CN114292406A - Preparation method of wrinkling cylinder sticking agent - Google Patents
Preparation method of wrinkling cylinder sticking agent Download PDFInfo
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- CN114292406A CN114292406A CN202111632039.1A CN202111632039A CN114292406A CN 114292406 A CN114292406 A CN 114292406A CN 202111632039 A CN202111632039 A CN 202111632039A CN 114292406 A CN114292406 A CN 114292406A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 67
- 239000000178 monomer Substances 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000004952 Polyamide Substances 0.000 claims abstract description 31
- 229920002647 polyamide Polymers 0.000 claims abstract description 31
- 229920000768 polyamine Polymers 0.000 claims abstract description 30
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000004593 Epoxy Substances 0.000 claims abstract description 16
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 43
- 239000007787 solid Substances 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 30
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 19
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 16
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 125000002091 cationic group Chemical group 0.000 claims description 12
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 12
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 12
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 12
- 150000001412 amines Chemical class 0.000 claims description 10
- 230000000844 anti-bacterial effect Effects 0.000 claims description 10
- 239000003899 bactericide agent Substances 0.000 claims description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 10
- 239000001361 adipic acid Substances 0.000 claims description 8
- 235000011037 adipic acid Nutrition 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- 239000002738 chelating agent Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 6
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000012986 chain transfer agent Substances 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 6
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 5
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 5
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 5
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 5
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229960001124 trientine Drugs 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-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
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 2
- MTEXJGQBDXDJRH-UHFFFAOYSA-N 3-[amino(ethyl)amino]propan-1-amine Chemical compound CCN(N)CCCN MTEXJGQBDXDJRH-UHFFFAOYSA-N 0.000 claims description 2
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 2
- STHWVYJPPPDLSL-UHFFFAOYSA-N CC(C)CCCC(C)OC(=O)C=C Chemical compound CC(C)CCCC(C)OC(=O)C=C STHWVYJPPPDLSL-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 2
- 239000004280 Sodium formate Substances 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 claims description 2
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 claims description 2
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 2
- 235000019254 sodium formate Nutrition 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-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
- UZNHKBFIBYXPDV-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)C UZNHKBFIBYXPDV-UHFFFAOYSA-N 0.000 claims description 2
- KTLIZDDPOZZHCD-UHFFFAOYSA-N 3-(2-aminoethylamino)propan-1-ol Chemical compound NCCNCCCO KTLIZDDPOZZHCD-UHFFFAOYSA-N 0.000 claims 1
- 239000004927 clay Substances 0.000 claims 1
- 239000011347 resin Substances 0.000 abstract description 13
- 229920005989 resin Polymers 0.000 abstract description 13
- 239000000853 adhesive Substances 0.000 abstract description 8
- 230000001070 adhesive effect Effects 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract description 6
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 3
- 239000011247 coating layer Substances 0.000 abstract 2
- 125000003700 epoxy group Chemical group 0.000 abstract 1
- 238000007142 ring opening reaction Methods 0.000 abstract 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 abstract 1
- 239000000047 product Substances 0.000 description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 2
- WEAQXVDSAUMZHI-UHFFFAOYSA-M 2-methylprop-2-enamide;trimethyl(propyl)azanium;chloride Chemical compound [Cl-].CC(=C)C(N)=O.CCC[N+](C)(C)C WEAQXVDSAUMZHI-UHFFFAOYSA-M 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- -1 polyoxyethylene Polymers 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- ZHAONEHNCCQNSC-UHFFFAOYSA-M ethyl-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC[N+](C)(C)CCOC(=O)C(C)=C ZHAONEHNCCQNSC-UHFFFAOYSA-M 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 239000003906 humectant Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- LQAVWYMTUMSFBE-UHFFFAOYSA-N pent-4-en-1-ol Chemical group OCCCC=C LQAVWYMTUMSFBE-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000962 poly(amidoamine) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Abstract
The invention discloses a preparation method of a wrinkling cylinder sticking agent, belonging to the field of papermaking and comprising the preparation of a polymer A containing an epoxy end group containing a carbon-carbon double bond, an acrylamide group, a flexible group and a quaternary ammonium salt cationic group; preparing a polyamide polyamine polymer B; performing ring-opening reaction on the epoxy group in the polymer A and the secondary amine group in the polymer B; and adjusting the auxiliary parameters. The present invention obtains the cylinder sticking agent product through free radical polymerization of epoxy end group monomer containing carbon-carbon double bond, acrylamide monomer, flexible monomer and quaternary ammonium salt cationic monomer, and further reaction with polyamide polyamine polymer. The defects that a single PAE resin wrinkling coating layer becomes hard and brittle at high temperature can be effectively overcome, the adhesive force, the film forming property and the water resistance of a product are improved at a higher level, and the PAE resin wrinkling coating layer can adapt to toilet paper machines with different configuration levels and various types of household paper for producing different paper types.
Description
Technical Field
The invention belongs to the field of papermaking, and particularly relates to a preparation method of a wrinkling cylinder sticking agent.
Background
At present, the most used cylinder sticking agent in the market is polyamide polyamine-epichlorohydrin resin, namely PAE resin, and the cylinder sticking agent can form a hard water-resistant coating film on a drying cylinder. However, since the crosslinking degree of epichlorohydrin and polyamide has a great influence on the removability and the adhesion of the PAE resin, the properties of the PAE resin are difficult to change in a given creping process, and when the moisture content of the paper web is low or the temperature of the drying cylinder is too high, the PAE resin on the surface of the drying cylinder becomes hard and brittle, so that the adhesion is reduced, the creping effect is poor, and the requirements of different household paper products or different paper machines on coating cannot be met well.
Many researchers have also synthesized other cylinder sticking agents such as polyacrylamide-dimethylallylammonium chloride copolymer, polyethyleneimine cylinder sticking agent and polyvinyl alcohol cylinder sticking agent, which can solve some problems in the process of paper wrinkling, but have the following defects: 1. although the phenomena of paper tearing and uneven wrinkling in the paper wrinkling process are improved, the problem of poor film forming property is not solved; 2. the synthesis of polyethyleneimine is difficult, and the product price is expensive; 3. the synthetic cylinder sticking agent of polyacrylamide is added with flexible monomer and plasticizer, which improves the film forming property and remoistenability of the product, but reduces the adhesive force of the product.
Disclosure of Invention
In order to overcome the technical defects, the invention provides a preparation method of a wrinkling cylinder sticking agent, which aims to solve the problems related to the background technology.
The invention provides a preparation method of a cylinder sticking agent for wrinkling, which comprises the following steps:
adding water, an epoxy end group monomer containing a carbon-carbon double bond, an acrylamide monomer, a flexible monomer and a cationic monomer into a reaction bottle, adjusting the pH value of the solution to 3.5-4.5, adding a chelating agent and a chain transfer agent, introducing nitrogen to remove oxygen, slowly heating to 70 ℃, slowly dropwise adding an ammonium persulfate solution initiator and a part of acrylamide monomer, keeping the temperature at 75-85 ℃ for 4 hours after dropwise adding, stopping heating, adding water to adjust the solid content to 10-20 wt%, and cooling to room temperature to obtain a polymer A solution;
reacting polybasic organic amine and dibasic organic carboxylic acid at 140-180 ℃ for 1-8 hours, and adding water accounting for 80-90% of the total mass of the organic amine and the organic carboxylic acid to obtain a polyamide polyamine polymer B solution;
uniformly mixing the polymer A and the polymer B, then reacting for 1-5h at 40-80 ℃, and adding water to stop the reaction when the solution viscosity reaches 250-400mPa.s to obtain a reactant;
cooling the reactant to 30-35 ℃, adding 32% liquid alkali to adjust the pH of the solution to 8-10, then adding a bactericide, and uniformly stirring to obtain a cylinder sticking agent; the viscosity of the product is controlled to be 30-250mPa.s, and the solid content is controlled to be 10-20 wt%.
Preferably or optionally, the epoxy terminal monomer containing the carbon-carbon double bond is one or more of glycidyl ether-based allyl alcohol polyoxyethylene ether, Allyl Glycidyl Ether (AGE), Glycidyl Acrylate (GA) and Glycidyl Methacrylate (GMA);
the mass of the epoxy end group monomer containing the carbon-carbon double bond is 10-50% of the total mass of the polymer monomer.
Preferably or alternatively, the glycidyl ether-based allyl alcohol polyoxyethylene ether has the following structure:
wherein q is more than or equal to 9 and less than or equal to 15.
Preferably or optionally, the acrylamide monomer is selected from one or more of acrylamide, N-methylacrylamide, N-dimethylacrylamide, N-diethylacrylamide, N-methylolacrylamide and N-hydroxyethyl acrylamide;
the mass of the acrylamide monomer is 50-80% of the total mass of the polymer monomer.
Preferably or optionally, the flexible monomer is one or more of methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, 2-isooctyl acrylate, 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate;
the mass of the flexible monomer is 1-45% of the total mass of the polymer monomer.
Preferably or alternatively, the cationic monomer is selected from one or more of (meth) acryloyloxyethyltrimethyl ammonium chloride (DMC or DAC), methacrylamidopropyl trimethylammonium chloride (PMC), and dimethyldiallylammonium chloride (DMDAAC);
the mass of the cationic monomer is 1-45% of the total mass of the polymer monomer.
Preferably or optionally, the chelating agent is one of the chelating agents EDTA-2Na or DTPA-Na 5;
the mass fraction of the chelating agent in the polymer solution is 0.003-0.02%.
The chain transfer agent is one or more of sodium hypophosphite, isopropanol, sodium formate, thioglycolic acid and mercaptopropionic acid;
the mass fraction of the chain transfer agent in the polymer solution is 0.005-0.05%.
The initiator is ammonium persulfate solution;
the mass fraction of the initiator in the polymer solution is 0.05-0.5%.
Preferably or optionally, the polybasic organic amine is selected from one or a mixture of diethylenetriamine, triethylene tetramine, tetraethylene pentamine, hydroxyethyl ethylene diamine, hydroxypropyl ethylene diamine and amino ethyl amino propylamine;
the dibasic organic carboxylic acid is selected from one or a mixture of more of succinic acid, glutaric acid, adipic acid and azelaic acid;
the molar ratio of the polybasic organic amine to the dibasic organic carboxylic acid is (1.30-1.01): 1.
Preferably or alternatively, the mass of the polymer A is 5-40% of the mass of the aqueous solution of the polyamide polyamine polymer.
Preferably or alternatively, the weight parts of the raw materials used in each step are as follows: 0.075-2 parts of epoxy end group monomer containing carbon-carbon double bond, 0.375-5 parts of acrylamide monomer, 0.05-1 part of flexible monomer, 0.05-1 part of cationic monomer, 3.5-8.5 parts of polybasic organic amine, 5-10 parts of binary organic carboxylic acid, 0-0.2 part of sodium hydroxide, 0.01-0.2 part of bactericide and 80-90 parts of water.
The invention relates to a preparation method of a wrinkling cylinder sticking agent, which has the following beneficial effects compared with the prior art:
1. because acrylamide monomer, flexible monomer or quaternary ammonium salt cationic monomer and polyamide polyamine polymer are difficult to directly react or polymerize, in the invention, glycidyl ether group allyl alcohol polyoxyethylene ether with vinyl double bond is introduced, and the vinyl group can be polymerized with acrylamide, flexible monomer and quaternary ammonium salt cationic monomer by free radicals, and then reacted with polyamide polyamine polymer to successfully combine the two together, thereby leading the adhesive force of the product and the hardness of the film to reach better level.
2. The glycidyl ether allyl alcohol polyoxyethylene ether is preferably used as the epoxy end group monomer, and because the repeating unit containing polyoxyethylene has hydrophilicity, the rewettability of the cylinder sticking agent product can be improved, and the cylinder sticking agent product can be applied under the condition that the moisture of paper is greatly changed without additionally adding polyethylene glycol or glycerin and other humectants.
3. The polymer A takes an acrylamide monomer as a main body, provides the adhesive force of the cylinder sticking agent and the paper surface and the drying cylinder surface, and has larger adhesive force than that of pure PAE resin, thereby meeting the adhesive force requirements of products in paper machines with different configurations and different paper products.
4. By introducing the flexible monomer with good film-forming property and flexibility into the polymer A, the defects of poor film-forming property, hard coating of a film and the like of a single polyamide polyamine epichlorohydrin resin cylinder-sticking agent are effectively overcome, and meanwhile, the hand feeling and flexibility of paper can be improved without additionally adding a softening agent.
5. According to the invention, methacryloyloxyethyl trimethyl ammonium chloride is preferably used as a cationic monomer, and the cationic group has strong affinity to a large number of carboxyl groups in the fiber, so that the bonding force between the cylinder sticking agent and the paper surface and the cylinder drying surface is increased.
6. The polymer A with the epoxy end group and the secondary amine group of the polyamide polyamine polymer are subjected to crosslinking reaction, so that the use of a micromolecule crosslinking agent epichlorohydrin is avoided, the reaction process is more green and environment-friendly, and the product does not contain organic chlorine byproducts such as DCP, CPD and the like, so that the product can be well used for manufacturing paper products for daily use and is non-toxic and harmless.
7. The mass of the polymer A solution is designed to be 5-40% of the polyamide polyamine polymer aqueous solution. On one hand, the epoxy end group in the polymer A can be ensured to be capable of fully reacting with the polyamide polyamine polymer, and simultaneously, the flexible monomer can fully play a role so as to improve the film forming property of the product and reduce the film forming hardness of the product, thereby being more suitable for being used on a paper machine. On the other hand, the amount of polymer A should not be too great for cost reasons.
In conclusion, the preparation method disclosed by the invention has the advantages of relatively low cost, high production efficiency, easiness in reaction control, environmental friendliness and the like. The obtained product has large cohesive force, good moisture retention performance, film forming property and film hardness, and can be better combined with fiber, so that the hand feeling after paper forming is softer.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a more thorough understanding of the present invention. It will be apparent, however, to one skilled in the art, that the present invention may be practiced without one or more of these specific details. In other instances, well-known features have not been described in order to avoid obscuring the invention.
Summary of The Invention
The invention relates to a preparation method of a cylinder sticking agent product which is sprayed on a yankee dryer to help paper sheet wrinkling in the process of manufacturing household paper. The defects are solved by introducing glycidyl ether group allyl alcohol polyoxyethylene ether containing epoxy end groups, acrylamide monomers, flexible monomers and quaternary ammonium salt cationic monomer copolymers to react with polyamide polyamine resin, and meanwhile, the film forming property, the hardness and the rewetting property of a coating can be adjusted by the amount of the added glycidyl ether group allyl alcohol polyoxyethylene ether, the added acrylamide monomers, the added flexible monomers and the added quaternary ammonium salt cationic monomer, so that the requirements of paper machines for living paper with different speeds and types can be met, and in addition, the hand feeling and the softness of the produced living paper can be better.
Therefore, the wrinkling cylinder-sticking agent is obtained by reacting a polymer A obtained by free radical polymerization of an epoxy end group monomer containing a carbon-carbon double bond, an acrylamide monomer, a flexible monomer and a quaternary ammonium salt cationic monomer with a polyamide polyamine polymer B, and the specific reaction process is as follows:
1. preparation of Polymer A:
2. preparation of a polyamide polyamine polymer B:
3. preparing a wrinkling cylinder sticking agent:
wherein m is 8-13, n is 180-310, o is 12-20, p is 7-12, q is 9-15, r is 8-13, and m, n, o, p, q, r are all positive integers.
The invention will now be further described with reference to the following examples, which are intended to be illustrative of the invention and are not to be construed as limiting the invention. The examples, where specific techniques and reaction conditions are not indicated, can be carried out according to the techniques or conditions or product specifications described in the literature in the field. Reagents, instruments or equipment of any manufacturer not indicated are commercially available.
Example 1
Adding 30 parts of water, 5 parts of glycidyl ether allyl alcohol polyoxyethylene ether 400, 6.25 parts of 40% acrylamide aqueous solution (AM-40), 1.875 parts of n-butyl acrylate and 1.875 parts of 80% methacryloyloxyethyl trimethyl ammonium chloride aqueous solution (DMC-80) into a reaction bottle, adjusting the pH of the solution to 3.5-4.5 by using 50% sulfuric acid, adding 0.01 part of EDTA-Na2 and 0.02 part of sodium hypophosphite, stirring for dissolving, introducing nitrogen for removing oxygen for half an hour, slowly heating to 70 ℃, slowly dropwise adding 0.6 part of 3% ammonium persulfate solution and 10 parts of 40% acrylamide aqueous solution (AM-40), dropwise adding for 2 hours, keeping the temperature at 75-85 ℃ for 4 hours after dropwise adding is finished, stopping heating, then adding a proper amount of water for adjusting the solid content to 15 wt%, and cooling to room temperature to obtain a polymer A solution.
Adding 26 parts of diethylenetriamine into a reaction bottle, slowly adding 32 parts of adipic acid under stirring, uniformly stirring, heating to 150 ℃, continuously evaporating generated water, reacting for 1 hour, heating to 165 ℃, continuing to react for 4 hours, slowly adding 22 parts of warm water to terminate the reaction, finally adding a proper amount of diluent water, and uniformly stirring to obtain the polyamide polyamine polymer B with the solid content of 50%.
Adding 27 parts of polyamide polyamine polymer into a reaction flask, adding 18 parts of water to adjust the solid content, then dropwise adding 9 parts of polymer A solution (the solid content is 15%), heating to 60 ℃ to react for 2-2.5 hours, sampling every 15 minutes to measure the viscosity after reacting for 1.5 hours at 60 ℃, adding water to stop the reaction when the solution viscosity reaches 250-400mPa.s, and obtaining a reactant. Cooling the materials to below 35 ℃, adding 0.02 part of 10% liquid alkali to adjust the pH, then adding 0.1 part of bactericide BIT-20, and finally adding water to adjust the solid content to 15%, thus obtaining the jar-sticking agent product.
Example 2
Adding 30 parts of water, 5 parts of glycidyl ether allyl alcohol polyoxyethylene ether 600, 6.25 parts of 40% acrylamide aqueous solution (AM-40), 1.875 parts of isobutyl acrylate and 1.875 parts of 80% methacryloyloxyethyl trimethyl ammonium chloride aqueous solution (DMC-80) into a reaction bottle, adjusting the pH of the solution to 3.5-4.5 by using 50% sulfuric acid, adding 0.01 part of EDTA-Na2 and 0.02 part of sodium hypophosphite, stirring for dissolving, introducing nitrogen for removing oxygen, slowly heating for half an hour, slowly dropwise adding 0.6 part of 3% ammonium persulfate solution and 10 parts of 40% acrylamide aqueous solution (AM-40), dropwise adding for 2 hours, keeping the temperature at 75-85 ℃ for 4 hours after dropwise adding is finished, stopping heating, then adding a proper amount of water for adjusting the solid content to 15 wt%, and cooling to room temperature to obtain a polymer A solution.
Adding 26.5 parts of diethylenetriamine into a reaction bottle, slowly adding 31.5 parts of adipic acid under the stirring state, uniformly stirring, heating to 150 ℃, continuously evaporating generated water, reacting for 1 hour, heating to 165 ℃, continuously reacting for 4 hours, slowly adding 22 parts of warm water to terminate the reaction, finally adding a proper amount of diluent water, and uniformly stirring to obtain the polyamide polyamine polymer B with the solid content of 50%.
Adding 27 parts of polyamide polyamine polymer into a reaction flask, adding 18 parts of water to adjust the solid content, then dropwise adding 9.2 parts of polymer A solution (the solid content is 15%), heating to 60 ℃ to react for 2-2.5 hours, sampling every 15 minutes after reacting for 1.5 hours at 60 ℃ to measure the viscosity, and adding water to stop the reaction when the solution viscosity reaches 250-400mPa.s to obtain a reactant. Cooling the materials to below 35 ℃, adding 0.02 part of 10% liquid alkali to adjust the pH, then adding 0.1 part of bactericide BIT-20, and finally adding water to adjust the solid content to 15%, thus obtaining the jar-sticking agent product.
Example 3
Adding 30 parts of water, 5 parts of Glycidyl Methacrylate (GMA), 6.25 parts of 40% acrylamide aqueous solution (AM-40), 1.875 parts of isobutyl acrylate and 3.0 parts of 50% methacrylamide propyl trimethyl ammonium chloride (MAPTAC) into a reaction bottle, adjusting the pH of the solution to 3.5-4.5 by using 50% sulfuric acid, adding 0.01 part of EDTA-Na2 and 0.02 part of sodium hypophosphite, stirring and dissolving, introducing nitrogen and removing oxygen for half an hour, slowly heating to 70 ℃, slowly dropwise adding 0.6 part of 3% ammonium persulfate solution and 10 parts of 40% acrylamide aqueous solution (AM-40), wherein the dropwise adding time is 2 hours, keeping the temperature at 75-85 ℃ for 4 hours after the dropwise adding is finished, stopping heating, then adding a proper amount of water to adjust the solid content to 15 wt%, and cooling to room temperature to obtain the polymer A solution.
Adding 21 parts of triethylene tetramine into a reaction bottle, slowly adding 21 parts of adipic acid under the stirring state, uniformly stirring, heating to 150 ℃, continuously evaporating generated water, heating to 175 ℃ after reacting for 1 hour, continuously reacting for 4 hours, slowly adding 20 parts of warm water to terminate the reaction, finally adding a proper amount of dilution water, and uniformly stirring to obtain the polyamide polyamine polymer B with the solid content of 50%.
Adding 27.5 parts of polyamide polyamine polymer into a reaction flask, adding 18.2 parts of water to adjust the solid content, then dropwise adding 9.1 parts of polymer A solution (the solid content is 15%), heating to 60 ℃ to react for 2-2.5 hours, sampling every 15 minutes to measure the viscosity after reacting for 1.5 hours at 60 ℃, and adding water to stop the reaction when the solution viscosity reaches 250-400mPa.s to obtain a reactant. Cooling the materials to below 35 ℃, adding 0.02 part of 10% liquid alkali to adjust the pH, then adding 0.1 part of bactericide BIT-20, and finally adding water to adjust the solid content to 15%, thus obtaining the jar-sticking agent product.
Example 4
Adding 30 parts of water, 5 parts of Allyl Glycidyl Ether (AGE), 6.25 parts of 40% acrylamide aqueous solution (AM-40), 1.875 parts of isobutyl acrylate and 2.5 parts of 60% dimethyl diallyl ammonium chloride (DMDAAC) into a reaction bottle, adjusting the pH of the solution to 3.5-4.5 by using 50% sulfuric acid, adding 0.01 part of EDTA-Na2 and 0.02 part of sodium hypophosphite, stirring to dissolve, introducing nitrogen to remove oxygen for half an hour, slowly heating to 70 ℃, slowly dropwise adding 0.6 part of 3% ammonium persulfate solution and 10 parts of 40% acrylamide aqueous solution (AM-40) for 2 hours, keeping the temperature at 75-85 ℃ for 4 hours after dropwise adding is finished, stopping heating, adding a proper amount of water to adjust the solid content to 15 wt%, and cooling to room temperature to obtain the polymer A solution.
Adding 21 parts of triethylene tetramine into a reaction bottle, slowly adding 21 parts of adipic acid under the stirring state, uniformly stirring, heating to 150 ℃, continuously evaporating generated water, heating to 175 ℃ after reacting for 1 hour, continuously reacting for 4 hours, slowly adding 20 parts of warm water to terminate the reaction, finally adding a proper amount of dilution water, and uniformly stirring to obtain the polyamide polyamine polymer B with the solid content of 50%.
Adding 27.5 parts of polyamide polyamine polymer into a reaction flask, adding 18.2 parts of water to adjust the solid content, then dropwise adding 9.2 parts of polymer A solution (the solid content is 15%), heating to 60 ℃ to react for 2-2.5 hours, sampling every 15 minutes to measure the viscosity after reacting for 1.5 hours at 60 ℃, and adding water to stop the reaction when the solution viscosity reaches 250-400mPa.s to obtain a reactant. Cooling the materials to below 35 ℃, adding 0.02 part of 10% liquid alkali to adjust the pH, then adding 0.1 part of bactericide BIT-20, and finally adding water to adjust the solid content to 15%, thus obtaining the jar-sticking agent product.
Comparative example 1
Adding 26.5 parts of diethylenetriamine into a reaction bottle, slowly adding 31.5 parts of adipic acid under the stirring state, uniformly stirring, heating to 150 ℃, continuously evaporating generated water, reacting for 1 hour, heating to 165 ℃, continuously reacting for 4 hours, slowly adding 22 parts of warm water to terminate the reaction, finally adding a proper amount of diluent water, and uniformly stirring to obtain the polyamide polyamine polymer with the solid content of 50%.
Adding 26.6 parts of polyamide polyamine polymer into a reaction flask, adding 17 parts of water to adjust the solid content, then dropwise adding 1.3 parts of epoxy chloropropane, heating to 60 ℃ to react for 2-2.5 hours, sampling every 15 minutes after reacting for 1.5 hours at 60 ℃, measuring the viscosity, adding water to stop the reaction when the solution viscosity reaches 250-400mPa.s, and obtaining a reactant. Cooling the materials to below 35 ℃, adding 0.02 part of 10% liquid alkali to adjust the pH, then adding 0.1 part of bactericide BIT-20, and finally adding water to adjust the solid content to 15%, thus obtaining the jar-sticking agent product.
Comparative example 2
Adding 21 parts of triethylene tetramine into a reaction bottle, slowly adding 21 parts of adipic acid under the stirring state, uniformly stirring, heating to 150 ℃, continuously evaporating generated water, reacting for 1 hour, heating to 175 ℃, continuously reacting for 4 hours, slowly adding 20 parts of warm water to terminate the reaction, finally adding a proper amount of dilution water, and uniformly stirring to obtain the polyamide polyamine polymer with the solid content of 50%.
Adding 26.6 parts of polyamide polyamine polymer into a reaction flask, adding 17 parts of water to adjust the solid content, then dropwise adding 1.4 parts of epoxy chloropropane, heating to 65 ℃ for reaction for 2-2.5 hours, sampling every 15 minutes after reacting for 1.5 hours at 65 ℃, measuring the viscosity, adding water when the solution viscosity reaches 300-450mPa.s to terminate the reaction, and obtaining a reactant. Cooling the materials to below 35 ℃, adding 0.05 part of 10% liquid alkali to adjust the pH, then adding 0.1 part of bactericide BIT-20, and finally adding water to adjust the solid content to 15%, thus obtaining the jar-sticking agent product.
The cylinder-sticking agent samples prepared in the examples 1-4 and the comparative examples 1-2 of the invention and comparative samples (the commercially available product 1 and the commercially available product 2 are both polyamide-epichlorohydrin resin cylinder-sticking agents) are respectively tested for viscosity, pH value, solid content, adhesion force, film hardness and rewettability, wherein the solid content is tested by an oven method, the pH value is tested by a conventional pH meter at 25 ℃, the viscosity is tested by a commonly used Brookfiled viscometer (25 ℃, unit is mPa.s), the adhesion force testing method refers to a method (unit is Kg) disclosed in the preparation of a polyamide-epichlorohydrin resin cylinder-sticking agent in the patent CN101235610A, and the film-forming hardness is tested by the following method: and spraying the cylinder sticking agent onto a stainless steel platform heated to 110 ℃, and performing a coating scratch experiment by using pencils with different hardness after the cylinder sticking agent is solidified into a film. Rewettability test methods refer to the methods disclosed in CN103415550B polyamine polyamidoamine epihalohydrin compositions and methods of making and using the same. The specific test results are shown in the following table:
discussion of the related Art
Based on the above test results, we can find that: examples 1 to 4 compared to comparative examples, commercially available products, by introducing glycidyl ether based allyl alcohol polyoxyethylene ether having vinyl double bond, it is possible to successfully combine the vinyl group with acrylamide, a flexible monomer and a quaternary ammonium salt cationic monomer by radical polymerization of the vinyl group and then by reaction with a polyamide polyamine polymer, and since glycidyl ether based allyl alcohol polyoxyethylene ether is used as an epoxy terminal monomer and contains a large amount of repeating units of polyoxyethylene having hydrophilicity, it is possible to improve rewettability of the jar adhesive product; by introducing the flexible monomer with good film forming property and flexibility, the defects of poor film forming property, hard coating of the film and the like of the single polyamide polyamine epichlorohydrin resin cylinder adhesive are effectively improved, and simultaneously, the hand feeling and flexibility of paper can be improved without additionally adding a softening agent; the methyl methacryloyloxyethyl trimethyl ammonium chloride is selected as the cationic monomer, and the cationic group has strong affinity to a large number of carboxyl groups in the fiber, so that the bonding force between the cylinder sticking agent and the paper surface and the cylinder drying surface is increased.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
Claims (10)
1. The preparation method of the cylinder sticking agent for wrinkling is characterized by comprising the following steps of:
adding water, an epoxy end group monomer containing a carbon-carbon double bond, an acrylamide monomer, a flexible monomer and a cationic monomer into a reaction bottle, adjusting the pH value of the solution to 3.5-4.5, adding a chelating agent and a chain transfer agent, introducing nitrogen to remove oxygen, slowly heating to 70 ℃, slowly dropwise adding an ammonium persulfate solution initiator and a part of acrylamide monomer, keeping the temperature at 75-85 ℃ for 4 hours after dropwise adding, stopping heating, adding water to adjust the solid content to 10-20 wt%, and cooling to room temperature to obtain a polymer A solution;
reacting polybasic organic amine and dibasic organic carboxylic acid at 140-180 ℃ for 1-8 hours, and adding water accounting for 80-90% of the total mass of the organic amine and the organic carboxylic acid to obtain a polyamide polyamine polymer B solution;
uniformly mixing the polymer A and the polymer B, then reacting for 1-5h at 40-80 ℃, and adding water to stop the reaction when the solution viscosity reaches 250-400mPa.s to obtain a reactant;
cooling the reactant to 30-35 ℃, adding 32% liquid alkali to adjust the pH of the solution to 8-10, then adding a bactericide, and uniformly stirring to obtain a cylinder sticking agent; the viscosity of the cylinder sticking agent is controlled to be 30-250mPa.s, and the solid content is controlled to be 10-20 wt%.
2. The method for preparing the cylinder sticking agent for wrinkling according to claim 1, wherein the epoxy end group monomer containing the carbon-carbon double bond is one or more of glycidyl ether group allyl alcohol polyoxyethylene ether, allyl glycidyl ether, glycidyl acrylate and glycidyl methacrylate;
the mass of the epoxy end group monomer containing the carbon-carbon double bond is 10-50% of the total mass of the polymer monomer.
3. The method of claim 2, wherein the glycidyl ether-based allyl alcohol polyoxyethylene ether has the following structure:
wherein q is more than or equal to 9 and less than or equal to 15.
4. The method for preparing the cylinder sticking agent for wrinkling according to claim 1, wherein the acrylamide monomer is one or more selected from acrylamide, N-methylacrylamide, N-dimethylacrylamide, N-diethylacrylamide, N-methylolacrylamide and N-hydroxyethyl acrylamide;
the mass of the acrylamide monomer is 50-80% of the total mass of the polymer monomer.
5. The method for preparing the creping cylinder sticking agent according to claim 1, wherein the flexible monomer is one or more of methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, 2-isooctyl acrylate, 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate;
the mass of the flexible monomer is 1-45% of the total mass of the polymer monomer.
6. The method for preparing the creping cylinder sticking agent according to claim 1, wherein the cationic monomer is one or more selected from acryloyloxyethyl trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, methacrylamidopropyl trimethyl ammonium chloride and dimethyl diallyl ammonium chloride;
the mass of the cationic monomer is 1-45% of the total mass of the polymer monomer.
7. The method for preparing the cylinder sticking agent for wrinkling according to claim 1, wherein the chelating agent is one of chelating agent EDTA-2Na or DTPA-Na 5;
the mass fraction of the chelating agent in the polymer solution is 0.003-0.02%;
the chain transfer agent is one or more of sodium hypophosphite, isopropanol, sodium formate, thioglycolic acid and mercaptopropionic acid;
the mass fraction of the chain transfer agent in the polymer solution is 0.005-0.05%;
the initiator is ammonium persulfate solution;
the mass fraction of the initiator in the polymer solution is 0.05-0.5%.
8. The method for preparing the cylinder sticking agent for wrinkling according to claim 1, wherein the polybasic organic amine is selected from one or a mixture of more of diethylenetriamine, triethylene tetramine, tetraethylenepentamine, hydroxyethyl ethylenediamine, hydroxypropyl ethylenediamine and amino ethyl amino propylamine;
the dibasic organic carboxylic acid is selected from one or a mixture of more of succinic acid, glutaric acid, adipic acid and azelaic acid;
the molar ratio of the polybasic organic amine to the dibasic organic carboxylic acid is (1.30-1.01): 1.
9. The method for preparing the creping clay cylinder agent according to claim 1, wherein the mass of the polymer A is 5-40% of the mass of the aqueous solution of the polyamide polyamine polymer.
10. The preparation method of the cylinder sticking agent for wrinkling according to claim 1, wherein the weight parts of the raw materials used in each step are as follows: 0.075-2 parts of epoxy end group monomer containing carbon-carbon double bond, 0.375-5 parts of acrylamide monomer, 0.05-1 part of flexible monomer, 0.05-1 part of cationic monomer, 3.5-8.5 parts of polybasic organic amine, 5-10 parts of binary organic carboxylic acid, 0-0.2 part of sodium hydroxide, 0.01-0.2 part of bactericide and 80-90 parts of water.
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