer that adds certain mol proportion, cationic monomer, anionic monomer, appropriate ammonium sulfate and make its consoluet dispersion stabilizer Poly Dimethyl Diallyl Ammonium Chloride with appropriate distilled water, and guarantee required monomer concentration and ammoniumsulphate soln concentration, regulate the pH value, put it into again in water bath with thermostatic control, pass into nitrogen, add initiator, stir.After polyreaction 8-10 hour, namely obtain the water dispersion of amphiprotic polyacrylamide, it is characterized in that monomer concentration is 10～35%, preferred 10～20%; Initiator concentration is 0.0005%～0.5%, preferred 0.005～0.1%.
2. the preparation method of novel long-time stable amphiprotic polyacrylamide according to claim 1, it is characterized in that: the cationic monomer monomer is that cationic monomer has dimethyl diallyl ammonium chloride (DMDAAC), MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (DMC) or vinylformic acid dimethylamine ethyl ester methyl chloride salt (DAC), preferred DMDAAC.
3. the preparation method of novel long-time stable amphiprotic polyacrylamide according to claim 1, it is characterized in that: anionic monomer is vinyl sulfonate, acrylate, maleate or maleic acid salt, preferred maleic acid salt.
4. the preparation method of novel long-time stable amphiprotic polyacrylamide according to claim 1, it is characterized in that: cationic monomer/acrylamide monomer/anionic monomer is that mol ratio is 1/ (1～18)/1, preferred 1/ (5～8)/l.
5. the preparation method of novel long-time stable amphiprotic polyacrylamide according to claim 1, it is characterized in that: temperature of reaction system should be controlled at 30～65 ℃ preferred 50～55 ℃; Polymerization time 2～10 hours, preferred 4～8 hours.
6. the preparation method of novel long-time stable amphiprotic polyacrylamide according to claim 1, it is characterized in that: the pH value of reaction system should be controlled at 2～10, and preferred 6～9.
7. the preparation method of novel long-time stable amphiprotic polyacrylamide according to claim 1, it is characterized in that: the reaction system dispersion stabilizer is controlled at 0.25～0.60g/g, preferred 0.40～0.55g/g.
8. the preparation method of according to claim 1～4 described novel long-time stable amphiprotic polyacrylamides, it is characterized in that: initiator is that the azo initiator system is azo two (4-cyanopentanoic acid sodium) class water-soluble azo salt, ring azo amidine class initiator, and azobisisobutyronitrile class oil soluble azo-compound, preferably encircle azo amidine class initiator.
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