CN112210069B - Silane hybrid quaternary ammonium salt modified polyisocyanate curing agent and preparation method thereof - Google Patents
Silane hybrid quaternary ammonium salt modified polyisocyanate curing agent and preparation method thereof Download PDFInfo
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- CN112210069B CN112210069B CN202011080410.3A CN202011080410A CN112210069B CN 112210069 B CN112210069 B CN 112210069B CN 202011080410 A CN202011080410 A CN 202011080410A CN 112210069 B CN112210069 B CN 112210069B
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- Prior art keywords
- curing agent
- quaternary ammonium
- ammonium salt
- polyisocyanate curing
- silane
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 93
- 239000005056 polyisocyanate Substances 0.000 title claims abstract description 86
- 229920001228 polyisocyanate Polymers 0.000 title claims abstract description 86
- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims abstract description 51
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 31
- -1 alcohol amine Chemical class 0.000 claims abstract description 22
- 150000008053 sultones Chemical class 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003112 inhibitor Substances 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000007822 coupling agent Substances 0.000 claims description 14
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 13
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 6
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 6
- 239000007810 chemical reaction solvent Substances 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 claims description 6
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000010409 thin film Substances 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 claims description 5
- 229940008406 diethyl sulfate Drugs 0.000 claims description 5
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims description 5
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 claims description 5
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 5
- ZYWUVGFIXPNBDL-UHFFFAOYSA-N n,n-diisopropylaminoethanol Chemical compound CC(C)N(C(C)C)CCO ZYWUVGFIXPNBDL-UHFFFAOYSA-N 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 238000012544 monitoring process Methods 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000004809 thin layer chromatography Methods 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 32
- 239000003607 modifier Substances 0.000 abstract description 12
- 238000003860 storage Methods 0.000 abstract description 4
- 238000009396 hybridization Methods 0.000 abstract 1
- NTQDELBZOMWXRS-IWGUZYHVSA-N Asp-Thr Chemical compound C[C@@H](O)[C@@H](C(O)=O)NC(=O)[C@@H](N)CC(O)=O NTQDELBZOMWXRS-IWGUZYHVSA-N 0.000 description 16
- 239000004814 polyurethane Substances 0.000 description 14
- 229920002635 polyurethane Polymers 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 230000004048 modification Effects 0.000 description 12
- 238000012986 modification Methods 0.000 description 12
- 239000010408 film Substances 0.000 description 11
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 9
- 239000003973 paint Substances 0.000 description 9
- 239000000178 monomer Substances 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000004383 yellowing Methods 0.000 description 5
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- 230000000845 anti-microbial effect Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 125000001453 quaternary ammonium group Chemical class 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000013638 trimer Substances 0.000 description 3
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 description 2
- PJWWRFATQTVXHA-UHFFFAOYSA-N Cyclohexylaminopropanesulfonic acid Chemical compound OS(=O)(=O)CCCNC1CCCCC1 PJWWRFATQTVXHA-UHFFFAOYSA-N 0.000 description 2
- MKWKNSIESPFAQN-UHFFFAOYSA-N N-cyclohexyl-2-aminoethanesulfonic acid Chemical compound OS(=O)(=O)CCNC1CCCCC1 MKWKNSIESPFAQN-UHFFFAOYSA-N 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000975 bioactive effect Effects 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- UDGSVBYJWHOHNN-UHFFFAOYSA-N n',n'-diethylethane-1,2-diamine Chemical compound CCN(CC)CCN UDGSVBYJWHOHNN-UHFFFAOYSA-N 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000001038 titanium pigment Substances 0.000 description 1
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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/775—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur sulfur
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- 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
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/722—Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates
-
- 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
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Plant Pathology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a silane hybrid quaternary ammonium salt modified polyisocyanate curing agent and a preparation method thereof, wherein the preparation method comprises the steps of reacting 1.0-3.0% of alcohol amine, 2.0-4.0% of silane coupling agent and 90-94% of polyisocyanate in percentage by mass of raw materials under the protection of nitrogen at 40-60 ℃ until the content of NCO in a system reaches a theoretical value, and adding 0.05-0.5% of polymerization inhibitor to prepare the tertiary amine-containing silane hybrid polyisocyanate curing agent. Then 2.0-4.0% of sultone and silane hybridization polyisocyanate curing agent containing tertiary amine are added to react until the sultone is consumed, and the mixture is cooled and discharged. The invention adopts the sultone hydrophilic modifier with strong hydrophilicity, and the prepared curing agent can be dispersed in water, has low viscosity, is environment-friendly, and has the characteristics of excellent scratch resistance, transparency, storage stability and the like.
Description
Technical Field
The invention relates to the technical field of curing agents, and particularly relates to a silane hybrid quaternary ammonium salt modified polyisocyanate curing agent and a preparation method thereof.
Background
With the rapid development of the polyurethane industry, polyisocyanate curing agents are gradually applied to various fields in the polyurethane industry in order to overcome the defects of poor heat resistance, low softening temperature, and the like in polyurethane materials. The traditional polyisocyanate curing agent has low viscosity and high NCO content, but does not have hydrophilicity, cannot be emulsified and dispersed in hydroxyl water-based resin, causes the defects of uneven coating, non-density, low glossiness and the like of the coating, and has very limited application in the production and living fields. Hydrophilic groups or components are introduced to carry out hydrophilic modification on the traditional polyisocyanate curing agent, so that the water dispersibility of the polyisocyanate curing agent is improved.
At present, the modification of polyisocyanates is mainly divided into: ionic modification, nonionic modification and mixed modification. The nonionic modification is to introduce nonionic hydrophilic groups into the polyisocyanate to make it hydrophilic. The nonionic hydrophilic modifier is polyether and polyester polyol. Although there are many patent applications such as US5200489 and chinese patent CN101381443A, a large amount of polyether still needs to be introduced in the modification process, resulting in low isocyanate functionality, low NCO%, insufficient crosslinking degree of the coating film, and high water sensitivity.
The mixed modification refers to that the ionic hydrophilic monomer and the nonionic hydrophilic monomer are used for modifying the polyisocyanate to obtain the product. Chinese patent CN105820302A proposes a method for modifying polyisocyanate by mixing oligomer polyol and carboxylic acid anion modifier, the modified waterborne polyurethane curing agent can be very easily dispersed in water after neutralization, and the obtained curing agent has light color, high NCO content, yellowing resistance and good storage stability. The mixing modification mode can solve the problems of poor water resistance, low hardness and high viscosity of the nonionic water-based curing agent to a certain extent and can also relieve the problem of acid-base sensitivity of the nonionic water-based curing agent. However, few studies have been made on the hybrid modified aqueous curing agent.
In order to solve the problems of poor water resistance, low hardness and high viscosity of the nonionic waterborne curing agent, researchers have achieved wide success by adopting an anionic hydrophilic group modified polyurethane curing agent with stronger hydrophilicity. Due to the strong hydrophilicity of the anionic hydrophilic groups, the using amount of the modifier is reduced, and the obtained waterborne polyurethane curing agent has higher NCO content and lower viscosity. Common anionic modifiers are sulfonates and carboxylates.
Patent EP0548669A proposes a process for modifying polyisocyanates by introducing carboxylic acid groups. When the carboxylic acid groups are neutralized to form carboxylate salts, the modified polyisocyanates can be well dispersed in water without high speed agitation. However, the curing agent of the carboxylate system has high sensitivity to pH and is easy to decompose when meeting water. Therefore, in recent years, researchers have focused more on sulfonic acid-type hydrophilic modifiers.
Chinese patent CN109320687A proposes that cyclic sultone and aliphatic diol are reacted to prepare a novel anionic hydrophilic modifier for modifying polyisocyanate. The modified waterborne polyurethane curing agent has the characteristics of excellent scratch resistance, stain resistance, storage stability and the like. However, since the curing agent contains a benzene ring, the aromatic isocyanate is easily oxidized to cause yellowing, which reduces yellowing resistance of the coating film.
In the Chinese patent CN108976371A, amino disulfonic acid is used as a hydrophilic modifier to carry out hydrophilic modification on polyisocyanate, so that the using amount of the hydrophilic modifier is greatly reduced, and the waterborne curing agent disclosed by the invention is low in viscosity, good in water dispersibility and high in NCO content. U.S. Pat. No. 4,67958, U.S. Pat. No. 4,675,958, employs N, N-dimethylcyclohexylamine as catalyst and 2-cyclohexylaminoethanesulfonic acid and 3-cyclohexylaminopropanesulfonic acid as hydrophilic modifier to modify polyisocyanate in hydrophilic manner, to prepare a waterborne polyurethane curing agent with good hydrophilicity and ideal coating performance. However, the polyisocyanate has strong hydrophilicity and poor lipid solubility to the sulfonic acid monomer modifier (such as 3, 3-iminobis-1-propanesulfonic acid, 2-cyclohexylaminoethanesulfonic acid, 3-cyclohexylaminopropanesulfonic acid and the like), and is easy to have poor compatibility or even incompatibility with other components of a system, so that the system is turbid or a coating is opaque.
Although the hydrophilic modified polyisocyanate curing agent can keep better stability and gloss in a water system, the water resistance of a paint film is greatly reduced due to the existence of hydrophilic groups. In order to maintain the water resistance and hydrophilicity of the paint film, patent document CN111116865A adopts butane sultone and a silane coupling agent containing primary amine to modify HDI trimer in one step to prepare a polyisocyanate curing agent containing organosilicone sulfonate. Although the silicon modified waterborne polyurethane curing agent can ensure the hydrophilicity and water resistance of a bi-component paint film, the reaction temperature is higher, the reaction process is easy to implode, and the energy consumption is high.
In general, the existing water-based curing agents in the market have the defects of low NCO content, high viscosity, large energy consumption and long time consumption in the synthesis process. It has poor compatibility with aqueous hydroxy resin, and the coating film has poor gloss and transparency. Therefore, the preparation of the waterborne polyurethane curing agent with high NCO, low viscosity and excellent paint film performance is still the focus and difficulty of research.
Disclosure of Invention
The invention provides a silane hybrid quaternary ammonium salt modified polyisocyanate curing agent and a preparation method thereof, wherein the silane hybrid quaternary ammonium salt modified polyisocyanate curing agent has the advantages of excellent water dispersibility and good storage stability, and a two-component coating prepared from the curing agent has excellent water resistance and chemical resistance.
In order to achieve the purpose, the technical scheme of the invention is as follows: the silane hybrid quaternary ammonium salt modified polyisocyanate curing agent provided by the invention is subjected to hydrophilic modification by adopting a sultone modifier.
In order to overcome the defects and shortcomings of the prior art and achieve the above purpose, the invention provides the following technical scheme, and the preparation method of the silane hybrid quaternary ammonium salt modified polyisocyanate curing agent comprises the following preparation steps:
a) adding 90-94% of polyisocyanate into a reactor with a mechanical stirrer, a reflux pipe, a constant-pressure separating funnel and N according to the mass percentage of the raw materials2Adjusting the viscosity of an imported and exported four-mouth round-bottom flask by using an organic solvent, slowly dropwise adding 1.0-3.0% of alcohol amine and 2.0-4.0% of silane coupling agent, slowly heating to 40-60 ℃ under the protection of nitrogen atmosphere, reacting under the action of low-speed stirring until the mass content of the NCO in the system reaches a theoretical value, adding a polymerization inhibitor to terminate the reaction, preserving the temperature for 1 hour, and cooling to room temperature to obtain the tertiary amine-containing silane hybrid polyisocyanate curing agent for later use.
b) Slowly dripping 2.0-4.0% of sultone into the tertiary amine-containing silane hybrid polyisocyanate curing agent obtained in the step a), reacting for 2-3 hours at 40-60 ℃ after dripping is finished, and monitoring the reaction process by a thin layer chromatography until the sultone is completely reacted. And (3) cooling, and removing the reaction solvent by using a thin film distillation method to obtain the silane hybrid quaternary ammonium salt modified polyisocyanate curing agent.
The silane coupling agent is a self-made D-T coupling agent, and the preparation method of the D-T coupling agent comprises the following steps: according to the molar parts, 1.0-2.0 parts of one or more of N, N-dimethylethylenediamine, N-diethylethylenediamine and diethanolamine and 1.1-2.0 parts of gamma-methacryloxypropyltrimethoxysilane (TMSPM) react for 24-48 hours under the protection of nitrogen and at the temperature of 25-60 ℃, and finally light yellow liquid is obtained.
Preferably, the alcohol amine is one or a mixture of more than two of N, N-dimethylethanolamine, N-methyldiethanolamine, N-diethylethanolamine, triethanolamine and N, N-diisopropylethanolamine.
Preferably, the sultone is one or more of 1, 3-propane sultone, propenyl-1, 3-sultone and 1, 4-butane sultone.
Preferably, the polyisocyanate is one or more of Hexamethylene Diisocyanate (HDI), HDI trimer, isophorone diisocyanate (IPDI) and IPDI trimer.
Preferably, the organic solvent is one or more of propylene glycol monomethyl ether acetate (PMA), dimethyl sulfoxide, N-dimethylacetamide, N-dimethylformamide, ethyl acetate, petroleum ether and tetrahydrofuran.
Preferably, the polymerization inhibitor is one or more of methyl p-toluenesulfonate, dimethyl sulfate and diethyl sulfate.
Preferably, the slow dropping rate of 1.0-3.0% of alcohol amine and 2.0-4.0% of silane coupling agent is 3-5 s/drop for 10-20 min.
Preferably, the adding amount of the polymerization inhibitor is 0.05-0.5% of the total mass of the raw materials.
The curing agent is prepared by the preparation method, the solid content of the silane hybrid quaternary ammonium salt modified polyisocyanate curing agent is 100 wt%, the NCO mass content is 17-22%, the viscosity at 25 ℃ is 2000-4500mPa & s, and the appearance is colorless or light yellow transparent viscous liquid.
The silane hybrid quaternary ammonium salt modified polyisocyanate can be used as a cross-linking agent to be dispersed in a water-based paint adhesive or used as a component of the paint adhesive, and the components contain groups which react with NCO, especially hydroxyl groups.
The chemical reaction of the quaternary ammonium salt sulfonic acid modified polyisocyanate curing agent is illustrated by HDI tripolymer, N-dimethylethanolamine, 1, 3-propane sultone and D-T coupling agent, and before the chemical reaction is illustrated, the reaction process of the D-T silane coupling agent is illustrated by N, N-diethylethylenediamine and gamma-methacryloxypropyltrimethoxysilane (TMSPM), wherein the chemical reaction formula is as follows:
the chemical reaction formula of the quaternary ammonium salt sulfonic acid modified polyisocyanate curing agent prepared by the D-T silane coupling agent is as follows:
compared with the prior art, the invention has the following advantages and beneficial effects:
(1) in the preparation of the quaternary ammonium salt sulfonic acid modified polyisocyanate curing agent, alcohol amine, a silane coupling agent and sultone are all fat-soluble substances or are easily soluble in an organic solvent, and a homogeneous system is formed in the reaction, so that the synthesized curing agent is clear and transparent, light in color, low in viscosity, high in NCO content and good in water dispersibility. Solves the problems of poor water dispersibility, poor water resistance of a coating film and the like of the existing waterborne polyurethane curing agent.
(2) In the preparation of the quaternary ammonium salt sulfonic acid modified polyisocyanate curing agent, the synthesis reaction condition is mild, the reaction time is short, the cost is greatly saved, the adopted polyisocyanate monomer is HDI or IPDI, and the curing agent synthesized by the monomer has better yellowing resistance and water dispersion stability.
(3) The silane hybrid quaternary ammonium salt modified polyisocyanate curing agent prepared by the invention has excellent antimicrobial and bactericidal effects because the quaternary ammonium salt is a cationic bioactive compound, and the aqueous curing agent with antimicrobial, bactericidal and antifouling effects can be obtained by introducing the quaternary ammonium salt to a polyurethane skeleton.
Detailed Description
In order to better understand the present invention, the following further description is made with reference to the following examples, which should be construed as limiting the scope of the present invention.
Example 1.
185g of HDI trimer were added to a stirred tank with mechanical stirring, reflux tube, constant pressure separatory funnel and N2Adding a small amount of PMA into a four-mouth round-bottom flask at an inlet and an outlet to adjust the viscosity, slowly dripping 3g of N, N-dimethylethanolamine and 6g of silane coupling agent within 10 minutes under the protection of nitrogen atmosphere. Slowly heating to 50 ℃, reacting for 2 hours under the action of low-speed stirring until the mass content of the NCO in the system reaches a theoretical value, adding diethyl sulfate to terminate the reaction, keeping the temperature for 1 hour, cooling to room temperature, slowly dripping 6g of 1, 3-sultone within 5 minutes, and reacting for 2.5 hours at 50 ℃ after dripping is finished. And (3) cooling, and removing the reaction solvent by using a thin film distillation method to obtain a light yellow transparent viscous liquid, wherein the NCO mass content of the silane hybrid quaternary ammonium salt modified polyisocyanate curing agent is 20.3%. In this example, PMA was added in an amount to ensure that the silane-hybrid quaternary ammonium salt-modified polyisocyanate curing agent had a viscosity of 2500 mPas at 25 ℃ and the rate of slowly adding 3g of N, N-dimethylethanolamine and 6g of silane coupling agent dropwise was 4 sec/drop. The NCO mass content reaching the theoretical value means that the final NCO mass content of the silane hybrid quaternary ammonium salt modified polyisocyanate curing agent is 20.3 percentIn the examples, the solid content of the silane hybrid quaternary ammonium salt modified polyisocyanate curing agent is 100 wt%. Wherein the addition amount of the polymerization inhibitor is 0.05-0.5% of the total mass of the raw materials, and the total mass of the raw materials refers to the total mass of the polyisocyanate, the alcohol amine, the silane coupling agent and the sultone.
The silane coupling agent is a self-made D-T coupling agent, and the preparation method of the D-T coupling agent comprises the following steps: according to the molar parts, 1.0 part of N, N-dimethylethylenediamine and 2.0 parts of gamma-methacryloxypropyltrimethoxysilane (TMSPM) react for 24 to 48 hours under the protection of nitrogen and at a temperature of between 25 and 60 ℃ to finally obtain a light yellow liquid.
Example 2.
185g of Hexamethylene Diisocyanate (HDI) were added to a stirred tank equipped with a mechanical stirrer, reflux tube, constant pressure separatory funnel and N2And adding a small amount of dimethyl sulfoxide into an inlet-outlet four-mouth round-bottom flask to adjust the viscosity, and slowly dropwise adding 3g of N-methyldiethanolamine and 6g of silane coupling agent within 15 minutes under the protection of nitrogen atmosphere. Slowly heating to 40 ℃, reacting for 2 hours under the action of low-speed stirring until the mass content of NCO in the system reaches a theoretical value, adding methyl tosylate to terminate the reaction, keeping the temperature for 1 hour, cooling to room temperature, slowly dripping 6g of propenyl-1, 3-sultone within 4 minutes, and reacting for 2 hours at 60 ℃ after dripping is finished. And (3) cooling, and removing the reaction solvent by using a thin film distillation method to obtain a light yellow transparent viscous liquid, wherein the NCO mass content of the silane hybrid quaternary ammonium salt modified polyisocyanate curing agent is 17%. In this example, the amount of dimethyl sulfoxide added was such that the viscosity of the silane-hybridized quaternary ammonium salt-modified polyisocyanate curing agent at 25 ℃ was 4000 mPas, and the rate of slowly adding 3g of N-methyldiethanolamine and 6g of the silane coupling agent dropwise was 3 sec/droplet. The NCO mass content of the silane hybrid quaternary ammonium salt modified polyisocyanate curing agent reaching the theoretical value means that the final NCO mass content of the silane hybrid quaternary ammonium salt modified polyisocyanate curing agent is 17%, and in the embodiment, the solid content of the silane hybrid quaternary ammonium salt modified polyisocyanate curing agent is 100 wt%. Wherein the addition amount of the polymerization inhibitor is 0.05-0.5% of the total mass of the raw materials, and the total mass of the raw materials refers to the total mass of the polyisocyanate, the alcohol amine, the silane coupling agent and the sultone.
The silane coupling agent is a self-made D-T coupling agent, and the preparation method of the D-T coupling agent comprises the following steps: according to the molar parts, 1.5 parts of N, N-dimethylethylenediamine and 1.5 parts of gamma-methacryloxypropyltrimethoxysilane (TMSPM) react for 24-48 hours under the protection of nitrogen and at the temperature of 25-60 ℃, and finally light yellow liquid is obtained.
Example 3.
185g of isophorone diisocyanate (IPDI) were added to a reactor with mechanical stirring, reflux tube, constant pressure separatory funnel and N2Adding a small amount of N, N-dimethylacetamide into an inlet and outlet four-mouth round-bottom flask to adjust viscosity, slowly dripping 3g of triethanolamine and 6g of silane coupling agent within 20 minutes under the protection of nitrogen atmosphere. Slowly heating to 60 ℃, reacting for 2 hours under the action of low-speed stirring until the mass content of the NCO in the system reaches a theoretical value, adding dimethyl sulfate to terminate the reaction, keeping the temperature for 1 hour, cooling to room temperature, slowly dripping 6g of 1, 4-butyl sultone within 6 minutes, and reacting for 3 hours at 40 ℃ after dripping is finished. And (3) cooling, and removing the reaction solvent by using a thin film distillation method to obtain a light yellow transparent viscous liquid, wherein the NCO mass content of the silane hybrid quaternary ammonium salt modified polyisocyanate curing agent is 22%. In this example, the amount of N, N-dimethylacetamide added was such that the viscosity of the silane-hybridized quaternary ammonium salt-modified polyisocyanate curing agent at 25 ℃ was 4500 mPas, and the rate of slowly adding 3g of triethanolamine and 6g of silane coupling agent dropwise was 5 sec/drop. The NCO mass content reaches the theoretical value, which means that the NCO mass content of the final silane hybrid quaternary ammonium salt modified polyisocyanate curing agent is 22%, and in the embodiment, the solid content of the silane hybrid quaternary ammonium salt modified polyisocyanate curing agent is 100 wt%.
The silane coupling agent is a self-made D-T coupling agent, and the preparation method of the D-T coupling agent comprises the following steps: according to the molar parts, 2.0 parts of N, N-dimethylethylenediamine and 1.1 parts of gamma-methacryloxypropyltrimethoxysilane (TMSPM) react for 24-48 hours under the protection of nitrogen and at the temperature of 25-60 ℃, and finally light yellow liquid is obtained. Wherein the addition amount of the polymerization inhibitor is 0.05-0.5% of the total mass of the raw materials, and the total mass of the raw materials refers to the total mass of the polyisocyanate, the alcohol amine, the silane coupling agent and the sultone.
Example 4.
185g of IPDI trimer were added to a stirred tank with mechanical stirring, reflux tube, constant pressure separating funnel and N2Adding a small amount of ethyl acetate into a four-mouth round-bottom flask at an inlet and an outlet to adjust the viscosity, slowly dripping 3g of N, N-diisopropylethanolamine and 6g of silane coupling agent within 18 minutes under the protection of nitrogen atmosphere. Slowly heating to 50 ℃, reacting for 2 hours under the action of low-speed stirring until the mass content of the NCO of the system reaches a theoretical value, adding a mixture of methyl tosylate, dimethyl sulfate and diethyl sulfate to terminate the reaction, wherein the mass ratio of the methyl tosylate to the dimethyl sulfate to the diethyl sulfate is 1:1:1, keeping the temperature for 1 hour, cooling to room temperature, slowly dropwise adding 6g of 1, 3-propane sultone, propenyl-1, 3-sultone and 1, 4-butane sultone within 7 minutes, wherein the mass ratio of the 1, 3-propane sultone, propenyl-1, 3-sultone and 1, 4-butane sultone is 1:2:1, and reacting for 2.8 hours at 50 ℃ after dropwise adding. And (3) cooling, and removing the reaction solvent by using a thin film distillation method to obtain the silane hybrid quaternary ammonium salt modified polyisocyanate curing agent which is light yellow transparent viscous liquid and has the NCO mass content of 20.9%. In this example, the amount of ethyl acetate added was such that the viscosity of the silane-hybrid quaternary ammonium salt-modified polyisocyanate curing agent at 25 ℃ was 2000 mPas, and the rate of slowly adding 3g of N, N-diisopropylethanolamine and 6g of the silane coupling agent dropwise was 4 sec/drop. The NCO mass content of the silane hybrid quaternary ammonium salt modified polyisocyanate curing agent reaching the theoretical value means that the NCO mass content of the final silane hybrid quaternary ammonium salt modified polyisocyanate curing agent is 20.9%, and in the embodiment, the solid content of the silane hybrid quaternary ammonium salt modified polyisocyanate curing agent is 100 wt%. Wherein the addition amount of the polymerization inhibitor is 0.05-0.5% of the total mass of the raw materials, and the total mass of the raw materials refers to the total mass of the polyisocyanate, the alcohol amine, the silane coupling agent and the sultone.
The silane coupling agent is a self-made D-T coupling agent, and the preparation method of the D-T coupling agent comprises the following steps: according to the molar parts, 1.0 part of N, N-dimethylethylenediamine and 2.0 parts of gamma-methacryloxypropyltrimethoxysilane (TMSPM) react for 24-48 hours under the protection of nitrogen and at the temperature of 25-60 ℃, and finally light yellow liquid is obtained.
Examples 5 to 10.
The differences between the preparation methods of the silane hybrid quaternary ammonium salt modified polyisocyanate curing agents of examples 5-10 and example 1 are shown in table 1.
TABLE 1 differences between the preparation of examples 5 to 10 and example 1
In examples 5 to 10, the polyisocyanate was one or a mixture of Hexamethylene Diisocyanate (HDI), HDI trimer, isophorone diisocyanate (IPDI), IPDI trimer; the alcohol amine is one or a mixture of more than two of N, N-dimethylethanolamine, N-methyldiethanolamine, N-diethylethanolamine, triethanolamine and N, N-diisopropylethanolamine; the sultone sulfonate is one or more of 1, 3-propane sultone, propenyl-1, 3-sultone and 1, 4-butane sultone. Wherein the addition amount of the polymerization inhibitor is 0.05-0.5% of the total mass of the raw materials, and the total mass of the raw materials refers to the total mass of the polyisocyanate, the alcohol amine, the silane coupling agent and the sultone.
Example 11.
This example is the application in a water-borne two-component coating. According to the mass fraction, 0.2 percent of pH regulator DMEA, 11 percent of deionized water, 0.5 percent of dispersant (German Digao TEGO-755W dispersant), 0.5 percent of MA-100 carbon black, 25 percent of titanium pigment and 0.1 percent of defoamer (TEGO-810 aqueous defoamer) are placed in a dispersing barrel for dispersing for 20 minutes at the rotating speed of 600r/min, then the dispersing barrel is placed in a sand mill for grinding until the fineness is lower than 15 mu m, 60 percent of aqueous hydroxy resin (aqueous resin 3AH0519W, Gagming chemical industry Co., Ltd. of Fushan city), 0.2 percent of flatting agent (TEGO-450 flatting agent), 2 percent of film forming auxiliary agent (dipropylene glycol methyl ether DPM/dipropylene glycol butyl ether DPNB ═ 1:1) and 0.5 percent of thickener RHEOLATE 299 are added for dispersing for 20 minutes at the rotating speed of 700r/min to obtain aqueous hydroxy component, then the aqueous curing agent prepared in the embodiment and the comparative example is added slowly according to the molar ratio of NCO/OH 1:1, stirring, and adding a proper amount of deionized water to adjust the construction viscosity of the paint. After being stirred uniformly, the mixture is filtered by a filter cloth of 200 meshes to obtain a bi-component water-based paint which is sprayed on an unground base material, and the film coating performance of the bi-component water-based paint is shown in the following table 2:
TABLE 2 coating film Properties
The chemical reaction of the quaternary ammonium salt sulfonic acid modified polyisocyanate curing agent is illustrated by HDI tripolymer, N-dimethylethanolamine, 1, 3-propane sultone and D-T coupling agent, and before the chemical reaction is illustrated, the reaction process of the D-T silane coupling agent is illustrated by N, N-diethylethylenediamine and gamma-methacryloxypropyltrimethoxysilane (TMSPM), wherein the chemical reaction formula is as follows:
the chemical reaction formula of the quaternary ammonium salt sulfonic acid modified polyisocyanate curing agent prepared by the D-T silane coupling agent is as follows:
compared with the prior art, the invention has the following advantages and beneficial effects: (1) in the preparation of the quaternary ammonium salt sulfonic acid modified polyisocyanate curing agent, alcohol amine, a silane coupling agent and sultone are all fat-soluble substances or are easily soluble in an organic solvent, and a homogeneous system is formed in the reaction, so that the synthesized curing agent is clear and transparent, light in color, low in viscosity, high in NCO content and good in water dispersibility. Solves the problems of poor water dispersibility, poor water resistance of a coating film and the like of the existing waterborne polyurethane curing agent. (2) In the preparation of the quaternary ammonium salt sulfonic acid modified polyisocyanate curing agent, the synthesis reaction condition is mild, the reaction time is short, the cost is greatly saved, the adopted polyisocyanate monomer is HDI or IPDI, and the curing agent synthesized by the monomer has better yellowing resistance and water dispersion stability. (3) The silane hybrid quaternary ammonium salt modified polyisocyanate curing agent prepared by the invention has excellent antimicrobial and bactericidal effects because the quaternary ammonium salt is a cationic bioactive compound, and the aqueous curing agent with antimicrobial, bactericidal and antifouling effects can be obtained by introducing the quaternary ammonium salt to a polyurethane skeleton.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. It will be apparent to those skilled in the art that various other changes and modifications can be made in the invention without departing from the spirit and scope of the invention.
Claims (8)
1. A preparation method of silane hybrid quaternary ammonium salt modified polyisocyanate curing agent is characterized in that the preparation steps of the silane hybrid quaternary ammonium salt modified polyisocyanate curing agent are as follows:
a) adding 90-94% of polyisocyanate into a reactor with a mechanical stirrer, a reflux pipe, a constant-pressure separating funnel and N according to the mass percentage of the raw materials2Regulating the viscosity of an imported and exported four-mouth round-bottom flask by using an organic solvent, slowly dropwise adding 1.0-3.0% of alcohol amine and 2.0-4.0% of silane coupling agent, slowly heating to 40-60 ℃ under the protection of nitrogen atmosphere, reacting under the action of low-speed stirring until the mass content of the NCO in the system reaches a theoretical value, adding a polymerization inhibitor to terminate the reaction, preserving the temperature for 1 hour, and cooling to room temperature to obtain a silane hybrid polyisocyanate curing agent containing tertiary amine for later use; the alcohol amine is one or a mixture of more than two of N, N-dimethylethanolamine, N-methyldiethanolamine, N-diethylethanolamine, triethanolamine and N, N-diisopropylethanolamine;
b) slowly dripping 2.0-4.0% of sultone into the tertiary amine-containing silane hybrid polyisocyanate curing agent obtained in the step a), reacting for 2-3 hours at 40-60 ℃ after dripping is finished, and monitoring the reaction process by a thin layer chromatography until the sultone is completely reacted; cooling, and removing the reaction solvent by using a thin film distillation method to obtain a silane hybrid quaternary ammonium salt modified polyisocyanate curing agent;
the silane coupling agent is a self-made D-T coupling agent, and the preparation method of the D-T coupling agent comprises the following steps: according to the molar parts, 1.0-2.0 parts of one or more of N, N-dimethylethylenediamine, N-diethylethylenediamine and diethanolamine and 1.1-2.0 parts of gamma-methacryloxypropyltrimethoxysilane (TMSPM) react for 24-48 hours under the protection of nitrogen and at the temperature of 25-60 ℃, and finally light yellow liquid is obtained.
2. The preparation method of the silane hybrid quaternary ammonium salt modified polyisocyanate curing agent according to claim 1, characterized in that: the sultone sulfonate is one or more of 1, 3-propane sultone, propenyl-1, 3-sultone and 1, 4-butane sultone.
3. The preparation method of the silane hybrid quaternary ammonium salt modified polyisocyanate curing agent according to claim 1, characterized in that: the polyisocyanate is one or a mixture of Hexamethylene Diisocyanate (HDI), HDI tripolymer, isophorone diisocyanate (IPDI) and IPDI tripolymer.
4. The preparation method of the silane hybrid quaternary ammonium salt modified polyisocyanate curing agent according to claim 1, characterized in that: the organic solvent is one or more mixed solvents of propylene glycol monomethyl ether acetate (PMA), dimethyl sulfoxide, N-dimethylacetamide, N-dimethylformamide, ethyl acetate, petroleum ether and tetrahydrofuran.
5. The preparation method of the silane hybrid quaternary ammonium salt modified polyisocyanate curing agent according to claim 1, characterized in that: the polymerization inhibitor is one or more of methyl p-toluenesulfonate, dimethyl sulfate and diethyl sulfate.
6. The preparation method of the silane hybrid quaternary ammonium salt modified polyisocyanate curing agent according to claim 1, characterized in that: the addition amount of the polymerization inhibitor is 0.05-0.5% of the total mass of the raw materials.
7. The preparation method of the silane hybrid quaternary ammonium salt modified polyisocyanate curing agent according to claim 1, characterized in that: slowly dripping 1.0-3.0% of alcohol amine and 2.0-4.0% of silane coupling agent at the rate of 3-5 s/drop for 10-20 min.
8. A silane hybrid quaternary ammonium salt modified polyisocyanate curing agent is characterized in that: the preparation method is as described in any one of claims 1-7, the solid content of the silane hybrid quaternary ammonium salt modified polyisocyanate curing agent is 100 wt%, the NCO mass content is 17-22%, the viscosity at 25 ℃ is 2000-4500 mPa.s, and the appearance is colorless or light yellow transparent viscous liquid.
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