CN113336664B - Bio-based aqueous polyurethane resin and preparation method and application thereof - Google Patents
Bio-based aqueous polyurethane resin and preparation method and application thereof Download PDFInfo
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- CN113336664B CN113336664B CN202110495182.4A CN202110495182A CN113336664B CN 113336664 B CN113336664 B CN 113336664B CN 202110495182 A CN202110495182 A CN 202110495182A CN 113336664 B CN113336664 B CN 113336664B
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- aqueous polyurethane
- chain extender
- polyurethane resin
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- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000004970 Chain extender Substances 0.000 claims description 53
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 239000003153 chemical reaction reagent Substances 0.000 claims description 30
- 239000004472 Lysine Substances 0.000 claims description 25
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 22
- 150000002009 diols Chemical class 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000003960 organic solvent Substances 0.000 claims description 18
- -1 maleic acid ester Chemical class 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 229920000728 polyester Polymers 0.000 claims description 11
- 229920005862 polyol Polymers 0.000 claims description 11
- 150000003077 polyols Chemical class 0.000 claims description 11
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 125000005442 diisocyanate group Chemical group 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 229920000570 polyether Polymers 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 238000006845 Michael addition reaction Methods 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000012043 crude product Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 7
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 6
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 6
- 229940035437 1,3-propanediol Drugs 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- 125000004427 diamine group Chemical group 0.000 claims description 6
- 230000003472 neutralizing effect Effects 0.000 claims description 6
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 6
- 125000003158 alcohol group Chemical group 0.000 claims description 5
- 238000006264 debenzylation reaction Methods 0.000 claims description 5
- 229920000515 polycarbonate Polymers 0.000 claims description 5
- 239000004417 polycarbonate Substances 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- XXAYGJGDVLSEML-LBPRGKRZSA-N benzyl (2s)-2,6-diaminohexanoate Chemical group NCCCC[C@H](N)C(=O)OCC1=CC=CC=C1 XXAYGJGDVLSEML-LBPRGKRZSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims 1
- 239000001530 fumaric acid Substances 0.000 claims 1
- 229920002635 polyurethane Polymers 0.000 abstract description 25
- 239000004814 polyurethane Substances 0.000 abstract description 25
- 230000007062 hydrolysis Effects 0.000 abstract description 10
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 230000032683 aging Effects 0.000 abstract description 3
- 125000001931 aliphatic group Chemical group 0.000 abstract description 3
- 235000018977 lysine Nutrition 0.000 description 23
- 239000012948 isocyanate Substances 0.000 description 17
- 150000002513 isocyanates Chemical class 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- 125000000962 organic group Chemical group 0.000 description 14
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 4
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- GFQYFRTWQLDRCH-LBPRGKRZSA-N (2s)-6-amino-2-(benzylamino)hexanoic acid Chemical group NCCCC[C@@H](C(O)=O)NCC1=CC=CC=C1 GFQYFRTWQLDRCH-LBPRGKRZSA-N 0.000 description 3
- 235000001014 amino acid Nutrition 0.000 description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229920003009 polyurethane dispersion Polymers 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- GQZXRLWUYONVCP-UHFFFAOYSA-N 3-[1-(dimethylamino)ethyl]phenol Chemical compound CN(C)C(C)C1=CC=CC(O)=C1 GQZXRLWUYONVCP-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 2
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical group COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-L fumarate(2-) Chemical compound [O-]C(=O)\C=C\C([O-])=O VZCYOOQTPOCHFL-OWOJBTEDSA-L 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical group OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 235000019766 L-Lysine Nutrition 0.000 description 1
- 206010024769 Local reaction Diseases 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000003588 lysine group Chemical group [H]N([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(N([H])[H])C(*)=O 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- KPNBUPJZFJCCIQ-LURJTMIESA-N methyl L-lysinate Chemical compound COC(=O)[C@@H](N)CCCCN KPNBUPJZFJCCIQ-LURJTMIESA-N 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
- 229920001778 nylon Polymers 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- QIQCZROILFZKAT-UHFFFAOYSA-N tetracarbon dioxide Chemical group O=C=C=C=C=O QIQCZROILFZKAT-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C229/24—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having more than one carboxyl group bound to the carbon skeleton, e.g. aspartic acid
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7862—Nitrogen containing cyano groups or aldimine or ketimine groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a bio-based aqueous polyurethane resin, a preparation method and application thereof, which can fundamentally solve the problem of poor hydrolysis resistance of aqueous polyurethane products. In addition, the bio-based aqueous polyurethane with the structure has higher bio-based content, higher environmental protection effect, is aliphatic aqueous polyurethane resin, has excellent weather resistance and ageing resistance, and can be used outdoors or in occasions with higher weather resistance requirements.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a bio-based aqueous polyurethane resin and a preparation method and application thereof.
Background
With the improvement of human life quality, the emission of Volatile Organic Compounds (VOCs) and the content of harmful solvents are required to be more strictly limited, so that the production of aqueous polyurethane by adopting biomass raw materials with higher environmental protection effect has become the mainstream of the development of the era.
In recent years, the main raw materials for preparing the waterborne polyurethane, such as isocyanate, dihydric alcohol and polyester dihydric alcohol, are mainly petroleum, and the use amount of the raw materials needs to be controlled in the face of the severe reality that petroleum resources are gradually depleted. At present, the bio-based waterborne polyurethane is mainly prepared by adopting natural renewable resources as the basis to replace or partially replace polyester diol or modifying the waterborne polyurethane, so that the performance of the product is improved, the energy crisis caused by petroleum resources can be relieved, and the current sustainable development requirement is met. Therefore, continuously increasing the bio-based proportion of the raw materials of the aqueous polyurethane resin, further reducing the long-term harm to the environment caused by excessive exploitation of petroleum, and simultaneously improving the stability, hydrolysis resistance, weather resistance and other properties of the polyurethane, and gradually becoming a major research and development direction and a problem to be solved in the field.
Disclosure of Invention
Based on the above, it is necessary to provide a bio-based aqueous polyurethane resin with high environmental protection effect, and a preparation method and application thereof.
A secondary amino bio-based hydrophilic chain extender having the structure of formula (I):
Wherein R 1 and R 2 are each independently an isocyanate non-reactive organic group, preferably C 1-4 alkyl;
R 3 and R 4 are each independently hydrogen or an isocyanate non-reactive organic group.
A preparation method of a bio-based secondary amine hydrophilic chain extender comprises the following steps:
carrying out Michael addition reaction on the first reagent and the second reagent, and carrying out de-esterification reaction on the obtained product to obtain the bio-based secondary amine hydrophilic chain extender;
Wherein the first reagent is lysine ester; the second reagent is maleate or fumarate.
In some of these embodiments, the lysine ester is a C 1-4 alkyl ester of lysine or a benzyl ester of lysine;
the second reagent has the following structure:
R1OOC-CR3＝CR4-COOR2
Wherein R 1 and R 2 are each independently an isocyanate non-reactive organic group, preferably C 1-4 alkyl; r 3 and R 4 are each independently hydrogen or an isocyanate non-reactive organic group.
In some of these embodiments, the molar ratio of the first reagent to the second reagent is 1 (2.3-2.5).
In some of these embodiments, the first reagent is benzyl lysine, and the method of preparation comprises the steps of:
Mixing lysine benzyl ester, alkali and a solvent, dropwise adding a solution of the second reagent in an inert gas atmosphere at the temperature of 40-50 ℃, reacting completely at the temperature of 60-65 ℃ after the completion of the dropwise adding, and obtaining a crude product after post-treatment;
and (3) carrying out debenzylation reaction on the crude product to obtain the bio-based secondary amine hydrophilic chain extender.
The application of the secondary biological amine hydrophilic chain extender or the secondary biological amine hydrophilic chain extender prepared by the preparation method in the preparation of the bio-based aqueous polyurethane resin.
The preparation method of the bio-based aqueous polyurethane resin comprises the following steps:
mixing the raw materials for polymerization reaction to obtain the bio-based aqueous polyurethane resin;
wherein, the raw materials comprise, by weight:
the secondary biological amine hydrophilic chain extender is prepared from the secondary biological amine hydrophilic chain extender or the preparation method.
In some of these embodiments, the step of preparing the bio-based aqueous polyurethane resin comprises the steps of:
Reacting the dehydrated polyol, the bio-based diisocyanate, the bio-based polycarbodiimide and the catalyst at 70 ℃ to 90 ℃ for a predetermined time;
cooling to 50-65 ℃, adding the micromolecular alcohol chain extender and an organic solvent, and reacting for a preset time under the condition of 70-90 ℃;
Cooling to below 30 ℃, adding the bio-based secondary amine hydrophilic chain extender and an organic solvent, and reacting for a preset time under the condition of 15-30 ℃;
adding a neutralizing agent and water, uniformly dispersing, adding an aqueous solution of the bio-based diamine chain extender, stirring, and distilling to remove an organic solvent to obtain the bio-based aqueous polyurethane resin;
Wherein the organic solvent is an organic solvent which is miscible with water.
In some of these embodiments, the biobased diisocyanate is 1, 5-pentamethylene diisocyanate; and/or
The biobased polycarbodiimide is a small molecular oligomer taking 1, 5-pentamethylene diisocyanate as a reaction monomer, and the polymerization degree of the oligomer is less than or equal to 6;
the polyol is polyester diol, polycarbonate diol and polyether diol with the number average molecular weight of 500-5000, preferably polyester diol, polycarbonate diol and polyether diol with the number average molecular weight of 1000-3000;
the catalyst is an organotin catalyst or an organozinc catalyst;
the neutralizing agent is triethylamine or triethanolamine;
the small molecular alcohol chain extender is bio-based 1, 3-propanediol;
The bio-based diamine chain extender is at least one of 1, 5-pentamethylene diamine and lysine.
A bio-based aqueous polyurethane resin comprising structural units of:
Wherein: r is ethyl or hydroxyethyl;
R 1 and R 2 are each independently an isocyanate non-reactive organic group, preferably C 1-4 alkyl;
R 3 and R 4 are each independently hydrogen or an isocyanate non-reactive organic group; n is an integer less than or equal to 6, preferably 4, 5 and 6;
r' is C 5H10 or
The bio-based aqueous polyurethane resin prepared by the preparation method or the application of the bio-based aqueous polyurethane resin in preparing paint or adhesive.
The invention has the following beneficial effects:
The bio-based hydrophilic secondary amine chain extender can effectively and continuously improve the bio-based proportion of the aqueous polyurethane dispersion raw material, improve the stability of aqueous polyurethane emulsion, add bio-based polycarbodiimide to react with other components, introduce the bio-based polycarbodiimide into the main chain structure of polyurethane, and radically solve the problem of poor hydrolysis resistance of aqueous polyurethane products. And most of the components belong to biological base materials, so that the content of biological base in the aqueous polyurethane can be effectively improved, the sources of raw materials are wide, the dependence on non-renewable resources such as petroleum can be effectively reduced, and the environment-friendly polyurethane has a high environment-friendly effect.
The bio-based aqueous polyurethane is aliphatic aqueous polyurethane resin, has excellent weather resistance and ageing resistance, can be used outdoors or in occasions with higher weather resistance requirements, and has the advantages of mild preparation process conditions, low energy consumption, good product stability, excellent performance and easy scale-up production.
Detailed Description
The present invention will be described more fully hereinafter in order to facilitate an understanding of the present invention, and preferred embodiments of the present invention are set forth. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
In the description of the present invention, it should be understood that the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
The weights of the relevant components mentioned in the description of the embodiments of the present invention may refer not only to the specific contents of the components, but also to the proportional relationship between the weights of the components, so long as the contents of the relevant components in the description of the embodiments of the present invention are scaled up or down within the scope of the disclosure of the embodiments of the present invention. Specifically, the weight described in the specification of the embodiment of the invention can be mass units known in the chemical industry field such as mu g, mg, g, kg.
The first aspect of the invention provides a bio-based secondary amine hydrophilic chain extender having a structure represented by formula (I):
Wherein R 1 and R 2 are each independently an isocyanate non-reactive organic group;
R 3 and R 4 are each independently hydrogen or an isocyanate non-reactive organic group.
The invention adopts the bio-based secondary amine hydrophilic chain extender with an asymmetric structure shown in the formula (I) as a bio-based reagent, and has at least the following advantages:
1) Compared with primary amine with higher reactivity, the conversion rate of the polyurethane resin prepared by using the polyurethane resin as a raw material can be greatly improved (the conversion rate of secondary amine of the invention can reach 100 percent basically). And the secondary amino group of the biological secondary amine hydrophilic chain extender can form a urea bond with isocyanate, so that the mechanical property of polyurethane can be obviously improved.
2) The bio-based secondary amine hydrophilic chain extender can be obtained only by adopting lysine ester and maleic acid ester or fumaryl acid ester to carry out Michael addition reaction, has wide raw material sources, mild reaction and low energy consumption, solves the problems of high reaction activity, difficult control of a reaction process, easy occurrence of gel phenomenon and the like of the common primary amine hydrophilic chain extender, and can also solve the problems of high reaction temperature and high energy consumption of the traditional hydroxy carboxylic acid hydrophilic chain extender.
3) The bio-based secondary amine hydrophilic chain extender is a bio-based renewable resource, can improve the bio-based proportion of the water-based polyurethane dispersion raw material, can be used by being compounded with other bio-based reagents (such as bio-based diisocyanate), has a large bio-based source proportion of a final product, and meets the requirements of modern environmental protection and sustainable development.
It is understood that the term "isocyanate non-reactive organic group" as used herein refers to an organic group that is not reactive with isocyanate, and the specific type is not particularly limited and is understood to be within the scope of the present invention.
In some embodiments, R 1 and R 2 are each independently C 1-4 alkyl; further, R 1 and R 2 are each independently methyl, ethyl or n-butyl.
In some embodiments, R 3、R4 is hydrogen.
The second aspect of the invention provides a preparation method of a bio-based secondary amine hydrophilic chain extender, which comprises the following steps:
S100: carrying out Michael addition reaction on the first reagent and the second reagent, and carrying out de-esterification reaction on the obtained product to obtain the bio-based secondary amine hydrophilic chain extender; wherein the first reagent is lysine ester; the second agent is maleate or fumarate.
The technical staff of the invention find in the research that the bio-based secondary amine hydrophilic chain extender with asymmetric secondary amine and carboxyl can be obtained by taking asymmetric lysine ester as a raw material and performing the de-esterification reaction of the lysine ester, the stability of polyurethane emulsion can be improved, the conversion rate of the bio-based secondary amine hydrophilic chain extender is high, and the conversion rate of the secondary amine can reach 100%. In contrast, if lysine is directly used as a reactant without protecting an ester group, the yield is affected because lysine is easily subjected to self-polymerization. The carboxyl is protected by adopting the ester group, the second reagent can be slightly excessive in the reaction process, the reaction is stopped after the reaction degree reaches 100% by adopting the iodometry, and then the esterification is carried out for protection, so that the bio-based secondary amine hydrophilic chain extender is obtained, the operation is simple, and the yield is high; meanwhile, the secondary amine group can form urea bond with isocyanate, so that the mechanical property of the product can be improved.
It is understood that the "bio-based secondary amine hydrophilic chain extender" of the present invention may be separated from the reaction system, may be used as a pure substance without separation, or may be used as a mixture, and is understood to be within the scope of the present invention.
It will be appreciated that in step S100, the ester groups removed by the de-esterification reaction may be selected as desired, preferably to form the structure of formula (I).
In some embodiments, the lysine ester is a lysine alkyl ester and/or a lysine aryl ester; further, the lysine ester is lysine C 1-4 alkyl ester and/or lysine benzyl ester; further, the lysine ester is one or more of lysine benzyl ester, lysine methyl ester and lysine tert-butyl ester; preferably benzyl lysine; further, lysine dibenzyl ester p-toluenesulfonate is preferable; the method is easy to hydrogenate and remove benzyl in the synthesis process, so that the product yield can be improved.
In some embodiments, the second agent has the following structure:
R1OOC-CR3＝CR4-COOR2
Wherein R 1 and R 2 are each independently an isocyanate non-reactive organic group;
R 3 and R 4 are each independently hydrogen or an isocyanate non-reactive organic group.
Further, R 1 and R 2 are each independently C 1-4 alkyl; further, R 1 and R 2 are each independently methyl, ethyl or n-butyl.
In some embodiments, R 3、R4 is hydrogen.
In some embodiments, the second agent is dimethyl maleate, diethyl maleate, dipropyl maleate, dibutyl maleate, dimethyl maleate, diethyl maleate, dipropyl maleate, or dibutyl maleate.
In some embodiments, the molar ratio of the first reagent to the second reagent is 1:2.3-2.5. On the basis that the ratio of raw materials is controlled within the range, the yield and purity can be ensured, the residues of unreacted raw materials and byproducts are reduced as much as possible, and the difficulty of post-treatment is reduced.
Further, the preparation method of the bio-based secondary amine hydrophilic chain extender comprises the following steps:
S101: carrying out Michael addition reaction on the first reagent and the second reagent to obtain a crude product;
the first reagent and the second reagent are characterized as described above and will not be described in detail herein.
In some embodiments, the first reagent is benzyl lysine, which may be present in the form of a salt, such as dibenzyl lysine p-toluenesulfonate.
In some embodiments, step S101 includes the steps of: mixing lysine dibenzyl ester p-toluenesulfonate, alkali and solvent, dropwise adding a solution of a second reagent in an inert gas atmosphere at 40-50 ℃, and reacting at 60-65 ℃ after the completion of dropwise adding.
In some embodiments, in step S101, the base employed in the michael addition is sodium ethoxide and the solvent is Dimethylformamide (DMF).
In some embodiments, step S101 further includes a post-processing step, where the post-processing method is: the reaction solution was washed with water, extracted, and the solvent was distilled off.
S102: and (3) carrying out debenzylation reaction on the crude product to obtain the biological secondary amine hydrophilic chain extender.
The prior art debenzylation method may be used in step S102, and is not particularly limited herein, and should be understood to be within the scope of the present invention.
The third aspect of the invention provides an application of the secondary bio-amine hydrophilic chain extender prepared by the preparation method of the first aspect or the secondary bio-amine hydrophilic chain extender prepared by the preparation method of the second aspect in preparation of the secondary bio-amine aqueous polyurethane resin.
In a fourth aspect, the present invention provides a biobased polycarbodiimide, which is a small molecular oligomer using 1, 5-pentamethylene diisocyanate as a reaction monomer, and further, which is a small molecular polymer prepared by MPPO (3-methyl-1-phenyl-2-phosphole-1-oxide) catalyzed reaction of 1, 5-Pentamethylene Diisocyanate (PDI), specifically:
Wherein R is pentamethylene; n is an integer greater than or equal to 1;
in some embodiments, n.ltoreq.6; further, n is 4, 5 or 6. Wherein the polymerization degree can be obtained by titrating NCO% by using di-n-butylamine method (HG-T4144-2010).
The polymerization degree (n) is controlled within the range, so that the proper number of imino groups is ensured, the water resistance of the resin is improved, the emulsion can have better stability, and the problem that the solid content of the product is influenced by adding a large amount of water when the viscosity is too high, or even the stability of the product is influenced by the too high viscosity is avoided.
According to a fifth aspect of the present invention, there is provided a method for preparing the bio-based polycarbodiimide according to the fourth aspect, comprising the steps of:
and (3) placing 1, 5-Pentamethylene Diisocyanate (PDI) and a catalyst (such as MPPO) in an inert gas atmosphere to react at 160-220 ℃, and after a preset time of reaction, carrying out post-treatment to obtain the bio-based polycarbodiimide.
In some embodiments, the reaction temperature is 170 ℃ to 190 ℃; in some embodiments, the MPPO is added in an amount of 0.2wt.% to 0.5wt.% of the mass of the biobased diisocyanate.
In some embodiments, the post-treatment is by distillation under reduced pressure to remove the catalyst and unreacted complete biobased diisocyanate.
The sixth aspect of the invention provides a preparation method of a bio-based aqueous polyurethane resin, comprising the following steps:
s200: mixing the raw materials for polymerization reaction to obtain bio-based aqueous polyurethane resin;
the secondary amino acid hydrophilic chain extender is the secondary amino acid hydrophilic chain extender of the first aspect of the invention or the secondary amino acid hydrophilic chain extender of the second aspect of the invention.
The bio-based secondary amine hydrophilic chain extender can effectively improve the stability of the aqueous polyurethane emulsion, and the bio-based polycarbodiimide is added into the components to react with other components, so that the bio-based polycarbodiimide is introduced into the main chain structure of polyurethane, the problem of poor hydrolysis resistance of the existing aqueous polyurethane product can be fundamentally solved, and the bio-based aqueous polyurethane resin has better mechanical properties. And most of the components belong to biological base materials, so that the content of biological base in the aqueous polyurethane can be effectively improved, the sources of raw materials are wide, the dependence on non-renewable resources such as petroleum can be effectively reduced, and the environment-friendly polyurethane has a high environment-friendly effect.
In some embodiments, the bio-based polycarbodiimide and the preparation method thereof are as described in the fourth and fifth aspects of the present invention, and will not be described in detail herein.
In some embodiments, the biobased diisocyanate is 1, 5-pentamethylene diisocyanate;
In some embodiments, the polyol is one or more of a polyester diol, a polycarbonate diol, and a polyether diol. In some embodiments, the polyol is a combination of a polyester diol and a polyether diol; further, the mass ratio of the polyester diol to the polyether diol is 1:0.05-0.2.
In some embodiments, the polyester diol has a number average molecular weight of 500 to 5000; preferably 1000 to 3000; further, the polyester diol is poly (1, 4-butylene glycol) adipate (PBA).
In some embodiments, the polyether glycol has a number average molecular weight of 500 to 5000; preferably 1000 to 3000; further, the polyether glycol is one or more of 1, 3-propanediol polyether glycol and castor oil glycol.
In some embodiments, the catalyst is one or more of an organotin-based catalyst and an organozinc-based catalyst, preferably an organotin-based catalyst; further, the catalyst is dibutyl tin laurate.
In some embodiments, the neutralizing agent is one or more of triethylamine, diethanolamine, and triethanolamine.
In some embodiments, the small molecule alcohol chain extender is one or more of 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol. Preferably 1, 3-propanediol is used to increase the biobased content.
In some embodiments, the biobased diamine chain extender is one or more of 1, 5-pentamethylene diamine and lysine.
Further, step S200 includes the steps of:
S201: reacting the polyol, the bio-based diisocyanate, the bio-based polycarbodiimide and the catalyst after vacuum dehydration for a preset time at the temperature of 70-90 ℃;
S202: cooling to 50-65 ℃, adding a small molecular alcohol chain extender and an organic solvent, and reacting for a preset time at 70-90 ℃;
S203: cooling to below 30 ℃, adding a bio-based secondary amine hydrophilic chain extender and an organic solvent, and reacting for a preset time under the condition of 15-30 ℃;
s204: adding a neutralizing agent and water, uniformly dispersing, adding an aqueous solution of a bio-based diamine chain extender, stirring, and distilling to remove an organic solvent to obtain bio-based aqueous polyurethane resin;
wherein the organic solvent is water-miscible organic solvent.
The reagents in steps S201 to S204 are as described above, and will not be described in detail here.
In some embodiments, the step of step S201 further comprises a step of pre-treating the polyol to bring the water content of the polyol to below 0.05 wt%; further, the step S201 includes the following steps: placing the polyol under vacuum degree-0.09 MPa, at 115-120deg.C, drying for more than 2h until the water content is below 0.05wt%.
In some embodiments, the reaction time in step S201 is 1-3 hours; in some embodiments, in step S202, the reaction time is 0.5h to 1.5h; in some embodiments, in step S203, the reaction time is 20min-40min;
In some embodiments, step S204 includes the steps of: adding a neutralizing agent and an organic solvent, stirring for 20-40min, adding water, dispersing at high speed (preferably at a rotation speed of 1500-3000 rpm) for 15-20min, distilling to remove the organic solvent, and filtering the rest water solution to obtain the required aqueous polyurethane resin.
In some embodiments, the organic solvent is acetone.
The preparation method of the bio-based aqueous polyurethane resin is simple to operate, wide in sources of production raw materials, mild in conditions, low in energy consumption, good in product stability and excellent in water resistance.
The seventh aspect of the invention provides a bio-based aqueous polyurethane resin comprising the following structural units:
Wherein: r is ethyl or hydroxyethyl; r 1 and R 2 are each independently an isocyanate non-reactive organic group; r 3 and R 4 are each independently hydrogen or an isocyanate non-reactive organic group; n is an integer less than or equal to 6, preferably 4, 5 and 6; r' is C 5H10 or
In some embodiments, R 1 and R 2 are each independently C 1-4 alkyl; further, R 1 and R 2 are each independently methyl, ethyl or n-butyl. In some embodiments, R 3、R4 is hydrogen.
The bio-based aqueous polyurethane resin can fundamentally solve the problem of poor hydrolysis resistance of aqueous polyurethane products. In addition, the bio-based aqueous polyurethane with the structure has higher bio-based content, higher environmental protection effect, is aliphatic aqueous polyurethane resin, has excellent weather resistance and ageing resistance, and can be used outdoors or in occasions with higher weather resistance requirements.
The present invention is described below by way of specific examples, which are given by way of illustration only and should not be construed to limit the present invention.
Example 1
(1) Synthesis of biological polycarbodiimide
Introducing nitrogen into a reactor provided with an electric stirring, temperature control, reflux condensation and nitrogen protection device, slowly adding 1, 5-pentamethylene diisocyanate, heating to 180 ℃, adding an organophosphorus catalyst MPPO (3-methyl-1-phenyl-2-phosphole-1-oxide), wherein the catalyst dosage is 0.2-0.5 wt.% of reactant 1, 5-pentamethylene diisocyanate, controlling the value (HG-T4144-2010) for measuring the reduction of the-NCO content of the solution in real time to obtain the bio-based polycarbodiimide with the average polymerization degree of not more than 6, removing the catalyst and unreacted PDI by reduced pressure distillation, and sealing and preserving at low temperature after rapid cooling to obtain the bio-based polycarbodiimide for later use;
(2) Synthesis of bio-based secondary amine hydrophilic chain extender
Adding a certain amount of L-lysine benzyl ester p-toluenesulfonic acid disodium salt (cas: 16259-78-2) into a reactor with a stirring, temperature control and nitrogen protection device at room temperature, starting stirring, introducing nitrogen, and slowly dropwise adding diethyl maleate after heating to 40-50 ℃ under alkaline conditions (wherein the mass ratio of the diethyl maleate to the L-lysine is 2.3-2.5:1); after the dripping is finished, heating to 60-65 ℃ to continue the reaction for 20-24 hours, measuring the unsaturation degree of the system according to an iodometry, and stopping the reaction after the conversion rate of the reactant reaches 100% to obtain a reaction solution; and then washing, extracting and distilling the reaction solution to obtain a crude product, and then carrying out hydrogenation debenzylation reaction under the action of a catalyst Pd/C to obtain a bio-based secondary amine hydrophilic chain extender product for later use.
(3) Synthesis of bio-based aqueous polyurethane
600G of PBA (Mn=2000) is added into a reaction device with stirring, temperature control and reflux condensation, and vacuum drying is carried out for more than 2 hours at the temperature of 115-120 ℃ under the vacuum degree of minus 0.09MPa until the moisture content reaches below 0.05wt% and the vacuum is replaced by nitrogen; cooling to 60 ℃, sequentially adding 300g of PDI, 15g of biological polycarbodiimide in the step (1) and 0.8g of dibutyl tin laurate (T12), heating to 80 ℃ and reacting for 2 hours; cooling to 60 ℃, adding 50g of 1, 3-propanediol and 50g of acetone, heating to 80 ℃ and continuing to react for 1 hour; cooling to 25 ℃, adding 60g of the bio-based secondary amine hydrophilic chain extender (3-6%) obtained in the step (2), and 100g of acetone, and keeping the temperature at 25 ℃ for continuous reaction for 0.5h; 100g of acetone and 13g of triethylamine are added, and 1700g of distilled water is added after 30min of reaction; transferring all materials in the reactor to a high-speed dispersing agent, dispersing at a high speed of 2000rpm, slowly dripping 36g of lysine water solution, and stirring at a high speed for 15-20 min; finally, acetone is removed by reduced pressure distillation, and the bio-based aqueous polyurethane resin product of the example 1 is obtained after filtering by a 100-mesh nylon net and discharging.
Example 2-example 4
The preparation process of examples 2-4 is substantially similar to example 1, except for the types and amounts of raw materials, as shown in Table 1.
Comparative example 1
The preparation process of comparative example 1 is substantially similar to that of example 1, except for the kinds and amounts of raw materials, see Table 1. In comparative example 1, a low-temperature reaction (below 5 ℃) was required when the hydrophilic chain extender was added, otherwise, the reactivity was large, the local reaction rate was easily too high, and the gel reaction was easily controlled to occur.
Performance testing
The bio-based aqueous polyurethane resin products of examples 1 to 4 and comparative example 1 were subjected to performance tests, and each index test method was as follows, and the test results are shown in table 1.
The solid content was tested according to GB 1725-2007;
The tensile strength of the cured film was tested according to GB/T1040.3-2006;
the tensile strength after hydrolysis is that the product is placed in water for 3 days and then the tensile property is tested;
The tensile strength retention refers to the number of tensile strength after hydrolysis divided by the percentage of tensile strength before hydrolysis.
TABLE 1
* Note 1: lysine is primary amine, has high reaction activity, and when used as a hydrophilic chain extender, the reaction time, the dripping speed and the reaction temperature need to be strictly controlled, and the experiment is completed in a manner of dripping for 30 minutes at 5 ℃ and reducing the dosage in the embodiment, so that the step is not easy to control during the amplified production.
Experimental results:
As can be seen from Table 1 above, the bio-based aqueous polyurethanes of examples 1 to 4 have very excellent mechanical strength and hydrolysis resistance, and each property is significantly improved as compared with comparative example 1. The bio-based aqueous polyurethane resin disclosed by the invention can fundamentally solve the problem of poor hydrolysis resistance of aqueous polyurethane products, and has better mechanical properties. In addition, the water-based polyurethane dispersion raw material has high bio-based proportion, can further reduce the long-term harm to the environment caused by excessive exploitation of petroleum, and has higher environmental protection effect.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. The preparation method of the bio-based aqueous polyurethane resin is characterized by comprising the following steps of:
carrying out polymerization reaction on the raw materials to obtain the bio-based aqueous polyurethane resin;
wherein, the raw materials comprise, by weight:
The bio-based secondary amine hydrophilic chain extender has a structure shown in a formula (I):
（I）；
Wherein R 1 and R 2 are each independently C 1-4 alkyl;
R 3 and R 4 are each independently hydrogen;
the small molecular alcohol chain extender is bio-based 1, 3-propanediol;
the bio-based diamine chain extender is at least one of 1, 5-pentamethylene diamine and lysine;
the biobased diisocyanate is 1, 5-pentamethylene diisocyanate;
the biobased polycarbodiimide is a small molecular oligomer taking 1, 5-pentamethylene diisocyanate as a reaction monomer, and the polymerization degree of the oligomer is less than or equal to 6;
The step of preparing the bio-based aqueous polyurethane resin comprises the following steps:
Reacting the dehydrated polyol, the bio-based diisocyanate, the bio-based polycarbodiimide and the catalyst at 70 ℃ to 90 ℃ for a predetermined time;
cooling to 50-65 ℃, adding the micromolecular alcohol chain extender and an organic solvent, and reacting for a preset time under the condition of 70-90 ℃;
Cooling to below 30 ℃, adding the bio-based secondary amine hydrophilic chain extender and an organic solvent, and reacting for a preset time under the condition of 15-30 ℃;
Adding the neutralizer and water, dispersing uniformly, adding the aqueous solution of the bio-based diamine chain extender, stirring, and distilling to remove the organic solvent to obtain the bio-based aqueous polyurethane resin;
Wherein the organic solvent is an organic solvent which is miscible with water.
2. The preparation method of claim 1, wherein the preparation method of the bio-based secondary amine hydrophilic chain extender is as follows:
S101: carrying out Michael addition reaction on the first reagent and the second reagent to obtain a crude product; the first reagent is lysine benzyl ester, the second reagent is maleic acid ester or fumaric acid ester, and the molar ratio of the first reagent to the second reagent is 1 (2.3-2.5);
The method also comprises a post-treatment step, and the post-treatment method comprises the following steps: washing the reaction solution with water, extracting, and distilling to remove the solvent;
S102: and (3) carrying out debenzylation reaction on the crude product to obtain the bio-based secondary amine hydrophilic chain extender.
3. The method according to claim 2, wherein the base used in the michael addition is sodium ethoxide and the solvent is dimethylformamide.
4. The method according to claim 1, wherein the polyol is a polyester diol, a polycarbonate diol, or a polyether diol having a number average molecular weight of 500 to 5000;
the catalyst is an organotin catalyst or an organozinc catalyst;
the neutralizing agent is triethylamine or triethanolamine.
5. The method according to claim 1, wherein the polyol is a polyester diol, a polycarbonate diol, or a polyether diol having a number average molecular weight of 1000 to 3000.
6. The preparation method of claim 1, wherein the 1, 5-pentamethylene diisocyanate and the catalyst MPPO are placed in an inert gas atmosphere for reaction at 160-220 ℃, and after the reaction is carried out for a preset time, the bio-based polycarbodiimide is obtained by post-treatment.
7. The preparation method according to claim 6, wherein the catalyst MPPO is added in an amount of 0.2wt.% to 0.5wt.% based on the mass of the bio-based diisocyanate.
8. The method according to claim 6, wherein the reaction temperature is 170 ℃ to 190 ℃.
9. The bio-based aqueous polyurethane resin is characterized by being prepared by the preparation method according to any one of claims 1-8.
10. The application of the bio-based aqueous polyurethane resin prepared by the preparation method of any one of claims 1-8 or the bio-based aqueous polyurethane resin of claim 9 in the preparation of paint or adhesive.
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