CN112159502A - Preparation method of formaldehyde-free glue for impregnated paper - Google Patents
Preparation method of formaldehyde-free glue for impregnated paper Download PDFInfo
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- CN112159502A CN112159502A CN202011081522.0A CN202011081522A CN112159502A CN 112159502 A CN112159502 A CN 112159502A CN 202011081522 A CN202011081522 A CN 202011081522A CN 112159502 A CN112159502 A CN 112159502A
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- emulsion
- methacrylate
- total dosage
- acrylate
- initiator
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- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000003292 glue Substances 0.000 title claims description 8
- 239000000839 emulsion Substances 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 239000003999 initiator Substances 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 19
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000004132 cross linking Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000007599 discharging Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000006172 buffering agent Substances 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- -1 hydroxypropyl ammonium methacrylate Chemical compound 0.000 claims description 18
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 16
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 16
- 229920000056 polyoxyethylene ether Polymers 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 10
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 4
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical group [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 4
- 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 3
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 3
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 claims description 3
- DYUHNIQFZDWPJI-UHFFFAOYSA-N C(C=C/C(=O)O)(=O)O.C(CCCCCCCCCCCCCCCCC)N Chemical compound C(C=C/C(=O)O)(=O)O.C(CCCCCCCCCCCCCCCCC)N DYUHNIQFZDWPJI-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 3
- 150000004712 monophosphates Chemical class 0.000 claims description 3
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 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
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- 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 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 2
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 239000000872 buffer Substances 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 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
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 10
- 239000000853 adhesive Substances 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 239000002904 solvent Substances 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 16
- 238000003756 stirring Methods 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 7
- 125000005336 allyloxy group Chemical group 0.000 description 7
- 238000007720 emulsion polymerization reaction Methods 0.000 description 7
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 5
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000002313 adhesive film Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007731 hot pressing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- RGNCFKBLXRSNIV-UHFFFAOYSA-N CC(C(OCCCO)=O)=C.N Chemical compound CC(C(OCCCO)=O)=C.N RGNCFKBLXRSNIV-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- CUHVTYCUTYWQOR-UHFFFAOYSA-N formaldehyde Chemical compound O=C.O=C CUHVTYCUTYWQOR-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
Images
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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying 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
- 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
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a preparation method of an aldehyde-free adhesive for impregnated paper. Then, adding part of the pre-emulsion and the initiator solution into the aqueous solution containing the buffering agent and the reactive emulsifier simultaneously, heating to 65-90 ℃, and then preserving the temperature for 5-30 min to form the seed emulsion. And finally, slowly dripping the residual pre-emulsion and the initiator solution into the base solution for reaction for 1.5 to 8 hours, preserving the heat for 0.5 to 2.5 hours, cooling and discharging. The dosage of each component is calculated by the mass of the main monomer, wherein the total dosage of the functional crosslinking monomer is 0.05-50%, the total dosage of the reactive emulsifier is 0.1-20%, the total dosage of water is 100-1000%, the total dosage of the buffering agent is 0.01-10%, and the total dosage of the initiator is 0.01-10%. The method is simple to operate, the medium is water, the method is safe and environment-friendly, the reaction is easy to control, and the obtained acrylate impregnating adhesive is high in stability, long in storage period and good in water resistance and solvent resistance.
Description
Technical Field
The invention relates to a preparation method of aldehyde-free glue for impregnated paper, in particular to a method for modifying acrylate emulsion by using one or more reactive emulsifiers and functional crosslinking monomers and then using the acrylate emulsion as decorative paper aldehyde-free impregnated glue.
Background
The impregnated bond paper is a bond paper with certain resin and volatile content obtained by impregnating and drying plain color paper or printing decorative paper with impregnating resin. The impregnated bond paper can be combined with an artificial board to form a decorative artificial board through hot pressing, and the surface gloss, the attractiveness, the water resistance, the stain resistance, the weather resistance, the wear resistance and the like of the artificial board can be greatly improved. However, the decorative paper impregnating adhesive generally adopts a formaldehyde-formaldehyde adhesive which can release harmful substances such as formaldehyde, phenol and the like in the production and impregnation processes, is harmful to the health of people and does not accord with the environmental protection concept. The invention provides a preparation method of an acrylate emulsion impregnating adhesive, which aims to solve the problem of formaldehyde release of the impregnating adhesive in the decorative paper industry.
The acrylate emulsion polymerization usually uses small-molecule free emulsifier, and the mechanical property, the adhesive property, the water resistance and the solvent resistance of the acrylate emulsion polymerization are generally shown. The invention utilizes the reactive emulsifier to replace the traditional micromolecular emulsifier, and avoids the defects caused by the migration and aggregation of the free micromolecular emulsifier in the film-forming drying process. Meanwhile, the invention introduces post-crosslinking functional monomers, and the prepared acrylate emulsion is subjected to secondary crosslinking in the processes of polymerization, dipping drying and hot pressing, so that the water resistance, the wear resistance, the stain resistance, the heat resistance and the surface bonding strength with an artificial board of the adhesive film paper are further improved.
The technical problem to be solved is as follows: the invention uses the acrylate emulsion adhesive prepared by the emulsion polymerization technology as the adhesive for impregnating the decorative paper, and solves the problem of formaldehyde release in the impregnated bond paper industry.
Technical scheme
The invention discloses a preparation method of aldehyde-free glue for impregnated paper, which comprises the following polymerization processes:
firstly, adding an acrylate monomer into an aqueous solution of a reactive emulsifier, and stirring and dispersing to obtain a pre-emulsion; uniformly mixing part of the reactive emulsifier, the initiator and water to obtain a reaction base solution, heating the reaction base solution to 60-90 ℃ in a water bath kettle, adding a small amount of pre-emulsion and initiator solution into the base solution, reacting for 10-40 min, dropwise adding the rest of pre-emulsion and initiator solution, continuously reacting for 1.5-8 h, keeping the temperature for 0.5-2.5 h, cooling and discharging.
The dosage of each component is calculated by the mass of the main monomer, wherein the total dosage of the functional crosslinking monomer is 0.05-50%, the total dosage of the reactive emulsifier is 0.1-20%, the total dosage of water is 100-1000%, the total dosage of the buffering agent is 0.01-10%, and the total dosage of the initiator is 0.01-10%.
The main monomer of the acrylic ester is one or more of methyl methacrylate, propyl methacrylate, isooctyl methacrylate, methyl acrylate, butyl acrylate and n-octyl acrylate.
The reactive emulsifier is one or more of ammonium hydroxypropyl methacrylate sulfonate, allyloxy nonylphenol polyoxyethylene ether sulfate, allyloxy hydroxypropane sulfonic acid sodium salt, allyloxy nonylphenol polyoxyethylene ether monophosphate, sodium p-styrene sulfonate and sodium vinyl sulfonate.
The functional crosslinking monomer is one or more of hydroxyethyl methacrylate, itaconic acid, maleic acid, glycidyl methacrylate, allyl methacrylate, acetoacetoxyethyl methacrylate, ethylene glycol dimethacrylate, vinyl hydroxybutylaminopropyl urea, N-hydroxymethyl acrylamide, N-hydroxyethyl acrylamide and N-octadecylamide monomaleate.
The initiator is one or more of ammonium persulfate, potassium persulfate, sodium persulfate, azodiisobutyronitrile and benzoyl peroxide.
The above buffer is Na2HPO4、Na2CO3、NaHCO3One or more of them.
Advantageous effects
The invention discloses a preparation method of non-formaldehyde glue for impregnated paper, which has the following characteristics compared with the traditional 'three-formaldehyde glue':
(1) the acrylate emulsion impregnating adhesive prepared by using the reactive emulsifier has the advantages of long storage period, high stability, low viscosity, excellent water resistance, excellent corrosion resistance and excellent adhesion capability in a humid environment.
(2) The acrylic ester emulsion modified by the functional crosslinking monomer is used for dipping the adhesive, and the dipped adhesive film paper can react with fiber hydroxyl and free formaldehyde in the artificial board in the hot pressing process to be crosslinked and cured for the second time, so that the bonding strength between the adhesive film paper and the artificial board is improved, and the free formaldehyde in the artificial board can be absorbed.
Drawings
FIG. 1 is a reaction equation of acetoacetoxyethyl methacrylate and aldehyde group
Detailed Description
The effects of the present invention will be further illustrated by the following specific examples:
the embodiments are implemented on the premise of the technical scheme of the invention, and the technical means used is conventional means well known to those skilled in the art, and the technical scheme is not to be construed as limiting the invention.
Example 1
(1) Preparing a pre-emulsion: 65g of methyl methacrylate, 65g of butyl acrylate, 2.0g of vinylhydroxybutylaminepropyl urea, 2g of hydroxyethyl methacrylate and 2g of N-octadecylamide monomaleate were mixed in a beaker. 0.5g of ammonium allyloxy nonylphenol polyoxyethylene ether sulfate, 0.5g of allyloxy nonylphenol polyoxyethylene ether and 50g of deionized water are put into a 500ml three-neck flask with a stirring device, and mixed monomers are dropwise added into the flask at a constant speed under the stirring condition to prepare the pre-emulsion.
(2) Emulsion polymerization: mixing 1.5g of ammonium allyloxy nonylphenol polyoxyethylene ether sulfate, 0.5g of allyloxy nonylphenol polyoxyethylene ether, 80g of water and 0.4g of disodium hydrogen phosphate, placing the mixture into a four-neck flask with a mechanical stirrer, a condensation reflux device and a thermometer, and placing the flask into a water bath kettle for heating; 10g of ammonium persulfate was dissolved in 22g of water. And when the reaction temperature reaches 85 ℃, pouring a small amount of the pre-emulsion and the initiator solution into a four-neck flask at the same time, reacting for 30min, slowly dropwise adding the rest of the pre-emulsion and the initiator solution, continuously reacting for 1.5h, preserving heat for 2.5h, cooling and discharging.
Example 2
(1) Preparing a pre-emulsion: 50g of isooctyl methacrylate, 50g of methyl acrylate, 30g of n-octyl acrylate, 0.1g of hydroxyethyl methacrylate, 0.05g of itaconic acid and 0.05g of maleic acid were mixed in a beaker. 5g of allyloxy hydroxy propane sulfonic acid sodium salt, 5g of allyloxy nonyl phenol polyoxyethylene ether monophosphate and 80g of water are placed in a 500ml three-neck flask with a stirring device, and mixed monomers are dropwise added into the flask at a constant speed under the stirring condition to prepare the pre-emulsion.
(2) Emulsion polymerization: taking 3g of ammonium allyloxy nonylphenol polyoxyethylene ether sulfate, 5g of allyloxy nonylphenol polyoxyethylene ether, 200g of water and 10g of sodium carbonate, mixing, placing in a four-neck flask with a mechanical stirring device, a condensation reflux device and a thermometer, and placing in a water bath kettle for heating; 1g of potassium persulfate was dissolved in 10g of water. And when the reaction temperature reaches 90 ℃, pouring a small amount of the pre-emulsion and the initiator solution into a four-neck flask at the same time, reacting for 40min, slowly dropwise adding the rest of the pre-emulsion and the initiator solution, continuously reacting for 8h, preserving the temperature for 0.5h, cooling and discharging.
Example 3
(1) Preparing a pre-emulsion: 15g of propyl methacrylate, 15g of butyl acrylate, 0.5g of ethylene glycol dimethacrylate, 0.5g of vinylhydroxybutylaminopropyl urea and 0.5g of N-methylolacrylamide were mixed in a beaker. 0.1g of ammonium allyloxy nonylphenol polyoxyethylene ether sulfate, 0.05g of allyloxy nonylphenol polyoxyethylene ether and 180g of water are put into a 250ml three-neck flask with a stirring device, and mixed monomers are dropwise added into the flask at a constant speed under the stirring condition to prepare the pre-emulsion.
(2) Emulsion polymerization: mixing 0.05g of ammonium allyloxy nonyl phenol polyoxyethylene ether sulfate, 0.01g of sodium p-styrene sulfonate, 100g of water and 0.1g of sodium bicarbonate, placing the mixture into a four-neck flask with a mechanical stirrer, a condensation reflux device and a thermometer, and placing the flask into a water bath kettle for heating; 0.15g of ammonium persulfate was dissolved in 5g of water. And when the reaction temperature reaches 75 ℃, pouring a small amount of the pre-emulsion and the initiator solution into a four-neck flask at the same time, reacting for 30min, slowly dropwise adding the rest of the pre-emulsion and the initiator solution, continuously reacting for 6h, preserving the temperature for 2h, cooling and discharging.
Example 4
(1) Preparing a pre-emulsion: 65g of methyl methacrylate, 65g of butyl acrylate and 50g of acetoacetoxyethyl methacrylate were mixed in a beaker. 0.1g of ammonium allyloxy nonyl phenol polyoxyethylene ether sulfate and 50g of water are put into a 500ml three-neck flask with a stirring device, and mixed monomers are dropwise added into the flask at a constant speed under the stirring condition to prepare the pre-emulsion.
(2) Emulsion polymerization: mixing 0.15g of ammonium allyloxy nonylphenol polyoxyethylene ether sulfate, 88g of water and 0.4g of disodium hydrogen phosphate, placing the mixture into a four-neck flask with a mechanical stirrer, a condensation reflux device and a thermometer, and placing the flask into a water bath kettle for heating; 0.05g of ammonium persulfate was dissolved in 22g of water. And when the reaction temperature reaches 65 ℃, pouring a small amount of the pre-emulsion and the initiator solution into a four-neck flask at the same time, reacting for 10min, slowly dropwise adding the rest of the pre-emulsion and the initiator solution, continuously reacting for 4h, preserving the temperature for 1h, cooling and discharging.
EXAMPLES results
| Examples | Pre-emulsion | Particle size of emulsion | Monomer conversion% | Polymerization Effect |
| 1 | The pre-emulsion is relatively stable | 230 | 91 | The emulsion is stable and bright and white |
| 2 | The pre-emulsion is very stable | 73 | 94 | Emulsion stabilization, bluish |
| 3 | Pre-emulsion latent layering | 80 | 92 | Emulsion stabilization, bluish |
| 4 | Pre-emulsion stratification | - | - | - |
Claims (6)
1. A preparation method of the formaldehyde-free glue for impregnated paper is characterized in that firstly, a (methyl) acrylate main monomer and a functional crosslinking monomer are sequentially added into an aqueous solution containing a reactive emulsifier to obtain a pre-emulsion. Then, adding part of the pre-emulsion and the initiator solution into the aqueous solution containing the buffering agent and the reactive emulsifier simultaneously, heating to 65-90 ℃, preserving the heat for 5-30 min, dripping the rest of the pre-emulsion and the initiator solution into the base solution simultaneously for reacting for 1.5-8 h, preserving the heat for 0.5-2.5 h, cooling and discharging.
The dosage of each component is calculated by the mass of the main monomer, wherein the total dosage of the functional crosslinking monomer is 0.05-50%, the total dosage of the reactive emulsifier is 0.1-20%, the total dosage of water is 100-1000%, the total dosage of the buffering agent is 0.01-10%, and the total dosage of the initiator is 0.01-10%.
2. The method of claim 1, wherein the method comprises the steps of: the (methyl) acrylate main monomer is one or more of methyl methacrylate, propyl methacrylate, isooctyl methacrylate, methyl acrylate, butyl acrylate and n-octyl acrylate.
3. The method of claim 1, wherein the method comprises the steps of: the reactive emulsifier is one or more of hydroxypropyl ammonium methacrylate, allyloxy nonylphenol polyoxyethylene ether sulfate, allyloxy hydroxypropane sulfonic acid sodium salt, allyloxy nonylphenol polyoxyethylene ether monophosphate, sodium p-styrene sulfonate and sodium vinyl sulfonate.
4. The method of claim 1, wherein the method comprises the steps of: the functional crosslinking monomer is one or more of hydroxyethyl methacrylate, itaconic acid, maleic acid, glycidyl methacrylate, allyl methacrylate, acetoacetoxyethyl methacrylate, ethylene glycol dimethacrylate, vinyl hydroxybutylaminopropyl urea, N-hydroxymethyl acrylamide, N-hydroxyethyl acrylamide and N-octadecylamide monomaleate.
5. The method of claim 1, wherein the method comprises the steps of: the initiator is one or more of ammonium persulfate, potassium persulfate, sodium persulfate, azodiisobutyronitrile and benzoyl peroxide.
6. The method of claim 1, wherein the method comprises the steps of: the buffer is Na2HPO4、Na2CO3、NaHCO3One or more of them.
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| CN202011081522.0A CN112159502A (en) | 2020-10-10 | 2020-10-10 | Preparation method of formaldehyde-free glue for impregnated paper |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115197661A (en) * | 2022-07-05 | 2022-10-18 | 湖南林特科技有限公司 | High-surface-bonding-strength zero-VOC aldehyde-free back coating adhesive for impregnated paper and preparation method thereof |
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2020
- 2020-10-10 CN CN202011081522.0A patent/CN112159502A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115197661A (en) * | 2022-07-05 | 2022-10-18 | 湖南林特科技有限公司 | High-surface-bonding-strength zero-VOC aldehyde-free back coating adhesive for impregnated paper and preparation method thereof |
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Application publication date: 20210101 |