CN117362580A - Intrinsic matte waterborne polyurethane and preparation method thereof - Google Patents
Intrinsic matte waterborne polyurethane and preparation method thereof Download PDFInfo
- Publication number
- CN117362580A CN117362580A CN202311440795.3A CN202311440795A CN117362580A CN 117362580 A CN117362580 A CN 117362580A CN 202311440795 A CN202311440795 A CN 202311440795A CN 117362580 A CN117362580 A CN 117362580A
- Authority
- CN
- China
- Prior art keywords
- diisocyanate
- prepolymer
- amount
- glycol
- polyurethane
- 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.)
- Granted
Links
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 81
- 239000004814 polyurethane Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- -1 polysiloxane units Polymers 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 76
- 238000006243 chemical reaction Methods 0.000 claims description 69
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 66
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 38
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- 125000005442 diisocyanate group Chemical group 0.000 claims description 32
- 239000000126 substance Substances 0.000 claims description 31
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 21
- 150000002009 diols Chemical class 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 17
- 238000012644 addition polymerization Methods 0.000 claims description 16
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 15
- 239000004970 Chain extender Substances 0.000 claims description 14
- 229920000728 polyester Polymers 0.000 claims description 14
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 13
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 12
- 150000002191 fatty alcohols Chemical class 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 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 12
- 229920000570 polyether Polymers 0.000 claims description 12
- KCLIFOXATBWLMW-UHFFFAOYSA-M sodium;ethane-1,2-diamine;ethanesulfonate Chemical compound [Na+].NCCN.CCS([O-])(=O)=O KCLIFOXATBWLMW-UHFFFAOYSA-M 0.000 claims description 12
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 11
- 229910052797 bismuth Inorganic materials 0.000 claims description 11
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 11
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 11
- 125000002947 alkylene group Chemical group 0.000 claims description 10
- 125000002524 organometallic group Chemical group 0.000 claims description 10
- 239000004417 polycarbonate Substances 0.000 claims description 10
- 229920000515 polycarbonate Polymers 0.000 claims description 10
- GKNOFYAURJKRPM-UHFFFAOYSA-N hydroxymethyl 2-hydroxyacetate Chemical compound OCOC(=O)CO GKNOFYAURJKRPM-UHFFFAOYSA-N 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 230000003472 neutralizing effect Effects 0.000 claims description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 229920001451 polypropylene glycol Polymers 0.000 claims description 7
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 6
- 229920000768 polyamine Polymers 0.000 claims description 6
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 4
- 208000007848 Alcoholism Diseases 0.000 claims description 4
- 201000007930 alcohol dependence Diseases 0.000 claims description 4
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 claims description 3
- AXIWPQKLPMINAT-UHFFFAOYSA-N 1-ethyl-2,3-diisocyanatobenzene Chemical compound CCC1=CC=CC(N=C=O)=C1N=C=O AXIWPQKLPMINAT-UHFFFAOYSA-N 0.000 claims description 3
- 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 description 3
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-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
- RNSLCHIAOHUARI-UHFFFAOYSA-N butane-1,4-diol;hexanedioic acid Chemical compound OCCCCO.OC(=O)CCCCC(O)=O RNSLCHIAOHUARI-UHFFFAOYSA-N 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- WPEOOEIAIFABQP-UHFFFAOYSA-N hexanedioic acid;hexane-1,6-diol Chemical compound OCCCCCCO.OC(=O)CCCCC(O)=O WPEOOEIAIFABQP-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 3
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 3
- 239000012974 tin catalyst Substances 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 2
- 238000001035 drying Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 125000000217 alkyl group Chemical group 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 6
- 229920001296 polysiloxane Polymers 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000000843 powder Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 10
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 239000008213 purified water Substances 0.000 description 9
- QILXPCHTWXAUHE-UHFFFAOYSA-N [Na].NCCN Chemical compound [Na].NCCN QILXPCHTWXAUHE-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- XZUAPPXGIFNDRA-UHFFFAOYSA-N ethane-1,2-diamine;hydrate Chemical compound O.NCCN XZUAPPXGIFNDRA-UHFFFAOYSA-N 0.000 description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000005034 decoration Methods 0.000 description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- 229920006264 polyurethane film Polymers 0.000 description 4
- 229920003009 polyurethane dispersion Polymers 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010257 thawing Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000921 polyethylene adipate Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000001291 vacuum drying 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
- C08G18/08—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
- C08G18/34—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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—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
-
- 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
- C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
-
- 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
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 provides intrinsic matte waterborne polyurethane and a preparation method thereof, and belongs to the technical field of waterborne polyurethane. The main chain of the intrinsic matte waterborne polyurethane provided by the invention contains polysiloxane units, and the chain end group is long-chain alkyl, and in the process of drying and film forming, a microphase separation structure inside the film is formed due to poor compatibility among the waterborne polyurethane units, the polysiloxane and the long-chain alkyl, so that the matte effect is realized. The glossiness of the dry film is not affected by the drying mode and the solvent type because of the intrinsic characteristic of polyurethane molecular chain. In addition, the intrinsic matte waterborne polyurethane prepared by the invention has good storage stability.
Description
Technical Field
The invention relates to the technical field of waterborne polyurethane, in particular to intrinsic matte waterborne polyurethane and a preparation method thereof.
Background
The aqueous polyurethane is polyurethane with water as a dispersion medium, and can be classified into aqueous polyurethane dispersion and polyurethane emulsion according to the particle size of polyurethane. At present, the waterborne polyurethane is commonly used in different fields of clothing, furniture, interior decoration and the like. The aqueous polyurethane can be classified into high-gloss aqueous polyurethane, matte aqueous polyurethane and matt aqueous polyurethane according to the difference of film gloss after the aqueous polyurethane is dried and formed. The matte waterborne polyurethane and the matte waterborne polyurethane have low film glossiness, and can endow the surfaces of clothes and decorations with elegant styles. In order to create a matte or matt effect, there are generally two methods. First, a matting powder or a matte powder is added into the aqueous polyurethane. Matte or matting powders are generally inorganic powders which are only dispersible in polyurethane without dissolution. After the film is formed on the surfaces of clothes and decorations by the aqueous polyurethane containing the matte powder or the matting powder, the matting powder can form uneven particles on the surfaces of the clothes and decorations, and diffuse reflection can be formed when light irradiates on the uneven surfaces, so that the effects of matte and matting are achieved. The disadvantage of this method is that the fluidity of the aqueous polyurethane is deteriorated with the addition of the matte powder or matting powder, and the formed film is more likely to be broken, or the like. Second, a self-extinction waterborne polyurethane. The water-based polyurethane does not need to be added with matte powder or matting powder, and can realize the matte or matting effect after film formation. However, such aqueous polyurethanes generally have large particle sizes of dispersion or emulsion particles and poor storage stability.
Disclosure of Invention
The invention aims to provide intrinsic matte waterborne polyurethane and a preparation method thereof, and the intrinsic matte waterborne polyurethane provided by the invention can achieve a matte effect after film formation without adding matting powder or matte powder, and has good storage stability.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides intrinsic matte waterborne polyurethane, which has a molecular chain structure shown in a formula 1:
in the formula 1, R 4 Is thatR 1 Is alkylene, cycloalkyl or aralkyl, R 2 Is methyl or ethyl, R 3 Is alkylene, m is greater than or equal to 5 and is an integer, n>10 and is an integer.
The invention provides a preparation method of the intrinsic matte waterborne polyurethane, which comprises the following steps:
mixing polyether glycol, polyester glycol, polyhydroxysiloxane, dimethylol carboxylic acid, diisocyanate and an organic metal catalyst, and performing first addition polymerization reaction to obtain a first prepolymer; the structural formula of the diisocyanate is O=C=N-R 1 -N＝C＝O，R 1 Is alkylene, cycloalkyl or aralkyl; the dimethylol carboxylic acid is dimethylol propionic acid or dimethylol butyric acid;
the structural formula of the polyhydroxysiloxane is
Mixing the first prepolymer with acetone, and performing a second addition polymerization reaction to obtain a second prepolymer;
mixing the second prepolymer with long-chain fatty alcohol, and performing end capping reaction to obtain a third prepolymer; the structural formula of the long-chain fatty alcohol ism is more than or equal to 5 and is an integer;
mixing the third prepolymer with a neutralizing agent, and carrying out a neutralization reaction to obtain a polyurethane prepolymer;
dispersing the polyurethane prepolymer into water, mixing the obtained dispersion with a chain extender, performing chain extension reaction, and removing acetone to obtain the intrinsic matte waterborne polyurethane.
Preferably, the polyether glycol comprises one or more of polyethylene glycol, polypropylene glycol and polytetramethylene glycol;
the polyester diol comprises one or more of polyethylene glycol adipate glycol, 1, 4-butanediol adipate glycol, 1, 6-hexanediol adipate glycol, neopentyl glycol adipate glycol and polycarbonate glycol;
the polyhydroxysiloxane is polyhydroxysiloxane containing primary hydroxyl groups;
the diisocyanate comprises toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, ethylbenzene diisocyanate, methylcyclohexyl diisocyanate or trimethylhexamethylene diisocyanate;
the organometallic catalyst comprises an organometallic tin catalyst or an organometallic bismuth catalyst.
Preferably, the ratio of the amount of hydroxyl groups in the polyether diol and the polyester diol to the amount of isocyanate groups in the diisocyanate is (0.1 to 0.3): 1, a step of; the ratio of the amount of the hydroxyl group-containing substance in the polyhydroxysiloxane to the amount of the isocyanate group-containing substance in the diisocyanate is (0.02 to 0.1): 1, a step of; the ratio of the amount of hydroxyl groups in the dimethylol carboxylic acid to the amount of isocyanate groups in the diisocyanate is (0.2 to 0.3): 1; the mass of the organic metal catalyst is 0.001-0.1% of the mass of diisocyanate.
Preferably, the temperature of the first addition polymerization reaction is 75-85 ℃ and the time is 1-3 hours.
Preferably, the mass of the acetone is 5-40% of the mass of the first prepolymer; the temperature of the second addition polymerization reaction is 75-85 ℃ and the time is 2 hours.
Preferably, the amount of the second prepolymer is calculated as the amount of diisocyanate, and the ratio of the amount of the long-chain fatty alcohol to the amount of the substance of isocyanate groups in the diisocyanate is (0.2 to 0.3): 1, a step of; the end capping reaction temperature is 75-85 ℃ and the time is 2-4 hours.
Preferably, the neutralizing agent comprises triethylamine and/or triethanolamine.
Preferably, the chain extender comprises one or more of polyamine and sodium ethylenediamine ethanesulfonate; the ratio of the amount of the substance of the primary amino group in the chain extender to the amount of the substance of the isocyanate group in the diisocyanate is (0.2 to 0.3): 1, a step of; the time of the chain extension reaction is 0.5-3 hours.
Preferably, the polyamine comprises one or more of ethylenediamine, propylenediamine, butylenediamine, 2-methylpentylenediamine, hexamethylenediamine and isophoronediamine.
The main chain of the intrinsic matte waterborne polyurethane contains polysiloxane units, the chain end group is long-chain alkyl, and in the process of drying and film forming, a microphase separation structure inside the film is formed due to poor compatibility among the waterborne polyurethane units, the polysiloxane and the long-chain alkyl, so that the matte effect is realized. The glossiness of the dry film is not affected by the drying mode and the solvent type because of the intrinsic characteristic of polyurethane molecular chain.
The intrinsic matte waterborne polyurethane prepared by the invention can adjust the glossiness of the film by adjusting the composition and the proportion of the intrinsic matte waterborne polyurethane.
In addition, the particle size of the intrinsic matte waterborne polyurethane prepared by the invention is relatively low, so that the intrinsic matte waterborne polyurethane also has good storage stability.
Detailed Description
The invention provides intrinsic matte waterborne polyurethane, which has a molecular chain structure shown in a formula 1:
in the formula 1, R 4 Is thatR 1 Is alkylene, cycloalkyl or aralkyl, R 2 Is methyl or ethyl, R 3 Is alkylene, m is greater than or equal to 5 and is an integer, n>10 and is an integer.
In the present invention, the R 1 Preferably one or more of tolyl group, methylene-3, 5-trimethylcyclohexyl group, hexamethylene group, ethylphenyl group, methylcyclohexyl group and trimethylhexyl group.
In the present invention, the R 3 Preferably methylene group,Ethylene or propylene.
In the present invention, m is preferably an integer of 5 to 17, more preferably 5, 7, 11 or 17.
The main chain of the intrinsic matte waterborne polyurethane contains polysiloxane units, the chain end group is long-chain alkyl, and in the process of drying and film forming, a microphase separation structure inside the film is formed due to poor compatibility among the waterborne polyurethane units, the polysiloxane and the long-chain alkyl, so that the matte effect is realized. The glossiness of the dry film is not affected by the drying mode and the solvent type because of the intrinsic characteristic of polyurethane molecular chains.
The invention provides a preparation method of the intrinsic matte waterborne polyurethane, which comprises the following steps:
mixing polyether glycol, polyester glycol, polyhydroxysiloxane, dimethylol carboxylic acid, diisocyanate and an organic metal catalyst, and performing first addition polymerization reaction to obtain a first prepolymer; the structural formula of the diisocyanate is O=C=N-R 1 -N＝C＝O，R 1 Is alkylene, cycloalkyl or aralkyl; the dimethylol carboxylic acid is dimethylol propionic acid or dimethylol butyric acid; the structural formula of the polyhydroxysiloxane is
Mixing the first prepolymer with acetone, and performing a second addition polymerization reaction to obtain a second prepolymer;
mixing the second prepolymer with long-chain fatty alcohol, and performing end capping reaction to obtain a third prepolymer; the structural formula of the long-chain fatty alcohol ism is more than or equal to 5 and is an integer;
mixing the third prepolymer with a neutralizing agent, and carrying out a neutralization reaction to obtain a polyurethane prepolymer;
dispersing the polyurethane prepolymer into water, mixing the obtained dispersion with a chain extender, performing chain extension reaction, and removing acetone to obtain the intrinsic matte waterborne polyurethane.
In the present invention, the raw materials used are commercially available products well known in the art, unless specifically described otherwise.
The invention mixes polyether glycol, polyester glycol, polyhydroxy siloxane, dimethylol carboxylic acid, diisocyanate and organic metal catalyst, and carries out first addition polymerization reaction to obtain a first prepolymer.
The polyether glycol, polyester glycol, polyhydroxysiloxane and dimethylolcarboxylic acid are preferably dried separately before the mixing.
In the present invention, the polyether glycol preferably includes one or more of polyethylene glycol, polypropylene glycol and polytetramethylene glycol; the molecular weight of the polyether glycol is preferably 1000-2000 Da; the polyester diol preferably comprises one or more of polyethylene adipate glycol (PEA), 1, 4-butanediol adipate glycol (PBA), 1, 6-hexanediol adipate glycol (PHA), neopentyl glycol adipate glycol (PNA) and polycarbonate diol (PCD); the molecular weight of the polyester diol is preferably 1000-2000 Da. In the present invention, the ratio of the amount of the hydroxyl group-containing substance in the polyether diol and the polyester diol to the amount of the isocyanate group-containing substance in the diisocyanate is preferably (0.1 to 0.3): 1, more preferably (0.15 to 0.25): 1, more preferably 0.2:1.
In the present invention, the polyhydroxysiloxane is preferably a polyhydroxysiloxane containing primary hydroxyl groups; the polyhydroxy siloxane preferably comprises one or more of RHODOORSIL 1647 organosilicon, dow Corning OFX-3667, dow Corning SF8427 organosilicon, xinyue KF-6001 organosilicon and Wackeer IM 22 organosilicon; the ratio of the amount of the substance of hydroxyl groups in the polyhydroxysiloxane to the amount of the substance of isocyanate groups in the diisocyanate is preferably (0.02 to 0.1): 1, more preferably (0.04 to 0.09): 1, still more preferably (0.05 to 0.06): 1.
in the present invention, the dimethylol carboxylic acid is dimethylol propionic acid or dimethylol butyric acid; the ratio of the amount of the hydroxyl group-containing substance in the dimethylol carboxylic acid to the amount of the isocyanate group-containing substance in the diisocyanate is preferably (0.2 to 0.3): 1, more preferably (0.22 to 0.28): 1, more preferably (0.24 to 0.26): 1.
in the present invention, the diisocyanate has the structural formula o=c=n—r 1 -N＝C＝O，R 1 Is alkylene, cycloalkyl or aralkyl; the diisocyanate preferably comprises toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, ethylbenzene diisocyanate, methylcyclohexyl diisocyanate or trimethylhexamethylene diisocyanate.
In the present invention, the organometallic catalyst preferably includes an organometallic tin catalyst or an organometallic bismuth catalyst; the mass of the organometallic catalyst is preferably 0.001 to 0.1%, more preferably 0.01 to 0.09%, and even more preferably 0.04 to 0.07% of the mass of the diisocyanate.
In the present invention, the temperature of the first addition polymerization reaction is preferably 75 to 85 ℃, more preferably 78 to 82 ℃; the time is preferably 1 to 3 hours, more preferably 1.5 to 2.5 hours.
After the first prepolymer is obtained, the first prepolymer is mixed with acetone, and a second addition polymerization reaction is carried out to obtain a second prepolymer.
In the present invention, it is preferable to carry out the second addition polymerization by directly adding acetone to the obtained reaction system after the completion of the first prepolymerization. In the present invention, the mass of the acetone is preferably 5 to 40%, more preferably 10 to 35%, still more preferably 20 to 30% of the mass of the first prepolymer; the temperature of the second polycondensation reaction is preferably 75 to 85℃and the time is preferably 2 hours. The purpose of adding acetone is to adjust the viscosity of a reaction system to a proper range so as to ensure that the addition polymerization reaction is smoothly carried out.
In the present invention, the temperature of the second addition polymerization reaction is preferably 75 to 85 ℃, more preferably 78 to 82 ℃; the time is preferably 2 hours.
After the second prepolymer is obtained, the second prepolymer is mixed with long-chain fatty alcohol to carry out end capping reaction, so as to obtain a third prepolymer.
In the present invention, theThe structural formula of the long-chain fatty alcohol ism is more than or equal to 5 and is an integer; the long-chain fatty alcohol is preferably n-hexanol, n-octanol, n-dodecanol or n-octadecanol; the amount of the second prepolymer is preferably such that the ratio of the amount of the long-chain fatty alcohol to the amount of the substance of isocyanate groups in the diisocyanate is (0.2 to 0.3) based on the amount of diisocyanate: 1, more preferably (0.22 to 0.28): 1, more preferably (0.24 to 0.26): 1.
in the present invention, the temperature of the end-capping reaction is preferably 75 to 85 ℃, more preferably 78 to 82 ℃; the time for the end-capping reaction is preferably 2 to 4 hours, more preferably 2.5 to 3.5 hours. After completion of the end-capping reaction, the present invention preferably cools to room temperature to provide a third prepolymer.
After the third prepolymer is obtained, the third prepolymer is mixed with a neutralizing agent to perform a neutralization reaction to obtain the polyurethane prepolymer.
The present invention preferably adds a neutralizing agent to the third prepolymer. In the present invention, the ratio of the amounts of the substances of the dimethylol carboxylic acid and the neutralizing agent is preferably 1:0.6 to 1.
In the present invention, the neutralization reaction is preferably performed under stirring, and the time of the neutralization reaction is preferably 5 to 10 minutes.
After obtaining polyurethane prepolymer, dispersing the polyurethane prepolymer into water, mixing the obtained dispersion liquid with a chain extender, carrying out chain extension reaction, and removing acetone to obtain the intrinsic matte waterborne polyurethane.
In the invention, the water is preferably used in an amount such that the solid content of the intrinsic matte waterborne polyurethane is 30-40%. In the present invention, the temperature of the water is preferably 2 to 10 ℃, more preferably 4 to 8 ℃.
In the present invention, the dispersion is preferably performed under stirring, and the time for the dispersion is preferably 1 to 10 minutes, more preferably 4 to 8 minutes.
In the present invention, the chain extender is preferably used in the form of an aqueous solution of the chain extender; the mass concentration of the aqueous chain extender solution is preferably 30 to 100%, more preferably 50 to 80%. When the mass concentration of the chain extender aqueous solution is 100%, water is not needed. In the present invention, the chain extender preferably includes one or more of polyamine and sodium ethylenediamine ethanesulfonate; the polyamine preferably comprises one or more of ethylenediamine, propylenediamine, butylenediamine, 2-methylpentylenediamine, hexamethylenediamine and isophoronediamine. In the present invention, the ratio of the amount of the substance of the primary amino group in the chain extender to the amount of the substance of the isocyanate group in the diisocyanate is preferably (0.2 to 0.3): 1, more preferably (0.22 to 0.28): 1, more preferably (0.24 to 0.26): 1.
in the present invention, the chain extension reaction is preferably carried out under stirring at room temperature, and the time of the chain extension reaction is preferably 0.5 to 3 hours, more preferably 1 to 2.5 hours, and still more preferably 1.5 to 2 hours.
After the chain extension reaction is completed, acetone is removed, and the intrinsic matte waterborne polyurethane is obtained. In the present invention, the acetone is preferably removed by distillation.
The synthetic route of the intrinsic matte waterborne polyurethane is as follows:
the intrinsic type matte aqueous polyurethane and the preparation method thereof provided by the invention are described in detail below with reference to examples, but they are not to be construed as limiting the scope of the invention.
Example 1
200 g of dry polyethylene glycol (PEG 2000, molecular weight 2000Da, shanghai Dongda), 2400 g of polypropylene glycol (PPG 2000, molecular weight 2000Da, lanxing Dongda), 200 g of RHODOSIL 1647 organosilicon, 200 g of polyester diol (PE-9956, molecular weight 2000Da, jiangsu Huafeng) 1000 g, 201 g of dimethylol propionic acid, 1112 g of isophorone diisocyanate and 0.50 g of bismuth catalyst (MC-710, beijing Baiyuan chemical industry) are added into a reaction kettle, stirred uniformly, heated to 75 ℃ for reaction for 1.5 hours, 600 g of acetone is added, the reaction is continued for 2 hours, 130 g of n-octanol is added, the reaction is continued for 3 hours, and the temperature is reduced to room temperature, so as to obtain the polyurethane prepolymer.
150 g of triethylamine is added into the polyurethane prepolymer, stirred for 5 minutes, 9840 g of purified water with the temperature of 2-10 ℃ is rapidly added, high-speed stirring is carried out for 5 minutes, under the stirring condition, 60 g of ethylenediamine water solution with the mass concentration of 50% and 190 g of sodium ethylenediamine (A95) water solution with the mass concentration of 50% are dropwise added within 4 minutes, and the stirring is carried out for 1 hour, and acetone is removed under reduced pressure, thus obtaining the intrinsic matte waterborne polyurethane.
Example 2
200 g of dry polyethylene glycol (PEG 2000, molecular weight 2000Da, shanghai Dong Da) and 2400 g of polypropylene glycol (PPG 2000, molecular weight 2000Da, lanxing Dong Da) are added into a reaction kettle, then the mixture is stirred uniformly, the temperature is raised to 75 ℃ for 1.5 hours, 600 g of acetone is added, the reaction is continued for 2 hours, 130 g of n-octanol is added, the reaction is continued for 3 hours, and the temperature is lowered to room temperature to obtain polyurethane prepolymer, wherein 1000 g of polyester diol (PE-9956, molecular weight 2000Da, jiangsu Hua peak), 201 g of dimethylol propionic acid, 556 g of isophorone diisocyanate, 420 g of hexamethylene diisocyanate and 0.50 g of bismuth catalyst (MC-710, beijing Baiyuan chemical industry) are added into the reaction kettle.
150 g of triethylamine is added into the polyurethane prepolymer, stirred for 5 minutes, 9590 g of purified water at 2-10 ℃ is rapidly added, stirred for 5 minutes at high speed, and under the stirring condition, 60 g of 50% ethylenediamine water solution with mass concentration and 190 g of 50% ethylenediamine sodium sulfonate (A95) water solution with mass concentration are dropwise added in 4 minutes, stirred for 1 hour, and acetone is removed under reduced pressure, so that the intrinsic matte waterborne polyurethane is obtained.
Example 3
Dry polytetramethylene glycol (PTMG 2000, molecular weight 2000Da, BASF) 2400 g, xinyue KF-6001 organosilicon 200 g, polycarbonate diol (AS-302, molecular weight 2000Da, asahi chemical) 1000 g, dimethylolpropionic acid 201 g, isophorone diisocyanate 556 g, hexamethylene diisocyanate 420 g and bismuth catalyst 0.50 g (MC-710, beijing Bai chemical) are added into a reaction kettle, stirred evenly, heated to 75 ℃ for reaction for 1.5 hours, acetone 600 g is added, the reaction is continued for 2 hours, n-octanol 130 g is added, the reaction is continued for 3 hours, and the temperature is reduced to room temperature, thus obtaining polyurethane prepolymer.
150 g of triethylamine is added into the polyurethane prepolymer, the mixture is stirred for 5 minutes, 9225 g of purified water with the temperature of 2-10 ℃ is rapidly added, the mixture is stirred for 5 minutes at a high speed, 74 g of aqueous solution of ethylenediamine with the mass concentration of 50% and 190 g of aqueous solution of sodium ethylenediamine (A95) with the mass concentration of 50% are dropwise added in 4 minutes under the stirring condition, the mixture is stirred for 1 hour, acetone is removed under reduced pressure, and the intrinsic matte waterborne polyurethane is obtained.
Example 4
Dry polytetramethylene glycol (PTMG 2000, molecular weight 2000Da, BASF) 2400 g, xinyue KF-6001 organosilicon 200 g, polycarbonate diol (AS-302, molecular weight 2000Da, asahi chemical) 1000 g, isophorone diisocyanate 556 g, hexamethylene diisocyanate 420 g, dimethylol propionic acid 201 g and bismuth catalyst 0.50 g (MC-710, beijing Bai Yuan chemical) are added into a reaction kettle, stirred evenly, heated to 75 ℃ for reaction for 1.5 hours, added with acetone 600 g, continued for 2 hours, added with n-hexanol 102 g, continued for reaction for 3 hours, cooled to room temperature, and finally polyurethane prepolymer is obtained.
150 g of triethylamine is added into the polyurethane prepolymer, stirred for 5 minutes, quickly added into 9170 g of purified water with the temperature of 2-10 ℃ and stirred for 5 minutes at a high speed, 74 g of 50% ethylenediamine water solution with the mass concentration and 190 g of 50% sodium ethylenediamine ethanesulfonate (A95) water solution with the mass concentration are dropwise added in 4 minutes under the stirring condition, stirred for 1 hour, and acetone is removed under reduced pressure, so that the intrinsic matte waterborne polyurethane is obtained.
Example 5
Dry polytetramethylene glycol (PTMG 2000, molecular weight 2000Da, BASF) 2400 g, xinyue KF-6001 organosilicon 200 g, polycarbonate diol (AS-302, molecular weight 2000Da, asahi chemical) 1000 g, dimethylolpropionic acid 201 g, isophorone diisocyanate 556 g, hexamethylene diisocyanate 420 g and bismuth catalyst 0.50 g (MC-710, beijing Bai chemical) are added into a reaction kettle, stirred evenly, heated to 75 ℃ for reaction for 1.5 hours, acetone 600 g is added, the reaction is continued for 2 hours, n-dodecanol 186 g is added, the reaction is continued for 3 hours, and the temperature is reduced to room temperature, thus obtaining polyurethane prepolymer.
150 g of triethylamine is added into the polyurethane prepolymer, stirred for 5 minutes, 9330 g of purified water with the temperature of 2-10 ℃ is rapidly added, and stirred for 5 minutes at a high speed, under the stirring condition, 74 g of an aqueous solution of ethylenediamine with the mass concentration of 50% and 190 g of an aqueous solution of sodium ethylenediamine (A95) with the mass concentration of 50% are dropwise added in 4 minutes, and the mixture is stirred for 1 hour, acetone is removed under reduced pressure, and then the intrinsic matte waterborne polyurethane is obtained.
Example 6
2400 g of dry polytetramethylene glycol (PTMG 2000, molecular weight 2000Da, BASF), 200 g of Xinyue KF-6001 organosilicon, 1000 g of polycarbonate diol (AS-302, molecular weight 2000Da, asahi chemical compound), 201 g of dimethylol propionic acid, 556 g of isophorone diisocyanate, 420 g of hexamethylene diisocyanate and 0.50 g of dibutyltin dilaurate are added into a reaction kettle, stirred evenly, heated to 75 ℃ for reaction for 1.5 hours, 600 g of acetone is added, the reaction is continued for 2 hours, 270 g of n-octadecanol is added, the reaction is continued for 3 hours, and the temperature is reduced to room temperature, thus obtaining the polyurethane prepolymer.
150 g of triethylamine is added into the polyurethane prepolymer, the mixture is stirred for 5 minutes, 9485 g of purified water with the temperature of 2-10 ℃ is rapidly added, the mixture is stirred for 5 minutes at a high speed, 74 g of 50% ethylenediamine water solution with the mass concentration and 190 g of 50% ethylenediamine sodium sulfonate (A95) water solution with the mass concentration are dropwise added in 4 minutes under the stirring condition, the mixture is stirred for 1 hour, acetone is removed under reduced pressure, and the intrinsic matte waterborne polyurethane is obtained.
Comparative example 1
2400 g of dry polytetramethylene glycol (PTMG 2000, molecular weight 2000Da, BASF), 1000 g of polycarbonate dihydric alcohol (AS-302, molecular weight 2000Da, asahi chemical reaction), 556 g of isophorone diisocyanate, 420 g of hexamethylene diisocyanate, 201 g of dimethylol propionic acid and 0.50 g of bismuth catalyst (MC-710, beijing Bai Yuan chemical industry) are added into a reaction kettle, stirred uniformly, heated to 75 ℃ for reaction for 1.5 hours, 600 g of acetone is added, the reaction is continued for 2 hours, 130 g of n-octanol is added, the reaction is continued for 3 hours, and the temperature is reduced to room temperature, thus obtaining the polyurethane prepolymer.
150 g of triethylamine is added into the polyurethane prepolymer, stirred for 5 minutes, 8860 g of purified water with the temperature of 2-10 ℃ is rapidly added, stirred for 5 minutes at a high speed, 86 g of 50% ethylenediamine water solution with the mass concentration and 190 g of 50% sodium ethylenediamine ethanesulfonate (A95) water solution with the mass concentration are dropwise added in 4 minutes under stirring, stirred for 1 hour, and acetone is removed under reduced pressure, so that aqueous polyurethane is obtained.
Comparative example 2
2400 g of dry polytetramethylene glycol (PTMG 2000, molecular weight 2000Da, BASF), 200 g of Xinyue KF-6001 organosilicon, 1000 g of polycarbonate diol (AS-302, molecular weight 2000Da, asahi chemical compound), 556 g of isophorone diisocyanate, 420 g of hexamethylene diisocyanate, 201 g of dimethylol propionic acid and 0.50 g of bismuth catalyst (MC-710, beijing Bai Yuan chemical industry) are added into a reaction kettle, stirred uniformly, heated to 75 ℃ for reaction for 1.5 hours, 600 g of acetone is added, the reaction is continued for 3 hours, and the temperature is reduced to room temperature, thus obtaining the polyurethane prepolymer.
150 g of triethylamine is added into the polyurethane prepolymer, stirred for 5 minutes, 9010 g of purified water at 2-10 ℃ is rapidly added, stirred for 5 minutes at a high speed, 134 g of 50% ethylenediamine aqueous solution and 190 g of 50% ethylenediamine sodium (A95) ethylenediamine sodium sulfonate aqueous solution are dropwise added in 4 minutes under stirring, stirred for 1 hour, and acetone is removed under reduced pressure to obtain aqueous polyurethane.
Comparative example 3
2400 g of dry polytetramethylene glycol (PTMG 2000, molecular weight 2000Da, BASF), 1000 g of polycarbonate diol (AS-302, molecular weight 2000Da, asahi chemical reaction), 556 g of isophorone diisocyanate, 420 g of hexamethylene diisocyanate, 201 g of dimethylol propionic acid and 0.50 g of bismuth catalyst (MC-710, beijing Bai Yuan chemical industry) are added into a reaction kettle, stirred uniformly, heated to 75 ℃ for reaction for 1.5 hours, 600 g of acetone is added, the reaction is continued for 3 hours, and the temperature is reduced to room temperature, thus obtaining the polyurethane prepolymer.
150 g of triethylamine is added into the polyurethane prepolymer, stirred for 5 minutes, 8640 g of purified water at 2-10 ℃ is rapidly added, stirred for 5 minutes at a high speed, and under the stirring condition, 146 g of 50% ethylenediamine aqueous solution and 190 g of 50% ethylenediamine sodium (A95) aqueous solution are dropwise added in 4 minutes, stirred for 1 hour, and acetone is removed under reduced pressure to obtain the aqueous polyurethane.
Aqueous polyurethane dispersion parameters and results analysis
The aqueous polyurethanes obtained in examples 1 to 6 and comparative examples 1 to 3 of the present invention were subjected to performance test, and the test results are shown in Table 1. Wherein, appearance, solid content, viscosity, freeze thawing stability and centrifugal stability are tested with reference to GB/T11175-2002; viscosity testing instrument: brookfield viscometer DV1, method of measurement: direct testing at 25 ℃. Volatile organics: the test was performed with reference to GB/T23986-2009. Freeze thawing stability: taking 50mL of aqueous polyurethane, putting the aqueous polyurethane in a low-temperature box at the temperature of minus 5 plus or minus 2 ℃ for 18 hours, taking out the aqueous polyurethane, standing the aqueous polyurethane at the temperature of 23 plus or minus 2 ℃ for 6 hours, and repeatedly operating to observe whether sediment exists or not; thermal storage stability: 100mL of aqueous polyurethane is heated for 12 hours at 50 ℃, cooled to room temperature and stored for 12 hours, and repeated operation is carried out to observe whether sediment exists or not; centrifugal stability: taking 30mL of aqueous polyurethane in a centrifuge, and testing the centrifugal stability of the aqueous polyurethane under the condition of 3000r/min and 30 min; gloss level: placing a certain amount of aqueous polyurethane in a polytetrafluoroethylene mould, placing for 1-2 days, naturally drying, then drying the polyurethane film in a vacuum drying oven at 25 ℃ for 2 days, measuring 60 0 The gloss level was measured at an angle of incidence of 60℃using a microscopic tri-spectral gloss meter (CS-380).
TABLE 1 Property parameters of waterborne polyurethane
The results in Table 1 show that the aqueous polyurethanes of examples 1 to 6 and comparative examples 1 to 3 have similar pH and have better stability, but the aqueous polyurethanes of examples 1 to 6 have lower viscosity. The dry films of the waterborne polyurethanes of examples 1-6 have significantly lower glossiness than comparative examples 1-3, which indicates that the gloss of the waterborne polyurethane film can be effectively reduced by simultaneously introducing long-chain alkyl and polysiloxane into the molecular chain of the waterborne polyurethane, and a matte polyurethane film is obtained.
The intrinsic matte aqueous polyurethane of example 3 of the present invention and some commercial aqueous matte polyurethane on the market (abbreviated as comparative commercial product) were diluted from 35% to 20% in different solvents, dried to form films, and the gloss of the dry films was measured, and the test results are shown in table 2.
TABLE 2 gloss of dry films formed by aqueous polyurethane dispersion in different solvents (60 ° Gloss level
The results in table 2 show that the gloss of the intrinsic type matte aqueous polyurethane film of example 3 is not affected by the drying manner and solvent, compared to the comparative commercial product, indicating that the matte effect of the dry film is due to the molecular chain structure of the aqueous polyurethane.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. An intrinsic matte waterborne polyurethane is characterized by having a molecular chain structure shown in a formula 1:
in the formula 1, R 4 Is thatR 1 Is an alkylene group, a cycloalkyl group or an aralkyl group,R 2 is methyl or ethyl, R 3 Is alkylene, m is greater than or equal to 5 and is an integer, n>10 and is an integer.
2. The method for preparing the intrinsic matte waterborne polyurethane according to claim 1, which comprises the following steps:
mixing polyether glycol, polyester glycol, polyhydroxysiloxane, dimethylol carboxylic acid, diisocyanate and an organic metal catalyst, and performing first addition polymerization reaction to obtain a first prepolymer; the structural formula of the diisocyanate is O=C=N-R 1 -N＝C＝O，R 1 Is alkylene, cycloalkyl or aralkyl; the dimethylol carboxylic acid is dimethylol propionic acid or dimethylol butyric acid; the structural formula of the polyhydroxysiloxane is
Mixing the first prepolymer with acetone, and performing a second addition polymerization reaction to obtain a second prepolymer;
mixing the second prepolymer with long-chain fatty alcohol, and performing end capping reaction to obtain a third prepolymer; the structural formula of the long-chain fatty alcohol ism is more than or equal to 5 and is an integer;
mixing the third prepolymer with a neutralizing agent, and carrying out a neutralization reaction to obtain a polyurethane prepolymer;
dispersing the polyurethane prepolymer into water, mixing the obtained dispersion with a chain extender, performing chain extension reaction, and removing acetone to obtain the intrinsic matte waterborne polyurethane.
3. The method of claim 2, wherein the polyether glycol comprises one or more of polyethylene glycol, polypropylene glycol, and polytetramethylene glycol;
the polyester diol comprises one or more of polyethylene glycol adipate glycol, 1, 4-butanediol adipate glycol, 1, 6-hexanediol adipate glycol, neopentyl glycol adipate glycol and polycarbonate glycol;
the polyhydroxysiloxane is polyhydroxysiloxane containing primary hydroxyl groups;
the diisocyanate comprises toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, ethylbenzene diisocyanate, methylcyclohexyl diisocyanate or trimethylhexamethylene diisocyanate;
the organometallic catalyst comprises an organometallic tin catalyst or an organometallic bismuth catalyst.
4. The process according to claim 3, wherein the ratio of the amount of hydroxyl groups in the polyether diol and the polyester diol to the amount of isocyanate groups in the diisocyanate is (0.1 to 0.3): 1, a step of; the ratio of the amount of the hydroxyl group-containing substance in the polyhydroxysiloxane to the amount of the isocyanate group-containing substance in the diisocyanate is (0.02 to 0.1): 1, a step of; the ratio of the amount of hydroxyl groups in the dimethylol carboxylic acid to the amount of isocyanate groups in the diisocyanate is (0.2 to 0.3): 1; the mass of the organic metal catalyst is 0.001-0.1% of the mass of diisocyanate.
5. The process according to any one of claims 2 to 4, wherein the first addition polymerization is carried out at a temperature of 75 to 85℃for a period of 1 to 3 hours.
6. The preparation method according to claim 2, wherein the mass of the acetone is 5 to 40% of the mass of the first prepolymer; the temperature of the second addition polymerization reaction is 75-85 ℃ and the time is 2 hours.
7. The method according to claim 2, wherein the amount of the second prepolymer is calculated as the amount of diisocyanate, and the ratio of the amount of the long-chain fatty alcohol to the amount of the substance of the isocyanate group in the diisocyanate is (0.2 to 0.3): 1, a step of; the end capping reaction temperature is 75-85 ℃ and the time is 2-4 hours.
8. The preparation method according to claim 2, wherein the neutralizing agent comprises triethylamine and/or triethanolamine.
9. The method of claim 2, wherein the chain extender comprises one or more of polyamine and sodium ethylenediamine ethanesulfonate; the ratio of the amount of the substance of the primary amino group in the chain extender to the amount of the substance of the isocyanate group in the diisocyanate is (0.2 to 0.3): 1, a step of; the time of the chain extension reaction is 0.5-3 hours.
10. The method of claim 9, wherein the polyamine comprises one or more of ethylenediamine, propylenediamine, butylenediamine, 2-methylpentylenediamine, hexamethylenediamine, and isophoronediamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311440795.3A CN117362580B (en) | 2023-11-01 | 2023-11-01 | Intrinsic matte waterborne polyurethane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311440795.3A CN117362580B (en) | 2023-11-01 | 2023-11-01 | Intrinsic matte waterborne polyurethane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117362580A true CN117362580A (en) | 2024-01-09 |
| CN117362580B CN117362580B (en) | 2024-06-21 |
Family
ID=89396403
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311440795.3A Active CN117362580B (en) | 2023-11-01 | 2023-11-01 | Intrinsic matte waterborne polyurethane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117362580B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030198819A1 (en) * | 2002-04-17 | 2003-10-23 | Gerhard Reusmann | Aqueous polysiloxane-polyurethane dispersion, its preparation and use in coating compositions |
| CN104774307A (en) * | 2015-04-08 | 2015-07-15 | 武汉纺织大学 | Preparation method and product of modified polyurethane flexible high-molecular emulsion containing side long chain alkyl |
| 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 |
| CN116041653A (en) * | 2022-12-14 | 2023-05-02 | 湖南工业大学 | Room temperature self-crosslinking single-component water solution-based polyurethane and preparation method and application thereof |
| CN116410433A (en) * | 2022-12-30 | 2023-07-11 | 广州海豚新材料有限公司 | Silicon-containing polyurethane resin, preparation method thereof and synthetic leather bass |
-
2023
- 2023-11-01 CN CN202311440795.3A patent/CN117362580B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030198819A1 (en) * | 2002-04-17 | 2003-10-23 | Gerhard Reusmann | Aqueous polysiloxane-polyurethane dispersion, its preparation and use in coating compositions |
| CN104774307A (en) * | 2015-04-08 | 2015-07-15 | 武汉纺织大学 | Preparation method and product of modified polyurethane flexible high-molecular emulsion containing side long chain alkyl |
| 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 |
| CN116041653A (en) * | 2022-12-14 | 2023-05-02 | 湖南工业大学 | Room temperature self-crosslinking single-component water solution-based polyurethane and preparation method and application thereof |
| CN116410433A (en) * | 2022-12-30 | 2023-07-11 | 广州海豚新材料有限公司 | Silicon-containing polyurethane resin, preparation method thereof and synthetic leather bass |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117362580B (en) | 2024-06-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109438655B (en) | Carbon dioxide-based polycarbonate ether polyol polyurethane and preparation method and application thereof | |
| CN107353394B (en) | Coating, polyurethane and preparation method thereof | |
| CN109970940B (en) | Silicone-modified aqueous polyurethane dispersions and aqueous nail polishes prepared therefrom | |
| CN107141434B (en) | Waterborne polyurethane resin for synthetic leather fabric and preparation method thereof | |
| CN112851898B (en) | Self-extinction waterborne polyurethane resin, preparation method and application | |
| CN104693403B (en) | A kind of use for synthetic leather colour polyurethane resin and preparation method thereof | |
| CN111909351A (en) | Synthetic method and application of waterborne polyurethane for microfiber impregnation | |
| Athawale et al. | Interpenetrating polymer networks based on polyol modified castor oil polyurethane and polymethyl methacrylate | |
| CN108330712A (en) | Printing mortar is used poly-（Carbonic ester-ether）Type polyurethane lotion and preparation method | |
| CN109575228A (en) | A kind of polyurethane resin and its preparation method and application | |
| CN111789779A (en) | High-adhesion water-based nail polish and preparation method thereof | |
| CN105622886A (en) | Alcohol/water-soluble polyurethane resin used for intaglio ink and preparation method thereof | |
| CN114085349A (en) | Silicone-modified polyurethane resin and method for producing same | |
| CN108707412A (en) | High bright resin of a kind of Weak solvent and preparation method thereof | |
| CN108794723A (en) | A kind of biology base dumb light aqueous polyurethane dispersion and preparation method thereof | |
| CN117362588A (en) | Controllably crosslinked waterborne polyurethane and synthetic method thereof | |
| CN117362580B (en) | Intrinsic matte waterborne polyurethane and preparation method thereof | |
| CN106009903B (en) | A kind of preparation method of low crystallization aqueous polyurethane oil ink connecting material | |
| CN113509405B (en) | Preparation method of environment-friendly Maya blue-like water-resistant nail polish | |
| CN113121773A (en) | Sulfonic acid type solvent-free aqueous polyurethane resin and preparation method thereof | |
| CN106589310B (en) | A kind of heatproof transfer coatings aqueous polyurethane emulsion and preparation method thereof | |
| CN113861371A (en) | Preparation method of self-extinction waterborne polyurethane | |
| CN107778447A (en) | A kind of aqueous one-component moisture polyurethane curing agent and preparation method thereof | |
| CN112900107B (en) | Waterborne polyurethane/organic silicon composite mirror leather and preparation method thereof | |
| CN113621304B (en) | Self-extinction waterborne polyurethane resin and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20240117 Address after: 518101 Tea Tree Commercial Building B, Building 407, Sanwei Inner Ring Road, Sanwei Community, Hangcheng Street, Bao'an District, Shenzhen City, Guangdong Province Applicant after: Shenzhen Borui Technology Co.,Ltd. Address before: 300071 Weijin Road, Nankai District, Tianjin Nankai University North Village 12-2-304 Applicant before: Zhang Wangqing |
|
| GR01 | Patent grant |