CN112358591A - TPU hot melt powder modified waterborne polyurethane resin and preparation method thereof - Google Patents
TPU hot melt powder modified waterborne polyurethane resin and preparation method thereof Download PDFInfo
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- CN112358591A CN112358591A CN202011238459.7A CN202011238459A CN112358591A CN 112358591 A CN112358591 A CN 112358591A CN 202011238459 A CN202011238459 A CN 202011238459A CN 112358591 A CN112358591 A CN 112358591A
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- China
- Prior art keywords
- hot melt
- melt powder
- tpu hot
- polyurethane resin
- diisocyanate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000843 powder Substances 0.000 title claims abstract description 45
- 239000012943 hotmelt Substances 0.000 title claims abstract description 41
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000004970 Chain extender Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920005862 polyol Polymers 0.000 claims abstract description 16
- 150000003077 polyols Chemical class 0.000 claims abstract description 16
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 238000002844 melting Methods 0.000 claims abstract description 7
- 230000008018 melting Effects 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 56
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 36
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 36
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 15
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000000839 emulsion Substances 0.000 claims description 13
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 11
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229960004063 propylene glycol Drugs 0.000 claims description 9
- 239000004417 polycarbonate Substances 0.000 claims description 8
- 229920000515 polycarbonate Polymers 0.000 claims description 8
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical group OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 7
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 7
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical group OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 3
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 3
- 229940043276 diisopropanolamine Drugs 0.000 claims description 3
- 238000004945 emulsification Methods 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 235000013772 propylene glycol Nutrition 0.000 claims description 3
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims 2
- YRTNMMLRBJMGJJ-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;hexanedioic acid Chemical compound OCC(C)(C)CO.OC(=O)CCCCC(O)=O YRTNMMLRBJMGJJ-UHFFFAOYSA-N 0.000 claims 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims 1
- 238000005406 washing Methods 0.000 abstract description 7
- 239000000853 adhesive Substances 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 150000002009 diols Chemical class 0.000 description 13
- -1 polyoxypropylene Polymers 0.000 description 12
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229910052797 bismuth Inorganic materials 0.000 description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000010023 transfer printing Methods 0.000 description 2
- 229920000715 Mucilage Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
Classifications
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- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- 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
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
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- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines containing two hydroxy 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
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- 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
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- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
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- 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
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- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- 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
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- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- 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
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- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- 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
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- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/6622—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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- 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
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- 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
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- 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
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- C08G18/6655—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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- 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
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- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the technical field of adhesives, and particularly discloses a TPU hot melt powder modified waterborne polyurethane resin and a preparation method thereof, wherein the TPU hot melt powder, deionized water, diisocyanate, oligomer polyol, a small molecular chain extender, a hydrophilic chain extender, a salt forming agent and a catalyst are used as raw materials; the contents of the components are respectively as follows according to the mass portion: 35-50 parts of deionized water, 10-25 parts of diisocyanate, 25-40 parts of oligomer polyol, 0.2-3 parts of chain extender, 0.2-3 parts of hydrophilic chain extender, 5-30 parts of TPU hot melt powder, 0.05-0.5 part of salt forming agent and 0.1-0.4 part of catalyst; wherein the particle size of the TPU hot melt powder is as follows: less than or equal to 80um, and the melting point range is as follows: 95-105 ℃, heat bonding temperature: 150 ℃ and 160 ℃. The invention overcomes the defects of the prior art, and the modified waterborne polyurethane resin prepared by adding the medium-high temperature TPU hot-melt powder increases the cohesive force of the product and improves the water washing resistance, thereby improving the comprehensive performance of the product and meeting the industrial requirements.
Description
Technical Field
The invention relates to the field of coating printing materials, and particularly belongs to TPU (thermoplastic polyurethane) hot melt powder modified waterborne polyurethane resin and a preparation method thereof.
Background
The thermal transfer printing process is to melt various patterns on a transfer printing film in a heating mode and transfer print the patterns on a base material. The heat transfer film comprises a carrier layer, a release layer, a protective layer, an ink layer and a bonding layer, wherein the coatings are closely connected and mutually influenced. Among them, the adhesive layer must have high adhesion, water-washing resistance, retort resistance and chemical resistance.
The existing water-based resin technology in the market is not mature, most of the water-based resins are various water-based resins, and the adhesive force and the water washing resistance of the water-based resins can not meet the production requirements far away.
Disclosure of Invention
The invention aims to provide a TPU hot melt powder modified waterborne polyurethane resin and a preparation method thereof, overcomes the defects of the prior art, increases the cohesive force of the product, improves the washing resistance and improves the comprehensive performance of the product.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the TPU hot melt powder modified waterborne polyurethane resin comprises TPU hot melt powder, deionized water, diisocyanate, oligomer polyol, a small molecular chain extender, a hydrophilic chain extender, a salt forming agent and a catalyst;
the contents of the components are respectively as follows according to the mass portion:
wherein the particle size of the TPU hot melt powder is as follows: less than or equal to 80um, and the melting point range is as follows: 95-105 ℃, heat bonding temperature: 150 ℃ and 160 ℃.
Preferably, the diisocyanate is toluene diisocyanate, 4 '-diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and/or 4,4' -dicyclohexylmethane diisocyanate.
Preferably, the oligomer polyol is polycarbonate diol, polyoxypropylene polyol, polyoxyethylene diol, polytetrahydrofuran diol, polyethylene glycol adipate diol and/or neopentyl glycol adipate diol.
Preferably, the chain extender is 1, 4-butanediol, 1, 6-hexanediol, ethylene glycol, 1, 2-propanediol, diethylene glycol, trimethylolpropane, ethylenediamine, diethylenetriamine, isophoronediamine and/or a sulfamate.
Preferably, the hydrophilic chain extender is dimethylolpropionic acid.
Preferably, the salt forming agent is triethylamine, NaOH, diethanolamine or diisopropanolamine.
A preparation method of TPU hot melt powder modified waterborne polyurethane resin comprises the following specific steps:
step S1, dehydrating TPU hot melt powder and oligomer polyol at the temperature of 110-120 ℃ for 1-1.5h, cooling to 70 ℃, adding diisocyanate, stirring at the temperature of 85-110 ℃ for reaction for 1.5-2h, sequentially adding a small molecular chain extender, a hydrophilic chain extender and a catalyst, reacting at the temperature of 60-70 ℃ for 4.5-5.5h, and adjusting the viscosity of a reaction system by using acetone in the whole reaction process to obtain a polyurethane prepolymer;
step S2, transferring the prepolymer into an emulsification barrel, adding a salt forming agent at the temperature of 25-40 ℃, adding deionized water and stirring for 2-10min at the rotating speed of 1500-;
and step S3, transferring the emulsion containing acetone prepared in the second step into a flask for removing acetone, controlling the temperature at 35-55 ℃, and removing acetone under a vacuum condition to obtain the waterborne polyurethane emulsion.
Compared with the prior art, the invention has the following implementation effects:
according to the TPU hot melt powder modified waterborne polyurethane resin and the preparation method thereof, the modified waterborne polyurethane resin prepared by adding the TPU hot melt powder with medium and high temperature is added, so that the adhesive force of the product is increased, and the water washing resistance is also improved, so that the comprehensive performance of the product is improved, and the industrial requirement is met.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples, and any modification is within the scope of the present invention without departing from the spirit of the present invention.
The TPU hot melt powder modified waterborne polyurethane resin comprises TPU hot melt powder, deionized water, diisocyanate, oligomer polyol, a micromolecule chain extender, a hydrophilic chain extender, a salt forming agent and a catalyst; the diisocyanate is toluene diisocyanate, 4 '-diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and/or 4,4' -dicyclohexylmethane diisocyanate; the oligomer polyol is polycarbonate diol, polypropylene oxide polyol, polyethylene oxide diol, polytetrahydrofuran diol, polyethylene glycol adipate diol and/or neopentyl glycol adipate diol; the chain extender is 1, 4-butanediol, 1, 6-hexanediol, ethylene glycol, 1, 2-propanediol, diethylene glycol, trimethylolpropane, ethylenediamine, diethylenetriamine, isophoronediamine and/or sulfamate, the hydrophilic chain extender is dimethylolpropionic acid, and the salt forming agent is triethylamine, NaOH, diethanolamine or diisopropanolamine.
A preparation method of TPU hot melt powder modified waterborne polyurethane resin comprises the following specific steps:
step S1, dehydrating TPU hot melt powder and oligomer polyol at the temperature of 110-120 ℃ for 1-1.5h, cooling to 70 ℃, adding diisocyanate, stirring at the temperature of 85-110 ℃ for reaction for 1.5-2h, sequentially adding a small molecular chain extender, a hydrophilic chain extender and a catalyst, reacting at the temperature of 60-70 ℃ for 4.5-5.5h, and adjusting the viscosity of a reaction system by using acetone in the whole reaction process to obtain a polyurethane prepolymer;
step S2, transferring the prepolymer into an emulsification barrel, adding a salt forming agent at the temperature of 25-40 ℃, adding deionized water and stirring for 2-10min at the rotating speed of 1500-;
and step S3, transferring the emulsion containing acetone prepared in the second step into a flask for removing acetone, controlling the temperature at 35-55 ℃, and removing acetone under a vacuum condition to obtain the waterborne polyurethane emulsion.
Example 1
In the embodiment, the TPU hot melt powder is selected from powder with the particle size of 60um, the melting point range of 85 ℃ and the thermal bonding temperature of 150 ℃, the oligomer polyol is selected from poly neopentyl glycol adipate diol (Mn ═ 2000), a mixture of poly neopentyl glycol adipate diol and polycarbonate diol (Mn ═ 2000), the diisocyanate is selected from isophorone diisocyanate, the chain extender is selected from 1, 2-propylene glycol, and the salt forming agent is selected from triethylamine. Dehydrating 30g of TPU hot melt powder, 70g of poly neopentyl glycol adipate diol and 10g of polycarbonate diol (Mn is 2000) at 110 ℃ for 1h, adding 35.52g of isophorone diisocyanate, stirring at 100 ℃ for reaction for 2h, sequentially adding 1.47g of dimethylolpropionic acid, 6.25g of 1, 2-propylene glycol and 0.36g of bismuth catalyst, reacting at 70 ℃ for 3.5h, adjusting the viscosity with 180g of acetone, cooling to 40 ℃, continuously adding 1.875g of A95 (solid content is 50%), and reacting at a constant temperature for 0.3h to obtain a polyurethane prepolymer; transferring the prepolymer into an emulsion barrel, adding 1g of triethylamine at 40 ℃, after 2min, adding 150g of deionized water at a rotating speed of 1600r/min, and stirring for 5 min; transferring the prepared emulsion containing acetone into a flask for removing acetone, controlling the temperature between 35 and 55 ℃, and removing the acetone under the vacuum condition of-0.075 MPa to obtain the product.
Example 2
In the embodiment, the TPU hot melt powder is powder with the particle size of 80um, the melting point range of 87 ℃ and the thermal bonding temperature of 155 ℃, the oligomer polyol is poly neopentyl glycol adipate diol (Mn is 2000), the diisocyanate is isophorone diisocyanate, the chain extender is 1, 2-propylene glycol, and the salt forming agent is triethylamine. Dehydrating 20g of TPU hot melt powder and 80g of poly neopentyl glycol adipate diol at 110 ℃ for 1h, adding 35.52g of isophorone diisocyanate, stirring at 110 ℃ for reaction for 1.5h, sequentially adding 5.88g of dimethylolpropionic acid, 6.25g of 1, 2-propylene glycol and 0.3g of bismuth catalyst, reacting at 70 ℃ for 4.5h, and adjusting the viscosity by using 100g of acetone to obtain a polyurethane prepolymer; transferring the prepolymer into an emulsion barrel, adding 1g of triethylamine at 40 ℃, adding 145g of deionized water at 1600r/min after 2min, and stirring for 5 min; transferring the prepared emulsion containing acetone into a flask for removing acetone, controlling the temperature between 35 and 55 ℃, and removing the acetone under the vacuum condition of-0.075 MPa to obtain the product.
Example 3
In the embodiment, the TPU hot melt powder is powder with the particle size of 75um, the melting point range of 90 ℃ and the thermal bonding temperature of 155 ℃, the oligomer polyol is a mixture of polytetrahydrofuran diol (Mn ═ 2000) and polycarbonate diol (Mn ═ 2000), the diisocyanate is isophorone diisocyanate, the chain extender is 1, 2-propylene glycol, and the salt former is triethylamine. Dehydrating 25g of TPU hot melt powder, 80g of polytetrahydrofuran dihydric alcohol and 20g of polycarbonate dihydric alcohol at 110 ℃ for 1h, adding 38.3g of isophorone diisocyanate, stirring at 90 ℃ for reaction for 2h, sequentially adding 1.8g of dimethylolpropionic acid, 6g of 1, 2-propylene glycol and 0.4g of bismuth catalyst, reacting at 70 ℃ for 4.5h, adjusting the viscosity with 200g of acetone, cooling to 40 ℃, continuously adding 2.5g of A95 (solid content: 50%), and reacting for 0.5h in a heat preservation manner to obtain a polyurethane prepolymer; transferring the prepolymer into an emulsifying barrel, adding 1g of triethylamine at 40 ℃, after 2min, adding 170g of deionized water at the rotating speed of 1900r/min and stirring for 5 min; transferring the prepared emulsion containing acetone into a flask for removing acetone, controlling the temperature between 35 and 55 ℃, and removing the acetone under the vacuum condition of-0.075 MPa to obtain the product.
Example 4
In this example, the TPU hot melt powder is a powder having a particle size of 75um, a melting point range of 90 ℃, and a thermal bonding temperature of 155 ℃, the oligomer polyol is a mixture of polytetrahydrofuran diol (Mn 2000) and polycarbonate diol (Mn 2000), the diisocyanate is isophorone diisocyanate, the chain extender is diethylene glycol, and the salt former is triethylamine. Dehydrating 20g of TPU hot melt powder, 70g of poly neopentyl glycol adipate diol and 10g of polytetrahydrofuran diol at 110 ℃ for 1h, adding 36g of isophorone diisocyanate, stirring at 100 ℃ for reaction for 1.5h, sequentially adding 1.67g of dimethylolpropionic acid, 6.3g of diethylene glycol and 0.3g of bismuth catalyst, reacting at 70 ℃ for 3.5h, adjusting the viscosity with 190g of acetone, cooling to 40 ℃, continuously adding 2g of A95 (50% of solid), and reacting at a constant temperature for 0.3h to obtain a polyurethane prepolymer; transferring the prepolymer into an emulsion barrel, adding 1g of triethylamine at 40 ℃, adding 145g of deionized water at 1600r/min after 2min, and stirring for 5 min; transferring the prepared emulsion containing acetone into a flask for removing acetone, controlling the temperature between 35 and 55 ℃, and removing the acetone under the vacuum condition of-0.075 MPa to obtain the product.
Performance detection analysis
The TPU hot melt powder modified waterborne polyurethane resins obtained in the embodiments 1-4 are respectively added with 0.4 percent of silane coupling agent and 4 percent of local closed curing agent according to the weight of the resin, mixed with a proper amount of thickening agent to prepare mucilage, blade-coated on a film, dried at 60 ℃, thermally transferred on cloth at the temperature of 150-170 ℃, placed at room temperature for 24 hours, and subjected to 60 ℃ water washing test, wherein each cycle is 1.5 hours.
The above test item data are shown in the following table:
| item | Example 1 | Example 2 | Example 3 | Example 4 |
| Number of washes | 12 | 10 | 7 | 9 |
As can be seen from the above table, the TPU hot melt powder modified waterborne polyurethane resin prepared by the invention has better washing resistance and can meet the requirements of industrial application.
The foregoing is merely exemplary and illustrative of the present inventive concept and various modifications, additions and substitutions of similar embodiments may be made to the specific embodiments described by those skilled in the art without departing from the inventive concept or exceeding the scope of the claims as defined in the accompanying claims.
Claims (7)
1. The TPU hot melt powder modified waterborne polyurethane resin is characterized in that: the TPU hot melt powder modified waterborne polyurethane resin comprises TPU hot melt powder, deionized water, diisocyanate, oligomer polyol, a small molecular chain extender, a hydrophilic chain extender, a salt forming agent and a catalyst;
the contents of the components are respectively as follows according to the mass portion:
wherein the particle size of the TPU hot melt powder is as follows: less than or equal to 80um, and the melting point range is as follows: 95-105 ℃, heat bonding temperature: 150 ℃ and 160 ℃.
2. The TPU hot melt powder modified aqueous polyurethane resin as claimed in claim 1, wherein: the diisocyanate is toluene diisocyanate, 4 '-diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and/or 4,4' -dicyclohexylmethane diisocyanate.
3. The TPU hot melt powder modified aqueous polyurethane resin as claimed in claim 1, wherein: the oligomer polyalcohol is polycarbonate dihydric alcohol, polypropylene oxide polyalcohol, polyethylene oxide dihydric alcohol, polytetrahydrofuran dihydric alcohol, polyethylene glycol adipate dihydric alcohol and/or neopentyl glycol adipate dihydric alcohol.
4. The TPU hot melt powder modified aqueous polyurethane resin as claimed in claim 1, wherein: the chain extender is 1, 4-butanediol, 1, 6-hexanediol, ethylene glycol, 1, 2-propanediol, diethylene glycol, trimethylolpropane, ethylenediamine, diethylenetriamine, isophoronediamine and/or sulfamate.
5. The TPU hot melt powder modified aqueous polyurethane resin as claimed in claim 1, wherein: the hydrophilic chain extender is dimethylolpropionic acid.
6. The TPU hot melt powder modified aqueous polyurethane resin as claimed in claim 1, wherein: the salt forming agent is triethylamine, NaOH, diethanolamine or diisopropanolamine.
7. The method for preparing the TPU hot melt powder modified aqueous polyurethane resin according to any one of claims 1 to 6, characterized in that: the method comprises the following specific steps:
step S1, dehydrating TPU hot melt powder and oligomer polyol at the temperature of 110-120 ℃ for 1-1.5h, cooling to 70 ℃, adding diisocyanate, stirring at the temperature of 85-110 ℃ for reaction for 1.5-2h, sequentially adding a small molecular chain extender, a hydrophilic chain extender and a catalyst, reacting at the temperature of 60-70 ℃ for 4.5-5.5h, and adjusting the viscosity of a reaction system by using acetone in the whole reaction process to obtain a polyurethane prepolymer;
step S2, transferring the prepolymer into an emulsification barrel, adding a salt forming agent at the temperature of 25-40 ℃, adding deionized water and stirring for 2-10min at the rotating speed of 1500-;
and step S3, transferring the emulsion containing acetone prepared in the second step into a flask for removing acetone, controlling the temperature at 35-55 ℃, and removing acetone under a vacuum condition to obtain the waterborne polyurethane emulsion.
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| CN113025211A (en) * | 2021-03-01 | 2021-06-25 | 陈猛 | TPU glue for jean groove bottom flocking and production process thereof |
| CN113637144A (en) * | 2021-08-30 | 2021-11-12 | 安徽聚合辐化化工有限公司 | HDPE hot melt powder modified waterborne polyurethane resin |
| CN115260429A (en) * | 2021-11-10 | 2022-11-01 | 佳化化学科技发展（上海）有限公司 | Polyether composition, thermoplastic polyurethane and preparation method thereof |
| CN115746243A (en) * | 2022-11-11 | 2023-03-07 | 安徽聚合辐化化工有限公司 | Waterborne polyurethane resin and preparation method thereof |
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| CN110396290A (en) * | 2019-07-19 | 2019-11-01 | 安徽聚合辐化化工有限公司 | A kind of thermal fusing powder modified aqueous polyurethane resin and preparation method thereof |
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| CN109503799A (en) * | 2018-10-30 | 2019-03-22 | 合肥科天水性科技有限责任公司 | A kind of waterborne polyurethane resin and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113025211A (en) * | 2021-03-01 | 2021-06-25 | 陈猛 | TPU glue for jean groove bottom flocking and production process thereof |
| CN113637144A (en) * | 2021-08-30 | 2021-11-12 | 安徽聚合辐化化工有限公司 | HDPE hot melt powder modified waterborne polyurethane resin |
| CN115260429A (en) * | 2021-11-10 | 2022-11-01 | 佳化化学科技发展（上海）有限公司 | Polyether composition, thermoplastic polyurethane and preparation method thereof |
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