CN116120517B - Water-dispersible composite hydrophilic modified curing agent and preparation method thereof - Google Patents
Water-dispersible composite hydrophilic modified curing agent and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- 239000003607 modifier Substances 0.000 claims abstract description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 20
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 17
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 15
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 15
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 150000002978 peroxides Chemical class 0.000 claims abstract description 7
- 230000001376 precipitating effect Effects 0.000 claims abstract description 7
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 7
- 238000001291 vacuum drying Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000007599 discharging Methods 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims abstract description 3
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims abstract description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 15
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- -1 ethyleneoxy groups Chemical group 0.000 claims description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 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 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000013638 trimer Substances 0.000 claims description 4
- DJEQZVQFEPKLOY-UHFFFAOYSA-N N,N-dimethylbutylamine Chemical compound CCCCN(C)C DJEQZVQFEPKLOY-UHFFFAOYSA-N 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- IIFFFBSAXDNJHX-UHFFFAOYSA-N 2-methyl-n,n-bis(2-methylpropyl)propan-1-amine Chemical compound CC(C)CN(CC(C)C)CC(C)C IIFFFBSAXDNJHX-UHFFFAOYSA-N 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- PDAVOLCVHOKLEO-UHFFFAOYSA-N acetyl benzenecarboperoxoate Chemical compound CC(=O)OOC(=O)C1=CC=CC=C1 PDAVOLCVHOKLEO-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N dimethylacetone Natural products CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- SRLHDBRENZFCIN-UHFFFAOYSA-N n,n-di(butan-2-yl)butan-2-amine Chemical compound CCC(C)N(C(C)CC)C(C)CC SRLHDBRENZFCIN-UHFFFAOYSA-N 0.000 claims description 2
- KLVOSHOFGYMCCP-UHFFFAOYSA-N n,n-di(propan-2-yl)butan-1-amine Chemical compound CCCCN(C(C)C)C(C)C KLVOSHOFGYMCCP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 2
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 32
- 238000012986 modification Methods 0.000 abstract description 24
- 230000004048 modification Effects 0.000 abstract description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 13
- 239000003973 paint Substances 0.000 description 10
- 239000010408 film Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 239000011527 polyurethane coating Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- 208000005156 Dehydration Diseases 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- XYFRHHAYSXIKGH-UHFFFAOYSA-N 3-(5-methoxy-2-methoxycarbonyl-1h-indol-3-yl)prop-2-enoic acid Chemical compound C1=C(OC)C=C2C(C=CC(O)=O)=C(C(=O)OC)NC2=C1 XYFRHHAYSXIKGH-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000005829 trimerization reaction Methods 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
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5066—Polyethers having heteroatoms other than oxygen having nitrogen having halogens in addition to nitrogen
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/323—Polymers modified by chemical after-treatment with inorganic compounds containing halogens
- C08G65/3233—Molecular halogen
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
- C08G65/33306—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group acyclic
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
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- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention discloses a water-dispersible composite hydrophilic modified curing agent and a preparation method thereof. The structure of the curing agent is shown below
Description
Technical Field
The invention belongs to the field of polymers, and particularly relates to a water-dispersible composite hydrophilic modified curing agent and a preparation method thereof.
Background
At present, solvent-based polyurethane coating has been fully developed and applied, and has excellent performance, but the solvent-based polyurethane coating has high content of Volatile Organic Compounds (VOCs), causes serious environmental pollution in the construction process, and along with the enhancement of social environmental awareness and related laws and regulations, a low-VOC or VOC-free coating system is demanded in the market. Therefore, environmental-friendly water-based paint is increasingly paid attention to, and a water-based polyurethane system is gradually developed, so that the water-based polyurethane system is one of important directions of paint development in the future. Wherein the bi-component aqueous polyurethane coating uses aqueous polyurethane dispersoid or aqueous emulsion and aqueous curing agent as film forming materials, and water as dispersion medium. The two-component aqueous polyurethane coating is cured into a film through the reaction of NCO and OH, and the chemical principle is similar to that of solvent polyurethane coating. Compared with other types of water-based paint, the double-component water-based polyurethane paint has good appearance effect and good physical and mechanical properties after being cured into a film, and has certain water resistance and chemical resistance, and the performance is closest to that of solvent-based polyurethane paint. Among them, the aqueous curing agent providing NCO groups is one of the key factors determining the properties of the coating, and the research and development of the aqueous curing agent is one of the hot directions of the aqueous coating.
Isocyanate curing agents in oily polyurethane coating are generally hydrophobic, NCO groups can react with water, and traditional oily curing agents are difficult to disperse in water and need hydrophilic modification. The aqueous curing agent is usually modified by nonionic modification, ionic modification or composite modification. The nonionic modification is mostly modified by monohydroxy polyether, wherein U.S. Pat. No. 5,0489 discloses a water-based curing agent modified by monofunctional polyethylene glycol with a molecular weight of 200-1000, but the modification proportion is more than 10% to obtain certain water dispersibility, the hand stirring property is general, the NCO% content is low, the modification proportion is further improved to increase the hydrophilicity, and besides the NCO% is continuously reduced, the hardness of a paint film is reduced. The ionic modification often adopts sulfonate modification, the hydrophilicity is obviously improved, but the pH value is limited, meanwhile, the price of the modifying reagent is high, the cost is high, and the main production technology is monopoly by an external enterprise, so that the further popularization of the water-based bi-component polyurethane coating is limited. The composite modification combines the advantages of nonionic modification and ionic modification, but the conventional composite modification technology is realized by two modifications, two modifiers are needed, and practical cases are seen. For example, CN105949436A uses two modifiers of polyether polyol and hydroxycarboxylic acid to obtain an aqueous curing agent, and the aqueous curing agent is realized by a multi-step process of modification, trimerization, thin film evaporation and post-modification, and the NCO% value of the obtained product is slightly lower.
In addition, CN110760055A discloses that a polyisocyanate composition having a quaternary ammonium salt structure is obtained by using a quaternary ammonium salt catalyst system containing hydroxyl groups, and the composition has excellent moisture stability, but the ionic structure is introduced through a catalyst form, the modification ratio is low, the product has weak hydrophilicity and no water dispersibility.
The slow development of the current water-based curing agent is still an important factor for limiting the popularization of the water-based paint, and along with the increasing importance of the state on green health and environmental protection, the new water-based curing agent technology is urgently required.
Disclosure of Invention
The invention aims to provide a water-dispersible composite hydrophilic modified curing agent and a preparation method thereof. The non-ionic and ionic composite hydrophilic modification is realized through the modifier, and the obtained curing agent has good water dispersibility and high NCO content.
The invention is realized by the following technical scheme:
a water-dispersible composite hydrophilic modified curing agent has the following structural formula:
Wherein the method comprises the steps of Represents an isocyanurate ring structure: Or an adduct structure of trimethylolpropane: Wherein R 1 is selected from one or a combination of a plurality of capromorphenyl, 2, 4-toluylene, 2, 6-toluylene and 1-methylene-1, 3-trimethylcyclohexyl; r 2 is selected from one or a combination of several of C1-C4 fatty alkyl, such as methyl, ethyl, propyl and butyl; wherein n represents the number of repeating units of ethyleneoxy groups selected from 9 to 54.
A preparation method of a water-dispersible composite hydrophilic modified curing agent comprises the following steps:
a) Adding propenyl polyethylene glycol, peroxide and solvent into a reactor, introducing hydrogen bromide gas under stirring at 30-55 ℃, then continuously reacting for 30-150 min, then introducing nitrogen for 30-60 min, then adding tertiary amine for continuous reaction for 4-12 h, cooling, precipitating the product by diethyl ether, washing for 2-5 times, and vacuum drying to obtain the composite hydrophilic modifier;
b) Under the protection of nitrogen, polyisocyanate is added into a reactor, stirred and heated to 60-100 ℃, a composite hydrophilic modifier is added into the reactor for continuous reaction for 2-6 h, and the water-dispersible composite hydrophilic modified curing agent is obtained after cooling and discharging.
Preferably, the molecular weight of the propylene-based polyethylene glycol is 450-2400, preferably 450-1000.
Preferably, the peroxide is one or more of dibenzoyl peroxide, tert-butyl peroxyacetate, acetyl benzoyl peroxide and ethyl ketone peroxide.
Preferably, the solvent is one or more of acetone, ethanol, pyridine, epoxy hexacyclic ring, dichloromethane and chloroform, preferably acetone.
Preferably, the propylene-based polyethylene glycol of the present invention: peroxide: the mass ratio of the solvent is 100:0.5 to 1.5: 100-700 parts.
Preferably, the tertiary amine is one or more of trimethylamine, triethylamine, dimethylbutylamine, tri-n-propylamine, diisopropylbutylamine, tri-sec-butylamine and triisobutylamine, and preferably one or more of trimethylamine, triethylamine and dimethylbutylamine.
Preferably, the mass ratio of the tertiary amine to the propenyl polyethylene glycol is 8-35: 100.
Preferably, the polyisocyanate of the present invention comprises one or more of HDI trimer, IPDI trimer, TDI/HDI mixed trimer, HDI-TMP adduct, IPDI-TMP adduct, TDI-TMP adduct, preferably HDI trimer.
Preferably, the mass ratio of the composite hydrophilic modifier to the polyisocyanate is 3-10: 100, preferably 5 to 8:100.
The invention obtains the composite hydrophilic modifier with two hydrophilic structures of ethyleneoxy group and quaternary ammonium salt ion through the addition reaction and quaternization reaction of propenyl polyethylene glycol, and the modifier has the characteristics of strong hydrophilicity, ionic modifier and nonionic modifier. The two hydrophilic structures can be simultaneously introduced into the polyisocyanate through the modifier, on one hand, the ionic modified structure has strong hydrophilicity, the water-dispersible curing agent can be obtained by using a small amount of the modifier, the NCO group consumption is low, and the product is ensured to have enough functionality. On the other hand, nonionic modified structures can improve the in-water stability of the product. Finally, one modifier introduces two modified structures at the same time, simplifies the process, does not need to use two modifiers, and further reduces the consumption of NCO groups.
Compared with the prior art, the preparation method provided by the invention has the following advantages: the nonionic and ionic composite hydrophilic modification is realized by using only one modifier, the obtained curing agent has good water dispersibility and high NCO content, and a paint film further cured by the curing agent has good water resistance and hardness.
Detailed Description
The method for preparing the water-dispersible composite hydrophilic modified curing agent according to the present invention is further described below with reference to specific embodiments. It should be understood that the examples given herein are for the purpose of illustration only and are not intended to limit the scope of the present invention.
Example 1:
a) The dehydration treatment is carried out on the propenyl polyethylene glycol, the acetone and the triethylamine in advance. 100g of propenyl polyethylene glycol (APEG 500), 1.5g of benzoyl peroxide and 500g of acetone were added to the reactor, and the reaction was continued for 120min with stirring at 40 ℃. Introducing nitrogen for 60min, adding 20g of triethylamine to react for 12h, cooling, precipitating with diethyl ether, washing for 3 times, and vacuum drying to obtain the composite hydrophilic modifier Ⅰ：HO-(CH2CH2O)nCH2CH2CH2N+(CH2CH3)3Br—,n≈10.
B) Under the protection of nitrogen, 950g WANNATE HT-100 is added into a reactor, stirred and heated to 90 ℃, 50g of composite hydrophilic modifier I is added into the reactor, the reaction is continued for 240min, and the material is discharged after cooling.
As a result of HNMR nuclear magnetic analysis of the product of example 1, characteristic peaks of urethane-linked methylene groups (NHCOO-CH 2,. Delta.4.22), ethyleneoxy groups (-CH 2CH2 O,. Delta.3.61), quaternary ammonium salts N + -linked methylene groups (N +CH2,. Delta.3.32), and adjacent methyl groups (N +CH2CH3,. Delta.1.29) were observed in addition to the peak positions (. Delta.3.83, 3.23, 1.60, 1.37) of the HDI trimer.
Example 2:
a) The dehydration treatment is carried out on the propenyl polyethylene glycol, the acetone and the triethylamine in advance. 100g of propenyl polyethylene glycol (APEG 700), 1.5g of dibenzoyl peroxide and 600g of acetone were added to the reactor, and the reaction was continued for 120min with stirring at 40 ℃. Introducing nitrogen for 60min, adding 14.4g of triethylamine to react for 12h, cooling, precipitating with diethyl ether, washing for 3 times, and vacuum drying to obtain the composite hydrophilic modifier Ⅱ：HO-(CH2CH2O)nCH2CH2CH2N+(CH2CH3)3Br—,n＝14～15.
B) Under the protection of nitrogen, 940g WANNATE HT-600 polyisocyanate is added into a reactor, stirred and heated to 80 ℃, 60g of composite hydrophilic modifier II is added into the reactor, the reaction is continued for 240min, and the material is discharged after cooling.
Example 3:
a) The dehydration treatment is carried out on the propenyl polyethylene glycol, the acetone and the trimethylamine in advance. 100g of propenyl polyethylene glycol (APEG 1000), 1g of tert-butyl peroxyacetate and 700g of acetone were added to the reactor, and the reaction was continued for 150min with stirring at 40 ℃. Introducing nitrogen for 60min, adding 5.9g trimethylamine for continuous reaction for 12h, cooling, precipitating the product with diethyl ether, washing for 3 times, and vacuum drying to obtain the composite hydrophilic modifier Ⅲ：HO-(CH2CH2O)nCH2CH2CH2N+(CH3)3Br—,n＝21～22.
B) Under the protection of nitrogen, 930g WANNATE HT-600 polyisocyanate is added into a reactor, stirred and heated to 90 ℃, 70g of composite hydrophilic modifier III is added into the reactor, the reaction is continued for 240min, and the material is cooled and discharged.
Comparative example 1:
Adopting the preparation method disclosed in US5200489 to dehydrate the monomethyl ether polyethylene glycol (MPEG 550), adding 880g WANNATE HT-100 polyisocyanate into a reactor under the protection of nitrogen, stirring and heating to 100 ℃, adding 120g of MPEG 550 into the reactor, continuously reacting for 360min, cooling and discharging.
Comparative example 2:
In the preparation method of CN110760055A, 1000g of HDI was heated at 70℃and 0.5g of a 20 mass% N-butanol solution of 2-hydroxy-N, N, N-trimethyl-1-propylamine formate was added thereto, and the NCO content in the reaction mixture was 39 mass%, and 0.16g of di-N-butyl phosphate was added thereto to terminate the reaction. The resultant was purified 2 times at 130℃under 0.2Torr using a thin film evaporator to obtain a polyisocyanate composition. The polyisocyanate composition was heat treated at 80℃for 120min.
Comparative example 3:
a) The dehydration treatment is carried out on the propenyl polyethylene glycol, the acetone and the triethylamine in advance. 100g of propenyl polyethylene glycol (APEG 350), 1.5g of benzoyl peroxide and 500g of acetone were added to the reactor, and the reaction was continued for 120min with stirring at 40 ℃. Introducing nitrogen for 60min, then adding 29g of triethylamine for continuous reaction for 12h, cooling, precipitating the product by diethyl ether, washing for 3 times, and vacuum drying to obtain a modifier IV;
b) Under the protection of nitrogen, 950g WANNATE HT-100 is added into a reactor, stirred and heated to 90 ℃, 50g of modifier IV is added into the reactor, the reaction is continued for 240min, and the material is cooled and discharged.
The basic index and the water dispersibility test results of the above 6 sets of curing agents are shown in table 1 below.
Table 1 base index and water dispersibility test results for examples 1 to 3 and comparative examples 1 to 2
Centrifugal stability test method: the examples and comparative examples were hand stirred in water for 3min, then dispersed at high speed at 1200rpm for 15 min, and then centrifuged at 2500rpm for 10 min to observe delamination.
As is clear from Table 1, the water-dispersible complex hydrophilic modified curing agents of examples 1 to 3 have a high NCO content and good water dispersibility, since examples 1 to 3 all have double hydrophilicity of a nonionic hydrophilic group and a quaternary ammonium salt group, and only a small amount of modification is performed.
Comparative example 1 uses only monomethyl ether polyethylene glycol as a hydrophilic modifier, and has limited hydrophilicity, but the hydrophilicity is still insufficient even though the modification ratio is large. Comparative example 2 has little hydrophilicity although the NCO content is high, and is difficult to disperse in water. Comparative example 3 has a slightly lower NCO content and, although good in water dispersibility by hand stirring, has a slightly poorer stability due to a smaller number of segments with a smaller number of ethyleneoxy groups.
The paint formulations of examples 1, 2,3, 1, 2 and 3 were prepared as curing agents according to the formulations shown in Table 2, respectively, for performance testing.
Table 2 test formulations
TABLE 3 film Forming Performance test results for examples 1 to 3 and comparative examples 1 to 3
* : Comparative example 2 was unable to uniformly form a film, so that the performance test result could not be detected
Pencil hardness test standard: GB/T6739-2006; pendulum rod hardness test standard: GB/T1730-2007; flexibility test criteria: GB/T6742-2007; adhesion test criteria: GB/T9286-1998; water resistance test standard: GB/T5029-1985.
As is clear from Table 3, examples 1 to 3 have low modification ratio, high NCO content and high crosslinking density, and thus exhibit good hardness and water resistance. While the modification proportion of comparative example 1 is large, the plasticity of the polyether segment influences the hardness of the paint film. Comparative example 2 has little hydrophilicity, is difficult to disperse in water, and is difficult to uniformly form a film. Comparative example 3 was slightly inferior in water resistance.
Claims (10)
1. A water-dispersible composite hydrophilic modified curing agent has the following structural formula:
Wherein the method comprises the steps of Represents an isocyanurate ring structure: Or an adduct structure of trimethylolpropane: Wherein R 1 is selected from one or a combination of a plurality of capromorphenyl, 2, 4-toluylene, 2, 6-toluylene and 1-methylene-1, 3-trimethylcyclohexyl; r 2 is selected from one or a combination of several of C1-C4 fatty alkyl; wherein n represents the number of repeating units of ethyleneoxy groups selected from 9 to 54.
2. The water-dispersible complex hydrophilically modified curing agent of claim 1, wherein R 2 is selected from methyl, ethyl, propyl, butyl.
3. A method of preparing the water-dispersible composite hydrophilically modified curative of claim 1, comprising the steps of:
a) Adding propenyl polyethylene glycol, peroxide and solvent into a reactor, introducing hydrogen bromide gas under stirring at 30-55 ℃, then continuously reacting for 30-150 min, then introducing nitrogen for 30-60 min, then adding tertiary amine for continuous reaction for 4-12 h, cooling, precipitating the product by diethyl ether, washing for 2-5 times, and vacuum drying to obtain the composite hydrophilic modifier;
b) Under the protection of nitrogen, polyisocyanate is added into a reactor, stirred and heated to 60-100 ℃, a composite hydrophilic modifier is added into the reactor for continuous reaction for 2-6 h, and the water-dispersible composite hydrophilic modified curing agent is obtained after cooling and discharging.
4. A method according to claim 3, wherein the peroxide is one or more of dibenzoyl peroxide, t-butyl peroxyacetate, acetyl benzoyl peroxide, ethyl ketone peroxide.
5. A method according to claim 3, wherein the propylene-based polyethylene glycol: peroxide: the mass ratio of the solvent is 100:0.5 to 1.5: 100-700 parts.
6. A process according to claim 3, wherein the tertiary amine is one or more of trimethylamine, triethylamine, dimethylbutylamine, tri-n-propylamine, diisopropylbutylamine, tri-sec-butylamine, triisobutylamine.
7. A method according to claim 3, wherein the mass ratio of tertiary amine to propenyl polyethylene glycol is 8-35: 100.
8. A method according to claim 3, wherein the polyisocyanate comprises one or more of HDI trimer, IPDI trimer, TDI/HDI mixed trimer, HDI-TMP adduct, IPDI-TMP adduct, TDI-TMP adduct.
9. A method according to claim 3, wherein the mass ratio of the composite hydrophilic modifier to polyisocyanate is 3 to 10:100.
10. A method according to claim 3, wherein the mass ratio of the composite hydrophilic modifier to polyisocyanate is from 5 to 8:100.
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| CN1153542A (en) * | 1994-05-03 | 1997-07-02 | 巴斯福股份公司 | Use of hydrophilically modified polyisocyanates in field of textiles |
| CN105949436A (en) * | 2016-05-17 | 2016-09-21 | 华南理工大学 | Water-dispersible HDI-TDI mixed tripolymer curing agent and preparation method thereof |
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| DE3406998A1 (en) * | 1984-02-27 | 1985-08-29 | Bayer Ag, 5090 Leverkusen | AQUEOUS SOLUTIONS OR DISPERSIONS OF CATIONIC OLIGOURETHANES, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR THE PRODUCTION OF COATING |
| DE10328064A1 (en) * | 2003-06-23 | 2005-01-13 | Bayer Materialscience Ag | Blocked polyisocyanates |
| JP7377706B2 (en) * | 2019-12-26 | 2023-11-10 | 旭化成株式会社 | Polyisocyanate compositions, coating compositions and coating substrates |
| CN111423343B (en) * | 2020-03-20 | 2021-04-09 | 佛山市精信汇明科技有限公司 | Hydrophilic diisocyanate and preparation method and application thereof |
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| CN1153542A (en) * | 1994-05-03 | 1997-07-02 | 巴斯福股份公司 | Use of hydrophilically modified polyisocyanates in field of textiles |
| CN105949436A (en) * | 2016-05-17 | 2016-09-21 | 华南理工大学 | Water-dispersible HDI-TDI mixed tripolymer curing agent and preparation method thereof |
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