CN103044629B - Preparation method of acrylamide cross-linked urea glyoxal resin wet strength agent - Google Patents
Preparation method of acrylamide cross-linked urea glyoxal resin wet strength agent Download PDFInfo
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- 229920005989 resin Polymers 0.000 title claims abstract description 61
- 239000011347 resin Substances 0.000 title claims abstract description 61
- ZQUAGYUZGXDEIA-UHFFFAOYSA-N oxaldehyde;urea Chemical compound NC(N)=O.O=CC=O ZQUAGYUZGXDEIA-UHFFFAOYSA-N 0.000 title claims abstract description 28
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 title abstract description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000178 monomer Substances 0.000 claims abstract description 37
- 239000004202 carbamide Substances 0.000 claims abstract description 25
- 238000004132 cross linking Methods 0.000 claims abstract description 25
- 229920001807 Urea-formaldehyde Polymers 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 238000010790 dilution Methods 0.000 claims abstract description 6
- 239000012895 dilution Substances 0.000 claims abstract description 6
- 230000007935 neutral effect Effects 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims abstract description 3
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 125000002091 cationic group Chemical group 0.000 claims description 17
- 229920006037 cross link polymer Polymers 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims description 8
- LSWADWIFYOAQRZ-UHFFFAOYSA-N n-(ethoxymethyl)prop-2-enamide Chemical compound CCOCNC(=O)C=C LSWADWIFYOAQRZ-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 5
- SBVKVAIECGDBTC-UHFFFAOYSA-N 4-hydroxy-2-methylidenebutanamide Chemical compound NC(=O)C(=C)CCO SBVKVAIECGDBTC-UHFFFAOYSA-N 0.000 claims description 5
- GSQZCNGOIFGRPU-UHFFFAOYSA-M [Cl-].C(C=C)(=O)C(C1=CC=CC=C1)([N+](C)(C)C)CC Chemical compound [Cl-].C(C=C)(=O)C(C1=CC=CC=C1)([N+](C)(C)C)CC GSQZCNGOIFGRPU-UHFFFAOYSA-M 0.000 claims description 5
- QLIBJPGWWSHWBF-UHFFFAOYSA-N 2-aminoethyl methacrylate Chemical compound CC(=C)C(=O)OCCN QLIBJPGWWSHWBF-UHFFFAOYSA-N 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 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 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 abstract description 14
- 230000001105 regulatory effect Effects 0.000 abstract description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 7
- 229940015043 glyoxal Drugs 0.000 abstract description 7
- 150000001768 cations Chemical class 0.000 abstract 2
- 150000004820 halides Chemical class 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- 238000006068 polycondensation reaction Methods 0.000 description 6
- RGSMDLROAMCLFQ-UHFFFAOYSA-N acetaldehyde;urea Chemical compound CC=O.NC(N)=O RGSMDLROAMCLFQ-UHFFFAOYSA-N 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 150000002896 organic halogen compounds Chemical class 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 229950003988 decil Drugs 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- -1 hydroxylethyl Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- BONVROUPOZRCDU-UHFFFAOYSA-N 2-hydroxyprop-2-enamide Chemical class NC(=O)C(O)=C BONVROUPOZRCDU-UHFFFAOYSA-N 0.000 description 1
- SHXWCVYOXRDMCX-UHFFFAOYSA-N 3,4-methylenedioxymethamphetamine Chemical compound CNC(C)CC1=CC=C2OCOC2=C1 SHXWCVYOXRDMCX-UHFFFAOYSA-N 0.000 description 1
- BPOFERVZWUJYOW-UHFFFAOYSA-N [Cl-].[NH4+].CC(=CC)C Chemical compound [Cl-].[NH4+].CC(=CC)C BPOFERVZWUJYOW-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- PYNUOAIJIQGACY-UHFFFAOYSA-N propylazanium;chloride Chemical compound Cl.CCCN PYNUOAIJIQGACY-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Paper (AREA)
Abstract
The invention relates to a preparation method of acrylamide cross-linked urea glyoxal resin wet strength agent. The preparation method is characterized by comprising the following steps: mixing glyoxal and urea as per mole ratio of 1 to 2: 0.3 to 1, regulating pH value to be 1.5 to 3 with acid, reacting for 2.5 to 6 h under the temperature of 35 DEG C to 75 DEG C, cooling, regulating pH value to be neutral with alkali after adding the glyoxal with the adding amount of moles of 15% to 40 % of first glyoxal weight, reacting for 1 to 2 h under the temperature of 20 DEG C to 35 DEG C, regulating pH value to be neutral so as to obtain urea resin, adding cross-linking monomers and cation monomers into the urea resin (the mole ratio of the cross-linking monomers, the cation monomers and the urea is 0.5 to 3.5:0.2 to 2:5, reacting for 1 to 2 h under the temperature of 50 DEG C to 80 DEG C, and adding deionized water for dilution until the solid content occupies 12% of total content so as to obtain acrylamide cross-linked urea glyoxal resin wet strength agent. The invention has the benefits that formaldehyde and organic halide are not added during preparation process, so that damage to environment and human health is eliminated.
Description
Technical field
The invention belongs to wet strength agent for paper making, particularly relate to a kind of preparation method of acrylamide crosspolymer urea glyoxal resin Wet Strength Resin.
Background technology
Along with the fast development of paper industry, traditional Wet Strength Resin that paper-making industry uses, as urea-formaldehyde resin (UF) and terpolycyantoamino-formaldehyde resin (MF) etc., due to reasons such as working conditions and releases objectionable impurities (A0X), the demand of user more and more can not be met.
PAE is the wet strength agent for paper making that application is more at present, its performance is subject to general accreditation, become the main product of Wet Strength Resin, but from being subject to the impact of reaction conditions during preparation technology, as high in production temperature, the time is longer, volatility of raw material is comparatively serious, raw material ratio reaction is on the low side in theoretical reacting value etc., easily cause end-group termination in polycondensation process too early, make polymericular weight on the low side, have impact on result of use, many detrimentally affects are brought to papermaking, as poly-material easily produce bubble, wadding gathers, becomes paper, takes off paper difficulty, paper uniformity coefficient difference etc.More crucial problem is that the more PAE Wet Strength Resin of application is not suitable at present simultaneously, and United Nations's health organization works out requirement, does not allow to apply the industrial chemicals containing Organohalogen compounds (AOX) to paper product in 2015.
Summary of the invention
The object of the invention is to the deficiency overcoming above-mentioned technology, there is provided a kind of preparation method of acrylamide crosspolymer urea second glyoxal resin Wet Strength Resin, the Wet Strength Resin of this manufacture technics has high retention rate performance in slurry, and not only wet tenacity is high, and environmentally safe, not containing Organohalogen compounds.
The present invention for achieving the above object, by the following technical solutions: a kind of preparation method of acrylamide crosspolymer urea glyoxal resin Wet Strength Resin, is characterized in that, comprise the steps,
1) urea-formaldehyde resin is prepared
Be that 1-2:0.3-1 is miscible by the mol ratio of oxalic dialdehyde and urea, with the pH value 1.5-3 of acid-conditioning solution, temperature is 35 DEG C-75 DEG C, carries out reaction 2.5-6h, cooling, add oxalic dialdehyde again, add-on be first oxalic dialdehyde 12%-15% mole number, be neutral by the pH value of alkali regulator solution, at 20-35 DEG C of temperature, react 1-2h, be neutral by the pH value of alkali regulator solution again, namely obtain urea-formaldehyde resin;
2) by cross-linking monomer, cationic monomer adds in urea-formaldehyde resin prepared by step 1), cross-linking monomer, the mol ratio 0.5-3.5:0.2-2:5 of cationic monomer and urea, temperature 50 C-80 DEG C, reaction 1-2h stops, and adds deionized water dilution, wherein all admittedly account for 12% of overall aqueous solution total amount containing thing, acrylamide crosspolymer urea glyoxal resin Wet Strength Resin can be obtained.
Described acid is one or both in hydrochloric acid, sulfuric acid, formic acid, acetic acid.
Described alkali is one or both in potassium hydroxide, sodium hydroxide, calcium hydroxide.
Described cross-linking monomer is one or both in n-methylolacrylamide, hydroxyethyl acrylamide, ethoxymethyl acrylamide, methacrylic acid ammonium ethyl ester.
Described cationic monomer is one or both in dimethyl diallyl ammonium chloride, acryloyl ethyl-trimethyl benzyl ammonium chloride, dimethylaminoethyl methacrylate, vinylformic acid dimethylamine ethyl ester.
Beneficial effect: preparation process of the present invention is not added containing formaldehyde and Organohalogen compounds (AOX), eliminates the source worked the mischief to HUMAN HEALTH.With acrylic amide cross-linking monomer and cationic monomer cross-linking modified after urea glyoxal resin, add molecular weight product, improve the performance of modified urea glyoxal resin, thus improve humidity usefulness, the crosslinking activity adding increase molecule segment of acrylic amide and cationic monomer, enhances at the reticulated structure that fiber peripheral is formed between polymkeric substance, can limit the activity between fiber better, stop the profit of fiber rise and absorb water, reduce paper retractable.The hydroxyl of Wet Strength Resin resin and adjacent fiber can form more multichain key (covalent linkage and hydrogen bond etc.) and can greatly improve the wet tenacity of paper simultaneously.
Present invention process is simple, starting material are cheap and easy to get, temperature of reaction is low, volatility of raw material loss is few, cationic monomer is with the addition of in technique, high with the electric density of cross-linking monomer polymkeric substance, molecular weight great achievement reticulated structure, after application, paper adsorption strengthens, and paper retention and wet tenacity are improved significantly.
Embodiment
The specific embodiment of the present invention is described in detail below in conjunction with preferred embodiment.Comprise following component, in molar ratio,
Embodiment 1
The present embodiment wet strength agent for paper making, by cross-linking monomer n-methylolacrylamide and cationic monomer dimethyl propylene ammonium chloride, modified urea glyoxal resin, its molecular chain has three-dimensional net structure, wherein glyoxal resin is that the urea glyoxal resin that oxalic dialdehyde synthesizes through polycondensation with urea obtains with cross-linking monomer n-methylolacrylamide and cationic monomer methyl diallyl sodium-chlor crosslinking polymerization again, acrylamide crosspolymer urea glyoxal resin Wet Strength Resin.
The present embodiment wet strength agent for paper making be with oxalic dialdehyde, urea, n-methylolacrylamide, dimethyl two olefine aldehydr propyl ammonium chloride undertake by comprising following key step for main raw material.
Add in reactor by oxalic dialdehyde and urea mol ratio 2:1, be 2 by hydrochloric acid conditioning solution pH value, 65 DEG C of reaction 3h are warmed up under stirring, cool to 30 DEG C, add oxalic dialdehyde again, add-on be first oxalic dialdehyde 15% mole number, regulator solution pH value is regulated to be 7 with potassium hydroxide, reaction 1.5h, thereafter regulator solution pH value is regulated to be 7 with potassium hydroxide again, n-methylolacrylamide is added under stirring, dimethyl diallyl is 0.5:0.2:5 by the mol ratio of urea, be warming up to 70 DEG C of reaction 1.5h, reaction terminating, add deionized water dilution, wherein all admittedly account for 12% of overall aqueous solution total amount containing thing.Acrylamide crosspolymer urea glyoxal resin Wet Strength Resin can be obtained.
Embodiment 2
The present embodiment wet strength agent for paper making, by cross-linking monomer hydroxyethyl acrylamide and cationic monomer acryloyl ethyl-trimethyl benzyl ammonium chloride, modified urea glyoxal resin, its molecular chain has three-dimensional net structure, wherein glyoxal resin is that oxalic dialdehyde obtains with hydroxylethyl cross-linking monomer acid amides and cationic monomer acryloyl ethyl-trimethyl benzyl ammonium chloride, crosslinking polymerization through the urea glyoxal resin of polycondensation and Reactive Synthesis with urea again, acrylamide crosspolymer urea glyoxal resin Wet Strength Resin.
The present embodiment wet strength agent for paper making be with oxalic dialdehyde, urea, hydroxyethyl acrylamide, acryloyl ethyl-trimethyl benzyl ammonium chloride for main raw material, undertaken by comprising following key step.
Reactor is added by oxalic dialdehyde and urea 1:0.3 mol ratio, regulator solution pH value 2 is regulated with sulfuric acid, 70 DEG C of reaction 2.5h are warming up under stirring, cool to 25 DEG C, add oxalic dialdehyde again, add-on be first oxalic dialdehyde 12% mole number, regulator solution pH value is regulated to be 7 with sodium hydroxide, reaction 1h, regulator solution pH value is regulated to be 7 with sodium hydroxide again, hydroxyethyl acrylamide and acryloyl ethyl-trimethyl Benzylmagnesium chloride amine is added under stirring, be 3.5:2:5 by urea mol ratio, be warming up to 70 DEG C of reaction 1h to stop, add deionized water dilution, wherein all admittedly account for 12% of overall aqueous solution total amount containing thing.Namely acquisition acyl is wished acid amides and is cross-linked urea glyoxal resin Wet Strength Resin.
Embodiment 3
The present embodiment is by crosslinked methylenedioxymethamphetamine acrylamide and cationic vinylformic acid dimethylamine ethyl ester, modified urea glyoxal resin, its molecular chain has three-dimensional network-like structure, wherein urea acetaldehyde resin is that the urea acetaldehyde resin that oxalic dialdehyde synthesizes through polycondensation with urea obtains with cross-linking monomer ethoxymethyl acrylamide, cationic monomer dimethylaminoethyl acrylate methyl amine second fat, crosslinking polymerization again, acrylamide crosspolymer urea glyoxal resin Wet Strength Resin.
The present embodiment wet strength agent for paper making, be with oxalic dialdehyde, urea, ethoxymethyl acrylamide, dimethylaminoethyl methacrylate, modified urea glyoxal resin, its molecular chain has three-dimensional network-like structure, wherein the urea acetaldehyde resin urea glyoxal resin that to be oxalic dialdehyde synthesize through polycondensation with urea again with ethoxymethyl acrylamide cross-linking monomer, cationic monomer dimethylaminoethyl acrylate methyl amine second fat, crosslinking polymerization and obtaining.
The present embodiment be with oxalic dialdehyde, urea, ethoxymethyl acrylamide, dimethylaminoethyl methacrylate, be main raw material, following key step is carried out.
Reactor is added by oxalic dialdehyde and urea 2:1 mol ratio, regulator solution pH value 2 is regulated with formic acid, 70 DEG C are warming up under stirring, reaction 2.5h, cooling, be cooled to 30 DEG C and add oxalic dialdehyde again, its add-on be first oxalic dialdehyde 15% mole number, regulator solution pH value is regulated to be 7 with calcium hydroxide, react 1.5 hours, regulator solution pH value is regulated to be 7 with calcium hydroxide again, ethoxymethyl acrylamide and dimethylaminoethyl methacrylate is added under stirring, be 1.6:0.4:5.0 by urea mol ratio, be warming up to 70 DEG C, reaction 1.5h stops, add deionized water dilution, wherein all admittedly account for 12% of overall aqueous solution total amount containing thing.Namely acrylamide crosspolymer urea glyoxal resin Wet Strength Resin is obtained.
Embodiment 4:
The present embodiment wet strength agent for paper making is by cross-linking monomer aminoethyl methacrylate and cationic monomer vinylformic acid dimethylamine ethyl ester, modified urea second glyoxal resin, its molecular chain has three-dimensional network-like structure, wherein urea acetaldehyde resin is the urea glyoxal resin that oxalic dialdehyde synthesizes through polycondensation with urea, again with cross-linking monomer aminoethyl methacrylate, cationic monomer vinylformic acid decil fat crosslinking polymerization and obtaining, acrylamide crosspolymer urea glyoxal resin Wet Strength Resin.
The present embodiment wet strength agent for paper making, be with oxalic dialdehyde, urea, methyl acyl wish sour amino ethyl ester, vinylformic acid decil fat for main raw material, undertaken by comprising following key step:
Reactor is added by oxalic dialdehyde and urea 2:1 mol ratio, regulator solution pH value 3-4 is regulated with acetic acid, 70 DEG C of reaction 2.5h are warming up under stirring, cool to 25 DEG C, add oxalic dialdehyde again, its add-on be first oxalic dialdehyde 12% mole number, regulator solution pH value is regulated to be 7 reaction 1.5 hours with sodium hydroxide, saving solution ph by sodium hydroxide key is again 7, aminoethyl methacrylate and vinylformic acid decil fat is added under stirring, by urea mol ratio 1.5:1.2:5.0, be warming up to 70 DEG C of reaction 1.5h to stop, wherein all admittedly account for 12% of overall aqueous solution total amount containing thing, namely acrylamide crosspolymer urea acetaldehyde resin Wet Strength Resin is obtained.
The present invention because not adding environment and human body nuisance, so relieve the various harm that nuisance and Organohalogen compounds (AOX) cause.Through hydroxyacrylamide class the product that is cross-linked, its molecular weight greatly increases and reticulates structure, the electric density of molecule segment strengthens, adsorbing fiber ability and retention significantly promote, not only increase page wet tenacity for this reason, and the folding endurance of page can be increased, tensile strength, with physical and chemical performances such as dry strength.
The above is only preferred embodiment of the present invention, not does any pro forma restriction to structure of the present invention.Every above embodiment is done according to technical spirit of the present invention any simple modification, equivalent variations and modification, all still belong in the scope of technical scheme of the present invention.
Claims (3)
1. a preparation method for acrylamide crosspolymer urea glyoxal resin Wet Strength Resin, is characterized in that, comprise the steps, in molar ratio,
1) urea-formaldehyde resin is prepared
It is 1-2:0.3-1 mixing by the mol ratio of oxalic dialdehyde and urea, with the pH value 1.5-3 of acid-conditioning solution, temperature is 35 DEG C-75 DEG C, carries out reaction 2.5-6h, cooling, add oxalic dialdehyde again, add-on be first oxalic dialdehyde 12%-15% mole number, be neutral by the pH value of alkali regulator solution, at 20-35 DEG C of temperature, react 1-2h, be neutral by the pH value of alkali regulator solution again, namely obtain urea-formaldehyde resin;
2) by cross-linking monomer, cationic monomer adds in urea-formaldehyde resin prepared by step 1), cross-linking monomer, the mol ratio 0.5-3.5:0.2-2:5 of cationic monomer and urea, temperature 50 C-80 DEG C, reaction 1-2h stops, and adds deionized water dilution, wherein all admittedly account for 12% of overall aqueous solution total amount containing thing, acrylamide crosspolymer urea glyoxal resin Wet Strength Resin can be obtained;
Described cross-linking monomer is one or both in n-methylolacrylamide, hydroxyethyl acrylamide, ethoxymethyl acrylamide, aminoethyl methacrylate;
Described cationic monomer is one or both in dimethyl diallyl ammonium chloride, acryloyl ethyl-trimethyl benzyl ammonium chloride, dimethylaminoethyl methacrylate, vinylformic acid dimethylamine ethyl ester.
2. the preparation method of acrylamide crosspolymer urea glyoxal resin Wet Strength Resin according to claim 1, is characterized in that, described acid is one or both in hydrochloric acid, sulfuric acid, formic acid, acetic acid.
3. the preparation method of acrylamide crosspolymer urea glyoxal resin Wet Strength Resin according to claim 1 and 2, is characterized in that, described alkali is one or both in potassium hydroxide, sodium hydroxide, calcium hydroxide.
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| CN113045711B (en) * | 2021-04-15 | 2022-09-02 | 浙江九本环保技术有限公司 | Preparation method and application of emulsion type polyester block low-organochlorine wet strength agent |
| CN114085383B (en) * | 2021-12-27 | 2022-11-04 | 上海东升新材料有限公司 | High-solid-content wet strength agent and preparation method thereof |
| CN115160520B (en) * | 2022-08-03 | 2023-07-04 | 西南林业大学 | Net-shaped hyperbranched amino copolycondensation resin and preparation method and application thereof |
| CN116856199A (en) * | 2023-06-30 | 2023-10-10 | 碳氢氧(天津)科技有限公司 | Wet strength agent for chlorine-free papermaking and preparation method thereof |
| CN117736390A (en) * | 2024-01-05 | 2024-03-22 | 西南林业大学 | N-methylolacrylamide-glyoxal-urea copolycondensation resin and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4279959A (en) * | 1977-11-03 | 1981-07-21 | Rohm And Haas Company | Water-insoluble copolymers containing amide-polyaldehyde thermosettable system |
| CN101858045A (en) * | 2010-04-30 | 2010-10-13 | 华中师范大学 | Epoxy modified urea resin wet strength agent and preparation method thereof |
| CN102190773A (en) * | 2010-03-11 | 2011-09-21 | 段全义 | Preparation method of urea-formaldehyde resin wet strength agent for papermaking |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4279959A (en) * | 1977-11-03 | 1981-07-21 | Rohm And Haas Company | Water-insoluble copolymers containing amide-polyaldehyde thermosettable system |
| CN102190773A (en) * | 2010-03-11 | 2011-09-21 | 段全义 | Preparation method of urea-formaldehyde resin wet strength agent for papermaking |
| CN101858045A (en) * | 2010-04-30 | 2010-10-13 | 华中师范大学 | Epoxy modified urea resin wet strength agent and preparation method thereof |
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