CN102321208A - Water-in-water polymer dispersion and preparation method thereof - Google Patents
Water-in-water polymer dispersion and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a water-in-water polymer dispersion and a preparation method thereof. The water-in-water polymer dispersion consists of a polymer formed from a water soluble monomer, water soluble protein, water soluble salt and de-ionized water. The water-in-water polymer dispersion preparation method comprises the sequentially process steps of: 1, adding a stabilizing agent and the de-ionized water under stirring into a reaction vessel, adding the water soluble monomer and the water soluble salt after the stabilizing agent is completely dissolved, continuously stirring for completely dissolving the mixed liquid, regulating the PH (Potential of Hydrogen) of the formed mixed liquid to 3.0-7.0 after the water soluble monomer and the water-soluble salt are completely dissolved, and then inletting nitrogen and removing oxygen; and 2, adding an initiating agent into the reaction vessel and making the monomers in the mixed liquid to perform a free radical reaction for at least 3 hours at a normal atmospheric pressure and 20-85 DEG C. The water soluble monomer is a water soluble nonionic monomer, or a water soluble anionic monomer, or a water soluble nonionic monomer and a water soluble anionic monomer, or a water soluble nonionic monomer and a water soluble cationic monomer; and the stabilizing agent is a water soluble protein.
Description
Technical field
The invention belongs to water-soluble polymers synthetic field, particularly water-in-water polymer dispersion and preparation method thereof.
Background technology
Water-in-water polymer dispersion is claimed the water-in-water polymer emulsion again, and its disperse phase and external phase are water miscible dispersion system all, has solid content height, the easy advantage of dissolving of cold water.The characteristics of water-in-water polymer displersions preparation are that water-soluble monomer and stablizer can both be dissolved in before polymerization and form homogeneous system in the brine media; After the initiation; With growth polymers precipitating from salt solution of molecular chain, being separated and adsorbing stablizer with stablizer simultaneously forms stable water bag aqueous dispersion.Therefore, the key of preparation water-in-water polymer dispersion is to select suitable stabilizers.
Among the preparation method of existing water-in-water polymer dispersion; Usually the stablizer that adopts has cationic oligomeric thing (for example CN101016352A), anionic oligomer (for example CN101649024A), and CN101735388A discloses the stablizer that a kind of PGE series, Vinylpyrrolidone polymer and Z 150PH that contains polyoxyethylene glycol formed.Cationic polymers costs an arm and a leg, and has caused the cost up of preparation water-in-water polymer dispersion.Though its price of anionic polymer and non-ionic polymers is low than cationic polymers, can only be used to prepare the water-in-water polymer dispersion of anionic or non-ionic type mostly, make the range of application of polymkeric substance receive certain influence.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, a kind of water-in-water polymer dispersion and preparation method thereof is provided,, adapt to the polymerization of multiple water-soluble monomer, realize the recycling of refuse to reduce cost.
Water-in-water polymer dispersion according to the invention is made up of polymkeric substance, water-soluble protein, water-soluble salt and deionized water that water-soluble monomer forms, and the mass percent of each component is following:
A kind of in the polymkeric substance of polymkeric substance, water-soluble nonionic monomer and soluble anionic monomers formation that the polymkeric substance that the polymkeric substance that the polymkeric substance that said water-soluble monomer forms forms for the water-soluble nonionic monomer, soluble anionic monomers form, water-soluble nonionic monomer and water-soluble cationic monomer form.
The preparation method of water-in-water polymer dispersion according to the invention, its raw material is water-soluble monomer, stablizer, water-soluble salt, deionized water and initiator, the mass percent of water-soluble monomer, stablizer, water-soluble salt, deionized water is following:
Initiator is 0.05～1.4% of a water-soluble monomer quality;
Said water-soluble monomer is the water-soluble nonionic monomer, or soluble anionic monomers, or water-soluble nonionic monomer and soluble anionic monomers, or water-soluble nonionic monomer and water-soluble cationic monomer; Said stablizer is a water-soluble protein;
Process step is followed successively by:
(1) under agitation stablizer and deionized water are added reaction vessel;, stablizer adds water-soluble monomer and water-soluble salt after dissolving fully; Continuing to stir dissolves them fully; After water-soluble monomer and water-soluble salt dissolve fully, the pH value of formed mixed solution is transferred to 3.0～7.0, feed nitrogen then and remove oxygen;
(2) initiator is added reaction vessel, make the monomer in the mixed solution carry out free radical reaction at least 3 hours, promptly obtain water-in-water polymer dispersion in normal pressure, 20 ℃～85 ℃.
In above-mentioned water-in-water polymer dispersion and preparation method thereof, said water-soluble protein is at least a in gelatin, collagen protein, the Sunlover 10.Preferred 30KD～the 300KD of the molecular weight of gelatin or collagen protein.
In above-mentioned water-in-water polymer dispersion and preparation method thereof, the monomeric general structure of said water-soluble nonionic is following:
In the said structure general formula, R
1Be hydrogen or methyl, R
2And R
3Alkyl or hydroxyalkyl for hydrogen, 1～5 carbon atoms.
In above-mentioned water-in-water polymer dispersion and preparation method thereof, said water-soluble cationic monomer has multiple:
(1) the following cationic monomer of general structure:
In the said structure general formula, R
1Be hydrogen or methyl, Z
1Be O or NH or NR4, R4 is the alkyl that contains 1～4 carbon atoms, and Y is in following two groups:
In the above-mentioned group, Y
0And Y
1For containing the alkylidene group or the hydroxy alkylidene of 2～6 carbon atoms, Y
2, Y
3, Y
5, Y
6And Y
7For containing the alkyl of 1～6 carbon atoms, Z
-Be halogen or acetate or SO
4CH
3 -
(2) the following cationic monomer of general structure:
In the said structure general formula, Z
1Be O or NH or NR4, R4 is the alkyl that contains 1～4 carbon atoms, R
1Be hydrogen or methyl, R
0For containing the alkylidene group of 1～6 carbon atoms, R
5And R
6For containing the alkyl of 1～6 carbon atoms, R
7For containing alkyl, aryl and/or the aralkyl of 8～32 carbon atoms, Z
-Be halogen or acetate or SO
4CH
3 -
(3) dimethyl diallyl ammonium chloride.
In above-mentioned water-in-water polymer dispersion and preparation method thereof, said anionic monomer is double bond containing unsaturated carboxylic acid, carboxylic acid anhydride, and their ammonium salt, an alkali metal salt and alkaline earth salt; Or be double bond containing unsaturated sulfonic acid and their ammonium salt, an alkali metal salt and alkaline earth salt; Or be double bond containing unsaturated phosphonic acids and their ammonium salt, an alkali metal salt and alkaline earth salt; Or be acrylic amide and their ammonium salt, an alkali metal salt and the alkaline earth salt of sulfomethylation or phosphonatoization.
In above-mentioned water-in-water polymer dispersion and preparation method thereof, said water-soluble salt is at least a in sodium sulfate, ammonium sulfate, sal epsom, ammonium chloride, sodium-chlor, sodium phosphate, the Sodium phosphate, dibasic.
Among the above-mentioned water-in-water polymer dispersion preparation method, regulate the pH of mixed value and use weak acid, comprise organic acid and mineral acid, preferred acetate, formic acid, sulfuric acid or phosphoric acid.
Among the above-mentioned water-in-water polymer dispersion preparation method; Said initiator is a kind of in Potassium Persulphate, Sodium Persulfate, the ammonium persulphate; Or form by a kind of and sodium sulfite anhy 96 in them; Or be water-soluble azo thermal decomposition initiating [for example, two (two miaow base propane) dihydrochlorides of azo bis propane amine dihydrochloride or azo].
The present invention has following beneficial effect:
1, the method for the invention adopts water-soluble protein as polymerization stabilizer; Since the price of water-soluble protein be about cationic polymers 1/10th to 1/5th, be about 1/3rd of non-ionic polymers such as T 46155; Therefore compare with the method that the non-ionic polymers used as stabilizers prepares water-in-water polymer dispersion with adopting cationic polymers, cost reduces significantly.
2, gelatin and collagen protein can extract from a large amount of reluctant tanning wastes, and water-soluble soybean protein can extract from soybean residue, and the source is very abundant, thereby can realize the recycling of refuse, meet the development trend of green industry and green product.
3, the water-in-water polymer dispersion excellent property of the method for the invention preparation, the solid content of its polymkeric substance can reach 40wt%, at room temperature stably stored half a year at least, with cold water its dissolved time is no more than 7min.
4, use the method for the invention to prepare water-in-water polymer dispersion, can practice thrift the production energy, enhance productivity; Practice thrift the packing and the transportation cost of product; Reductionization material cost and shorteningization material time in use.
Embodiment
Through embodiment water-in-water polymer dispersion according to the invention and preparation method thereof is described further below.
Embodiment 1
In the present embodiment; Reaction vessel is the four-hole bottle that temperature controller, constant speed stirrer, prolong and constant voltage feeder are housed, and raw material is following: acrylamide monomer 20g, molecular weight are gelatin 0.8g, ammonium sulfate 18g, deionized water 61.2g, ammonium persulphate 0.02g and the sodium sulfite anhy 96 0.02g of 100KD.
Process step is followed successively by:
(1) under agitation gelatin and deionized water are added reaction vessel in room temperature;, gelatin adds acrylamide monomer and ammonium sulfate after dissolving fully; Continuing to stir dissolves them fully; After acrylamide monomer and ammonium sulfate dissolve fully, with acetate the pH value of formed mixed solution is transferred to 4.6, feed nitrogen then and remove oxygen (about 30min of time);
(2) ammonium persulphate and sodium sulfite anhy 96 are added reaction vessel, be warming up to 40 ℃, make the monomer in the mixed solution carry out free radical reaction 4 hours, promptly obtain milky water bag water polyacrylamide dispersion in normal pressure, 40 ℃.The AV of said dispersion-s is 4.36 * 10
4MPas, median size is about 1.3 μ m.
Embodiment 2
In the present embodiment; Reaction vessel is the four-hole bottle that temperature controller, constant speed stirrer, prolong and constant voltage feeder are housed, and raw material is following: methyl acrylamide monomer 20g, molecular weight are gelatin 1.2g, ammonium sulfate 18g, deionized water 60.8g, ammonium persulphate 0.02g and the sodium sulfite anhy 96 0.02g of 100KD.
Process step is followed successively by:
(1) under agitation gelatin and deionized water are added reaction vessel in room temperature;, gelatin adds methyl acrylamide monomer and ammonium sulfate after dissolving fully; Continuing to stir dissolves them fully; After methyl acrylamide monomer and ammonium sulfate dissolve fully, with acetate the pH value of formed mixed solution is transferred to 4.6, feed nitrogen then and remove oxygen (about 30min of time);
(2) ammonium persulphate and sodium sulfite anhy 96 are added reaction vessel, be warming up to 40 ℃, make the monomer in the mixed solution carry out free radical reaction 5 hours, promptly obtain milky water bag water polyacrylamide dispersion in normal pressure, 40 ℃.The AV of said dispersion-s is 4.68 * 10
4MPas, median size is about 1.45 μ m.
Embodiment 3
In the present embodiment; Reaction vessel is the four-hole bottle that temperature controller, constant speed stirrer, prolong and constant voltage feeder are housed, and raw material is following: acrylamide monomer 25g, molecular weight are gelatin 0.8g, ammonium sulfate 18g, deionized water 56.2g, ammonium persulphate 0.02g and the sodium sulfite anhy 96 0.02g of 100KD.
Process step is followed successively by:
(1) under agitation gelatin and deionized water are added reaction vessel in room temperature;, gelatin adds acrylamide monomer and ammonium sulfate after dissolving fully; Continuing to stir dissolves them fully; After acrylamide monomer and ammonium sulfate dissolve fully, with acetate the pH value of formed mixed solution is transferred to 4.8, feed nitrogen then and remove oxygen (about 30min of time);
(2) ammonium persulphate and sodium sulfite anhy 96 are added reaction vessel, be warming up to 30 ℃, make the monomer in the mixed solution carry out free radical reaction 4 hours, promptly obtain milky water bag water polyacrylamide dispersion in normal pressure, 30 ℃.The AV of said dispersion-s is 5.26 * 10
4MPas, median size is about 0.8 μ m.
Embodiment 4
In the present embodiment; Reaction vessel is the four-hole bottle that temperature controller, constant speed stirrer, prolong and constant voltage feeder are housed, and raw material is following: acrylamide monomer 10g, methyl acrylamide monomer 10g, molecular weight are gelatin 0.8g, ammonium sulfate 18g, deionized water 61.2g, ammonium persulphate 0.02g and the sodium sulfite anhy 96 0.02g of 100KD.
Process step is followed successively by:
(1) under agitation gelatin and deionized water are added reaction vessel in room temperature;, gelatin adds acrylamide monomer, methyl acrylamide monomer and ammonium sulfate after dissolving fully; Continuing to stir dissolves them fully; After acrylamide monomer, methyl acrylamide monomer and ammonium sulfate dissolve fully, with formic acid the pH value of formed mixed solution is transferred to 4.2, feed nitrogen then and remove oxygen (about 30min of time);
(2) ammonium persulphate and sodium sulfite anhy 96 are added reaction vessel, be warming up to 35 ℃, make the monomer in the mixed solution carry out free radical reaction 4 hours, promptly obtain milky water bag water polyacrylamide dispersion in normal pressure, 35 ℃.The AV of said dispersion-s is 3.6 * 10
4MPas, median size is about 1.60 μ m.
Embodiment 5
In the present embodiment; Reaction vessel is the four-hole bottle that temperature controller, constant speed stirrer, prolong and constant voltage feeder are housed, and raw material is following: acrylamide monomer 30g, molecular weight are gelatin 2g, ammonium sulfate 10g, deionized water 58g, Potassium Persulphate 0.02g and the sodium sulfite anhy 96 0.02g of 50KD.
Process step is followed successively by:
(1) under agitation gelatin and deionized water are added reaction vessel in room temperature;, gelatin adds acrylamide monomer and ammonium sulfate after dissolving fully; Continuing to stir dissolves them fully; After acrylamide monomer and ammonium sulfate dissolve fully, with formic acid the pH value of formed mixed solution is transferred to 4.6, feed nitrogen then and remove oxygen (about 30min of time);
(2) Potassium Persulphate and sodium sulfite anhy 96 are added reaction vessel, be warming up to 40 ℃, make the monomer in the mixed solution carry out free radical reaction 4 hours, promptly obtain the water bag water polyacrylamide dispersion of milk yellow in normal pressure, 40 ℃.The AV of said dispersion-s is 1.4 * 10
4MPas, median size is about 0.75 μ m.
Embodiment 6
In the present embodiment; Reaction vessel is the four-hole bottle that temperature controller, constant speed stirrer, prolong and constant voltage feeder are housed, and raw material is following: acrylamide monomer 40g, molecular weight are gelatin 4.0g, ammonium sulfate 32g, deionized water 24g, Potassium Persulphate 0.02g and the sodium sulfite anhy 96 0.02g of 30KD.
Process step is followed successively by:
(1) under agitation gelatin and deionized water are added reaction vessel in room temperature;, gelatin adds acrylamide monomer and ammonium sulfate after dissolving fully; Continuing to stir dissolves them fully; After acrylamide monomer and ammonium sulfate dissolve fully, with formic acid the pH value of formed mixed solution is transferred to 3.0, feed nitrogen then and remove oxygen (about 30min of time);
(2) Potassium Persulphate and sodium sulfite anhy 96 are added reaction vessel, be warming up to 40 ℃, make the monomer in the mixed solution carry out free radical reaction 4 hours, promptly obtain the water bag water polyacrylamide dispersion of milk yellow in normal pressure, 40 ℃.The AV of said dispersion-s is 2.4 * 10
4MPas, median size is about 0.25 μ m.
Embodiment 7
In the present embodiment; Reaction vessel is the four-hole bottle that temperature controller, constant speed stirrer, prolong and constant voltage feeder are housed, and raw material is following: methyl acrylamide monomer 8g, molecular weight are collagen protein 0.15g, ammonium sulfate 19.85g, deionized water 72g, ammonium persulphate 0.02g and the sodium sulfite anhy 96 0.02g of 300KD.
Process step is followed successively by:
(1) under agitation collagen protein and deionized water are added reaction vessel in room temperature;, collagen protein adds methyl acrylamide monomer and ammonium sulfate after dissolving fully; Continuing to stir dissolves them fully; After methyl acrylamide monomer and ammonium sulfate dissolve fully, with sulfuric acid the pH value of formed mixed solution is transferred to 4.6, feed nitrogen then and remove oxygen (about 30min of time);
(2) ammonium persulphate and sodium sulfite anhy 96 are added reaction vessel, be warming up to 20 ℃, make the monomer in the mixed solution carry out free radical reaction 6 hours, promptly obtain milky water bag water polyacrylamide dispersion in normal pressure, 20 ℃.The AV of said dispersion-s is 7.24 * 10
4MPas, median size is about 1.69 μ m.
Embodiment 8
In the present embodiment, reaction vessel is the four-hole bottle that temperature controller, constant speed stirrer, prolong and constant voltage feeder are housed, and raw material is following: acrylamide monomer 25g, water-soluble soybean protein 3g, ammonium sulfate 15g, deionized water 57g, Sodium Persulfate 0.04g.
Process step is followed successively by:
(1) under agitation water-soluble soybean protein and deionized water are added reaction vessel in room temperature;, water-soluble soybean protein adds acrylamide monomer and ammonium sulfate after dissolving fully; Continuing to stir dissolves them fully; After acrylamide monomer and ammonium sulfate dissolve fully, with sulfuric acid the pH value of formed mixed solution is transferred to 4.6, feed nitrogen then and remove oxygen (about 30min of time);
(2) Sodium Persulfate is added reaction vessel, be warming up to 80 ℃, make the monomer in the mixed solution carry out free radical reaction 4 hours, promptly obtain milky water bag water polyacrylamide dispersion in normal pressure, 80 ℃.Said dispersion-s AV is greater than 10.0 * 10
4MPas, median size is about 1.78 μ m.
Embodiment 9
In the present embodiment; Reaction vessel is the four-hole bottle that temperature controller, constant speed stirrer, prolong and constant voltage feeder are housed; Raw material is following: N, collagen protein 0.8g, ammonium sulfate 15g, deionized water 64.2g, ammonium persulphate 0.02g and the sodium sulfite anhy 96 0.02g of N-DMAA monomer 10g, acrylamide monomer 10g, 100KD.
Process step is followed successively by:
(1) under agitation collagen protein and deionized water are added reaction vessel in room temperature; After collagen protein dissolves fully, add N, N-DMAA monomer, acrylamide monomer and ammonium sulfate continue stirring they are dissolved fully; Work as N; After N-DMAA monomer, acrylamide monomer and ammonium sulfate dissolve fully, the pH value of formed mixed solution is transferred to 4.6, feed nitrogen then and remove oxygen (about 30min of time) with phosphoric acid;
(2) ammonium persulphate and sodium sulfite anhy 96 are added reaction vessel, be warming up to 30 ℃, make the monomer in the mixed solution carry out free radical reaction 4 hours, promptly obtain milky water bag water dispersion in normal pressure, 30 ℃.Said dispersion-s AV is greater than 11.8 * 10
4MPas, median size is about 1.68 μ m.
Embodiment 10
In the present embodiment; Reaction vessel is the four-hole bottle that temperature controller, constant speed stirrer, prolong and constant voltage feeder are housed, and raw material is following: dimethyldiallylammonchloride chloride monomer 2g, methyl acrylamide monomer 18g, water-soluble soybean protein 0.8g, ammonium sulfate 25g, deionized water 54.2g, Potassium Persulphate 0.04g.
Process step is followed successively by:
(1) under agitation water-soluble soybean protein and deionized water are added reaction vessel in room temperature;, water-soluble soybean protein adds dimethyldiallylammonchloride chloride monomer, methyl acrylamide monomer and ammonium sulfate after dissolving fully; Continuing to stir dissolves them fully; After dimethyldiallylammonchloride chloride monomer, methyl acrylamide monomer and ammonium sulfate dissolve fully, with phosphoric acid the pH value of formed mixed solution is transferred to 4.6, feed nitrogen then and remove oxygen (about 30min of time);
(2) Potassium Persulphate is added reaction vessel, be warming up to 82 ℃, make the monomer in the mixed solution carry out free radical reaction 4 hours, promptly obtain milky water bag water dispersion in normal pressure, 82 ℃.The AV of said dispersion-s is 4.12 * 10
4MPas, median size is about 1.25 μ m.
Embodiment 11
In the present embodiment; Reaction vessel is the four-hole bottle that temperature controller, constant speed stirrer, prolong and constant voltage feeder are housed; Raw material is following: acrylamide monomer 12g, (methyl) acrylyl oxy-ethyl-trimethyl salmiac monomer 8.0g, molecular weight is gelatin 0.8g, ammonium sulfate 18g, deionized water 61.2g, ammonium persulphate 0.02g and the sodium sulfite anhy 96 0.02g of 100KD.
Process step is followed successively by:
(1) under agitation gelatin and deionized water are added reaction vessel in room temperature;, gelatin adds acrylamide monomer, (methyl) acrylyl oxy-ethyl-trimethyl salmiac monomer and ammonium sulfate after dissolving fully; Continuing to stir dissolves them fully; After acrylamide monomer, (methyl) acrylyl oxy-ethyl-trimethyl salmiac monomer and ammonium sulfate dissolve fully, with formic acid the pH value of formed mixed solution is transferred to 4.6, feed nitrogen then and remove oxygen (about 30min of time);
(2) ammonium persulphate and sodium sulfite anhy 96 are added reaction vessel, be warming up to 40 ℃, make the monomer in the mixed solution carry out free radical reaction 4 hours, promptly obtain milky water bag water dispersion in normal pressure, 40 ℃.The AV of said dispersion-s is 4.02 * 10
4MPas, median size is about 1.18 μ m.
Embodiment 12
In the present embodiment; Reaction vessel is the four-hole bottle that temperature controller, constant speed stirrer, prolong and constant voltage feeder are housed; Raw material is following: methyl acrylamide monomer 8g, methacryloyl amido propyl-dimethyl benzyl ammonium chloride monomer 8g, molecular weight is gelatin 0.8g, ammonium sulfate 18g, deionized water 65.2g, ammonium persulphate 0.02g and the sodium sulfite anhy 96 0.02g of 100KD.
Process step is followed successively by:
(1) under agitation gelatin and deionized water are added reaction vessel in room temperature;, gelatin adds methyl acrylamide monomer, methacryloyl amido propyl-dimethyl benzyl ammonium chloride monomer and ammonium sulfate after dissolving fully; Continuing to stir dissolves them fully; After methyl acrylamide monomer, methacryloyl amido propyl-dimethyl benzyl ammonium chloride monomer and ammonium sulfate dissolve fully; With formic acid the pH value of formed mixed solution is transferred to 4.6, feed nitrogen then and remove oxygen (about 30min of time);
(2) ammonium persulphate and sodium sulfite anhy 96 are added reaction vessel, be warming up to 40 ℃, make the monomer in the mixed solution carry out free radical reaction 4 hours, promptly obtain milky water bag water dispersion in normal pressure, 40 ℃.The AV of said dispersion-s is 4.14 * 10
4MPas, median size is about 1.28 μ m.
Embodiment 13
In the present embodiment; Reaction vessel is the four-hole bottle that temperature controller, constant speed stirrer, prolong and constant voltage feeder are housed; Raw material is following: methyl acrylamide monomer 17g, methacrylic acid monomer 3g, molecular weight are gelatin 0.8g, ammonium sulfate 18g, deionized water 61.2g, Sodium Persulfate 0.02g and the sodium sulfite anhy 96 0.02g of 100KD.
Process step is followed successively by:
(1) under agitation gelatin and deionized water are added reaction vessel in room temperature;, gelatin adds methyl acrylamide monomer, methacrylic acid monomer and ammonium sulfate after dissolving fully; Continuing to stir dissolves them fully; After methyl acrylamide monomer, methacrylic acid monomer and ammonium sulfate dissolve fully, with formic acid the pH value of formed mixed solution is transferred to 4.8, feed nitrogen then and remove oxygen (about 30min of time);
(2) Sodium Persulfate and sodium sulfite anhy 96 are added reaction vessel, be warming up to 40 ℃, make the monomer in the mixed solution carry out free radical reaction 4 hours, promptly obtain milky water bag water dispersion in normal pressure, 40 ℃.The AV of said dispersion-s is 4.34 * 10
4MPas, median size is about 1.29 μ m.
Embodiment 14
In the present embodiment; Reaction vessel is the four-hole bottle that temperature controller, constant speed stirrer, prolong and constant voltage feeder are housed; Raw material is following: acrylamide monomer 17g, Acrylic Acid Monomer 8g, molecular weight are gelatin 1g, ammonium sulfate 18g, deionized water 56g, ammonium persulphate 0.02g and the sodium sulfite anhy 96 0.02g of 100KD.
Process step is followed successively by:
(1) under agitation gelatin and deionized water are added reaction vessel in room temperature;, gelatin adds acrylamide monomer, Acrylic Acid Monomer and ammonium sulfate after dissolving fully; Continuing to stir dissolves them fully; After acrylamide monomer, Acrylic Acid Monomer and ammonium sulfate dissolve fully, with formic acid the pH value of formed mixed solution is transferred to 7.0, feed nitrogen then and remove oxygen (about 30min of time);
(2) ammonium persulphate and sodium sulfite anhy 96 are added reaction vessel, be warming up to 40 ℃, make the monomer in the mixed solution carry out free radical reaction 4 hours, promptly obtain milky water bag water dispersion in normal pressure, 40 ℃.The AV of said dispersion-s is 4.50 * 10
4MPas, median size is about 1.19 μ m.
Embodiment 15
In the present embodiment; Reaction vessel is the four-hole bottle that temperature controller, constant speed stirrer, prolong and constant voltage feeder are housed, and raw material is following: acrylamide monomer 20g, molecular weight are gelatin 2g, ammonium sulfate 18g, deionized water 60g, ammonium persulphate 0.005g and the sodium sulfite anhy 96 0.005g of 100KD.
Process step is followed successively by:
(1) under agitation gelatin and deionized water are added reaction vessel in room temperature;, gelatin adds acrylamide monomer and ammonium sulfate after dissolving fully; Continuing to stir dissolves them fully; After acrylamide monomer and ammonium sulfate dissolve fully, with acetate the pH value of formed mixed solution is transferred to 4.6, feed nitrogen then and remove oxygen (about 30min of time);
(2) ammonium persulphate and sodium sulfite anhy 96 are added reaction vessel, be warming up to 40 ℃, make the monomer in the mixed solution carry out free radical reaction 4 hours, promptly obtain milky water bag water polyacrylamide dispersion in normal pressure, 40 ℃.The AV of said dispersion-s is 4.36 * 10
4MPas, median size is about 1.50 μ m.
Embodiment 16
In the present embodiment; Reaction vessel is the four-hole bottle that temperature controller, constant speed stirrer, prolong and constant voltage feeder are housed, and raw material is following: acrylamide monomer 20g, molecular weight are gelatin 0.8g, ammonium sulfate 18g, deionized water 61.2g, ammonium persulphate 0.14g and the sodium sulfite anhy 96 0.14g of 100KD.
Process step is followed successively by:
(1) under agitation gelatin and deionized water are added reaction vessel in room temperature;, gelatin adds acrylamide monomer and ammonium sulfate after dissolving fully; Continuing to stir dissolves them fully; After acrylamide monomer and ammonium sulfate dissolve fully, with acetate the pH value of formed mixed solution is transferred to 4.6, feed nitrogen then and remove oxygen (about 30min of time);
(2) ammonium persulphate and sodium sulfite anhy 96 are added reaction vessel, be warming up to 40 ℃, make the monomer in the mixed solution carry out free radical reaction 4 hours, promptly obtain milky water bag water polyacrylamide dispersion in normal pressure, 40 ℃.The AV of said dispersion-s is 1.95 * 10
4MPas, median size is about 1.58 μ m.
Embodiment 17
In the present embodiment; Reaction vessel is the four-hole bottle that temperature controller, constant speed stirrer, prolong and constant voltage feeder are housed, and raw material is following: acrylamide monomer 20g, molecular weight are two (two miaow base propane) dihydrochloride (V044) 0.08g of gelatin 0.5g, ammonium sulfate 18g, deionized water 61.5g, azo of 100KD.
Process step is followed successively by:
(1) under agitation gelatin and deionized water are added reaction vessel in room temperature;, gelatin adds acrylamide monomer and ammonium sulfate after dissolving fully; Continuing to stir dissolves them fully; After acrylamide monomer and ammonium sulfate dissolve fully, with acetate the pH value of formed mixed solution is transferred to 4.6, feed nitrogen then and remove oxygen (about 30min of time);
(2) two (the two miaow base propane) dihydrochlorides of azo are added reaction vessel, be warming up to 30 ℃, make the monomer in the mixed solution carry out free radical reaction 4.5 hours, promptly obtain milky water bag water polyacrylamide dispersion in normal pressure, 30 ℃.The AV of said dispersion-s is 5.28 * 10
4MPas, median size is about 1.18 μ m.
Embodiment 18
In the present embodiment; Reaction vessel is the four-hole bottle that temperature controller, constant speed stirrer, prolong and constant voltage feeder are housed, and raw material is following: methyl acrylamide monomer 40g, molecular weight are gelatin 0.8g, ammonium sulfate 10g, ammonium chloride 8g, deionized water 41.2g, ammonium persulphate 0.02g and the sodium sulfite anhy 96 0.02g of 100KD.
Process step is followed successively by:
(1) under agitation gelatin and deionized water are added reaction vessel in room temperature;, gelatin adds methyl acrylamide monomer, ammonium sulfate and ammonium chloride after dissolving fully; Continuing to stir dissolves them fully; After methyl acrylamide monomer, ammonium sulfate and ammonium chloride dissolve fully, with acetate the pH value of formed mixed solution is transferred to 4.6, feed nitrogen then and remove oxygen (about 30min of time);
(2) ammonium persulphate and sodium sulfite anhy 96 are added reaction vessel, be warming up to 40 ℃, make the monomer in the mixed solution carry out free radical reaction 4 hours, promptly obtain milky water bag water polyacrylamide dispersion in normal pressure, 40 ℃.The AV of said dispersion-s is 5.26 * 10
4MPas, median size is about 1.37 μ m.
Embodiment 19
In the present embodiment; Reaction vessel is the four-hole bottle that temperature controller, constant speed stirrer, prolong and constant voltage feeder are housed, and raw material is following: acrylamide monomer 20g, water-soluble soybean protein 3g, ammonium sulfate 12g, ammonium chloride 6g, deionized water 59g, Sodium Persulfate 0.02g and sodium sulfite anhy 96 0.02g.
Process step is followed successively by:
(1) under agitation water-soluble soybean protein and deionized water are added reaction vessel in room temperature;, water-soluble soybean protein adds acrylamide monomer, ammonium sulfate and ammonium chloride after dissolving fully; Continuing to stir dissolves them fully; After acrylamide monomer, ammonium sulfate and ammonium chloride dissolve fully, with acetate the pH value of formed mixed solution is transferred to 4.6, feed nitrogen then and remove oxygen (about 30min of time);
(2) Sodium Persulfate and sodium sulfite anhy 96 are added reaction vessel, be warming up to 40 ℃, make the monomer in the mixed solution carry out free radical reaction 4 hours, promptly obtain milky water bag water polyacrylamide dispersion in normal pressure, 40 ℃.The AV of said dispersion-s is 5.13 * 10
4MPas, median size is about 1.34 μ m.
Embodiment 20
In the present embodiment; Reaction vessel is the four-hole bottle that temperature controller, constant speed stirrer, prolong and constant voltage feeder are housed, and raw material is following: acrylamide monomer 20g, molecular weight are gelatin 0.8g, ammonium sulfate 8g, sodium sulfate 12g, deionized water 61.2g, azo bis propane amine dihydrochloride (V50) 0.1g of 100KD.
Process step is followed successively by:
(1) under agitation gelatin and deionized water are added reaction vessel in room temperature;, gelatin adds acrylamide monomer, ammonium sulfate and sodium sulfate after dissolving fully; Continuing to stir dissolves them fully; After acrylamide monomer, ammonium sulfate and sodium sulfate dissolve fully, with acetate the pH value of formed mixed solution is transferred to 4.6, feed nitrogen then and remove oxygen (about 30min of time);
(2) azo bis propane amine dihydrochloride is added reaction vessel, be warming up to 50 ℃, make the monomer in the mixed solution carry out free radical reaction 4 hours, promptly obtain milky water bag water polyacrylamide dispersion in normal pressure, 50 ℃.The AV of said dispersion-s is 5.10 * 10
4MPas, median size is about 1.36 μ m.
Embodiment 21
In the present embodiment; Reaction vessel is the four-hole bottle that temperature controller, constant speed stirrer, prolong and constant voltage feeder are housed, and raw material is following: methyl acrylamide monomer 30g, molecular weight are gelatin 0.8g, ammonium sulfate 10g, sodium phosphate 8g, deionized water 51.2g, the ammonium persulphate 0.04g of 100KD.
Process step is followed successively by:
(1) under agitation gelatin and deionized water are added reaction vessel in room temperature;, gelatin adds methyl acrylamide monomer, ammonium sulfate and sodium phosphate after dissolving fully; Continuing to stir dissolves them fully; After methyl acrylamide monomer, ammonium sulfate and sodium phosphate dissolve fully, with acetate the pH value of formed mixed solution is transferred to 6.8, feed nitrogen then and remove oxygen (about 30min of time);
(2) ammonium persulphate is added reaction vessel, be warming up to 85 ℃, make the monomer in the mixed solution carry out free radical reaction 5 hours, promptly obtain milky water bag water polyacrylamide dispersion in normal pressure, 85 ℃.The AV of said dispersion-s is 4.98 * 10
4MPas, median size is about 1.42 μ m.
Claims (10)
1. water-in-water polymer dispersion is characterized in that the polymkeric substance, water-soluble protein, water-soluble salt and the deionized water that are formed by water-soluble monomer form, and the mass percent of each component is following:
A kind of in the polymkeric substance of polymkeric substance, water-soluble nonionic monomer and soluble anionic monomers formation that the polymkeric substance that the polymkeric substance that the polymkeric substance that said water-soluble monomer forms forms for the water-soluble nonionic monomer, soluble anionic monomers form, water-soluble nonionic monomer and water-soluble cationic monomer form.
2. water-in-water polymer dispersion according to claim 1 is characterized in that water-soluble protein is at least a in gelatin, collagen protein, the Sunlover 10.
3. water-in-water polymer dispersion according to claim 2, the molecular weight that it is characterized in that gelatin or collagen protein is 30KD～300KD.
4. according to the described water-in-water polymer dispersion of arbitrary claim in the claim 1 to 3, it is characterized in that the monomeric general structure of said water-soluble nonionic is following:
In the said structure general formula, R
1Be hydrogen or methyl, R
2And R
3Alkyl or hydroxyalkyl for hydrogen, 1～5 carbon atoms; The general structure of said water-soluble cationic monomer is following:
In the said structure general formula, R
1Be hydrogen or methyl, Z
1Be O or NH or NR4, R4 is the alkyl that contains 1～4 carbon atoms, and Y is in following two groups:
In the above-mentioned group, Y
0And Y
1For containing the alkylidene group or the hydroxy alkylidene of 2～6 carbon atoms, Y
2, Y
3, Y
5, Y
6And Y
7For containing the alkyl of 1～6 carbon atoms, Z
-Be halogen or acetate or SO
4CH
3 -
Or the general structure of said water-soluble cationic monomer is following:
In the said structure general formula, Z
1Be O or NH or NR4, R4 is the alkyl that contains 1～4 carbon atoms, R
1Be hydrogen or methyl, R
0For containing the alkylidene group of 1～6 carbon atoms, R
5And R
6For containing the alkyl of 1～6 carbon atoms, R
7For containing alkyl, aryl and/or the aralkyl of 8～32 carbon atoms, Z
-Be halogen or acetate or SO
4CH
3 -
Or said water-soluble cationic monomer is a dimethyl diallyl ammonium chloride;
Said soluble anionic monomers is double bond containing unsaturated carboxylic acid, carboxylic acid anhydride, and their ammonium salt, an alkali metal salt and alkaline earth salt; Or be double bond containing unsaturated sulfonic acid and their ammonium salt, an alkali metal salt and alkaline earth salt; Or be double bond containing unsaturated phosphonic acids and their ammonium salt, an alkali metal salt and alkaline earth salt; Or be acrylic amide and their ammonium salt, an alkali metal salt and the alkaline earth salt of sulfomethylation or phosphonatoization.
5. according to the described water-in-water polymer dispersion of arbitrary claim in the claim 1 to 3, it is characterized in that said water-soluble salt is at least a in sodium sulfate, ammonium sulfate, sal epsom, ammonium chloride, sodium-chlor, sodium phosphate, the Sodium phosphate, dibasic.
6. the preparation method of the said water-in-water polymer dispersion of claim 1; It is characterized in that raw material is water-soluble monomer, stablizer, water-soluble salt, deionized water and initiator, the mass percent of water-soluble monomer, stablizer, water-soluble salt, deionized water is following:
Initiator is 0.05～1.4% of a water-soluble monomer quality;
Said water-soluble monomer is the water-soluble nonionic monomer, or soluble anionic monomers, or water-soluble nonionic monomer and soluble anionic monomers, or water-soluble nonionic monomer and water-soluble cationic monomer; Said stablizer is a water-soluble protein;
Process step is followed successively by:
(1) under agitation stablizer and deionized water are added reaction vessel;, stablizer adds water-soluble monomer and water-soluble salt after dissolving fully; Continuing to stir dissolves them fully; After water-soluble monomer and water-soluble salt dissolve fully, the pH value of formed mixed solution is transferred to 3.0～7.0, feed nitrogen then and remove oxygen;
(2) initiator is added reaction vessel, make the monomer in the mixed solution carry out free radical reaction at least 3 hours, promptly obtain water-in-water polymer dispersion in normal pressure, 20 ℃～85 ℃.
7. according to the preparation method of the said water-in-water polymer dispersion of claim 6, it is characterized in that water-soluble protein is at least a in gelatin, collagen protein, the Sunlover 10.
8. according to the preparation method of the said water-in-water polymer dispersion of claim 7,, the molecular weight that it is characterized in that gelatin or collagen protein is 30KD～300KD.
9. according to the preparation method of the said water-in-water polymer dispersion of arbitrary claim in the claim 6 to 8, it is characterized in that the monomeric general structure of said water-soluble nonionic is following:
In the said structure general formula, R
1Be hydrogen or methyl, R
2And R
3Alkyl or hydroxyalkyl for hydrogen, 1～5 carbon atoms;
The general structure of said water-soluble cationic monomer is following:
In the said structure general formula, R
1Be hydrogen or methyl, Z
1Be O or NH or NR4, R4 is the alkyl that contains 1～4 carbon atoms, and Y is in following two groups:
In the above-mentioned group, Y
0And Y
1For containing the alkylidene group or the hydroxy alkylidene of 2～6 carbon atoms, Y
2, Y
3, Y
5, Y
6And Y
7For containing the alkyl of 1～6 carbon atoms, Z
-Be halogen or acetate or SO
4CH
3 -
Or the general structure of said water-soluble cationic monomer is following:
In the said structure general formula, Z
1Be O or NH or NR4, R4 is the alkyl that contains 1～4 carbon atoms, R
1Be hydrogen or methyl, R
0For containing the alkylidene group of 1～6 carbon atoms, R
5And R
6For containing the alkyl of 1～6 carbon atoms, R
7For containing alkyl, aryl and/or the aralkyl of 8～32 carbon atoms, Z
-Be halogen or acetate or SO
4CH
3 -
Or said water-soluble cationic monomer is a dimethyl diallyl ammonium chloride;
Said soluble anionic monomers is double bond containing unsaturated carboxylic acid, carboxylic acid anhydride, and their ammonium salt, an alkali metal salt and alkaline earth salt; Or be double bond containing unsaturated sulfonic acid and their ammonium salt, an alkali metal salt and alkaline earth salt; Or be double bond containing unsaturated phosphonic acids and their ammonium salt, an alkali metal salt and alkaline earth salt; Or be acrylic amide and their ammonium salt, an alkali metal salt and the alkaline earth salt of sulfomethylation or phosphonatoization.
10. according to the preparation method of the said water-in-water polymer dispersion of arbitrary claim in the claim 6 to 8, it is characterized in that said water-soluble salt is at least a in sodium sulfate, ammonium sulfate, sal epsom, ammonium chloride, sodium-chlor, sodium phosphate, the Sodium phosphate, dibasic;
Said initiator is a kind of in Potassium Persulphate, Sodium Persulfate, the ammonium persulphate, or is made up of a kind of and sodium sulfite anhy 96 in Potassium Persulphate, Sodium Persulfate, the ammonium persulphate, or is the water-soluble azo thermal decomposition initiating.
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| CN107337940A (en) * | 2017-06-28 | 2017-11-10 | 常州文诺纺织品有限公司 | A kind of preparation method of titanium dioxide suspension stabilizer |
| CN113150207A (en) * | 2021-03-11 | 2021-07-23 | 西安长庆化工集团有限公司 | Water-in-water polymer dispersion and preparation method thereof |
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| JP2006182816A (en) * | 2004-12-27 | 2006-07-13 | Hymo Corp | Crosslinked water-soluble polymer dispersion liquid and paper making method using the same |
| CN1884324A (en) * | 2006-05-23 | 2006-12-27 | 青岛科技大学 | Cation acrylamide copolymer water-in-water emulsion and its preparation method |
| CN101735388A (en) * | 2009-12-25 | 2010-06-16 | 同济大学 | Preparation method of water-in-water cation polyacrylamide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006182816A (en) * | 2004-12-27 | 2006-07-13 | Hymo Corp | Crosslinked water-soluble polymer dispersion liquid and paper making method using the same |
| CN1884324A (en) * | 2006-05-23 | 2006-12-27 | 青岛科技大学 | Cation acrylamide copolymer water-in-water emulsion and its preparation method |
| CN101735388A (en) * | 2009-12-25 | 2010-06-16 | 同济大学 | Preparation method of water-in-water cation polyacrylamide |
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| CN107337940A (en) * | 2017-06-28 | 2017-11-10 | 常州文诺纺织品有限公司 | A kind of preparation method of titanium dioxide suspension stabilizer |
| CN107337940B (en) * | 2017-06-28 | 2018-10-02 | 上海深竹化工科技有限公司 | A kind of preparation method of titanium dioxide suspension stabilizer |
| CN107325299A (en) * | 2017-08-16 | 2017-11-07 | 山东诺尔生物科技有限公司 | A kind of method for preparing water-in-water type non-ionic polyacrylamide |
| CN113150207A (en) * | 2021-03-11 | 2021-07-23 | 西安长庆化工集团有限公司 | Water-in-water polymer dispersion and preparation method thereof |
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