CN116462805A - Preparation method and application of water-resistant impact-resistant waterborne polyurethane - Google Patents
Preparation method and application of water-resistant impact-resistant waterborne polyurethane Download PDFInfo
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 72
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 72
- XXSPGBOGLXKMDU-UHFFFAOYSA-M 2-bromo-2-methylpropanoate Chemical compound CC(C)(Br)C([O-])=O XXSPGBOGLXKMDU-UHFFFAOYSA-M 0.000 claims abstract description 22
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 12
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920003192 poly(bis maleimide) Polymers 0.000 claims abstract description 11
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims abstract description 10
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims abstract description 10
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 8
- 229920000570 polyether Polymers 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- XXSPGBOGLXKMDU-UHFFFAOYSA-N 2-bromo-2-methylpropanoic acid Chemical compound CC(C)(Br)C(O)=O XXSPGBOGLXKMDU-UHFFFAOYSA-N 0.000 claims description 23
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 12
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 11
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 10
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000005886 esterification reaction Methods 0.000 claims description 10
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 238000010008 shearing Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 230000001804 emulsifying effect Effects 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 abstract description 8
- 101710141544 Allatotropin-related peptide Proteins 0.000 abstract description 4
- 239000004970 Chain extender Substances 0.000 abstract description 3
- 238000005452 bending Methods 0.000 abstract description 3
- HLVFKOKELQSXIQ-UHFFFAOYSA-N 1-bromo-2-methylpropane Chemical group CC(C)CBr HLVFKOKELQSXIQ-UHFFFAOYSA-N 0.000 abstract description 2
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- 238000010382 chemical cross-linking Methods 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract description 2
- 230000002209 hydrophobic effect Effects 0.000 abstract description 2
- 229920001577 copolymer Polymers 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000004945 emulsification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- KCYAFUBVBKYBNO-UHFFFAOYSA-N 2-bromo-2-methylpropanoic acid;ethane-1,2-diol Chemical compound OCCO.CC(C)(Br)C(O)=O KCYAFUBVBKYBNO-UHFFFAOYSA-N 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 229920003225 polyurethane elastomer Polymers 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the technical field of polyurethane, and discloses a preparation method and application of water-resistant and impact-resistant waterborne polyurethane, wherein 2-bromoisobutyrate-based ethylene glycol is used as a micromolecular chain extender and polymerized with polyether glycol, isophorone diisocyanate and 2, 2-dimethylolpropionic acid to obtain novel 2-bromoisobutyrate-based waterborne polyurethane; and then the isobutyl bromide atom is catalyzed by 2, 2-dipyridine and cuprous bromide, and the bismaleimide and gamma-methacryloxypropyl trimethoxysilane copolymer is controllably grafted to the side chain of the aqueous polyurethane through an ATRP atom transfer radical polymerization process, and a hydrophobic siloxane and aromatic ring structure is introduced to the side chain of the aqueous polyurethane, so that the water resistance of the polyurethane is improved, and meanwhile, the rigid bismaleimide forms a chemical crosslinking network on the side chain of the polyurethane, so that the crosslinking degree of the polyurethane is improved, and the impact resistance, hardness and bending strength of the polyurethane are enhanced.
Description
Technical Field
The invention relates to the technical field of polyurethane, in particular to a preparation method and application of water-resistant impact-resistant waterborne polyurethane.
Background
The water-based polyurethane takes water as a solvent, has the advantage of green environmental protection, is widely applied to the aspects of paint, adhesives and the like, is a research hot spot for developing novel high-performance water-based polyurethane, and the current method for improving the performance of the water-based polyurethane mainly comprises filling modification, copolymerization modification, grafting modification and the like; the maleimide resin has the advantages of good heat resistance and mechanical strength, and the grafting modification of the polyurethane by utilizing the maleimide is an effective method for improving the comprehensive performance of the polyurethane; the literature, "study of heat-resistant polyurethane elastomer", reports that polyester, isophorone diisocyanate, 4' -diphenylmethane-bismaleimide chain extender and the like are used as raw materials to prepare polyurethane elastomer with high hardness and good temperature resistance.
The ATRP atom transfer radical polymerization is an effective active controllable polymerization method, can be used for carrying out molecular design on a polymer, and has wide application prospect in the aspects of preparing materials such as functional polyurethane, acrylic resin and the like, and the invention aims to graft bismaleimide and gamma-methacryloxypropyl trimethoxy silane to the side chain of the polyurethane by the ATRP atom transfer radical polymerization method so as to improve the performances such as water resistance, impact resistance, hardness and the like of the waterborne polyurethane.
Disclosure of Invention
The invention provides water-resistant and impact-resistant waterborne polyurethane, which solves the problems of poor impact resistance, water resistance and hardness of the waterborne polyurethane.
The invention provides the following technical scheme: preparation method of water-resistant impact-resistant waterborne polyurethane
(1) Drying and dehydrating polyether glycol, adding isophorone diisocyanate and dibutyltin dilaurate into a reaction bottle, introducing nitrogen, reacting for 2-3 hours at 65-75 ℃, then cooling to 40-55 ℃, adding 2-bromoisobutyrate-based ethylene glycol, reacting for 30-60min, adding 2, 2-dimethylolpropionic acid, reacting for 20-40min, and dropwise adding triethylamine for neutralization to obtain the 2-bromoisobutyrate-based waterborne polyurethane.
(2) Adding a solvent of 2-bromoisobutyrate-based waterborne polyurethane, bismaleimide, gamma-methacryloxypropyl trimethoxysilane and N, N-dimethylformamide into a reaction bottle, stirring uniformly, introducing nitrogen, adding 2, 2-bipyridine and cuprous bromide, adding a methanol solvent after reaction until precipitation is achieved, filtering, washing with ethanol, adding the product into deionized water, and shearing and emulsifying at a high speed to obtain the water-resistant and impact-resistant waterborne polyurethane.
Further, the polyether glycol in (1) includes polyethylene glycol, polypropylene glycol or polytetrahydrofuran ether glycol.
Further, the mass of the 2-bromoisobutyric acid ester glycol in the (1) is 3 to 7 percent of the total mass of the polyether glycol and the isophorone diisocyanate.
Further, the mass of the bismaleimide and the gamma-methacryloxypropyl trimethoxysilane in the step (2) is 2-10% and 1.2-6% of that of the 2-bromoisobutyrate-based waterborne polyurethane respectively.
Further, the reaction control temperature in the step (2) is 25-35 ℃ and the reaction time is 6-12h.
Further, the preparation method of the 2-bromoisobutyric acid ester glycol in the (1) comprises the following steps: adding 2-bromoisobutyric acid, glycidol and a catalyst N, N-dimethylbenzylamine (BDMA) into a solvent, performing esterification reaction, removing the solvent by rotary evaporation, washing with diethyl ether, and drying to obtain 2-bromoisobutyric acid ester ethylene glycol; the reaction formula is as follows:
further, the reaction solvent is acetone, tetrahydrofuran, 1, 4-dioxane or ethyl acetate.
Further, the molar ratio of the 2-bromoisobutyric acid, the glycidol and the catalyst N, N-dimethylbenzylamine is 1:0.8-1.3:0.06-0.1.
Further, the temperature of the esterification reaction is controlled to be 80-100 ℃ and the time is 4-12h.
The invention has the following technical effects: the invention uses N, N-dimethylbenzylamine as a catalyst, 2-bromoisobutyric acid and glycidol undergo carboxyl-epoxy esterification reaction to obtain 2-bromoisobutyric acid ester group glycol, and the 2-bromoisobutyric acid ester group glycol is used as a micromolecular chain extender to polymerize with polyether glycol, isophorone diisocyanate and 2, 2-dimethylolpropionic acid to obtain novel 2-bromoisobutyric acid ester group waterborne polyurethane; and then the isobutyl bromide atom is grafted to the side chain of the aqueous polyurethane through an ATRP atom transfer radical polymerization process under the catalysis of 2, 2-bipyridine and cuprous bromide, and the hydrophobic siloxane and aromatic ring structure is introduced to the side chain of the aqueous polyurethane, so that the waterproof performance of the polyurethane is improved, and meanwhile, the rigid bismaleimide forms a chemical crosslinking network on the side chain of the polyurethane, so that the crosslinking degree of the polyurethane is improved, and the impact resistance, hardness and bending strength of the polyurethane are enhanced.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below. Unless defined otherwise, technical terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention pertains.
Example 1
(1) 40mmol of 2-bromoisobutyric acid, 52mmol of glycidol and 4mmol of catalyst N, N-dimethylbenzylamine are added into acetone, esterification reaction is carried out for 4 hours at 100 ℃, solvent is removed by rotary evaporation, washing is carried out by diethyl ether, and drying is carried out, thus obtaining 2-bromoisobutyric acid ester ethylene glycol.
(2) 57g of polytetrahydrofuran ether glycol is dried and dehydrated, 30g of isophorone diisocyanate and 0.4g of dibutyltin dilaurate are added into a reaction bottle, nitrogen is introduced, the temperature is reduced to 40 ℃ for 3 hours, 2.6g of 2-bromoisobutyrate ethylene glycol is added for 60 minutes, 6g of 2, 2-dimethylolpropionic acid is added for 40 minutes, and triethylamine is added dropwise for neutralization, so that 2-bromoisobutyrate aqueous polyurethane is obtained.
(3) 80g of 2-bromoisobutyrate-based waterborne polyurethane, 1.6g of bismaleimide, 0.96g of gamma-methacryloxypropyl trimethoxysilane and N, N-dimethylformamide are added into a reaction bottle, nitrogen is introduced after stirring uniformly, 12mg of 2, 2-bipyridine and 5mg of cuprous bromide are added for reaction for 10 hours at 25 ℃, methanol solvent is added until precipitation is caused, suction filtration is carried out, and the product is added into deionized water after washing with ethanol, and is subjected to high-speed shearing emulsification, thus obtaining the water-resistant and impact-resistant waterborne polyurethane.
Example 2
(1) 40mmol of 2-bromoisobutyric acid, 32mmol of glycidol and 2.4mmol of catalyst N, N-dimethylbenzylamine are added into ethyl acetate to perform esterification reaction for 8 hours at 90 ℃, the solvent is removed by rotary evaporation, and the mixture is washed by diethyl ether and dried to obtain 2-bromoisobutyric acid ester ethylene glycol.
(2) 52g of polypropylene glycol is dried and dehydrated, 30g of isophorone diisocyanate and 0.4g of dibutyltin dilaurate are added into a reaction bottle, nitrogen is introduced, the temperature is reduced to 50 ℃ for 3 hours, 3.8g of 2-bromoisobutyrate-based ethylene glycol is added for 30 minutes, 6g of 2, 2-dimethylolpropionic acid is added for 40 minutes, triethylamine is dripped for neutralization, and 2-bromoisobutyrate-based waterborne polyurethane is obtained.
(3) Adding 80g of 2-bromoisobutyrate-based waterborne polyurethane, 2.5g of bismaleimide, 1.6g of gamma-methacryloxypropyl trimethoxysilane and N, N-dimethylformamide into a reaction bottle, stirring uniformly, introducing nitrogen, adding 20mg of 2, 2-bipyridine and 12mg of cuprous bromide, reacting at 25 ℃ for 12 hours, adding a methanol solvent until precipitation, suction filtering, washing with ethanol, adding the product into deionized water, and shearing and emulsifying at high speed to obtain the water-resistant and impact-resistant waterborne polyurethane.
Example 3
(1) 40mmol of 2-bromoisobutyric acid, 45mmol of glycidol and 3.3mmol of catalyst N, N-dimethylbenzylamine are added into tetrahydrofuran for esterification reaction at 80 ℃ for 12 hours, the solvent is removed by rotary evaporation, and the mixture is washed by diethyl ether and dried to obtain 2-bromoisobutyric acid ester ethylene glycol.
(2) 48g of polyethylene glycol is dried and dehydrated, 30g of isophorone diisocyanate and 0.4g of dibutyltin dilaurate are added into a reaction bottle, nitrogen is introduced, the temperature is reduced to 55 ℃ for 2 hours, 4.6g of 2-bromoisobutyrate ethylene glycol is added for 40 minutes, 6g of 2, 2-dimethylolpropionic acid is added for 30 minutes, and triethylamine is added dropwise for neutralization, so that 2-bromoisobutyrate aqueous polyurethane is obtained.
(3) 80g of 2-bromoisobutyrate-based waterborne polyurethane, 7.2g of bismaleimide, 3.9g of gamma-methacryloxypropyl trimethoxysilane and N, N-dimethylformamide are added into a reaction bottle, nitrogen is introduced after stirring uniformly, 50mg of 2, 2-bipyridine and 18mg of cuprous bromide are added for reaction for 6 hours at 35 ℃, methanol solvent is added until precipitation is caused after reaction, suction filtration and ethanol washing are carried out, and then the product is added into deionized water for high-speed shearing emulsification, thus obtaining the water-resistant and impact-resistant waterborne polyurethane.
Example 4
(1) 40mmol of 2-bromoisobutyric acid, 32mmol of glycidol and 2.4mmol of catalyst N, N-dimethylbenzylamine are added into 1, 4-dioxane for esterification reaction at 90 ℃ for 12 hours, the solvent is removed by rotary evaporation, and the mixture is washed by diethyl ether and dried to obtain 2-bromoisobutyric acid ester ethylene glycol.
(2) Drying and dehydrating 57g of polytetrahydrofuran ether glycol, adding 30g of isophorone diisocyanate and 0.4g of dibutyltin dilaurate into a reaction bottle, introducing nitrogen, reacting for 3 hours at 65 ℃, then reducing the temperature to 45 ℃, adding 6.1g of 2-bromoisobutyrate ethylene glycol, reacting for 60 minutes, adding 6g of 2, 2-dimethylolpropionic acid, reacting for 20 minutes, and dropwise adding triethylamine for neutralization to obtain the 2-bromoisobutyrate aqueous polyurethane.
(3) Adding 80g of 2-bromoisobutyrate-based waterborne polyurethane, 8g of bismaleimide, 4.8g of gamma-methacryloxypropyl trimethoxysilane and N, N-dimethylformamide into a reaction bottle, stirring uniformly, introducing nitrogen, adding 60mg of 2, 2-bipyridine and 25mg of cuprous bromide, reacting at 30 ℃ for 12 hours, adding a methanol solvent until precipitation is separated out, filtering, washing with ethanol, adding the product into deionized water, and performing high-speed shearing emulsification to obtain the water-resistant and impact-resistant waterborne polyurethane.
Comparative example 1
(1) 40mmol of 2-bromoisobutyric acid, 52mmol of glycidol and 4mmol of catalyst N, N-dimethylbenzylamine are added into acetone, esterification reaction is carried out for 4 hours at 100 ℃, solvent is removed by rotary evaporation, washing is carried out by diethyl ether, and drying is carried out, thus obtaining 2-bromoisobutyric acid ester ethylene glycol.
(2) 57g of polytetrahydrofuran ether glycol is dried and dehydrated, 30g of isophorone diisocyanate and 0.4g of dibutyltin dilaurate are added into a reaction bottle, nitrogen is introduced, the temperature is reduced to 40 ℃ for 3 hours, 2.6g of 2-bromoisobutyrate ethylene glycol is added for 60 minutes, 6g of 2, 2-dimethylolpropionic acid is added for 40 minutes, and triethylamine is added dropwise for neutralization, so that 2-bromoisobutyrate aqueous polyurethane is obtained.
Comparative example 2
(1) 80g of the 2-bromoisobutyrate-based waterborne polyurethane prepared in the example 1, 1.6g of bismaleimide and N, N-dimethylformamide are added into a reaction bottle, nitrogen is introduced after uniform stirring, 12mg of 2, 2-bipyridine and 5mg of cuprous bromide are added for reaction for 10 hours at 25 ℃, methanol solvent is added until precipitation is achieved after reaction, suction filtration is carried out, and the product is added into deionized water after ethanol washing, and is subjected to high-speed shearing emulsification, thus obtaining the waterborne polyurethane.
Comparative example 3
(1) 80g of the 2-bromoisobutyrate-based waterborne polyurethane prepared in the example 1, 0.96g of gamma-methacryloxypropyl trimethoxysilane and N, N-dimethylformamide are added into a reaction bottle, nitrogen is introduced after uniform stirring, 12mg of 2, 2-bipyridine and 5mg of cuprous bromide are added for reaction for 10 hours at 25 ℃, methanol solvent is added until precipitation is caused after reaction, suction filtration and ethanol washing are carried out, and the product is added into deionized water for high-speed shearing emulsification, thus obtaining the waterborne polyurethane.
The aqueous polyurethane is dried and cured at a temperature of 80 ℃. Obtaining polyurethane samples
Impact strength test of polyurethane samples: according to GB/T1843-2008 standard.
Hardness test of polyurethane test pieces: according to GB/T6739-2006 standard.
Bending strength test of polyurethane samples: according to GB/T9341-2008 standard.
Water absorption test: polyurethane samples with the specification of 2cm multiplied by 2cm are weighed for m 0 Then immersing in water overnight, taking out, draining the residual water and weighing m 1 The water absorption W was calculated.
While specific embodiments of the invention have been described above, it will be appreciated by those skilled in the art that the specific embodiments described are illustrative only and not intended to limit the scope of the invention, and that equivalent modifications and variations of the invention in light of the spirit of the invention will be covered by the claims of the present invention.
Claims (9)
1. A preparation method of water-resistant and impact-resistant waterborne polyurethane is characterized by comprising the following steps: the preparation method of the water-resistant and impact-resistant waterborne polyurethane comprises the following steps: (1) Drying and dehydrating polyether glycol, adding isophorone diisocyanate and dibutyltin dilaurate into a reaction bottle, introducing nitrogen, reacting for 2-3 hours at 65-75 ℃, then cooling to 40-55 ℃, adding 2-bromoisobutyrate-based ethylene glycol, reacting for 30-60min, adding 2, 2-dimethylolpropionic acid, reacting for 20-40min, and dropwise adding triethylamine for neutralization to obtain 2-bromoisobutyrate-based waterborne polyurethane;
(2) Adding a solvent of 2-bromoisobutyrate-based waterborne polyurethane, bismaleimide, gamma-methacryloxypropyl trimethoxysilane and N, N-dimethylformamide into a reaction bottle, stirring uniformly, introducing nitrogen, adding 2, 2-bipyridine and cuprous bromide, adding a methanol solvent after reaction until precipitation is achieved, filtering, washing, adding the product into deionized water, and shearing and emulsifying at a high speed to obtain the water-resistant and impact-resistant waterborne polyurethane.
2. The method for preparing the water-resistant impact-resistant aqueous polyurethane according to claim 1, which is characterized in that: the polyether glycol in the step (1) comprises polyethylene glycol, polypropylene glycol or polytetrahydrofuran ether glycol.
3. The method for preparing the water-resistant impact-resistant aqueous polyurethane according to claim 2, wherein the method comprises the following steps: the mass of the 2-bromoisobutyric acid ester glycol in the (1) is 3-7% of the total mass of the polyether glycol and the isophorone diisocyanate.
4. The method for preparing the water-resistant impact-resistant aqueous polyurethane according to claim 1, which is characterized in that: the mass of the bismaleimide and the gamma-methacryloxypropyl trimethoxysilane in the step (2) is respectively 2-10% and 1.2-6% of that of the 2-bromoisobutyrate-based waterborne polyurethane.
5. The method for preparing the water-resistant impact-resistant aqueous polyurethane according to claim 1, which is characterized in that: (2) The reaction temperature is controlled to be 25-35 ℃ and the reaction time is controlled to be 6-12h.
6. The method for preparing the water-resistant impact-resistant aqueous polyurethane according to claim 1, which is characterized in that: the preparation method of the 2-bromoisobutyric acid ester ethylene glycol in the step (1) comprises the following steps: adding 2-bromoisobutyric acid, glycidol and a catalyst N, N-dimethylbenzylamine into a solvent, performing esterification reaction, removing the solvent by rotary evaporation, washing and drying to obtain the 2-bromoisobutyric acid ester ethylene glycol.
7. The method for preparing the water-resistant impact-resistant aqueous polyurethane according to claim 6, wherein the method comprises the following steps: the reaction solvent is acetone, tetrahydrofuran, 1, 4-dioxane or ethyl acetate.
8. The method for preparing the water-resistant impact-resistant aqueous polyurethane according to claim 6, wherein the method comprises the following steps: the molar ratio of the 2-bromoisobutyric acid to the glycidol to the catalyst N, N-dimethylbenzylamine is 1:0.8-1.3:0.06-0.1.
9. The method for preparing the water-resistant impact-resistant aqueous polyurethane according to claim 6, wherein the method comprises the following steps: the temperature of the esterification reaction is controlled to be 80-100 ℃ and the time is controlled to be 4-12h.
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