CN115820090B - Single-component hybrid non-isocyanate polyurethane coating and preparation method thereof - Google Patents
Single-component hybrid non-isocyanate polyurethane coating and preparation method thereof Download PDFInfo
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- CN115820090B CN115820090B CN202211425639.5A CN202211425639A CN115820090B CN 115820090 B CN115820090 B CN 115820090B CN 202211425639 A CN202211425639 A CN 202211425639A CN 115820090 B CN115820090 B CN 115820090B
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- diglycidyl ether
- isocyanate polyurethane
- polyurethane coating
- cyclic carbonate
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- 239000012948 isocyanate Substances 0.000 title claims abstract description 43
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000011527 polyurethane coating Substances 0.000 title claims description 29
- -1 cyclic carbonate compound Chemical class 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 239000004593 Epoxy Substances 0.000 claims abstract description 29
- 239000003822 epoxy resin Substances 0.000 claims abstract description 21
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 239000011248 coating agent Substances 0.000 claims abstract description 17
- 238000000576 coating method Methods 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 9
- 150000001412 amines Chemical class 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000002562 thickening agent Substances 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 12
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 8
- 229920001296 polysiloxane Polymers 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000004359 castor oil Substances 0.000 claims description 5
- 235000019438 castor oil Nutrition 0.000 claims description 5
- 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 claims description 5
- 229910052755 nonmetal Inorganic materials 0.000 claims description 5
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 4
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 4
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 claims description 4
- UUODQIKUTGWMPT-UHFFFAOYSA-N 2-fluoro-5-(trifluoromethyl)pyridine Chemical compound FC1=CC=C(C(F)(F)F)C=N1 UUODQIKUTGWMPT-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 4
- RXMRGBVLCSYIBO-UHFFFAOYSA-M tetramethylazanium;iodide Chemical compound [I-].C[N+](C)(C)C RXMRGBVLCSYIBO-UHFFFAOYSA-M 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- YQMXOIAIYXXXEE-UHFFFAOYSA-N 1-benzylpyrrolidin-3-ol Chemical compound C1C(O)CCN1CC1=CC=CC=C1 YQMXOIAIYXXXEE-UHFFFAOYSA-N 0.000 claims description 3
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000440 bentonite Substances 0.000 claims description 3
- 229910000278 bentonite Inorganic materials 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- 239000013530 defoamer Substances 0.000 claims description 3
- 229910021485 fumed silica Inorganic materials 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920000768 polyamine Polymers 0.000 claims description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000003973 paint Substances 0.000 abstract description 10
- 239000004814 polyurethane Substances 0.000 abstract description 10
- 229920002635 polyurethane Polymers 0.000 abstract description 10
- 238000001816 cooling Methods 0.000 abstract description 9
- 238000001914 filtration Methods 0.000 abstract description 8
- 231100000331 toxic Toxicity 0.000 abstract description 4
- 230000002588 toxic effect Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000002518 antifoaming agent Substances 0.000 description 4
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 229960001124 trientine Drugs 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000011120 smear test Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002937 thermal insulation foam Substances 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to single-component hybridized non-isocyanate polyurethane, in particular to single-component hybridized non-isocyanate polyurethane paint and a preparation method thereof. The method comprises the following steps: firstly, adding a multifunctional epoxy compound and a nonmetallic catalyst into a high-pressure reaction kettle, introducing nitrogen to discharge air in the high-pressure kettle, and introducing CO when the temperature rises to a set temperature 2 Starting the reaction of the gas under a certain pressure, cooling and exhausting after a certain time of reaction, and filtering the product to obtain a cyclic carbonate compound; then, adding the obtained cyclic carbonate compound, an amine curing agent, a solvent and a catalyst into a reactor, and stirring and reacting for a period of time at a certain temperature; finally, adding epoxy resin, other micromolecular epoxy compounds and solvent, continuously stirring at a certain temperature, and adding an auxiliary agent. The coating obtained by the invention is a single-component coating, is simple and convenient to construct, avoids the use of toxic isocyanate compounds during synthesis, and is safer.
Description
Technical Field
The invention relates to single-component hybridized non-isocyanate polyurethane, in particular to single-component hybridized non-isocyanate polyurethane paint and a preparation method thereof.
Background
Polyurethane is a generic name of polymers containing repeated carbamate groups in molecular structures, has wide application due to excellent flexibility, wear resistance and other properties, and can be used as coating, adhesive, thermal insulation foam materials and the like; among them, in the paint application, it is generally used for advanced wooden furniture, and also for metal surfaces.
At present, common raw materials for synthesizing polyurethane materials comprise polymer polyol, isocyanate compound, small molecular chain extender and auxiliary agent, wherein the isocyanate compound is used as a main raw material, has strong volatility, has higher irritation and certain toxicity, and thus has larger harm to human bodies and the environment. The synthesis of industrial isocyanate mainly adopts a phosgene method, and extremely toxic phosgene can cause irreversible injury to operators and the environment; and the phosgene synthesis route has complex process and higher cost. In addition, isocyanate compounds are chemically active and easily react with compounds containing active hydrogen, and are easily reacted with water to generate CO 2 Thereby changing the stoichiometric ratio of the reactants, and simultaneously causing the defects of the surface and the inside of the polyurethane product and affecting the quality of the product.
Therefore, the application aims to provide a preparation method of a non-isocyanate polyurethane coating, which avoids the use of toxic isocyanate compounds in the preparation process, thereby effectively solving a series of problems brought about in the use process of isocyanate.
CN113999606a provides a two-component non-isocyanate polyurethane waterproof coating and a preparation method thereof, the polyurethane waterproof coating comprises two components, diamine resin, cyclic carbonate compound and catalyst are mixed or reacted to prepare macromolecular resin component, and then the macromolecular resin component is mixed with polyamine curing agent, auxiliary agent, additive and the like to prepare the coating.
CN114933846a discloses a non-isocyanate polyurethane coating, a preparation method and application thereof, the coating is prepared by mixing siloxane-containing cyclic carbonate and pentaerythritol cyclic carbonate and then curing the mixture with an amine curing agent, and the hydrophobic and oleophobic properties of the coating are improved through the introduction of organosilicon.
The paint is a bi-component non-isocyanate polyurethane paint, and when the paint is applied, the paint is firstly mixed according to the metering ratio and then is constructed, and the performance of the paint is possibly influenced due to the fact that the metering is wrong or the mixing is insufficient in the construction process; compared with the two-component coating, the one-component coating has the advantage of convenient storage and use, so the application process is relatively simple.
Disclosure of Invention
Based on the prior art, aiming at the defects of the two-component non-isocyanate polyurethane coating in the construction process, the invention aims to provide the one-component non-isocyanate polyurethane coating which is convenient to construct, does not need to be proportioned again before use and avoids the use of toxic compound isocyanate.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a preparation method of a one-component hybrid non-isocyanate polyurethane coating comprises the following steps:
(1) Firstly, adding a certain amount of multifunctional epoxy compound and nonmetal catalyst into an autoclave, introducing nitrogen to discharge air in the autoclave, and introducing CO when the temperature rises to a set temperature 2 Starting the reaction of the gas under a certain pressure, cooling and exhausting after a certain time of reaction, and filtering the product to obtain a cyclic carbonate compound;
(2) Then, adding the obtained cyclic carbonate compound, a certain amount of amine curing agent, solvent and catalyst into a reactor, and stirring and reacting for a period of time at a certain temperature;
(3) Finally, adding epoxy resin, other micromolecular epoxy compounds and solvent, continuously stirring at a certain temperature, and adding an auxiliary agent to obtain the single-component hybrid non-isocyanate polyurethane coating.
Further, in the step (1), the reaction temperature is 110-170 ℃, the reaction time is 10-50 h, and the pressure is 0.5-3.0 MPa; the reaction temperature in the step (2) is 50-70 ℃ and the reaction time is 2-5 h; the reaction temperature in the step (3) is 60-80 ℃ and the reaction time is 2-5 h.
Further, the multifunctional epoxy compound in the step (1) is one or more of 1, 4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether and neopentyl glycol diglycidyl ether; the amine curing agent in the step (2) is one or more of diethylenetriamine, triethylenetetramine, tetraethylenepentamine and polyethylene polyamine; the epoxy resin in the step (3) is one or more of bisphenol A type epoxy resin E-51, bisphenol A type epoxy resin E-54, bisphenol A type epoxy resin E-44, bisphenol F type epoxy resin, bisphenol S type epoxy resin and hydrogenated epoxy resin; the other small molecule epoxy compound in the step (3) is one or a combination of one or more of difunctional epoxy compounds polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, resorcinol diglycidyl ether and 1, 4-cyclohexanedimethanol diglycidyl ether and one or a combination of a plurality of trifunctional cycloaliphatic epoxy compounds TT386 and trimethylolpropane triglycidyl ether.
Further, the usage amount of the amine curing agent in the step (2) is 0.85 to 1.15 times of the amount of theoretical curing agent substances required by the cyclic carbonate and the epoxy compound; the dosage of the epoxy resin and other small molecular epoxy compounds in the step (3) is 0.9-1.1 times of the mass of the cyclic carbonate compound, wherein the proportion of the epoxy resin and other small molecular epoxy compounds is 0.3-0.5, and the proportion of the small molecular epoxy compounds is 0.8-1.5 as the combination of difunctional epoxy compounds and trifunctional epoxy compounds.
Further, the nonmetallic catalyst in the step (1) is macroporous resin loaded quaternary ammonium salt amine compound or carbon nitride catalyst; the catalyst in the step (2) is one or more of 1, 8-diazabicyclo [5.4.0] undec-7-ene, triethylene diamine and 2,4, 6-tris (dimethylaminomethyl) phenol; the auxiliary agent in the step (3) is one of modified polysiloxane flatting agent, organosilicon defoamer, organic bentonite thickener, hydrogenated castor oil thickener, polyamide wax thickener and fumed silica thickener.
Further, the non-metal catalyst in the step (1) is used in an amount of 5 to 15wt% (weight ratio) of the addition amount of the multifunctional epoxy compound; the dosage of the catalyst in the step (2) is 5-10% of the mass of the cyclic carbonate compound; the dosage of the auxiliary agent in the step (3) is 0.1-0.5% of the solid content except the solvent.
Further, the solvent in the step (2) is any one of N, N-dimethylformamide, N-dimethylacetamide, toluene, xylene, butanol and isopropanol; the solvent in the step (3) is any one of N, N-dimethylformamide, N-dimethylacetamide, toluene, xylene, butanol and isopropanol.
Further, the amount of the solvent used in the step (2) is 0.8 to 1.2 times the mass of the cyclic carbonate compound; the solid content of the single-component hybridized non-isocyanate polyurethane coating in the step (3) is 10-18%.
Further, the macroporous resin loaded quaternary ammonium salt amine compound in the step (1) is any one of tetrabutylammonium bromide, tetramethyl ammonium iodide and tetrabutylammonium chloride; the carbon nitride catalyst is prepared from urea or melamine precursor by roasting and washing.
A one-component hybrid non-isocyanate polyurethane coating is prepared by the preparation method; the hardness of a coating film formed by the single-component hybridized non-isocyanate polyurethane coating; the hardness of a coating film formed by the single-component hybridized non-isocyanate polyurethane coating is 2H-3H, the impact strength is more than or equal to 40cm, and the adhesive force is 1-2 grade; the flexibility was 1mm.
Compared with the prior art, the invention has the following advantages:
1. the cyclic carbonate compound is prepared by taking carbon dioxide as a raw material, so that the recycling utilization of the carbon dioxide is realized;
2. the use of toxic isocyanate compounds is avoided, the sensitivity of the paint to water vapor is reduced, and the foaming in the curing process of the paint is avoided;
3. the obtained coating is a single-component product, has simple construction process and does not need to be proportioned according to the metering ratio before use.
Drawings
FIG. 1 is an infrared spectrum of the one-component hybrid non-isocyanate polyurethane coating obtained by the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the following examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
(1) 75g of 1, 4-butanediol diglycidyl ether and 7.5g of tetramethyl ammonium iodide are added into a high-pressure reaction kettle, nitrogen is introduced to discharge air in the high-pressure kettle, and CO is introduced when the temperature rises to 130 DEG C 2 Gas, maintaining the pressure in the kettle at 2.0MPa to start reaction, cooling and exhausting after the reaction is carried out for 30 hours, and filtering the product to obtain the 1, 4-butanediol diglycidyl ether cyclic carbonate compound;
(2) 12g of 1, 4-butanediol diglycidyl ether cyclic carbonate compound, 5.04g of diethylenetriamine, 10g of N, N-dimethylformamide and 0.80g of 1, 8-diazabicyclo [5.4.0] undec-7-ene are added into a reactor, and stirred at 65 ℃ for reaction for 3 hours;
(3) Adding 4g bisphenol A epoxy resin E-51, 4g polypropylene glycol diglycidyl ether, 4gTT386 and N, N-dimethylformamide 180g into the reactor, continuously stirring at 80 ℃ for 3.5 hours, adding 0.035g modified polysiloxane flatting agent, 0.04g organosilicon defoamer and 0.045g hydrogenated castor oil thickener to obtain a one-component hybridized non-isocyanate polyurethane coating, as shown in figure 1, wherein the carbonyl group in the cyclic carbonate group in the raw material cyclic carbonate compound is 1790cm -1 The stretching vibration peak and epoxy group in the epoxy compound are at 846cm -1 And 910cm -1 The characteristic peak at the position is disappeared, and the corresponding position is 1700cm -1 Characteristic stretching vibration peaks of carbamate groups appear nearby, which prove that the polyurethane coating is successfully synthesized.
Example 2
(1) 75g of ethylene glycol diglycidyl ether and 3.75g of urea are added into a high-pressure reaction kettle, nitrogen is introduced to discharge air in the high-pressure kettle, and CO is introduced when the temperature rises to 120 DEG C 2 Maintaining the pressure in the kettle at 3.0MPa to start reaction, cooling and exhausting after 50 hours of reaction, and filtering the product to obtain the ethylene glycol diglycidyl ether cyclic carbonate compound;
(2) 12g of ethylene glycol diglycidyl ether cyclic carbonate compound, 5.80g of triethylene tetramine, 10g of N, N-dimethylacetamide and 0.80g of triethylene diamine are added into a reactor, and stirred at 50 ℃ for reaction for 5 hours;
(3) 3g of bisphenol A epoxy resin E-54, 4g of polypropylene glycol diglycidyl ether, 5gTT386 and 160g of dimethylbenzene are added into the reactor, and after the mixture is continuously stirred at 60 ℃ for 5 hours, 0.1g of modified polysiloxane flatting agent, 0.12g of organosilicon antifoaming agent and 0.005g of polyamide wax thickener are added to obtain the single-component hybrid non-isocyanate polyurethane coating.
Example 3
(1) 75g of 1, 4-butanediol diglycidyl ether and 11.25g of tetramethyl ammonium iodide are added into a high-pressure reaction kettle, nitrogen is introduced to discharge air in the high-pressure kettle, and CO is introduced when the temperature rises to 110 DEG C 2 Gas, maintaining the pressure in the kettle at 0.5MPa to start reaction, cooling and exhausting after 50 hours of reaction, and filtering the product to obtain the 1, 4-butanediol diglycidyl ether cyclic carbonate compound;
75g of neopentyl glycol diglycidyl ether and 11.25g of tetrabutylammonium bromide are added into an autoclave, nitrogen is introduced to discharge air in the autoclave, and CO is introduced when the temperature rises to 110 DEG C 2 Gas is used for maintaining the pressure in the kettle at 1.2MPa to start reaction, cooling and exhausting are carried out after the reaction is carried out for 43h, and the product is filtered to obtain the neopentyl glycol diglycidyl ether cyclic carbonate compound；
(2) 9g of butanediol diglycidyl ether cyclic carbonate compound and 3g of neopentyl glycol diglycidyl ether cyclic carbonate compound are added into a reactor, and reacted for 2 hours at 70 ℃ with 5.56g of diethylenetriamine, 14.4g of isopropanol and 0.85g of 2,4, 6-tris (dimethylaminomethyl) phenol;
(3) 4g of bisphenol A epoxy resin E-44, 2g of polypropylene glycol diglycidyl ether, 2g of polyethylene glycol diglycidyl ether, 4gTT g of N, N-dimethylformamide and 180g of N, N-dimethylformamide are added into the reactor, and after the mixture is continuously stirred and reacted for 4 hours at 72 ℃, 0.032g of modified polysiloxane leveling agent, 0.03g of organosilicon antifoaming agent, 0.025g of hydrogenated castor oil thickening agent and 0.02g of fumed silica thickening agent are added to obtain the single-component hybrid non-isocyanate polyurethane coating.
Example 4
(1) 75g of neopentyl glycol diglycidyl ether and 3.75g of tetrabutylammonium bromide were added to an autoclave, and nitrogen was introduced to discharge air from the autoclave, and CO was introduced when the temperature was raised to 115 ℃ 2 Maintaining the pressure in the kettle at 1.5MPa to start reaction, cooling and exhausting after 21h of reaction, and filtering the product to obtain the neopentyl glycol diglycidyl ether cyclic carbonate compound;
adding 75g of resorcinol diglycidyl ether and 3.75g of tetrabutylammonium chloride catalyst into a high-pressure reaction kettle, introducing nitrogen to discharge air in the high-pressure kettle, and introducing CO when the temperature rises to 118 DEG C 2 Maintaining the pressure in the kettle at 2.5MPa to start reaction, cooling and exhausting after 21h of reaction, and filtering the product to obtain resorcinol diglycidyl ether cyclic carbonate compound;
(2) 10g of neopentyl glycol diglycidyl ether cyclic carbonate compound and 2g of resorcinol diglycidyl ether cyclic carbonate compound are added to a reactor, and reacted with 9.62g of tetraethylenepentamine, 10g of toluene, 1.0g of 2,4, 6-tris (dimethylaminomethyl) phenol and 0.2g of triethylenediamine at 59℃for 3.2 hours with stirring;
(3) 3g of bisphenol A epoxy resin E-51, 4g of polyethylene glycol diglycidyl ether, 2g of resorcinol diglycidyl ether, 4gTT386 and 180g of dimethylbenzene are added into the reactor, and after the mixture is continuously stirred at 76 ℃ for 3.1h, 0.025g of modified polysiloxane leveling agent, 0.035g of organosilicon antifoaming agent and 0.045g of organic bentonite thickener are added to obtain the single-component hybrid non-isocyanate polyurethane coating.
Example 5
(1) 75g of ethylene glycol diglycidyl ether and 11.25g of urea are added into a high-pressure reaction kettle, nitrogen is introduced to discharge air in the high-pressure kettle, and CO is introduced when the temperature rises to 119 DEG C 2 Maintaining the pressure in the kettle at 1.8MPa to start reaction, cooling and exhausting after the reaction is carried out for 30.5 hours, and filtering the product to obtain the ethylene glycol diglycidyl ether cyclic carbonate compound;
(2) 12g of ethylene glycol diglycidyl ether cyclic carbonate compound, 2.4g of diethylenetriamine, 3.12g of triethylenetetramine, 10g of isopropanol and 0.80g of 1, 8-diazabicyclo [5.4.0] undec-7-ene are added into a reactor, and stirred and reacted for 4.7 hours at 56 ℃;
(3) 3g of bisphenol A type epoxy resin E-51, 1g of bisphenol A type epoxy resin E-54, 3g of polypropylene glycol diglycidyl ether, 1g of 1, 4-cyclohexanedimethanol diglycidyl ether, 2gTT g of trimethylolpropane triglycidyl ether and 195g of dimethylbenzene are added into the reactor, and after the mixture is continuously stirred at 80 ℃ for 3.5 hours, 0.032g of modified polysiloxane leveling agent, 0.045g of organosilicon antifoaming agent and 0.04g of hydrogenated castor oil thickening agent are added to obtain the single-component hybrid non-isocyanate polyurethane coating.
The coating obtained in each example was applied to the surface layer of a tinplate, and then left at room temperature for one week to obtain a corresponding smear, and performance test was performed, and the coating performance test results are shown in the following table:
as can be seen from the table, the obtained single-component hybrid non-isocyanate polyurethane coating has good adhesive force, higher hardness and good physical properties.
What is not described in detail in the present specification belongs to the prior art known to those skilled in the art. While the foregoing describes illustrative embodiments of the present invention to facilitate an understanding of the present invention by those skilled in the art, it should be understood that the present invention is not limited to the scope of the embodiments, but is to be construed as protected by the accompanying claims insofar as various changes are within the spirit and scope of the present invention as defined and defined by the appended claims.
Claims (6)
1. The preparation method of the single-component hybrid non-isocyanate polyurethane coating is characterized by comprising the following steps of:
(1) Firstly, adding a certain amount of multifunctional epoxy compound and nonmetal catalyst into an autoclave, introducing nitrogen to discharge air in the autoclave, and introducing CO when the temperature rises to a set temperature 2 The gas starts to react under a certain pressure, after a certain time of reaction, the temperature is reduced, the gas is exhausted, and the product is filtered and the solvent is removed to obtain the cyclic carbonate compound;
(2) Then, adding the obtained cyclic carbonate compound, a certain amount of amine curing agent, solvent and catalyst into a reactor, and stirring and reacting for a period of time at a certain temperature;
(3) Finally, adding epoxy resin, other micromolecular epoxy compounds and solvent, continuously stirring at a certain temperature, and adding an auxiliary agent to obtain the single-component hybrid non-isocyanate polyurethane coating;
the reaction temperature in the step (1) is 110-170 ℃, the reaction time is 10-50 h, and the pressure is 0.5-3.0 MPa; the reaction temperature in the step (2) is 50-70 ℃ and the reaction time is 2-5 h; the reaction temperature in the step (3) is 60-80 ℃ and the reaction time is 2-5 h;
the dosage of the nonmetal catalyst in the step (1) is 5-15 wt% of the adding amount of the multifunctional epoxy compound; the dosage of the amine curing agent in the step (2) is 0.85 to 1.15 times of the theoretical amount of the curing agent required by the cyclic carbonate and the epoxy compound; the dosage of the catalyst in the step (2) is 5-10% of the mass of the cyclic carbonate compound; the dosage of the solvent in the step (2) is 0.8 to 1.2 times of the mass of the cyclic carbonate compound; the dosage of the auxiliary agent in the step (3) is 0.1-0.5% of the solid except the solvent; the solid content of the single-component hybridized non-isocyanate polyurethane coating in the step (3) is 10% -18%;
the other small molecular epoxy compounds in the step (3) are the combination of one or more of difunctional epoxy compounds polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, resorcinol diglycidyl ether and 1, 4-cyclohexanedimethanol diglycidyl ether and one or more of trifunctional cycloaliphatic epoxy compounds TT386 and trimethylolpropane triglycidyl ether;
the total consumption of epoxy resin and other small molecular epoxy compounds in the step (3) is 0.9-1.1 times of the mass of the cyclic carbonate compound, wherein the ratio of the epoxy resin to the other small molecular epoxy compounds is 0.3-0.5, and the ratio of the small molecular epoxy compounds is 0.8-1.5 which are the combination of difunctional epoxy compounds and trifunctional epoxy compounds;
the catalyst in the step (2) is one or more of 1, 8-diazabicyclo [5.4.0] undec-7-ene, triethylene diamine and 2,4, 6-triphenol.
2. The method for preparing a one-component hybrid non-isocyanate polyurethane coating according to claim 1, wherein the multifunctional epoxy compound in the step (1) is one or more of 1, 4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, and neopentyl glycol diglycidyl ether; the amine curing agent in the step (2) is one or more of diethylenetriamine, triethylenetetramine, tetraethylenepentamine and polyethylene polyamine; the epoxy resin in the step (3) is one or more of bisphenol A type epoxy resin E-51, E-54, E-44, bisphenol F type epoxy resin, bisphenol S type epoxy resin and hydrogenated epoxy resin.
3. The method for preparing the one-component hybrid non-isocyanate polyurethane coating according to claim 1, wherein the non-metal catalyst in the step (1) is a macroporous resin supported quaternary ammonium salt amine compound or a carbon nitride catalyst; the auxiliary agent in the step (3) is one of modified polysiloxane flatting agent, organosilicon defoamer, organic bentonite thickener, hydrogenated castor oil thickener, polyamide wax thickener and fumed silica thickener.
4. The method for preparing the one-component hybrid non-isocyanate polyurethane coating according to claim 1, wherein the solvent in the step (2) is any one of N, N-dimethylformamide, N-dimethylacetamide, toluene, xylene, butanol and isopropanol; the solvent in the step (3) is any one of N, N-dimethylformamide, N-dimethylacetamide, toluene, xylene, butanol and isopropanol.
5. The preparation method of the one-component hybrid non-isocyanate polyurethane coating according to claim 3, wherein the macroporous resin loaded quaternary ammonium salt amine compound in the step (1) is any one of tetrabutylammonium bromide, tetramethylammonium iodide and tetrabutylammonium chloride; the carbon nitride catalyst is prepared from urea or melamine precursor by roasting and washing.
6. The coating prepared by the preparation method of the one-component hybrid non-isocyanate polyurethane coating according to any one of claims 1-5, wherein the hardness of a coating film formed by the one-component hybrid non-isocyanate polyurethane coating is 2H-3H, the impact strength is more than or equal to 40cm, and the adhesive force is 1-2 grade; the flexibility was 1mm.
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