CN1286866C - Double water-phase polymerization method for composite disperse medium field of water soluble polymer or copolymer - Google Patents
Double water-phase polymerization method for composite disperse medium field of water soluble polymer or copolymer Download PDFInfo
- Publication number
- CN1286866C CN1286866C CN 200410089586 CN200410089586A CN1286866C CN 1286866 C CN1286866 C CN 1286866C CN 200410089586 CN200410089586 CN 200410089586 CN 200410089586 A CN200410089586 A CN 200410089586A CN 1286866 C CN1286866 C CN 1286866C
- Authority
- CN
- China
- Prior art keywords
- water
- soluble
- polymerization
- composite
- double
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 82
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 229920003169 water-soluble polymer Polymers 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 24
- 229920001577 copolymer Polymers 0.000 title claims description 3
- 239000000178 monomer Substances 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003999 initiator Substances 0.000 claims abstract description 21
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 11
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 11
- 230000000977 initiatory effect Effects 0.000 claims abstract description 5
- 239000008346 aqueous phase Substances 0.000 claims description 31
- 239000002612 dispersion medium Substances 0.000 claims description 26
- 239000002609 medium Substances 0.000 claims description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 15
- -1 polyoxyethylene Polymers 0.000 claims description 11
- 238000007334 copolymerization reaction Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 229920002401 polyacrylamide Polymers 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 5
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 3
- 150000003016 phosphoric acids Chemical class 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 22
- 229920000642 polymer Polymers 0.000 abstract description 12
- 239000002270 dispersing agent Substances 0.000 abstract description 10
- 239000000243 solution Substances 0.000 abstract description 6
- 229920000578 graft copolymer Polymers 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 239000012267 brine Substances 0.000 abstract 1
- 238000005191 phase separation Methods 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 abstract 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 abstract 1
- 239000000047 product Substances 0.000 description 70
- 239000006185 dispersion Substances 0.000 description 29
- 239000012071 phase Substances 0.000 description 26
- 238000003756 stirring Methods 0.000 description 25
- 239000007864 aqueous solution Substances 0.000 description 16
- 230000009466 transformation Effects 0.000 description 16
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 14
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 14
- 235000011130 ammonium sulphate Nutrition 0.000 description 14
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 13
- 238000007789 sealing Methods 0.000 description 12
- 230000031709 bromination Effects 0.000 description 9
- 238000005893 bromination reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229910017053 inorganic salt Inorganic materials 0.000 description 9
- 235000015110 jellies Nutrition 0.000 description 7
- 239000008274 jelly Substances 0.000 description 7
- 239000012266 salt solution Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 241000237502 Ostreidae Species 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 238000005352 clarification Methods 0.000 description 4
- 235000020636 oyster Nutrition 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 229920002307 Dextran Polymers 0.000 description 3
- CDGOGRINGXZSJO-UHFFFAOYSA-N [Cl-].C[NH+](C)C.C(C=C)(=O)OC=C Chemical compound [Cl-].C[NH+](C)C.C(C=C)(=O)OC=C CDGOGRINGXZSJO-UHFFFAOYSA-N 0.000 description 3
- 150000003926 acrylamides Chemical class 0.000 description 3
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004815 dispersion polymer Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- RXWMEZGISAOCEY-UHFFFAOYSA-N [Cl-].C[NH+](C)C.C(C=C)(=O)OC=C.C[NH+](C)C.[Cl-] Chemical compound [Cl-].C[NH+](C)C.C(C=C)(=O)OC=C.C[NH+](C)C.[Cl-] RXWMEZGISAOCEY-UHFFFAOYSA-N 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 235000010419 agar Nutrition 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- WPKYZIPODULRBM-UHFFFAOYSA-N azane;prop-2-enoic acid Chemical class N.OC(=O)C=C WPKYZIPODULRBM-UHFFFAOYSA-N 0.000 description 1
- DZGUJOWBVDZNNF-UHFFFAOYSA-N azanium;2-methylprop-2-enoate Chemical class [NH4+].CC(=C)C([O-])=O DZGUJOWBVDZNNF-UHFFFAOYSA-N 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229920000591 gum Polymers 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000015598 salt intake Nutrition 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical class Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The present invention discloses a double water phase polymerizing method of a composite dispersing medium field for synthesizing water solution polymers. In the method, a certain quantity of water-soluble vinyl monomers are dissolved in a brine solution which can form double water phase together with polymers; simultaneously, a certain quantity of water-soluble polymers are added as composite dispersing agents; water-soluble free radical initiator is used for initiating polymerization; phase separation of a system is generated by the interaction between the polymers and the composite dispersing mediums; the polymers and the composite dispersing mediums are respectively enriched in respective phases; the composite dispersing mediums form a graft copolymer by physical adsorption and protect dispersing phase liquid drops by electrostatic action; finally, the polymerization process of and the stability of products are improved.
Description
Technical field
Involved in the present invention is a kind of novel method for preparing water-soluble polymers, more specifically says, relates to the composite disperse medium field double-aqueous phase polymerization method of a kind of water-soluble polymers or multipolymer.
Background technology
Double-aqueous phase polymerization is that a certain amount of water-soluble vinyl monomer is dissolved in the aqueous solution of another kind of polymkeric substance or specific salts, carry out polyreaction, by the polymkeric substance of generation and the interaction between the dispersion medium, system is separated, during polymkeric substance and dispersion medium are enriched in separately mutually respectively, form the polyreaction of mutual exclusive water-soluble polymer dispersion.Mentioned in the United States Patent (USP) 4380600 with the double-aqueous phase polymerization (this patent claim " water Bao Shui " letex polymerization) of vinyl water-soluble monomer in polyoxyethylene glycol (PEG) aqueous solution, this patent relates generally to the double-aqueous phase polymerization of water-soluble polymers and composition thereof for dispersion medium; This class water-soluble polymers dispersion medium mainly comprises polypropylene glycol, polyoxyethylene glycol, polyvinyl alcohol, methylcellulose gum, dextran, gum arabic, agar, starch and derivative thereof etc.This patent does not relate to inorganic salt solution, comprises that ammonium sulfate, sal epsom, aqueous phosphatic are the double-aqueous phase polymerization of dispersion medium.
It is dispersion medium that this United States Patent (USP) adopts aqueous solutions of polymers, but the viscosity of aqueous solutions of polymers dispersion medium own big (with 30%, molecular weight is that 20000 the polyoxyethylene glycol aqueous solution is example, its viscosity is 0.156Pas), though polymerization system viscosity is lower than the polymerization of vinyl water-soluble monomer homogeneous phase aqueous solution, but to be that the system of dispersion medium is compared its viscosity still higher with inorganic salt solution.In addition, with the polymkeric substance is in the system of dispersion medium, the consumption of polymer dispersed medium is big, for reaching dispersion effect preferably, its consumption even will be higher than the consumption of vinyl water-soluble monomer, and the price of polymer dispersed medium is far above inorganic salt, therefore is that the cost of double-aqueous phase polymerization dispersion liquid product of dispersion medium is high with the aqueous solutions of polymers, and prospects for commercial application is little.
(application number: 200410067860.3), disclosing is the preparation and the performance of the double-aqueous phase polymerization product of dispersion medium with the inorganic salt solution in the inventor's existing patent application.Be that system viscosity is extremely low all the time in the double-aqueous phase polymerization process of dispersion medium with the inorganic salt solution, in certain monomer concentration scope, reaction and stirring all can be carried out smoothly, products obtained therefrom is the lower dispersion liquid of viscosity, it is water-soluble fabulous, can dissolve in 10 seconds under the product continuous stirring condition of good dispersity.With inorganic salt is dispersion medium, and strict control reaction conditions can obtain low, the water-soluble good product of viscosity, but its reaction conditions is comparatively harsh, the stability in the polymerization process and the less stable of polymerization product.
The present invention further improves the technology that double-aqueous phase polymerization prepares water-soluble polymers, has proposed homopolymerization or the copolymerization of water-soluble vinyl monomer under the complex media field condition.
Summary of the invention
The water-soluble polymers that the present invention proposes or the composite disperse medium field double-aqueous phase polymerization method of multipolymer, comprise the monomer that participates in double-aqueous phase polymerization or copolymerization, dispersion medium and initiator, must comprise that one or more can form the vinyl monomer of water-soluble polymers in the monomer of participation double-aqueous phase polymerization or copolymerization, the water-insoluble amount of monomer that participates in copolymerization must be controlled in the scope that can form water solubility copolymer, the initiator that polymerization is adopted is the redox composite initiation system of water-soluble radical initiator or employing and reducing substance composition, polymerization temperature is variable between-10～90 ℃, its feature is that described dispersion medium is a kind ofly can form the water-soluble salt of double water-phase and the composite disperse medium of water-soluble polymers with water-soluble polymers, is aggregated in the composite disperse medium solution and carries out; By weight calculating, composite disperse medium accounts for 1～60% of reaction system total amount, and monomer and composite disperse medium consumption are pressed its weight ratio between 1: 10～10: 1.
Can comprise vitriol, phosphoric acid salt, hydrophosphate, dihydrogen phosphate and water-soluble polymers salt with the water-soluble salt that water-soluble polymers forms double water-phase as composite disperse medium; Comprise Polyvinylpyrolidone (PVP), water-soluble cellulose derivative, water soluble starch and derivative, polyacrylic acid derivative, polyoxyethylene glycol and polyacrylamide derivative as the water-soluble polymers in the composite disperse medium.The usage ratio of water-soluble salt and water-soluble polymers is pressed its total amount than between 1: 40～100: 1 in the composite disperse medium.
(number of patent application: 200410067860.3) improve about the high molecular method of single inorganic salt solution dispersion medium synthesizing water-solubility, products obtained therefrom still is an aqueous polymer dispersion to the present invention is directed to last invention.This dispersion liquid is compared with the double-aqueous phase polymerization product that single inorganic salt solution dispersion medium obtains has better polymerization stability and product stock stability; Compare with the double-aqueous phase polymerization product that single polymers aqueous solution dispersion medium obtains have better polymerization flowability, product viscosity is lower.Must comprise a kind of water-soluble vinyl monomer that can form water-soluble polymers (consumption be system total amount 1～40%) in the polymerization formula, be dissolved in the water-soluble salt and the polymkeric substance compound aqueous solution (the water-soluble salt consumption be 1%～salt loading solubleness, the polymer loading of system total amount be the system total amount 0.01%～40%), initiator concentration is variable between 0.0001～1g/L, and is variable between the water-content 30～98%.Composite disperse medium is by forming with water-soluble salt and water-soluble polymers that water-soluble polymers forms double water-phase.
The effect of water-soluble salt not only can reduce viscosity, the increase flowability of system in the composite disperse medium, and can also reduce production cost of products; Water-soluble polymers then can or form graft copolymer by physical adsorption, electrostatic interaction and form the stability that protective layer comes raising system and product on the drop surface.
With the double-aqueous phase polymerization of acrylamide in ammonium sulfate and Polyvinylpyrolidone (PVP) mixed aqueous solution is example, the dispersed phase drop that the finished product of double-aqueous phase polymerization are formed by polyacrylamide solution and the external phase of ammonium sulfate and Polyvinylpyrolidone (PVP) mixed aqueous solution are formed, disperse phase mainly is dispersed in the external phase with psephitic and balled form, according to different prescriptions and processing condition Molecular Weight for Polyacrylamide between 50～10,000 ten thousand.By the CONTROL PROCESS condition, the transformation efficiency of acrylamide monomer is near 100%.The double-aqueous phase polymerization product is soluble in water, can form the aqueous solution of homogeneous after big water gaging dilution.
In a word, the double-aqueous phase polymerization product that has than single inorganic salt solution or single polymers medium field of the double-aqueous phase polymerization product that makes under the complex media field condition has more advantages of excellent stability and flowability.
Is that the double-aqueous phase polymerization of dispersion medium is an example with acrylamide at ammonium sulfate and Polyvinylpyrolidone (PVP) mixed aqueous solution, initial monomer concentration is 20%, system viscosity rises gradually with polyreaction in the polymerization process, but system remains low viscosity, unstability, phenomenon such as sudden and violent poly-do not appear, transformation efficiency reaches at 95% o'clock, and the about 0.25Pas of system viscosity, polymerization system finally are the dispersion liquid of homogeneous; The acrylamide of same amount carries out the double-aqueous phase polymerization system in the single dispersion medium of ammonium sulfate solution, polymerization starting stage, the phase-splitting of system energy, but after reacting 1 hour, the system unstability, viscosity sharply increases, stirring can not be carried out smoothly, and the finished product are milky jelly shape product; The acrylamide of same amount carries out homogeneous phase aqueous solution radical polymerization, and system becomes transparent glue at short notice, carries out viscosity and sharply increases along with reaction, and in half an hour, system loses flowability, and the finished product are transparent jelly shape product.
The used vinyl monomer that can form water-soluble homopolymer and multipolymer mainly comprises following three kinds among the present invention:
In the structural formula 1, R
1Can be H or CH
3, R
2, R
3Can be H or C
1-C
5Aliphatic chain, the monomer with structural formula 1 mainly comprises acrylamide, Methacrylamide, N methacrylamide, N-methyl acrylamide, N,N-DMAA, N, N-diethyl acrylamide etc.
In the structural formula 2, R
1Can be H or CH
3, X can be H, basic metal or ammonium, the monomer with structural formula 2 mainly comprises vinylformic acid, methacrylic acid, alkali metal salts of acrylic acids (sodium or potassium), methacrylic acid alkali metal salt (sodium or potassium), ammonium acrylate and ammonium methacrylate etc.
In the structural formula 3, R
1Can be H or CH
3, Y can be two kinds of forms in figure below:
R wherein
4And R
7Can be C
2-C
5Aliphatic chain, R
5, R
6, R
8And R
9Be C
1-C
5Aliphatic chain, R
10Can be C
1-C
5Aliphatic chain and phenyl etc., Z is halide-ions, SO
3OCH
3, CH
3COO etc.Monomer with structural formula 3 mainly comprises:
CH
2＝CHCOOC
2H
4N(CH
3)
2、CH
2＝CHCOOC
3H
6N(CH
3)
2、CH
2＝CHCOOC
4H
8N(CH
3)
2、
CH
2＝CHCOOC
2H
4N(CH
3)C
2H
5、CH
2＝C(CH
3)COOC
2H
4N(CH
3)
2、
CH
2＝C(CH
3)COOC
3H
6N(CH
3)
2、CH
2＝C(CH
3)COOC
4H
8N(CH
3)
2、
CH
2＝C(CH
3)COOC
2H
4N(CH
3)C
2H
5、CH
2＝C(CH
3)COOC
2H
4N
(CH
3)
3Cl
、
CH
2＝CHCOOC
2H
4N
(CH
3)
3Cl
、CH
2＝C(CH
3)COOC
3H
6N
(CH
3)
3Cl
、
CH
2＝C(CH
3)COOC
2H
4N
(CH
3)
3OOCCH
3 、CH
2＝C(CH
3)COOC
2H
4N
(CH
3)
3SO
4CH
3 、
(CH
2=CHCH
2)
2(CH
3)
2N
Cl
Deng.
Other vinyl monomer that can form water-soluble polymers also can be used as the monomer of double-aqueous phase polymerization, such as Sodium styrene sulfonate, vinyl pyridine and vinyl pyrrolidone etc.More than the monomer of Jie Shaoing can carry out the equal polymerization of double water-phase, also can mix in accordance with the appropriate ratio and carry out copolymerization.The monomer that can not form water-soluble polymers also can carry out the double water-phase copolymerization, but add-on is answered strict control, should be able to guarantee that formed multipolymer still is water-soluble polymers.
Used composite disperse medium is by forming with water-soluble salt and water-soluble polymers that water-soluble polymers forms double water-phase among the present invention.This water-soluble salt mainly comprises vitriol (ammonium, magnesium, sodium, potassium etc.), phosphoric acid salt (ammonium, sodium, potassium etc.), hydrophosphate, dihydrogen phosphate and water-soluble polymers salt (dextran sulfonate and vitriol etc.), and consumption is 1%～saturation solubility of system total amount; Water-soluble polymers mainly comprises Polyvinylpyrolidone (PVP), hydroxypropylcellulose, polyacrylic acid, polyoxyethylene glycol, poly-trimethylammonium acryloyl-oxy ethene trimethyl ammonium chloride and multipolymer thereof, and consumption is 0.01～40% of a system total amount.
In the polymerization process, monomeric concentration also should strict control, monomer concentration hour, the stability of system is generally all better, still can not get the high-molecular weight polymerization product; Monomer content can not be too high, and along with the increase of monomer concentration, monomer content increases in the polymerization system, and disperse phase needs more water, makes external phase concentration raise, and the viscosity of system also will raise.Double-aqueous phase polymerization is heterogeneous polymerization, system viscosity is along with the branch rate of dispersed phase drop increases and increases, disperseing phase fraction hour, viscosity change trend is less, but when disperse phase concentration is big, viscosity will become nonlinear relationship with disperse phase concentration, and continuing increases disperse phase concentration, and system viscosity will sharply increase.Therefore the ratio control of recommended hour dispersion media and monomer concentration is between 1: 10～10: 1.
Among the present invention, the initiator that is adopted is water-soluble radical initiator, also can adopt means such as light-initiated.The water-soluble radical initiator that adopts among the present invention has hydrogen peroxide and persulphate, also adopts redox composite initiation system initiated polymerization simultaneously, and the reducing substance that is added comprises primary amine class, tertiary amine alcohol and sulphite etc.The content of initiator is between 0.0001～1g/L.
According to the initiator system that is adopted, polymerization temperature is variable between-10～90 ℃.Selected temperature can be considered from final transformation efficiency and polymerization time two aspects.Because the monomer of acrylamide and so on has certain toxicity, therefore the residual quantity in the finished product should strictly be controlled, and therefore requires final transformation efficiency high as far as possible, and the final transformation efficiency of monomer all can be near 100% in the processing condition that adopt of the present invention.
Embodiment
To introduce the present invention by example more specifically below:
Example 1:
Be reflected in the jacketed reactor of 0.5L and carry out.Nitrogen inlet, thermometer socket, agitator socket, thief hole and condenser socket are arranged on the reactor.In reactor, add 60～190 gram water, 2～100 gram ammonium sulfate, 1～80 gram Polyvinylpyrolidone (PVP) are as composite dispersing agent, in system, add 0.5～50 gram acrylamide monomer again, system temperature while stirring raises, temperature further is elevated to 30～75 ℃, add 0.00003～0.3 gram Ammonium Persulfate 98.5 initiator in system, polyreaction begins.Carrying out along with polyreaction, system becomes milky dispersion liquid from the clarifying aqueous solution gradually, carry out polymerization simultaneously in the system and be separated this moment, under certain stirring intensity, the polyacrylamide that forms in the system is separated out from external phase, form psephitic and globular drop, be dispersed in the external phase.Because in the double-aqueous phase polymerization system, system viscosity is determined by external phase, therefore carries out with polyreaction, system viscosity increases gradually, does not have viscosity sharp increase phenomenon, stirs in the polymerization process and conducts heat and all can carry out smoothly.After the polymerization 1～8 hour, finish polyreaction, the polymerization the finished product are measured transformation efficiency with bromination method, final transformation efficiency is near 100%.With the viscosity of Reheolab MCI rheometer measurement the finished product, the viscosity of the finished product is 0.1～0.75Pas in the time of 30 ℃.
Product is carried out dissolution experiment, 100 gram water are poured in the beaker that stirs magneton, get the dispersion liquid of 1 gram double-aqueous phase polymerization product and put into, product can dissolving fully in 30 seconds after the agitation as appropriate.The contrast experiment gets the identical solid content Powdered polyacrylamide amine product close with the double water-phase product with molecular weight, puts into 100 gram water, in the continuously stirring 1 hour, Powdered polyacrylamide can only be partly dissolved, major part still is in solvent swelling state, after 24 hours, could dissolve fully.
Product stability is experimentized, find polymerization product sealing placement after 1 year, system still is the dispersion liquid of homogeneous, and proterties is stable.
Comparative example 1:
Be the comparative experiments of example 1, under all identical situation of all conditions, do not add ammonium sulfate and Polyvinylpyrolidone (PVP) in the system, carry out common homogeneous phase aqueous solution polymerization.In half an hour, system viscosity sharply increases behind the adding initiator, and until stirring, the finished product are transparent jelly shape.
In the dissolubility test of identical polypropylene acid amides quality, continuously stirring 1 hour, still have not solute of part, after 5 hours, could dissolve fully.
Product stability is experimentized, find polymerization product sealing placement after 1 year, system still is transparent jelly shape.
Comparative example 2:
Be the comparative experiments of example 1, only add ammonium sulfate in the system, do not add Polyvinylpyrolidone (PVP), and the total amount of dispersion agent be constant.When monomer consumption during less than certain value, system phase-splitting smoothly, polymerization process is stable; But after the monomer consumption is greater than certain value, the polymerization starting stage, system is phase-splitting smoothly still, but behind polymerase 10 .5～1 hour, system loss of stability, dispersed phase drop generation coalescence, system viscosity sharply raises, cause stirring and the heat radiation difficulty, obtain oyster white jelly shape product at last, and have portion water to separate out.
With stable prod with the identical solubility experiment of example 1, dissolving fully in the continuously stirring 10 seconds; Oyster white jelly shape product then needs 30 minutes ability to dissolve fully.
Product stability is experimentized, find polymerization-stable product sealing placement after 1 year, system still is the dispersion liquid of homogeneous, and proterties is stable; But oyster white jelly shape product is placed and layering promptly occurred in 1 day, and prolongs the demixing phenomenon aggravation in time.
Comparative example 3:
Be the comparative experiments of example 1, only add Polyvinylpyrolidone (PVP) in the system, do not add ammonium sulfate, and the total amount of dispersion agent be constant.Carry out with polymerization, system phase-splitting smoothly, polymerization process is stable, obtains the oyster white dispersion liquid at last, and viscosity is 5～15Pas.
With the identical solubility experiment of example 1, dissolving fully in the continuously stirring 10 minutes.
Product stability is experimentized, find product sealing placement after 1 year, system still is the dispersion liquid of homogeneous, and proterties is stable.
Example 2:
60～190 gram water, 0.5～50 gram acrylamide, 2～100 gram sal epsom, 1～80 gram hydroxypropylcellulose are as composite dispersing agent, and initiator amount and polymerization temperature are identical with example 1.Along with the carrying out of polyreaction, system phase-splitting was smoothly reacted after 1～g hour, finished polyreaction, and the polymerization the finished product are measured transformation efficiency with bromination method, and final transformation efficiency is near 100%.Viscosity 0.1～the 0.95Pas of the finished product aqueous dispersions.
With the identical solubility experiment of example 1, dissolving fully in the continuously stirring 30 seconds.
Product stability is experimentized, find product sealing placement after 1 year, system still is the dispersion liquid of homogeneous, and proterties is stable.
Example 3:
60～190 gram water, 0.5～50 gram acrylamide, the polyoxyethylene glycol of 2～100 gram potassiumphosphates, 1～80 gram molecular weight 20000 is as composite dispersing agent, and initiator amount and polymerization temperature are identical with example 1.Along with the carrying out of polyreaction, system phase-splitting smoothly.React after 1～8 hour, finish polyreaction, the polymerization the finished product are measured transformation efficiency with bromination method, final transformation efficiency is near 100%.Viscosity 0.1～the 0.55Pas of the finished product aqueous dispersions.
With the identical solubility experiment of example 1, dissolving fully in the continuously stirring 30 seconds.
Product stability is experimentized, find product sealing placement after 1 year, system still is the dispersion liquid of homogeneous, and proterties is stable.
Example 4:
60～190 gram water, 0.5～50 gram acrylamide, 2～100 gram dextran ammonium sulfate, 1～80 gram Polyvinylpyrolidone (PVP) are as composite dispersing agent, and initiator amount and polymerization temperature are identical with example 1.Along with the carrying out of polyreaction, system phase-splitting smoothly.React after 1～8 hour, finish polyreaction, the polymerization the finished product are measured transformation efficiency with bromination method, final transformation efficiency is near 100%.Viscosity 0.75～the 1.70Pas of the finished product aqueous dispersions.
With the identical solubility experiment of example 1, dissolving fully in the continuously stirring 1 minute.
Product stability is experimentized, find product sealing placement after 1 year, system still is the dispersion liquid of homogeneous, and proterties is stable.
Example 5:
60～190 gram water, 0.5～50 gram vinylformic acid, 0.3～30 gram sodium hydroxide is regulated pH value to 12 with sodium hydroxide solution again, add 2～100 gram ammonium sulfate, 1～80 gram Polyvinylpyrolidone (PVP) as composite dispersing agent, initiator amount and polymerization temperature are identical with example 1.Polyreaction begins, and system begins to take place phase-splitting, becomes milky dispersion liquid from clarification gradually, in the whole polymerization process, does not have the process of viscosity drastic change, stirs and can carry out smoothly all the time.Measure the final transformation efficiency of system near 100% with bromination titration method.The viscosity of the finished product is 0.1～0.75Pas.
With the identical solubility experiment of example 1, dissolving fully in the continuously stirring 30 seconds.
Product stability is experimentized, find product sealing placement after 1 year, system still is the dispersion liquid of homogeneous, and proterties is stable.
Example 6:
60～190 gram water, 0.5～35 gram acrylamides, 0.5～35 gram methylacryoyloxyethyl trimethyl ammonium chlorides, 2～100 gram ammonium sulfate, the poly-trimethylammonium acryloyl-oxy ethene trimethyl ammonium chloride of 1～80 gram are composite dispersing agent, and initiator amount and polymerization temperature are identical with example 1.Polyreaction begins, and system begins to take place phase-splitting, becomes milky dispersion liquid from clarification gradually, in the whole polymerization process, does not have the process of viscosity drastic change, stirs and can carry out smoothly all the time.Measure the final conversion of system near 100% with bromination method.The viscosity of the finished product is 0.05～0.50Pas.
With the identical dissolubility test of example 1, dissolving fully in the continuously stirring 30 seconds.
Product stability is experimentized, find product sealing placement after 1 year, system still is the dispersion liquid of homogeneous, and proterties is stable.
Comparative example 4:
Be the comparative experiments of example 6, under all identical situation of all conditions, addition polymerization trimethylammonium acryloyl-oxy ethene trimethyl ammonium chloride not in the system.Polyreaction begins, and system begins to take place phase-splitting, becomes milky dispersion liquid from clarification gradually, in the whole polymerization process, does not have the process of viscosity drastic change, stirs and can carry out smoothly all the time.Measure the final conversion of system near 100% with bromination method.The viscosity of the finished product is 0.01～0.50Pas.Compare with Comparative Examples 2 in the example 1, in acrylamide and cationic monomer copolymerization system, when not adding any composite dispersing agent, when monomer concentration was higher, the stability of system was still better.This is because itself contain a large amount of positively charged ions in the multipolymer of acrylamide and methylacryoyloxyethyl trimethyl ammonium chloride, contain a large amount of ions in the dispersed phase drop that forms after their phase-splittings, these ionic existence have been played stabilization preferably to drop.
With the identical dissolubility test of example 1, dissolving fully in the continuously stirring 30 seconds.
Product stability is experimentized, find product sealing placement after 1 year, system still is the dispersion liquid of homogeneous, and proterties is stable.
Example 7:
60～190 gram water, 0.5～35 gram acrylamides, 0.5～35 gram Dimethylaminoethyl Methacrylate, 2～100 gram ammonium sulfate, the poly-trimethylammonium acryloyl-oxy ethene trimethyl ammonium chloride of 1～80 gram are composite dispersing agent, and initiator amount and polymerization temperature are identical with example 1.Polyreaction begins, and system begins to take place phase-splitting, becomes milky dispersion liquid from clarification gradually, in the whole polymerization process, does not have the process of viscosity drastic change, stirs and can carry out smoothly all the time.Measure the final conversion of system near 100% with bromination method.The viscosity of the finished product is 0.05～0.50Pas.
With the identical dissolubility test of example 1, dissolving fully in the continuously stirring 30 seconds.
Product stability is experimentized, find product sealing placement after 1 year, system still is the dispersion liquid of homogeneous, and proterties is stable.
Example 8:
60～190 gram water, 0.5～50 gram acrylamides, the polyoxyethylene glycol of 2～100 gram ammonium sulfate, 1～80 gram molecular weight 20000 adopts the redox composite initiation system initiated polymerization of Potassium Persulphate and trolamine composition, 10～65 ℃ of polymerization temperatures as composite dispersing agent.Along with the carrying out of polyreaction, system phase-splitting was smoothly reacted after 1～8 hour, finished polyreaction, and the polymerization the finished product are measured transformation efficiency with bromination method, and final transformation efficiency is near 100%.Viscosity 0.1～the 0.55Pas of the finished product aqueous dispersions.
With the identical solubility experiment of example 1, dissolving fully in the continuously stirring 30 seconds.
Product stability is experimentized, find product sealing placement after 1 year, system still is the dispersion liquid of homogeneous, and proterties is stable.
Claims (3)
1, the composite disperse medium field double-aqueous phase polymerization method of water-soluble polymers or multipolymer, comprise the monomer that participates in double-aqueous phase polymerization or copolymerization, dispersion medium and initiator, must comprise that one or more can form the vinyl monomer of water-soluble polymers in the monomer of participation double-aqueous phase polymerization or copolymerization, the water-insoluble amount of monomer that participates in copolymerization must be controlled in the scope that can form water solubility copolymer, the initiator that polymerization is adopted is the redox composite initiation system of water-soluble radical initiator or employing and reducing substance composition, polymerization temperature is variable between-10～90 ℃, it is characterized in that: described dispersion medium is the composite disperse medium that water-soluble salt and water-soluble polymers dispersion medium are formed, described water-soluble salt comprises vitriol, phosphoric acid salt, hydrophosphate, a kind of in the dihydrogen phosphate, described water-soluble polymers dispersion medium comprises Polyvinylpyrolidone (PVP), water-soluble cellulose derivative, water soluble starch and derivative, polyacrylic acid and derivative, a kind of in polyoxyethylene glycol and the polyacrylamide derivative is aggregated in the composite disperse medium solution and carries out.
2, according to the composite disperse medium field double-aqueous phase polymerization method of described water-soluble polymers of claim 1 or multipolymer, it is characterized in that: by weight calculating, composite disperse medium accounts for 1～60% of reaction system total amount, and monomer and composite disperse medium consumption are pressed its weight ratio between 1: 10～10: 1.
3, according to the composite disperse medium field double-aqueous phase polymerization method of claim 1 and 2 described water-soluble polymerss or multipolymer, it is characterized in that: the usage ratio of water-soluble salt and water-soluble polymers dispersion medium is pressed its weight ratio between 1: 40～100: 1 in the described composite disperse medium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410089586 CN1286866C (en) | 2004-12-15 | 2004-12-15 | Double water-phase polymerization method for composite disperse medium field of water soluble polymer or copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410089586 CN1286866C (en) | 2004-12-15 | 2004-12-15 | Double water-phase polymerization method for composite disperse medium field of water soluble polymer or copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1640896A CN1640896A (en) | 2005-07-20 |
| CN1286866C true CN1286866C (en) | 2006-11-29 |
Family
ID=34869322
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410089586 Expired - Fee Related CN1286866C (en) | 2004-12-15 | 2004-12-15 | Double water-phase polymerization method for composite disperse medium field of water soluble polymer or copolymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1286866C (en) |
-
2004
- 2004-12-15 CN CN 200410089586 patent/CN1286866C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1640896A (en) | 2005-07-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1131243C (en) | Process for producing water-soluble anionic dispersion polymers | |
| CN1039421C (en) | Process for the production of highly water absorptive polymers | |
| CN1884324A (en) | Cation acrylamide copolymer water-in-water emulsion and its preparation method | |
| CN102532375A (en) | Polyacrylamide microsphere | |
| CN1896112A (en) | Random and copolymer cation macromolecular emulsion and its preparation | |
| CN1147511C (en) | Process for producing high-purity vinylpyrolidone polymer | |
| CN100347209C (en) | Inverse emulsion process of preparing amphoteric polymer | |
| CN100535020C (en) | Amphoteric ion high polymer sludge dehydration agent and its preparation method | |
| CN1872911A (en) | Method for preparing transparent hybridization material of polymetal oxygen cluster / polymer | |
| CN1526747A (en) | Environment responding aquogel copolymer and its prepn | |
| CN1884322A (en) | Preparation method of repeatedly usable high oil-absorbent material | |
| CN1286866C (en) | Double water-phase polymerization method for composite disperse medium field of water soluble polymer or copolymer | |
| CN100418900C (en) | High molecular weight, hydrophilic and oleophilic cation type flocculant and its preparing method | |
| CN100570055C (en) | The preparation method of cationic polyacrylamide paper making intensifier | |
| CN1266173C (en) | Method for double aqueous polymerization of water soluble polymer or copolymer | |
| CN1231509C (en) | Method for producing gel-type cation exchangers | |
| CN1137146C (en) | Process for the production of acrylamide polymer dispersion | |
| CN1061033A (en) | The gel acid that acidifying strata is used | |
| CN101724125B (en) | Hydrophobic association polymer containing cationic surface active monomer and synthesis method thereof | |
| CN1856511A (en) | Improved solventless sulfonation of exchange resins | |
| JP3101714B1 (en) | Copolymer showing reversible hydrophilic-hydrophobic change and method for producing the same | |
| CN85104864A (en) | The manufacture method of water absurbing polymer | |
| CN102504081A (en) | Preparation method of medicinal methacrylate resin polymer | |
| CN1147507C (en) | Polyacrylonitrile particles by surfmer polymerization and sodium removal by chemical exhcnage | |
| CN1560096A (en) | Nano macromolecule microball of carboxy function type cross-linked nucleocapsid structure and preparation process thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20061129 Termination date: 20101215 |