USRE34903E - Vinylamine copolymer, flocculating agent and paper strength increasing agent using the same, as well as process for producing the same - Google Patents
Vinylamine copolymer, flocculating agent and paper strength increasing agent using the same, as well as process for producing the same Download PDFInfo
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- USRE34903E USRE34903E US08/148,384 US14838493A USRE34903E US RE34903 E USRE34903 E US RE34903E US 14838493 A US14838493 A US 14838493A US RE34903 E USRE34903 E US RE34903E
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 18
- 239000008394 flocculating agent Substances 0.000 title abstract description 17
- 230000001965 increasing effect Effects 0.000 title abstract description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 17
- 150000001450 anions Chemical class 0.000 claims abstract description 11
- 150000001768 cations Chemical class 0.000 claims abstract description 11
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 239000000178 monomer Substances 0.000 claims description 13
- 230000000379 polymerizing effect Effects 0.000 claims description 13
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 11
- 230000002378 acidificating effect Effects 0.000 claims description 10
- 239000007870 radical polymerization initiator Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 7
- 230000003301 hydrolyzing effect Effects 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- -1 azo compound Chemical class 0.000 claims description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 239000000243 solution Substances 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 15
- 230000018044 dehydration Effects 0.000 description 12
- 238000006297 dehydration reaction Methods 0.000 description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 125000002560 nitrile group Chemical group 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 125000002091 cationic group Chemical group 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 230000003311 flocculating effect Effects 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 229920003169 water-soluble polymer Polymers 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229920006317 cationic polymer Polymers 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000012673 precipitation polymerization Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000013055 pulp slurry Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 150000003840 hydrochlorides Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011369 resultant mixture Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000012360 testing method 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
- 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
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical group [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000006105 Hofmann reaction Methods 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 101150108015 STR6 gene Proteins 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229950003937 tolonium Drugs 0.000 description 1
- HNONEKILPDHFOL-UHFFFAOYSA-M tolonium chloride Chemical compound [Cl-].C1=C(C)C(N)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 HNONEKILPDHFOL-UHFFFAOYSA-M 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- USFMMZYROHDWPJ-UHFFFAOYSA-N trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium Chemical compound CC(=C)C(=O)OCC[N+](C)(C)C USFMMZYROHDWPJ-UHFFFAOYSA-N 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229920003176 water-insoluble polymer Polymers 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
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
-
- 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
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
-
- 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
- C08F2810/00—Chemical modification of a polymer
- C08F2810/50—Chemical modification of a polymer wherein the polymer is a copolymer and the modification is taking place only on one or more of the monomers present in minority
Definitions
- This invention relates to a novel vinylamine copolymer, a flocculating agent for the treatment of waste water using the vinylamine copolymer and a paper strength increasing agent using the vinylamine copolymer in the paper making industry, as well as a process for producing the vinylamine copolymer. More particularly, the present invention relates to a vinylamine copolymer having structural units represented by the following formulas (I), (II), (III).[.,.].
- a flocculating agent for the treatment of waste water and a paper strength increasing agent using the vinylamine copolymer in the papermaking industry as well as a process for producing the vinylamine copolymer, a flocculating agent using the vinylamine copolymer, a paper strength increasing agent using the vinylamine copolymer and a process for producing the vinylamine copolymer.
- novel vinylmine copolymer according to the present invention exhibits excellent effects in the field of application of cationic polymers such as flocculating agents for use in the treatment of waste water, dehydrating agents for organic sludges, drainage aids, retention aids, paper strength increasing agents, etc. in the papermaking industry.
- cationic polymers such as flocculating agents for use in the treatment of waste water, dehydrating agents for organic sludges, drainage aids, retention aids, paper strength increasing agents, etc. in the papermaking industry.
- the method of hydrolysis of a homopolymer of N-vinylformamide is an excellent method which is capable of synthesizing a polyvinylamine of high molecular weight with high stability.
- the resultant polymer is extremely hydrophilic and has only an insufficient effect in the case of using it as a flocculating agent for dehydration.
- a method of copolymerizing N-vinylformamide and ethylene and then hydrolyzing the resulting product there has been known.
- the present inventors had previously proposed a method of preparing a flocculating agent with good dehydrating properties by copolymerizing N-vinylamide with acrylonitrile, followed by hydrolysis thereby modifying not less than 10 mol % of nitrile groups into carboxyl groups [refer to Japanese Patent Application Laid Open (KOKAI) No. 59-39399(1984)].
- KKAI Japanese Patent Application Laid Open
- N-vinylacetamide copolymer shown in the examples, there has been a problem for N-vinylformamide copolymer in that the dehydrating property is remarkably reduced in the case where not less than 10 mol % of the nitrile groups are modified into carboxyl groups.
- the proposed hydrolyzate still involves a problem in that most of the nitrile groups are modified into carboxyl groups and, in the case where the content of the nitrile group in the starting copolymer is high, water-insoluble polymer is formed or an amphoteric polymer predominantly containing artionic groups results and accordingly, it had been difficult to reduce the water content in the dehydrated sludges in the case of its use as a flocculating agent for dehydration.
- a vinylamine copolymer having the structural units represented by the following formulas (I), (II), (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).].: ##STR3## wherein X ⁇ represents an anion or hydroxyl ion, R represents a hydrogen atom or a methyl group, M ⁇ represents a hydrogen ion or a monovalent cation, in which the molar fraction of the structural unit (I) is 5 to 85% by mole, the molar fraction of the structural unit (II) is 2 to 85% by mole, the molar fraction of the structural unit (III) is 5 to 80% by mole, the molar fraction of the structural unit (IV) .[.is 0 to 40% by mole, and all of said molar fractions being based on the vinylamine copolymer, the molar fraction of the structural unit (V).].
- the total molar fractions for structural units (I), (II) and (III) is preferably at least 60%. .Iaddend.
- a flocculating agent comprising a vinylamine copolymer having the structural units represented by the following formulas (I), (II), (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).].: ##STR4## wherein X ⁇ represents an anion or hydroxyl ion, R represents a hydrogen atom or a methyl group, M ⁇ represents a hydrogen ion or a monovalent cation, in which the molar fraction of the structural unit (I) is 5 to 85% by mole, the molar fraction of the structural unit (II) is 2 to 85% by mole, the molar fraction of the structural unit (III) is 5 to 80% by mole, the molar fraction of the structural unit (IV) .[.is 0 to 40% by mole, all of said molar fractions being based on the vinylamine copolymer, and the molar fraction of the structural unit
- the total molar fractions for structural units (I), (II) and (III) is preferably at least 60%.
- a paper strength increasing agent comprising a vinylamine copolymer having the structural units represented by the following formulas (I), (II), (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).].: ##STR5## wherein X ⁇ represents an anion or hydroxyl ion, R represents a hydrogen atom or a methyl group, M ⁇ represents a hydrogen ion or a monovalent cation, in which the molar fraction of the structural unit (I) is 5 to 85% by mole, the molar fraction of the structural unit (II) is 2 to 85% by mole, the molar fraction of the structural unit (III) is 5 to 80% by mole, the molar fraction of the structural unit (IV) .[.is 0 to 40% by mole, all of said molar fractions being based on the vinylamine copolymer and the molar fraction of the structural unit (V).].: ##STR5## wherein X
- the total molar fractions for structural units (I), (II) and (III) is preferably at least 60%. .Iaddend.
- a drainage aid for papermaking comprising a vinylamine copolymer having the structural units represented by the following formulas (I), (II), (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).].: ##STR6## wherein X ⁇ represents an anion or hydroxyl ion, R represents a hydrogen atom or a methyl group, M ⁇ represents a hydrogen ion or a monovalent cation, in which the molar fraction of the structural unit (I) is 5 to 85% by mole, the molar fraction of the structural unit (II) is 2 to 85% by mole, the molar fraction of the structural unit (III) is 5 to 80% by mole, the molar fraction of the structural unit (IV) .[.is 0 to 40% by mole, all of said molar fractions being based on the vinylamine copolymer, and the molar fraction of the structural unit
- the total molar fractions for structural units (I), (II) and (III) is preferably at least 60%. .Iaddend.
- a retention aid for papermaking comprising a vinylamine copolymer having the structural units represented by the following formulas (I), (II), (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).].: ##STR7## wherein X ⁇ represents an anion or hydroxyl ion, R represents a hydrogen atom or a methyl group, M ⁇ represents a hydrogen ion or a monovalent cation, in which the molar fraction of the structural unit (I) is 5 to 85% by mole, the molar fraction of the structural unit (II) is 2 to 85% by mole, the molar fraction of the structural unit (III) is 5 to 80% by mole, the molar fraction of the structural unit (IV) .[.is 0 to 40% by mole, all of said molar fractions being based on the vinylamine copolymer, and the molar fraction of the structural unit
- the total molar fractions for structural units (I), (II) and (III) is preferably at least 60%. .Iaddend.
- a process for producing a vinylamine copolymer having structural units comprising the following formulas (I), (II), (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).].: ##STR8## wherein X ⁇ represents an anion or hydroxyl ion, R represents a hydrogen atom or a methyl group, M ⁇ represents a hydrogen ion or a monovalent cation, in which the molar fraction of the structural unit (I) is 5 to 85% by mole, the molar fraction of the structural unit (II) is 2 to 85% by mole, the molar fraction of the structural unit (III) is 5 to 80% by mole, the molar fraction of the structural unit (IV) .[.is 0 to 40% by mole, all of said molar fractions being based on the vinylamine copolymer, and the molar fraction of the structural unit (V).].
- R represents a hydrogen atom or a methyl group
- the vinylamine copolymer according to the present invention has the structural units represented by the formula (I), (II), (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).].: ##STR9## (wherein X ⁇ represents an anion or hydroxyl ion, R represents a hydrogen atom or a methyl group, M ⁇ represents a hydrogen ion or a monovalent cation), in which the molar fraction of the structural unit (I) is 5 to 85% by mole, the molar fraction of the structural unit (II) is 2 to 85% by mole, the molar fraction of the structural unit (III) is 5 to 80% by mole, the molar fraction of the structural unit (IV) .[.is 0 to 40% by mole, all of said molar fractions being based on the vinylamine copolymer, and the molar fraction of the structural unit (V).].
- the total molar fractions for structural units (I), (II) and (III) is preferably at least 60%. .Iaddend.
- a preferred structural unit composition for the copolymer according to the present invention is : from 5 to 85 mol % of the structural unit (I) in the molar fraction, from 2 to 85 mol % of the structural unit (II) in the molar fraction, from 5 to 60 mol % of the structural unit (III) in the molar fraction, .[.from 0 to 30 mol % of the structural unit (IV) in the molar fraction,.]. all of said molar fractions being based on vinylamine copolymer, and from 0 to 5 mol % of the structural unit .[.(V).].
- (.Iadd.IV) .Iaddend.in the molar fraction which is based on the total content of the structural units (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).]., and a particularly preferred structural unit composition is: from 5 to 85 mol % of the structural unit (I) in the molar fraction, from 5 to 60 mole % of the structural unit (II) in the molar fraction, from 10 to 60 mol % of the structural unit (III) in the molar fraction, .[.from 0 to 30 mol % of the structural unit (IV) in the molar fraction,.].
- the novel vinylamine copolymer according to the present invention is a water soluble polymer having a reduced viscosity from 0.1 to 1.0 dl/g, preferably from 0.5 to 10 dl/g measured as a solution thereof prepared by dissolving the copolymer in aqueous 1N sodium chloride solution to a concentration of 0.1 g/dl at a temperature of 25° C.
- the novel vinylamine copolymer according to the present invention can be easily obtained by modifying the formyl groups in an N-vinylformamide copolymer under acidic conditions.
- the N-vinylformamide copolymer used as the starting material is a copolymer prepared by polymerizing a mixture of N-vinylformamide and a compound represented by the following general formula (VI)
- R represents a hydrogen atom or a methyl group
- R that is, acrylonitrile or methacrylonitrile at a molar ratio from 20:80 to 95:5, preferably, from 40:60 to 95:5 and, more preferably, from 40:60 to 90:10, in the presence of a radical polymerization initiator. It is, preferably, a copolymer of N-vinylformamide and acrylonitrile.
- a polymerization method for producing the N-polyvinylamide copolymer there can be used mass polymerization, solution polymerization or precipitation polymerization using various solvents, and aqueous solution polymerization or the precipitation polymerization which initiates the polymerization by using an aqueous solution of the monomer is preferred.
- the monomer concentration, polymerization method and a polymerizing reactor are properly selected in consideration with the molecular weight of an objective polymer and the calorific control from heat of polymerization.
- the polymerization is conducted, for example, by the following method: (1) a method of polymerizing in a state of solution with a monomer concentration of from 5 to 20% by weight and preparing the polymer as a precipitate, (2) a method of polymerizing in a state of hydrous gel with a monomer concentration of from 20 to 60% by weight and preparing the polymer as a hydrous gel-like product or precipitate, (3) a method of polymerizing an aqueous solution of the mixture with a monomer concentration of 20 to 60% by weight in a state of an oil-in-water or water-in-oil type emulsion by using a hydrophobic solvent and an emulsifier, and (4) a method of polymerizing an aqueous solution of the mixture with a monomer concentration of 20 to 60% by weight in a state of a water-in-oil type dispersion by using a hydrophobic solvent and a dispersion stabilizer, etc.
- a particularly preferred polymerization method is precipitation polymerization in water
- the radical polymerization initiator there can be used any of the ordinary initiators which are commonly used for the polymerization of water-soluble or hydrophilic monomers.
- Azo compounds are preferred for producing a polymer in high yield.
- Particularly preferred are water-soluble azo compounds, for example, hydrochlorides and acetates of 2,2'-azobis-2-amidinopropane; sodium salt of 4,4'-azobis-4-cyanovaleric acid; and hydrochlorides and sulfates of azobis-N,N'-dimethylene isobutylamidine.
- the amount of the polymerization initiator used is usually within a range from 0.01 to 1% by weight based on the weight of the monomer. Further, the polymerization reaction is usually carried out under an inert gas stream at a temperature from 30° to 100° C.
- N-vinylformamide copolymer can be modified in the form it is, in a solution, in a dispersion or in a dilute solution of the polymer or in a powder obtained by alehydrating or drying the polymer in the known method, under acidic conditions, whereby a novel polyvinylamine can be obtained.
- a novel polyvinylamine can be obtained.
- the resultant N-vinylformamide copolymer is subjected to basic hydrolysis in water, nitrile groups in the polymer are substantially eliminated.
- the content of the nitrile group in the polymer is high, it tends to result in an insoluble polymer or an amphoteric copolymer predominantly containing anionic groups.
- the modification method for the N-vinylformamide copolymer there can be mentioned, for example, (1) a method of hydrolyzing in water under acidic conditions, (2) a method of hydrolyzing in a hydrophilic solvent such as water-containing alcohol, and (3) a method of subjecting to alcohol-addition degration and modifying formyl groups while separating as an ester of formic acid.
- a method of hydrolyzing in water under acidic conditions for example, (1) a method of hydrolyzing in water under acidic conditions, (2) a method of hydrolyzing in a hydrophilic solvent such as water-containing alcohol, and (3) a method of subjecting to alcohol-addition degration and modifying formyl groups while separating as an ester of formic acid.
- the alcohols in the case of alcohol-addition degration those alcohols of 1 to 4 carbon atoms can be mentioned and methanol is preferred.
- the structural unit (V) may partially be converted into esters depending on the case by the alcohol-addition deg
- any strongly acidic of compounds can be used, such as hydrochloric acid, bromic acid, hydrofluoric acid, sulfuric acid, nitric acid, phosphoric acid, sulfamic acid and alkanesulfonic acid.
- the amount of the modifying agent used may properly be selected from a range of 0.1 to 2 times to the molar quantity of the formyl groups in the polymer according to the desired rate of modification.
- the modifying reaction is usually earned out under temperature conditions of from 40° to 100° C., by which a novel vinylamine copolymer containing nitric groups in the molecules with low carboxyl group content and having preferable water solubility is formed.
- the vinylamine copolymer according to the present invention exhibits an excellent effect as a cationic flocculating agent for the treatment of waste water for flocculating organic suspensions, a flocculating agent for the dehydration of organic sludges, etc. Particularly, it exhibits an excellent effect as a dehydrating flocculating agent for primary settled raw sludges in the treatment of sewage, sludges produced by the activated sludge treatment of water soluble organic materials, the sludges produced in the aerophobic treatment of water soluble organic materials and mixtures thereof.
- the novel vinylamine copolymer is used in the same manner as in the method of using the conventional cationic flocculating agent, for example, polymers of dimethylaminoethyl methacrylate. That is, the vinylamine copolymer is used in the form of a 0.1-0.5% by weight aqueous solution, and it is added and mixed in an organic sludge-containing suspension in an amount of 20 to 20,000 ppm based on the weight of the suspention.
- the vinylamine copolymer according to the present invention is a water soluble polymer having a reduced viscosity of 1 to 10 dl/g measured as a solution thereof prepared by dissolving the copolymer in aqueous 1N sodium chloride solution to a concentration of 0.1 g/dl at a temperature of 25° C.
- the organic sludges subjected to the flocculating treatment by using the vinylamine copolymer according to the present invention are formed more firm and solid flocks than in the case of using a polymer obtained by modifying a homopolymer of N-vinylformaraide, the dehydrating speed is improved, the throughput rate is increased and the water content in the dehydrated sludges is reduced by subjecting to machine dehydration such as compression dehydration, centrifuging vacuum filtration etc. by use of a belt press, screw press, filter press, etc.
- the vinylamine copolymer according to the present invention can be used also as a cationic water-soluble polymer for the papermaking industry and exhibits an excellent effect in use as a drainage aid, retention aid and paper strength increasing agent.
- a water-soluble polymer having a reduced viscosity of 0.5 to 10 dl/g measured as a solution thereof is prepared by dissolving the copolymer in 1N aqueous sodium chloride solution to a concentration of 0.1 g/dl at a temperature of 25° C.
- the vinylamine copolymer as a drainage aid, a retention aid and a paper strength increasing agent
- 0 to 8% by mole of the structural unit (V) in the molar fraction based on the total content of the structural units (III) to (V) is preferred.
- the molar fraction of the structural unit is not restricted to the above-mentioned value.
- the molar fraction of the structural unit (V) of 0 to 20% by mole based on the total content of the structural units (III) to (V) can be adapted. It can be used by any of the known papermaking methods.
- a cationic polymer of an amount equivalent to 0.05-2% by weight based on the dry weight of pulp is added as a 0.1-5 wt % aqueous solution to a pulp slurry containing 0.5-3 wt % of pulp and then subjected to a papermaking step.
- a method of adding it to the pulp slurry as an internal additive to the pulp slurry may be used, or it may be coated onto wet or dry web by a roll coater, size press or dipping machine.
- cationic starch, aluminum sulfate and anionic polyacrylamide may be used jointly with the polymer of the present invention. It can be used with ground pulp, sulfide pulp, craft pulp and beaten wastepaper with no restriction to the type of the pulps.
- the cationic polymer is extremely stable in the form of an aqueous solution irrespective of the quality of the solution in which the polymer is dissolved or even if in a diluted aqueous solution. Further, it is stable and does not lose its effect even under weakly alkaline papermaking conditions when using calcium carbonate as a filler.
- the additive is excellent under neutral or weakly alkaline papermaking conditions.
- novel vinylamine copolymer containing nitrile groups in the molecule according to the present invention contributes much to the field of applying flocculating agents and papermaking additives.
- polymer A-J A concentrated hydrochloric acid in an amount equivalent to the molar quantity of formyl groups in the polymer was added and maintained under stirring at 75° C. for 8 hours to hydrolyze the polymer.
- the solution of the resultant polymer was added in acetone to precipitate the polymer, which was dried in vacuum to obtain a solid polymer (hereinafter referred to as polymer A-J).
- compositions of the formed products were determined based on the composition of the copolymer before hydrolysis, the colloidal equivalent value of the product, the atomic ratio for carbon, nitrogen and chlorine based on the elemental analysis, as well as the 13 C-NMR spectrum shown together with the reduced viscosity of the product.
- Solid polymer was dissolved into distilled water to a concentration of 0.1% by weight. After diluting 5.0 g of the aqueous solution into 200 ml of desalted water and adjusting pH value of the solution to 3 by using a diluted hydrochloric acid, the colloidal equivalent value was determined by the colloidal titration method by using 1/400 N polyvinyl potassium sulfate and using toluidine blue as an indicator.
- the solid polymer was dissolved in 1N aqueous solution of sodium chloride to a concentration of 0.1 g/dl. and the reduced viscosity at 25° C. was measured by using an Ostwald viscometer.
- Example A5 The procedures are the same as those in Example A5 except for using one equivalent of an aqueous sodium hydroxide solution to the formyl groups of the N-vinylformamide copolymer instead of concentrated hydrochloric acid in Example 5.
- the resultant polymer was a slightly soluble amphoteric copolymer not substantially containing the nitrile groups.
- a portion of the gravity-filtered sludges was charged in a centrifuging basket having a dish drainer at the bottom and centrifuged at a speed of 3000 rpm for 30 sec for dehydration.
- the sludges after the dehydration were dried at 110° C. for 6 hours and the solid contents were measured to calculate the water contents in the sludges after centrifuging dehydration.
- the sludges are gravity-filtered under the same conditions as described above.
- the sludges after the filtration were put between polyester filter cloths, which were put between polyvinyl chloride plates provided with draining grooves and dehydrated by a hydraulic press having a piston of 20 mm in diameter under the conditions of a piston pressure at 50 kg/cm 2 for 30 sec.
- the sludges after the dehydration were dried at 110°C. for 6 hours and the solid contents were measured to calculate the water contents in the sludges after the press dehydration.
- a 0.6 % LBKP slurry having a freeness of 400 ml measured by Canadian Standard was present together with calcium carbonate in an amount of 17% based on the pulp, and the mixture was put into a 500 ml-beaker.
- papers of 60 g of basis weight were made by using a TAPPI Standard square type paper machine, pH value upon paper making being 8.5.
- paper was made in the same manner without adding any of the polymers A-G, I and J among the added chemicals.
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Abstract
Disclosed herein is a vinylamine copolymer having the structural units represented by the following formulas (I), (II), (III)[,] and (IV) [and (VI)]: represents an anion or hydroxyl ion R represents a hydrogen atom or a methyl group, M(+) represents a hydrogen ion or a monovalent cation, in which the molar fraction of the structural unit (I) is 5 to 85% by mole, the molar fraction of the structural unit (II) is 2 to 85% by mole, the molar fraction of the structural unit (III) is 5 to 80% by mole,[the molar fraction of the structural unit (IV) is 0 to 40% by mole,] all of said molar fractions being based on the vinylamine copolymer, and the molar fraction of the structural unit [(V)] (IV) is 0 to 8% by mole which is based on the total content of the structural units (III)[,] and (IV), [and (V),] a flocculating agent and a paper strength increasing agent using the vinylamine copolymer, and a process for producing the vinylamine copolymer.
Description
This is a divisional of copending application Ser. No. 07/470,395 filed on Jan. 25, 1990, .Iadd.now U.S. Pat. No. 4,957,977, .Iaddend.which is a continuation of U.S. Ser. No. 07/065,296, filed Jun. 22, 1987, .Iadd.now abandoned.Iaddend..
This invention relates to a novel vinylamine copolymer, a flocculating agent for the treatment of waste water using the vinylamine copolymer and a paper strength increasing agent using the vinylamine copolymer in the paper making industry, as well as a process for producing the vinylamine copolymer. More particularly, the present invention relates to a vinylamine copolymer having structural units represented by the following formulas (I), (II), (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).].: ##STR2## (wherein X⊖ represents an anion or hydroxyl ion, R represents a hydrogen atom or a methyl group, M⊕ represents a hydrogen ion or a monovalent cation), in which the molar fraction of the structural unit (I) is 5 to 85% by mole, the molar fraction of the structural unit (II) is 2 to 85% by mole, the molar fraction of the structural unit (III) is 5 to 80% by mole, the molar fraction of the structural unit (IV) .[.is 0 to 40% by mole, all of said molar fractions being bases on the vinylamine copolymer, and the molar fraction of the structural unit (V).]. is 0 to 8% by mole which is based on the total content of the structural units (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).]., a flocculating agent for the treatment of waste water and a paper strength increasing agent using the vinylamine copolymer in the papermaking industry, as well as a process for producing the vinylamine copolymer, a flocculating agent using the vinylamine copolymer, a paper strength increasing agent using the vinylamine copolymer and a process for producing the vinylamine copolymer.
The novel vinylmine copolymer according to the present invention exhibits excellent effects in the field of application of cationic polymers such as flocculating agents for use in the treatment of waste water, dehydrating agents for organic sludges, drainage aids, retention aids, paper strength increasing agents, etc. in the papermaking industry.
For the preparation of the polyvinylamine, a method by Hofmann reaction of polyacrylamide and hydrolysis of poly-N-vinylamide has been known. Particularly, the method of hydrolysis of a homopolymer of N-vinylformamide is an excellent method which is capable of synthesizing a polyvinylamine of high molecular weight with high stability. However, the resultant polymer is extremely hydrophilic and has only an insufficient effect in the case of using it as a flocculating agent for dehydration. For providing a polyvinylamine with hydrophobic properties, a method of copolymerizing N-vinylformamide and ethylene and then hydrolyzing the resulting product there has been known. However, it was difficult to solve the problem by use of the copolymer of N-vinyl formamide and ethylene, since copolymerizability between N-vinylformamide and ethylene is not favorable and, in addition, it is difficult to obtain a copolymer of high-molecular weight.
The present inventors had previously proposed a method of preparing a flocculating agent with good dehydrating properties by copolymerizing N-vinylamide with acrylonitrile, followed by hydrolysis thereby modifying not less than 10 mol % of nitrile groups into carboxyl groups [refer to Japanese Patent Application Laid Open (KOKAI) No. 59-39399(1984)]. Although the effect was remarkable for N-vinylacetamide copolymer shown in the examples, there has been a problem for N-vinylformamide copolymer in that the dehydrating property is remarkably reduced in the case where not less than 10 mol % of the nitrile groups are modified into carboxyl groups. As a result of a further study, the present inventors had proposed a process for producing a flocculating agent by using a basic hydrolyzate of a copolymer of N-vinylformamide and (metha)acrylonitrile [refer to Japanese Patent Application Laid Open (KOKAI) No. 61-118406(1986)]. However, the proposed hydrolyzate still involves a problem in that most of the nitrile groups are modified into carboxyl groups and, in the case where the content of the nitrile group in the starting copolymer is high, water-insoluble polymer is formed or an amphoteric polymer predominantly containing artionic groups results and accordingly, it had been difficult to reduce the water content in the dehydrated sludges in the case of its use as a flocculating agent for dehydration.
For overcoming the foregoing drawbacks, as a result of the present inventors' further studies, it has been found that a vinylamine copolymer of high-molecular weight having a hydrophobic properties is obtained by partially modifying a vinylformamide copolymer under acidic conditions such vinylamine copolymer has an excellent flocculating effect in the treatment of waste water and also has an excellent paper strength increasing effect in the papermaking industry; The present invention has been attained based on the above findings.
In a first aspect of the present invention, there is provided a vinylamine copolymer having the structural units represented by the following formulas (I), (II), (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).].: ##STR3## wherein X⊖ represents an anion or hydroxyl ion, R represents a hydrogen atom or a methyl group, M⊕ represents a hydrogen ion or a monovalent cation, in which the molar fraction of the structural unit (I) is 5 to 85% by mole, the molar fraction of the structural unit (II) is 2 to 85% by mole, the molar fraction of the structural unit (III) is 5 to 80% by mole, the molar fraction of the structural unit (IV) .[.is 0 to 40% by mole, and all of said molar fractions being based on the vinylamine copolymer, the molar fraction of the structural unit (V).]. is 0 to 8% by mole which is based on the total content of the structural units (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).].. .Iadd.The total molar fractions for structural units (I), (II) and (III) is preferably at least 60%. .Iaddend.
In a second aspect of the present invention, there is provided a flocculating agent comprising a vinylamine copolymer having the structural units represented by the following formulas (I), (II), (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).].: ##STR4## wherein X⊖ represents an anion or hydroxyl ion, R represents a hydrogen atom or a methyl group, M⊕ represents a hydrogen ion or a monovalent cation, in which the molar fraction of the structural unit (I) is 5 to 85% by mole, the molar fraction of the structural unit (II) is 2 to 85% by mole, the molar fraction of the structural unit (III) is 5 to 80% by mole, the molar fraction of the structural unit (IV) .[.is 0 to 40% by mole, all of said molar fractions being based on the vinylamine copolymer, and the molar fraction of the structural unit (V).]. is 0 to 8% by mole which is based on the total content of the structural units (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).].. .Iadd.The total molar fractions for structural units (I), (II) and (III) is preferably at least 60%.
In a third aspect of the present invention, there is provided a paper strength increasing agent comprising a vinylamine copolymer having the structural units represented by the following formulas (I), (II), (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).].: ##STR5## wherein X⊖ represents an anion or hydroxyl ion, R represents a hydrogen atom or a methyl group, M⊕ represents a hydrogen ion or a monovalent cation, in which the molar fraction of the structural unit (I) is 5 to 85% by mole, the molar fraction of the structural unit (II) is 2 to 85% by mole, the molar fraction of the structural unit (III) is 5 to 80% by mole, the molar fraction of the structural unit (IV) .[.is 0 to 40% by mole, all of said molar fractions being based on the vinylamine copolymer and the molar fraction of the structural unit (V).]. is 0 to 20% by mole which is based on the total content of the structural units (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).].. .Iadd.The total molar fractions for structural units (I), (II) and (III) is preferably at least 60%. .Iaddend.
In a fourth aspect of the present invention, there is provided a drainage aid for papermaking comprising a vinylamine copolymer having the structural units represented by the following formulas (I), (II), (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).].: ##STR6## wherein X⊖ represents an anion or hydroxyl ion, R represents a hydrogen atom or a methyl group, M⊕ represents a hydrogen ion or a monovalent cation, in which the molar fraction of the structural unit (I) is 5 to 85% by mole, the molar fraction of the structural unit (II) is 2 to 85% by mole, the molar fraction of the structural unit (III) is 5 to 80% by mole, the molar fraction of the structural unit (IV) .[.is 0 to 40% by mole, all of said molar fractions being based on the vinylamine copolymer, and the molar fraction of the structural unit (V).]. is 0 to 20% by mole which is based on the total content of the structural units (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).].. .Iadd.The total molar fractions for structural units (I), (II) and (III) is preferably at least 60%. .Iaddend.
In a fifth aspect of the present invention, there is provided a retention aid for papermaking comprising a vinylamine copolymer having the structural units represented by the following formulas (I), (II), (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).].: ##STR7## wherein X⊖ represents an anion or hydroxyl ion, R represents a hydrogen atom or a methyl group, M⊕ represents a hydrogen ion or a monovalent cation, in which the molar fraction of the structural unit (I) is 5 to 85% by mole, the molar fraction of the structural unit (II) is 2 to 85% by mole, the molar fraction of the structural unit (III) is 5 to 80% by mole, the molar fraction of the structural unit (IV) .[.is 0 to 40% by mole, all of said molar fractions being based on the vinylamine copolymer, and the molar fraction of the structural unit (V).]. is 0 to 20% by mole which is based on the total content of the structural units (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).].. .Iadd.The total molar fractions for structural units (I), (II) and (III) is preferably at least 60%. .Iaddend.
In a sixth aspect of the present invention, there is provided a process for producing a vinylamine copolymer having structural units comprising the following formulas (I), (II), (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).].: ##STR8## wherein X⊖ represents an anion or hydroxyl ion, R represents a hydrogen atom or a methyl group, M⊕ represents a hydrogen ion or a monovalent cation, in which the molar fraction of the structural unit (I) is 5 to 85% by mole, the molar fraction of the structural unit (II) is 2 to 85% by mole, the molar fraction of the structural unit (III) is 5 to 80% by mole, the molar fraction of the structural unit (IV) .[.is 0 to 40% by mole, all of said molar fractions being based on the vinylamine copolymer, and the molar fraction of the structural unit (V).]. is 0 to 8% by mole which is based on the total content of the structural units (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).]., which comprises polymerizing a mixture of N-vinylformamide and a compound of the following general formula (VI)
CH.sub.2 ═CR--CN (VI)
(wherein R represents a hydrogen atom or a methyl group) at a molar ratio from 20:80 to 95:5 under the presence of a radical polymerization initiator, and then modifying formyl groups in the resultant polymer under acidic conditions.
The vinylamine copolymer according to the present invention has the structural units represented by the formula (I), (II), (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).].: ##STR9## (wherein X⊖ represents an anion or hydroxyl ion, R represents a hydrogen atom or a methyl group, M⊕ represents a hydrogen ion or a monovalent cation), in which the molar fraction of the structural unit (I) is 5 to 85% by mole, the molar fraction of the structural unit (II) is 2 to 85% by mole, the molar fraction of the structural unit (III) is 5 to 80% by mole, the molar fraction of the structural unit (IV) .[.is 0 to 40% by mole, all of said molar fractions being based on the vinylamine copolymer, and the molar fraction of the structural unit (V).]. is 0 to 8% by mole which is based on the total content of the structural units (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).].. .Iadd.The total molar fractions for structural units (I), (II) and (III) is preferably at least 60%. .Iaddend.
A preferred structural unit composition for the copolymer according to the present invention is : from 5 to 85 mol % of the structural unit (I) in the molar fraction, from 2 to 85 mol % of the structural unit (II) in the molar fraction, from 5 to 60 mol % of the structural unit (III) in the molar fraction, .[.from 0 to 30 mol % of the structural unit (IV) in the molar fraction,.]. all of said molar fractions being based on vinylamine copolymer, and from 0 to 5 mol % of the structural unit .[.(V).]. (.Iadd.IV) .Iaddend.in the molar fraction which is based on the total content of the structural units (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).]., and a particularly preferred structural unit composition is: from 5 to 85 mol % of the structural unit (I) in the molar fraction, from 5 to 60 mole % of the structural unit (II) in the molar fraction, from 10 to 60 mol % of the structural unit (III) in the molar fraction, .[.from 0 to 30 mol % of the structural unit (IV) in the molar fraction,.]. all of said molar fractions being based on vinylamine copolymer, and from 0 to 2.5 mol % of the structural unit .[.(V).]. (.Iadd.IV) .Iaddend.in the molar fraction which is based on the total content of the structural units (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).].. .Iadd.The total molar fractions for structural units (I), (II) and (III) is preferably at least 70%. .Iaddend.
The novel vinylamine copolymer according to the present invention is a water soluble polymer having a reduced viscosity from 0.1 to 1.0 dl/g, preferably from 0.5 to 10 dl/g measured as a solution thereof prepared by dissolving the copolymer in aqueous 1N sodium chloride solution to a concentration of 0.1 g/dl at a temperature of 25° C.
The novel vinylamine copolymer according to the present invention can be easily obtained by modifying the formyl groups in an N-vinylformamide copolymer under acidic conditions. The N-vinylformamide copolymer used as the starting material is a copolymer prepared by polymerizing a mixture of N-vinylformamide and a compound represented by the following general formula (VI)
CH.sub.2 ═CR--CN (VI)
wherein R represents a hydrogen atom or a methyl group), that is, acrylonitrile or methacrylonitrile at a molar ratio from 20:80 to 95:5, preferably, from 40:60 to 95:5 and, more preferably, from 40:60 to 90:10, in the presence of a radical polymerization initiator. It is, preferably, a copolymer of N-vinylformamide and acrylonitrile.
As a polymerization method for producing the N-polyvinylamide copolymer, there can be used mass polymerization, solution polymerization or precipitation polymerization using various solvents, and aqueous solution polymerization or the precipitation polymerization which initiates the polymerization by using an aqueous solution of the monomer is preferred. In the case of polymerizing the monomer in the form of an aqueous solution, the monomer concentration, polymerization method and a polymerizing reactor are properly selected in consideration with the molecular weight of an objective polymer and the calorific control from heat of polymerization. The polymerization is conducted, for example, by the following method: (1) a method of polymerizing in a state of solution with a monomer concentration of from 5 to 20% by weight and preparing the polymer as a precipitate, (2) a method of polymerizing in a state of hydrous gel with a monomer concentration of from 20 to 60% by weight and preparing the polymer as a hydrous gel-like product or precipitate, (3) a method of polymerizing an aqueous solution of the mixture with a monomer concentration of 20 to 60% by weight in a state of an oil-in-water or water-in-oil type emulsion by using a hydrophobic solvent and an emulsifier, and (4) a method of polymerizing an aqueous solution of the mixture with a monomer concentration of 20 to 60% by weight in a state of a water-in-oil type dispersion by using a hydrophobic solvent and a dispersion stabilizer, etc. A particularly preferred polymerization method is precipitation polymerization in water.
As the radical polymerization initiator, there can be used any of the ordinary initiators which are commonly used for the polymerization of water-soluble or hydrophilic monomers. Azo compounds are preferred for producing a polymer in high yield. Particularly preferred are water-soluble azo compounds, for example, hydrochlorides and acetates of 2,2'-azobis-2-amidinopropane; sodium salt of 4,4'-azobis-4-cyanovaleric acid; and hydrochlorides and sulfates of azobis-N,N'-dimethylene isobutylamidine. The amount of the polymerization initiator used is usually within a range from 0.01 to 1% by weight based on the weight of the monomer. Further, the polymerization reaction is usually carried out under an inert gas stream at a temperature from 30° to 100° C.
The thus obtained N-vinylformamide copolymer can be modified in the form it is, in a solution, in a dispersion or in a dilute solution of the polymer or in a powder obtained by alehydrating or drying the polymer in the known method, under acidic conditions, whereby a novel polyvinylamine can be obtained. While on the other hand, in the case where the resultant N-vinylformamide copolymer is subjected to basic hydrolysis in water, nitrile groups in the polymer are substantially eliminated. Particularly, in the case where the content of the nitrile group in the polymer is high, it tends to result in an insoluble polymer or an amphoteric copolymer predominantly containing anionic groups.
As the modification method for the N-vinylformamide copolymer, there can be mentioned, for example, (1) a method of hydrolyzing in water under acidic conditions, (2) a method of hydrolyzing in a hydrophilic solvent such as water-containing alcohol, and (3) a method of subjecting to alcohol-addition degration and modifying formyl groups while separating as an ester of formic acid. As the alcohols in the case of alcohol-addition degration, those alcohols of 1 to 4 carbon atoms can be mentioned and methanol is preferred. The structural unit (V) may partially be converted into esters depending on the case by the alcohol-addition degration, but the effect of the copolymer according to the present invention does not substantially change even when it contains not more than 5 mol % of esters.
As the modifying agent used in the case of the acidic modification, any strongly acidic of compounds can be used, such as hydrochloric acid, bromic acid, hydrofluoric acid, sulfuric acid, nitric acid, phosphoric acid, sulfamic acid and alkanesulfonic acid. The amount of the modifying agent used may properly be selected from a range of 0.1 to 2 times to the molar quantity of the formyl groups in the polymer according to the desired rate of modification. The modifying reaction is usually earned out under temperature conditions of from 40° to 100° C., by which a novel vinylamine copolymer containing nitric groups in the molecules with low carboxyl group content and having preferable water solubility is formed.
The vinylamine copolymer according to the present invention exhibits an excellent effect as a cationic flocculating agent for the treatment of waste water for flocculating organic suspensions, a flocculating agent for the dehydration of organic sludges, etc. Particularly, it exhibits an excellent effect as a dehydrating flocculating agent for primary settled raw sludges in the treatment of sewage, sludges produced by the activated sludge treatment of water soluble organic materials, the sludges produced in the aerophobic treatment of water soluble organic materials and mixtures thereof. The novel vinylamine copolymer is used in the same manner as in the method of using the conventional cationic flocculating agent, for example, polymers of dimethylaminoethyl methacrylate. That is, the vinylamine copolymer is used in the form of a 0.1-0.5% by weight aqueous solution, and it is added and mixed in an organic sludge-containing suspension in an amount of 20 to 20,000 ppm based on the weight of the suspention.
In the case of using the vinylamine copolymer according to the present invention as a flocculating agent, it is preferred that the vinylamine copolymer is a water soluble polymer having a reduced viscosity of 1 to 10 dl/g measured as a solution thereof prepared by dissolving the copolymer in aqueous 1N sodium chloride solution to a concentration of 0.1 g/dl at a temperature of 25° C. Since the organic sludges subjected to the flocculating treatment by using the vinylamine copolymer according to the present invention are formed more firm and solid flocks than in the case of using a polymer obtained by modifying a homopolymer of N-vinylformaraide, the dehydrating speed is improved, the throughput rate is increased and the water content in the dehydrated sludges is reduced by subjecting to machine dehydration such as compression dehydration, centrifuging vacuum filtration etc. by use of a belt press, screw press, filter press, etc.
The vinylamine copolymer according to the present invention can be used also as a cationic water-soluble polymer for the papermaking industry and exhibits an excellent effect in use as a drainage aid, retention aid and paper strength increasing agent. In the case of using the vinylamine copolymer for these applications, a water-soluble polymer having a reduced viscosity of 0.5 to 10 dl/g measured as a solution thereof is prepared by dissolving the copolymer in 1N aqueous sodium chloride solution to a concentration of 0.1 g/dl at a temperature of 25° C.
Also, for using the vinylamine copolymer as a drainage aid, a retention aid and a paper strength increasing agent, 0 to 8% by mole of the structural unit (V) in the molar fraction based on the total content of the structural units (III) to (V) is preferred. However, the molar fraction of the structural unit is not restricted to the above-mentioned value. The molar fraction of the structural unit (V) of 0 to 20% by mole based on the total content of the structural units (III) to (V) can be adapted. It can be used by any of the known papermaking methods. That is, a cationic polymer of an amount equivalent to 0.05-2% by weight based on the dry weight of pulp is added as a 0.1-5 wt % aqueous solution to a pulp slurry containing 0.5-3 wt % of pulp and then subjected to a papermaking step. Particularly, in the case of using the polymer of the present invention as a paper strength increasing agent, a method of adding it to the pulp slurry as an internal additive to the pulp slurry may be used, or it may be coated onto wet or dry web by a roll coater, size press or dipping machine. If necessary, cationic starch, aluminum sulfate and anionic polyacrylamide may be used jointly with the polymer of the present invention. It can be used with ground pulp, sulfide pulp, craft pulp and beaten wastepaper with no restriction to the type of the pulps.
The cationic polymer is extremely stable in the form of an aqueous solution irrespective of the quality of the solution in which the polymer is dissolved or even if in a diluted aqueous solution. Further, it is stable and does not lose its effect even under weakly alkaline papermaking conditions when using calcium carbonate as a filler. The additive is excellent under neutral or weakly alkaline papermaking conditions.
The novel vinylamine copolymer containing nitrile groups in the molecule according to the present invention contributes much to the field of applying flocculating agents and papermaking additives.
The present invention will now be described in more detail by way of examples, but it should be noted that the invention is in no way limited to the following examples:
Into a 50 ml four-necked flask equipped with a stirrer, a nitrogen introduction tube and a cooling tube, 39.9 g of an aqueous solution containing 4.0 g of a mixture of each of the monomer compositions as shown in Table 1 was charged. After increasing the temperature to 60° C. under stiring in a nitrogen gas stream, 0.12 g of 10 wt % aqueous solution of 2,2'-azobis-2-amidinopropane dihydrochloride was added. The resultant mixture was maintained under stirring at 60° C. for three hours to obtain suspension in which a polymer was precipitated in water. The remaining monomer in the water was measured by liquid chromatography to calculate the composition of the polymer.
A concentrated hydrochloric acid in an amount equivalent to the molar quantity of formyl groups in the polymer was added and maintained under stirring at 75° C. for 8 hours to hydrolyze the polymer. The solution of the resultant polymer was added in acetone to precipitate the polymer, which was dried in vacuum to obtain a solid polymer (hereinafter referred to as polymer A-J).
Each of the compositions of the formed products was determined based on the composition of the copolymer before hydrolysis, the colloidal equivalent value of the product, the atomic ratio for carbon, nitrogen and chlorine based on the elemental analysis, as well as the 13 C-NMR spectrum shown together with the reduced viscosity of the product.
Solid polymer was dissolved into distilled water to a concentration of 0.1% by weight. After diluting 5.0 g of the aqueous solution into 200 ml of desalted water and adjusting pH value of the solution to 3 by using a diluted hydrochloric acid, the colloidal equivalent value was determined by the colloidal titration method by using 1/400 N polyvinyl potassium sulfate and using toluidine blue as an indicator.
The solid polymer was dissolved in 1N aqueous solution of sodium chloride to a concentration of 0.1 g/dl. and the reduced viscosity at 25° C. was measured by using an Ostwald viscometer.
Reduced viscosity (dl/g)=(t--t.sub.0)/t.sub.0 /0.1
(wherein t0 represents descending speed of aqueous sodium chloride and t represents descending speed of polymer solution).
TABLE 1
______________________________________
Monomer composition (mol %)
Example VF.sup.1 AN.sup.2
AC.sup.3
______________________________________
A1 90 10 0
A2 75 25 0
A3 60 40 0
A4 60 40 0
A5 50 50 0
A6 40 60 0
A7 40 60 0
A8 50 50 0
A9 50 46.5 3.5
A10 50 45 5
______________________________________
Note:
.sup.1 VF: Nvinylformamide
.sup.2 AN: acrylonitrile
.sup.3 AC: sodium acrylate
.[.TABLE 2
______________________________________
Structural unit of the
Reduced
product (mol %) viscosity
Example
Polymer I II III IV V (dl/g)
______________________________________
A1 A 75 15 8 2 0 1.9
A2 B 64 11 18 7 0 2.5
A3 C 57 3 25 14 1 3.6
A4 D 30 30 34 6 0 2.0
A5 E 33 17 35 14 1 2.5
A6 F 35 5 30 29 1 3.1
A7 G 17 23 47 11 2 2.5
A8 H 46 4 32 16 2 3.0
A9 I 32 18 33 13 4 2.8
A10 J 31 19 32 12 6 2.9
______________________________________
Note:
0.5 eq of hydrochloric acid was used to the formyl groups in the polymer
upon modification in Examples A4 and A7.
Modifying reaction was carried out at 95° C. in Example A8.
X is chlorine ion in the structural unit (I), and R and M are hydrogen
atom in the structural units (III) and (V).
The procedures are the same as those in Example A5 except for using one equivalent of an aqueous sodium hydroxide solution to the formyl groups of the N-vinylformamide copolymer instead of concentrated hydrochloric acid in Example 5. The resultant polymer was a slightly soluble amphoteric copolymer not substantially containing the nitrile groups.
100 ml (2.0% by weight of solid content) of mixed raw sludges obtained from a city sewage treatment plant put into a 200 ml-polyethylene beaker and 6 ml of an aqueous 0.2 wt % solution of each of the polymers shown in Table 3 was added thereto. The suspension was agitated by using a stirrer having at its end three rods 5 mm in diameter and 20 mm in length, at a speed of 1000 rpm for 10 sec. The flocculated sludges were charged in a cylinder bottomed with a 60 mesh nylon screen having a diameter of 65 mm and subjected to gravity filtration, and after 10 sec, the amount of the tiltrate was measured. Further, a portion of the gravity-filtered sludges was charged in a centrifuging basket having a dish drainer at the bottom and centrifuged at a speed of 3000 rpm for 30 sec for dehydration. The sludges after the dehydration were dried at 110° C. for 6 hours and the solid contents were measured to calculate the water contents in the sludges after centrifuging dehydration.
While on the other hand, the sludges are gravity-filtered under the same conditions as described above. The sludges after the filtration were put between polyester filter cloths, which were put between polyvinyl chloride plates provided with draining grooves and dehydrated by a hydraulic press having a piston of 20 mm in diameter under the conditions of a piston pressure at 50 kg/cm2 for 30 sec. The sludges after the dehydration were dried at 110°C. for 6 hours and the solid contents were measured to calculate the water contents in the sludges after the press dehydration.
These results are shown collectively in Table 3.
TABLE 3
______________________________________
Amount of Water content
Water content
Example filtrate 10
of sludges
of sludges
and sec. after
after after
Com- the gravity
centrifuging
press-
parative
Poly- filtration
dehydration
dehydration
Example
mer (ml) (wt %) (wt %)
______________________________________
B1 A 55 78.2 75.4
B2 B 60 78.4 75.2
B3 C 60 78.0 74.6
B4 E 65 77.6 74.6
B5 F 65 77.2 74.4
B6 H 65 77.0 73.8
B7 I 60 78.8 75.6
B8 J 55 81.6 77.8
B9 .sup. K.sup.1
45 83.4 80.5
B10 .sup. L.sup.2
not -- --
agulated
______________________________________
(Note)
.sup.1 Polymer K: Copolymer of 2methacryloyloxyethyl trimethyl ammonium
chloride and acrylamide (molar ratio: 2/8) (reduced viscosity: 10.7 dl/g)
.sup.2 Polymer L: Hydrolyzate of Nvinylamide ethylene copolymer (molar
ratio: 56/44) Modification ratio: 59 mol %, reduced viscosity: 0.2 dl/g
A 0.6 % LBKP slurry having a freeness of 400 ml measured by Canadian Standard was present together with calcium carbonate in an amount of 17% based on the pulp, and the mixture was put into a 500 ml-beaker. After adding the chemicals shown below in the form of an aqueous solution under stirring, papers of 60 g of basis weight were made by using a TAPPI Standard square type paper machine, pH value upon paper making being 8.5.
______________________________________
(Condition of Using Added Chemicals)
Concentration
of aqueous Addition amount
solution to pulp dry weight
(wt %) (wt %)
______________________________________
Cationic starch
1.0 0.5
Polymers A-G, I and J
0.5 0.5
Sizing agent 1.0 0.2
(alkyl ketene dimer)
Filler retention improving
0.1 0.02
agent
______________________________________
For the comparison, paper was made in the same manner without adding any of the polymers A-G, I and J among the added chemicals.
The thus obtained wet papers were dried for three minutes by using a drum drier at 120° C. After allowing to stand the resultant papers under the conditions of a temperature of 20° C. and relative humidity of 60%, the specific burst factor and the burst length were measured according to JIS-P and JIS-P 8113. ##EQU1## where S1 : burst strength (kg/cm2)
W: basis weight of test paper (g/m2)
S2 tensile strength (kg)
B: width of the test piece (mm)
The results are shown in Table 4.
TABLE 4
______________________________________
Specific burst
factor Burst length
Example Polymer (Kg/cm.sup.2)
(Km)
______________________________________
C1 A 1.46 2.55
C2 B 1.47 2.54
C3 C 1.63 2.69
C4 D 1.57 2.38
C5 E 1.39 2.44
C6 F 1.39 2.17
C7 G 1.38 2.40
C8 I 1.42 2.38
C9 J 1.35 2.21
Comparative
not 1.12 1.92
Example added
C10
______________________________________
1% slurry of waster liner board paper having a freeness of 300 ml measured by Canadian Standard was put into a 500 ml-beaker and an aqueous 0.5 wt % solution of each of the polymers A-G was added in an amount of 0.3% by weight based on the dry weight of the pulp and then the resultant mixture was maintained for one minute. Papers of basis weight of 120 g were made by using a TAPPI Standard square type paper machine. After treating the thus resultant wet papers in the same procedures as in Example C1, the paper strength of the resultant papers was measured. For the comparison, paper was made in the same procedures as above but without adding any of the polymers and the strength of the resultant paper was measured. The results are shown in Table 5.
TABLE 5
______________________________________
Specific burst factor
Example Polymer (Kg/cm.sup.2)
______________________________________
C11 A 2.51
C12 B 2.71
C13 C 2.72
C14 D 2.71
C15 E 2.86
C16 F 2.82
C17 G 2.71
C18 I 2.76
C19 J 2.52
Comparative not 2.26
Example added
C20
______________________________________
One liter of 0.3% slurry of LBKP having a freeness of 220 ml measured by Canadian Standard was put into a 2 liter-beaker and each of the polymers A-G, I and J in the form of 0.2 wt aqueous solution was added in an amount of 0.2% by weight based on the dry weight of the pulp under stirring. After stirring the mixture at a speed of 200 rpm for one minute, the freeness of each product was measured by using a Canadian Freeness Tester. For the comparison, an experiment was conducted in the same way without adding any of the polymers. The results are shown in Table 6.
TABLE 6 ______________________________________ Example Polymer Freeness (ml) ______________________________________ D1 A 270 D2 B 260 D3 C 300 D4 D 285 D5 E 285 D6 F 255 D7 G 250 D8 I 280 D9 J 260 Comparative not 220 Example added D10 ______________________________________
One liter of 0.5% LBKP slurry having a freeness of 410 ml measured by Canadian Standard was put into a 2 liter-beaker and 30% by weight of papermaking talc, 0.3% by weight of reinforcing rosin and 4% by weight of aluminum sulfate based on the dry weight of the pulp were respectively added under stirring. Further, after adding an aqueous 0.2 wt % solution of each of the polymers A-G, I and J in an amount of 0.03 by weight based on the pulp and stiring at a speed of 200 rpm for one minutes, papers of 70 g basis weight were made by the same procedures as in Example C1.
The ash content in the thus obtained resultant papers was measured and the results are shown in Table 7.
For the comparison, paper was made in the same procedures but without adding any of the polymers.
TABLE 7 ______________________________________ Example Polymer Ash content (%) ______________________________________ E1 A 15.7 E2 B 15.6 E3 C 17.1 E4 D 18.0 E5 E 16.7 E6 F 16.5 E7 G 15.7 E8 I 15.5 E9 J 15.0 Comparative not 12.7 Example added E10 ______________________________________
Claims (10)
1. A process for producing a vinylamine copolymer having the structural units comprising following formulas (I), (II), (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).].: ##STR10## wherein X⊖ represents an anion or hydroxyl ion, R represents a hydrogen atom or a methyl group, M⊕ represents a hydrogen ion or a monovalent cation, in which the molar fraction of the structural unit (I) is 5 to 85% by mole, the molar fraction of the structural unit (II) is 2 to 85% by mole, the molar fraction of the structural unit (III) is 5 to 80% by mole, the molar fraction of the structural unit (IV) .[.is 0 to 40% by mole, and the molar fraction of the structural unit (V).]. is 0 to 8% by mole based on the total content of the structural units (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).]., which comprises polymerizing a mixture of N-vinylformamide and a compound of the following general formula (VI)
CH.sub.2 ═CR--CN (VI)
(wherein R represents a hydrogen atom or a methyl group) at a molar ratio from 20:80 to 95:5 in the presence of a radical polymerization initiator, and then modifying formyl groups in the resultant polymer under an acidic condition.
2. A process for producing a vinylamine copolymer having the structural units comprising the following formulas (I), (II), (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).].: ##STR11## wherein X⊖ represents an anion, R represents a hydrogen atom or a methyl group, M⊕ represents a hydrogen ion or a monovalent cation, in which the molar fraction of the structural unit (I) is 5 to 85% by mole, the molar fraction of the structural unit (II) is 2 to 85% by mole, the molar fraction of the structural unit (II) is 5 to 80% by mole, ; .[.the molar fraction of the structural unit (IV) is 0 to 40% by mole,.]. all of said molar fractions being based on the vinylamine copolymer, and the molar fraction of the structural unit .[.(V).]. (.Iadd.IV) .Iaddend.is 0 to 8% by mole based on the total content of the structural units (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).]., which comprise polymerizing a mixture of N-vinylformamide and a compound of the following general formula (VI):
CH.sub.2 ═CR--CN (VI)
wherein R represent a hydrogen atom or a methyl group) at a molar ratio from 20:80 to 95:5 in the presence of a radical polymerization initiator to obtain an N-vinylformamide copolymer, and then modifying the thus obtained N-vinylformamide copolymer under an acidic condition in the presence of a modifying agent to obtain the vinylamine copolymer defined above.
3. A process according to claim 2, wherein the radical polymerization initiator is from 0.01 to 1% by weight based on the monomer.
4. A process according to claim 2, wherein the polymerizing reaction is carried out in an inert gas stream at a temperature from 30 to 100° C.
5. A process according to claim 2, wherein the modification is carried out under an acidic condition by (1) a method of hydrolyzing in water, (2) a method of hydrolyzing in a hydrophilic solvent of a water-containing alcohol or (3) a method of subjecting to alcohol-addition degration and then modifying while separating the formyl groups as esters of formic acid.
6. A process according to claim 2, wherein the modifying agent is hydrochloric acid, bromic acid, hydrofluoric acid, sulfuric acid, nitric acid, phosphoric acid, sulfamic acid or alkane sulfonic acid.
7. A process according to claim 2, wherein the modifying agent is from 0.1 to 2 molar times to the formyl group in the polymer.
8. A process according to claim 2, wherein the modification is carried out at a temperature from 40° C. to 100° C.
9. A process according to claim 2, wherein the radical polymerization initiator is an azo compound. .Iadd.10. A process for producing a vinylamine copolymer, said process comprising:
polymerizing, in the presence of a radical polymerization initiator, a mixture of (i)N-vinylformamide and (ii) a compound of the following general formula:
CH.sub.2 ═CR--CN
wherein R represents a hydrogen atom or a methyl group at a molar ratio from 20:80 to 95:5 and
hydrolyzing the resultant polymer. .Iadd.11. A process for producing a vinylamine copolymer, said process comprising:
polymerizing, in the presence of a radical polymerization initiator, a mixture of (i)N-vinylformamide and (ii) a compound of the following general formula:
CH.sub.2 ═CR--CN
wherein R represents a hydrogen atom or a methyl group at a molar ratio from 20:80 to 95:5 and
hydrolyzing the resultant polymer under acid conditions to modify formyl groups. .Iaddend.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/148,384 USRE34903E (en) | 1987-06-22 | 1993-11-08 | Vinylamine copolymer, flocculating agent and paper strength increasing agent using the same, as well as process for producing the same |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US6529687A | 1987-06-22 | 1987-06-22 | |
| US07/470,395 US4957977A (en) | 1986-06-25 | 1990-01-25 | Vinylamine copolymer, flocculating agent etc. |
| US07/564,042 US5064909A (en) | 1986-06-25 | 1990-08-07 | Vinylamine copolymer, flocculating agent and paper strength increasing agent using the same, as well as process for producing the same |
| US08/148,384 USRE34903E (en) | 1987-06-22 | 1993-11-08 | Vinylamine copolymer, flocculating agent and paper strength increasing agent using the same, as well as process for producing the same |
Related Parent Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/470,395 Division US4957977A (en) | 1986-06-25 | 1990-01-25 | Vinylamine copolymer, flocculating agent etc. |
| US07/564,042 Reissue US5064909A (en) | 1986-06-25 | 1990-08-07 | Vinylamine copolymer, flocculating agent and paper strength increasing agent using the same, as well as process for producing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USRE34903E true USRE34903E (en) | 1995-04-11 |
Family
ID=27490481
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US08/148,384 Expired - Lifetime USRE34903E (en) | 1987-06-22 | 1993-11-08 | Vinylamine copolymer, flocculating agent and paper strength increasing agent using the same, as well as process for producing the same |
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| Country | Link |
|---|---|
| US (1) | USRE34903E (en) |
Cited By (2)
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| US5516852A (en) * | 1993-11-12 | 1996-05-14 | W. R. Grace & Co.-Conn. | Method of producing water-soluble cationic copolymers |
| US20050087091A1 (en) * | 2003-10-23 | 2005-04-28 | Bowden A. G. | Friction wedge with mechanical bonding matrix augmented composition liner material |
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| US5516852A (en) * | 1993-11-12 | 1996-05-14 | W. R. Grace & Co.-Conn. | Method of producing water-soluble cationic copolymers |
| US20050087091A1 (en) * | 2003-10-23 | 2005-04-28 | Bowden A. G. | Friction wedge with mechanical bonding matrix augmented composition liner material |
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