CN116217442A - Modified amine chain extender, polyurethane coating and preparation method thereof - Google Patents
Modified amine chain extender, polyurethane coating and preparation method thereof Download PDFInfo
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- CN116217442A CN116217442A CN202211702588.6A CN202211702588A CN116217442A CN 116217442 A CN116217442 A CN 116217442A CN 202211702588 A CN202211702588 A CN 202211702588A CN 116217442 A CN116217442 A CN 116217442A
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- Prior art keywords
- chain extender
- parts
- weight
- modified amine
- carbonate
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- 239000004970 Chain extender Substances 0.000 title claims abstract description 83
- 239000011527 polyurethane coating Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 125000003277 amino group Chemical class 0.000 title abstract description 34
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 35
- 239000004814 polyurethane Substances 0.000 claims abstract description 32
- 229920002635 polyurethane Polymers 0.000 claims abstract description 32
- -1 cyclic carbonate compound Chemical class 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims description 33
- 229920000570 polyether Polymers 0.000 claims description 32
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 31
- 239000012948 isocyanate Substances 0.000 claims description 31
- 150000002513 isocyanates Chemical class 0.000 claims description 31
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 27
- 238000001816 cooling Methods 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 21
- 229920005862 polyol Polymers 0.000 claims description 20
- 150000003077 polyols Chemical class 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 19
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical group [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- 239000002270 dispersing agent Substances 0.000 claims description 17
- 239000002318 adhesion promoter Substances 0.000 claims description 16
- 239000013530 defoamer Substances 0.000 claims description 16
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 claims description 16
- 238000007599 discharging Methods 0.000 claims description 16
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- 238000007872 degassing Methods 0.000 claims description 12
- 238000009775 high-speed stirring Methods 0.000 claims description 12
- 239000012188 paraffin wax Substances 0.000 claims description 12
- 239000004014 plasticizer Substances 0.000 claims description 12
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 8
- 238000010907 mechanical stirring Methods 0.000 claims description 7
- 239000000454 talc Substances 0.000 claims description 7
- 229910052623 talc Inorganic materials 0.000 claims description 7
- 235000012222 talc Nutrition 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 150000004982 aromatic amines Chemical class 0.000 claims description 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 6
- 239000000049 pigment Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000011065 in-situ storage Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000003973 paint Substances 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- GPXCORHXFPYJEH-UHFFFAOYSA-N 3-[[3-aminopropyl(dimethyl)silyl]oxy-dimethylsilyl]propan-1-amine Chemical compound NCCC[Si](C)(C)O[Si](C)(C)CCCN GPXCORHXFPYJEH-UHFFFAOYSA-N 0.000 claims description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 2
- MRUXVMBOICABIU-UHFFFAOYSA-N [3,5-bis(methylsulfanyl)phenyl]methanediamine Chemical compound CSC1=CC(SC)=CC(C(N)N)=C1 MRUXVMBOICABIU-UHFFFAOYSA-N 0.000 claims description 2
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 claims description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 239000002518 antifoaming agent Substances 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical group 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- FKELYXQUAFOQSG-UHFFFAOYSA-N carbonic acid;1-ethenylcyclohexene Chemical compound OC(O)=O.C=CC1=CCCCC1 FKELYXQUAFOQSG-UHFFFAOYSA-N 0.000 claims description 2
- XTUSLLYSMVWGPS-UHFFFAOYSA-N carbonic acid;cyclohexene Chemical compound OC(O)=O.C1CCC=CC1 XTUSLLYSMVWGPS-UHFFFAOYSA-N 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000009849 vacuum degassing Methods 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 1
- MYXJUONNAJPJJT-UHFFFAOYSA-N carbonochloridic acid;prop-1-ene Chemical compound CC=C.OC(Cl)=O MYXJUONNAJPJJT-UHFFFAOYSA-N 0.000 claims 1
- 125000001475 halogen functional group Chemical group 0.000 claims 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 7
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000012467 final product Substances 0.000 abstract description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 16
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 15
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 15
- 238000000576 coating method Methods 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 241001112258 Moca Species 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000011668 ascorbic acid Substances 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 239000000806 elastomer Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- AETJTBDBQRMLLQ-UHFFFAOYSA-N 4-chloro-5-methyl-1,3-dioxolan-2-one Chemical compound CC1OC(=O)OC1Cl AETJTBDBQRMLLQ-UHFFFAOYSA-N 0.000 description 1
- AOFIWCXMXPVSAZ-UHFFFAOYSA-N 4-methyl-2,6-bis(methylsulfanyl)benzene-1,3-diamine Chemical compound CSC1=CC(C)=C(N)C(SC)=C1N AOFIWCXMXPVSAZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000004148 curcumin Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
- C08G18/3831—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing urethane groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/04—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from amines with formation of carbamate groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
- C07C271/26—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
- C07C271/28—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring to a carbon atom of a non-condensed six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
Abstract
The invention provides a modified amine chain extender, a polyurethane coating and a preparation method thereof. According to the modified amine chain extender, the active cyclic carbonate compound reacts with the amino chain extender to convert the amino group with higher activity in the amino chain extender into hydroxyl group, and meanwhile, the active cyclic carbonate compound reacts with the amino chain extender to generate a compound containing urethane bonds, so that the urethane in the modified amine chain extender is introduced into a polyurethane main chain and is converted into a part of polyurethane molecular chains, and the generated final product polyurethane coating is low in viscosity and excellent in mechanical property.
Description
Technical Field
The invention belongs to the field of elastomer materials, and particularly relates to a modified amine chain extender, a polyurethane coating and a preparation method thereof.
Background
Polyurethanes, also known as polyurethanes, are a class of polymers that contain a large number of urethane linkage repeat units in the macromolecular chain, which are obtained primarily by the addition reaction of isocyanate groups (-NCO) and hydroxyl groups (-OH). Polyurethane has been developed to have industrial practical value since the development of an isocyanate and polyol addition route by Otto Bayer et al in 1937. After decades of development, the polymer has become an important member in the polymer material family, and has been widely applied to various engineering fields including chemical industry, electronics, construction, textile, automobile, medical treatment, national defense, aerospace and other fields.
Urethane linkages are characteristic functional groups of polyurethane materials, and the linkages are characterized by both a donor and an acceptor having hydrogen bonds. Under the action of hydrogen bonds, a plurality of urethane bonds are aggregated to form hard segment domains. The existence of the hard segment micro-areas enables the material to macroscopically show physical properties such as high strength, wear resistance and the like. On the other hand, the polyol component generally refers to oligomers of different molecular weights having hydroxyl groups at the ends. The hydroxyl functional groups are reacted chemically and then participate in hydrogen bonds, the rest chain segment parts exist in a loose state and are called soft segments, and the soft segment parts of the polymer molecules are gathered together and called soft segment micro-regions. The existence of soft segment micro-area can make the material macroscopically have high elasticity, high extension and other performances. Because of the existence of the soft and hard segment micro-areas, the polyurethane material integrates excellent performances such as elasticity, strength, wear resistance, hardness and the like.
On the other hand, due to the wide variety of selectivity of the raw materials, materials having different properties can be developed by different combinations. For example, the properties of polyurethane materials can be widely modified by selecting different isocyanates, polyols (polyethers, polyesters, etc.), catalysts, auxiliaries, or different shaping processes and post-treatment methods, for example, elastomers, adhesives, plastics, etc. At present, polyurethane is the only synthetic polymer material with great application value in seven fields of paint, foam, plastic, rubber, fiber, adhesive and functional polymer, and has become the special organic synthetic material with the most variety, the most wide application and the fastest development at present.
Chain extenders are one of the important materials in the composition of polyurethane materials and contribute to the hard segment content in the polyurethane molecule. It is also called a chain extender and is a substance that can expand a molecular chain and increase a molecular weight by a reaction of functional groups. The chain extender generally has the characteristics of low molecular weight, reactive reaction, strong reaction competition probability for isocyanate and a polyol system, and the like. The polyurethane molecular weight regulator not only can effectively regulate the reaction speed of a reaction system and process parameters such as viscosity increase of reactants, but also can introduce certain characteristic groups in the chain extender into a polyurethane main chain through chain extension reaction, thereby endowing polyurethane molecules with certain properties.
The polyurethane chain extender contains two or more functional groups, such as dihydric alcohols (fatty alcohols, aromatic alcohols), diamines, alcohol amines, polyols, etc. Chain extenders are used in a variety of types of polyurethane products including foams, adhesives, coatings, cast Polyurethane (CPU), thermoplastic Polyurethane (TPU), and the like. Different types or structures of chain extenders are selected according to different end applications or processing techniques. Among them, compared with the glycol chain extender, the polyurethane material prepared by adopting the amine chain extender is excellent in tensile strength, tear resistance, wear resistance and the like, because: 1) The amino reacts with isocyanate to generate urea bond, and the cohesive energy of hard segment/hard region formed by the urea bond is higher; 2) The reactivity of the amino group and isocyanate is higher, so that the reaction probability of the isocyanate and water is reduced, and the defect is reduced; 3) The amino activity is higher, the probability of side reaction is reduced, and the chain extension effect is higher. Typical side reactions are: isocyanate and active hydrogen crosslinking of urethane bonds, isocyanate self-polymerization and the like. In the academia and industry, various types of amine chain extenders are widely used. Most typically, MOCA (4, 4' -methylenebis (2-chloroaniline)) has been widely used in two-component polyurethane coatings and cast elastomers because of its reduced reactivity to amino groups due to the presence of the chlorine atom in the amino clinic, but is a solid and has a high viscosity after dissolution of the coating system. E300 (Dimethylthiotoluene diamine), E100 (diethyltoluene diamine) are also chain extenders commonly used in the industry, have relatively low viscosity at room temperature, but are highly reactive and are commonly used in spray polyurea systems.
In summary, amino chain extenders, although widely used, have a considerable difficulty: 1) The operation time is short; 2) The chain extender with a common aromatic ring structure is usually solid (crystal), such as MOCA, and the solid chain extender needs to be dissolved or melted to participate in the reaction, so that the viscosity of the system is high, the risk of precipitation (crystallization) in the storage process is caused, and great process operation difficulty is brought to the manufacture of downstream end products; 3) Aromatic amine chain extender which is liquid at normal temperature has high reaction activity and can only be used by spraying; 4) Amine chain extenders are mostly defined as dangerous chemicals.
By combining the above factors, a novel modified amine chain extender technology is developed, the chain segment of the amine chain extender can be introduced into a polyurethane polymer chain, and meanwhile, convenience can be brought to the production and manufacturing process, so that the technology is an urgent requirement of the industry.
Disclosure of Invention
In order to solve the problems, the invention provides a modified amine chain extender technology, wherein an active cyclic carbonate compound reacts with an amino chain extender to convert amino groups with higher activity in the amino chain extender into hydroxyl groups, and meanwhile, the active cyclic carbonate compound reacts with the amino chain extender to generate a compound containing a urethane bond, so that the urethane in the modified amine chain extender is introduced into a polyurethane main chain and is converted into a part of polyurethane molecular chains, and the generated final product polyurethane coating has low viscosity and more excellent mechanical properties.
The technical scheme of the invention is as follows:
the invention provides a modified amine chain extender, which is prepared from a cyclic carbonate compound and an amino chain extender by the following reaction formula (I):
wherein R is 1 Is C 2 -C n One or more molecular segments of alkyl (n is greater than or equal to 2), halogenated aromatic hydrocarbon or halogenated alkyl, ether bond, ester bond, carbonyl and siloxane;
R 2 、R 3 each independently is a hydrogen atom, C 1 -C n Alkyl (n is greater than or equal to 1), halo, and unsaturated hydrocarbyl.
Further, R 2 、R 3 Each independently H, CH 3 、CH 2 -CH 3 Any one of Cl, br, I, alkenyl and alkynyl.
Further, the amino chain extender is one or more of aromatic, aliphatic and siloxane groups.
Further, the amino chain extender is one or more of aromatic amines such as ethanolamine, methyldiethanolamine, 3 '-dichloro-4, 4' -diphenylmethane, 3, 5-dimethylthiotoluenediamine, 4 '-diaminodiphenylmethane, m-xylylenediamine, diethyltoluenediamine, methylcyclohexamethylenediamine isophoronediamine, 1, 6-hexanediamine, 4' -methylenedicyclohexylamine, propylenediamine, pentylene diamine, octylenediamine, 1, 3-bis (aminomethyl) cyclohexane, 1, 3-bis (aminopropyl) tetramethyldisiloxane, polyetheramine and the like, aliphatic amines and siloxane amines.
Further, the cyclic carbonate is one or more of ethylene carbonate, fluoroethylene carbonate, vinylene carbonate, propylene carbonate, chloropropylene carbonate, butylene carbonate, cyclohexene carbonate, vinyl cyclohexene carbonate, styrene cyclic carbonate, and the like.
The invention also provides a polyurethane coating prepared by using the modified amine chain extender, which comprises the following main raw materials in parts by weight:
isocyanate: 3-17 parts by weight;
polyol: 10-45 parts by weight;
amino chain extender: 1-15 parts by weight;
cyclic carbonates: 0.1-10 parts by weight
And (3) a plasticizer: 10-30 parts by weight;
dispersing agent: 0.05-0.5 part by weight;
inorganic powder: 20-60 parts by weight;
defoaming agent: 0-1 parts by weight;
adhesion promoters: 0-2 parts by weight;
catalyst: 0-0.5 parts by weight;
solvent: 0-10 parts by weight.
Further, the polyol is a polyether polyol having a molecular weight of 2000 to 5000.
Further, the amino chain extender is an aromatic amine, such as aromatic amine MOCA.
Further, the plasticizer is one or more of phthalic acid and chlorinated paraffin, such as one or two of diisononyl phthalate (DINP) and chlorinated paraffin number 52.
Further, the dispersant is a polycarboxylic acid, such as an alkyl ammonium salt solution of a polycarboxylic acid BYK-AT203.
Further, the inorganic powder is one or more of organic bentonite, calcium carbonate, talcum powder and the like.
Further, the pigment is iron brown.
Further, the defoamer is a silicone-based oily defoamer, such as BYK065.
Further, the adhesion promoter is one or more of a siloxane oligomer, such as siloxane oligomer silok-6654.
Further, the catalyst is an organotin-based catalyst, such as organotin T-12.
Further, the solvent is No. 150 solvent oil.
The invention also provides a preparation method of the polyurethane coating, which comprises the following steps:
step S1: preparation of A component
Adding polyether polyol into a reactor, starting a vacuum environment in the reactor, stirring and heating to 110-120 ℃, and keeping the temperature for 2-3h; then cooling to 65-70 ℃, adding stoichiometric isocyanate under high-speed stirring, reacting for 0.5h, heating to 80-85 ℃, continuing to react for 3-4h at the temperature, cooling to below 50 ℃, removing bubbles in vacuum for 0.5-1h, discharging to obtain isocyanate prepolymer for later use;
step S2: preparation of component B
S2-1: adding an amino chain extender, cyclic carbonate, polyhydric alcohol, plasticizer and dispersing agent into a reactor, starting mechanical stirring until the mixture is uniform, dehydrating raw materials, and synthesizing a modified amine chain extender in situ;
s2-2: gradually heating the reactor to 90-100 ℃, adding inorganic powder such as pigment, calcium carbonate, talcum powder and the like, and mechanically stirring uniformly;
s2-3: starting vacuum at least-0.095 MPa, continuously heating the reactor to 110-120 ℃, and carrying out dehydration reaction for 2-3h after the temperature reaches the set temperature, wherein the process is that the raw materials are dehydrated, and the modified amine chain extender is synthesized in situ;
s2-4: after dehydration, the temperature of the reactor is reduced to 50-55 ℃, and the catalyst, the defoamer, the adhesion promoter and the solvent are added under the stirring condition and stirred for 1-2h; then cooling to below 50 ℃, degassing for 30min-1h under the condition that the vacuum degree is minus 0.095MPa, and discharging for later use;
step S3: preparation of polyurethane paint
The component A and the component B are mixed according to the weight ratio A, B=1 (0.5-4).
Further, in the step S1, the isocyanate prepolymer is obtained by polyaddition reaction of isocyanate and polyether polyol. Wherein the polyether polyol has an R value of 1.9 to 2.1.
Further, in step S2-1, the mechanical stirring rate is 300rpm.
The invention also provides a preparation method of the polyurethane coating, which comprises the following steps:
step T1: raw material dehydration, in situ synthesis comprising modified amine chain extender
T1-1: adding an amino chain extender, cyclic carbonate, polyol, plasticizer and dispersing agent into a reactor, and starting mechanical stirring until the mixture is uniform;
t1-2: gradually heating the reactor to 90-100 ℃, adding inorganic powder such as pigment, calcium carbonate, talcum powder and the like, and mechanically stirring uniformly;
t1-3: starting vacuum at least-0.095 MPa, continuously heating the reactor to 110-120 ℃, and carrying out dehydration reaction for 2-3h after the temperature reaches the set temperature, and marking the mixture as a mixture M;
step T2: preparation of polyurethane paint
Cooling the obtained mixture M to 65-70 ℃, adding stoichiometric isocyanate, reacting for 0.5h, heating to 80-85 ℃, continuing to react for more than 3h after the temperature reaches the set temperature, cooling to 50-55 ℃, adding auxiliary agents such as defoamer, adhesion promoter, catalyst, solvent and the like, stirring uniformly, vacuum degassing, soaking for 0.5h, and discharging.
Further, in step T1-1, the mechanical stirring rate is 300rpm.
Further, in step T1-2, the mechanical stirring rate is 500rpm.
The invention has the following beneficial effects:
1. the invention synthesizes a novel modified amine chain extender. The modified amine chain extender is prepared by converting amino groups with higher activity in the amino chain extender into hydroxyl groups through the reaction of an active cyclic carbonate compound and the amino chain extender. In one aspect, the reactive cyclic carbonate compound reacts with the amino chain extender to form a urethane-linked compound, which is further reacted, incorporated into the polyurethane backbone, and converted to a portion of the polyurethane molecular chain, i.e., the resin. On the other hand, the modified amine chain extender obtained by reacting the easily crystallized amino chain extender with the cyclic carbonate is a liquefied product, so that the viscosity of a polyurethane reaction system is reduced, and the operation time for reacting with isocyanate is prolonged. In conclusion, by adopting the synthesis and modification technology of the amino chain extender, the addition amount of the resin (the cyclic carbonate is changed into a resin chain segment to be fixed on a molecular chain) is reduced, and the application range of the amino chain extender is expanded.
2. Aiming at the problems that the amino chain extender has higher reaction activity and short operation time, partial solid amino chain extender is difficult to dissolve in a system and is easy to separate out in the storage process, and the like, the invention adopts the cyclic carbonate compound as a reactant and utilizes the mechanism of the ring-opening reaction of the cyclic carbonate compound and the amino chain extender/amino compound to prepare the modified chain extender/oligomer containing the carbamate bond. Although the amino groups of the amino chain extender are not converted to urea bonds with isocyanate, one amino group is converted to one urethane bond first, and the hydroxyl groups generated after ring opening are further reacted with isocyanate to form urethane bonds, i.e., one amino group is finally converted to two urethane bonds. Compared with the method that amino is directly reacted with isocyanate to be converted into urea bond, the polyurethane polymer generated by the technical route has larger molecular weight and higher hard segment content.
3. The modification method of the chain extender/amino compound has the outstanding advantages of simple process, easy realization, low cost and the like, and the product has low viscosity and more excellent performance, and is particularly suitable for preparing materials in the fields of coating, elastomer, adhesive and the like.
Drawings
FIG. 1 is a Fourier transform infrared (FI-IR) spectrum of a modified amine chain extender.
Wherein the amine chain extender is a modified amine chain extender product obtained by continuously reacting MOCA with Propylene Carbonate (PC) for 7-10 hours at 110 ℃ in a nitrogen atmosphere. And uniformly spreading a sample of the modified amine chain extender product on the glass of the transmission panel, and scanning after compacting by using a rotary upper arm. Setting the scanning range to 4000-400cm -1 The number of scans was 32, the resolution was 4cm -1 。
The designations in the drawings are as follows:
1. propylene carbonate; 2. modified amine chain extender products; 3. MOCA.
Detailed Description
The invention will be described in detail with reference to examples, but the invention is not limited thereto.
The experimental methods described in the following examples are conventional methods unless otherwise specified.
The reagents and materials are well known materials and can be prepared or obtained commercially by those skilled in the art.
The polyether polyols, isocyanates, and cyclic carbonates used in the examples were provided for the Wanhua chemistry; MOCA (4, 4' -methylenebis (2-chloroaniline)) is supplied by Jiangsu xiangyuan; e300 is provided by Zhangjia Kong elegance chemical Co., ltd; calcium carbonate, talc, etc. are provided by Jiangxi Guangdong sources.
In order to clearly and intuitively illustrate the characteristics of the modification technical route, the following examples and comparative examples adopt the same formula system, and the mass ratio of the component A to the component B is 1:1.
example 1:
the polyurethane coating comprises the following raw materials in parts by weight:
the component A comprises the following components in parts by weight:
isocyanate (MDI): 27.5 parts by weight
Polyether glycol (molecular weight 2000): 63.5 parts by weight
Polyether triol (molecular weight 5000): 9 parts by weight:
the component B comprises the following components in parts by weight:
polyether polyol (molecular weight 5000): 5 parts by weight;
MOCA chain extender: 13.8 parts by weight;
propylene carbonate: 5.3 parts by weight;
diisononyl phthalate plasticizers: 8.4 parts by weight;
BYK-AT203 dispersant: 0.5 parts by weight;
chlorinated paraffin No. 52: 24.3 parts by weight;
inorganic powder: comprises 1 part of iron oxide brown, 33 parts of calcium carbonate and 6.5 parts of talcum powder;
BYK065 defoamer: 0.3 parts by weight;
adhesion promoter Silok-6654:0.1 parts by weight;
t-12 catalyst: 0.05 parts by weight;
no. 150 solvent oil: 2 parts by weight;
the preparation method comprises the following steps:
and (3) preparing a component A: 63.5 parts of polyether glycol (molecular weight 2000) and 9 parts of polyether triol (molecular weight 5000) are added into a four-neck flask, stirred and heated to 110 ℃, and dehydrated for 2-3 hours under the condition of vacuum degree of-0.095 MPa. Cooling to 65 ℃, adding 27.5 parts of isocyanate MDI under high-speed stirring, reacting for 0.5h, then heating to 85 ℃, and continuing to react for 3h. Cooling to below 50deg.C, degassing under vacuum degree of-0.095 MPa for 0.5 hr, and discharging.
And (2) preparing a component B: into a four-necked flask, 5 parts of polyether triol (molecular weight: 5000), 5.3 parts of Propylene Carbonate (PC), 8.4 parts of diisononyl phthalate (DINP), 24.3 parts of No. 52 chlorinated paraffin, 0.5 part of dispersant BYK-AT203, and 1 part of iron oxide brown, 33 parts of calcium carbonate, 6.5 parts of talc and 13.8 parts of MOCA were added while stirring and heating to 90 ℃. After stirring evenly, heating to 110-115 ℃, simultaneously starting vacuum to-0.095 MPa, and dehydrating for 2-3h. The temperature is reduced to below 55 ℃, 0.05 part of catalyst T-12,0.3 parts of defoamer BYK065,0.1 part of adhesion promoter Silok-6654 and 2 parts of No. 150 solvent oil are added under high-speed stirring, and stirring is carried out for 1.5h. Cooling to below 50deg.C, degassing under vacuum degree of-0.095 MPa for 0.5 hr, and discharging.
And (3) preparing a coating: and (3) uniformly stirring the component B before batching, accurately mixing the component A and the component B according to the weight ratio required by the product, stirring for 3-4min to obtain the uniformly mixed coating, preparing a sample, curing for 7d under the standard condition, and testing.
Example 2:
the polyurethane coating comprises the following raw materials in parts by weight:
the component A comprises the following components in parts by weight:
isocyanate (MDI): 27.5 parts by weight
Polyether glycol (molecular weight 2000): 63.5 parts by weight
Polyether triol (molecular weight 5000): 9 parts by weight:
the component B comprises the following components in parts by weight:
polyether triol (molecular weight 5000): 5 parts by weight;
MOCA chain extender: 13.8 parts by weight;
propylene carbonate: 2.7 parts by weight;
diisononyl phthalate plasticizers: 8.4 parts by weight;
BYK-AT203 dispersant: 0.5 parts by weight;
chlorinated paraffin No. 52: 26.9 parts by weight;
inorganic powder: comprises 1 part of iron oxide brown, 33 parts of calcium carbonate and 6.5 parts of talcum powder;
BYK065 defoamer: 0.3 parts by weight;
adhesion promoter Silok-6654:0.1 parts by weight;
t-12 catalyst: 0.05 parts by weight;
no. 150 solvent oil: 2 parts by weight;
the preparation method comprises the following steps:
and (3) preparing a component A: 63.5 parts of polyether glycol (molecular weight 2000) and 9 parts of polyether triol (molecular weight 5000) are added into a four-neck flask, stirred and heated to 110 ℃, and dehydrated for 2-3 hours under the condition of vacuum degree of-0.095 MPa. Cooling to 65 ℃, adding 27.5 parts of isocyanate MDI under high-speed stirring, reacting for 0.5h, then heating to 85 ℃, and continuing to react for 3h. Cooling to below 50deg.C, degassing under vacuum degree of-0.095 MPa for 0.5 hr, and discharging.
And (2) preparing a component B: into a four-necked flask, 5 parts of polyether triol (molecular weight: 5000), 2.7 parts of Propylene Carbonate (PC), 8.4 parts of diisononyl phthalate (DINP), 26.9 parts of No. 52 chlorinated paraffin, 0.5 part of dispersant BYK-AT203, and 1 part of iron oxide brown, 33 parts of calcium carbonate, 6.5 parts of talc and 13.8 parts of MOCA were added while stirring and heating to 90 ℃. After stirring evenly, heating to 110-115 ℃, simultaneously starting vacuum to-0.095 MPa, and dehydrating for 2-3h. The temperature is reduced to below 55 ℃, 0.05 part of catalyst T-12,0.3 parts of defoamer BYK065,0.1 part of adhesion promoter Silok-6654 and 2 parts of No. 150 solvent oil are added under high-speed stirring, and stirring is carried out for 1.5h. Cooling to below 50deg.C, degassing under vacuum degree of-0.095 MPa for 0.5 hr, and discharging.
And (3) preparing a coating: and (3) uniformly stirring the component B before batching, accurately mixing the component A and the component B according to the weight ratio required by the product, stirring for 3-4min to obtain the uniformly mixed coating, preparing a sample, curing for 7d under the standard condition, and testing.
Example 3:
the polyurethane coating comprises the following raw materials in parts by weight:
the component A comprises the following components in parts by weight:
isocyanate (MDI): 27.5 parts by weight
Polyether glycol (molecular weight 2000): 63.5 parts by weight
Polyether triol (molecular weight 5000): 9 parts by weight:
the component B comprises the following components in parts by weight:
polyether triol (molecular weight 5000): 7.2 parts by weight;
e00 chain extender: 7.5 parts by weight;
propylene carbonate: 3.5 parts by weight;
diisononyl phthalate plasticizers: 8.4 parts by weight;
BYK-AT203 dispersant: 0.5 parts by weight;
chlorinated paraffin No. 52: 26.9 parts by weight;
inorganic powder: comprises 1 part of iron oxide brown, 33 parts of calcium carbonate and 6.5 parts of talcum powder;
BYK065 defoamer: 0.3 parts by weight;
adhesion promoter Silok-6654:0.1 parts by weight;
t-12 catalyst: 0.05 parts by weight;
no. 150 solvent oil: 2 parts by weight;
the preparation method comprises the following steps:
and (3) preparing a component A: 63.5 parts of polyether glycol (molecular weight 2000) and 9 parts of polyether triol (molecular weight 5000) are added into a four-neck flask, stirred and heated to 110 ℃, and dehydrated for 2-3 hours under the condition of vacuum degree of-0.095 MPa. Cooling to 65 ℃, adding 27.5 parts of isocyanate MDI under high-speed stirring, reacting for 0.5h, then heating to 85 ℃, and continuing to react for 3h. Cooling to below 50deg.C, degassing under vacuum degree of-0.095 MPa for 0.5 hr, and discharging.
And (2) preparing a component B: into a four-necked flask, 7.2 parts of polyether triol (molecular weight: 5000), 3.5 parts of Propylene Carbonate (PC), 9 parts of diisononyl phthalate (DINP), 29.6 parts of No. 52 chlorinated paraffin, 0.5 part of dispersant BYK-AT203, and 1 part of iron oxide brown, 33 parts of calcium carbonate, 6.5 parts of talc and 7.5 parts of E300 were added while stirring and heating to 90 ℃. After stirring evenly, heating to 110-115 ℃, simultaneously starting vacuum to-0.095 MPa, and dehydrating for 2-3h. The temperature is reduced to below 55 ℃, 0.05 part of catalyst T-12,0.3 parts of defoamer BYK065,0.1 part of adhesion promoter Silok-6654 and 2 parts of No. 150 solvent oil are added under high-speed stirring, and stirring is carried out for 1.5h. Cooling to below 50deg.C, degassing under vacuum degree of-0.095 MPa for 0.5 hr, and discharging.
And (3) preparing a coating: and (3) uniformly stirring the component B before batching, accurately mixing the component A and the component B according to the weight ratio required by the product, stirring for 3-4min to obtain the uniformly mixed coating, preparing a sample, curing for 7d under the standard condition, and testing.
Comparative example 1:
and (3) preparing a component A: 63.5 parts of polyether glycol (molecular weight 2000) and 9 parts of polyether triol (molecular weight 5000) are added into a four-neck flask, stirred and heated to 110 ℃, and dehydrated for 2-3 hours under the condition of vacuum degree of-0.095 MPa. Cooling to 65 ℃, adding 27.5 parts of isocyanate MDI under high-speed stirring, reacting for 0.5h, then heating to 85 ℃, and continuing to react for 3h. Cooling to below 50deg.C, degassing under vacuum degree of-0.095 MPa for 0.5 hr, and discharging.
And (2) preparing a component B: into a four-necked flask, 5 parts of polyether triol (molecular weight: 5000), 9 parts of diisononyl phthalate (DINP), 29 parts of chlorinated paraffin No. 52 and 0.5 part of dispersant BYK-AT203 were added, and the mixture was stirred and heated to 90 ℃, followed by addition of 1 part of iron oxide brown, 33 parts of calcium carbonate, 6.5 parts of talc and 13.8 parts of MOCA. After stirring evenly, heating to 110-115 ℃, simultaneously starting vacuum to-0.095 MPa, and dehydrating for 2-3h. The temperature is reduced to below 55 ℃, 0.05 part of catalyst T-12,0.3 parts of defoamer BYK065,0.1 part of adhesion promoter Silok-6654 and 2 parts of No. 150 solvent oil are added under high-speed stirring, and stirring is carried out for 1.5h. Cooling to below 50deg.C, degassing under vacuum degree of-0.095 MPa for 0.5 hr, and discharging.
And (3) preparing a coating: and (3) uniformly stirring the component B before batching, accurately mixing the component A and the component B according to the weight ratio required by the product, stirring for 3-4min to obtain the uniformly mixed coating, preparing a sample, curing for 7d under the standard condition, and testing.
Comparative example 2:
and (3) preparing a component A: 63.5 parts of polyether glycol (molecular weight 2000) and 9 parts of polyether triol (molecular weight 5000) are added into a four-neck flask, stirred and heated to 110 ℃, and dehydrated for 2-3 hours under the condition of vacuum degree of-0.095 MPa. Cooling to 65 ℃, adding 27.5 parts of isocyanate MDI under high-speed stirring, reacting for 0.5h, then heating to 85 ℃, and continuing to react for 3h. Cooling to below 50deg.C, degassing under vacuum degree of-0.095 MPa for 0.5 hr, and discharging.
And (2) preparing a component B: into a four-necked flask, 7.2 parts of polyether triol (molecular weight: 5000), 9 parts of diisononyl phthalate (DINP), 33 parts of chlorinated paraffin No. 52 and 0.5 part of dispersant BYK-AT203 were charged, and the mixture was stirred and heated to 90 ℃, followed by addition of 1 part of iron oxide brown, 33 parts of calcium carbonate, 6.5 parts of talc and 7.5 parts of E300. After stirring evenly, heating to 110-115 ℃, simultaneously starting vacuum to-0.095 MPa, and dehydrating for 2-3h. The temperature is reduced to below 55 ℃, 0.05 part of catalyst T-12,0.3 parts of defoamer BYK065,0.1 part of adhesion promoter Silok-6654 and 2 parts of No. 150 solvent oil are added under high-speed stirring, and stirring is carried out for 1.5h. Cooling to below 50deg.C, degassing under vacuum degree of-0.095 MPa for 0.5 hr, and discharging.
And (3) preparing a coating: and (3) uniformly stirring the component B before batching, accurately mixing the component A and the component B according to the weight ratio required by the product, stirring for 3-4min to obtain the uniformly mixed coating, preparing a sample, curing for 7d under the standard condition, and testing.
TABLE 1 results of Performance test of polyurethane coatings of examples 1-3 and comparative examples 1-3
In table 1, the comparison of comparative example 1, example 1 and example 2 shows that the viscosity of the B-component is significantly reduced by modification of the solid MOCA with PC, and that the elongation at break of the polyurethane is significantly increased after the reaction of MOCA with PC, indicating that the molecular weight of the polyurethane molecular chain is increased. It was further found by comparative example 2 and example 3 that modification of liquid E300 by PC did not increase the viscosity of the B component, but the elongation at break was significantly increased. Examples 1-3 show that the physical and mechanical properties of the waterproof coating can still meet the requirements of the polyurethane waterproof coating directly used for the waterproof layer in TB/T2965-2018 no matter how modified by PC.
The above description is only of the preferred embodiment of the present invention, and is not intended to limit the present invention in any other way, but is intended to cover any modifications or equivalent variations according to the technical spirit of the present invention, which fall within the scope of the present invention as defined by the appended claims.
Claims (20)
1. The modified amine chain extender is characterized in that the modified amine chain extender is prepared from a cyclic carbonate compound and an amino chain extender through the following reaction formula (I):
wherein R is 1 Is C 2 -C n One or more molecular segments of alkyl (n is greater than or equal to 2), halogenated aromatic hydrocarbon or halogenated alkyl, ether bond, ester bond, carbonyl and siloxane;
R 2 、R 3 each independently is a hydrogen atom, C 1 -C n Alkyl (n is greater than or equal to 1), halo, and unsaturated hydrocarbyl.
2. The modified amine chain extender of claim 1 which isCharacterized in that R 2 、R 3 Each independently H, CH 3 、CH 2 -CH 3 Any one of Cl, br, I, alkenyl and alkynyl.
3. The modified amine chain extender of claim 1 or 2, wherein the amino chain extender is one or more of aromatic, aliphatic, and silicone based.
4. The modified amine chain extender of claim 3, wherein the amino chain extender is one or more of ethanolamine, methyldiethanolamine, 3 '-dichloro-4, 4' -diphenylmethane, 3, 5-dimethylthiotoluenediamine, 4 '-diaminodiphenylmethane, m-xylylenediamine, diethyltoluenediamine, methylcyclohexamethylenediamine isophoronediamine, 1, 6-hexanediamine, 4' -methylenedicyclohexylamine, propylenediamine, pentylene diamine, octylamine, 1, 3-bis (aminomethyl) cyclohexane, 1, 3-bis (aminopropyl) tetramethyldisiloxane, polyetheramine and other aromatic amines, aliphatic amines, and siloxane-based amines.
5. The modified amine chain extender of claim 1 or 2, wherein the cyclic carbonate is one or more of ethylene carbonate, fluoroethylene carbonate, vinylene carbonate, propylene chlorocarbonate, butylene carbonate, cyclohexene carbonate, vinylcyclohexene carbonate, styrene cyclic carbonate, and the like.
6. A polyurethane coating prepared with the modified amine chain extender of any one of the preceding claims 1-5, characterized in that the polyurethane coating comprises the following main raw materials in parts by weight:
isocyanate: 3-17 parts by weight;
polyol: 10-45 parts by weight;
amino chain extender: 1-15 parts by weight;
cyclic carbonates: 0.1-10 parts by weight
And (3) a plasticizer: 10-30 parts by weight;
dispersing agent: 0.05-0.5 part by weight;
inorganic powder: 20-60 parts by weight;
defoaming agent: 0-1 parts by weight;
adhesion promoters: 0-2 parts by weight;
catalyst: 0-0.5 parts by weight;
solvent: 0-10 parts by weight.
7. The method of claim 6, wherein the polyol is a polyether polyol having a molecular weight of 2000 to 5000.
8. The method of claim 7, wherein the amino chain extender is an aromatic amine.
9. The method of claim 7, wherein the plasticizer is one or more of ortho-benzene, chlorinated paraffin.
10. The method according to claim 9, wherein the plasticizer is one or both of diisononyl phthalate and chlorinated paraffin number 52.
11. The method of claim 7, wherein the dispersant is a polycarboxylic acid.
12. The method of claim 11, wherein the dispersant is BYK-AT203, which is an alkylammonium salt solution of a polycarboxylic acid.
13. The method of claim 7, wherein the inorganic powder is one or more of organobentonite, calcium carbonate, talc, and the like.
14. The method of claim 7, wherein the pigment is iron oxide brown.
15. The method of claim 7, wherein the defoamer is a silicone-based oily defoamer.
16. The method of claim 7, wherein the adhesion promoter is a siloxane oligomer.
17. The method of claim 7, wherein the catalyst is an organotin-based catalyst.
18. The method of claim 7, wherein the solvent is No. 150 solvent oil.
19. A process for preparing a polyurethane coating as claimed in any one of claims 6 to 18, which comprises:
step S1: preparation of A component
Adding polyether polyol into a reactor, starting a vacuum environment in the reactor, stirring and heating to 110-120 ℃, and keeping the temperature for 2-3h; then cooling to 65-70 ℃, adding stoichiometric isocyanate under high-speed stirring, reacting for 0.5h, heating to 80-85 ℃, continuing to react for 3-4h at the temperature, cooling to below 50 ℃, removing bubbles in vacuum for 0.5-1h, discharging to obtain isocyanate prepolymer for later use;
step S2: preparation of component B
S2-1: adding an amino chain extender, cyclic carbonate, polyol, plasticizer and dispersing agent into a reactor, and starting mechanical stirring until the mixture is uniform;
s2-2: gradually heating the reactor to 90-100 ℃, adding inorganic powder such as pigment, calcium carbonate, talcum powder and the like, and mechanically stirring uniformly;
s2-3: starting vacuum at least-0.095 MPa, continuously heating the reactor to 110-120 ℃, and carrying out dehydration reaction for 2-3h after the temperature reaches the set temperature, wherein the process is that the raw materials are dehydrated, and the modified amine chain extender is synthesized in situ;
s2-4: after dehydration, the temperature of the reactor is reduced to 50-55 ℃, and the catalyst, the defoamer, the adhesion promoter and the solvent are added under the stirring condition and stirred for 1-2h; then cooling to below 50 ℃, degassing for 30min-1h under the condition that the vacuum degree is minus 0.095MPa, and discharging for later use;
step S3: preparation of polyurethane paint
The component A and the component B are mixed according to the weight ratio A, B=1 (0.5-4).
20. A process for preparing a polyurethane coating as claimed in any one of claims 6 to 19, which comprises:
step T1: raw material dehydration, in situ synthesis comprising modified amine chain extender
T1-1: adding an amino chain extender, cyclic carbonate, polyol, plasticizer and dispersing agent into a reactor, and starting mechanical stirring until the mixture is uniform;
t1-2: gradually heating the reactor to 90-100 ℃, adding inorganic powder such as pigment, calcium carbonate, talcum powder and the like, and mechanically stirring uniformly;
t1-3: starting vacuum at least-0.095 MPa, continuously heating the reactor to 110-120 ℃, and carrying out dehydration reaction for 2-3h after the temperature reaches the set temperature, and marking the mixture as a mixture M;
step T2: preparation of polyurethane paint
Cooling the obtained mixture M to 65-70 ℃, adding stoichiometric isocyanate, reacting for 0.5h, heating to 80-85 ℃, continuing to react for more than 3h after the temperature reaches the set temperature, cooling to 50-55 ℃, adding auxiliary agents such as defoamer, adhesion promoter, catalyst, solvent and the like, stirring uniformly, vacuum degassing, soaking for 0.5h, and discharging.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105732939A (en) * | 2016-02-19 | 2016-07-06 | 中国科学院长春应用化学研究所 | Waterborne polyurethane, preparing method and waterborne polyurethane adhesive |
| CN110862336A (en) * | 2019-10-29 | 2020-03-06 | 中国科学院山西煤炭化学研究所 | Alcohol amine chain extender, preparation method and application |
| CN110894275A (en) * | 2019-12-19 | 2020-03-20 | 山东一航新材料科技有限公司 | Environment-friendly polyurethane chain extender and preparation method and application thereof |
| CN111004152A (en) * | 2019-12-19 | 2020-04-14 | 山东一航新材料科技有限公司 | Environment-friendly polyurethane chain extender and preparation method and application thereof |
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- 2022-12-29 CN CN202211702588.6A patent/CN116217442A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105732939A (en) * | 2016-02-19 | 2016-07-06 | 中国科学院长春应用化学研究所 | Waterborne polyurethane, preparing method and waterborne polyurethane adhesive |
| CN110862336A (en) * | 2019-10-29 | 2020-03-06 | 中国科学院山西煤炭化学研究所 | Alcohol amine chain extender, preparation method and application |
| CN110894275A (en) * | 2019-12-19 | 2020-03-20 | 山东一航新材料科技有限公司 | Environment-friendly polyurethane chain extender and preparation method and application thereof |
| CN111004152A (en) * | 2019-12-19 | 2020-04-14 | 山东一航新材料科技有限公司 | Environment-friendly polyurethane chain extender and preparation method and application thereof |
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