CN116535603A - Modified aqueous polyurethane dispersion and preparation method and application thereof - Google Patents
Modified aqueous polyurethane dispersion and preparation method and application thereof Download PDFInfo
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- CN116535603A CN116535603A CN202310166822.6A CN202310166822A CN116535603A CN 116535603 A CN116535603 A CN 116535603A CN 202310166822 A CN202310166822 A CN 202310166822A CN 116535603 A CN116535603 A CN 116535603A
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- aqueous polyurethane
- modified aqueous
- polyurethane dispersion
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- 229920003009 polyurethane dispersion Polymers 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 43
- 239000002131 composite material Substances 0.000 claims abstract description 39
- -1 adipoyl hydrazine Chemical compound 0.000 claims abstract description 32
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 239000004970 Chain extender Substances 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 229920005862 polyol Polymers 0.000 claims abstract description 13
- 150000003077 polyols Chemical class 0.000 claims abstract description 13
- 229920002635 polyurethane Polymers 0.000 claims abstract description 11
- 239000004814 polyurethane Substances 0.000 claims abstract description 11
- 239000003112 inhibitor Substances 0.000 claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000003973 paint Substances 0.000 description 15
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- WNPVSRSMIAXYIZ-UHFFFAOYSA-N 8-fluorohenicosan-8-ol Chemical compound CCCCCCCCCCCCCC(O)(F)CCCCCCC WNPVSRSMIAXYIZ-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229940087291 tridecyl alcohol Drugs 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229920000715 Mucilage Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000006120 scratch resistant coating Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002966 varnish Substances 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3802—Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
- C08G18/3834—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing hydrazide or semi-carbazide groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
-
- 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
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The application relates to the technical field of aqueous polyurethane dispersion, and particularly discloses a modified aqueous polyurethane dispersion, a preparation method and application thereof. The modified aqueous polyurethane dispersion comprises the following raw materials in parts by weight: 10-20 parts of composite material, 1.2-3.5 parts of polyalcohol, 0.02-0.05 part of catalyst, 0.01-0.05 part of polymerization inhibitor, 1-5 parts of neutralizer, 1-3 parts of chain extender and 50-70 parts of water, wherein the composite material is prepared by modifying polyurethane prepolymer by adipoyl hydrazine; the preparation method comprises the following steps: uniformly mixing the composite material, the polyol, the catalyst and the polymerization inhibitor, heating and preserving heat to obtain a mixture, adding a chain extender, a neutralizer and water into the mixture, heating and preserving heat to obtain the modified aqueous polyurethane dispersoid. The modified aqueous polyurethane dispersion has the advantage of improving the stain resistance through the synergistic effect among the raw materials.
Description
Technical Field
The application relates to the technical field of aqueous polyurethane dispersion, in particular to a modified aqueous polyurethane dispersion and a preparation method and application thereof.
Background
With the development of material technology, high performance, low VOC has become a direction of paint development. The aqueous polyurethane dispersion mainly uses water as a dispersion medium, is not easy to burn, is environment-friendly, has the advantages of excellent low temperature resistance, hand feeling, hardness and the like due to a unique soft and hard segment copolymerization structure, is attractive, and is widely used in the fields of textile, leather, mucilage, printing ink and the like.
In the field of commercially available electronic devices, such as cell phones, tablet computers, laptop computers and automotive interiors, the use of various substrates such as plastics, metals and release is generally desirable for these substrates to be easily cleaned, have excellent adhesion, and also require a stain and scratch resistant coating over the various types of plastic substrates.
The aqueous polyurethane structure is formed by copolymerizing hard-segment isocyanate and soft-segment polyol, hydrophilic groups are introduced, and the soft-segment polyester polyol is easy to hydrolyze and the polyether polyol is easy to absorb water, so that the existing aqueous polyurethane dispersoid has good adhesive force and pencil hardness, but has poor stain resistance.
Disclosure of Invention
In order to improve the stain resistance of the aqueous polyurethane dispersion, the application provides a modified aqueous polyurethane dispersion, and a preparation method and application thereof.
In a first aspect, the present application provides a modified aqueous polyurethane dispersion, which adopts the following technical scheme:
a modified aqueous polyurethane dispersion comprising the following raw materials in parts by weight: 10-20 parts of composite material, 1.2-3.5 parts of polyol, 0.02-0.05 part of catalyst, 0.01-0.05 part of polymerization inhibitor, 1-5 parts of neutralizer, 1-3 parts of chain extender and 50-70 parts of water, wherein the composite material is prepared by modifying polyurethane prepolymer by adipoyl hydrazine.
Through the adoption of the technical scheme, the modified aqueous polyurethane dispersion can keep good hardness, glossiness and adhesive force through the synergistic effect among the raw materials, and improves the stain resistance, wherein the pencil hardness is F-H, the 60-degree angle gloss is 92-98, the adhesive force is 0-2 level, and the stain resistance is 3-5 minutes.
The composite material is prepared by modifying a polyurethane prepolymer by using adipoyl hydrazine, wherein the adipoyl hydrazine is a hydrazide monomer, the adipoyl hydrazine is utilized to crosslink and modify the polyurethane prepolymer, a hydrazide group is introduced into a molecular chain of the polyurethane prepolymer, and along with evaporation of water, a ketone carbonyl group and the hydrazide group undergo dehydration condensation reaction to generate a crosslinking bond, so that the composite material has lower surface tension, the stability of the composite material can be improved, and the stain resistance of the composite material can be obviously improved while the good pencil hardness, adhesive force and the like of the modified aqueous polyurethane dispersion are maintained, thereby improving the stain resistance of the modified aqueous polyurethane dispersion.
The polyol is taken as a basic component, and the catalyst can promote the reaction, so that the time is saved, and the efficiency is improved; polymerization inhibitor, neutralizer and chain extender are also used as basic components, which is convenient for preparing the modified aqueous polyurethane dispersoid.
As preferable: the composite material is prepared by the following method: the polyurethane prepolymer is put into water for dispersion, diacetone acrylic acid amine and potassium persulfate are added, and the mixture is obtained after uniform mixing; and adding adipoyl hydrazine into the mixture, uniformly mixing, and drying to obtain the composite material.
Further, the composite material is prepared by the following method: dispersing polyurethane prepolymer in water at 2500-3000r/min for 10-30min, adding diacetone acrylic acid amine and potassium persulfate, and mixing to obtain mixture; adding adipoyl hydrazine into the mixture, uniformly mixing, and drying to obtain a composite material;
wherein the addition amount of water in each 1g of polyurethane prepolymer is 5-7mL, and the weight ratio of the polyurethane prepolymer to diacetone acrylic amine is 1: (0.3-0.5), the weight ratio of the polyurethane prepolymer to the potassium persulfate is 1: (0.002-0.005).
Through adopting above-mentioned technical scheme, at first prepare the mixture, the more even of each raw materials mixture of being convenient for, then add adipoyl hydrazine to the complex, prepare combined material, the better crosslinking modification of adipoyl hydrazine and complex of being convenient for is convenient for improve combined material's dirt resistance to improve modified waterborne polyurethane dispersion's dirt resistance.
As preferable: the weight ratio of the polyurethane prepolymer to the adipoyl hydrazine is 1: (0.6-0.8).
Too little adipoyl hydrazine is added, so that the polyurethane prepolymer cannot be sufficiently crosslinked and modified with adipoyl hydrazine, and the pollution resistance of the modified aqueous polyurethane dispersion cannot be improved; the excessive addition of adipoyl hydrazine not only increases the production cost, but also causes waste. By adopting the technical scheme, when the weight ratio of the polyurethane prepolymer to the adipoyl hydrazine is in the range, the cost can be saved, and the pollution resistance of the composite material can be improved, so that the pollution resistance of the modified aqueous polyurethane dispersion is improved.
As preferable: the polyurethane prepolymer is prepared by the following method: uniformly mixing hydroxyethyl acrylate, toluene diisocyanate and dimethylolpropionic acid, adding triethylene diamine, heating, preserving heat, adding tridecyl fluorine octanol, heating for reaction, adding acetone, uniformly mixing, adding triethylamine for chain extension, and performing rotary evaporation to obtain the polyurethane prepolymer.
Further, the polyurethane prepolymer is prepared by the following method: uniformly mixing hydroxyethyl acrylate, toluene diisocyanate and dimethylolpropionic acid, adding triethylene diamine, heating to 50-60 ℃, preserving heat for 1.5-2.5 hours, adding tridecyl alcohol, heating to 70-90 ℃ for reaction for 1-3 hours, adding acetone, uniformly mixing, adding triethylamine for chain extension, and performing rotary evaporation to obtain a polyurethane prepolymer;
wherein, the addition amount of hydroxyethyl acrylate in each 1g of toluene diisocyanate is 0.5-1mL, the addition amount of dimethylolpropionic acid in each 1g of toluene diisocyanate is 0.5-1.5g, the addition amount of triethylene diamine in each 1g of toluene diisocyanate is 0.5-1g, the addition amount of acetone in each 1g of toluene diisocyanate is 1-2mL, and the addition amount of triethylamine in each 1g of toluene diisocyanate is 0.1-0.5mL.
By adopting the technical scheme, the preparation method is utilized to prepare the polyurethane prepolymer, tridecyl fluorooctanol is added into the raw material of the polyurethane prepolymer, fluorine-containing groups are introduced, and triethylene diamine can introduce vinyl, so that the compatibility of tridecyl fluorooctanol and toluene diisocyanate can be enhanced, the polyurethane prepolymer has extremely low surface energy, the hydrophobicity and the hydrophobicity are enhanced, the surface tension is reduced, the stain resistance is further improved, and the stain resistance of the modified aqueous polyurethane dispersion is further improved.
As preferable: the weight ratio of toluene diisocyanate to tridecafluorooctanol is 1: (0.4-0.6).
The addition amount of tridecafluorooctanol is too small, so that the introduced fluorine-containing groups are less, and the pollution resistance of the modified aqueous polyurethane dispersion cannot be improved better; the addition amount of tridecyl fluorooctanol is excessive, and when fluorine-containing groups introduced on toluene diisocyanate reach saturation, the pollution resistance is not improved any more, and the waste of tridecyl fluorooctanol is caused. By adopting the technical scheme, when the addition amount of toluene diisocyanate and tridecafluorooctanol is in the range, the pollution resistance of the modified aqueous polyurethane dispersion can be improved better.
As preferable: the polyol is one or more of polyether glycol, polycarbonate glycol and polyester glycol, and the catalyst is one or more of dimethyl cyclohexylamine, dibutyl tin dilaurate and N-ethylmorpholine.
As preferable: the neutralizing agent is one or more of ammonia water and N, N-dimethylethanolamine, and the chain extender is one or more of ethylenediamine, hexamethylenediamine and m-xylylenediamine.
By adopting the technical scheme, the polyol, the catalyst, the neutralizer and the chain extender are limited, so that the pollution resistance of the modified aqueous polyurethane dispersion is improved.
In a second aspect, the present application provides a method for preparing a modified aqueous polyurethane dispersion, which adopts the following technical scheme: a method for preparing a modified aqueous polyurethane dispersion, comprising the following steps:
uniformly mixing the composite material, the polyol, the catalyst and the polymerization inhibitor, heating and preserving heat to obtain a mixture, adding a chain extender, a neutralizer and water into the mixture, heating and preserving heat to obtain the modified aqueous polyurethane dispersoid.
Further, a preparation method of the modified aqueous polyurethane dispersion comprises the following steps:
uniformly mixing the composite material, the polyol, the catalyst and the polymerization inhibitor, heating to the temperature of 60-80 ℃ for reaction, preserving heat for 2-4 hours to obtain a mixture, adding a chain extender, a neutralizer and water into the mixture, heating to the temperature of 80-90 ℃, and preserving heat for 3-6 hours to obtain the modified aqueous polyurethane dispersoid.
By adopting the technical scheme, the modified aqueous polyurethane dispersion is prepared by the method, so that the raw materials are more uniformly mixed, and the pollution resistance of the modified aqueous polyurethane dispersion is improved.
In a third aspect, the present application provides an application of a modified aqueous polyurethane dispersion, which adopts the following technical scheme:
use of modified aqueous polyurethane dispersion in coating, wherein the addition amount of the modified aqueous polyurethane dispersion is 85-90wt%
By adopting the technical scheme, the modified aqueous polyurethane dispersoid is used in the coating, so that the stain resistance of the prepared paint film can be improved.
In summary, the present application includes at least one of the following beneficial technical effects:
1. as the adipoyl hydrazine is adopted to crosslink and modify the polyurethane prepolymer, and the hydrazyl group is introduced on the molecular chain of the polyurethane prepolymer to generate a crosslinking bond, so that the polyurethane prepolymer has lower surface tension, and the stain resistance of the composite material can be obviously improved, thereby improving the stain resistance of the modified aqueous polyurethane dispersion, enabling the pencil hardness to reach H, the 60-DEG angle gloss to reach 98, the adhesive force to reach 0 level and the stain resistance to reach 5 minutes.
2. In the application, the polyurethane prepolymer is preferably prepared by using tridecyl fluorine octanol and toluene diisocyanate as main materials, and fluorine-containing groups are introduced, so that the polyurethane prepolymer has extremely low surface energy, the hydrophobicity and the hydrophobicity are enhanced, the surface tension is reduced, the stain resistance of the polyurethane prepolymer can be further improved, and the stain resistance of the modified aqueous polyurethane dispersion is improved.
Detailed Description
The present application is described in further detail below in conjunction with the detailed description.
Raw materials
The polyalcohol is polyhexamethylene carbonate glycol, the molecular weight of the polyhexamethylene carbonate glycol is 860, and the viscosity is 350-850 mPa.s; the catalyst is dimethyl cyclohexylamine; the neutralizing agent is N, N-dimethylethanolamine; the chain extender is ethylenediamine.
Preparation example
Preparation example 1
A polyurethane prepolymer prepared by the following method:
1.4L of hydroxyethyl acrylate, 2kg of toluene diisocyanate and 2kg of dimethylolpropionic acid are uniformly mixed, 1.4kg of triethylene diamine is added, the mixture is heated to the temperature of 55 ℃, the heat preservation is carried out for 2 hours, 0.8kg of tridecyl alcohol is added, the mixture is heated to the temperature of 80 ℃ for 2 hours, 3L of acetone is added, the mixture is uniformly mixed, and then 0.5L of triethylamine is added for chain extension, and rotary evaporation is carried out, so as to obtain the polyurethane prepolymer.
Preparation example 2
A polyurethane prepolymer which was different from that of preparation example 1 in the amount of tridecanfluorooctanol added, and in preparation example 2, the amount of tridecanfluorooctanol added was 1L.
Preparation example 3
A polyurethane prepolymer which was different from that of preparation example 1 in the amount of tridecanfluorooctanol added, and in preparation example 3, the amount of tridecanfluorooctanol added was 1.2L.
Preparation example 4
A composite material prepared by the method comprising:
2kg of the polyurethane prepolymer prepared in preparation example 1 is put into 12L of water, dispersed for 20min at the rotating speed of 2700r/min, added with 0.8kg of diacetone acrylic acid amine and 0.006kg of potassium persulfate, and uniformly mixed to obtain a mixture; adding 1.2kg of adipoyl hydrazine into the mixture, uniformly mixing, and drying to obtain the composite material.
Preparation example 5
A composite material is different from preparation example 4 in that the source of the polyurethane prepolymer is different, and the polyurethane prepolymer in preparation example 5 is prepared by adopting preparation example 2.
Preparation example 6
A composite material is different from preparation example 4 in that the source of the polyurethane prepolymer is different, and the polyurethane prepolymer in preparation example 6 is prepared by adopting preparation example 3.
Preparation example 7
A composite material was different from that of preparation example 5 in that the amount of adipoyl hydrazine added was 1.4kg in preparation example 7.
Preparation example 8
A composite material was different from that of preparation example 5 in that the amount of adipoyl hydrazine added was 1.6kg in preparation example 8.
Examples
Example 1
The raw material proportion of the modified aqueous polyurethane dispersoid is shown in table 1.
A method for preparing a modified aqueous polyurethane dispersion, comprising the following steps:
the composite material, the polyol, the catalyst and the polymerization inhibitor which are prepared by adopting the preparation example 4 are uniformly mixed, heated to the temperature of 70 ℃ for reaction, kept for 3 hours to obtain a mixture, added with the chain extender, the neutralizer and the water, heated to the temperature of 85 ℃ and kept for 4.5 hours to obtain the modified aqueous polyurethane dispersoid.
Examples 2 to 3
A modified aqueous polyurethane dispersion is different from example 1 in that the raw material ratios of the polyurethane dispersion are shown in Table 1.
TABLE 1 raw materials for polyurethane dispersions in different examples
Examples 4 to 5
A modified aqueous polyurethane dispersion is different from example 2 in that the raw material ratios of the polyurethane dispersion are shown in Table 2.
TABLE 2 raw materials for polyurethane dispersions in different examples
| Raw materials | Example 4 | Example 5 |
| Composite material | 15 | 15 |
| Polyhydric alcohol | 2.8 | 3.5 |
| Catalyst | 0.03 | 0.05 |
| Polymerization inhibitor | 0.03 | 0.05 |
| Neutralizing agent | 3 | 5 |
| Chain extender | 2 | 3 |
| Water and its preparation method | 60 | 70 |
Example 6
A modified aqueous polyurethane dispersion which differs from example 4 in that the source of the composite material in the polyurethane dispersion is different and is prepared using preparation example 5.
Example 7
A modified aqueous polyurethane dispersion which differs from example 4 in that the source of the composite material in the polyurethane dispersion is different and is prepared using preparation example 6.
Example 8
A modified aqueous polyurethane dispersion which differs from example 4 in that the source of the composite material in the polyurethane dispersion is different and is prepared using preparation example 7.
Example 9
A modified aqueous polyurethane dispersion which differs from example 4 in that the source of the composite material in the polyurethane dispersion is different and is prepared using preparation example 8.
Comparative example
Comparative example 1
A modified aqueous polyurethane dispersion is distinguished from example 1 in that the polyurethane dispersion is a composite material replaced by an equivalent amount of the polyurethane prepolymer prepared in preparation example 1.
Application example
Application example 1
A coating comprising the steps of: the modified aqueous polyurethane dispersion prepared in example 1 was uniformly mixed with 87wt%, BYK346 leveling agent 0.6wt%, EEH5wt%, isoamyl alcohol 0.5wt%, hydroxymethyl cellulose 0.2wt% and water 6.7wt%, to obtain a coating.
Application examples 2 to 9
A coating material differing from application example 1 in that a modified aqueous polyurethane dispersion was prepared using examples 2 to 9.
Comparative example 1 was used
A coating material differing from application example 1 in that a modified aqueous polyurethane dispersion was prepared using comparative example 1.
Performance test
The following performance tests were carried out on the modified aqueous polyurethane dispersions in application examples 1 to 9 and application comparative example 1:
pencil hardness: the hardness of the coating was measured according to GB/T6739-1996 pencil test for coating hardness, and the test results are shown in Table 3.
Adhesion force: the adhesion of the coatings was determined according to GB/T9286-1998 cross-cut test of paint films of colored and clear paints, and the results of the measurements are shown in Table 3.
60 ° angle gloss: the coatings were subjected to a 60℃angular gloss measurement according to GB/T9754-2007 measurement of 20℃60℃85℃specular gloss of paint films of paints and varnishes free of metallic pigments, and the measurement results are shown in Table 3.
Stain resistance: the paint film is scrawled by an oily marker, the paint film is wiped by non-woven fabrics, the residual condition of the scrawling on the paint film is observed, and the score is calculated according to the residual marks after wiping, wherein the mark is divided into 5 marks without change, 0 marks are divided into 0 marks, and the marks are increased in sequence.
TABLE 3 detection results
As can be seen from table 3, the modified aqueous polyurethane dispersion of the present application can maintain good hardness, gloss and adhesion, and improve stain resistance by the synergistic effect between the raw materials, wherein the pencil hardness is F-H, the 60 ° angular gloss is 92-98, the adhesion is 0-2 grade, and the stain resistance is 3-5 minutes.
As can be seen from the combination of application example 1 and application comparative example 1, the pencil hardness of the paint film in application example 1 is F, the 60-degree angle gloss is 92, the adhesion is 2-grade, and the stain resistance is 3 minutes, which is superior to the application comparative example, and the application of adipoyl hydrazine to modify the polyurethane prepolymer by the composite material is more suitable, so that the good hardness, glossiness and adhesion of the paint film can be maintained, and the stain resistance of the modified polyurethane dispersion can be improved.
As can be seen from the combination of application examples 1 to 3, the pencil hardness of the paint film in application example 2 is F, the 60-degree angular gloss is 93, the adhesive force is 2 grades, and the stain resistance is 4 minutes, which is superior to other application examples, and shows that the addition amount of the composite material in application example 2 is more suitable, so that the good hardness, glossiness and adhesive force of the paint film can be maintained, and the stain resistance of the modified polyurethane dispersion can be improved.
It can be seen from the combination of application example 4 and application example 5 that the other raw materials in the modified aqueous polyurethane dispersion except the composite material have little influence on the properties thereof.
As can be seen from the combination of application examples 6 to 9, the pencil hardness of the paint film in application example 8 is H, the 60-degree angular gloss is 98, the adhesive force is 0 grade, and the stain resistance is 5 minutes, which is superior to other application examples, and the polyurethane prepolymer is more suitable to be prepared by adopting the preparation example 2, and the composite material is more suitable to be prepared by adopting the preparation example 7, so that the good hardness, the good glossiness and the good adhesive force of the paint film can be maintained, and the stain resistance of the modified polyurethane dispersion can be improved.
The foregoing embodiments are all preferred examples of the present application, and are not intended to limit the scope of the present application in any way, therefore: all equivalent changes in structure, shape and principle of this application should be covered in the protection scope of this application.
Claims (9)
1. A modified aqueous polyurethane dispersion characterized in that: the material comprises the following raw materials in parts by weight: 10-20 parts of composite material, 1.2-3.5 parts of polyol, 0.02-0.05 part of catalyst, 0.01-0.05 part of polymerization inhibitor, 1-5 parts of neutralizer, 1-3 parts of chain extender and 50-70 parts of water, wherein the composite material is prepared by modifying polyurethane prepolymer by adipoyl hydrazine.
2. A modified aqueous polyurethane dispersion according to claim 1, characterized in that: the composite material is prepared by the following method: the polyurethane prepolymer is put into water for dispersion, diacetone acrylic acid amine and potassium persulfate are added, and the mixture is obtained after uniform mixing; and adding adipoyl hydrazine into the mixture, uniformly mixing, and drying to obtain the composite material.
3. A modified aqueous polyurethane dispersion according to claim 2, characterized in that: the weight ratio of the polyurethane prepolymer to the adipoyl hydrazine is 1: (0.6-0.8).
4. A modified aqueous polyurethane dispersion according to claim 2, characterized in that: the polyurethane prepolymer is prepared by the following method: uniformly mixing hydroxyethyl acrylate, toluene diisocyanate and dimethylolpropionic acid, adding triethylene diamine, heating, preserving heat, adding tridecyl fluorine octanol, heating for reaction, adding acetone, uniformly mixing, adding triethylamine for chain extension, and performing rotary evaporation to obtain the polyurethane prepolymer.
5. A modified aqueous polyurethane dispersion according to claim 4, characterized in that: the weight ratio of toluene diisocyanate to tridecafluorooctanol is 1: (0.4-0.6).
6. A modified aqueous polyurethane dispersion according to claim 1, characterized in that: the polyol is one or more of polyether glycol, polycarbonate glycol and polyester glycol, and the catalyst is one or more of dimethyl cyclohexylamine, dibutyl tin dilaurate and N-ethylmorpholine.
7. A modified aqueous polyurethane dispersion according to claim 1, characterized in that: the neutralizing agent is one or more of ammonia water and N, N-dimethylethanolamine, and the chain extender is one or more of ethylenediamine, hexamethylenediamine and m-xylylenediamine.
8. A process for the preparation of a modified aqueous polyurethane dispersion as claimed in any one of claims 1 to 7, comprising the steps of: uniformly mixing the composite material, the polyol, the catalyst and the polymerization inhibitor, heating and preserving heat to obtain a mixture, adding a chain extender, a neutralizer and water into the mixture, heating and preserving heat to obtain the modified aqueous polyurethane dispersoid.
9. A modified aqueous polyurethane dispersion as claimed in any of claims 1 to 7 for use in coatings
The application is carried out, and the addition amount of the modified aqueous polyurethane dispersoid is 85-90wt%.
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