CN113943409B - Synthesis method of amphoteric polyacrylamide, reinforcing agent for waste paper recycling papermaking and preparation method of reinforcing agent - Google Patents
Synthesis method of amphoteric polyacrylamide, reinforcing agent for waste paper recycling papermaking and preparation method of reinforcing agent Download PDFInfo
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- CN113943409B CN113943409B CN202111124179.8A CN202111124179A CN113943409B CN 113943409 B CN113943409 B CN 113943409B CN 202111124179 A CN202111124179 A CN 202111124179A CN 113943409 B CN113943409 B CN 113943409B
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- 229920002401 polyacrylamide Polymers 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 239000012744 reinforcing agent Substances 0.000 title claims abstract description 38
- 239000010893 paper waste Substances 0.000 title claims abstract description 22
- 238000001308 synthesis method Methods 0.000 title claims abstract description 7
- 238000004064 recycling Methods 0.000 title claims description 8
- 230000000977 initiatory effect Effects 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- NNTWKXKLHMTGBU-UHFFFAOYSA-N 4,5-dihydroxyimidazolidin-2-one Chemical compound OC1NC(=O)NC1O NNTWKXKLHMTGBU-UHFFFAOYSA-N 0.000 claims abstract description 24
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims description 45
- 238000003756 stirring Methods 0.000 claims description 42
- 239000007788 liquid Substances 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 14
- 239000004202 carbamide Substances 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- 229940015043 glyoxal Drugs 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 9
- 125000000129 anionic group Chemical group 0.000 claims description 9
- 125000002091 cationic group Chemical group 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 6
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 6
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 6
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 5
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- 125000003172 aldehyde group Chemical group 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- LUTFTISESXWDHG-UHFFFAOYSA-N 3-aminopropyl 2-methylprop-2-enoate;hydrochloride Chemical compound Cl.CC(=C)C(=O)OCCCN LUTFTISESXWDHG-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 claims description 2
- AJURYMCOXVKKFB-UHFFFAOYSA-M trimethyl(3-prop-2-enoyloxypropyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCOC(=O)C=C AJURYMCOXVKKFB-UHFFFAOYSA-M 0.000 claims description 2
- 239000003623 enhancer Substances 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 36
- 229920001131 Pulp (paper) Polymers 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000835 fiber Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920002522 Wood fibre Polymers 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 239000002025 wood fiber Substances 0.000 description 3
- 239000004593 Epoxy Chemical group 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001299 aldehydes Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- -1 papermaking Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material 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
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
-
- 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
- C08F220/00—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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/10—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of amides or imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/10—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with acyclic compounds having the moiety X=C(—N<)2 in which X is O, S or —N
- C08G12/12—Ureas; Thioureas
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
- D21H17/43—Carboxyl groups or derivatives thereof
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
- D21H17/45—Nitrogen-containing groups
- D21H17/455—Nitrogen-containing groups comprising tertiary amine or being at least partially quaternised
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/47—Condensation polymers of aldehydes or ketones
- D21H17/49—Condensation polymers of aldehydes or ketones with compounds containing hydrogen bound to nitrogen
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
- D21H21/20—Wet strength agents
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
Abstract
The invention discloses a synthesis method of amphoteric polyacrylamide, an enhancer for paper making by waste paper recovery and a preparation method thereof, wherein the amphoteric polyacrylamide is obtained by initiating reaction on the basis of acrylamide; the reinforcing agent for paper making by waste paper recovery comprises amphoteric polyacrylamide and glyoxal urea polymer in a weight ratio of 1:1-3. The reinforcing agent disclosed by the invention can obviously improve the strength of paper.
Description
Technical Field
The invention relates to the technical field of papermaking additives, in particular to a synthesis method of amphoteric polyacrylamide, an enhancer for waste paper recovery and papermaking and a preparation method thereof.
Background
In the current domestic market, waste paper pulp used in China reaches 5363 ten thousand tons in 2020 due to the large amount of waste paper, and the consumption is huge; in addition, since the import of waste is forbidden, many paper factories in China use wood fiber, sludge and the like to fill the waste paper to the recovery process, and the length and the strength of the fiber are obviously reduced after the waste paper pulp is pulped, and in addition, the strength of paper is reduced due to the filling of common wood fiber, sludge, calcium carbonate and the like, so that a reinforcing agent special for waste paper pulp is needed to improve the strength of the paper.
Polyacrylamide (PAM) is an important water-soluble high polymer, can be introduced with various ionic groups to obtain specific properties, is widely applied to various fields of chemical industry, metallurgy, geology, coal, petroleum, papermaking, water treatment and the like, and has the name of 'department assistant'; however, the conventional polyacrylamide is used as a reinforcing agent in papermaking, and a large amount of calcium carbonate slurry is used for filling, or sludge is recycled, or some wood fibers are used in the papermaking process, so that the strength of paper is reduced; and the problems of short fiber, reduced fiber strength and the like caused by pulping the recycled waste paper which is used in a large quantity at present, the improvement of the strength of the paper by the polyacrylamide such as the polyacrylamide, the cation, the anion and the like which are used at present is less and less obvious, and in the current state, the recycled waste paper pulping is more and more, so that the performance of the reinforcing agent is more and more required, and the polyacrylamide reinforcing agent used in the current papermaking has a great improvement and optimization space; therefore, the invention aims to develop a synthetic method of the amphoteric polyacrylamide, and the amphoteric polyacrylamide is used for preparing the reinforcing agent so as to solve the problems of the traditional reinforcing agent.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the synthesis method of the amphoteric polyacrylamide, the reinforcing agent for waste paper recycling and papermaking and the preparation method thereof, the amphoteric polyacrylamide with a special structure is prepared, and the amphoteric polyacrylamide is used for preparing the reinforcing agent for papermaking, so that the strength of paper can be obviously improved, and particularly for waste paper pulp recycled for multiple times, the connection between fine fibers can be effectively realized, and the strength of the paper is enhanced;
the technical scheme adopted for solving the technical problems is as follows:
the synthesis method of the amphoteric polyacrylamide comprises the following steps:
s1, preparation of substrate
Adding deionized water, acrylamide, cationic monomer, anionic monomer, sodium bisulphite and EDTA into a reaction kettle, stirring and dissolving, and heating to 50-70 ℃ to obtain a substrate for later use;
s2, preparation of solution A
Adding acrylamide and deionized water into a monomer kettle, then adding an anionic monomer and a cationic monomer, uniformly stirring, then adding alkali liquor, and adjusting the pH of the system to 3-4 to obtain a solution A for later use;
s3, preparation of solution B
Adding a functional monomer 1, a functional monomer 2, acrylamide and deionized water into a monomer kettle, and uniformly stirring to obtain a solution B for later use;
s4, preparation of initiating liquid
Preparing an initiator, adding a proper amount of deionized water, and uniformly stirring to obtain an initiating liquid for later use;
s5, initiating reaction
Taking a half amount of initiating liquid in the step S4, and simultaneously, dropwise adding the solution A and the initiating liquid into the substrate in the step S1 in parallel to obtain a mixed liquid C after the completion of dropwise adding; and (3) dropwise adding the solution B and the rest of the initiating liquid into the mixed liquid C in parallel, and after the completion of dropwise adding, preserving heat, cooling and discharging to obtain the amphoteric polyacrylamide.
Preferably, the anionic monomer is selected from: one or more of acrylic acid, methacrylic acid, fumaric acid, itaconic acid, sulfonic acid unsaturated monomers (such as 2-acrylamido-2-methylpropanesulfonic acid, sodium allylsulfonate, etc.);
preferably, the cationic monomer is selected from: one or more of methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, diallyl dimethyl ammonium chloride, methacryloyloxypropyl ammonium chloride, acryloyloxypropyl trimethyl ammonium chloride and the like;
preferably, the functional monomer 1 is selected from hydroxy-containing olefins such as hydroxyethyl methacrylate, hydroxyethyl acrylate and the like;
preferably, the functional monomer 2 is selected from: glycidyl methacrylate;
preferably, the initiator is selected from the following materials: ammonium persulfate, potassium persulfate, or sodium persulfate;
preferably, the alkali liquor in the step S2 is sodium hydroxide solution or ammonia water;
preferably, in the step S5, half of the initiator and the solution a are dropwise added in parallel into the reaction kettle (dropwise adding is performed in the substrate), the dropwise adding time is 1-2h, the dropwise adding temperature is kept at 50-70 ℃, after the dropwise adding is completed, the rest of the initiator and the solution B are continuously dropwise added into the reaction kettle in parallel, the dropwise adding time is 1-2h, the temperature is 50-70 ℃, after the dropwise adding is completed, the temperature is kept for 1-2h, and then the temperature is reduced and the material is discharged.
Specifically, the usage amounts of the above raw materials are shown in the following table:
in the invention, firstly, acrylamide, an anionic monomer and a cationic monomer are used for copolymerization, and then functional monomers are connected to two ends for grafting modification, so that the amphoteric polyacrylamide polymer is obtained, and the two ends of a molecular chain of the amphoteric polyacrylamide are respectively connected with special groups containing hydroxyl and epoxy groups, so that a stable crosslinking structure can be better formed with fibers;
in addition, the invention also provides a reinforcing agent for paper making to be used for waste paper recycling through the amphoteric polyacrylamide and GU resin, which comprises the following raw materials in parts by weight: 1 part of amphoteric polyacrylamide and 1-3 parts of glyoxal urea polymer;
wherein the viscosity of the amphoteric polyacrylamide is 5000-8000cps, and the aldehyde group viscosity of the glyoxal urea polymer at both ends is less than 100cps
The glyoxal urea polymer is obtained by polymerization reaction of glyoxal and urea, and is prepared according to the following steps: the molar ratio of urea is 2-4:1, and aldehyde groups are contained at both ends of glyoxal urea polymer.
Similarly, the invention also provides a preparation method of the papermaking reinforcing agent, which comprises the following steps:
1. preparation of glyoxal urea polymers
S6, adding glyoxal and urea into a reaction kettle according to a molar ratio, then adjusting the pH value of the system to 3-4 by using alkali liquor, reacting at normal temperature, keeping the pH value of the system to 3-4, and reacting for 6-8 hours to obtain glyoxal urea polymer;
2. preparation of reinforcing agent
S7, according to the weight ratio of the amphoteric polyacrylamide to the glyoxal urea polymer of 1:1-3, preparing the amphoteric polyacrylamide and glyoxal urea polymer, and storing separately to obtain the reinforcing agent. When the reinforcing agent is used, the prepared amphoteric polyacrylamide and glyoxal urea polymer are put into paper pulp and uniformly mixed for use.
Preferably, the alkali liquor in the step S6 is sodium hydroxide solution;
preferably, glyoxal in step S6: the urea reacts according to the molar ratio of 2-4:1, and both ends of the glyoxal urea polymer are provided with aldehyde groups, so that the molecular chain of the glyoxal urea polymer is prolonged, and the glyoxal urea polymer and the amphoteric polyacrylamide are subjected to crosslinking reaction more easily to form a netlike polymer.
The beneficial effects of the invention are as follows:
(1) Compared with the common amphoteric polyacrylamide reinforcing agent products in the current market, the amphoteric polyacrylamide disclosed by the invention has the advantages that the special functional monomers are connected to the two ends of a molecular chain, so that a special structure is formed, and even if the amphoteric polyacrylamide has the special structure containing hydroxyl and epoxy groups, a stable crosslinking structure can be better formed with fibers.
(2) In the reinforcing agent, glyoxal urea polymer contains a large number of hydroxyl and aldehyde functional groups, can carry out crosslinking reaction with hydroxyl, amino and epoxy functional groups contained in amphoteric polyacrylamide, and can also react with hydroxyl contained in fiber, so that a crosslinked reticular structure is formed between the hydroxyl, amino and epoxy functional groups, the strength of paper can be obviously improved, and especially for waste paper pulp recycled for many times, the connection between fine fibers can be effectively realized, and the strength (including dry strength and wet strength) of paper is enhanced.
Drawings
The invention will be further described with reference to the drawings and examples.
FIG. 1 is a table of raw materials used in examples 1-15 according to the present invention;
FIG. 2 is a table of raw materials used in comparative examples 1 to 9 according to the present invention;
FIG. 3 is a summary of the results of the detection of the amphoteric polyacrylamides prepared according to examples 1-15 of the present invention;
FIG. 4 is a summary of the results of the detection of the amphoteric polyacrylamides prepared according to comparative examples 1-9 of the present invention;
FIG. 5 is a summary of the results of the detection of the enhancers prepared in examples 1-15 and comparative examples 1-9 according to the present invention;
FIG. 6 is a chemical reaction equation for preparing glyoxal urea polymers in accordance with the present invention;
FIG. 7 is a chemical reaction equation for preparing amphoteric polyacrylamide according to the present invention.
Detailed Description
The invention will be further illustrated by the following examples, which are not intended to limit the scope of the invention, in order to facilitate the understanding of those skilled in the art.
Example 1 a method of making a papermaking reinforcing agent comprising the steps of:
1. preparation of amphoteric Polyacrylamide (Compound (2) having the Structure shown in FIG. 7)
S1, preparation of substrate
Adding 400g of deionized water into a reaction kettle, then adding 42g of acrylamide, 0.3g of sodium bisulphite, stirring for dissolution, adding 18g of acrylic acid and 30.7g of methacryloyloxyethyl trimethyl ammonium chloride, uniformly stirring, adding 0.03g of EDTA, uniformly stirring, and heating to 60 ℃ to obtain a substrate for later use;
s2, preparation of solution A
Adding 30g of acrylamide into a monomer kettle, stirring and dissolving, adding 18g of acrylic acid, 30.7g of methacryloyloxyethyl trimethyl ammonium chloride and 200g of water, stirring and dissolving, and adding 10% concentration sodium hydroxide solution to adjust the pH value to 3.5 to obtain a solution A for later use;
s3, preparation of solution B
Adding 12g of acrylamide and 192g of water into a monomer kettle, stirring and dissolving, adding 4g of hydroxyethyl methacrylate and 1g of glycidyl methacrylate, and stirring uniformly to obtain a solution B for later use;
s4, preparation of initiating liquid
Adding 136g of water into 0.8g of sodium persulfate, and uniformly stirring to prepare an initiator solution for later use; dividing the mixture into two parts;
s5, initiating reaction
Taking half of the initiating liquid in the step S4, and simultaneously, dropwise adding the solution A and the initiating liquid into the substrate in the step S1 in parallel, wherein the dropwise adding time is 2 hours, and the temperature is 70 ℃; after the dripping is finished, obtaining a mixed solution C; simultaneously, dripping the solution B and the rest initiating liquid in the step S4 into the mixed liquid C in parallel, wherein the dripping time is 2 hours, the temperature is 70 ℃, the temperature is kept for 2 hours after the dripping is finished, the temperature is reduced to below 35 ℃, and the amphoteric polyacrylamide is obtained after discharging;
2. preparation of glyoxal Urea Polymer (GU resin) (Compound (3) having the structure shown in FIG. 6)
S6, the following glyoxal, urea (molar ratio, urea 50 g) =2: 1, adding glyoxal into a reaction kettle, then adding urea (50 g), stirring and dissolving completely, adjusting the pH value to 3.5 by using 10% sodium hydroxide solution, reacting at normal temperature for 6 hours, and discharging after the reaction is finished;
3. preparation of reinforcing agent
And S7, respectively preparing materials of the amphoteric polyacrylamide and GU resin according to the weight ratio of 1:3 at normal temperature, and separately storing, and simultaneously adding the materials into paper pulp and uniformly stirring when the paper pulp is used.
Example 2
A method for preparing a papermaking reinforcing agent, comprising the following steps:
1. preparation of amphoteric Polyacrylamide (Compound (2) having the Structure shown in FIG. 7)
S1, preparation of substrate
Adding 400g of deionized water into a reaction kettle, then adding 30g of acrylamide, 0.3g of sodium bisulphite, stirring for dissolution, adding 18g of acrylic acid and 30.7g of methacryloyloxyethyl trimethyl ammonium chloride, uniformly stirring, adding 0.03g of EDTA, uniformly stirring, and heating to 50 ℃ to obtain a substrate for later use;
s2, preparation of solution A
Adding 42g of acrylamide into a monomer kettle, stirring and dissolving, adding 18g of acrylic acid, 30.7g of methacryloyloxyethyl trimethyl ammonium chloride and 200g of water, stirring and dissolving, and adding 30% sodium hydroxide solution to adjust the pH value to 3 to obtain a solution A for later use;
s3, preparation of solution B
Adding 12g of acrylamide and 192g of water into a monomer kettle, stirring and dissolving, adding 4g of hydroxyethyl methacrylate and 1g of glycidyl methacrylate, and stirring uniformly to obtain a solution B for later use;
s4, preparation of initiating liquid
0.8g of ammonium persulfate is used, 136g of water is added, and the mixture is uniformly stirred to prepare an initiator solution for later use; dividing the mixture into two parts;
s5, initiating reaction
Taking half of the initiating liquid in the step S4, and simultaneously, dropwise adding the solution A and the initiating liquid into the substrate in the step S1 in parallel, wherein the dropwise adding time is 2 hours, and the temperature is 70 ℃; after the dripping is finished, obtaining a mixed solution C; simultaneously, dripping the solution B and the rest initiating liquid in the step S4 into the mixed liquid C in parallel, wherein the dripping time is 2 hours, the temperature is 70 ℃, the temperature is kept for 2 hours after the dripping is finished, the temperature is reduced to below 35 ℃, and the amphoteric polyacrylamide is obtained after discharging;
2. preparation of glyoxal Urea Polymer (Compound (3) having the structure shown in FIG. 6)
S6, adding glyoxal into a reaction kettle according to the molar ratio of glyoxal to urea (urea 50 g) =3:1, adding urea (50 g), stirring and dissolving completely, adjusting the pH value to 3 by using 30% sodium hydroxide solution, reacting at normal temperature for 7h, and discharging after the reaction is finished;
3. preparation of reinforcing agent
S7, amphoteric polyacrylamide according to the mass ratio: GU resin=1: 2, mixing, namely respectively preparing the amphoteric polyacrylamide and GU resin according to the weight ratio of 1:3 at normal temperature, and separately storing, and simultaneously adding the amphoteric polyacrylamide and the GU resin into paper pulp and uniformly stirring when the amphoteric polyacrylamide and GU resin are used.
Example 3
A method for preparing a papermaking reinforcing agent, comprising the following steps:
1. preparation of amphoteric Polyacrylamide (Compound (2) having the Structure shown in FIG. 7)
S1, preparation of substrate
Adding 400g of deionized water into a reaction kettle, then adding 42g of acrylamide, 0.3g of sodium bisulphite, stirring for dissolution, adding 9g of acrylic acid, 30.7g of methacryloyloxyethyl trimethyl ammonium chloride, uniformly stirring, adding 0.03g of EDTA, uniformly stirring, and heating to 50-70 ℃ to obtain a substrate for later use;
s2, preparation of solution A
Adding 30g of acrylamide into a monomer kettle, stirring and dissolving, adding 18g of acrylic acid, 30.7g of methacryloyloxyethyl trimethyl ammonium chloride and 200g of water, stirring and dissolving, and adding a proper amount of liquid alkali to adjust the pH value to 3-4 to obtain a solution A for later use;
s3, preparation of solution B
Adding 12g of acrylamide and 192g of water into a monomer kettle, stirring and dissolving, adding 4g of hydroxyethyl methacrylate and 1g of glycidyl methacrylate, and stirring uniformly to obtain a solution B for later use;
s4, preparation of initiating liquid
Adding 136g of water into 0.8g of potassium persulfate, and uniformly stirring to prepare an initiator solution for later use; dividing the mixture into two parts;
s5, initiating reaction
Taking half of the initiating liquid in the step S4, and simultaneously, dropwise adding the solution A and the initiating liquid into the substrate in the step S1 in parallel, wherein the dropwise adding time is 2 hours, and the temperature is 70 ℃; after the dripping is finished, obtaining a mixed solution C; simultaneously, dripping the solution B and the rest initiating liquid in the step S4 into the mixed liquid C in parallel, wherein the dripping time is 2 hours, the temperature is 70 ℃, the temperature is kept for 2 hours after the dripping is finished, the temperature is reduced to below 35 ℃, and the amphoteric polyacrylamide is obtained after discharging;
2. preparation of glyoxal Urea Polymer (Compound (3) having the structure shown in FIG. 6)
S6, adding glyoxal into a reaction kettle according to the molar ratio of glyoxal to urea (urea 50 g) =4:1, adding urea, stirring and dissolving completely, adjusting the pH value to be 4 by using 20% sodium hydroxide solution, reacting at normal temperature for 8 hours, and discharging after the reaction is finished;
3. preparation of reinforcing agent
And S7, respectively preparing materials of the amphoteric polyacrylamide and GU resin according to the weight ratio of 1:3 at normal temperature, and separately storing, and simultaneously adding the materials into paper pulp and uniformly stirring when the paper pulp is used.
The other examples 4-15 were all carried out according to the procedure of example 1, and the corresponding raw materials were replaced to obtain the final product; the specific raw material content is shown in figure 1
Comparative examples 1-7 the synthesis process was exactly the same as example 1, except for the proportions and choice of raw materials, comparative example 8 was according to the process: all raw materials are added at one time, and then initiator is added dropwise for synthesis (the initiator is added dropwise for the same time and reaction temperature); the amount of comparative example 9 was shown in FIG. 2, and the functional monomer was prepared by adding all the monomers together to perform the reaction. The specific raw material content is shown in figure 2.
Test
1. The detection of the amphoteric polyacrylamide, wherein the viscosity range is 5000-8000cps, the content range is 14-18%, the specific result is shown in figure 3 and figure 4, and the results of the specific results are shown in figure 3, and the viscosity 6200-7500cps and the content 15.02-15.18% of the amphoteric polyacrylamide prepared in the examples 1-15 can be known from figure 3; as can be seen from FIG. 4, the viscosity of the amphoteric polyacrylamide prepared in the comparative example is 6820-8520cps, and the content is 15.08-15.13%. Therefore, the viscosity and the content of the amphoteric polyacrylamide are correspondingly changed under the condition of different raw material proportions, but the change range is not obvious.
2. Enhancer performance test
And (3) papermaking process:
quantification: 150g
Aluminum sulfate dosage: 5kg/T (absolute dry/absolute dry)
The consumption of the reinforcing agent is as follows: 3kg/T (absolute dry/absolute dry)
And (3) papermaking process: taking waste paper pulp, wherein the beating degree is 380SR, fluffing the waste paper pulp, adding aluminum sulfate according to 0.5% of absolute dryness of the paper pulp, adding an enhancer according to 0.3% of absolute dryness of the paper pulp, fully stirring, papermaking according to a certain amount of 150g, vacuum drying, and cooling.
The reinforcing agents were obtained from examples 1 to 15 and comparative examples 1 to 9, and papermaking was carried out; the paper strength was measured.
Performance test data is shown in fig. 5;
referring to fig. 5, by comparison, it is found that: examples 1 to 15 are compared with comparative examples 1 to 9, and the amphoteric polyacrylamide synthesized in examples 1 to 15 of the present invention is used as a reinforcing agent, and the properties of the reinforcing agent are obviously improved in terms of folding endurance, ring crush index, burst index, dry tensile index, wet tensile index and wet strength, compared with those of the reinforcing agent prepared in comparative examples 1 to 9.
Better and more obvious for improving the strength of the paper.
The above embodiments are preferred embodiments of the present invention, and besides, the present invention may be implemented in other ways, and any obvious substitution is within the scope of the present invention without departing from the concept of the present invention.
Claims (4)
1. The reinforcing agent for waste paper recycling and papermaking is characterized by comprising the following raw materials in parts by weight: an amphoteric polyacrylamide, glyoxal urea polymer;
the weight ratio of the amphoteric polyacrylamide to the glyoxal urea polymer is 1:1-3;
the synthesis method of the amphoteric polyacrylamide comprises the following steps:
s1, preparation of substrate
Adding deionized water, acrylamide, cationic monomer, anionic monomer, sodium bisulphite and EDTA into a reaction kettle, stirring and dissolving, and heating to 50-70 ℃ to obtain a substrate for later use;
s2, preparation of solution A
Adding acrylamide and deionized water into a monomer kettle, then adding an anionic monomer and a cationic monomer, uniformly stirring, then adding alkali liquor, and adjusting the pH of the system to 3-4 to obtain a solution A for later use;
s3, preparation of solution B
Adding a functional monomer 1, a functional monomer 2, acrylamide and deionized water into a reaction kettle, and uniformly stirring to obtain a solution B for later use;
s4, preparation of initiating liquid
Preparing an initiator, adding a proper amount of deionized water, and uniformly stirring to obtain an initiating liquid for later use;
s5, initiating reaction
Taking a half amount of initiating liquid in the step S4, and simultaneously, dropwise adding the solution A and the initiating liquid into the substrate in the step S1 in parallel to obtain a mixed liquid C after the completion of dropwise adding; dropwise adding the solution B and the rest of the initiating liquid into the mixed liquid C in parallel, and after the completion of dropwise adding, preserving heat, cooling and discharging to obtain the amphoteric polyacrylamide;
the anionic monomer is any one or more of acrylic acid, methacrylic acid, fumaric acid, itaconic acid and sulfonic acid unsaturated monomers;
the cationic monomer is any one or more of methacryloxyethyl trimethyl ammonium chloride, acryloxyethyl trimethyl ammonium chloride, diallyl dimethyl ammonium chloride, methacryloxypropyl ammonium chloride and acryloxypropyl trimethyl ammonium chloride;
the functional monomer 1 is one of hydroxyethyl methacrylate and hydroxyethyl acrylate;
the functional monomer 2 is glycidyl methacrylate;
the initiator is selected from the following components: ammonium persulfate, potassium persulfate, or sodium persulfate.
2. The reinforcing agent for paper making by waste paper recycling as claimed in claim 1, wherein the viscosity of the amphoteric polyacrylamide is 5000-8000cps, aldehyde groups are present at both ends of glyoxal urea polymer, and the viscosity is < 100cps.
3. A method for producing the reinforcing agent for waste paper recycling papermaking according to claim 1 or 2, characterized by comprising the steps of:
(1) Preparation of amphoteric polyacrylamide
S1, preparation of substrate
Adding deionized water, acrylamide, cationic monomer, anionic monomer, sodium bisulphite and EDTA into a reaction kettle, stirring and dissolving, and heating to 50-70 ℃ to obtain a substrate for later use;
s2, preparation of solution A
Adding acrylamide and deionized water into a monomer kettle, then adding an anionic monomer and a cationic monomer, uniformly stirring, then adding alkali liquor, adjusting the pH of the system to 3-4, and obtaining a solution A for later use;
s3, preparation of solution B
Adding a functional monomer 1, a functional monomer 2, acrylamide and deionized water into a monomer kettle, and uniformly stirring to obtain a solution B for later use;
s4, preparation of initiating liquid
Preparing an initiator, adding a proper amount of deionized water, and uniformly stirring to obtain an initiating liquid for later use;
s5, initiating reaction
Taking a half amount of initiating liquid in the step S4, and simultaneously, dropwise adding the solution A and the initiating liquid into the substrate in the step S1 in parallel to obtain a mixed liquid C after the completion of dropwise adding; dropwise adding the solution B and the rest of the initiating liquid into the mixed liquid C in parallel, and after the completion of dropwise adding, preserving heat, cooling and discharging to obtain the amphoteric polyacrylamide;
(2) Preparation of glyoxal urea polymers
S6, adding glyoxal and urea into a reaction kettle according to a molar ratio, then adjusting the pH value of the system to 3-4 by using alkali liquor, reacting at normal temperature, keeping the pH value of the system to 3-4, and reacting for 6-8 hours to obtain glyoxal urea polymer;
(3) Preparation of reinforcing agent
S7, mixing the amphoteric polyacrylamide obtained in the step S5 with the glyoxal urea polymer obtained in the step S6 according to the weight ratio of 1:1-3, preparing materials, and storing separately to obtain the reinforcing agent.
4. The method for producing an reinforcing agent for waste paper recycling papermaking according to claim 3, wherein: the alkali liquor in the step S6 is sodium hydroxide solution.
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| US5470918A (en) * | 1993-05-28 | 1995-11-28 | Mitsui Toatsu Chemicals, Inc. | Water-resistant surface coating formulations and paper coated therewith |
| CN102312395A (en) * | 2011-04-21 | 2012-01-11 | 深圳市瑞成科讯实业有限公司 | A kind of water-repellent for paper making and preparation method thereof |
| CN105384870A (en) * | 2015-12-03 | 2016-03-09 | 浙江传化华洋化工有限公司 | Preparation method for papermaking dry-strength agent with temporary wet-strength improving effect |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5470918A (en) * | 1993-05-28 | 1995-11-28 | Mitsui Toatsu Chemicals, Inc. | Water-resistant surface coating formulations and paper coated therewith |
| CN102312395A (en) * | 2011-04-21 | 2012-01-11 | 深圳市瑞成科讯实业有限公司 | A kind of water-repellent for paper making and preparation method thereof |
| CN105384870A (en) * | 2015-12-03 | 2016-03-09 | 浙江传化华洋化工有限公司 | Preparation method for papermaking dry-strength agent with temporary wet-strength improving effect |
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