CN116285505B - Water-based treating agent suitable for high-elasticity EVA material and preparation method thereof - Google Patents
Water-based treating agent suitable for high-elasticity EVA material and preparation method thereof Download PDFInfo
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- CN116285505B CN116285505B CN202211633243.XA CN202211633243A CN116285505B CN 116285505 B CN116285505 B CN 116285505B CN 202211633243 A CN202211633243 A CN 202211633243A CN 116285505 B CN116285505 B CN 116285505B
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000000463 material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000004359 castor oil Substances 0.000 claims abstract description 54
- 235000019438 castor oil Nutrition 0.000 claims abstract description 54
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims abstract description 54
- 229920001046 Nanocellulose Polymers 0.000 claims abstract description 35
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 15
- 239000000839 emulsion Substances 0.000 claims abstract description 12
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 6
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 5
- 239000008158 vegetable oil Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 22
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 18
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 16
- 125000003396 thiol group Chemical class [H]S* 0.000 claims description 16
- 239000004925 Acrylic resin Substances 0.000 claims description 15
- 229920005749 polyurethane resin Polymers 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000080 wetting agent Substances 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000002562 thickening agent Substances 0.000 claims description 10
- 229920002545 silicone oil Polymers 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- -1 sulfhydryl ethanol Chemical compound 0.000 claims description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002518 antifoaming agent Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- 235000019198 oils Nutrition 0.000 claims description 3
- 229940035024 thioglycerol Drugs 0.000 claims description 3
- 150000003573 thiols Chemical class 0.000 claims description 3
- FETFXNFGOYOOSP-UHFFFAOYSA-N 1-sulfanylpropan-2-ol Chemical compound CC(O)CS FETFXNFGOYOOSP-UHFFFAOYSA-N 0.000 claims description 2
- MJQWABQELVFQJL-UHFFFAOYSA-N 3-Mercapto-2-butanol Chemical compound CC(O)C(C)S MJQWABQELVFQJL-UHFFFAOYSA-N 0.000 claims description 2
- UGZAJZLUKVKCBM-UHFFFAOYSA-N 6-sulfanylhexan-1-ol Chemical compound OCCCCCCS UGZAJZLUKVKCBM-UHFFFAOYSA-N 0.000 claims description 2
- 244000226021 Anacardium occidentale Species 0.000 claims description 2
- 235000019483 Peanut oil Nutrition 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 235000020226 cashew nut Nutrition 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- RBNPOMFGQQGHHO-UHFFFAOYSA-N glyceric acid Chemical compound OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004006 olive oil Substances 0.000 claims description 2
- 235000008390 olive oil Nutrition 0.000 claims description 2
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 2
- 239000000312 peanut oil Substances 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 239000003549 soybean oil Substances 0.000 claims description 2
- 235000012424 soybean oil Nutrition 0.000 claims description 2
- 230000008719 thickening Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 235000019486 Sunflower oil Nutrition 0.000 claims 1
- 239000002600 sunflower oil Substances 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 15
- 230000001070 adhesive effect Effects 0.000 abstract description 15
- 229920002635 polyurethane Polymers 0.000 abstract description 12
- 239000004814 polyurethane Substances 0.000 abstract description 12
- 239000011248 coating agent Substances 0.000 abstract description 7
- 238000000576 coating method Methods 0.000 abstract description 7
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 29
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 29
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 28
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 19
- 229920002678 cellulose Polymers 0.000 description 14
- 239000001913 cellulose Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000758 substrate Substances 0.000 description 9
- 239000002131 composite material Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000013530 defoamer Substances 0.000 description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 5
- 230000009467 reduction Effects 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 235000004443 Ricinus communis Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000012650 click reaction Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 235000020238 sunflower seed Nutrition 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
- C09D101/08—Cellulose derivatives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2423/00—Presence of polyolefin
- C09J2423/04—Presence of homo or copolymers of ethene
- C09J2423/046—Presence of homo or copolymers of ethene in the substrate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a water-based treating agent suitable for a high-elasticity EVA material and a preparation method thereof, wherein the water-based treating agent has good compatibility with an EVA base material and a water-based polyurethane adhesive, and a formed coating has higher mechanical strength and bonding property; the aqueous treating agent comprises an oligomer resin, polyhydroxy castor oil, modified nano cellulose, acetone, deionized water, vegetable oil and an aqueous auxiliary agent; the preparation method of the water-based treating agent comprises the following steps: s1, preparing polyhydroxy castor oil; s2, preparing a modified nano cellulose acetone solution; s3, preparing modified emulsion; s4, preparing an aqueous treating agent; the preparation method has the characteristics of simple modification process and warm reaction conditions.
Description
Technical Field
The invention belongs to the technical field of EVA (ethylene-vinyl acetate) surface treatment agents, and relates to an aqueous treatment agent suitable for a high-elasticity EVA material and a preparation method thereof.
Background
The middle soles of the sports shoes on the market are mostly formed by foaming EVA (ethylene-vinyl acetate copolymer) and a blend thereof, wherein the EVA is a copolymer synthesized by a nonpolar ethylene monomer and a polar vinyl acetate monomer through various polymerization modes such as bulk polymerization, solution polymerization, emulsion polymerization and the like, and the polarity of an EVA material is weak because the vinyl in the EVA molecule is a nonpolar group, so that the water-based polyurethane adhesive widely used in the shoe industry is not good in adhesion, and the EVA material which is not subjected to surface treatment is difficult to achieve ideal adhesive strength. In order to improve the adhesion of the adhesive to EVA, the EVA must be surface pre-treated. However, more than 80% of the surface treating agents on the market are solvent-type products, the existence of volatile organic solvents can cause environmental pollution, the health of operators can be endangered, and the risks of fire and explosion exist. The aqueous EVA treating agent is still in the development stage, and the solvent water is used for simply replacing an organic solvent to prepare the EVA treating agent, so that the problems of reduced polarity of the treating agent, reduced applicability of the treating agent to EVA substrates, mismatching of the treating agent and an adhesive, reduced bonding strength and peeling strength of the treating agent and the like occur, and in addition, the peeling strength in the initial drying stage is low, so that the requirement on efficiency in actual production cannot be met.
Castor oil is low in price, can carry out a plurality of chemical reactions through hydroxyl groups, double bonds and ester bonds, and is a renewable resource with great development prospect. The castor oil is mainly obtained by squeezing or solvent extracting castor seeds, the main component of the castor oil is fatty acid triglyceride, each fatty acid carbon chain consists of 18 carbon atoms, ester groups, unsaturated carbon-carbon double bonds and hydroxyl groups exist on the carbon chain, and the active groups provide possibility for chemical modification of the castor oil, and the addition of the castor oil can enable the polymer to form a compact polymer structure during reaction.
Cellulose molecules have a plurality of research surfaces, and the cellulose molecules are introduced into a composite material, so that the mechanical strength of a system can be greatly improved, and a coating film formed by a treating agent can be prevented from being stripped easily, but abundant hydroxyl groups in the cellulose molecules enable the cellulose molecules to have hydrophilicity, so that moisture in air is easily adsorbed to cause collapse of a pore structure, and the application of the cellulose molecules in the field of adhesive treating agents is limited.
Disclosure of Invention
The invention aims to provide a water-based treating agent suitable for a high-elasticity EVA material and a preparation method thereof, wherein the water-based treating agent has good compatibility with an EVA base material and a water-based polyurethane adhesive, and a formed coating film has higher mechanical strength and bonding property; the preparation method of the water-based treating agent has the characteristics of simple modification process and mild reaction conditions.
The aim of the invention can be achieved by the following technical scheme:
the water-based treating agent suitable for the high-elasticity EVA material comprises the following components in parts by weight:
the preparation method of the aqueous treating agent comprises the following steps:
s1, mixing castor oil, mercapto alcohol and a photoinitiator, reacting for 2 hours at room temperature under the irradiation of an ultraviolet lamp, diluting a product obtained by the reaction with chloroform, washing with saturated sodium chloride and distilled water for 3 times, drying with anhydrous magnesium sulfate, and evaporating a solvent to obtain the polyhydroxy castor oil;
s2, preparing a dopamine hydrochloride solution, regulating the pH value to 9-10, adding a nano cellulose aqueous dispersion, separating a water phase, adding acetone, stirring for 10-30min, standing, and stirring at a speed of 100-200rpm to obtain a modified nano cellulose acetone solution;
s3, adding modified nano cellulose acetone solution into the polyhydroxy castor oil prepared in the step S1, finally, centrifuging, freeze-drying, sequentially adding deionized water and vegetable oil, uniformly mixing, and performing ultrasonic dispersion under a cell pulverizer for 5min to obtain modified emulsion;
s4, adding the oligomer resin into the modified emulsion to adjust the hardness, stirring uniformly, adding the aqueous auxiliary agent under the stirring condition, dispersing uniformly, and filtering to obtain the aqueous treating agent.
In a preferred embodiment of the present invention, in step S1, the thiol-group-containing alcohol is a monohydric thiol having at least one hydroxyl group; the photoinitiator is 1173 photoinitiator; the irradiance of the ultraviolet lamp is 20mW/cm 2 。
As a preferable technical scheme of the invention, the mercapto alcohol is one or more of mercapto ethanol, thioglycerol, 1-mercapto-2-propanol, 2-mercapto-3-butanol or 6-mercapto hexanol, wherein the mercapto ethanol is preferably 2-mercapto ethanol.
As a preferable technical scheme of the invention, the ratio of the double bond of the castor oil to the mercapto-containing substance of the mercapto alcohol is 1:1.5.
as a preferable technical scheme of the invention, in the step S2, the volume ratio of the dopamine hydrochloride solution to the nano-cellulose aqueous dispersion is 1:0.5-1, and the concentration of the dopamine hydrochloride solution is 0.5-5g/L; the concentration of the nano cellulose aqueous dispersion is 15-45g/L.
As a preferable technical scheme of the invention, the oligomer resin is polyacrylic resin and polyurethane resin, wherein the weight ratio of the polyacrylic resin to the polyurethane resin is 1.5:0.5-1.
As a preferable technical scheme of the invention, the aqueous auxiliary agent is one or more of an aqueous thickener, an aqueous wetting agent, an aqueous defoaming agent and an aqueous leveling agent.
As a preferred embodiment of the present invention, the aqueous thickener contains an acidic group, which has alkali thickening properties; the aqueous wetting agent is an organosilicon wetting agent; the water-based defoaming agent is one or more of polyoxyethylene polyoxypropylene alcohol ether, emulsified silicone oil BYK-1660, polyoxypropylene glycerol ether and polyoxypropylene; the water-based leveling agent is one or more of polyacrylic acid copolymer and organosilicon compound.
In a preferred embodiment of the present invention, in step S3, the vegetable oil is one or more of castor oil, olive oil, sunflower seed oil, soybean oil, cashew nut shell oil, and peanut oil.
As a preferred embodiment of the present invention, in step S4, after adding the aqueous auxiliary agent under stirring, the viscosity at 25℃is brought to 1000-3000 mpa.s.
The invention has the beneficial effects that:
(1) Unsaturated carbon-carbon double bonds in castor oil can be utilized to introduce more hydroxyl groups with a substance containing sulfhydryl groups through sulfhydryl-alkene clicking reaction under the irradiation of ultraviolet light or the initiation of heat, and the method has mild reaction conditions, simplicity, rapidness and high yield; in addition, the mercapto compounds containing hydroxyl such as mercaptoethanol, thioglycerol and the like in the mercapto alcohols have been commercialized, and the acquisition path is convenient; when the ratio of the amount of the double bond of the castor oil to the mercapto group-containing substance of the mercapto alcohol is 1:1.5, the multi-functionality water-based treating agent prepared by the polyhydroxy castor oil and the oligomer resin has better stability.
(2) The nanocellulose adopted by the invention is extracted from natural cellulose materials, has wide sources and low price, and reduces the preparation cost; the polyhydroxy castor oil, the modified nanocellulose and the oligomer resin are utilized to form a composite material, and the nanocellulose is used for making up the defect of poor mechanical strength of a coating film, so that the EVA substrate is not easy to peel after surface treatment; according to the invention, the nano-cellulose is modified by adopting the dopamine hydrochloride solution, more hydroxyl groups are introduced into the castor oil through the mercapto-alkene click reaction, the castor oil contains a large amount of hydrophobic long carbon chains, the nano-cellulose has a compact internal structure, the polyhydroxy castor oil, the modified nano-cellulose and the oligomer resin complement each other to form a matched reaction, the finally prepared film has the advantages that the entanglement of the long carbon chains of the film increases the compactness of the surface of the film, the crosslinking degree is increased to prevent the penetration of water molecules to a certain extent, so that the water resistance of the water-based treating agent is better, namely, the capability of stabilizing the water-based treating agent is enhanced by introducing more active functional groups into the modified material.
(3) The preparation steps S1-S4 of the water-based treating agent have the advantages of simple modification process, mild reaction conditions, capability of finishing modification reaction at room temperature, and good biocompatibility, and no secondary pollution to the environment, and particularly, the dopamine hydrochloride and the castor oil are renewable and biodegradable materials.
(4) The aqueous treating agent synthesized by the components has similar polarity of vinyl acetate groups and vinyl acetate groups of EVA substrates, has strong interaction, and also contains polyurethane groups which have good compatibility with aqueous polyurethane adhesive, so that the aqueous treating agent contains a nonpolar chain segment of an EVA substrate and a polar chain segment of the hydrophilic polyurethane adhesive, and can be used as a good medium between the EVA substrate and the aqueous polyurethane adhesive; the adhesion is increased by introducing the urethane chain segment into the oligomer resin, and the oligomer resin has-NH-and-O-groups capable of forming hydrogen bonds, so that the capability of forming the hydrogen bonds between the coating film and the substrate is enhanced, and the adhesion is also enhanced; therefore, the polyhydroxy castor oil and the modified nanocellulose both contain a plurality of hydroxyl groups, the oligomer resin contains a plurality of carboxyl groups, and when the polyhydroxy castor oil, the modified nanocellulose and the oligomer resin form a composite material, not only can better physical effect be formed between the components, but also covalent bond connection exists, so that the EVA base material and the aqueous polyurethane adhesive are perfectly integrated together by the aqueous treating agent.
Detailed Description
In order to further describe the technical means and effects adopted by the present invention for achieving the intended purpose, the following detailed description is given below with reference to the embodiments, structures, features and effects according to the present invention.
Example 1
The water-based treating agent suitable for the high-elasticity EVA material comprises the following components in parts by weight:
the aqueous auxiliary agent comprises an aqueous thickener SD-301, an aqueous wetting agent BYK-154, aqueous defoamer emulsified silicone oil BYK-1660 and an aqueous leveling agent Wet 270 in parts by weight as follows: 1:0.5:0.1;
the preparation method of the aqueous treating agent comprises the following steps:
s1, mixing castor oil, 2-mercaptoethanol and 1173 photoinitiator, wherein the irradiance of light is 20mW/cm 2 The reaction is carried out for 2 hours at room temperature under the irradiation of an ultraviolet lamp, the product obtained by the reaction is diluted by chloroform, washed by saturated sodium chloride and distilled water for 3 times, dried by anhydrous magnesium sulfate, and the solvent is evaporated to obtain polyhydroxy castor oil; wherein the mass ratio of the double bond of the castor oil to the mercapto group of the 2-mercaptoethanol is 1:1.5;
s2, preparing a dopamine hydrochloride solution, regulating the pH value to 9.5, adding a nano cellulose aqueous dispersion, reacting for 24 hours at room temperature, separating a water phase, adding acetone, stirring for 20 minutes, standing, and stirring at 150rpm to obtain a modified nano cellulose acetone solution; wherein the volume ratio of the dopamine hydrochloride solution to the nano cellulose aqueous dispersion is 1:0.8, and the concentration of the dopamine hydrochloride solution is 4g/L; the concentration of the nano cellulose aqueous dispersion is 30g/L;
s3, adding modified nanocellulose acetone solution into the polyhydroxy castor oil prepared in the step S1, finally, centrifuging, freeze-drying, sequentially adding deionized water and castor oil, uniformly mixing, and performing ultrasonic dispersion under a cell pulverizer for 5min to obtain modified emulsion;
s4, adding polyacrylic resin and polyurethane resin into the modified emulsion to adjust the hardness, stirring uniformly, adding a waterborne thickener SD-301, a waterborne wetting agent BYK-154, a waterborne defoamer emulsified silicone oil BYK-1660 and a waterborne leveling agent Wet 270 under the stirring condition, enabling the viscosity to reach 2000 mpa.s at 25 ℃, dispersing uniformly, and filtering to obtain the waterborne treating agent, wherein the weight portion ratio of the polyacrylic resin to the polyurethane resin is 1.5:0.5.
example 2
The water-based treating agent suitable for the high-elasticity EVA material comprises the following components in parts by weight:
the aqueous auxiliary agent comprises an aqueous thickener SD-301, an aqueous wetting agent BYK-154, aqueous defoamer emulsified silicone oil BYK-1660 and an aqueous leveling agent Wet 270 in parts by weight as follows: 1:0.5:0.1;
the preparation method of the aqueous treating agent comprises the following steps:
s1, mixing castor oil, 2-mercaptoethanol and 1173 photoinitiator, wherein the irradiance of light is 20mW/cm 2 The reaction is carried out for 2 hours at room temperature under the irradiation of an ultraviolet lamp, the product obtained by the reaction is diluted by chloroform, washed by saturated sodium chloride and distilled water for 3 times, dried by anhydrous magnesium sulfate, and the solvent is evaporated to obtain polyhydroxy castor oil; wherein the mass ratio of the double bond of the castor oil to the mercapto group of the 2-mercaptoethanol is 1:1.5;
s2, preparing a dopamine hydrochloride solution, regulating the pH value to 9.5, adding a nano cellulose aqueous dispersion, reacting for 24 hours at room temperature, separating a water phase, adding acetone, stirring for 20 minutes, standing, and stirring at 150rpm to obtain a modified nano cellulose acetone solution; wherein the volume ratio of the dopamine hydrochloride solution to the nano cellulose aqueous dispersion is 1:0.8, and the concentration of the dopamine hydrochloride solution is 4g/L; the concentration of the nano cellulose aqueous dispersion is 30g/L;
s3, adding modified nanocellulose acetone solution into the polyhydroxy castor oil prepared in the step S1, finally, centrifuging, freeze-drying, sequentially adding deionized water and castor oil, uniformly mixing, and performing ultrasonic dispersion under a cell pulverizer for 5min to obtain modified emulsion;
s4, adding polyacrylic resin and polyurethane resin into the modified emulsion to adjust the hardness, stirring uniformly, adding a waterborne thickener SD-301, a waterborne wetting agent BYK-154, a waterborne defoamer emulsified silicone oil BYK-1660 and a waterborne leveling agent Wet 270 under the stirring condition, enabling the viscosity to reach 2000 mpa.s at 25 ℃, dispersing uniformly, and filtering to obtain the waterborne treating agent, wherein the weight portion ratio of the polyacrylic resin to the polyurethane resin is 1.5:0.5.
example 3
The water-based treating agent suitable for the high-elasticity EVA material comprises the following components in parts by weight:
the aqueous auxiliary agent comprises an aqueous thickener SD-301, an aqueous wetting agent BYK-154, aqueous defoamer emulsified silicone oil BYK-1660 and an aqueous leveling agent Wet 270 in parts by weight as follows: 1:0.5:0.1;
the preparation method of the aqueous treating agent comprises the following steps:
s1, mixing castor oil, 2-mercaptoethanol and 1173 photoinitiator, wherein the irradiance of light is 20mW/cm 2 The reaction is carried out for 2 hours at room temperature under the irradiation of an ultraviolet lamp, the product obtained by the reaction is diluted by chloroform, washed by saturated sodium chloride and distilled water for 3 times, dried by anhydrous magnesium sulfate, and the solvent is evaporated to obtain polyhydroxy castor oil; wherein the mass ratio of the double bond of the castor oil to the mercapto group of the 2-mercaptoethanol is 1:1.5;
s2, preparing a dopamine hydrochloride solution, regulating the pH value to 9.5, adding a nano cellulose aqueous dispersion, reacting for 24 hours at room temperature, separating a water phase, adding acetone, stirring for 20 minutes, standing, and stirring at 150rpm to obtain a modified nano cellulose acetone solution; wherein the volume ratio of the dopamine hydrochloride solution to the nano cellulose aqueous dispersion is 1:0.8, and the concentration of the dopamine hydrochloride solution is 4g/L; the concentration of the nano cellulose aqueous dispersion is 30g/L;
s3, adding modified nanocellulose acetone solution into the polyhydroxy castor oil prepared in the step S1, finally, centrifuging, freeze-drying, sequentially adding deionized water and castor oil, uniformly mixing, and performing ultrasonic dispersion under a cell pulverizer for 5min to obtain modified emulsion;
s4, adding polyacrylic resin and polyurethane resin into the modified emulsion to adjust the hardness, stirring uniformly, adding a waterborne thickener SD-301, a waterborne wetting agent BYK-154, a waterborne defoamer emulsified silicone oil BYK-1660 and a waterborne leveling agent Wet 270 under the stirring condition, enabling the viscosity to reach 2000 mpa.s at 25 ℃, dispersing uniformly, and filtering to obtain the waterborne treating agent, wherein the weight portion ratio of the polyacrylic resin to the polyurethane resin is 1.5:0.5.
comparative example 1
The difference compared to example 2 is that the castor oil is not modified and the remaining preparation steps and parameters are the same.
Comparative example 2
The difference compared to example 2 is that the cellulose is not modified and the remaining preparation steps and parameters are the same.
Comparative example 3
Compared with example 2, the difference is that the oligomer resin added in step S4 is polyacrylic resin, polyurethane resin is not contained, and the rest preparation steps and parameters are the same.
Comparative example 4
Compared with example 2, the difference is that the oligomer resin added in step S4 is polyurethane resin, no polyacrylic resin exists, and the rest preparation steps and parameters are the same.
Comparative example 5
The difference compared to example 2 is that the ratio of the amount of double bonds of the castor oil to the mercapto group of 2-mercaptoethanol is 1:0.8, and the rest preparation steps and parameters are the same.
Comparative example 6
Compared with example 2, the difference is that the volume ratio of the dopamine hydrochloride solution to the nanocellulose aqueous dispersion is 1:3, and the rest preparation steps and parameters are the same.
Comparative example 7
Compared with example 2, the difference is that in step S3, deionized water is added after centrifugation and freeze-drying to mix uniformly, and the rest preparation steps and parameters are the same.
The aqueous treating agents prepared in examples 1 to 3 and comparative examples 1 to 7 of the present invention were used for bonding between EVA substrates and aqueous polyurethane adhesives to obtain substrate finished products, which were subjected to initial peel strength (1 minute) and post peel strength (3 days) tests according to the regulations in GB/T19340-2014 adhesive for shoes and bags, and the test results are shown in the following table.
As can be seen from the above table, the aqueous treating agents prepared according to the methods of examples 1 to 3 have better peel strength, and the greater the peel strength, the better the adhesion; the modified castor oil and the modified cellulose introduce a plurality of hydroxyl groups, so that a better physical effect can be formed between the components when the modified castor oil and the modified cellulose form a composite material with the polyhydroxy castor oil, the modified nanocellulose and the oligomer resin, covalent bond connection exists, and the vinyl acetate group and the polyurethane group of the modified castor oil can lead the coating film to have good compatibility with EVA base materials and adhesives, and finally the peeling strength and the cohesiveness of the coating film formed by the composite material are obviously improved.
Comparative examples 1-2 compared with example 2, it is evident from the above table that unmodified castor oil and unmodified cellulose are mainly caused by the reduction of the introduced active functional groups, the reduction of the carbon chain length of the composite system and the formation of a compact structure, resulting in the reduction of the hardness and the deterioration of the stability of the system.
Comparative examples 3-4 as compared to example 2, it is seen from the above table that the lack of the polyacrylic resin or polyurethane resin in the composition results in a decrease in the vinyl acetate groups and polyurethane groups in the composite system, resulting in a decrease in physical adhesion to the EVA substrate or polyurethane adhesive, and a decrease in adhesion due to a decrease in the macromolecular carbon chains in the system.
Comparative examples 5 to 6 compared with example 2, it is evident from the above table that the excessive amount of castor oil or nanocellulose, part of castor oil or nanocellulose is not modified, the introduction of active functional groups is reduced, the carbon chain length of the composite material system is reduced and the formation of compact structure is not dense enough, resulting in the reduction of hardness and deterioration of stability of the system.
Comparative example 7 compared with example 2, it is apparent from the above table that in step S3, deionized water and castor oil are sequentially added to mix uniformly after centrifugation and freeze-drying, hydroxyl groups in the castor oil component can fully react the polyacrylic resin and the polyurethane resin to form a more compact structure, and the castor oil can improve the adhesion of the modified emulsion to the polyacrylic resin and the polyurethane resin.
The present invention is not limited to the above embodiments, but is capable of modification and variation in detail, and other modifications and variations can be made by those skilled in the art without departing from the scope of the present invention.
Claims (7)
1. The water-based treating agent suitable for the high-elasticity EVA material is characterized by comprising the following components in parts by weight:
the preparation method of the aqueous treating agent comprises the following steps:
s1, mixing castor oil, mercapto alcohol and a photoinitiator, reacting for 2 hours at room temperature under the irradiation of an ultraviolet lamp, diluting a product obtained by the reaction with chloroform, washing with saturated sodium chloride and distilled water for 3 times, drying with anhydrous magnesium sulfate, and evaporating a solvent to obtain the polyhydroxy castor oil; wherein the thiol-containing alcohol is a monohydric thiol containing at least one hydroxyl group; the photoinitiator is 1173 photoinitiator; the irradiance of the ultraviolet lamp is 20mW/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The ratio of the amount of the double bond of the castor oil to the mercapto-containing substance of the mercapto alcohol is 1:1.5;
s2, preparing a dopamine hydrochloride solution, regulating the pH value to 9-10, adding a nano cellulose aqueous dispersion, separating a water phase, adding acetone, stirring for 10-30min, standing, and stirring at a speed of 100-200rpm to obtain a modified nano cellulose acetone solution; wherein the volume ratio of the dopamine hydrochloride solution to the nano cellulose aqueous dispersion is 1:0.5-1, and the concentration of the dopamine hydrochloride solution is 0.5-5g/L; the concentration of the nano cellulose aqueous dispersion is 15-45g/L;
s3, adding modified nano cellulose acetone solution into the polyhydroxy castor oil prepared in the step S1, finally, centrifuging, freeze-drying, sequentially adding deionized water and vegetable oil, uniformly mixing, and performing ultrasonic dispersion under a cell pulverizer for 5min to obtain modified emulsion;
s4, adding the oligomer resin into the modified emulsion to adjust the hardness, stirring uniformly, adding the aqueous auxiliary agent under the stirring condition, dispersing uniformly, and filtering to obtain the aqueous treating agent.
2. An aqueous treating agent for a highly elastic EVA material according to claim 1, wherein: the sulfhydryl-containing alcohol is one or more of sulfhydryl ethanol, thioglycerol, 1-sulfhydryl-2-propanol, 2-sulfhydryl-3-butanol or 6-sulfhydryl hexanol.
3. An aqueous treating agent for a highly elastic EVA material according to claim 1, wherein: the oligomer resin is polyacrylic resin and polyurethane resin; wherein, the weight portion ratio of the polyacrylic resin to the polyurethane resin is 1.5:0.5-1.
4. An aqueous treating agent for a highly elastic EVA material according to claim 1, wherein: the aqueous auxiliary agent is one or more of an aqueous thickener, an aqueous wetting agent, an aqueous defoaming agent and an aqueous leveling agent.
5. An aqueous treating agent for a highly elastic EVA material according to claim 4, wherein: the aqueous thickener contains acidic groups, which have alkali thickening properties; the aqueous wetting agent is an organosilicon wetting agent; the water-based defoaming agent is one or more of polyoxyethylene polyoxypropylene alcohol ether, emulsified silicone oil BYK-1660, polyoxypropylene glycerol ether and polyoxypropylene; the water-based leveling agent is one or more of polyacrylic acid copolymer and organosilicon compound.
6. An aqueous treating agent for a highly elastic EVA material according to claim 1, wherein: in step S3, the vegetable oil is one or more of castor oil, olive oil, sunflower oil, soybean oil, cashew nut shell oil and peanut oil.
7. An aqueous treating agent for a highly elastic EVA material according to claim 1, wherein: in step S4, after adding the aqueous auxiliary agent under stirring, the viscosity at 25 ℃ is up to 1000-3000 mpa.s.
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