CN1085568A - Preparation of low molecular weight water-soluble polymers - Google Patents
Preparation of low molecular weight water-soluble polymers Download PDFInfo
- Publication number
- CN1085568A CN1085568A CN 92111424 CN92111424A CN1085568A CN 1085568 A CN1085568 A CN 1085568A CN 92111424 CN92111424 CN 92111424 CN 92111424 A CN92111424 A CN 92111424A CN 1085568 A CN1085568 A CN 1085568A
- Authority
- CN
- China
- Prior art keywords
- water
- molecular weight
- salt
- monomer
- persulphate
- 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.)
- Pending
Links
- 229920003169 water-soluble polymer Polymers 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title claims description 8
- 239000000178 monomer Substances 0.000 claims abstract description 14
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 9
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000012966 redox initiator Substances 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- GRWZHXKQBITJKP-UHFFFAOYSA-N dithionous acid Chemical compound OS(=O)S(O)=O GRWZHXKQBITJKP-UHFFFAOYSA-N 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 235000010755 mineral Nutrition 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000005192 partition Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000008235 industrial water Substances 0.000 abstract description 2
- 239000007769 metal material Substances 0.000 abstract description 2
- 239000000049 pigment Substances 0.000 abstract description 2
- 238000010791 quenching Methods 0.000 abstract description 2
- 230000000171 quenching effect Effects 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 abstract 1
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 abstract 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000000034 method Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 239000011734 sodium Substances 0.000 description 5
- -1 polypropylene Polymers 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 241000345998 Calamus manan Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QLVHFTGKDGTJDH-UHFFFAOYSA-N acetic acid;ethenyl acetate Chemical compound CC(O)=O.CC(=O)OC=C QLVHFTGKDGTJDH-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 1
- 235000012950 rattan cane Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- UPDATVKGFTVGQJ-UHFFFAOYSA-N sodium;azane Chemical compound N.[Na+] UPDATVKGFTVGQJ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 235000020681 well water Nutrition 0.000 description 1
- 239000002349 well water Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/04—Acids, Metal salts or ammonium salts thereof
- C08F20/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention provides a ternary redox initiation system containing persulfate, bisulfite and ferrous salt, which can be used for preparing low molecular weight sodium polyacrylate and other low molecular weight water-soluble polymers or copolymers. When the concentration of the monomer in the solvent water is 1.0 to 50% by weight, the viscosity average molecular weight of the resulting water-soluble polymer can be controlled to 1X 103—2×104Within the range, the conversion rate is more than 95%. The product can be directly used as an anti-scaling and descaling agent for industrial water systems, and also can be used as a quenching agent of metal materials, a dispersing agent of pigments in the paper industry and the like.
Description
The invention belongs to the preparation method of low-molecular weight water-soluble polymer.
The water-soluble low molecular weight polymkeric substance has been used as antiscale, the scale remover of industrial water system, and dispersing of pigments agent etc. comes into one's own in the quenching medium of metallic substance and the paper industry.Be used for preparing the method for low-molecular-weight polypropylene acid at present, be mainly following several.One uses and dredges based compound as chain-transfer agent, and this method is more generally used in early days, but because product foul smelling, seldom use at present; Its two, polymerization in water-isopropyl alcohol mixed solvent (United States Patent (USP) 4301266,1981, BASF A.-G.Muenster, A.and Rohmann, M.) under pressure in 120-200 ℃ of polymerization, use H
2O
2Make initiator.This method need be carried out the loaded down with trivial details last handling process of removing Virahol; Its three, with metal-salt (as Cu
2+)-H
2O
2As initiator system (United States Patent (USP) 4314044,1982, Rohm and Haas Co., Hughes, K.A., Kine, B.B.and Swift, G.): adopt the continuous charging method at 90-100 ℃, in the reactor that the metal-salt and the tertiary amine aqueous solution are housed, add monomer and H respectively
2O
2The aqueous solution, finish until reaction.The shortcoming of this method is that institute's metal ion easily causes environmental pollution; Its four, use some water-soluble azoization and compound do initiator (Japanese Patent 64 38403,1989, Kao Corp, nearly rattan is clear abundant, 50 hazes just, Tianjin
The power hero): after the pH value of monomer, sulfurous acid (hydrogen) sodium and the azo-compound aqueous solution is adjusted to 5.1, carry out polymerization in 50 ℃, this method need prepare specific azo-compound.
The objective of the invention is with common mineral compound, promptly persulfuric acid comprises K, NH
2, water-soluble salts such as Na, hydrosulphite comprises K, NH
4, water-soluble salt such as Na and ferrous salt comprise water-soluble salt ternary redox initiation systems such as vitriol, nitrate, muriate, the preparation low-molecular weight water-soluble polymer, can avoid above-mentioned variety of issue, and raw material is easy to get inexpensively, equipment is not had particular requirement, operation is simple, pollution-free.
The present invention prepares monomer solution earlier, when containing acid monomer such as vinylformic acid, earlier with the NaOH aqueous solution or Na
2CO
3Powder slowly neutralizes, and when polymerization temperature gives heat to 50-95 ℃, adds hydrosulphite successively, as ammonium salt, sylvite, sodium salt and ferrous salt, as vitriol, the mixing solutions of nitrate, muriate, bromide and persulphate such as sylvite, ammonium salt sodium-salt aqueous solution, polymerization then.The total concn (by weight) of monomer in solution for the consumption (with mol ratio) of three kinds of components of 1.0-50% initiator system is: persulphate is 0.001～0.015 with respect to monomer, bisulfite salt pair persulphate is 0.1～5.0, and ferrous salt is 0.0002～0.075 to persulphate.
The present invention is applicable to the polymerization of water-soluble monomer, in order to preparation low-molecular weight water-soluble homopolymer and multipolymer, is specially adapted to contain the preparation of the homopolymer and the multipolymer of sodium acrylate.Also be applicable to the water-soluble monomer to be main ingredient, water-fast monomer is made component altogether, and the gained multipolymer is the polymerization system of water-soluble polymers, is specially adapted to contain the polymerization system of vinyl acetate and esters of acrylic acid.
The intrinsic viscosity of the low-molecular weight water-soluble polymer that the present invention obtains is 8-40ml/g.
The present invention has following advantage:
1, when carrying out polyreaction, needn't remove the oxygen in the polymerization system.
2, as the water of solvent, available distilled water, tap water and well water etc.
3, initiator system toxicological harmless, pollution-free problem.
4, can control the molecular weight of product easily.
5, product is a kind of aqueous solution, is specially adapted to water system and handles.
It is as follows to the invention provides embodiment:
Embodiment 1: add 0.56 mol propylene acid in three-necked bottle, use 85.2ml H
2The O dissolving adds normal Na gradually under stirring state
2CO
3Neutralize it.In 85 ℃ of water-baths, give hot 5min after, add the 0.0048 mole of NH that contains of on-the-spot preparation
4HSO
3With 0.00013 mole of FeCl
2Aqueous solution 10ml and contain 0.0044 mole of (NH
4)
2S
2O
8Aqueous solution 20ml, polyase 13 h, the intrinsic viscosity of product (25 ℃ with 1mol/L NaCl determination of aqueous solution, down with) is 31.8ml/g, Mr=4.80 * 10
3
Embodiment 2: add 0.56 mol propylene acid in three-necked bottle, use 125.4ml H
2The O dissolving neutralizes it with the 100ml NaOH aqueous solution.85 ℃ give hot 5min after, add and to contain 0.0038 mole of KHSO
3With 0.00011 mole of Fe(No
3)
2Aqueous solution 30ml and 0.0037 mole of K
2S
2O
8Aqueous solution 50ml, polyase 13 h, product property viscosity number are 11.4ml/g, Mv=1.53 * 10
3
Embodiment 3: add 0.28 mol propylene acid in three-necked bottle, use 133ml H
2O dissolving, with in the 100ml NaOH aqueous solution and after, add 0.12 molar acetate vinyl acetate and 0.14 mol propylene acid amides, then initiated polymerization similarly to Example 2.The product property viscosity number is 16.3ml/g.
Embodiment 4: prepare following solution at first respectively, solution A: 270.8 mol propylene acid are dissolved in 65LH
2Among the O, with in the 65L NaOH aqueous solution and after, add 91.5 mol propylene acid amides, stir.Solution B: 2.5 moles of NaHSO
3Be dissolved in 10L H
2Among the O.Solution C: 0.070 mole of FeSO
4Be dissolved in 16L H
2Among the O.Solution D: 2.4 moles of K
2S
2O
8Be dissolved in 34.5L H
2Among the O, then, add 1/5 of solution A in giving hot afterreaction still, be heated to and add 1/5 of each solution: B after 82 ℃ successively, C after the D, every 10min, adds 1/10 of each solution residual content: A, B, C, D at every turn successively.After treating all to add, polyase 13 h, the product property viscosity number is: 18.3ml/g.
Claims (1)
1, a kind of preparation method of low-molecular weight water-soluble polymer, be with water-soluble monomer homopolymerization and copolymerization, comprise that also water-fast monomer is as the polymerization of component altogether, the invention is characterized in, adopting common mineral compound is hydrosulphite, comprise ammonium salt, sylvite, sodium-salt aqueous solution, ferrous salt, comprise vitriol, nitrate, muriate, the mixing solutions of bromide and persulphate comprise sylvite, ammonium salt, sodium-salt aqueous solution ternary redox initiation system, and each composition partition ratio is as follows:
1) total concn (by weight) of monomer in solution is 1.0～50%,
2) consumption (with molar ratio computing) of three kinds of components of initiator system is:
Bisulfite salt pair persulphate is 0.1-5.0
Ferrous salt is 0.0002-0.075 to persulphate
Persulphate is 0.001-0.015 with respect to monomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92111424 CN1085568A (en) | 1992-10-14 | 1992-10-14 | Preparation of low molecular weight water-soluble polymers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92111424 CN1085568A (en) | 1992-10-14 | 1992-10-14 | Preparation of low molecular weight water-soluble polymers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1085568A true CN1085568A (en) | 1994-04-20 |
Family
ID=4945336
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92111424 Pending CN1085568A (en) | 1992-10-14 | 1992-10-14 | Preparation of low molecular weight water-soluble polymers |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1085568A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100413892C (en) * | 2003-01-22 | 2008-08-27 | 株式会社日本触媒 | Temperature-controlled process of producing polymer |
| CN101914181A (en) * | 2010-09-06 | 2010-12-15 | 长春工业大学 | Method for preparing low-gel content epoxy acrylate rubber |
| CN101469040B (en) * | 2007-12-27 | 2012-04-18 | 上海涂料有限公司技术中心 | Polyelectrolyte for dispersing aqueous inorganic color stuffing and preparation thereof |
| CN105566566A (en) * | 2015-12-29 | 2016-05-11 | 赵吉滨 | Polynary composite water-soluble high molecular polymer and preparation method thereof |
-
1992
- 1992-10-14 CN CN 92111424 patent/CN1085568A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100413892C (en) * | 2003-01-22 | 2008-08-27 | 株式会社日本触媒 | Temperature-controlled process of producing polymer |
| CN101469040B (en) * | 2007-12-27 | 2012-04-18 | 上海涂料有限公司技术中心 | Polyelectrolyte for dispersing aqueous inorganic color stuffing and preparation thereof |
| CN101914181A (en) * | 2010-09-06 | 2010-12-15 | 长春工业大学 | Method for preparing low-gel content epoxy acrylate rubber |
| CN105566566A (en) * | 2015-12-29 | 2016-05-11 | 赵吉滨 | Polynary composite water-soluble high molecular polymer and preparation method thereof |
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| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
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