CN117624554A - Flexible aqueous epoxy curing agent and preparation method and application thereof - Google Patents
Flexible aqueous epoxy curing agent and preparation method and application thereof Download PDFInfo
- Publication number
- CN117624554A CN117624554A CN202210973105.XA CN202210973105A CN117624554A CN 117624554 A CN117624554 A CN 117624554A CN 202210973105 A CN202210973105 A CN 202210973105A CN 117624554 A CN117624554 A CN 117624554A
- Authority
- CN
- China
- Prior art keywords
- epoxy
- curing agent
- epoxy resin
- reaction
- aqueous epoxy
- 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.)
- Pending
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 79
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 55
- 239000003822 epoxy resin Substances 0.000 claims abstract description 54
- 229920000768 polyamine Polymers 0.000 claims abstract description 28
- 239000004814 polyurethane Substances 0.000 claims abstract description 24
- 229920002635 polyurethane Polymers 0.000 claims abstract description 24
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 239000003085 diluting agent Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 48
- -1 aliphatic diamine Chemical class 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 239000004848 polyfunctional curative Substances 0.000 claims description 12
- 125000001931 aliphatic group Chemical group 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000007142 ring opening reaction Methods 0.000 claims description 9
- 150000002170 ethers Chemical class 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 229920005862 polyol Polymers 0.000 claims description 7
- 150000003077 polyols Chemical class 0.000 claims description 7
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 125000002723 alicyclic group Chemical group 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000013459 approach Methods 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 125000005442 diisocyanate group Chemical group 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 3
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 2
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 2
- SEFYJVFBMNOLBK-UHFFFAOYSA-N 2-[2-[2-(oxiran-2-ylmethoxy)ethoxy]ethoxymethyl]oxirane Chemical compound C1OC1COCCOCCOCC1CO1 SEFYJVFBMNOLBK-UHFFFAOYSA-N 0.000 claims description 2
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 claims description 2
- 239000004844 aliphatic epoxy resin Substances 0.000 claims description 2
- 150000004984 aromatic diamines Chemical group 0.000 claims description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 150000003141 primary amines Chemical class 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 21
- 239000000853 adhesive Substances 0.000 abstract description 7
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- 150000003839 salts Chemical class 0.000 abstract description 5
- 239000007921 spray Substances 0.000 abstract description 5
- 238000010276 construction Methods 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 3
- 239000000839 emulsion Substances 0.000 abstract description 3
- 230000009257 reactivity Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 150000002989 phenols Chemical class 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 5
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- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- 235000013824 polyphenols Nutrition 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 3
- HHRACYLRBOUBKM-UHFFFAOYSA-N 2-[(4-tert-butylphenoxy)methyl]oxirane Chemical group C1=CC(C(C)(C)C)=CC=C1OCC1OC1 HHRACYLRBOUBKM-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 2
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- WNISWKAEAPQCJQ-UHFFFAOYSA-N 2-[(2-nonylphenoxy)methyl]oxirane Chemical compound CCCCCCCCCC1=CC=CC=C1OCC1OC1 WNISWKAEAPQCJQ-UHFFFAOYSA-N 0.000 description 2
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 description 2
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
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- 150000002009 diols Chemical class 0.000 description 2
- 229920006334 epoxy coating Polymers 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 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 description 2
- 239000007788 liquid Substances 0.000 description 2
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- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- 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 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical group CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000002966 varnish Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention provides a flexible aqueous epoxy curing agent, a preparation method and application thereof. The raw materials of the aqueous epoxy curing agent comprise: 0.65-6 parts of polyamine compound; 1 part of polyurethane modified epoxy resin; 0.25-1.25 parts of mono-epoxy reactive diluent; 0.2-1 part of alkyl polyethylene glycol monoglycidyl ether. The flexible aqueous epoxy curing agent disclosed by the invention is controllable in reactivity, has good hydrophilicity and good water dispersion performance, can be dispersed or dissolved in water, and has good stability and construction performance; meanwhile, polyurethane structure is grafted on the molecular chain of the curing agent, so that a paint film prepared by matching the curing agent with the epoxy resin emulsion has excellent impact resistance, flexibility, salt spray resistance and strong adhesive force.
Description
Technical Field
The invention belongs to the technical field of waterborne epoxy coatings, and particularly relates to a flexible waterborne epoxy curing agent, a preparation method and application thereof.
Background
The epoxy resin coating has excellent adhesive force, mechanical property and chemical resistance, and is widely applied to the fields of coating corrosion resistance, civil engineering, adhesives and the like. With the increasing urgent environmental protection requirements, the research on the waterborne epoxy coating is an important trend of the development of the coating nowadays. The epoxy resin reacts with a proper curing agent to form a three-dimensional network structure, so that the epoxy resin has good mechanical property and corrosion resistance, and the curing agent is a key for generating application value of the epoxy resin. As the water-based anticorrosive paint, epoxy resin has the common defects of brittleness, poor impact toughness, easy falling of base material pulverization and the like due to more rigid chain segments and smaller curing volume shrinkage rate, so that the application of the epoxy resin is limited, and the toughening modification of the epoxy resin curing agent is always popular in domestic and foreign researches. At present, most of the existing waterborne epoxy curing agents in the market are prepared by taking polyamine and the like as basic raw materials through hydrophilic and lipophilic modification, and then nonionic hydrophilic chain segments with long alkyl chains are introduced to achieve the effect of improving toughness. For example:
in patent CN 1958639A, a two-step chain extension method is proposed for preparing a waterborne epoxy curing agent, the method firstly uses polyether polyol to carry out chain extension reaction on epoxy, then the chain extension product continues to carry out secondary chain extension reaction with polyethylene polyamine, and finally uses monobasic acid for neutralization, thus preparing the waterborne curing agent with a flexible chain segment. However, the addition of organic acid causes environmental pollution and film forming property to be reduced, and flash rust is easy to generate when the metal is used for corrosion prevention.
In patent CN1084864 a, it is proposed to prepare a polyamide curing agent by reacting oxidized polyethylene glycol with polyamine, the curing agent has better flexibility, but the synthesis technology is more difficult, and a catalyst needs to be added to achieve curing under room temperature.
At present, no good solution exists for the problems, and a curing agent with good water dispersion performance, good compatibility with epoxy resin and better flexibility is needed.
Disclosure of Invention
The first aim of the invention is to provide a flexible aqueous epoxy curing agent which has better hydrophilic property, controllable reaction activity and better compatibility with epoxy resin.
The second aim of the invention is to provide a preparation method of the flexible aqueous epoxy curing agent, which has simple process and easy operation.
A third object of the present invention is to provide the aforementioned flexible aqueous epoxy hardener and the use of the flexible aqueous epoxy hardener prepared according to the aforementioned method for preparing an epoxy resin coating.
In order to achieve the first object of the invention, the following technical scheme is adopted:
the flexible aqueous epoxy curing agent is prepared from the following raw materials in parts by weight:
wherein the polyamine compound is any one or a combination of a plurality of aliphatic polyamines, alicyclic polyamines and aromatic polyamines; in a specific embodiment, the polyamine compound is selected from primary amines having at least 4 active hydrogens, for example, the aliphatic polyamine is an aliphatic diamine and/or an aliphatic triamine, the alicyclic polyamine is an alicyclic diamine and/or an alicyclic triamine, and the aromatic polyamine is an aromatic diamine and/or an aromatic triamine.
In a specific embodiment, the polyamine compound is any one or a combination of more of ethylenediamine, propylenediamine, butylenediamine, 2-methyl-1, 5-pentylene diamine, 1, 6-hexamethylenediamine, diethylenetriamine, m-xylylenediamine, 1, 3-diaminomethylcyclohexane, 1-ethyl-1, 3-propylenediamine, p-aminodicyclohexylmethane, 2, 4-trimethyl-1, 6-hexamethylenediamine, p-xylylenediamine, polyetheramine, triethylenetetramine, tetraethylenepentamine, isophoronediamine, polyethyleneimine, and diethyltoluenediamine; preferably, it is a combination of any one or more of m-xylylenediamine, diethylenetriamine, polyetheramine, isophoronediamine and triethylenetetramine.
The polyurethane modified epoxy resin is shown as a formula I, in the structure shown as the formula I, n is an integer, and n is more than or equal to 1,
preferably n.ltoreq.20, R represents a linear or branched alkyl residue having C1-C10.
I
The polyurethane modified epoxy resin is prepared by reacting the following raw materials:
s1 at least one diisocyanate;
s2 at least one polymer polyol;
s3 at least one of the following structural formula (HO) x R(COOH) y Wherein R represents a linear or branched alkyl residue having C1-C10, x and y are independently of each other integers from 1 to 3; wherein the mole number of the component S3 is 2 times (S1 mole number-S2 mole number).
S4 is at least one epoxy resin, wherein the molar ratio of S4 to S3 is more than or equal to 1:1, and is preferably 1.5:1-3:1.
The polymer polyol is preferably a polyether glycol and/or a polyester glycol; the average molecular weight is 500-3000g/mol, preferably 1000-2000g/mol; wherein the molar ratio of component S1) to component S2) is from 1.25:1 to 2:1, preferably from 1.5:1 to 2:1.
In a specific embodiment, the diisocyanate is selected from one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate, preferably from one or more of isophorone diisocyanate (IPDI), hexamethylene Diisocyanate (HDI) and dicyclohexylmethane diisocyanate.
In a specific embodiment, the polymer polyol is selected from one or more of polyethylene glycol, polypropylene glycol, polyethylene glycol-propylene glycol, polytetrahydrofuran ether glycol, polycaprolactone diol, polycarbonate diol, polyethylene glycol adipate diol, poly 1, 4-butylene glycol adipate diol, poly neopentyl glycol adipate diol, poly 1, 6-hexanediol adipate diol, and poly neopentyl glycol-1, 6-hexanediol adipate diol, preferably poly neopentyl glycol-1, 6-hexanediol adipate diol (e.g., CMA 654).
In a specific embodiment, the hydroxycarboxylic acid is selected from the group consisting of 2, 2-dimethylolpropionic acid, dodecahydroxystearic acid, 2-dimethylolbutyric acid.
The epoxy resin according to the present invention refers to a compound having at least 2 epoxy groups, and may be aliphatic epoxy resin and/or aromatic epoxy resin, as will be understood by those skilled in the art. In one embodiment, the epoxy resin may be any one or more of a polyol glycidyl ether, a polyphenol glycidyl ether, and a polycarboxylic acid glycidyl ester, preferably a polyol glycidyl ether and/or a polyphenol glycidyl ether; it is further preferred that the epoxy resin has an epoxy equivalent of 150 to 4000g/mol, preferably 200 to 2000g/mol, such as 300g/mol, 500g/mol, 700g/mol, 1000g/mol, 1500g/mol and 1800g/mol. The molecular weight of the epoxy resin used in the present invention may be 1000 daltons or less. In further embodiments, the epoxy resin is any one or a combination of bisphenol a epoxy resin, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, and polyethylene glycol diglycidyl ether. For example, the polyepoxide is epoxy E51 or epoxy E44.
In the invention, the monoepoxy reactive diluent is any one or a combination of more of phenolic epoxy ether, unsaturated alcohol epoxy ester, unsaturated carboxylic acid epoxy ester, aliphatic glycidyl ether and aromatic glycidyl ether.
In one embodiment, the monoepoxy reactive diluent is preferably any one or more of a phenolic epoxy ether, a C1-C18 aliphatic glycidyl ether, and a C10-C18 aromatic glycidyl ether.
It will be appreciated by those skilled in the art that the epoxy ethers of phenols are selected from the group consisting of epoxy ethers of phenols, epoxy ethers of cresols, epoxy ethers of C1-C21 alkyl substituted phenols, epoxy ethers of C7-C21 aralkyl substituted phenols, epoxy ethers of C7-C21 alkylaryl substituted phenols, cardanol glycidyl ethers and epoxy ethers of alkoxy substituted phenols;
the epoxy ester of an unsaturated carboxylic acid is selected from the group consisting of glycidyl monocarboxylic acid esters (glycidyl octanoate, glycidyl decanoate, glycidyl laurate, glycidyl stearate, glycidyl eicosanoate), glycidyl neodecanoate, epoxidized methyl oleate, epoxidized n-butyl oleate, epoxidized methyl palmitoleate, and epoxidized ethyl linoleate.
The aromatic glycidyl ether of C10-C18 is selected from phenyl glycidyl ether, o-tolyl glycidyl ether and benzyl glycidyl ether.
The aliphatic glycidyl ether of C1-C18 is selected from butyl glycidyl ether, C12-C14 long alkyl chain glycidyl ether, tertiary butyl glycidyl ether, cyclohexyl glycidyl ether, allyl glycidyl ether, octyl glycidyl ether, isopropyl glycidyl ether, decyl glycidyl ether and p-tertiary butyl phenyl glycidyl ether.
In a preferred embodiment, the monoepoxy reactive diluent is any one or more of cardanol glycidyl ether, butyl glycidyl ether, C12-C14 alkyl glycidyl ether, tolyl glycidyl ether, phenyl glycidyl ether, nonylphenyl glycidyl ether and p-tert-butylphenyl glycidyl ether. In a further preferred embodiment, the monoepoxy reactive diluent is any one or more of butyl glycidyl ether, C12-C14 alkyl glycidyl ether, tolyl glycidyl ether, phenyl glycidyl ether, nonylphenyl glycidyl ether, and p-tert-butylphenyl glycidyl ether.
The alkyl polyethylene glycol monoglycidyl ether is shown as a formula II, wherein in the formula II, R is selected from H or C1-12 alkyl, preferably H or C1-4 alkyl; n is an integer, and n is not less than 5, preferably 11 to 180.
The second object of the invention is to provide a preparation method of polyurethane modified epoxy resin, which is characterized by comprising the following steps:
(1) Uniformly mixing the component S1, the component S2 and the polyurethane catalyst to react until NCO in the system basically reaches or approaches to a theoretical value, so as to generate isocyanate-terminated prepolymer;
(2) Optionally, adding an organic solvent into the reaction system in the step (1), and dissolving and diluting materials in the system to obtain diluted isocyanate-terminated prepolymer;
(3) Adding a component S3 into the reaction system in the step (2) to carry out end-capping reaction to obtain a polyurethane prepolymer;
(4) And adding the metered epoxy resin S4 and the epoxy catalyst into the polyurethane prepolymer, stirring and mixing uniformly, and carrying out ring-opening reaction to obtain the polyurethane modified epoxy resin.
The polyurethane catalyst is added in an amount of 0.01 to 0.05wt%, preferably 0.02 to 0.03wt%, based on the total weight of the components S1 and S2; the catalyst is preferably selected from dibutyltin dilaurate, cobaltous octoate or BiCat8108, more preferably BiCat8108.
The organic solvent is selected from solvents inert to NCO groups, such as butanone, acetone, butyl acetate, toluene, xylene, chlorobenzene, N-ethyl pyrrolidone, N-methyl pyrrolidone, propylene glycol methyl ether acetate, dimethyl carbonate, diethyl carbonate, caprolactone, aromatic compounds, and the like.
The epoxy catalyst in the step (4) is selected from any one or a combination of more of triphenylphosphine, triphenylphosphine and boron trifluoride diethyl ether; preferably, the catalyst is used in an amount of 0.05 to 1wt% based on the total amount of solids in the reaction system of the polyurethane prepolymer and the epoxy resin.
Preferably, the temperature of the reaction in the step (1) is 70-80 ℃ and the reaction time is 120-240 min;
preferably, the process conditions of the end capping reaction in step (3) are as follows: the reaction temperature is 40-50 ℃ and the reaction time is 15-25min.
Preferably, the process conditions of the epoxy ring-opening reaction in the step (4) include: the reaction temperature is 100-140 ℃ and the reaction time is 60-180min.
Preferably, the polyurethane modified epoxy resin has at least 2 epoxy groups. One skilled in the art will appreciate that in the polyurethane modified epoxy resin reaction, the epoxy resin may be selected from any one or a combination of more of the foregoing epoxy resins.
The third object of the invention is to provide a preparation method of the flexible aqueous epoxy curing agent, which comprises the following steps:
(1) Adding polyurethane modified epoxy resin into the polyamine compound for ring opening reaction, and then performing reduced pressure distillation to remove excessive polyamine compound to obtain an intermediate;
(2) Optionally, in the presence of a solvent or water, dropwise adding the monoepoxy reactive diluent and polyethylene glycol monoglycidyl ether into the intermediate for end-capping reaction, and preserving heat after the dropwise addition is finished to obtain an end-capped product;
(3) And adding deionized water into the end-capped product for mixing to obtain the flexible nonionic waterborne epoxy curing agent.
The skilled artisan will appreciate that the solvent of step (2) is an organic solvent commonly used in the art, such as any one or more of propylene glycol methyl ether, ethylene glycol butyl ether, dipropylene glycol dimethyl ether, acetone, butanone, and butanol.
It will be appreciated by those skilled in the art that in step (1), in order to obtain the structure of the intermediate, it is necessary to ensure that the polyamine compound is excessive during the reaction, and if the resin component is added too rapidly, it will result in a local resin component concentration that is too high, thereby affecting the structure of the resulting intermediate, so that the resin component is added dropwise (preferably dropwise) to the polyamine compound to avoid adverse effects caused by too rapid addition.
Preferably, in step (1), the reaction temperature of the ring-opening reaction is 60 to 120 ℃, preferably 80 to 100 ℃, such as 85 ℃, 90 ℃ and 95 ℃; the reaction time is from 0.5 to 5 hours, preferably from 1 to 3 hours, such as 1.5 hours, 2 hours and 2.5 hours.
Preferably, in step (2), the reaction temperature of the capping reaction is 60-120 ℃, preferably 80-100 ℃, such as 85 ℃, 90 ℃ and 95 ℃; the monoepoxide is added dropwise for 0.5 to 4 hours, preferably 1 to 3 hours, such as 1.5 hours, 2 hours and 2.5 hours; the heat preservation time is 0.5-3h.
In the present invention, it is preferable that the solid content of the prepared flexible aqueous epoxy curing agent is 40 to 80% by weight, such as 50% by weight, 60% by weight and 70% by weight.
According to the preparation method of the invention, other non-ideal structures (such as structures obtained by ring-opening reaction of a molecule of polyamine compound and a molecule of epoxy compound) can be generated in the obtained flexible aqueous epoxy curing agent product, but the preparation process does not involve separation of byproducts, and the flexible aqueous epoxy curing agent product is used as a whole, and all evaluation effects are also based on the whole. The progress of the reaction is monitored by a near infrared method and a nuclear magnetic method, the disappearance of the epoxy group proves that the reaction is finished, and the performance indexes of the finally obtained water-based epoxy curing agent system comprise: amine number, solids content, and pH. In one embodiment, the aqueous epoxy hardener has an amine value of 100 to 500mgKOH/g, preferably 150 to 350mgKOH/g, such as 200mgKOH/g, 250mgKOH/g and 300mgKOH/g; the solid content is 40-80wt%; the pH is 8-12, preferably 9-11, such as 9.5, 10 and 10.5.
Finally, the invention provides the flexible aqueous epoxy curing agent and application of the flexible aqueous epoxy curing agent prepared by the method in preparation of epoxy resin coating.
The invention has the beneficial effects that:
(1) The flexible aqueous epoxy curing agent has good hydrophilicity and good water dispersion performance, can be dispersed or dissolved in water, and has good stability and construction performance; meanwhile, an epoxy resin structure is introduced into the main chain, so that good compatibility with epoxy resin is ensured, and a paint film has excellent salt spray resistance, water resistance, strong adhesive force and high hardness when the epoxy resin paint prepared by matching the epoxy resin structure with the epoxy resin emulsion is used for coating.
(2) According to the invention, the polyurethane structure is introduced onto the molecular chain of the curing agent, the special soft and hard block structure and the micro-separation structure of the polyurethane greatly improve the defects of high rigidity and poor flexibility of the cured epoxy resin, and the flexibility of the chain segment is also beneficial to stress release of the epoxy resin in the curing process, so that the cured epoxy paint film is denser and has better performance. Meanwhile, the carbamate structure in the polyurethane provides more hydrogen bonds, so that the epoxy paint film has stronger adhesive force with the metal substrate, and the resistance of the coating is further improved.
(3) The preparation method of the quick-drying nonionic waterborne epoxy hardener has simple process and easy operation.
Detailed Description
The technical scheme and effects of the invention are further described by the following specific examples. The following examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. Simple modifications of the invention using the inventive concept are within the scope of the invention as claimed. The sources of the raw materials used in the following examples and comparative examples are shown in Table 1.
TABLE 1 sources of raw materials used in examples 1-12 and comparative examples 1-3 of the present invention
The test method is as follows:
paint film surface drying and drying test is referred to GB/T1728, paint film and putty film drying time determination method;
pendulum rod hardness reference GB/T1730 pendulum rod damping test by paint film hardness measurement;
adhesion is referred to GB/T9286 cross-hatch test of paint films of color paint and varnish;
water resistance reference GB/T1733 "paint film Water resistance assay";
salt spray resistance refers to GB/T1765 for preparation of paint film for measuring resistance to damp and heat, salt spray and weather (artificially accelerated).
30-day thermal storage stability test of aqueous epoxy curing agent: the sample to be tested is placed in a constant temperature oven at 50 ℃ and tested for delamination over 30 days.
Amine number test of waterborne epoxy curing agent: the method comprises the steps of firstly dissolving a sample to be tested in methanol by a titration method, then adding a di-n-butylamine-chlorobenzene solution into the solution, carrying out potentiometric titration by using a hydrochloric acid standard solution until mutation occurs, carrying out blank titration by using the same method, and finally calculating the obtained result according to the equivalent KOH mass of the sample, wherein the unit is mg KOH/g.
Infrared spectrum testing: in the reaction process of preparing the aqueous epoxy hardener, sampling is carried out from a reaction system and is taken as a sample to be tested; then the sample to be detected is measured by a Fourier infrared spectrometer until the sample to be detected is 913cm -1 The peak at wavenumber (epoxy group) was not seen and the reaction was considered complete.
Nuclear magnetic test: in the reaction process of preparing the aqueous epoxy hardener, sampling is carried out from a reaction system and is taken as a sample to be tested; then, the sample to be measured is dissolved by using deuterated reagent, then, the dissolved sample to be measured is subjected to hydrogen spectrum analysis by using nuclear magnetism, and the epoxy hydrogen has an absorption peak at the chemical displacement position of about 4.3 until the signal peak at the position completely disappears, so that the reaction is considered to be complete.
In the following examples and comparative examples, the reaction end point of the aqueous epoxy curing agent in the preparation process is judged by comprehensively considering the two test means of infrared spectrum and nuclear magnetism, namely, when both the two test means show that the signal peak of the epoxy group disappears, the aqueous epoxy curing agent can be judged to reach the reaction end point in the preparation process.
Examples 1 to 3 (i.e.S1.S3)
Preparation of polyurethane modified epoxy resin
Example 1 (i.e., S1)
(1) 33.6g of HDI and 200g PNA2000,0.024g BiCat8108 are added into a four-neck flask with a reflux condenser, a thermometer and mechanical stirring, stirred and heated to 80 ℃ for reaction for 120min until NCO in the system basically reaches or approaches to a theoretical value, and isocyanate-terminated prepolymer is generated;
(2) Then 50g of N-ethyl pyrrolidone is added, and the mixture is stirred uniformly, so that the materials in the system are dissolved and diluted to obtain diluted isocyanate-terminated prepolymer;
(3) 60g of dodecahydroxystearic acid is added into the prepolymer and stirred uniformly, and the system reacts for 20 minutes at 45 ℃;
(4) 76g of epoxy resin E51 and 0.2g of triphenylphosphine are added into the prepolymer, and the mixture is stirred and heated to 110 ℃ for reaction for 100min to obtain polyurethane modified epoxy resin A1;
examples 2 to 3 (i.e.S2.S3)
Polyurethane modified epoxy resins A2 and A3 were prepared according to the method of example 1, and the reaction conditions are shown in table 2.
Table 2 S1-3 substances and amounts thereof
Reaction conditions for each step in tables 2 S1-3
Examples 4 to 9 (i.e., S4 to 9)
Preparation of Flexible waterborne epoxy curing Agents
Example 4 (i.e., S4)
(1) 300g of isophorone diamine is added into a reaction bottle, and the temperature is preheated to 80 ℃; adding 80g of polyurethane modified epoxy resin into a reaction bottle for ring-opening reaction for 2h; then, carrying out reduced pressure distillation on materials in the reaction bottle by utilizing a vacuum pump, and removing redundant isophorone diamine in a reaction system; (2) Then adding 35g of propylene glycol methyl ether into the system, gradually dripping 52g of butyl glycidyl ether and 24g of methoxy polyethylene glycol monoglycidyl ether (450 molecular weight) into a reaction bottle by using a peristaltic pump to react for 1h, and keeping the temperature for 1h after the dripping is finished; (3) After the reaction is finished, adding 2g of modified anionic catalyst B1 into a reaction bottle, uniformly stirring, then adding 360g of deionized water into the reaction bottle, uniformly stirring and mixing, and discharging to obtain the nonionic waterborne epoxy hardener C1. The resulting flexible aqueous epoxy hardener C1 had a solids content of 45% by weight, an amine number of 180mgKOH/g and a pH of 9.
Examples 5 to 9 (i.e., S5 to 9) and comparative examples 1 to 3 (i.e., D1 to 3)
Aqueous epoxy curatives C2-6 and C1'-3' were prepared according to the procedure of example 4, the materials and amounts used in examples 5-9 are shown in Table 3, the materials and amounts used in comparative examples 1-3 are shown in Table 4, the reaction conditions for each step in examples 8-12 and comparative examples 1-3 are shown in Table 5, and the relevant parameters for the resulting flexible aqueous epoxy curatives are shown in Table 6.
The substances and amounts used in tables 3 S4-9
Table 4 D1-3 substances and amounts thereof
Table 5 reaction conditions and products obtained for each step in S4-9 and D1-3
Table 6 parameters relating to the waterborne epoxy curing agent obtained in S4-9 and D1-3
Performance test:
the aqueous epoxy curatives C1-6 and C1'-3' prepared in examples 4-9 and comparative examples 1-3 were mixed with aqueous epoxy emulsions to prepare paint films, wherein the formulations of the A and B components used for preparing the paint films are shown in tables 7 and 8 below.
Table 7 formulation of A Components
Table 8 formulations of the B components corresponding to S7-12 and D1-3
Mixing the component A obtained in the table 1 and the component B obtained in the table 2 according to the mass ratio of 10:1, stirring for 15min, adding a small amount of deionized water to adjust the construction viscosity (the viscosity of a coating cup is 20-50s, i.e. a sample flows down from the coating cup within 20-50 s), and preparing a mixed paint liquid; and then the mixed paint liquid is subjected to plate making according to industry operation standards (flash leveling for 10min and baking at 80 ℃ for 30 min) to obtain paint films Q1-6 and Q1'-3', respectively. And respectively standing and curing the paint films Q1-6 and Q1'-3' for 7d under the standard conditions of 23+/-2 ℃ and 50+/-5% of humidity, and then carrying out various tests according to the corresponding test methods.
The obtained paint film was tested according to the corresponding test method, and the obtained performance test results are shown in Table 9.
The aqueous epoxy curing agents obtained in tables 9 S4-9 and D1-3 and the properties of the paint films Q1-6 and Q1'-3' prepared therefrom
Each test is executed according to national standard, and the test method is specifically described in the section; tolerance data are test results after 20 days of tracking.
Wherein, the grade of the adhesive force test result is 0-5 grade, the 0 grade adhesive force is optimal, and the 5 grade is worst;
the water resistance test result has the grade of 0-5, the grade of 5 is optimal, and the grade of 0 is worst;
the salt spray resistance test results have the grade of 0-5, the grade of 5 is optimal, and the grade of 0 is worst.
Claims (10)
1. The flexible aqueous epoxy curing agent is characterized by being prepared from the following raw materials in parts by weight:
the polyurethane modified epoxy resin is shown as a formula I, wherein n is an integer, n is more than or equal to 1, preferably n is less than or equal to 20, and R represents a straight-chain or branched-chain alkyl residue with C1-C10.
2. The flexible aqueous epoxy curing agent of claim 1, wherein the polyamine compound is any one or a combination of a plurality of aliphatic polyamines, cycloaliphatic polyamines, and aromatic polyamines; preferably, the polyamine compound is selected from primary amines having at least 4 active hydrogens, for example, the aliphatic polyamine is aliphatic diamine and/or aliphatic triamine, the alicyclic polyamine is alicyclic diamine and/or alicyclic triamine, and the aromatic polyamine is aromatic diamine and/or aromatic triamine.
3. The flexible aqueous epoxy curing agent of claim 1 or 2, wherein the polyurethane modified epoxy resin is prepared by reacting raw materials comprising the following components:
s1 at least one diisocyanate;
s2 at least one polymer polyol;
s3 at least one of the following structural formula (HO) x R(COOH) y Wherein R represents a linear or branched alkyl residue having C1-C10, x and y are independently of each other integers from 1 to 3; wherein the mole number of the component S3 is 2 times (S1 mole number-S2 mole number).
S4 is at least one epoxy resin, wherein the molar ratio of S4 to S3 is more than or equal to 1:1, and is preferably 1.5:1-3:1.
4. A flexible aqueous epoxy hardener according to any one of the claims 1-3, wherein the hydroxycarboxylic acid is selected from the group consisting of 2, 2-dimethylolpropionic acid, dodecahydroxystearic acid, 2-dimethylolbutyric acid.
5. A flexible aqueous epoxy curing agent according to claim 3, wherein the epoxy resin is selected from the group consisting of compounds containing at least 2 epoxy groups, aliphatic epoxy resins and/or aromatic epoxy resins; preferably, the epoxy resin is any one or more of polyhydric alcohol glycidyl ether, polyhydric phenol glycidyl ether and polyhydric carboxylic acid glycidyl ester, and specifically, the epoxy resin is any one or more of bisphenol A epoxy resin, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether.
6. The flexible aqueous epoxy curing agent of any of claims 1-5, wherein the monoepoxy reactive diluent is any one or more of an epoxy ether of a phenol, an epoxy ester of an unsaturated alcohol, an epoxy ester of an unsaturated carboxylic acid, an aliphatic glycidyl ether, and an aromatic glycidyl ether; preferably any one or more of the group consisting of phenolic epoxy ethers, C1-C18 aliphatic glycidyl ethers and C10-C18 aromatic glycidyl ethers.
7. The flexible aqueous epoxy curing agent of any one of claims 1-5, wherein the method of preparing the polyurethane modified epoxy resin comprises the steps of:
(1) Uniformly mixing the component S1, the component S2 and the polyurethane catalyst to react until NCO in the system basically reaches or approaches to a theoretical value, so as to generate isocyanate-terminated prepolymer;
(2) Optionally, adding an organic solvent into the reaction system in the step (1), and dissolving and diluting materials in the system to obtain diluted isocyanate-terminated prepolymer;
(3) Adding a component S3 into the reaction system in the step (2) to carry out end-capping reaction to obtain a polyurethane prepolymer;
(4) And adding the metered epoxy resin S4 and the epoxy catalyst into the polyurethane prepolymer, stirring and mixing uniformly, and carrying out ring-opening reaction to obtain the polyurethane modified epoxy resin.
8. A method of preparing a flexible aqueous epoxy hardener as claimed in any one of claims 1 to 7, comprising the steps of:
(1) Adding polyurethane modified epoxy resin into the polyamine compound for ring opening reaction, and then performing reduced pressure distillation to remove excessive polyamine compound to obtain an intermediate;
(2) Optionally, in the presence of a solvent or water, dropwise adding the monoepoxy reactive diluent and polyethylene glycol monoglycidyl ether into the intermediate for end-capping reaction, and preserving heat after the dropwise addition is finished to obtain an end-capped product;
(3) And adding deionized water into the end-capped product for mixing to obtain the flexible nonionic waterborne epoxy curing agent.
9. The process according to claim 8, wherein in step (1), the reaction temperature of the ring-opening reaction is 60 to 120 ℃, preferably 80 to 100 ℃; the reaction time is 0.5-5h, preferably 1-3h;
preferably, in the step (2), the reaction temperature of the end capping reaction is 60-120 ℃, preferably 80-100 ℃; the dropping time of the monoepoxide is 0.5-4h, preferably 1-3h; the heat preservation time is 0.5-3h.
10. Use of a flexible aqueous epoxy hardener according to any of the claims 1-7 or a flexible aqueous epoxy hardener according to any of the claims 8-9 for the preparation of an epoxy resin coating.
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