CN115894847A - Polyurea composition and preparation method and application thereof - Google Patents
Polyurea composition and preparation method and application thereof Download PDFInfo
- Publication number
- CN115894847A CN115894847A CN202211476722.5A CN202211476722A CN115894847A CN 115894847 A CN115894847 A CN 115894847A CN 202211476722 A CN202211476722 A CN 202211476722A CN 115894847 A CN115894847 A CN 115894847A
- Authority
- CN
- China
- Prior art keywords
- polyurea composition
- titanium dioxide
- formula
- polyaluminium
- prepolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920002396 Polyurea Polymers 0.000 title claims abstract description 39
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- -1 titanium siloxane Chemical class 0.000 claims abstract description 74
- 239000010936 titanium Substances 0.000 claims abstract description 45
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 37
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000012948 isocyanate Substances 0.000 claims abstract description 33
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 33
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 239000001023 inorganic pigment Substances 0.000 claims abstract description 16
- 229920005862 polyol Polymers 0.000 claims abstract description 15
- 150000003077 polyols Chemical class 0.000 claims abstract description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 11
- 229920000570 polyether Polymers 0.000 claims abstract description 11
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 8
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 239000007822 coupling agent Substances 0.000 claims description 9
- 239000011159 matrix material Substances 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 239000000049 pigment Substances 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- QTRSWYWKHYAKEO-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-henicosafluorodecyl-tris(1,1,2,2,2-pentafluoroethoxy)silane Chemical compound FC(F)(F)C(F)(F)O[Si](OC(F)(F)C(F)(F)F)(OC(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F QTRSWYWKHYAKEO-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 3
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 229940089951 perfluorooctyl triethoxysilane Drugs 0.000 claims description 3
- BPCXHCSZMTWUBW-UHFFFAOYSA-N triethoxy(1,1,2,2,3,3,4,4,5,5,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F BPCXHCSZMTWUBW-UHFFFAOYSA-N 0.000 claims description 3
- AVYKQOAMZCAHRG-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F AVYKQOAMZCAHRG-UHFFFAOYSA-N 0.000 claims description 3
- 125000000391 vinyl group Chemical class [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Chemical class 0.000 claims description 3
- 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 2
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 claims description 2
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical compound [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 claims 2
- 150000001408 amides Chemical class 0.000 claims 1
- 239000003755 preservative agent Substances 0.000 claims 1
- 230000002335 preservative effect Effects 0.000 claims 1
- 125000003277 amino group Chemical group 0.000 abstract description 6
- 239000004970 Chain extender Substances 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000000704 physical effect Effects 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 238000005536 corrosion prevention Methods 0.000 abstract 1
- 125000000623 heterocyclic group Chemical group 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 239000011527 polyurethane coating Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 30
- 238000000034 method Methods 0.000 description 19
- 238000010992 reflux Methods 0.000 description 19
- 239000001054 red pigment Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 description 13
- 238000009472 formulation Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 10
- 229910052793 cadmium Inorganic materials 0.000 description 10
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 8
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000008096 xylene Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 7
- 239000000806 elastomer Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 6
- 150000001661 cadmium Chemical class 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- FSIJKGMIQTVTNP-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C=C)C=C FSIJKGMIQTVTNP-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 3
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 3
- 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 2
- 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 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910002661 O–Ti–O Inorganic materials 0.000 description 1
- 229910002655 O−Ti−O Inorganic materials 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000007901 in situ hybridization Methods 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000010107 reaction injection moulding Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 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
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- WROMPOXWARCANT-UHFFFAOYSA-N tfa trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F.OC(=O)C(F)(F)F WROMPOXWARCANT-UHFFFAOYSA-N 0.000 description 1
- IVZTVZJLMIHPEY-UHFFFAOYSA-N triphenyl(triphenylsilyloxy)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)O[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 IVZTVZJLMIHPEY-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
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- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
-
- 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
-
- 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
- C08G18/61—Polysiloxanes
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
-
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Abstract
The invention discloses a polyurea composition, a preparation method thereof and application thereof, wherein the isocyanate component comprises a prepolymer and an inorganic pigment, and the raw materials of the prepolymer comprise polyisocyanate, polyol and nano titanium dioxide hybrid polyaluminium titanium siloxane with a specific structure; the amino compound component comprises amino-terminated polyether and selective amine chain extender, and the nano titanium dioxide hybrid polyaluminium titanium siloxane with a specific structure is connected to a polyurea molecular structure through in-situ heterocyclic polymerization, so that the temperature resistance and flame retardance are greatly improved, the flexibility is also greatly improved, and the polyurethane coating has the characteristics of high curing speed, insensitivity to moisture and temperature, good thermal stability, excellent corrosion resistance and good physical property, and can be widely applied to corrosion prevention in the fields of chemical engineering and the like.
Description
Technical Field
The invention relates to the technical field of anticorrosive materials, and particularly relates to a polyurea composition and a preparation method and application thereof.
Background
Polyurea elastomer technology was developed on the basis of reaction injection molding in the middle and late years of the last century. The polyurea elastomers are defined by the american polyurea development society as follows: polyurea elastomers are elastomeric materials formed from the reaction of an isocyanate component, which may be a monomer, a derivative of an isocyanate, a prepolymer, and an amino compound component. The elastomer material has excellent physical and chemical properties, such as mechanical property, wear resistance, corrosion resistance and the like, does not contain a catalyst, and is not influenced by the environmental temperature and humidity during construction. However, the existing polyurea material also shows some defects, such as low crosslinking density, general chemical structure stability, low wetting capacity to a substrate and the like, and in order to break through the single limitation of the material, improve the comprehensive performance and expand the application range, other materials are required to be modified. The materials mainly comprise acrylic acid, epoxy resin and the like, the modified polyurea elastomer material achieves certain achievements, the performance of the modified polyurea elastomer material is improved to a certain extent, but the existing modified polyurea elastomer material has insufficient water repellency and water repellency, has general temperature resistance, can only be used below 150 ℃, has lower flame retardant grade and needs to be improved in mechanical strength.
Disclosure of Invention
It is an object of the present invention to overcome one or more of the deficiencies of the prior art and to provide an improved polyurea composition.
The invention also provides a preparation method of the polyurea composition.
The invention also provides the application of the polyurea composition in anticorrosive materials, for example, the polyurea composition is used for the anticorrosion of various metal chemical equipment in the petroleum and chemical industry, such as the anticorrosion of storage tanks, pickling tanks, crude oil tanks, gas pipelines, coastal steel structures, offshore drilling platforms and the like in the petroleum, chemical and steel enterprises.
In order to achieve the purpose, the invention adopts a technical scheme that:
a polyurea composition comprising an isocyanate component and an amino compound component, the isocyanate component comprising a prepolymer and an inorganic pigment, the prepolymer being prepared from: polyisocyanate, polyol and nano titanium dioxide hybrid polyaluminium titanium siloxane shown in formula (I);
wherein, X 1 、X 2 、X 3 、X 4 、X 5 Each independently selected from the group consisting of:
t1, t2, t3, t4, t5 are independently selected from 0-100 and are not 0 when the corresponding group comprises aluminum or titanium;
R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 are each independently selected from C 1-20 Alkyl, phenyl, C 1-6 Alkyl-substituted phenyl, C 2-10 An alkenyl group;
m is titanium dioxide, which is connected with silicon hydroxyl, aluminum hydroxyl or titanium hydroxyl through hydrogen bonds through hydroxyl contained on the surface.
In the present invention, X 1 、X 2 、X 3 、X 4 、X 5 The presence of terminal hydroxyl group(s) may mean that a silicon hydroxyl group, an aluminum hydroxyl group, a titanium hydroxyl group, or the like is present in the segment structure, or may mean that a hydroxyl group is present on the surface of the nano-titania.
In some embodiments of the invention, t1, t2, t3, t4, t5 are independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20.
According to some preferred aspects of the invention, in formula (I), t1, t2, t3, t4, and t5 are independently selected from 0 to 50, further from 0 to 30, and further from 0 to 20.
According to some preferred aspects of the invention, in formula (I), R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 Each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, neopentyl, n-hexyl, phenyl, C 1-6 Alkyl-substituted phenyl, vinyl, methylvinyl, ethylvinyl, propylvinyl.
According to some preferred aspects of the present invention, the nano titanium dioxide hybrid polyaluminium titanium siloxane represented by formula (i) has an average molecular weight of 500 to 10000, further 800 to 8000, and further 1000 to 5000.
In some embodiments of the present invention, the nano titania hybrid polyalumino titanium siloxane of formula (i) has an average molecular weight of 1500-4500.
According to the invention, the nano titanium dioxide hybrid polyalumino-titanium siloxane shown in the formula (I) can be in a high-viscosity liquid state or a paste state.
According to some preferred aspects of the invention, the feeding mass ratio of the polyol to the nano titanium dioxide hybrid polyaluminium titanium siloxane shown in the formula (I) is 2-10: 1.
According to some preferred aspects of the invention, the prepolymer has a 5% to 20% by mass content of isocyanate groups.
According to some preferable aspects of the invention, the inorganic pigment is prepared by reacting a pigment matrix with a fluorosilane coupling agent, the hydrophobic and water-repellent capacity of the material can be obviously improved by the method, and the practice proves that the contact angle of the material and water can be larger than 100 degrees, so that the polyurea material has the hydrophobic and water-repellent functions, and the use limitation of the existing polyurea material is broken through.
Further, the fluorosilane coupling agent comprises at least one of perfluorooctyl triethoxysilane, tridecafluorooctyl triethoxysilane, and perfluorodecyl triethoxysilane.
In some embodiments of the present invention, the method of preparing the inorganic pigment comprises: adding a pigment matrix dried under vacuum, a fluorosilane coupling agent accounting for 5-15% of the mass fraction of the pigment matrix and reflux dimethylbenzene with the amount of 10-30 times of the pigment matrix into a three-neck flask with a stirring paddle and a reflux condenser. Heating to 80-90 deg.C, dripping the catalyst trifluoroacetic acid in the formula amount within 10-60min, heating to 110-120 deg.C, and performing reflux reaction. And then filtering out the pigment matrix, removing the solvent and the redundant non-grafted fluorosilane coupling agent, drying in a vacuum oven, and sealing for recycling to obtain the inorganic pigment.
In some embodiments of the invention, the pigment matrix may be a cadmium red pigment or the like.
According to some preferred aspects of the invention, the amino compound component comprises an amino terminated polyether and optionally an amine chain extender.
Further, the amino compound component comprises polyoxypropylene diamine and optionally at least one of 3,5-diethyl-2,4-diaminotoluene, 3,3 '-dimethyl-4,4' -diaminodicyclohexylmethane, 4,4 '-diaminodicyclohexylmethane, and 4,4' -bis Zhong Dingan diylphenylmethane.
According to some preferred aspects of the invention, the feed mass ratio of the isocyanate component to the amino compound component is 1: 0.5-2.
The invention provides another technical scheme that: a method for preparing the polyurea composition, the method comprising a step of preparing an isocyanate component, the step of preparing the isocyanate component comprising: polyisocyanate, polyol and nano titanium dioxide hybrid polyaluminium titanium siloxane shown in formula (I) are mixed and reacted to generate prepolymer, and then the prepolymer is mixed with inorganic pigment.
According to some preferred aspects of the present invention, the preparation method of the nano titanium dioxide hybrid polyaluminium titanium siloxane shown in the formula (I) comprises the following steps: an alcoholysis reaction and a precondensation reaction of alkoxysilane in water are carried out, and then the following steps are carried out:
adding (R) 1 O) 3 Al and (R) 2 O) 4 One of Ti, reacting, adding (R) 1 O) 3 Al and (R) 2 O) 4 The other Ti reacts to generate the nano titanium dioxide hybrid polyaluminium titanium siloxane shown in the formula (I);
or,
adding (R) 1 O) 3 Al and (R) 2 O) 4 Ti, and reacting to generate the nano titanium dioxide hybrid polyaluminium titanium siloxane shown in the formula (I);
R 1 is selected from C 3-6 Alkyl radical, R 2 Is selected from C 3-6 An alkyl group.
According to some preferred aspects of the invention, the alkoxysilane may comprise a dihydrocarbyl hydrocarbyloxysilane, and optionally an alkenyltrihydrocarbyloxysilane and/or an aryltrihydrocarbyloxysilane; in some embodiments, the alkoxysilane may further comprise a dialkenyl tetraalkyldisiloxane and/or a hexahydrocarbyl disiloxane.
Further, the alkoxysilane includes:
(1) Diphenyldimethoxysilane and/or dimethyldimethoxysilane;
(2) Optionally vinyl trimethoxysilane and/or phenyl trimethoxysilane;
(3) At least one of divinyltetramethyldisiloxane, hexaphenyldisiloxane and hexamethyldisiloxane.
In the present invention, the hydrocarbon group includes alkyl, alkenyl, alkynyl, aryl, etc., and the alkyl group may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, neopentyl, isopentyl, n-hexyl, isohexyl, etc.; the alkenyl group may be vinyl, methylvinyl, ethylvinyl, propylvinyl, isopropylvinyl, etc., and the aromatic group includes phenyl, etc.
According to some preferred and specific aspects of the invention, R 1 Is n-propyl, isopropyl, n-butyl or isobutyl, R 2 Is n-propyl, n-butyl or n-pentyl.
In some embodiments of the invention, (R) 1 O) 3 Al may be aluminum isopropoxide.
In some embodiments of the invention, (R) 2 O) 4 Ti may be n-butyl titanate.
According to some preferred aspects of the present invention, the controlled alcoholysis reaction or precondensation reaction is carried out at a temperature of 80 to 95 ℃.
According to some preferred aspects of the invention, (R) is added 1 O) 3 Al or (R) 2 O) 4 After Ti, the temperature of each reaction was controlled to 75-85 ℃.
According to some preferred aspects of the invention, theThe (R) is 1 O) 3 Al and said (R) 2 O) 4 The feeding molar ratio of Ti is 1: 0.2-5. Further, said (R) 1 O) 3 Al and said (R) 2 O) 4 The feeding molar ratio of Ti is 1: 0.5-2.
According to some preferred aspects of the present invention, the molar ratio of silicon to aluminum in the nano titanium dioxide hybrid polyaluminotitanium siloxane shown in the formula (I) is controlled to be 3-10: 1. Further, the molar ratio of silicon to aluminum in the nano titanium dioxide hybrid polyaluminium titanium siloxane shown in the formula (I) is controlled to be 4-9: 1.
In some preferred embodiments of the present invention, embodiments of the method of making comprise: adding water and hydrolysis catalyst into a reactor, heating to a preset reaction temperature, dropwise adding alkoxy silane, performing reflux reaction, removing generated alcohol substances, and adding (R) 1 O) 3 Al, continuing the reflux reaction and removing the formed alcohol, then adding (R) 2 O) 4 And (3) continuously carrying out reflux reaction and removing generated alcohol substances, cooling to room temperature after the reaction is finished, extracting by using an organic solvent, removing a water layer, and separating the nano titanium dioxide hybrid polyaluminium titanium siloxane shown in the formula (I) from the organic layer.
In some embodiments of the invention, the hydrolysis catalyst may be glacial acetic acid or trifluoroacetic acid.
In some embodiments of the invention, the water may be distilled water.
In some embodiments of the invention, the alkoxysilane is controlled to be added dropwise over a period of 15 to 30 minutes.
In some embodiments of the invention, the organic solvent is xylene and/or acetylacetone.
In some embodiments of the present invention, the method for separating the nano titania hybrid polyalumino-titanium siloxane represented by formula (i) from the organic layer may be distillation under reduced pressure to remove xylene or acetylacetone and low molecular weight substances.
In some embodiments of the present invention, the polyurea composition comprises an isocyanate component and an amino compound component, the isocyanate component and the amino compound component being fed in a mass ratio of 1: 0.5-2;
the isocyanate component comprises the following raw materials in parts by mass: 150-350 parts of polyisocyanate, 120-200 parts of polyol, 10-80 parts of nano titanium dioxide hybrid polyaluminium titanium siloxane shown in formula (I) and 10-50 parts of inorganic pigment;
the amino compound component comprises the following raw materials in parts by mass: 70-120 parts of amine-terminated polyether and 0-15 parts of amine chain extender.
Further, the polyurea composition comprises an isocyanate component and an amino compound component, wherein the charging mass ratio of the isocyanate component to the amino compound component is 1: 0.8-1.5;
the isocyanate component comprises the following raw materials in parts by mass: 180-320 parts of polyisocyanate, 130-185 parts of polyol, 15-70 parts of nano titanium dioxide hybrid polyaluminium titanium siloxane shown in formula (I) and 15-45 parts of inorganic pigment;
the amino compound component comprises the following raw materials in parts by mass: 80-105 parts of amine-terminated polyether and 3-12 parts of amine chain extender.
In some embodiments of the present invention, the polyisocyanate may be a diisocyanate, for example, toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene Diisocyanate (HDI), lysine Diisocyanate (LDI), and the like. In some embodiments of the invention, the polyol is a hydroxyl terminated polyether polyol, and further may be a combination of a diol and a triol.
According to a specific aspect of the invention, the polyalcohol consists of polypropylene oxide ether dihydric alcohol and polypropylene oxide ether trihydric alcohol, and the feeding mass ratio of the polypropylene oxide ether dihydric alcohol to the polypropylene oxide ether trihydric alcohol is 1.1-2.8: 1.
The invention provides another technical scheme that: the application of the polyurea composition in anticorrosive materials.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
aiming at the defects of the existing modified polyurea material, the invention adopts an in-situ hybridization polymerization technology, and introduces a Si-O-Al-O-Ti-O chain segment and a nano titanium dioxide hybridization structure into a polyurea macromolecular structure, and practices show that the polyurea material obtained by the method not only greatly improves the temperature resistance and the flame retardant property, but also greatly improves the flexibility; and has the characteristics of high curing speed, insensitivity to moisture and temperature, good thermal stability, excellent corrosion resistance and good physical properties.
Drawings
FIG. 1 shows the preparation of nano-titania hybrid poly (al-ti-siloxane) prepared in example 1 1 H-NMR spectrum.
Detailed Description
The above-described scheme is further illustrated below with reference to specific examples; it is to be understood that these embodiments are illustrative of the principles, essential features and advantages of the invention, and that the invention is not limited in scope by the following embodiments; the implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions in routine experiments.
Not specifically illustrated in the following examples, all starting materials are commercially available or prepared by methods conventional in the art.
Among the following, diphenyldimethoxysilane was purchased from ait (shandong) new materials, ltd; dimethyl dimethoxy silane is purchased from Hangzhou silicon chemical industry Co., ltd; vinyltrimethoxysilane was purchased from Nanjing Rohn silicon materials, inc.; phenyltrimethoxysilane was purchased from Wo Xingman new materials science and technology ltd, zhejiang; divinyl tetramethyl disiloxane is purchased from Hangzhou silicon new materials Co., ltd; hexamethyldisiloxane is purchased from Hangzhou silicon new materials Co., ltd; aluminum isopropoxide was purchased from new materials, inc, zhongtianli, nyzhou; n-butyl titanate was purchased from Shandong Xin Ying Shunhi New Material Co.
Example 1
The present embodiment provides a nano titanium dioxide hybrid polyaluminium titanium siloxane and a preparation method thereof, and a raw material formula of the nano titanium dioxide hybrid polyaluminium titanium siloxane is shown in table 1.
TABLE 1
The reaction schematic process of the nano titanium dioxide hybrid polyaluminium titanium siloxane is as follows:
in the above-illustrated reaction process, the way of hydrogen bonding of the aluminum hydroxyl group and the silicon hydroxyl group with the hydroxyl group on the surface of the titanium dioxide is given by way of example only, in the actual reaction process, the Ti — OH on the main chain can also be hydrogen bonded with the hydroxyl group on the surface of the titanium dioxide with the titanium dioxide particle, and the charge amount is controlled so that the unconnected terminal hydroxyl group exists in the structure, which is the same as in the following examples.
The preparation method specifically comprises the following steps:
adding distilled water and a hydrolysis catalyst (acetic acid) according to the formula into a 1000mL three-neck flask, heating to 85 ℃, dropwise adding a dropping funnel into a mixed solution of all alkoxy silanes in the table 1, controlling the dropping to be finished within about 25min, stirring and carrying out reflux reaction at 80 ℃, removing alcohol generated by the reaction, reacting for 2h, then adding aluminum isopropoxide according to the formula into the flask, continuously refluxing and carrying out alcohol-discharging reaction for 2h, then adding n-butyl titanate according to the formula, continuously refluxing and carrying out alcohol-discharging reaction for 2h, finishing the reaction, after the product is cooled to room temperature, extracting by using excessive xylene, removing a water layer, finally carrying out reduced pressure distillation on an organic layer in a rotary evaporator, removing xylene and low molecular weight substances, obtaining nano titanium dioxide hybrid polyaluminumtitanosiloxane, 154.29g, wherein the yield is 90.02% (the theoretical yield is 171.39 g), and the organic layer is removed 1 The H-NMR spectrum is shown in FIG. 1, GPC (gel permeation)Chromatography) determined to be an average molecular weight of 1839 as a viscous liquid at 25 ℃.
Example 2
The present embodiment provides a nano titanium dioxide hybrid polyaluminium titanium siloxane and a preparation method thereof, and a raw material formula of the nano titanium dioxide hybrid polyaluminium titanium siloxane is shown in table 2.
TABLE 2
| Name of raw materials | Batch (g) |
| Phenyltrimethoxysilane | 110.67 |
| Dimethyldimethoxysilane | 19.93 |
| Diphenyldimethoxysilane | 32.79 |
| Aluminium isopropoxide | 28.98 |
| Distilled water | 48.6 |
| Titanium acid n-butyl ester | 48.31 |
| Divinyltetramethyldisiloxane | 7.69 |
| Acetyl groupAcetone (II) | 355.31 |
| Trifluoroacetic acid (trifluoroacetic acid) | 0.6523 |
The reaction schematic process of the nano titanium dioxide hybrid polyaluminium titanium siloxane is as follows:
the preparation method specifically comprises the following steps:
adding distilled water and a hydrolysis catalyst (trifluoroacetic acid) in a formula amount into a 1000mL three-neck flask, heating to 85 ℃, dropwise adding a mixed solution of all alkoxy silanes in the table 2 by using a dropping funnel, controlling the dropping at about 25min, stirring and carrying out a reflux reaction at 80 ℃, removing alcohol generated by the reaction, reacting for 2h, then adding aluminum isopropoxide in the formula amount into the flask, continuously refluxing and carrying out an alcohol-discharging reaction for 2h, adding n-butyl titanate in the formula amount, continuously refluxing and carrying out the alcohol-discharging reaction for 2h, finishing the reaction, extracting by using excessive acetylacetone after the product is cooled to room temperature, removing an aqueous layer, finally distilling an organic layer in a rotary evaporator under reduced pressure, removing acetylacetone and substances with low molecular weight, obtaining nano titanium dioxide hybrid polyaluminumtitanosiloxane, 135.28g, having a yield of 89.79% (theoretical yield of 3262 zxft), measuring an average molecular weight by GPC (gel permeation chromatography) to be 3568, and being pasty at 25 ℃.
Comparative example 1
It is essentially the same as example 1 except that: aluminum isopropoxide and n-butyl titanate are not added in the reaction process, and the polysiloxane is prepared.
Comparative example 2
It is essentially the same as example 1 except that: no n-butyl titanate is added in the reaction process to prepare the polysiloxane.
Examples 3 to 5
The embodiments provide an inorganic pigment, which is prepared by reacting a pigment matrix with a fluorosilane coupling agent, wherein the pigment matrix is a cadmium red pigment, and the preparation method comprises the following steps:
15g of cadmium red pigment dried for 24 hours under vacuum at 180 ℃, fluorosilane coupling agent (perfluorooctyl triethoxysilane/tridecafluorooctyl triethoxysilane/perfluorodecyl triethoxysilane) accounting for about 10 mass percent of the cadmium red pigment and refluxing xylene with 20 times of the amount of the cadmium red pigment are added into a 500mL three-neck flask provided with a stirring paddle and a refluxing condenser tube. The temperature is increased to about 85 ℃, the catalyst trifluoroacetic acid with the formula amount is dripped in within 30min, and the temperature is increased to 115 ℃ to carry out reflux reaction for more than 4 h. Then filtering the cadmium red pigment, removing the solvent and the redundant unligated fluorosilane coupling agent, drying for 2h in a vacuum oven at 120 ℃, sealing and reserving for recycling, thus obtaining the cadmium red pigment, wherein the raw materials and the using amount used in the examples 3-5 are shown in the table 3.
TABLE 3
The inorganic pigment prepared in example 3 is abbreviated as fluorine-silicon surface modified cadmium red pigment i, the inorganic pigment prepared in example 4 is abbreviated as fluorine-silicon surface modified cadmium red pigment ii, and the inorganic pigment prepared in example 5 is abbreviated as fluorine-silicon surface modified cadmium red pigment iii.
Application example 1
The embodiment provides a polyurea composition and a preparation method thereof, wherein the polyurea composition comprises an isocyanate component and an amino compound component, and the feeding mass ratio of the isocyanate component to the amino compound component is 1: 1; wherein the raw material formulation of the isocyanate component is shown in table 4.
TABLE 4
The route for synthesizing the prepolymer by combining the nano titanium dioxide hybrid polyaluminium titanium siloxane, the hydroxyl-terminated polyether polyol and the MDI-50 is shown as follows:
the terminal hydroxyl groups in the nano titanium dioxide hybrid polyaluminium titanium siloxane can react with the terminal isocyanate groups in the MDI-50, and other terminal isocyanate groups in the MDI-50 can react with the hydroxyl groups of the terminal hydroxyl polyether polyol, so that the structure shown in the specification can be formed.
Using the formulation shown in table 4, the isocyanate component was prepared by a method comprising: adding the nano titanium dioxide hybrid poly-aluminum titanium siloxane, hydroxyl-terminated polyether polyol and refluxing xylene in a formula amount into a 500mL four-neck flask with a stirring paddle and a refluxing condenser, refluxing and dehydrating for 60min at 140 ℃, cooling to 85 ℃, dripping the formula amount of MDI-50 in 30min, flushing residual materials in the flask with 10mL xylene after dripping, refluxing and reacting for 3h at 90 ℃ under nitrogen until the content of NCO reaches the requirement, adding the formula amount of inorganic pigment, distilling out xylene and low molecular substances generated by reaction at 100 +/-5 ℃ and the vacuum degree of 0.095MPa, cooling to room temperature to obtain an isocyanate component, and sealing and storing for later use.
The raw material formulation of the amino compound component is shown in table 5.
TABLE 5
The preparation method of the amino compound component comprises the following steps: adding the amino-terminated polyether and the amine chain extender in the formula amount into a 500mL three-neck flask with a stirring paddle, stirring at 5 ℃ until the components are uniformly mixed, sealing and storing for later use.
When in application: the isocyanate component and the amino compound component are mixed according to the feeding ratio and can be applied by adopting a spraying mode, and after the two components are mixed, the reaction process of the prepolymer and the amino-terminated polyether is schematically shown as follows:
the above process is merely exemplary, and it is easy to understand that the terminal amino group in the amino compound may react with any terminal isocyanate group during the reaction.
Application example 2
Basically, the method is the same as the application example 1, and only differs from the following steps:
the raw material formulation of the isocyanate component is shown in table 6.
TABLE 6
The raw material formulation of the amino compound component is shown in table 7.
TABLE 7
Application example 3
Basically, the method is the same as the application example 1, and only differs from the following steps:
the raw material formulation of the isocyanate component is shown in table 8.
TABLE 8
The raw material formulation of the amino compound component is shown in table 9.
TABLE 9
Application example 4
Basically, the method is the same as the application example 1, and only differs from the following steps:
the raw material formulation of the isocyanate component is shown in table 10.
TABLE 10
The raw material formulation of the amino compound component is shown in table 11.
TABLE 11
Application example 5
Basically, the method is the same as the application example 1, and only differs from the following steps:
the raw material formulation of the isocyanate component is shown in table 12.
TABLE 12
The raw material formulation of the amino compound component is shown in table 13.
Watch 13
Application example 6
Basically, the method is the same as the application example 1, and only differs from the following steps:
the raw material formulation of the isocyanate component is shown in table 14.
TABLE 14
The raw material formulation of the amino compound component is shown in table 15.
Watch 15
Application comparative example 1
Basically, the method is the same as the application example 1, and only differs from the following steps: the raw materials of the isocyanate component do not contain nano titanium dioxide hybrid poly aluminum titanium siloxane, and the fluorine-silicon surface modified cadmium red pigment I is replaced by untreated cadmium red pigment.
Comparative application example 2
Basically, the method is the same as the application example 1, and only differs from the following steps: in the raw materials of the isocyanate component, the nano titanium dioxide hybrid polyaluminum titanium siloxane is replaced by the polysiloxane prepared in the comparative example 1, and the fluorine-silicon surface modified cadmium red pigment I is replaced by the untreated cadmium red pigment.
Comparative application example 3
Basically, the method is the same as the application example 1, and only differs from the following steps: in the raw materials of the isocyanate component, the nano titanium dioxide hybrid poly-aluminum titanium siloxane is replaced by polysiloxane prepared in the comparative example 2, and the fluorine-silicon surface modified cadmium red pigment I is replaced by untreated cadmium red pigment.
Performance testing
The following performance tests were carried out on the products obtained in application examples 1 to 6 and application comparative examples 1 to 3, and the specific results are shown in Table 16.
TABLE 16
And (4) testing standard:
gel time/s: GB/T15022.2-2007; tensile strength: GB/T16777-2008; tear strength: GB/T16777-2008; adhesion (steel): GB/T31586.1-2015; water absorption: GB/T15022.2-2007; salt spray resistance (2000 h): GB/T1771-1991; oil resistance: GB/T9274-1988; hardness: GB/T6739-2006; impact strength: GB/T20624.2-2006; heat resistance index: GB/T15022.2-2007; limiting oxygen index LOI: GB/T2406.2-2009; contact angle with water: GB/T24368-2009.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered in the protection scope of the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Claims (10)
1. A polyurea composition comprising an isocyanate component and an amino compound component, characterized in that: the isocyanate component comprises prepolymer and inorganic pigment, wherein the prepolymer comprises the following raw materials: polyisocyanate, polyol and nano titanium dioxide hybrid polyaluminium titanium siloxane shown as a formula (I);
wherein, X 1 、X 2 、X 3 、X 4 、X 5 Each independently selected from the group consisting of:
and X 1 、X 2 、X 3 、X 4 、X 5 In which the terminal hydroxyl group is present, any two of which are not repeating, comprising at least
(ii) one of;
t1, t2, t3, t4, t5 are independently selected from 0-100 and are not 0 when the corresponding group comprises aluminum or titanium;
R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 are each independently selected from C 1-20 Alkyl, phenyl, C 1-6 Alkyl-substituted phenyl, C 2-10 An alkenyl group;
m is titanium dioxide, which is connected with silicon hydroxyl, aluminum hydroxyl or titanium hydroxyl through hydrogen bonds through hydroxyl contained on the surface.
2. The polyurea composition of claim 1, wherein: in formula (I), t1, t2, t3, t4 and t5 are independently selected from 0 to 50, further from 0 to 30, and further from 0 to 20.
3. The polyurea composition of claim 1, wherein: in the formula (I), R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 Each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, neopentyl, n-hexyl, phenyl, C 1-6 Alkyl-substituted phenyl, vinyl, methylvinyl, ethylvinyl, propylvinyl.
4. The polyurea composition of claim 1, wherein: the average molecular weight of the nano titanium dioxide hybrid polyaluminium titanium siloxane shown in the formula (I) is 500-10000, further 800-8000, and further 1000-5000.
5. The polyurea composition of claim 1, wherein: the feeding mass ratio of the polyalcohol to the nano titanium dioxide hybrid polyaluminium titanium siloxane shown in the formula (I) is 2-10: 1; and/or, the polyol is a hydroxyl terminated polyether polyol.
6. The polyurea composition of claim 1, wherein: the prepolymer contains 5-20% by mass of isocyanate groups.
7. The polyurea composition of claim 1, wherein: the inorganic pigment is prepared by reacting a pigment matrix with a fluorosilane coupling agent, wherein the fluorosilane coupling agent comprises at least one of perfluorooctyl triethoxysilane, tridecafluorooctyl triethoxysilane and perfluorodecyl triethoxysilane.
8. The polyurea composition of claim 1, wherein: the amide component comprises polyoxypropylene diamine and optionally at least one of 3,5-diethyl-2,4-diaminotoluene, 3,3 '-dimethyl-4,4' -diaminodicyclohexylmethane, 4,4 '-diaminodicyclohexylmethane, and 4,4' -bis Zhong Dingan diylphenylmethane; and/or the feeding mass ratio of the isocyanate component to the amino compound component is 1: 0.5-2.
9. A process for preparing a polyurea composition according to any one of claims 1 to 8, wherein: the preparation method comprises a preparation process of an isocyanate component, wherein the preparation process of the isocyanate component comprises the following steps: polyisocyanate, polyol and nano titanium dioxide hybrid polyaluminium titanium siloxane shown in formula (I) are mixed and reacted to generate prepolymer, and then the prepolymer is mixed with inorganic pigment.
10. Use of a polyurea composition according to any one of claims 1 to 8 in a preservative material.
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