CN116769135B - Bio-based waterborne polyurethane and preparation method and application thereof - Google Patents
Bio-based waterborne polyurethane and preparation method and application thereof Download PDFInfo
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- CN116769135B CN116769135B CN202311048341.1A CN202311048341A CN116769135B CN 116769135 B CN116769135 B CN 116769135B CN 202311048341 A CN202311048341 A CN 202311048341A CN 116769135 B CN116769135 B CN 116769135B
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- prepolymer
- polylactic acid
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- diisocyanate
- acid polyol
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 33
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 46
- 239000004626 polylactic acid Substances 0.000 claims abstract description 46
- 229920005862 polyol Polymers 0.000 claims abstract description 38
- 150000003077 polyols Chemical class 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 20
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 20
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 20
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012756 surface treatment agent Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- 125000002524 organometallic group Chemical group 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- -1 small molecule diol Chemical class 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- KCWDJXPPZHMEIK-UHFFFAOYSA-N isocyanic acid;toluene Chemical class N=C=O.N=C=O.CC1=CC=CC=C1 KCWDJXPPZHMEIK-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- DFPJRUKWEPYFJT-UHFFFAOYSA-N 1,5-diisocyanatopentane Chemical compound O=C=NCCCCCN=C=O DFPJRUKWEPYFJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- UZMKOEWHQQPOBJ-UHFFFAOYSA-M sodium;2,3-dihydroxypropane-1-sulfonate Chemical compound [Na+].OCC(O)CS([O-])(=O)=O UZMKOEWHQQPOBJ-UHFFFAOYSA-M 0.000 claims description 3
- CFQLQLSIZOWFNV-UHFFFAOYSA-M sodium;2-[bis(2-hydroxyethyl)amino]ethanesulfonate Chemical compound [Na+].OCCN(CCO)CCS([O-])(=O)=O CFQLQLSIZOWFNV-UHFFFAOYSA-M 0.000 claims description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims 1
- 229940051250 hexylene glycol Drugs 0.000 claims 1
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 230000006837 decompression Effects 0.000 description 5
- 239000000178 monomer Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000002649 leather substitute Substances 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920006264 polyurethane film Polymers 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 244000290333 Vanilla fragrans Species 0.000 description 1
- 235000009499 Vanilla fragrans Nutrition 0.000 description 1
- 235000012036 Vanilla tahitensis Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 231100000344 non-irritating Toxicity 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920003009 polyurethane dispersion Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 150000008054 sulfonate salts Chemical class 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 239000002699 waste material Substances 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
- C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- 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
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/428—Lactides
-
- 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
- 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)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides bio-based waterborne polyurethane, a preparation method and application thereof, and relates to the technical field of polyurethane surface treatment agents. Mixing polylactic acid polyol, polyethylene glycol, 2-dimethylolpropionic acid, an organic metal catalyst and diisocyanate, and performing a prepolymerization reaction to obtain a prepolymer; adding micromolecular dihydric alcohol into the prepolymer for chain extension reaction, and adding triethylamine to neutralize carboxylic acid to form salt after the reaction is completed to obtain SWPU prepolymer; dispersing the SWPU prepolymer and the sulfonate into water to obtain the bio-based waterborne polyurethane. The bio-based aqueous polyurethane provided by the invention has good performance as a surface treatment agent.
Description
Technical Field
The invention relates to the technical field of polyurethane surface treatment agents, in particular to bio-based waterborne polyurethane and a preparation method and application thereof.
Background
The Waterborne Polyurethane (WPU) has the advantages of high safety, low pollution, excellent mechanical property, capability of being modified in various aspects and the like, and is mainly applied to the fields of paint, adhesive, textile industry and the like. However, the traditional WPU coating can not meet the requirements of people on the performances of high efficiency, energy conservation, environmental protection, harmlessness, resource recycling and the like of the novel polymer material, so that the biodegradable WPU meets the requirements of the age. The biodegradable WPU avoids various health problems caused by volatilization of the organic solvent, and has the characteristics of environmental protection, energy saving, environmental protection, no pollution, no toxicity or harm of degradation products and the like.
Polylactic acid (PLA), also known as polylactide, is a polyester polymerized from lactic acid as a raw material. Polylactic acid has excellent biodegradability, compatibility and absorbability. AggregationLactic acid is a nontoxic and non-irritating synthetic polymer material, and is mainly prepared from starch (such as corn and rice) by fermenting, or cellulose, kitchen garbage or fish waste. PLA raw materials are widely available, and products prepared from the PLA raw materials can be directly subjected to composting or incineration treatment after being used, and finally can be completely degraded into CO 2 And H 2 And O, meeting the requirement of sustainable development.
PLA-WPU surface treating agent based on polylactic acid development meets the requirements of green pollution-free and sustainable development, but hydrophilic monomers of the existing PLA-WPU surface treating agent are easily concentrated in a hard segment or a soft segment, phase separation occurs, and the water resistance of products is seriously affected.
Disclosure of Invention
The invention aims to provide bio-based waterborne polyurethane, a preparation method and application thereof, and the bio-based waterborne polyurethane provided by the invention has good water resistance as a surface treatment agent.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of bio-based waterborne polyurethane, which comprises the following steps:
mixing polylactic acid polyol, polyethylene glycol, 2-dimethylolpropionic acid, an organic metal catalyst and diisocyanate, and performing a prepolymerization reaction to obtain a prepolymer;
mixing the prepolymer with small molecular dihydric alcohol for chain extension reaction, and adding triethylamine to neutralize carboxylic acid to form salt after the reaction is completed to obtain SWPU prepolymer;
dispersing the SWPU prepolymer and the sulfonate into water to obtain the bio-based waterborne polyurethane.
Preferably, the number average molecular weight of the polylactic acid polyol is 1000-2000; the number average molecular weight of the polyethylene glycol is 1000-2000.
Preferably, the mass ratio of the polylactic acid polyol to the 2, 2-dimethylolpropionic acid is 5.8-12: 1, a step of; the mass ratio of the polyethylene glycol to the polylactic acid polyol is 1:1.
preferably, the organic metal catalyst is one or more of an organic silver catalyst, an organic bismuth catalyst and an organic zinc catalyst; the mass of the organometallic catalyst is 0.1-0.14% of the mass of the polylactic acid polyol.
Preferably, the diisocyanate is one or more of isophorone diisocyanate, hydrogenated phenyl methane diisocyanate, hexamethylene diisocyanate, and 1, 5-pentanediisocyanate; the mass ratio of the polylactic acid polyol to the diisocyanate is 1-2.5: 1.
preferably, the temperature of the prepolymerization reaction is 85 ℃.
Preferably, the small molecular dihydric alcohol is one or more of ethylene glycol, butanediol and hexanediol; the mass of the micromolecular dihydric alcohol is 0.2-0.7% of that of the polylactic acid polyol.
Preferably, the sulfonate is one or more of sodium 2- [ (2-aminoethyl) amino ] ethanesulfonate, sodium N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonate and sodium 1, 2-dihydroxy-3-propanesulfonate; the mass of the sulfonate is 5-10% of that of the polylactic acid polyol.
The invention provides the bio-based aqueous polyurethane prepared by the preparation method.
The invention provides application of the bio-based aqueous polyurethane as a surface treatment agent.
The invention provides a preparation method of bio-based waterborne polyurethane, which comprises the following steps: mixing polylactic acid polyol, polyethylene glycol, 2-dimethylolpropionic acid, an organic metal catalyst and diisocyanate, and performing a prepolymerization reaction to obtain a prepolymer; mixing the prepolymer with small molecular dihydric alcohol for chain extension reaction, and adding triethylamine to neutralize carboxylic acid to form salt after the reaction is completed to obtain SWPU prepolymer; dispersing the SWPU prepolymer and the sulfonate into water to obtain the bio-based waterborne polyurethane.
The invention takes diisocyanate and micromolecular dihydric alcohol as hard segments, takes polylactic acid polyol as soft segments, adopts carboxylate (namely 2, 2-dimethylolpropionic acid salt formation)/sulfonate/nonionic hydrophilic monomer (namely polyethylene glycol) to compound, has higher flexibility and hydrophilicity on molecular chains of the carboxylate/sulfonate/nonionic hydrophilic monomer, has smaller particle size and better emulsion stability when being used as WPU synthesized by hydrophilic units, has excellent water resistance and tensile property, and can be used for artificial leather surface finishing and ink connecting material surface treating agent for food packaging after performance test.
Detailed Description
The invention provides a preparation method of bio-based waterborne polyurethane, which comprises the following steps:
mixing polylactic acid polyol, polyethylene glycol, 2-dimethylolpropionic acid, an organic metal catalyst and diisocyanate, and performing a prepolymerization reaction to obtain a prepolymer;
mixing the prepolymer with small molecular dihydric alcohol for chain extension reaction, and adding triethylamine to neutralize carboxylic acid to form salt after the reaction is completed to obtain SWPU prepolymer;
dispersing the SWPU prepolymer and the sulfonate into water to obtain the bio-based 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 polylactic acid polyol, polyethylene glycol, 2-dimethylolpropionic acid, an organic metal catalyst and diisocyanate for prepolymerization reaction to obtain prepolymer.
In the present invention, the number average molecular weight of the polylactic acid polyol is preferably 1000 to 2000, more preferably 1000 or 2000; the number average molecular weight of the polyethylene glycol is preferably 1000-2000. In the present invention, the polylactic acid polyol is preferably a bio-based polylactic acid polyol available from Fengyuan group under the model PLA1000 or PLA2000. In the invention, the mass ratio of the polylactic acid polyol to the 2, 2-dimethylolpropionic acid is preferably 5.8-12: 1, more preferably 6 to 10:1, still more preferably 7 to 8:1; the mass ratio of the polylactic acid polyol to the polyethylene glycol is preferably 1:1.
in the invention, the organometallic catalyst is preferably one or more of an organic silver catalyst, an organic bismuth catalyst and an organic zinc catalyst; the invention has no special requirements on specific types of the organic silver catalyst, the organic bismuth catalyst and the organic zinc catalyst, the corresponding catalysts for the prepolymerization reaction well known in the field can be all the catalysts, and the organic silver catalyst can be ESCAT#100deg.Ag of Korean chemistry; the organobismuth catalyst may be 710 of TMG corporation; the organozinc catalyst may be Vanilla 8330R. In the present invention, the mass of the organometallic catalyst is preferably 0.1 to 0.14%, more preferably 0.12 to 0.13% of the polylactic acid polyol.
In the present invention, the diisocyanate is preferably one or more of isophorone diisocyanate, hydrogenated phenyl methane diisocyanate, hexamethylene diisocyanate, and 1, 5-pentanediisocyanate; the mass ratio of the polylactic acid polyol to the diisocyanate is preferably 1-2.5: 1, more preferably 1.5 to 2:1.
In the present invention, the pre-polymerization preferably further comprises dehydrating the polylactic acid polyol, polyethylene glycol and 2, 2-dimethylolpropionic acid, and the dehydrating preferably comprises: adding polylactic acid polyol, polyethylene glycol and 2, 2-dimethylolpropionic acid into a reactor, constructing a decompression dehydration device, and dehydrating for 1h under the conditions of minus 0.095MPa and 130 ℃. The polylactic acid polyol, the polyethylene glycol and the 2, 2-dimethylolpropionic acid contain a small amount of water, so that the polylactic acid polyol, the polyethylene glycol and the 2, 2-dimethylolpropionic acid are easy to react with isocyanate, and the water is removed in advance, so that side reactions can be avoided. The device for decompression and dehydration has no special requirement, and the device can realize the decompression and dehydration function.
In the invention, the catalyst is preferably directly cooled to the temperature of the prepolymerization reaction after dehydration is finished, and the organometallic catalyst and diisocyanate are added for the prepolymerization reaction.
In the invention, the temperature of the prepolymerization reaction is preferably 85 ℃, the time of the prepolymerization reaction is not particularly required, and the reaction is carried out until the mass of the-NCO group in the prepolymer reaches 0.8-0.9% of the mass of the system.
In the process of the prepolymerization reaction, the hydroxyl groups in the polylactic acid polyol, the polyethylene glycol and the 2, 2-dimethylolpropionic acid react with the-NCO groups in the diisocyanate under the action of an organic metal catalyst to form a prepolymer.
After the prepolymer is obtained, the prepolymer is mixed with small molecular dihydric alcohol for chain extension reaction, and triethylamine is added to neutralize carboxylic acid to form salt after the reaction is completed, so that the SWPU prepolymer is obtained.
In the invention, the small molecular dihydric alcohol is preferably one or more of ethylene glycol, butanediol and hexanediol; the mass of the small molecular dihydric alcohol is preferably 0.2 to 0.7%, more preferably 0.3 to 0.6%, and even more preferably 0.4 to 0.5% of the mass of the polylactic acid polyol.
In the present invention, mixing the prepolymer with the small molecule diol preferably comprises: small molecule diols are added to the prepolymer. In the invention, the time of the chain extension reaction is preferably 0.5 to 1h.
After the chain extension reaction is completed, the obtained reactant is preferably cooled to 55-60 ℃, and then triethylamine is added to neutralize carboxylic acid to form salt.
In the invention, the triethylamine can neutralize the acid in the prepolymer to form an ionized acid-base pair, so that the prepolymer can be dispersed; if not ionized, it will not possess the hydrophilicity necessary to produce a polymer dispersion. In the present invention, the molar ratio of triethylamine to 2, 2-dimethylolpropionic acid is preferably 1:1.
After the SWPU prepolymer is formed, the SWPU prepolymer and the sulfonate are dispersed into water to obtain the bio-based waterborne polyurethane.
In the present invention, the sulfonate is preferably one or more of sodium 2- [ (2-aminoethyl) amino ] ethanesulfonate, sodium N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonate, and sodium 1, 2-dihydroxy-3-propanesulfonate; the mass of the sulfonate is preferably 5-10% of the mass of the polylactic acid polyol, more preferably 6-8%.
In the present invention, the sulfonate is preferably used in the form of an aqueous sulfonate solution; the mass concentration of the sulfonate aqueous solution is preferably 50-80%, more preferably 60-70%.
In the present invention, dispersing the SWPU prepolymer and sulfonate salt in water preferably comprises: water is added into the SWPU prepolymer for dispersion, and then water solution of sulfonate is dripped into the SWPU prepolymer in the water dispersion process. The sulfonate is introduced in the invention, so that the water-based polyurethane molecules can reach ideal ion concentration and hydration degree, and can be stably dispersed in water, the number of carboxyl groups with strong polarity is greatly reduced, and after the intermolecular force is greatly reduced, the thixotropic property of the product is greatly reduced under the condition of improving the solid content.
The invention provides the bio-based aqueous polyurethane prepared by the preparation method. The bio-based aqueous polyurethane prepared by using diisocyanate and micromolecular dihydric alcohol as hard segments, polylactic acid polyol as soft segments and carboxylate/sulfonate/nonionic hydrophilic monomer compounding has the advantages of amphiphilicity, non-toxicity and biodegradability.
The invention provides application of the bio-based aqueous polyurethane as a surface treatment agent. In the present invention, the surface treatment agent is preferably an artificial leather surface finishing surface treatment agent or an ink vehicle surface treatment agent for food packaging.
The bio-based aqueous polyurethane, the preparation method and application thereof provided by the present invention are described in detail with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
182.2g of weighed polylactic acid polyol (PLA 1000) with the number average molecular weight of 1000 and 31.2g of polyethylene glycol 182.2g with the number average molecular weight of 1000 and 2, 2-dimethylolpropionic acid are added into a reactor, a decompression dehydration device is built, the mixture is treated for 1h under the conditions of minus 0.095MPa and 130 ℃, then cooled to 85 ℃, after normal pressure is recovered, 0.182g of organic bismuth catalyst TMG710 and 145.2g of isophorone diisocyanate are added, the pre-polymerization is carried out for 2h until the number of actual-NCO groups of the prepolymer reaches a theoretical value, 1.2g of butanediol is added, the obtained reactant is cooled to 60 ℃ and is salified by triethylamine, the SWPU prepolymer is obtained, 1500.0g of deionized water is added for quick dispersion, and finally, in the water dispersion process, an aqueous solution with the mass concentration of 50 percent and 18.2g of 2- [ (2-aminoethyl) amino ] sodium ethane sulfonate is continuously dripped into a reaction system under high-speed stirring, so as to obtain the biological WPPLA aqueous PLA.
Preparation of polyurethane film: the bio-based aqueous polyurethane was poured into a polytetrafluoroethylene mold plate, dried at room temperature for 30 hours, and then dried in a vacuum oven at 50 ℃ for another 30 hours. The tensile strength of the film was found to be 25.6MPa, the elongation at break was found to be 572%, the water absorption was found to be 10.5%, the contact angle was found to be 62.3℃and the surface energy was found to be 25.6mJ/m 2 . The bio-based aqueous polyurethane disclosed by the invention has good performance as a surface treatment agent, and is particularly excellent in mechanical property and hydrophilic property and low in surface energy.
Example 2
364.4g (PLA 2000) of weighed polylactic acid polyol with the number average molecular weight of 2000 and 364.4g of polyethylene glycol with the number average molecular weight of 2000 and 31.2g of 2, 2-dimethylolpropionic acid are added into a reactor, a decompression dehydration device is built, the reactor is treated for 1h under the conditions of minus 0.095MPa and 130 ℃, then cooled to 85 ℃, after normal pressure is recovered, 0.364g of ESCAT#100deg.Ag of organic metal catalyst Korean chemistry is added, 171.4g of hydrogenated phenyl methane diisocyanate is added for prepolymerization for 2h until the number of actual NCO groups of the prepolymer reaches a theoretical value, 0.8g of ethylene glycol is added, the obtained reactant is cooled to 60 ℃, triethylamine is used for neutralizing carboxylic acid to form a salt, SWPU prepolymer is obtained, 2600.0g of deionized water is added for rapid dispersion, and finally, in the water dispersion process, 21.3g of aqueous solution containing 2- [ (2-aminoethyl) amino ] sodium ethane sulfonate with the mass concentration of 50% is continuously dripped into a reaction system under high-speed stirring, so as to obtain PLA-WPU (bio-polyurethane) based aqueous polyurethane dispersion.
Preparation of polyurethane film: the bio-based aqueous polyurethane was poured into a polytetrafluoroethylene mold plate, dried at room temperature for 30 hours, and then dried in a vacuum oven at 50 ℃ for another 30 hours. The film had a tensile strength of 19.8MPa, an elongation at break of 852%, a water absorption of 13.2%, a contact angle of 45.6℃and a surface energy of 33.5mJ/m 2 。
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 (7)
1. The preparation method of the bio-based aqueous polyurethane is characterized by comprising the following steps of:
mixing polylactic acid polyol, polyethylene glycol, 2-dimethylolpropionic acid, an organic metal catalyst and diisocyanate, and performing a prepolymerization reaction to obtain a prepolymer;
mixing the prepolymer with small molecular dihydric alcohol for chain extension reaction, and adding triethylamine to neutralize carboxylic acid to form salt after the reaction is completed to obtain SWPU prepolymer;
dispersing the SWPU prepolymer and the sulfonate into water to obtain bio-based waterborne polyurethane;
the organic metal catalyst is one or more of an organic silver catalyst, an organic bismuth catalyst and an organic zinc catalyst; the mass of the organometallic catalyst is 0.1-0.14% of the mass of the polylactic acid polyol;
the diisocyanate is one or more of isophorone diisocyanate, hydrogenated phenyl methane diisocyanate, hexamethylene diisocyanate and 1, 5-pentanediisocyanate; the mass ratio of the polylactic acid polyol to the diisocyanate is 1-2.5: 1, a step of;
the sulfonate is one or more of sodium 2- [ (2-aminoethyl) amino ] ethanesulfonate, sodium N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonate and sodium 1, 2-dihydroxy-3-propanesulfonate; the mass of the sulfonate is 5-10% of that of the polylactic acid polyol.
2. The preparation method according to claim 1, wherein the polylactic acid polyol has a number average molecular weight of 1000 to 2000; the number average molecular weight of the polyethylene glycol is 1000-2000.
3. The preparation method according to claim 1 or 2, wherein the mass ratio of the polylactic acid polyol to the 2, 2-dimethylolpropionic acid is 5.8-12: 1, a step of; the mass ratio of the polyethylene glycol to the polylactic acid polyol is 1:1.
4. the method of claim 1, wherein the temperature of the prepolymerization is 85 ℃.
5. The method of claim 1, wherein the small molecule diol is one or more of ethylene glycol, butylene glycol, and hexylene glycol; the mass of the micromolecular dihydric alcohol is 0.2-0.7% of that of the polylactic acid polyol.
6. The bio-based aqueous polyurethane prepared by the preparation method of any one of claims 1-5.
7. The use of the biobased aqueous polyurethane of claim 6 as a surface treatment agent.
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| CN106674992A (en) * | 2016-07-14 | 2017-05-17 | 安徽亳州喜宝鞋服有限公司 | Air-permeable and deodorant polylactic acid-based polyurethane composite material and preparation method thereof |
| CN108360263A (en) * | 2018-02-07 | 2018-08-03 | 航天材料及工艺研究所 | The compound 3D printing composite material high activity Interface enhancer of quick in situ and preparation method |
| CN111378262A (en) * | 2020-04-16 | 2020-07-07 | 孝感市易生新材料有限公司 | Polylactic acid-based thermoplastic polyurethane modified polylactic acid composite material, preparation method thereof and application thereof in 3D printing consumables |
| CN113651936A (en) * | 2021-06-17 | 2021-11-16 | 厦门威亮光学涂层技术有限公司 | Application of organic sulfonic amine salt |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106674992A (en) * | 2016-07-14 | 2017-05-17 | 安徽亳州喜宝鞋服有限公司 | Air-permeable and deodorant polylactic acid-based polyurethane composite material and preparation method thereof |
| CN108360263A (en) * | 2018-02-07 | 2018-08-03 | 航天材料及工艺研究所 | The compound 3D printing composite material high activity Interface enhancer of quick in situ and preparation method |
| CN111378262A (en) * | 2020-04-16 | 2020-07-07 | 孝感市易生新材料有限公司 | Polylactic acid-based thermoplastic polyurethane modified polylactic acid composite material, preparation method thereof and application thereof in 3D printing consumables |
| CN113651936A (en) * | 2021-06-17 | 2021-11-16 | 厦门威亮光学涂层技术有限公司 | Application of organic sulfonic amine salt |
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