CN104004160A - High thixotropy waterborne polyurethane dispersoid for soft coating and preparation method thereof - Google Patents
High thixotropy waterborne polyurethane dispersoid for soft coating and preparation method thereof Download PDFInfo
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- CN104004160A CN104004160A CN201410268071.XA CN201410268071A CN104004160A CN 104004160 A CN104004160 A CN 104004160A CN 201410268071 A CN201410268071 A CN 201410268071A CN 104004160 A CN104004160 A CN 104004160A
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- polyurethane prepolymer
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- soft feeling
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- 238000000576 coating method Methods 0.000 title claims abstract description 51
- 239000011248 coating agent Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 229920002635 polyurethane Polymers 0.000 title abstract description 6
- 239000004814 polyurethane Substances 0.000 title abstract description 6
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 105
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 21
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 20
- 229920000570 polyether Polymers 0.000 claims abstract description 20
- 239000000084 colloidal system Substances 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 230000001681 protective effect Effects 0.000 claims abstract description 12
- 229920000768 polyamine Polymers 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 206010016322 Feeling abnormal Diseases 0.000 claims description 41
- 229920003009 polyurethane dispersion Polymers 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 31
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 23
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 22
- 238000000605 extraction Methods 0.000 claims description 21
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 20
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 18
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 18
- 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 18
- 230000015572 biosynthetic process Effects 0.000 claims description 16
- 150000002334 glycols Chemical class 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 11
- 229920001451 polypropylene glycol Polymers 0.000 claims description 11
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 11
- DBXBTMSZEOQQDU-UHFFFAOYSA-N 3-hydroxyisobutyric acid Chemical class OCC(C)C(O)=O DBXBTMSZEOQQDU-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- -1 polyoxyethylene Polymers 0.000 claims description 7
- 150000003512 tertiary amines Chemical class 0.000 claims description 7
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 229920005906 polyester polyol Polymers 0.000 claims description 5
- 229920005862 polyol Polymers 0.000 claims description 5
- 150000003077 polyols Chemical class 0.000 claims description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 150000002009 diols Chemical class 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012970 tertiary amine catalyst Substances 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- ZMZQVAUJTDKQGE-UHFFFAOYSA-N 2-ethylhydracrylic acid Chemical compound CCC(CO)C(O)=O ZMZQVAUJTDKQGE-UHFFFAOYSA-N 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000012874 anionic emulsifier Substances 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 229960001124 trientine Drugs 0.000 claims description 3
- 229960004418 trolamine Drugs 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 239000003973 paint Substances 0.000 abstract description 6
- 239000013008 thixotropic agent Substances 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract 2
- 125000005442 diisocyanate group Chemical group 0.000 abstract 2
- 150000005846 sugar alcohols Polymers 0.000 abstract 1
- 239000002562 thickening agent Substances 0.000 abstract 1
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 32
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 17
- 230000006872 improvement Effects 0.000 description 17
- 239000005639 Lauric acid Substances 0.000 description 16
- 239000006185 dispersion Substances 0.000 description 13
- 239000007787 solid Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 description 9
- XQSFXFQDJCDXDT-UHFFFAOYSA-N hydroxysilicon Chemical compound [Si]O XQSFXFQDJCDXDT-UHFFFAOYSA-N 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000011806 microball Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 238000010008 shearing Methods 0.000 description 6
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 4
- 229920000053 polysorbate 80 Polymers 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000010985 leather Substances 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 3
- 230000009974 thixotropic effect Effects 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 1
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009459 flexible packaging Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000002889 sympathetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000009736 wetting Methods 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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- 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
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
-
- 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
- C08G18/48—Polyethers
- C08G18/4825—Polyethers 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
- 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
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
- C08G18/4845—Polyethers containing oxyethylene units and other oxyalkylene units containing oxypropylene or higher oxyalkylene end 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
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/61—Polysiloxanes
-
- 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
- C09D175/08—Polyurethanes from polyethers
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 invention discloses a high thixotropy waterborne polyurethane dispersoid for soft coating and a preparation method of the high thixotropy waterborne polyurethane dispersoid for the soft coating. The preparation method includes the following steps that S1, polyether dihydric alcohol, diisocyanate and catalysts are added; S2, micromolecule alcohol is added, and polyurethane prepolymer A is obtained; S3, polymer polyhydric alcohols, diisocyanate and catalysts are added; S4, carboxlic unimolecule dihydric alcohol is added, and polyurethane prepolymer B is obtained; S5, mixing is conducted; S6, water solutions formed by emulsifying agents or protective colloids are added, dispersing is conducted, and polyamine is added. The prepared dispersoid through the preparation method of the high thixotropy waterborne polyurethane dispersoid for the soft coating has highly flexible hand feeling, and adhesiveness and intensity of the dispersoid after paint film are improved comprehensively. Meanwhile, the obtained dispersoid through the preparation method has high thixotropism and greatly saves cost of thickening agents, anti-sinking agents and thixotropic agents which need to be added for improving storage stability.
Description
Technical field
The present invention relates to the field of chemical synthesis, particularly relate to a kind of high thixotroping aqueous polyurethane dispersion and preparation method thereof for soft feeling coating.
Background technology
Soft feeling coating, a kind of coating with submissive feel that resin-coating forms on base material.Above-mentioned soft feeling claims again elastic handfeel or fine hair feel sometimes, and coating and the elastic coating with soft feeling have essential distinction, and elastic coating refers to film to have high elongation at break, and touch feeling is not done to requirement.
At present, soft feeling coating is mainly used in three aspects: one, in most cases, can be coated on BOPP or BOPET and be used as precoating flexible packaging film by roll coating model; Two, the shells such as digital camera, notebook computer, mobile phone are applied in various electronics or electric equipment products, as all need to having in surface spraying protection and ornamental touch the coating of elastic handfeel after machine-shaping; Three, as hide finishes, be widely used on clothing leather, sofa leather and automobile cushion leather.
At present, about the preparation method of soft feeling coating, be in resin (vibrin, Synolac, acrylic resin and urethane etc.), to add elasticity powder or fine hair powder (such as the 5070D that refines large day), use various dispersion agents, anti-sedimentation agent etc. powder to be dispersed in resin and the coating forming.
For example, the patent No. is 201110183769.8, and name is called a kind of patent spraying by elastic polyurethane handfeel paint coating and purposes, discloses a kind of use in the preparation method of the elastic handfeel paint of electronic product casing.This method is mainly in two kinds of vibrin that contain hydroxyl, to fill the sub-light powder of elasticity, adds appropriate isocyanate curing agent to make to film continuously, strength increase before spraying.But the shortcoming in technique scheme is to have used dimethylbenzene and N-BUTYL ACETATE.Although in organic solvent, these two kinds is low toxicity reagent, can produce offensive odour unavoidably in construction process, causes the health hazards of human body.Secondly because need to add powder, although the vibrin that contains hydroxyl can be good at powder lot dispersing, long storage time, its stability there will be problem.In addition, at present commercially available elasticity powder or fine hair powder are expensive, and need to reach flexible feel, often need the powder amount of adding will surpass the more than 20% of coating, and for coating business and human consumer, cost is too expensive.
Therefore,, for the problems referred to above, be necessary to provide a kind of further improvement project.
Summary of the invention
In view of this, the invention provides high thixotroping aqueous polyurethane dispersion for a kind of soft feeling coating, and preparation method thereof, it has overcome in the existing method of preparing soft feeling coating by the drawback that adds elasticity powder, fine hair powder etc. to bring.
Preparation method of the present invention is based on following technical conceive: the urethane resin that the structure of the polyaminoester microball of soft feeling needs need possess certain flexibility, but also need to have certain hardness and toughness.Because, if make urethane resin intensity not high in order to pursue soft feeling, when applying film forming, not only easily cave in, and the bulk strength of filming forming is inadequate, easily damaged.And if by adding linking agent, make urethane resin there is high compactness, flexible hand is sympathetic so can disappear.Above-mentioned technical requirements has good soft feeling and to have again that the urethane of some strength is micro-has formed conflict forming, and therefore, need consider above-mentioned technical requirements, the relation of balance between the two.
Thus, soft feeling coating of the present invention is intended to synthetic a kind of interior soft outer close by the preparation method of high thixotroping aqueous polyurethane dispersion, and has the polyaminoester microball of certain size.This polyaminoester microball internal structure is base polyurethane prepolymer for use as A, and the molecular weight of this base polyurethane prepolymer for use as A is lower, not residual isocyano group on it, and hydrophobicity flexibility is good.Thereby inner base polyurethane prepolymer for use as A makes polyaminoester microball have certain flexibility.The layer structure of polyaminoester microball is base polyurethane prepolymer for use as B, and this base polyurethane prepolymer for use as B molecular weight is higher, contains a certain amount of isocyano group on it, and finer and close, good hydrophilic property.Thereby outer field base polyurethane prepolymer for use as B makes polyaminoester microball have certain stability.
First soft feeling coating of the present invention prepares base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B by the preparation method of high thixotroping aqueous polyurethane dispersion, then the two is mixed, make the amount of outer field base polyurethane prepolymer for use as B can encase the base polyurethane prepolymer for use as A of internal layer completely.Particularly, after base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B mix, neutralize, after water-dispersion, form a certain size polyaminoester microball.Wherein, due to base polyurethane prepolymer for use as, A has hydrophobicity, tend to the center at bead, and base polyurethane prepolymer for use as B has wetting ability, tends to be wrapped in bead around, the polyurethane aqueous dispersion body microballoon of soft outer close structure in so just having formed.
Under foregoing invention design is instructed, for realizing object of the present invention, the preparation method of high thixotroping aqueous polyurethane dispersion for a kind of soft feeling coating of the present invention, its spy comprises the steps, in following steps, the umber of material is in mass parts:
S1. in the first reactor, add 70～90 parts of polyether Glycols, dehydration; Cooling, then add the vulcabond of 10～30 parts and the catalyzer of 0.1～1 part;
S2. to the small molecular alcohol that adds excessive single functionality in the first reactor, continue reaction; Heat up, slough unnecessary small molecular alcohol, cooling, obtains base polyurethane prepolymer for use as A;
S3. to the polymer polyatomic alcohol that adds 30～80 parts in the second reactor, dehydration; Cooling, adds the vulcabond of 20～70 parts and the catalyzer of 0.1～1 part;
S4. in the second reactor, add the unit molecule dibasic alcohol that contains carboxyl of 1～6 part, continue reaction; Cooling, adds neutralizing agent, obtains base polyurethane prepolymer for use as B;
S5. base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B are mixed with the mass ratio of 1:3～2:1;
S6. in the mixed system of base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B formation, add the emulsifying agent of 5～30 parts or the aqueous solution of protective colloid formation, disperse, then add polyamine in mixed system, obtain target product.
As a further improvement on the present invention, in S1, described polyether Glycols comprises a kind of or two or more in polyoxyethylene glycol, polypropylene glycol, polytetrahydrofuran diol.
As a further improvement on the present invention, in S1, the scope of the molecular weight of described polyether Glycols is 2000～8000.
As a further improvement on the present invention, in S1 and S3, described vulcabond is a kind of in isophorone diisocyanate, hexamethylene diisocyanate or both combinations.
As a further improvement on the present invention, in S1 and S3, described catalyzer is tertiary amine catalyst, organic tin catalyzer or organo-bismuth class catalyzer.
As a further improvement on the present invention, described S1 specifically comprises: in the first reactor, add 70～90 parts of polyether Glycols, vacuum hydro-extraction 2h under at least 100 ℃ of conditions; Be cooled to 50～90 ℃, then add the vulcabond of 10～30 parts and the catalyzer of 0.1～1 part, reaction 2～5h.
As a further improvement on the present invention, in S2, described small molecular alcohol is selected from methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, ethylene glycol mono-ether, ethylene glycol ester, propylene glycol monoether, propylene glycol monoester, glycerol diether.
As a further improvement on the present invention, described S2 specifically comprises: the small molecular alcohol to adding excessive single functionality in the first reactor, continues to react at least 1h; Be warming up at least 80 ℃, vacuum is sloughed unnecessary small molecular alcohol, is cooled to 60 ℃, obtains base polyurethane prepolymer for use as A.
As a further improvement on the present invention, in S3, polymer polyatomic alcohol is a kind of in polyether polyol and polyester polyol or both combinations.
As a further improvement on the present invention, described S3 specifically comprises: to the polymer polyatomic alcohol that adds 30～80 parts in the second reactor, vacuum hydro-extraction 2h under at least 100 ℃ of conditions; Be cooled to 50～90 ℃, then add the vulcabond of 20～70 parts and the catalyzer of 0.1～1 part, reaction 2h.
As a further improvement on the present invention, in S4, described in contain carboxyl unit molecule dibasic alcohol be a kind of or the two combination in two hydroxymethyl propionic acids and two methylol butyric acid.
As a further improvement on the present invention, described S4 specifically comprises: in the second reactor, add the unit molecule dibasic alcohol that contains carboxyl of 1～6 part, continue reaction 1～3h; Be cooled to below 60 ℃, add tertiary amine neutralization, obtain base polyurethane prepolymer for use as B, described tertiary amine is a kind of in triethylamine and trolamine or both combinations.
As a further improvement on the present invention, when base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B are mixed in described S5, also comprise in the mixed system forming to base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B and add acetone.
As a further improvement on the present invention, in S6, described emulsifying agent and protective colloid are anionic emulsifier, cationic emulsifier, zwitter-ion emulsifying agent, nonionic emulsifying agent.
As a further improvement on the present invention, in S6, polyamine is a kind of or the two combination in diethylenetriamine and triethylene tetramine.
The present invention also provides high thixotroping aqueous polyurethane dispersion for a kind of soft feeling coating, and it is according to preparation method's acquisition as mentioned above.
Compared with prior art, the invention has the beneficial effects as follows: soft feeling coating of the present invention not only has strong flexible feel by dispersion prepared by the preparation method of high thixotroping aqueous polyurethane dispersion, and the tack after filming, intensity all obtain comprehensive improvement.
Meanwhile, the dispersion being obtained by preparation method of the present invention has high thixotropic, has greatly saved as improving the cost of thickening material that storage stability adds, anti-sedimentation agent and thixotropic agent.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, to the accompanying drawing of required use in embodiment or description of the Prior Art be briefly described below, apparently, the accompanying drawing the following describes is only some embodiment that record in the present invention, for those of ordinary skills, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the method flow schematic diagram of preparation method's one embodiment of high thixotroping aqueous polyurethane dispersion for soft feeling coating of the present invention.
Embodiment
As shown in Figure 1, the present invention discloses the preparation method of high thixotroping aqueous polyurethane dispersion for a kind of soft feeling coating, and it comprises the steps, in following steps, the umber of material is in mass parts:
S1. in the first reactor, add 70～90 parts of polyether Glycols, dehydration; Cooling, then add the vulcabond of 10～30 parts and the catalyzer of 0.1～1 part;
S2. to the small molecular alcohol that adds excessive single functionality in the first reactor, continue reaction; Heat up, slough unnecessary small molecular alcohol, cooling, obtains base polyurethane prepolymer for use as A;
S3. to the polymer polyatomic alcohol that adds 30～80 parts in the second reactor, dehydration; Cooling, adds the vulcabond of 20～70 parts and the catalyzer of 0.1～1 part;
S4. in the second reactor, add the unit molecule dibasic alcohol that contains carboxyl of 1～6 part, continue reaction; Cooling, adds neutralizing agent, obtains base polyurethane prepolymer for use as B;
S5. base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B are mixed with the mass ratio of 1:3～2:1;
S6. in the mixed system of base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B formation, add the emulsifying agent of 5～30 parts or the aqueous solution of protective colloid formation, disperse, then add polyamine in mixed system, obtain target product.
To achieve the object of the present invention, described S1 specifically comprises: in the first reactor, add 70～90 parts of polyether Glycols, vacuum hydro-extraction 2h under at least 100 ℃ of conditions; Be cooled to 50～90 ℃, then add the vulcabond of 10～30 parts and the catalyzer of 0.1～1 part, reaction 2～5h.
In present embodiment, the scope of the molecular weight of described polyether Glycols is 2000～8000, is preferably 4000～6000.Described polyether Glycols can comprise a kind of or two or more in polyoxyethylene glycol, polypropylene glycol, polytetrahydrofuran diol.
Described vacuum hydro-extraction is preferably carried out under 120 ℃ of conditions, can select to have accordingly the reactor of temp regulating function and dehydrating function.
Cooling is preferably down to 80 ℃, then adds the vulcabond of 10～30 parts and the catalyzer of 0.1～1 part, reaction 2～5h.
Described vulcabond can be a kind of in isophorone diisocyanate, hexamethylene diisocyanate or both combinations.
Described catalyzer can be tertiary amine catalyst, organic tin catalyzer or organo-bismuth class catalyzer.Preferably, catalyzer is the positive fourth tin of two lauric acid two.
To achieve the object of the present invention, described S2 specifically comprises: the small molecular alcohol to adding excessive single functionality in the first reactor, continues to react at least 1h; Be warming up at least 80 ℃, vacuum is sloughed unnecessary small molecular alcohol, is cooled to 60 ℃, obtains base polyurethane prepolymer for use as A.
In present embodiment, the alcohols of the small molecular alcohol of single functionality for only containing a hydroxyl, and do not contain the group that other react with NCO.Particularly, the small molecular alcohol of single functionality can be selected from methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, ethylene glycol mono-ether, ethylene glycol ester, propylene glycol monoether, propylene glycol monoester, glycerol diether.The small molecular alcohol of single functionality is preferably boiling point lower than the alcohols of 80 ℃, more preferably, is the less ethanol of toxicity and Virahol.Wherein, use the small molecular alcohol of excessive single functionality to refer to that its consumption is greater than the content of described vulcabond and the rear residual isocyano of polyether Glycols reaction, described polyether Glycols and vulcabond total amount are by 100 parts.So, be for isocyano can fully being reacted, avoiding residual isocyano.Afterwards, unnecessary small molecular alcohol is again by the method the heating up removal of volatilizing.
To achieve the object of the present invention, described S3 specifically comprises: to the polymer polyatomic alcohol that adds 30～80 parts in the second reactor, vacuum hydro-extraction 2h under at least 100 ℃ of conditions; Be cooled to 50～90 ℃, then add the vulcabond of 20～70 parts and the catalyzer of 0.1～1 part, reaction 2h.
In present embodiment, polymer polyatomic alcohol can be a kind of in polyether polyol and polyester polyol or both combinations.Wherein, the functionality of polyether polyol is preferably 2～3, and polyether polyol can be polyoxyethylene glycol, polypropylene glycol, polytetrahydrofuran diol.The functionality of polyester polyol is preferably 2～3, and polyester polyol can be aliphatic polyester, polycaprolactone, polycarbonate etc.Described polymer polyatomic alcohol and vulcabond total amount are by 100 parts.
In addition, described polymer polyatomic alcohol should at least comprise a kind of hydroxy silicon oil, and after its role is to make high thixotroping aqueous polyurethane dispersion of the present invention to film, surface has smooth performance, and the consumption of this hydroxy silicon oil is 1-6 part.
Described vulcabond can be a kind of in isophorone diisocyanate, hexamethylene diisocyanate or both combinations.
Described catalyzer can be tertiary amine catalyst, organic tin catalyzer or organo-bismuth class catalyzer.Preferably, catalyzer is the positive fourth tin of two lauric acid two.
To achieve the object of the present invention, described S4 specifically comprises: in the second reactor, add the unit molecule dibasic alcohol that contains carboxyl of 1～6 part, continue reaction 1～3h; Be cooled to below 60 ℃, add tertiary amine neutralization, obtain base polyurethane prepolymer for use as B.
In present embodiment, described in contain carboxyl unit molecule dibasic alcohol can be a kind of or the two combination in two hydroxymethyl propionic acids and two methylol butyric acid.Described tertiary amine can be a kind of in triethylamine and trolamine or both combinations, and the consumption of tertiary amine is identical with the consumption of the described unit molecule dibasic alcohol that contains carboxyl.
When base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B are mixed in described S5, also comprise in the mixed system of base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B formation and add acetone, the consumption of the acetone adding is the 0-50% of base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B total amount, is preferably 30%.
Wherein, adding acetone is to add in the situation that viscosity is larger, and the total amount of base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B is by 100 parts.
In order to reach object of the present invention; described S6 specifically comprises: at 30 ℃; in the mixed system of base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B formation, add the emulsifying agent of 5～30 parts or the aqueous solution of protective colloid formation; high-speed stirring is disperseed 30min, adds appropriate polyamine more afterwards in system.
Described emulsifying agent and protective colloid can be anionic emulsifier, cationic emulsifier, zwitter-ion emulsifying agent, nonionic emulsifying agent etc.Preferably, emulsifying agent or protective colloid are nonionic emulsifying agent OP-10.Particularly, protective colloid can, for polyvinyl alcohol, Walocel MT 20.000PV, Natvosol etc., be preferably polyvinyl alcohol.
In the aqueous solution that emulsifying agent or protective colloid form, water consumption is the amount when solid content of system is preset as to 20%-50%, and preferably solid content is 30%.System refers to the water dispersion forming after base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B are disperseed by the aqueous solution containing emulsifying agent or protective colloid herein.
Polyamine is a kind of or the two combination in diethylenetriamine and triethylene tetramine, and the consumption of polyamine is with till having reacted the isocyano in base polyurethane prepolymer for use as B.The effect of polyamine is to increase the thixotropy of dispersion.
The present invention also provides high thixotroping aqueous polyurethane dispersion for a kind of soft feeling coating, and it is according to preparation method's acquisition as mentioned above.
Below in conjunction with specific embodiment, soft feeling coating of the present invention is elaborated by the preparation method of high thixotroping aqueous polyurethane dispersion.
Embodiment 1
To adding molecular weight in the first reactor, be 70 parts of 4000 polypropylene glycols, 100 ℃ of vacuum hydro-extraction 2h; Be cooled to 80 ℃, then add the isophorone diisocyanate of 30 parts and the positive fourth tin of two lauric acid two of 0.1 part.In the first reactor, add 15 parts of Virahols, continue reaction 1h; Be warming up to 80 ℃, slough unnecessary Virahol, be cooled to 60 ℃, obtain base polyurethane prepolymer for use as A.
The hydroxy silicon oil that is 2000 to the molecular weight that adds the polytetrahydrofuran of 30 parts and 6 parts in the second reactor, 100 ℃ of vacuum hydro-extraction 2h; Be cooled to 50 ℃, add the isophorone diisocyanate of 64 parts and the positive fourth tin of two lauric acid two of 1 part.In the second reactor, add two hydroxymethyl propionic acids of 6 parts, continue reaction 1h; Be cooled to 60 ℃, add 4.53 parts of triethylamines, obtain base polyurethane prepolymer for use as B.
25 parts of base polyurethane prepolymer for use as A and 75 parts of base polyurethane prepolymer for use as B are mixed with the mass ratio of 1:3.In the mixed system of base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B formation, the aqueous solution that the OP-10 that polyvinyl alcohol that to add molecular weight be 1788 is 3 parts, 2 parts and the water of 271.36 parts form, dispersed with stirring 30min, to the diethylenetriamine that adds 11.3 parts in mixed system, in the present embodiment, default solid content is 30% again.
In the present embodiment, in the first reactor, the mol ratio of isocyano and hydroxyl is 7.71; In the second reactor, the ratio of the summation of isocyano and hydroxyl is 4.59.
Embodiment 2
To adding molecular weight in the first reactor, be 80 parts of 4000 polypropylene glycols, 100 ℃ of vacuum hydro-extraction 2h; Be cooled to 80 ℃, then add the isophorone diisocyanate of 20 parts and the positive fourth tin of two lauric acid two of 0.5 part.In the first reactor, add 9 parts of Virahols, continue reaction 1h; Be warming up to 80 ℃, slough unnecessary Virahol, be cooled to 60 ℃, obtain base polyurethane prepolymer for use as A.
The hydroxy silicon oil that is 2000 to the molecular weight that adds the polytetrahydrofuran of 55 parts and 1 part in the second reactor, 100 ℃ of vacuum hydro-extraction 2h; Be cooled to 50 ℃, add the isophorone diisocyanate of 44 parts and the positive fourth tin of two lauric acid two of 0.5 part.In the second reactor, add two hydroxymethyl propionic acids of 3.5 parts, continue reaction 1h; Be cooled to 60 ℃, add 2.68 parts of triethylamines, obtain base polyurethane prepolymer for use as B.
33.3 parts of base polyurethane prepolymer for use as A and 66.7 parts of base polyurethane prepolymer for use as B are mixed with the mass ratio of 1:2.In the mixed system of base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B formation, the aqueous solution that the tween 80 that polyvinyl alcohol that to add molecular weight be 1788 is 10 parts, 10 parts and the water of 295.56 parts form, dispersed with stirring 30min, to the diethylenetriamine that adds 6.67 parts in mixed system, in the present embodiment, default solid content is 30% again.
In the present embodiment, in the first reactor, the mol ratio of isocyano and hydroxyl is 4.5; In the second reactor, the ratio of the summation of isocyano and hydroxyl is 3.66.
Embodiment 3
To adding molecular weight in the first reactor, be 90 parts of 4000 polypropylene glycols, 100 ℃ of vacuum hydro-extraction 2h; Be cooled to 80 ℃, then add the isophorone diisocyanate of 10 parts and the positive fourth tin of two lauric acid two of 1 part.In the first reactor, add 2.5 parts of Virahols, continue reaction 1h; Be warming up to 80 ℃, slough unnecessary Virahol, be cooled to 60 ℃, obtain base polyurethane prepolymer for use as A.
The hydroxy silicon oil that is 2000 to the molecular weight that adds the polytetrahydrofuran of 80 parts and 3.5 parts in the second reactor, 100 ℃ of vacuum hydro-extraction 2h; Be cooled to 50 ℃, add the isophorone diisocyanate of 16.5 parts and the positive fourth tin of two lauric acid two of 0.1 part.In the second reactor, add two hydroxymethyl propionic acids of 1 part, continue reaction 1h; Be cooled to 60 ℃, add 0.76 part of triethylamine, obtain base polyurethane prepolymer for use as B.
66.7 parts of base polyurethane prepolymer for use as A and 33.3 parts of base polyurethane prepolymer for use as B are mixed with the mass ratio of 2:1.In the mixed system of base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B formation, the aqueous solution that the tween 80 that polyvinyl alcohol that to add molecular weight be 1788 is 15 parts, 15 parts and the water of 304.64 parts form, dispersed with stirring 30min, to the diethylenetriamine that adds 0.56 part in mixed system, in the present embodiment, default solid content is 30% again.
In the present embodiment, in the first reactor, the mol ratio of isocyano and hydroxyl is 2; In the second reactor, the ratio of the summation of isocyano and hydroxyl is 1.51.
Embodiment 4
To adding molecular weight in the first reactor, be 70 parts of 4000 polypropylene glycols, 100 ℃ of vacuum hydro-extraction 2h; Be cooled to 80 ℃, then add the isophorone diisocyanate of 30 parts and the positive fourth tin of two lauric acid two of 0.1 part.In the first reactor, add 15 parts of Virahols, continue reaction 1h; Be warming up to 80 ℃, slough unnecessary Virahol, be cooled to 60 ℃, obtain base polyurethane prepolymer for use as A.
The hydroxy silicon oil that is 2000 to the molecular weight that adds the polytetrahydrofuran of 55 parts and 1 part in the second reactor, 100 ℃ of vacuum hydro-extraction 2h; Be cooled to 50 ℃, add the isophorone diisocyanate of 44 parts and the positive fourth tin of two lauric acid two of 0.5 part.In the second reactor, add two hydroxymethyl propionic acids of 3.5 parts, continue reaction 1h; Be cooled to 60 ℃, add 2.68 parts of triethylamines, obtain base polyurethane prepolymer for use as B.
50 parts of base polyurethane prepolymer for use as A and 50 parts of base polyurethane prepolymer for use as B are mixed with the mass ratio of 1:1.In the mixed system of base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B formation, the aqueous solution that the tween 80 that polyvinyl alcohol that to add molecular weight be 1788 is 10 parts, 10 parts and the water of 291.67 parts form, dispersed with stirring 30min, to the diethylenetriamine that adds 5 parts in mixed system, in the present embodiment, default solid content is 30% again.
In the present embodiment, in the first reactor, the mol ratio of isocyano and hydroxyl is 7.71; In the second reactor, the ratio of the summation of isocyano and hydroxyl is 3.66.
Embodiment 5
To adding molecular weight in the first reactor, be 70 parts of 4000 polypropylene glycols, 100 ℃ of vacuum hydro-extraction 2h; Be cooled to 80 ℃, then add the isophorone diisocyanate of 30 parts and the positive fourth tin of two lauric acid two of 0.1 part.In the first reactor, add 15 parts of Virahols, continue reaction 1h; Be warming up to 80 ℃, slough unnecessary Virahol, be cooled to 60 ℃, obtain base polyurethane prepolymer for use as A.
The hydroxy silicon oil that is 2000 to the molecular weight that adds the polytetrahydrofuran of 80 parts and 3.5 parts in the second reactor, 100 ℃ of vacuum hydro-extraction 2h; Be cooled to 50 ℃, add the isophorone diisocyanate of 16.5 parts and the positive fourth tin of two lauric acid two of 0.1 part.In the second reactor, add two hydroxymethyl propionic acids of 1 part, continue reaction 1h; Be cooled to 60 ℃, add 0.76 part of triethylamine, obtain base polyurethane prepolymer for use as B.
50 parts of base polyurethane prepolymer for use as A and 50 parts of base polyurethane prepolymer for use as B are mixed with the mass ratio of 1:1.In the mixed system of base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B formation, the aqueous solution that the OP-10 that polyvinyl alcohol that to add molecular weight be 1788 is 8 parts, 8 parts and the water of 272.65 parts form, dispersed with stirring 30min, to the diethylenetriamine that adds 0.85 part in mixed system, in the present embodiment, default solid content is 30% again.
In the present embodiment, in the first reactor, the mol ratio of isocyano and hydroxyl is 7.71; In the second reactor, the ratio of the summation of isocyano and hydroxyl is 1.51.
Embodiment 6
To adding molecular weight in the first reactor, be 80 parts of 4000 polypropylene glycols, 100 ℃ of vacuum hydro-extraction 2h; Be cooled to 80 ℃, then add the isophorone diisocyanate of 20 parts and the positive fourth tin of two lauric acid two of 0.5 part.In the first reactor, add 9 parts of Virahols, continue reaction 1h; Be warming up to 80 ℃, slough unnecessary Virahol, be cooled to 60 ℃, obtain base polyurethane prepolymer for use as A.
The hydroxy silicon oil that is 2000 to the molecular weight that adds the polytetrahydrofuran of 30 parts and 6 parts in the second reactor, 100 ℃ of vacuum hydro-extraction 2h; Be cooled to 50 ℃, add the isophorone diisocyanate of 64 parts and the positive fourth tin of two lauric acid two of 1 part.In the second reactor, add two hydroxymethyl propionic acids of 6 parts, continue reaction 1h; Be cooled to 60 ℃, add 4.53 parts of triethylamines, obtain base polyurethane prepolymer for use as B.
50 parts of base polyurethane prepolymer for use as A and 50 parts of base polyurethane prepolymer for use as B are mixed with the mass ratio of 1:1.In the mixed system of base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B formation, the aqueous solution that the tween 80 that polyvinyl alcohol that to add molecular weight be 1788 is 8 parts, 8 parts and the water of 272.42 parts form, dispersed with stirring 30min, to the diethylenetriamine that adds 0.75 part in mixed system, in the present embodiment, default solid content is 30% again.
In the present embodiment, in the first reactor, the mol ratio of isocyano and hydroxyl is 4.5; In the second reactor, the ratio of the summation of isocyano and hydroxyl is 4.59.
Embodiment 7
To adding molecular weight in the first reactor, be 80 parts of 4000 polypropylene glycols, 100 ℃ of vacuum hydro-extraction 2h; Be cooled to 80 ℃, then add the isophorone diisocyanate of 20 parts and the positive fourth tin of two lauric acid two of 0.5 part.In the first reactor, add 9 parts of Virahols, continue reaction 1h; Be warming up to 80 ℃, slough unnecessary Virahol, be cooled to 60 ℃, obtain base polyurethane prepolymer for use as A.
The hydroxy silicon oil that is 2000 to the molecular weight that adds the polytetrahydrofuran of 80 parts and 3.5 parts in the second reactor, 100 ℃ of vacuum hydro-extraction 2h; Be cooled to 50 ℃, add the isophorone diisocyanate of 16.5 parts and the positive fourth tin of two lauric acid two of 0.1 part.In the second reactor, add two hydroxymethyl propionic acids of 1 part, continue reaction 1h; Be cooled to 60 ℃, add 0.76 part of triethylamine, obtain base polyurethane prepolymer for use as B.
50 parts of base polyurethane prepolymer for use as A and 50 parts of base polyurethane prepolymer for use as B are mixed with the mass ratio of 1:1.In the mixed system of base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B formation, the aqueous solution that the OP-10 that polyvinyl alcohol that to add molecular weight be 1788 is 8 parts, 8 parts and the water of 272.65 parts form, dispersed with stirring 30min, to the diethylenetriamine that adds 0.85 part in mixed system, in the present embodiment, default solid content is 30% again.
In the present embodiment, in the first reactor, the mol ratio of isocyano and hydroxyl is 4.5; In the second reactor, the ratio of the summation of isocyano and hydroxyl is 1.51.
For the product obtaining in the various embodiments described above, carry out respectively test experiments below, the test event of test experiments comprises: solid content, pH value, apparent, initial viscosity, static 24h mobility, recover viscosity, change base polyurethane prepolymer for use as A and the ratio (hereinafter to be referred as " change ratio ") of base polyurethane prepolymer for use as B, submissive sense, fine and smooth sense and smooth feeling.Wherein, solid content, pH value, apparent for characterizing the attribute of product; Initial viscosity, static 24h mobility, recovery viscosity, change ratio are for characterizing the thixotropic property of product; Submissive sense, fine and smooth sense and smooth feeling are for the touch feeling after characterizing product and filming, and test experiments result is as shown in table 1 below:
Table 1
Wherein, the mensuration > > that the testing method of solid content is used the non-volatile matter of paint base with reference to non-volatile matter and the paint and varnish of international standard ISO3251 < < paint and varnish.
PH value is used pH test paper to test.
Apparently by human eye, estimate.
Initial viscosity is with reference to U.S. ASTM D2196 < <, with the rheological > > of rotary viscosity design determining non-Newtonian material, to test after being cooled to room temperature after dispersion discharging.
Static 24h mobility, refers to products therefrom at room temperature after standing 24h, sees if there is viscosity and obviously increases or whether just have a mobility.
Recovery viscosity refers to, gives the certain shearing of product after standing 24h, rocks or the reactive force such as stirring, afterwards tested viscosity again.
Submissive sense, fine and smooth sense and smooth feeling be by touch the feel after product is filmed, specifically film be at 65 ℃, toast 20min after, with hand, go to touch see whether there is submissive (elastic sensation, fine hair sense or soft feel(ing)), fine and smooth sense, smooth feeling etc.
From above-mentioned test result, by soft feeling coating of the present invention, with the polyurethane dispersions of preparation method's acquisition of high thixotroping aqueous polyurethane dispersion, not only there is good soft feeling, there is certain intensity simultaneously.In addition, above-mentioned polyurethane dispersions also has thixotropy.
Wherein, thixotropy refers to that when object (as coating) is subject to shearing, denseness diminishes, and while stopping shearing, denseness increases again; Or while being subject to shearing, it is large that denseness becomes, while stopping shearing, the character that denseness diminishes again.For the former, be called for short " shear shinning ", for the latter, be called for short " shearing retrogradation ".
If the dispersion being obtained by preparation method of the present invention is as possessed the thixotropy of " shear shinning ", when being no, system has higher viscosity, even do not there is mobility, when using, stir and revert to again the state that viscosity is low, to the storage of dispersion, will there is permanent stability so.
Above-mentioned test result has confirmed that the product being obtained by the various embodiments described above has the thixotropy of " shear shinning " really, and above-mentioned thixotropy does not obtain by adding expensive thixotroping auxiliary agent.
In sum, soft feeling coating of the present invention not only has strong flexible feel by dispersion prepared by the preparation method of high thixotroping aqueous polyurethane dispersion, and the tack after filming, intensity all obtain comprehensive improvement.
Meanwhile, the dispersion that has preparation method of the present invention to obtain is added appropriate polyamine as chainextender by use, makes dispersion have high thixotropic, has greatly saved as improving the cost of thickening material that storage stability adds, anti-sedimentation agent and thixotropic agent.
To those skilled in the art, obviously the invention is not restricted to the details of above-mentioned one exemplary embodiment, and in the situation that not deviating from spirit of the present invention or essential characteristic, can realize the present invention with other specific form.Therefore, no matter from which point, all should regard embodiment as exemplary, and be nonrestrictive, scope of the present invention is limited by claims rather than above-mentioned explanation, is therefore intended to include in the present invention dropping on the implication that is equal to important document of claim and all changes in scope.Any Reference numeral in claim should be considered as limiting related claim.
In addition, be to be understood that, although this specification sheets is described according to embodiment, but not each embodiment only comprises an independently technical scheme, this narrating mode of specification sheets is only for clarity sake, those skilled in the art should make specification sheets as a whole, and the technical scheme in each embodiment also can, through suitably closing, form other embodiments that it will be appreciated by those skilled in the art that.
Claims (16)
1. a preparation method for high thixotroping aqueous polyurethane dispersion for soft feeling coating, is characterized in that, described preparation method comprises the steps, in following steps, the umber of material is in mass parts:
S1. in the first reactor, add 70～90 parts of polyether Glycols, dehydration; Cooling, then add the vulcabond of 10～30 parts and the catalyzer of 0.1～1 part;
S2. to the small molecular alcohol that adds excessive single functionality in the first reactor, continue reaction; Heat up, slough unnecessary small molecular alcohol, cooling, obtains base polyurethane prepolymer for use as A;
S3. to the polymer polyatomic alcohol that adds 30～80 parts in the second reactor, dehydration; Cooling, adds the vulcabond of 20～70 parts and the catalyzer of 0.1～1 part;
S4. in the second reactor, add the unit molecule dibasic alcohol that contains carboxyl of 1～6 part, continue reaction; Cooling, adds neutralizing agent, obtains base polyurethane prepolymer for use as B;
S5. base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B are mixed with the mass ratio of 1:3～2:1;
S6. in the mixed system of base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B formation, add the emulsifying agent of 5～30 parts or the aqueous solution of protective colloid formation, disperse, then add polyamine in mixed system, obtain target product.
2. the preparation method of high thixotroping aqueous polyurethane dispersion for soft feeling coating according to claim 1, is characterized in that, in S1, described polyether Glycols comprises a kind of or two or more in polyoxyethylene glycol, polypropylene glycol, polytetrahydrofuran diol.
3. the preparation method of high thixotroping aqueous polyurethane dispersion for soft feeling coating according to claim 1 and 2, is characterized in that, in S1, the scope of the molecular weight of described polyether Glycols is 2000～8000.
4. the preparation method of high thixotroping aqueous polyurethane dispersion for soft feeling coating according to claim 1, it is characterized in that, in S1 and S3, described vulcabond is a kind of in isophorone diisocyanate, hexamethylene diisocyanate or both combinations.
5. the preparation method of high thixotroping aqueous polyurethane dispersion for soft feeling coating according to claim 1, is characterized in that, in S1 and S3, described catalyzer is tertiary amine catalyst, organic tin catalyzer or organo-bismuth class catalyzer.
6. the preparation method of high thixotroping aqueous polyurethane dispersion for soft feeling coating according to claim 1, is characterized in that, described S1 specifically comprises: in the first reactor, add 70～90 parts of polyether Glycols, vacuum hydro-extraction 2h under at least 100 ℃ of conditions; Be cooled to 50～90 ℃, then add the vulcabond of 10～30 parts and the catalyzer of 0.1～1 part, reaction 2～5h.
7. the preparation method of high thixotroping aqueous polyurethane dispersion for soft feeling coating according to claim 1, it is characterized in that, in S2, described small molecular alcohol is selected from methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, ethylene glycol mono-ether, ethylene glycol ester, propylene glycol monoether, propylene glycol monoester, glycerol diether.
8. the preparation method of high thixotroping aqueous polyurethane dispersion for soft feeling coating according to claim 1, is characterized in that, described S2 specifically comprises: the small molecular alcohol to adding excessive single functionality in the first reactor, continues to react at least 1h; Be warming up at least 80 ℃, vacuum is sloughed unnecessary small molecular alcohol, is cooled to 60 ℃, obtains base polyurethane prepolymer for use as A.
9. the preparation method of high thixotroping aqueous polyurethane dispersion for soft feeling coating according to claim 1, is characterized in that, in S3, polymer polyatomic alcohol is a kind of in polyether polyol and polyester polyol or both combinations.
10. the preparation method of high thixotroping aqueous polyurethane dispersion for soft feeling coating according to claim 1, it is characterized in that, described S3 specifically comprises: to the polymer polyatomic alcohol that adds 30～80 parts in the second reactor, vacuum hydro-extraction 2h under at least 100 ℃ of conditions; Be cooled to 50～90 ℃, then add the vulcabond of 20～70 parts and the catalyzer of 0.1～1 part, reaction 2h.
The preparation method of high thixotroping aqueous polyurethane dispersion for 11. soft feeling coatings according to claim 1, is characterized in that, in S4, described in contain carboxyl unit molecule dibasic alcohol be a kind of or the two combination in two hydroxymethyl propionic acids and two methylol butyric acid.
The preparation method of high thixotroping aqueous polyurethane dispersion for 12. soft feeling coatings according to claim 1, is characterized in that, described S4 specifically comprises: in the second reactor, add the unit molecule dibasic alcohol that contains carboxyl of 1～6 part, continue reaction 1～3h; Be cooled to below 60 ℃, add tertiary amine neutralization, obtain base polyurethane prepolymer for use as B, described tertiary amine is a kind of in triethylamine and trolamine or both combinations.
The preparation method of high thixotroping aqueous polyurethane dispersion for 13. soft feeling coatings according to claim 1, it is characterized in that, when base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B are mixed in described S5, also comprise in the mixed system forming to base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B and add acetone.
The preparation method of high thixotroping aqueous polyurethane dispersion for 14. soft feeling coatings according to claim 1; it is characterized in that; in S6, described emulsifying agent and protective colloid are anionic emulsifier, cationic emulsifier, zwitter-ion emulsifying agent, nonionic emulsifying agent.
The preparation method of high thixotroping aqueous polyurethane dispersion for 15. soft feeling coatings according to claim 1, is characterized in that, in S6, polyamine is a kind of or the two combination in diethylenetriamine and triethylene tetramine.
16. 1 kinds of high thixotroping aqueous polyurethane dispersion for soft feeling coating, is characterized in that, described soft feeling coating obtains according to preparation method described in claim 1～15 any one with high thixotroping aqueous polyurethane dispersion.
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