CN118165251A - Nonionic type double-amino hydrophilic chain extender and preparation method thereof, and nonionic type water-based non-isocyanate polyurethane and preparation method thereof - Google Patents
Nonionic type double-amino hydrophilic chain extender and preparation method thereof, and nonionic type water-based non-isocyanate polyurethane and preparation method thereof Download PDFInfo
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- CN118165251A CN118165251A CN202410160141.3A CN202410160141A CN118165251A CN 118165251 A CN118165251 A CN 118165251A CN 202410160141 A CN202410160141 A CN 202410160141A CN 118165251 A CN118165251 A CN 118165251A
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- 239000012948 isocyanate Substances 0.000 title claims abstract description 117
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 117
- 239000004970 Chain extender Substances 0.000 title claims abstract description 85
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 59
- 239000004814 polyurethane Substances 0.000 title claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 150000002148 esters Chemical class 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 42
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 10
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 52
- 239000002202 Polyethylene glycol Substances 0.000 claims description 52
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 52
- 229920001223 polyethylene glycol Polymers 0.000 claims description 52
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 41
- 229920000570 polyether Polymers 0.000 claims description 38
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 37
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 36
- AHWALFGBDFAJAI-UHFFFAOYSA-N phenyl carbonochloridate Chemical compound ClC(=O)OC1=CC=CC=C1 AHWALFGBDFAJAI-UHFFFAOYSA-N 0.000 claims description 28
- 238000005886 esterification reaction Methods 0.000 claims description 25
- 230000032050 esterification Effects 0.000 claims description 24
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 22
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 18
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 18
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 9
- 238000005576 amination reaction Methods 0.000 claims description 9
- 150000004985 diamines Chemical class 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- 150000002009 diols Chemical class 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 6
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 6
- KOFSFYBXUYHNJL-UHFFFAOYSA-N 1-(cyclopenten-1-yl)pyrrolidine Chemical compound C1CCCN1C1=CCCC1 KOFSFYBXUYHNJL-UHFFFAOYSA-N 0.000 claims description 4
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 4
- 239000003426 co-catalyst Substances 0.000 claims description 4
- 229920000768 polyamine Polymers 0.000 claims description 4
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 4
- FUPAJKKAHDLPAZ-UHFFFAOYSA-N 1,2,3-triphenylguanidine Chemical compound C=1C=CC=CC=1NC(=NC=1C=CC=CC=1)NC1=CC=CC=C1 FUPAJKKAHDLPAZ-UHFFFAOYSA-N 0.000 claims description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 3
- KTZNVZJECQAMBV-UHFFFAOYSA-N 1-(cyclohexen-1-yl)pyrrolidine Chemical compound C1CCCN1C1=CCCCC1 KTZNVZJECQAMBV-UHFFFAOYSA-N 0.000 claims description 3
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 claims description 3
- BDXGMDGYOIWKIF-UHFFFAOYSA-N 2-methylpropane-1,3-diamine Chemical compound NCC(C)CN BDXGMDGYOIWKIF-UHFFFAOYSA-N 0.000 claims description 3
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 3
- IIQFBBQJYPGOHJ-UHFFFAOYSA-N 4-(cyclohexen-1-yl)morpholine Chemical compound C1CCCC(N2CCOCC2)=C1 IIQFBBQJYPGOHJ-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 3
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 3
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 3
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 3
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 3
- SCZVXVGZMZRGRU-UHFFFAOYSA-N n'-ethylethane-1,2-diamine Chemical compound CCNCCN SCZVXVGZMZRGRU-UHFFFAOYSA-N 0.000 claims description 3
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims 1
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 claims 1
- 239000000839 emulsion Substances 0.000 abstract description 32
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 abstract description 17
- 229910001424 calcium ion Inorganic materials 0.000 abstract description 17
- 230000000704 physical effect Effects 0.000 abstract description 14
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- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 7
- -1 1, 5-pentylene diamine Chemical class 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
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- 238000010998 test method Methods 0.000 description 5
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- 238000001816 cooling Methods 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
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- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- IWXAZSAGYJHXPX-BCEWYCLDSA-N Bisbentiamine Chemical compound C=1C=CC=CC=1C(=O)OCC/C(SS\C(CCOC(=O)C=1C=CC=CC=1)=C(/C)N(CC=1C(=NC(C)=NC=1)N)C=O)=C(/C)N(C=O)CC1=CN=C(C)N=C1N IWXAZSAGYJHXPX-BCEWYCLDSA-N 0.000 description 1
- 102100024133 Coiled-coil domain-containing protein 50 Human genes 0.000 description 1
- 101000910772 Homo sapiens Coiled-coil domain-containing protein 50 Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
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- 125000004432 carbon atom Chemical group C* 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- QIIPQYDSKRYMFG-UHFFFAOYSA-N phenyl hydrogen carbonate Chemical group OC(=O)OC1=CC=CC=C1 QIIPQYDSKRYMFG-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Natural products C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 1
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- 230000002588 toxic effect Effects 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a nonionic type double-amino hydrophilic chain extender and a preparation method thereof, and nonionic type water-based non-isocyanate polychlorinated ester and a preparation method thereof. The chain extender has a structure represented by the general formula (1), wherein R 1 is a C 2-C10 divalent aliphatic group; and n1 is an integer of 3 to 60. The nonionic type double-amino hydrophilic chain extender can be used for preparing nonionic type water-based non-isocyanate polyurethane, so that the environmental friendliness and safety of the water-based polychloroethyl ester production process are improved. The method for preparing the nonionic type double-amino hydrophilic chain extender can prepare the double-amino hydrophilic chain extender in a mode of simple process, low cost and high reaction rate. In addition, the nonionic aqueous non-isocyanate polychloroethyl ester obtained by the production method according to the present invention has excellent emulsion stability (including mechanical stability and calcium ion stability), and the cured product thereof has good physical properties (such as tensile strength, elongation at break, tear strength, etc.).
Description
Technical Field
The invention relates to the technical field of water-based polychlorinated ester materials, and in particular relates to a nonionic type double-amino hydrophilic chain extender and a preparation method thereof, and a nonionic type water-based non-isocyanate polychlorinated ester and a preparation method thereof.
Background
Polyurethane is widely used with its excellent properties. Currently, the polyurethane industry is developing towards adapting to environmental protection, safety, sanitation and the like. The non-isocyanate polyurethane is synthesized without isocyanate as raw material, and is safe and nontoxic during synthesis, so that the harm of isocyanate to health and safety is effectively solved. Thus, non-isocyanate polyurethanes have become an important research direction for polyurethane synthesis.
The aqueous polyurethane inherits the excellent performance of solvent polyurethane, is more friendly to the environment in the preparation and use processes, and therefore, has rapid development. Generally, 3 main raw materials are needed for preparing the aqueous polyurethane: isocyanate, high polymer containing active hydrogen and chain extender, and dispersing the system in water after reaction.
The nonionic hydrophilic chain segments are mainly introduced to a molecular main chain or a side chain to realize the dispersion of the polychloroethyl in water, and the nonionic aqueous polychloroethyl is insensitive to electrolyte because of the absence of an electric double layer structure in the ionic polychloroethyl, so that the nonionic aqueous polychloroethyl can be randomly blended with other emulsions with different pH values without the problems of demulsification and the like, and the application field of the aqueous polychloroethyl can be expanded. Therefore, the nonionic aqueous polychloroethyl ester has good development prospect.
At present, highly toxic isocyanates and a large amount of solvents are still required in the production of aqueous polychlorinated esters, and at the same time, the aqueous polychlorinated ester production products are still unsatisfactory in terms of application properties (for example, emulsion stability of aqueous polychlorinated esters as emulsion) and physical properties of the cured products. Thus, there is an urgent need for nonionic aqueous non-isocyanate polychlorinated products having good environmental protection and safety, while having good application properties (e.g., emulsion stability) and good physical properties of the product after curing.
Disclosure of Invention
Based on the technical problems set forth above, the invention aims to provide a nonionic type double-amino hydrophilic chain extender and a preparation method thereof, and a nonionic type water-based non-isocyanate polychlorinated ester and a preparation method thereof. The nonionic type double-amino hydrophilic chain extender can be used for preparing nonionic type water-based non-isocyanate polychlorinated ester, so that the environmental friendliness and safety of the water-based polychlorinated ester production process are improved. The preparation method of the nonionic type double-amino hydrophilic chain extender can prepare the nonionic type double-amino hydrophilic chain extender in a mode of simple process, low cost and high reaction rate. In addition, the nonionic aqueous non-isocyanate polyurethane obtained by the preparation method according to the present invention has excellent emulsion stability (including mechanical stability and calcium ion stability), and its cured product has good physical properties (such as tensile strength, elongation at break, tear strength, etc.).
Specifically, according to one aspect of the present invention, there is provided a nonionic type bisaminohydrophilic chain extender having a structure represented by the following general formula (1):
wherein R 1 is a C 2-C10 divalent aliphatic group; and n1 is an integer of 3 to 60.
According to certain preferred embodiments of the present invention, wherein R 1 is C 3-C6 straight, branched or cyclic alkylene.
According to certain preferred embodiments of the present invention, wherein n1 is an integer from 3 to 37.
According to another aspect of the present invention, there is provided a method for preparing a nonionic bis-amino hydrophilic chain extender, the method comprising the steps of:
(1) Mixing and heating trimethylolpropane polyethylene glycol monomethyl ether, phenyl chloroformate, an esterification main catalyst and an esterification cocatalyst to obtain phenyl carbonate end-capped trimethylolpropane polyethylene glycol monomethyl ether;
(2) Mixing the phenyl carbonate end capped trimethylolpropane polyethylene glycol monomethyl ether, diamine and an amination catalyst, heating and distilling under reduced pressure to remove phenol, so as to obtain the nonionic double-amino hydrophilic chain extender, wherein:
the trimethylolpropane polyethylene glycol monomethyl ether has a structure represented by the following general formula (2):
Wherein n1 is an integer from 3 to 60, and
The diamine has a structure represented by the following general formula (3):
Wherein R 1 is a C 2-C10 divalent aliphatic group,
The esterification main catalyst is selected from one or more of 1-morpholine-1-cyclopentene, 1-pyrrolidinyl-1-cyclopentene, 1-morpholinyl-1-cyclohexene, 1- (1-pyrrolidinyl) cyclohexene, 4-dimethylaminopyridine and triethylamine;
The esterification promoter is selected from one or more of dicyclohexylcarbodiimide, N' -diisopropylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide; and
The amination catalyst is selected from one or more of 1, 3-tetramethyl guanidine, 1-dimethyl guanidine and 1,2, 3-triphenyl guanidine.
According to certain preferred embodiments of the present invention, wherein R 1 is C 3-C6 straight, branched or cyclic alkylene.
According to certain preferred embodiments of the present invention, wherein n1 is an integer from 3 to 37.
According to certain preferred embodiments of the present invention, in step (1), the molar ratio of the phenyl chloroformate to the trimethylolpropane polyethylene glycol monomethyl ether is in the range of 2:1 to 3:1.
According to certain preferred embodiments of the present invention, in step (1), the weight ratio of the esterification procatalyst to the esterification cocatalyst is in the range of 1:1 to 10:1.
According to certain preferred embodiments of the present invention, in step (1), the ratio of the sum of the weights of the esterification procatalyst and the esterification cocatalyst to the sum of the weights of the trimethylolpropane polyethylene glycol monomethyl ether and phenyl chloroformate is in the range of 1X 10 -4:1 to 1X 10 -2:1.
According to certain preferred embodiments of the present invention, the diamine is selected from one or more of ethylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, 1, 5-pentylene diamine, hexamethylenediamine, 1, 2-propylenediamine, 2-methyl-1, 3-propylenediamine, 2-methylpentanediamine, phenylenediamine, m-xylylenediamine, m-cyclohexyldimethylamine, N-ethylethylenediamine, N-dimethylethylenediamine, cyclohexanediamine, p-aminocyclohexamethylenediamine, isophoronediamine, 4' -dicyclohexylmethane diamine, 3' -dimethyl-4, 4' -dicyclohexylmethane diamine.
According to certain preferred embodiments of the present invention, in step (2), the ratio of the amination catalyst to the sum of the weights of the phenyl carbonate end capped trimethylolpropane polyethylene glycol monomethyl ether and polyamine is in the range of 1X 10 -4:1 to 1X 10 -2:1.
In yet another aspect of the present invention, there is provided a nonionic aqueous non-isocyanate polyurethane having a structure represented by the following general formula (4):
wherein:
R 1 is a C 2-C10 divalent aliphatic radical;
r2 is a divalent residue obtained after removal of two hydroxyl groups from a polyether diol having a number average molecular weight in the range of 650 to 3000;
n1 is an integer from 3 to 60; and
N2 is an integer from 35 to 180.
According to certain preferred embodiments of the present invention, wherein R 1 is C 3-C6 straight, branched or cyclic alkylene.
According to certain preferred embodiments of the present invention, the polyether glycol is selected from one or more of polyethylene oxide glycol, polypropylene oxide glycol and polytetramethylene ether glycol.
According to certain preferred embodiments of the present invention, wherein n1 is an integer from 3 to 37.
According to certain preferred embodiments of the present invention, wherein n2 is an integer from 85 to 165.
In yet another aspect of the present invention, there is provided a method for preparing a nonionic aqueous non-isocyanate polychloroethyl ester, the method comprising: mixing, heating and distilling under reduced pressure the nonionic bis-amino hydrophilic chain extender and the phenyl carbonate terminated polyether of any one of claims 1-3 to remove phenol, wherein:
The phenyl carbonate terminated polyether has a structure represented by the following general formula (5):
wherein R 2 is a divalent residue obtained after removal of two hydroxyl groups from a polyether diol having a number average molecular weight in the range of 650 to 3000.
According to certain preferred embodiments of the present invention, the polyether glycol is selected from one or more of polyethylene oxide glycol, polypropylene oxide glycol and polytetramethylene ether glycol.
According to certain preferred embodiments of the present invention, the molar ratio of the nonionic bis-amino hydrophilic chain extender to the phenyl carbonate terminated polyether is in the range of 1:1 to 1.2:1.
According to certain preferred embodiments of the invention, the preparation process further comprises adding water to the product.
According to certain preferred embodiments of the present invention, the ratio of the weight of water added to the sum of the weight of the phenyl carbonate terminated polyether, the nonionic bis-amino hydrophilic chain extender is in the range of 1:1 to 5:1.
Compared with the prior art in the field, the invention has the advantages that:
1) In terms of the nonionic type double-amino hydrophilic chain extender, the nonionic type double-amino hydrophilic chain extender can be used for preparing nonionic type water-based non-isocyanate polyurethane which does not use isocyanate in the synthetic method, and is environment-friendly and high in safety in the production and use processes;
2) As for the method for preparing a nonionic bis-amino hydrophilic chain extender according to the present invention, the method can prepare the nonionic bis-amino hydrophilic chain extender in a manner of simple process, low cost and high reaction rate;
3) In the case of the process for preparing nonionic aqueous non-isocyanate polychlorinated esters according to the present invention, the present invention uses phenyl-terminated carbonate polyethers as the main starting reactant, with specific nonionic bis-amino hydrophilic chain extenders as hydrophilic segments. Compared with common aqueous polychloroethyl, the structural units and soft and hard molecular chain segments in the molecular structure of the obtained nonionic aqueous non-isocyanate polyurethane prepolymer are orderly arranged, and the soft and hard chain segments of the synthetic product are further improved in proportion, so that the coating film prepared from the nonionic aqueous non-isocyanate polyurethane emulsion has better mechanical properties (such as tensile strength, elongation at break, tearing strength and the like) in a macroscopic manner.
4) The nonionic water-based non-isocyanate polyurethane obtained by the preparation method disclosed by the invention has excellent acid-base stability, mechanical stability and calcium ion stability, and lays a foundation for the wider application field of the obtained nonionic water-based non-isocyanate polychlorinated ester.
Detailed Description
The present invention will be described in further detail with reference to the following specific embodiments. It will be appreciated that other embodiments are contemplated and may be made without departing from the scope or spirit of the invention. The following detailed description is, therefore, not to be taken in a limiting sense.
All numbers expressing feature sizes, amounts, and physical and chemical characteristics used in the specification and claims are to be understood as being modified in all instances by the term "about" unless otherwise indicated. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can be varied appropriately by those skilled in the art utilizing the desired properties sought to be obtained by the teachings disclosed herein. The use of numerical ranges by endpoints includes all numbers subsumed within that range and any range within that range, e.g., 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, 5, and the like.
The inventor of the present invention found that the most widely used non-isocyanate polychlorinated ester synthesis technology at present adopts the reaction synthesis of dicyclo carbonate and aliphatic polyamine, and the solvent type is mainly used. The yield of the raw material dicyclo carbonate is low and the industrialization degree is low, so that the wide application of non-isocyanate polychlorinated ester and downstream products thereof is severely restricted. In addition, along with the strict limitation of organic solvent emission in various countries, the realization of the waterborne of non-isocyanate polyurethane is imperative. Therefore, one of the purposes of the invention is to develop a novel nonionic type double amino hydrophilic chain extender and use the novel nonionic type double amino hydrophilic chain extender for preparing nonionic type waterborne non-isocyanate polyurethane so as to meet the development direction of the future waterborne polyurethane field.
According to an aspect of the present invention, there is provided a nonionic type bisaminohydrophilic chain extender having a structure represented by the following general formula (1):
wherein R 1 is a C 2-C10 divalent aliphatic group; and n1 is an integer of 3 to 60.
The preparation of the nonionic type double amino hydrophilic chain extender is a key technology for synthesizing high-performance nonionic type water-based non-isocyanate polychlorinated ester. The preparation method of the nonionic water-based polychlorinated ester is generally directly characterized in that trimethylolpropane polyethylene glycol monomethyl ether with two hydroxyl functional groups is used as a nonionic hydrophilic chain extender, and the nonionic water-based polychlorinated ester is prepared by introducing an amino-terminated nonionic hydrophilic chain extender which does not contain hydroxyl groups and contains urethane bonds and ether bonds in the self structure into a molecular main chain or a side chain to realize the dispersion of non-isocyanate polyurethane in water. The nonionic type double-amino hydrophilic chain extender has the structural advantages that:
1) The chain extension can be carried out with various substances by blocking with primary amino groups, and the application is wide. For example: can be used as an epoxy resin curing agent, can be reacted with polyether terminated by phenyl carbonate to prepare polyurethane, and can be reacted with polyisocyanate to prepare polyurethane-urea;
2) Under the condition of no participation of isocyanate, the polyurethane can react with the polyether blocked by phenyl carbonate to synthesize water-based non-isocyanate polyurethane, and is environment-friendly and high in safety;
3) Because the molecular structure is provided with urethane groups and ether bond flexible chain segments, when the molecular structure reacts with polyether capped by phenyl carbonate to synthesize water-based non-isocyanate polychloride, the proportion of the soft and hard chain segments of a synthesized product is further improved, and the macroscopically obtained film prepared from the nonionic water-based non-isocyanate polychloride emulsion has better mechanical properties (such as tensile strength, elongation at break, tear strength and the like);
4) Because no double-layer structure exists, the nonionic water-based non-isocyanate polychlorinated emulsion is insensitive to electrolyte, and can be arbitrarily blended with other emulsions with different pH values without demulsification and other problems, the emulsion stability is strong, and the application field of the water-based polychlorinated emulsion can be expanded.
In the structural general formula (1) of the nonionic type double-amino hydrophilic chain extender, n is an integer of 3-60. When n is less than 3, the nonionic bisaminohydrophilic chain extender used to provide hydrophilicity to the polyurea product will not provide sufficient hydrophilicity, resulting in that the produced polyurea is not emulsified well; when n is more than 60, the molecular weight of hydrophilic side chains in the resulting polyurea product is excessively large, resulting in deterioration of physical properties (in particular, tensile strength, etc.) of the polyurea product after curing. In order to achieve a good balance between improving hydrophilicity and improving physical properties of the cured product, n is preferably an integer of 3 to 37.
Furthermore, the inventors of the present invention have found that the specific choice of R 1 in the above general structural formula (1) also has an important influence on the hydrophilicity and physical properties of the resulting polyurea product. Specifically, R 1 is a C 2-C10 divalent aliphatic group. When the number of carbon atoms of the divalent aliphatic group is more than 10, the nonionic type double amino hydrophilic chain extender for providing hydrophilicity to the polyurea product will not provide sufficient hydrophilicity, resulting in that the produced polyurea is not emulsified well. In order to achieve a good balance between improving hydrophilicity and improving the physical properties of the cured product, preferably, R 1 is C 3-C6 straight, branched or cyclic alkylene.
According to another aspect of the present invention, there is provided a method for preparing a nonionic bis-amino hydrophilic chain extender, the method comprising the steps of:
(1) Mixing and heating trimethylolpropane polyethylene glycol monomethyl ether, phenyl chloroformate, an esterification main catalyst and an esterification cocatalyst to obtain phenyl carbonate end-capped trimethylolpropane polyethylene glycol monomethyl ether;
(2) Mixing the phenyl carbonate end capped trimethylolpropane polyethylene glycol monomethyl ether, diamine and an amination catalyst, heating and distilling under reduced pressure to remove phenol, so as to obtain the nonionic double-amino hydrophilic chain extender, wherein:
the trimethylolpropane polyethylene glycol monomethyl ether has a structure represented by the following general formula (2):
Wherein n1 is an integer from 3 to 60, and
The diamine has a structure represented by the following general formula (3):
Wherein R 1 is a C 2-C10 divalent aliphatic group,
The esterification main catalyst is selected from one or more of 1-morpholine-1-cyclopentene, 1-pyrrolidinyl-1-cyclopentene, 1-morpholinyl-1-cyclohexene, 1- (1-pyrrolidinyl) cyclohexene, 4-dimethylaminopyridine and triethylamine;
The esterification promoter is selected from one or more of dicyclohexylcarbodiimide, N' -diisopropylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide; and
The amination catalyst is selected from one or more of 1, 3-tetramethyl guanidine, 1-dimethyl guanidine and 1,2, 3-triphenyl guanidine.
Commercially available products of trimethylolpropane polyethylene glycol monomethyl ether that can be used in the present invention include, for example, ymer TM N120 (having a hydroxyl functionality of 2 and a number average molecular weight of 1000) or Ymer TM N90 (having a hydroxyl functionality of 2 and a number average molecular weight of 1200) produced and sold by Beston, sweden.
Preferably, in the above-described method for preparing a nonionic bisaminohydrophilic chain extender, a molar ratio of the phenyl chloroformate to the trimethylolpropane polyethylene glycol monomethyl ether is in a range of 2:1 to 3:1. When the molar ratio of phenyl chloroformate to the trimethylolpropane polyethylene glycol monomethyl ether is less than 2:1, the hydroxyl in the trimethylolpropane polyethylene glycol monomethyl ether cannot be completely converted into phenyl carbonate groups, so that the synthesis yield and purity of the nonionic hydrophilic chain extender are reduced, and the physical properties of the waterborne non-isocyanate polyurethane product are further affected. On the other hand, when the molar ratio of phenyl chloroformate to the trimethylolpropane polyethylene glycol monomethyl ether is more than 3:1, the phenyl chloroformate is excessively retained as small molecules in the resulting nonionic-type bisaminohydrophilic chain extender, which also results in deterioration of physical properties of the aqueous non-isocyanate polyurethane product.
In the above method according to the present invention, a combination of a main catalyst selected from one or more of 1-morpholin-1-cyclopentene, 1-pyrrolidinyl-1-cyclopentene, 1-morpholin-1-cyclohexene, 1- (1-pyrrolidine) cyclohexene, 4-dimethylaminopyridine and triethylamine and a cocatalyst selected from one or more of dicyclohexylcarbodiimide, N' -diisopropylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide is employed to catalyze the esterification reaction between trimethylolpropane polyethylene glycol monomethyl ether and phenyl chloroformate. The inventors of the present invention found that when only one of the above-described main catalyst and co-catalyst is used, a high reaction rate of 90% or more cannot be achieved. According to the invention, the reaction rate in the preparation method of the nonionic type double-amino hydrophilic chain extender is obtained by calculating the mass difference of the raw materials before and after the reaction. In order to increase the reaction rate, it is preferable that the weight ratio of the esterification main catalyst to the esterification co-catalyst is in the range of 1:1 to 10:1. Further, in order to increase the reaction rate, it is preferable that in step (1), the ratio of the sum of the weights of the esterification main catalyst and the esterification co-catalyst to the sum of the weights of the trimethylolpropane polyethylene glycol monomethyl ether and phenyl chloroformate is in the range of 1×10 -4:1 to 1×10 -2:1.
Preferably, in the preparation method of the nonionic type double-amino hydrophilic chain extender, the diamine is selected from one or more of ethylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, 1, 5-pentylene diamine, hexamethylenediamine, 1, 2-propylenediamine, 2-methyl-1, 3-propylenediamine, 2-methylpentylenediamine, phenylenediamine, m-xylylenediamine, m-cyclohexyldimethylamine, N-ethylethylenediamine, N-dimethylethylenediamine, cyclohexanediamine, p-aminocyclohexamethylenediamine, isophorone diamine, 4' -dicyclohexylmethane diamine and 3,3' -dimethyl-4, 4' -dicyclohexylmethane diamine.
Preferably, in the above-described method for producing a nonionic bisaminohydrophilic chain extender, in the step (2), the ratio of the amination catalyst to the sum of the weights of the trimethylolpropane polyethylene glycol monomethyl ether capped with phenyl carbonate and the polyamine is in the range of 1×10 -4:1 to 1×10 -2:1.
According to still another aspect of the present invention, there is provided a nonionic aqueous non-isocyanate polyurethane having a structure represented by the following general formula (4):
wherein:
R 1 is a C 2-C10 divalent aliphatic radical;
r2 is a divalent residue obtained after removal of two hydroxyl groups from a polyether diol having a number average molecular weight in the range of 650 to 3000;
n1 is an integer from 3 to 60; and
N2 is an integer from 35 to 180.
Preferably, R 1 is C 3-C6 straight, branched or cyclic alkylene.
Preferably, the polyether glycol is selected from one or more of polyethylene oxide glycol, polypropylene oxide glycol and polytetramethylene ether glycol.
Preferably, n1 is an integer from 3 to 37.
Preferably, n2 is an integer from 85 to 165.
The inventors of the present invention found that the specific choice of the number n2 of repeating units in the non-isocyanate aqueous polyurethane likewise has an important influence on the mechanical properties of the non-isocyanate aqueous polychloroethyl ester used as a base resin material for the non-isocyanate aqueous polychloroethyl ester-based flame retardant coating. By controlling n2 in the range of 35-180 and optimizing other parameters, the obtained non-isocyanate aqueous polyurethane matrix resin material can realize good performance in terms of substrate mechanical properties (including elongation at break, tensile strength, tear strength and the like). In particular, when n2 is further controlled in the range of 85 to 165, the resultant non-isocyanate aqueous polychloroethyl base resin material is greatly improved in the combination of properties concerning elongation at break, tensile strength, tear strength and the like, even far superior to the performance standard judged as "excellent" in the industry.
According to still another aspect of the present invention, there is provided a method for preparing a nonionic aqueous non-isocyanate polychloroethyl ester, the method comprising: mixing, heating and distilling under reduced pressure the nonionic bis-amino hydrophilic chain extender and the phenyl carbonate terminated polyether of any one of claims 1-3 to remove phenol, wherein:
The phenyl carbonate terminated polyether has a structure represented by the following general formula (5):
wherein R 2 is a divalent residue obtained after removal of two hydroxyl groups from a polyether diol having a number average molecular weight in the range of 650 to 3000.
According to certain preferred embodiments of the present invention, the phenyl carbonate terminated polyether is selected from the family of berliner manufactured and sold by Shanxi construction sciences group Co., ltd. Preferably, wherein the number average molecular weight of the phenyl carbonate terminated polyether is in the range of 650 to 3000.
According to certain preferred embodiments of the present invention, the polyether glycol is selected from one or more of polyethylene oxide glycol, polypropylene oxide glycol and polytetramethylene ether glycol.
According to certain preferred embodiments of the present invention, wherein the molar ratio of the nonionic amphiphilic amino hydrophilic chain extender to the phenyl carbonate terminated polyether is in the range of 1:1 to 1.2:1, preferably in the range of 1:1 to 1.1:1, more preferably in the range of 1:1 to 1.05:1.
According to the solution of the invention, optionally, water can be added to the above product to adjust it to the proper concentration and avoid possible further reaction precipitation. The water is preferably deionized water.
According to certain preferred embodiments of the present invention, the ratio of the weight of water added to the sum of the weight of the phenyl carbonate terminated polyether, the nonionic bis-amino hydrophilic chain extender is in the range of 1:1 to 5:1, preferably 1:1 to 4:1, more preferably 1:1 to 3:1. The solids content of the aqueous non-isocyanate polychloroethyl esters synthesized by the process according to the invention can be considerably higher than the solids content of other conventional aqueous polychloroethyl ester emulsions.
The present invention will be described in more detail with reference to examples. It should be noted that the description and examples are intended to facilitate an understanding of the invention and are not intended to limit the invention. The scope of the invention is defined by the appended claims.
Examples
In the present invention, unless otherwise indicated, the reagents employed were all commercially available products and were used directly without further purification treatment. Further, "%" is referred to as "% by weight", and "parts" is referred to as "parts by weight".
The present invention will be described in further detail with reference to examples and comparative examples. It should be understood that the present invention is not limited to the following examples.
In the present invention, unless otherwise indicated, the reagents employed were all commercially available products and were used directly without further purification treatment. Further, "%" is referred to as "% by weight", and "parts" is referred to as "parts by weight".
Test method
Tensile Strength, elongation at Break and tear Strength test after curing of coating films made of nonionic aqueous non-isocyanate polyurethane
In the following examples, the tensile strength, elongation at break and tear strength of the nonionic aqueous non-isocyanate polyurethane obtained in each of examples and comparative examples after curing were measured. The specific measurement method is as follows:
The resulting nonionic aqueous non-isocyanate polyurethane emulsion was coated on a polytetrafluoroethylene plate having a size of 350mm×320mm so that the final coating film thickness was 1.5±0.2mm. The polytetrafluoroethylene sheet coated with the coating film was dried at 23 ℃ and 50% humidity for 2 days. Followed by 4 days at a temperature of 23 ℃ and a humidity of 50%. The resulting coating film was then tested for tensile strength, elongation at break and tear strength according to the test methods specified in GB/T16777-2008.
Wherein, if the tensile strength of the coating film is more than or equal to 6.0MPa, the coating film is considered to meet the general industrial application requirements of the aqueous polyurethane emulsion material; if the tensile strength of the coating film is 10MPa or more, the aqueous non-isocyanate polychloroethyl emulsion material is considered to be excellent in tensile strength properties. If the elongation at break is greater than or equal to 400%, then the general industrial application requirements of the aqueous polychloroethyl emulsion material are considered to be met; if the elongation at break is 460% or more, the aqueous non-isocyanate polyurethane emulsion material is considered to be excellent in elongation at break performance. If the tear strength is greater than or equal to 40N/mm, then the general industrial application requirements of the aqueous polychloroethyl emulsion material are considered to be met; if the tear strength is greater than or equal to 80N/mm, the aqueous non-isocyanate polychloroethyl emulsion material is considered to be excellent in tear strength properties.
Solid content test of nonionic aqueous non-isocyanate polychloroethyl ester
The solid content of the nonionic aqueous non-isocyanate polyurethane obtained in each of the examples and comparative examples below was determined according to the test method in national standard GB/T20623-2006.
Specifically, the flat-bottomed disc (diameter about 75 mm) was baked in a forced air oven at (150.+ -. 2) ℃ for 15min, cooled to room temperature in a dryer, and weighed (m 0) to the nearest 1mg. About 1g of the test product (m 1) was weighed into the dish with the same precision and ensured that the sample was uniformly dispersed on the dish surface. If the viscosity of the sample is too high, the weighed sample may be diluted with water and homogenized. The discs, weighed samples, were placed in a forced air oven preheated to (150.+ -. 2) ℃ for 15 minutes. The tray was moved into a desiccator, cooled to room temperature and weighed (m 2) to the nearest 1mg.
The solids content is calculated according to equation (1):
Wherein:
w NV -solids (%) of nonionic aqueous non-isocyanate polychloroethyl;
m 2 -the mass of the sample and disc after heating, in (g);
m 0 -the mass of the disk in (g);
m 1 -mass of sample before heating, unit is (g).
The two tests were performed in parallel, and the difference between the results of the two tests was not more than 1%. The experimental results are expressed as the average of two determinations, accurate to the decimal point one digit later.
Mechanical stability test of nonionic aqueous non-isocyanate polychlorinated esters
The nonionic aqueous non-isocyanate polychlorinated esters obtained by the preparation method of the present invention have excellent emulsion stability, such as mechanical stability. The mechanical stability of the nonionic aqueous non-isocyanate polychlorinated esters obtained in the following examples and comparative examples was determined according to the test method in the national standard GB/T20623-2006.
Specifically, about 1000mL of the emulsion of filtered [ filter screen with a pore size of 17 μm (80 mesh) ] was weighed (400.+ -. 0.52) into a container (diameter 100mm, height 180 mm), placed on a high-speed dispersion machine base, fixed with a clamp, started up to a dispersion machine (stirring head is of a disk-tooth shape, diameter about 40 mm), dispersed for 0.5h at a speed of 2500r/min, filtered again, and the residue on the inner wall of the container was washed into the filter screen with tap water, and the filter screen was washed with tap water to see whether the emulsion was broken and whether there was an obvious flocculate. If the above is not present, mechanical stability is considered.
Calcium ion stability test of nonionic aqueous non-isocyanate polychloroethyl ester
The nonionic aqueous non-isocyanate polyurethanes obtained by the preparation process according to the invention have excellent emulsion stability, for example, good stability against substances (for example, calcium ions) present on the application surface which may lead to demulsification. The calcium ion stability of the nonionic aqueous non-isocyanate polychlorinated esters obtained in the following examples and comparative examples was measured according to the test method in national standard GB/T20623-2006. Specifically, 30mL of emulsion is added into a beaker, then 6mL of CaCl 2 solution with the mass fraction of 0.5% is added, the mixture is stirred uniformly and then is placed into a 50mL measuring cylinder with a plug, and after 48 hours, the phenomena of delamination, precipitation, flocculation and the like are observed. The presence or absence of flocs can be observed after the sample has been coated onto a glass plate with the aid of a glass rod in a uniform thin layer. If the above is not present, it is considered to have calcium ion stability.
Example 1
Adding 100 g of trimethylolpropane polyethylene glycol monomethyl ether Ymer TM N120 (the hydroxyl functionality of which is 2 and the number average molecular weight of which is 1000; the N value in the structure represented by the general formula (1) is about 19), 37.9 g of phenyl chloroformate, 0.012 g of 4-dimethylaminopyridine and 0.0012 g of dicyclohexylcarbodiimide into a three-neck flask provided with a stirrer, a thermometer and a reduced pressure distillation device, mixing, controlling the temperature of a reaction system to be 95 ℃, and reacting for 2.0 hours to obtain phenyl carbonate-terminated trimethylolpropane polyethylene glycol monomethyl ether; then 69 g of trimethylolpropane polyethylene glycol monomethyl ether capped by phenyl carbonate, 0.076 g of 1, 3-tetramethyl guanidine and 11.4 g of cyclohexanediamine are mixed, the temperature is raised to 130 ℃ and the reaction is continued for 2.0 hours, and then the excess cyclohexanediamine and phenol are removed by reduced pressure distillation to 160 ℃ under the condition of 100Pa of pressure, so as to obtain the nonionic type double amino hydrophilic chain extender. In the raw materials for preparing the nonionic type double-amino hydrophilic chain extender, the molar ratio of phenyl chloroformate to trimethylolpropane polyethylene glycol monomethyl ether is 2.42.
Adding 40 g of the prepared nonionic type double-amino hydrophilic chain extender and 100 g of phenyl carbonate polyether DP-1000 with the functionality of 2 and the number average molecular weight of 1238 produced by Shanxi institute of construction and sciences, inc. into a three-neck flask with a stirrer, a thermometer and a reflux device, heating to 80 ℃ for 2.0 hours, then distilling under reduced pressure to 160 ℃ under the condition of 100Pa to remove phenol, cooling, adding 175.9 g of deionized water, and dispersing at high speed to obtain the water-based non-isocyanate polychloride. The aqueous non-isocyanate polychloroethyl ester thus prepared was found to have n of 89 corresponding to the structure represented by the above-mentioned general formula (2) by chemical test means.
Then, the corresponding properties of the nonionic aqueous polyurea emulsion prepared above were tested according to the method for determining the solid content of the aqueous non-isocyanate polyurethane, the tensile strength, elongation at break and tear strength of the aqueous non-isocyanate polyurethane after curing, and the calcium ion stability of the aqueous non-isocyanate polychloroethyl ester described in detail above, and the results thereof are shown in table 1 below.
Example 2
100 G of trimethylolpropane polyethylene glycol monomethyl ether YmerTM N (having a hydroxyl functionality of 2 and a number average molecular weight of 1000; the structure represented by the general formula (1) having an N value of about 19), 43.8 g of phenyl chloroformate, 0.04 g of 4-dimethylaminopyridine and 0.01 g of N, N' -diisopropylcarbodiimide were added to a three-necked flask equipped with a stirrer, a thermometer and a vacuum distillation apparatus, and the mixture was reacted for 3.0 hours at 130℃under controlled temperature; then 69 g of trimethylolpropane polyethylene glycol monomethyl ether capped by phenyl carbonate, 0.008 g of 1, 1-dimethyl biguanide and 11.4 g of cyclohexanediamine are mixed, the mixture is heated to 160 ℃ and then reacted for 2.0 hours, and then the mixture is distilled to 160 ℃ under reduced pressure under the condition of 100Pa to remove the redundant cyclohexanediamine and phenol, so as to obtain the nonionic type double amino hydrophilic chain extender. In the raw materials for preparing the nonionic type double-amino hydrophilic chain extender, the molar ratio of phenyl chloroformate to trimethylolpropane polyethylene glycol monomethyl ether is 2.65.
50 G of the prepared nonionic type double amino hydrophilic chain extender and 200 g of phenyl carbonate polyether DP-1000 with the functionality of 2 and the number average molecular weight of 1238 produced by Shanxi institute of construction and sciences Co., ltd are added into a three-neck flask provided with a stirrer, a thermometer and a reflux device, heated to 80 ℃ for 2.0 hours, then phenol is removed by reduced pressure distillation to 160 ℃ under the condition of 100Pa, 350 g of deionized water is added after cooling, and the aqueous non-isocyanate polyurethane is obtained by high-speed dispersion. The aqueous non-isocyanate polyurethane prepared was found to have n 162 corresponding to the structure represented by the above general formula (2) by chemical test means.
Then, the corresponding properties of the nonionic aqueous polyurea emulsion prepared above were tested according to the method for determining the solid content of the aqueous non-isocyanate polychloride, the tensile strength, elongation at break and tear strength of the aqueous non-isocyanate polychloride after curing, and the calcium ion stability of the aqueous non-isocyanate polychloride described in detail above, and the results thereof are shown in table 1 below.
Example 3
100 G of trimethylolpropane polyethylene glycol monomethyl ether Ymer TM N120 (the hydroxyl functionality of which is 2 and the number average molecular weight of which is 1000; the N value in the structure represented by the general formula (1) is about 19), 37.9 g of phenyl chloroformate, 0.012 g of 4-dimethylaminopyridine and 0.008 g of N, N' -diisopropylcarbodiimide were added to a three-neck flask equipped with a stirrer, a thermometer and a vacuum distillation apparatus, and mixed, and the reaction system temperature was controlled at 98 ℃ to react for 2.0 hours; then 69 g of trimethylolpropane polyethylene glycol monomethyl ether capped by phenyl carbonate, 0.076 g of 1, 3-tetramethyl guanidine and 11.4 g of cyclohexanediamine are mixed, the mixture is heated to 130 ℃ and then reacted for 2.0 hours, and then the mixture is distilled to 160 ℃ under reduced pressure under the condition of 100Pa to remove the excessive cyclohexanediamine and phenol, so as to obtain the nonionic type double amino hydrophilic chain extender. In the raw materials for preparing the nonionic type double-amino hydrophilic chain extender, the molar ratio of phenyl chloroformate to trimethylolpropane polyethylene glycol monomethyl ether is 2.43.
50 G of the prepared nonionic type double-amino hydrophilic chain extender and 100 g of phenyl carbonate polyether DP-1000 with the functionality of 2 and the number average molecular weight of 1238 produced by Shanxi institute of construction and sciences Co., ltd are added into a three-neck flask provided with a stirrer, a thermometer and a reflux device, heated to 80 ℃ for 2.0 hours, then distilled under reduced pressure to 160 ℃ under the condition of 100Pa to remove phenol, cooled, added with 240.2 g of deionized water, and dispersed at a high speed to obtain the water-based non-isocyanate polychloride. The aqueous non-isocyanate polychloroethyl ester thus prepared was found to have n of 121 corresponding to the structure represented by the above-mentioned general formula (2) by chemical test means.
Then, the corresponding properties of the nonionic aqueous polyurea emulsion prepared above were tested according to the method for determining the solid content of the aqueous non-isocyanate polychloride, the tensile strength, elongation at break and tear strength of the aqueous non-isocyanate polychloride after curing, and the calcium ion stability of the aqueous non-isocyanate polychloride described in detail above, and the results thereof are shown in table 1 below.
Example 4
100G of trimethylolpropane polyethylene glycol monomethyl ether Ymer TM N120 (the hydroxyl functionality of which is 2 and the number average molecular weight of which is 1000; the N value in the structure represented by the general formula (1) is about 19), 37.9 g of phenyl chloroformate, 0.041 g of 4-dimethylaminopyridine and 0.001 g of dicyclohexylcarbodiimide are added into a three-neck flask equipped with a stirrer, a thermometer and a reduced pressure distillation device and mixed, and the temperature of the reaction system is controlled to 95 ℃ for 2.0 hours; then 69 g of phenyl carbonate end capped trimethylolpropane polyethylene glycol monomethyl ether, 0.05 g of 1, 3-tetramethyl guanidine and 11.4 g of cyclohexanediamine are mixed, the mixture is heated to 130 ℃ and then reacted for 2.0 hours, and then the mixture is distilled to 160 ℃ under reduced pressure under the condition of 100Pa to remove the excessive cyclohexanediamine and phenol, so as to obtain the nonionic type double amino hydrophilic chain extender. In the raw materials for preparing the nonionic type double-amino hydrophilic chain extender, the molar ratio of phenyl chloroformate to trimethylolpropane polyethylene glycol monomethyl ether is 2.43.
90 G of the prepared nonionic type double amino hydrophilic chain extender and 100 g of phenyl carbonate polyether DP-1000 with the functionality of 2 and the number average molecular weight of 1238 produced by Shanxi institute of construction and sciences Co., ltd are added into a three-neck flask provided with a stirrer, a thermometer and a reflux device, heated to 80 ℃ for 2.0 hours, then phenol is removed by reduced pressure distillation to 160 ℃ under the condition of 100Pa, 298 g of deionized water is added after cooling, and the aqueous non-isocyanate polychloride is obtained by high-speed dispersion. The aqueous non-isocyanate polychloroethyl ester thus prepared was found to have n of 59 corresponding to the structure represented by the above-mentioned general formula (2) by chemical test means.
Then, the corresponding properties of the nonionic aqueous polyurea emulsion prepared above were tested according to the method for determining the solid content of the aqueous non-isocyanate polychloroethyl, the tensile strength, elongation at break and tear strength of the aqueous non-isocyanate polyurethane after curing, and the calcium ion stability of the aqueous non-isocyanate polyurethane described in detail above, and the results thereof are shown in table 1 below.
Example 5
100G of trimethylolpropane polyethylene glycol monomethyl ether Ymer TM N120 (the hydroxyl functionality of which is 2 and the number average molecular weight of which is 1000; the N value in the structure represented by the general formula (1) is about 19), 37.9 g of phenyl chloroformate, 0.02 g of 4-dimethylaminopyridine and 0.0018 g of dicyclohexylcarbodiimide are added into a three-neck flask equipped with a stirrer, a thermometer and a reduced pressure distillation device and mixed, and the temperature of the reaction system is controlled to 95 ℃ for 2.0 hours; then 69 g of trimethylolpropane polyethylene glycol monomethyl ether capped by phenyl carbonate, 0.005 g of 1, 3-tetramethyl guanidine and 11.4 g of cyclohexanediamine are mixed, the mixture is heated to 130 ℃ and then reacted for 2.0 hours, and then the mixture is distilled to 160 ℃ under reduced pressure under the condition of 100Pa to remove the excessive cyclohexanediamine and phenol, so as to obtain the nonionic type double amino hydrophilic chain extender. In the raw materials for preparing the nonionic type double-amino hydrophilic chain extender, the molar ratio of phenyl chloroformate to trimethylolpropane polyethylene glycol monomethyl ether is 2.43. The aqueous non-isocyanate polychloroethyl ester thus prepared was found to have n of 72 corresponding to the structure represented by the above-mentioned general formula (2) by chemical test means.
50 G of the prepared nonionic type double-amino hydrophilic chain extender and 100 g of phenyl carbonate polyether DP-1000 with the functionality of 2 and the number average molecular weight of 1238 produced by Shanxi institute of construction and sciences Co., ltd are added into a three-neck flask provided with a stirrer, a thermometer and a reflux device, heated to 80 ℃ for 2.0 hours, then distilled under reduced pressure to 160 ℃ under the condition of 100Pa to remove phenol, cooled, then 611.4 g of deionized water is added, and the aqueous non-isocyanate polyurethane is obtained through high-speed dispersion. The chemical test means revealed that n in the prepared aqueous non-isocyanate polyurethane corresponds to the structure represented by the above general formula (2).
Then, the corresponding properties of the nonionic aqueous polyurea emulsion prepared above were tested according to the method for determining the solid content of the aqueous non-isocyanate polyurethane, the tensile strength, elongation at break and tear strength of the aqueous non-isocyanate polyurethane after curing, and the calcium ion stability of the aqueous non-isocyanate polyurethane described in detail above, and the results thereof are shown in table 1 below.
Example 6
100 G of trimethylolpropane polyethylene glycol monomethyl ether Ymer TM N120 (the hydroxyl functionality of which is 2 and the number average molecular weight of which is 1000; the N value in the structure represented by the general formula (1) is about 19), 29.8 g of phenyl chloroformate, 0.012 g of 4-dimethylaminopyridine and 0.0012 g of dicyclohexylcarbodiimide are added into a three-neck flask equipped with a stirrer, a thermometer and a reduced pressure distillation device and mixed, and the temperature of the reaction system is controlled to 95 ℃ and the reaction is carried out for 2.0 hours; then 69 g of phenyl carbonate end capped trimethylolpropane polyethylene glycol monomethyl ether, 0.056 g of 1, 3-tetramethyl guanidine and 7.4 g of 1, 2-propylene diamine are mixed, the mixture is heated to 130 ℃ and then reacted for 2.0 hours, and then the mixture is distilled to 160 ℃ under reduced pressure under the condition of 100Pa to remove redundant cyclohexanediamine and phenol, so as to obtain the nonionic type double amino hydrophilic chain extender. In the raw materials for preparing the nonionic type double-amino hydrophilic chain extender, the molar ratio of phenyl chloroformate to trimethylolpropane polyethylene glycol monomethyl ether is 1.9.
Adding 40 g of the prepared nonionic type double-amino hydrophilic chain extender and 100 g of phenyl carbonate polyether DP-1000 with the functionality of 2 and the number average molecular weight of 1238 produced by Shanxi institute of construction and sciences, inc. into a three-neck flask with a stirrer, a thermometer and a reflux device, heating to 80 ℃ for 2.0 hours, then distilling under reduced pressure to 160 ℃ under the condition of 100Pa to remove phenol, cooling, adding 175.9 g of deionized water, and dispersing at high speed to obtain the water-based non-isocyanate polychloride. The prepared aqueous non-isocyanate polyurethane was found to have n of 48 corresponding to the structure represented by the above general formula (2) by chemical test means.
Then, the corresponding properties of the nonionic aqueous polyurea emulsion prepared above were tested according to the method for determining the solid content of the aqueous non-isocyanate polyurethane, the tensile strength, elongation at break and tear strength of the aqueous non-isocyanate polyurethane after curing, and the calcium ion stability of the aqueous non-isocyanate polychloroethyl ester described in detail above, and the results thereof are shown in table 1 below.
Example 7
100 G of trimethylolpropane polyethylene glycol monomethyl ether Ymer TM N120 (the hydroxyl functionality of which is 2 and the number average molecular weight of which is 1000; the N value in the structure represented by the general formula (1) is about 19), 48.5 g of phenyl chloroformate, 0.012 g of 4-dimethylaminopyridine and 0.0012 g of dicyclohexylcarbodiimide are added into a three-neck flask equipped with a stirrer, a thermometer and a reduced pressure distillation device, and the mixture is reacted for 2.0 hours while controlling the temperature of the reaction system to 95 ℃; then 69 g of trimethylolpropane polyethylene glycol monomethyl ether capped by phenyl carbonate, 0.076 g of 1, 3-tetramethyl guanidine and 11.4 g of cyclohexanediamine are mixed, the mixture is heated to 130 ℃ and then reacted for 2.0 hours, and then the mixture is distilled to 160 ℃ under reduced pressure under the condition of 100Pa to remove the excessive cyclohexanediamine and phenol, so as to obtain the nonionic type double amino hydrophilic chain extender. In the raw materials for preparing the nonionic type double-amino hydrophilic chain extender, the molar ratio of phenyl chloroformate to trimethylolpropane polyethylene glycol monomethyl ether is 3.1.
40 G of the prepared nonionic type double amino hydrophilic chain extender and 100 g of phenyl carbonate polyether DP-1000 with the functionality of 2 and the number average molecular weight of 1238 produced by Shanxi institute of construction and sciences Co., ltd are added into a three-neck flask provided with a stirrer, a thermometer and a reflux device, heated to 80 ℃ for 2.0 hours, then distilled under reduced pressure to 160 ℃ under the condition of 100Pa to remove phenol, cooled and then added with 175.9 g of deionized water, and dispersed at a high speed to obtain the water-based non-isocyanate polyurethane. The aqueous non-isocyanate polychloroethyl ester thus prepared was found to have n of 62 corresponding to the structure represented by the above-mentioned general formula (2) by chemical test means.
Then, the corresponding properties of the nonionic aqueous polyurea emulsion prepared above were tested according to the method for determining the solid content of the aqueous non-isocyanate polychloride, the tensile strength, elongation at break and tear strength of the aqueous non-isocyanate polyurethane after curing, and the calcium ion stability of the aqueous non-isocyanate polychloride described in detail above, and the results thereof are shown in table 1 below.
Comparative example 1
Into a three-necked flask equipped with a stirrer, a thermometer and a reflux apparatus, 40 g of trimethylolpropane polyethylene glycol monomethyl ether Ymer TM N120 (having a hydroxyl functionality of 2 and a number average molecular weight of 1000; having an N value of about 19 in the structure represented by the general formula (1)), 100g of phenyl carbonate terminated polyether DP-1000 having a functionality of 2 and a number average molecular weight of 1238, which was produced by Shanxi institute of construction and sciences, were charged, heated to 80℃for 2.0 hours, then distilled under reduced pressure to 160℃under a pressure of 100Pa to remove phenol, cooled, and then added with 175.9 g of deionized water, and dispersed at a high speed to obtain an aqueous non-isocyanate polychloride. The aqueous non-isocyanate polyurethane prepared was found to have n of 36 corresponding to the structure represented by the above general formula (2) by chemical test means.
Then, the respective properties of the aqueous non-isocyanate polychloride prepared above were tested according to the methods for determining the solid content of the aqueous non-isocyanate polyurethane, the tensile strength, elongation at break and tear strength of the aqueous non-isocyanate polychloride after curing, and the calcium ion stability of the aqueous non-isocyanate polyurethane described in detail above, and the results thereof are shown in table 1 below.
TABLE 1 results of Performance test in examples 1-7 and comparative example 1
Examples 1 to 7 above demonstrate that the nonionic bis-amino hydrophilic chain extender according to the present invention can be used to prepare nonionic aqueous non-isocyanate polychlorinated esters, thereby greatly improving the physical properties of polyurethane products, and that the nonionic aqueous non-isocyanate polychlorinated esters obtained by using the preparation method according to the present invention have stability (including mechanical stability and calcium ion stability) conforming to industry standards and the cured products thereof have physical properties (such as tensile strength, elongation at break, tear strength, etc.) conforming to industry standards.
Further, as is apparent from comparison of examples 1 to 5 with examples 6 to 7, when a nonionic aqueous non-isocyanate polychlorinated ester is produced according to the technical scheme of the present invention and the molar ratio of phenyl chloroformate to the trimethylolpropane polyethylene glycol monomethyl ether in the production of the nonionic bisaminohydrophilic chain extender is controlled in the range of 2:1 to 3:1, it is possible to achieve balance and optimization of various excellent properties in terms of stability (including mechanical stability and calcium ion stability) and physical properties (such as tensile strength, elongation at break and tear strength, etc.).
In addition, as is apparent from the results of comparative example 1, when trimethylolpropane polyethylene glycol monomethyl ether is used instead of the nonionic bisaminohydrophilic chain extender, physical properties (such as tensile strength, elongation at break, and tear strength) of the resulting aqueous polyurethane are greatly deteriorated, as compared with the method for producing a nonionic aqueous non-isocyanate polyurethane using the nonionic bisaminohydrophilic chain extender according to the present invention.
Although specific embodiments of the application have been illustrated and described herein, it will be appreciated by those of ordinary skill in the art that a wide variety of alternate and/or equivalent implementations may be substituted for the specific embodiments shown and described without departing from the scope of the present application. This application is intended to encompass any modifications or alterations to the specific embodiments discussed in this application. Therefore, it is intended that this application be limited only by the claims and the equivalents thereof.
It will be understood by those skilled in the art that various modifications and changes may be made without departing from the scope of the present invention. Such modifications and variations are intended to fall within the scope of the invention as defined in the appended claims.
Claims (21)
1. A nonionic type bisaminohydrophilic chain extender having a structure represented by the following general formula (1):
wherein R 1 is a C 2-C10 divalent aliphatic group; and n1 is an integer of 3 to 60.
2. The nonionic, bis-amino, hydrophilic chain extender of claim 1, wherein R 1 is C 3-C6 straight, branched or cyclic alkylene.
3. The nonionic, bis-amino, hydrophilic chain extender of claim 1, wherein n1 is an integer from 3 to 37.
4. A method for preparing a nonionic bis-amino hydrophilic chain extender, the method comprising the steps of:
(1) Mixing and heating trimethylolpropane polyethylene glycol monomethyl ether, phenyl chloroformate, an esterification main catalyst and an esterification cocatalyst to obtain phenyl carbonate end-capped trimethylolpropane polyethylene glycol monomethyl ether;
(2) Mixing the phenyl carbonate end capped trimethylolpropane polyethylene glycol monomethyl ether, diamine and an amination catalyst, heating and distilling under reduced pressure to remove phenol, so as to obtain the nonionic double-amino hydrophilic chain extender, wherein:
the trimethylolpropane polyethylene glycol monomethyl ether has a structure represented by the following general formula (2):
Wherein n1 is an integer from 3 to 60, and
The diamine has a structure represented by the following general formula (3):
Wherein R 1 is a C 2-C10 divalent aliphatic group,
The esterification main catalyst is selected from one or more of 1-morpholine-1-cyclopentene, 1-pyrrolidinyl-1-cyclopentene, 1-morpholinyl-1-cyclohexene, 1- (1-pyrrolidinyl) cyclohexene, 4-dimethylaminopyridine and triethylamine;
The esterification promoter is selected from one or more of dicyclohexylcarbodiimide, N' -diisopropylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide; and
The amination catalyst is selected from one or more of 1, 3-tetramethyl guanidine, 1-dimethyl guanidine and 1,2, 3-triphenyl guanidine.
5. The method for preparing a nonionic amphiphilic amino hydrophilic chain extender of claim 4, wherein R 1 is C 3-C6 straight, branched or cyclic alkylene.
6. The method for preparing a nonionic amphiphilic amino hydrophilic chain extender of claim 4, wherein n1 is an integer from 3 to 37.
7. The method for preparing a non-ionic bis-amino hydrophilic chain extender as claimed in claim 4, wherein in the step (1), the molar ratio of the phenyl chloroformate to the trimethylolpropane polyethylene glycol monomethyl ether is in the range of 2:1 to 3:1.
8. The method for preparing a nonionic bis-amino hydrophilic chain extender as claimed in claim 4, wherein in step (1), the weight ratio of said esterification procatalyst to said esterification cocatalyst is in the range of 1:1 to 10:1.
9. The method for preparing a nonionic bis-amino hydrophilic chain extender as claimed in claim 4, wherein in the step (1), the ratio of the sum of the weights of the esterification main catalyst and the esterification co-catalyst to the sum of the weights of the trimethylolpropane polyethylene glycol monomethyl ether and phenyl chloroformate is in the range of 1 x 10 -4:1 to 1 x 10 -2:1.
10. The method for preparing a non-ionic bis-amino hydrophilic chain extender according to claim 4, wherein the diamine is one or more selected from ethylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, 1, 5-pentylenediamine, hexamethylenediamine, 1, 2-propylenediamine, 2-methyl-1, 3-propylenediamine, 2-methylpentylenediamine, phenylenediamine, m-xylylenediamine, m-cyclohexyldimethylamine, N-ethylethylenediamine, N-dimethylethylenediamine, cyclohexanediamine, p-aminocyclohexamethylenediamine, isophoronediamine, 4' -dicyclohexylmethane diamine, 3' -dimethyl-4, 4' -dicyclohexylmethane diamine.
11. The method for preparing a nonionic, bisaminohydrophilic chain extender as recited in claim 4, wherein a ratio of the amination catalyst to a sum of weights of the trimethylolpropane polyethylene glycol monomethyl ether and the polyamine capped with the phenyl carbonate in the step (2) is in a range of 1 x 10 -4:1 to 1 x 10 -2:1.
12. A nonionic aqueous non-isocyanate polychloroethyl ester having a structure represented by the following general formula (4):
wherein:
R 1 is a C 2-C10 divalent aliphatic radical;
R 2 is a divalent residue obtained after removal of two hydroxyl groups from a polyether diol having a number average molecular weight in the range of 650 to 3000;
n1 is an integer from 3 to 60; and
N2 is an integer from 35 to 180.
13. The nonionic aqueous non-isocyanate polychlorinated ester of claim 12, wherein R 1 is a C 3-C6 straight, branched or cyclic alkylene group.
14. The nonionic aqueous non-isocyanate polychlorinated ester of claim 12, wherein said polyether glycol is selected from one or more of polyethylene oxide glycol, polypropylene oxide glycol and polytetramethylene ether glycol.
15. The nonionic aqueous non-isocyanate polychloroethyl ester according to claim 12, wherein n1 is an integer from 3 to 37.
16. The nonionic aqueous non-isocyanate polychloroethyl ester according to claim 12, wherein n2 is an integer from 85 to 165.
17. A method for preparing a nonionic aqueous non-isocyanate polychloroethyl ester, the method comprising: mixing, heating and distilling under reduced pressure the nonionic bis-amino hydrophilic chain extender and the phenyl carbonate terminated polyether of any one of claims 1-3 to remove phenol, wherein:
The phenyl carbonate terminated polyether has a structure represented by the following general formula (5):
wherein R 2 is a divalent residue obtained after removal of two hydroxyl groups from a polyether diol having a number average molecular weight in the range of 650 to 3000.
18. The method for preparing a nonionic aqueous non-isocyanate polychloroethyl ester according to claim 17, wherein said polyether glycol is selected from one or more of polyethylene oxide glycol, polypropylene oxide glycol, and polytetramethylene ether glycol.
19. The method for preparing a nonionic aqueous non-isocyanate polyurethane according to claim 17, wherein the molar ratio of said nonionic bis-amino hydrophilic chain extender to said phenyl carbonate terminated polyether is in the range of 1:1 to 1.2:1.
20. The method of preparing a nonionic aqueous non-isocyanate polychloroethyl ester according to claim 17, further comprising adding water to the product.
21. The method for preparing a nonionic aqueous non-isocyanate polyurethane according to claim 20, wherein the ratio of the weight of added water to the sum of the weight of said phenyl carbonate terminated polyether, nonionic bis-amino hydrophilic chain extender is in the range of 1:1 to 5:1.
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