CN112625236A - Quick-drying anticorrosive epoxy asparagus hybrid resin and preparation method and application thereof - Google Patents
Quick-drying anticorrosive epoxy asparagus hybrid resin and preparation method and application thereof Download PDFInfo
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- CN112625236A CN112625236A CN202011426842.5A CN202011426842A CN112625236A CN 112625236 A CN112625236 A CN 112625236A CN 202011426842 A CN202011426842 A CN 202011426842A CN 112625236 A CN112625236 A CN 112625236A
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- asparagus
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- 229920005989 resin Polymers 0.000 title claims abstract description 71
- 239000011347 resin Substances 0.000 title claims abstract description 71
- 235000005340 Asparagus officinalis Nutrition 0.000 title claims abstract description 63
- 239000004593 Epoxy Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000001035 drying Methods 0.000 title claims abstract description 22
- 244000003416 Asparagus officinalis Species 0.000 title description 2
- 241000234427 Asparagus Species 0.000 claims abstract description 61
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000003822 epoxy resin Substances 0.000 claims abstract description 26
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- -1 unsaturated maleic acid ester Chemical class 0.000 claims abstract description 20
- 238000006845 Michael addition reaction Methods 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- 238000004321 preservation Methods 0.000 claims abstract description 8
- 150000003141 primary amines Chemical class 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 150000004985 diamines Chemical class 0.000 claims abstract description 3
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 3
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 claims description 16
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 229920002396 Polyurea Polymers 0.000 claims description 8
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 6
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 235000012424 soybean oil Nutrition 0.000 claims description 5
- 239000003549 soybean oil Substances 0.000 claims description 5
- SZEWALYSKVMFAD-UHFFFAOYSA-N 4-(4-aminocyclohexyl)oxycyclohexan-1-amine Chemical compound C1CC(N)CCC1OC1CCC(N)CC1 SZEWALYSKVMFAD-UHFFFAOYSA-N 0.000 claims description 4
- XIHHXQOKLHEXDJ-UHFFFAOYSA-N CCN(CC)C(C=C1)=CCC1=C Chemical compound CCN(CC)C(C=C1)=CCC1=C XIHHXQOKLHEXDJ-UHFFFAOYSA-N 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 claims description 4
- FNMTVMWFISHPEV-WAYWQWQTSA-N dipropan-2-yl (z)-but-2-enedioate Chemical compound CC(C)OC(=O)\C=C/C(=O)OC(C)C FNMTVMWFISHPEV-WAYWQWQTSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 3
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 3
- JJVKJJNCIILLRP-UHFFFAOYSA-N 2-ethyl-6-methylaniline Chemical compound CCC1=CC=CC(C)=C1N JJVKJJNCIILLRP-UHFFFAOYSA-N 0.000 claims description 2
- FEUISMYEFPANSS-UHFFFAOYSA-N 2-methylcyclohexan-1-amine Chemical compound CC1CCCCC1N FEUISMYEFPANSS-UHFFFAOYSA-N 0.000 claims description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 2
- OAPDPORYXWQVJE-UHFFFAOYSA-N 4-propylaniline Chemical compound CCCC1=CC=C(N)C=C1 OAPDPORYXWQVJE-UHFFFAOYSA-N 0.000 claims description 2
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 2
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 claims description 2
- TVWTZAGVNBPXHU-FOCLMDBBSA-N dioctyl (e)-but-2-enedioate Chemical compound CCCCCCCCOC(=O)\C=C\C(=O)OCCCCCCCC TVWTZAGVNBPXHU-FOCLMDBBSA-N 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 claims description 2
- 229920003986 novolac Polymers 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 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 claims 1
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims 1
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims 1
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims 1
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 12
- 238000005260 corrosion Methods 0.000 abstract description 12
- 150000003839 salts Chemical class 0.000 abstract description 10
- 239000007921 spray Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000010276 construction Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 4
- 230000006978 adaptation Effects 0.000 description 4
- 239000003595 mist Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 108010064470 polyaspartate Proteins 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005536 corrosion prevention Methods 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003335 secondary amines Chemical group 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 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 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 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
- 239000000463 material Substances 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- GHJOIQFPDMIKHT-UHFFFAOYSA-N propane-1,2,3-triol;prop-2-enoic acid Chemical compound OC(=O)C=C.OCC(O)CO GHJOIQFPDMIKHT-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
-
- 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
- C09D175/02—Polyureas
-
- 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
- C09D5/08—Anti-corrosive paints
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Epoxy Resins (AREA)
- Polyamides (AREA)
Abstract
A quick-drying anticorrosion epoxy asparagus hybrid resin and a preparation method and application thereof are disclosed, the epoxy asparagus hybrid resin is obtained by modifying epoxy resin and asparagus prepolymer through chemical grafting reaction; the epoxy resin is one or more of monoepoxy, diepoxy and polyepoxy; the aspartic prepolymer is obtained by Michael addition reaction of primary organic diamine and unsaturated maleic acid ester. The preparation method comprises the following specific steps: (1) under the protection of nitrogen, dropping unsaturated maleic acid ester into the binary organic primary amine, continuously stirring, controlling the reaction temperature, and performing heat preservation reaction after dropping to obtain an asparagus prepolymer; (2) and (2) adding epoxy resin into the asparagus prepolymer obtained in the step (1) to perform epoxy ring-opening end-capping reaction, thus obtaining the epoxy asparagus hybrid resin. The epoxy asparagus hybrid resin has the advantages of good corrosion resistance and salt spray resistance, quick drying at low temperature, simple preparation method, short production period and low production cost.
Description
Technical Field
The invention relates to epoxy asparagus hybrid resin, in particular to quick-drying anticorrosive epoxy asparagus hybrid resin and a preparation method and application thereof.
Background
The economic loss of China caused by metal corrosion is equal to 4.2% of national GDP every year, and the protection of the coating accounts for more than 70% of the total cost of metal corrosion prevention. Therefore, the development of advanced high-corrosion-resistance coating for engineering machinery is significant for economic development.
The aspartic Polyurea (PAE) coating is taken as a third-generation novel polyurea, because the secondary amine group of the PAE reacts with the NCO component slowly, the construction adaptation period can be conveniently regulated and controlled by adjusting a substituent, the construction adaptation period is longer, the base material is fully moistened, the coating can be cured at low temperature, the coating does not need to be baked, can be quickly recoated and thickly coated, and the formed coating is water-resistant, corrosion-resistant, high in hardness and glossiness and free from yellowing, and has wide application prospect in the aspects of engineering machinery, rail transit, bridge roofs and the like.
The problems of low raw material conversion rate, long synthesis time and the like generally exist in the preparation process of PAE, in addition, the cost of pure aspartyl polyurea is high, the salt spray resistance and the corrosion resistance are poor, and the problems seriously restrict the development and the application of aspartyl polyurea in the field of steel corrosion prevention. CN108164697A discloses that the synthesis rate of the resin of asparagus resin is rapidly stopped by using 30% excess maleate, which solves the problem of long synthesis time, but the excess maleate needs to be extracted in vacuum, which increases the process complexity, and the salt fog resistance of the pure asparagus resin is still poor. Luping (research on novel polyaspartate polyurea coating for marine concrete protection [ D ]. China oceanic university, 2007) and Hujin (Hujin, Yangqing Nu, Huang Shuli, etc.. preparation and research on epoxy soybean oil modified polyaspartate [ J ]. coating industry, 2015 08) adopt epoxy modified aspartic resin, and the main purpose is to accelerate the synthesis efficiency of polyaspartate, but the weakness of improving salt mist resistance and corrosion resistance of pure aspartic resin is not overcome.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provide the quick-drying anticorrosive epoxy asparagus hybrid resin which has the advantages of good corrosion resistance and salt spray resistance, simple preparation method, short production period and low production cost.
The invention further aims to solve the technical problem of providing a preparation method of the quick-drying anticorrosive epoxy asparagus hybrid resin.
The technical scheme adopted for solving the technical problems is that the quick-drying anticorrosive epoxy asparagus hybrid resin is obtained by modifying epoxy resin and asparagus prepolymer through a chemical grafting reaction; the epoxy resin is one or more of monoepoxy, diepoxy and polyepoxy; the aspartic prepolymer is obtained by Michael addition reaction of primary organic diamine and unsaturated maleic acid ester.
The invention further solves the technical problem by adopting the technical scheme that the preparation method of the quick-drying anticorrosive epoxy asparagus hybrid resin comprises the following specific steps:
(1) under the protection of nitrogen, dropping unsaturated maleic acid ester into the binary organic primary amine, continuously stirring, controlling the reaction temperature, and performing heat preservation reaction after dropping to obtain an asparagus prepolymer;
(2) and (2) adding epoxy resin into the asparagus prepolymer obtained in the step (1) to perform epoxy ring-opening end-capping reaction, thus obtaining the epoxy asparagus hybrid resin.
Further, in the step (1), the unsaturated maleic acid ester is one or more of dimethyl maleate, diethyl maleate, diisopropyl maleate, dibutyl maleate and dioctyl maleate.
Further, in the step (1), the organic dibasic primary amine is one or more of 4, 4-methylenebis (2-ethyl) aniline, 4-methylenebis (6-methyl-2-ethyl aniline), 4-methylenebis (2, 6-diethyl aniline), 4-diaminodiphenylmethane, 2-bis (4-aminophenyl) propane, 3-dimethyl-4, 4-diaminodiphenylmethane, 4-diaminodicyclohexylmethane, 4-methylenebis (2-methylcyclohexylamine), bis (4-aminocyclohexyl) ether, 4-diaminodiphenyl ether, and isophorone diamine.
Further, in the step (1), the molar ratio of the primary diamine to the unsaturated maleic acid ester is 1: 1.0 to 1.9, preferably 1: 1.2 to 1.7.
Further, in the step (1), the reaction temperature is 40-60 ℃, and the dripping time is 0.5-3 hours, preferably 1-2 hours.
Further, in the step (1), the temperature of the heat preservation is 60-80 ℃, and preferably 65-75 ℃; the heat preservation time is 6-15 hours, preferably 10-12 hours.
Further, in the step (2), the epoxy resin is preferably one or more of bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, hydrogenated bisphenol a epoxy resin, cardanol-modified epoxy, novolac epoxy, epoxidized soybean oil, glycidyl acrylate, glycidyl methacrylate, aliphatic monoglycidyl ether, and glycidyl versatate.
Further, in the step (2), the mass ratio of the asparagus prepolymer to the epoxy resin is 1: 0.1-2.
Further, in the step (2), the reaction temperature is 70-120 ℃, and preferably 80-90 ℃; the reaction time is 6-24 hours, preferably 10-15 hours.
An epoxy asparagus polyurea coating prepared by taking epoxy asparagus hybrid resin as a raw material is applied to production or use.
In the PAE synthesis process, a large amount of salt-mist-resistant and corrosion-resistant epoxy resin reacts with residual primary amine, so that the PAE synthesis reaction can be terminated quickly, and more epoxy resin molecular chains with good salt-mist-resistant and corrosion-resistant properties can be introduced into the asparagus resin, so that the obtained epoxy-asparagus hybrid resin has the high salt-mist-resistant and corrosion-resistant properties of the epoxy resin, and the properties of the asparagus resin, such as low-temperature quick curing and the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) the epoxy asparagus hybrid resin has high solid content, low viscosity, quick drying at low temperature, good corrosion resistance and salt spray resistance, low production cost, and environmental protection and health because the product does not contain organic primary amine and unsaturated maleic acid ester;
(2) according to the preparation method of the epoxy asparagus hybrid resin, the synthesis time of common asparagus resin is shortened to 1-2 days from several months to 1-2 years, so that the synthesis efficiency is greatly improved; the conversion rate of raw materials is high;
(3) the epoxy asparagus polyurea coating prepared by using the epoxy asparagus hybrid resin as a raw material has compact coating after film forming, high hardness, good flexibility and excellent corrosion resistance, and can be widely applied to corrosion resistance of engineering machinery.
Detailed Description
The following is a further description with reference to specific examples. However, these examples are only for the convenience of those skilled in the art to understand the present invention and the specific embodiments of the present invention, and should not be construed as limiting the scope of the claims of the present patent application.
The starting materials and equipment used in the following examples of the invention are, unless otherwise indicated, conventional chemical reagents and equipment known in the art.
Example 1
The epoxy-aspartic hybrid resin is prepared by modifying 160 parts by weight of 128E-51 epoxy resin and an aspartic prepolymer through a chemical grafting reaction; the aspartyl prepolymer was prepared from 250 parts by weight of 4, 4-methylenebis (2-ethyl) aniline and 250 parts by weight of dimethyl maleate by a Michael addition reaction.
The preparation method of the epoxy aspartic hybrid resin comprises the following specific steps:
(1) under the protection of nitrogen, 250 parts by weight of dimethyl maleate is added dropwise to 250 parts by weight of 4, 4-methylene bis (2-ethyl) aniline, the mixture is continuously stirred, the reaction temperature is controlled to be 55 ℃, the dropwise adding time is 1.5h, and then the temperature is kept at 75 ℃ for 10h, so that an asparagus prepolymer is obtained;
(2) and (2) adding 160 parts by weight of bisphenol A type E-51 epoxy resin into the asparagus prepolymer obtained in the step (1), and then reacting for 10 hours at 80 ℃ to obtain an epoxy asparagus hybrid resin product.
The performance test method of the epoxy asparagus hybrid resin product comprises the following steps: 15 parts by weight of the product of the epoxy-aspartic hybrid resin of the example and 80 parts by weight of zinc powder are taken, HDI (hexamethylene diisocyanate trimer) is added so that the molar ratio of isocyanate and active groups (secondary amine and hydroxyl) of the epoxy-aspartic hybrid resin of the example is 1.05:1, 5 parts by weight of diluent is added to prepare a zinc-rich primer, then the primer with the thickness of 100 microns is coated on a tin plate, after hard drying, the zinc-rich primer is dried in an oven at 80 ℃ for half an hour and cooled to room temperature, the salt spray resistance is tested according to BGD-882, and the construction adaptation period, the quick-drying performance and the salt spray performance test results are shown in Table 1.
The following methods for testing the performance of the hybrid resin product of epoxy resin and epoxy resin are the same as those for testing the product of epoxy resin and epoxy resin. The test results are also shown in Table 1.
Example 2
The epoxy-aspartic hybrid resin is prepared by modifying 140 parts by weight of bisphenol F type NPEF-170 epoxy resin and an aspartic prepolymer through a chemical grafting reaction; the aspartyl prepolymer was obtained by a Michael addition reaction of 170 parts by weight of isophorone diamine and 300 parts by weight of diethyl maleate.
The preparation method of the epoxy aspartic hybrid resin comprises the following specific steps:
(1) under the protection of nitrogen, 300 parts by weight of diethyl maleate is added into 170 parts by weight of isophorone diamine dropwise, the mixture is stirred continuously, the reaction temperature is controlled to be 45 ℃, the dropwise adding time is 2 hours, and then the temperature is kept at 70 ℃ for 12 hours, so that an asparagus prepolymer is obtained;
(2) adding 140 parts by weight of NPEF-170 epoxy resin into the asparagus prepolymer obtained in the step (1), and then reacting for 6 hours at 100 ℃ to obtain an epoxy asparagus hybrid resin product.
Example 3
This example of epoxy-aspartyl hybrid resin is obtained by modifying 100 parts by weight of F44 (novolac epoxy resin) and an aspartyl prepolymer through a chemical grafting reaction; the aspartic prepolymer is prepared from 170 parts by weight of 4, 4-diaminodicyclohexylmethane and 360 parts by weight of diisopropyl maleate through Michael addition reaction.
The preparation method of the epoxy aspartic hybrid resin comprises the following specific steps:
(1) under the protection of nitrogen, dripping 360 parts by weight of diisopropyl maleate into 170 parts by weight of 4, 4-diaminodicyclohexylmethane, continuously stirring, controlling the reaction temperature to be 55 ℃, dripping for 2.5 hours, and then keeping the temperature at 80 ℃ for 8 hours to obtain an asparagus prepolymer;
(2) and (2) adding 100 parts by weight of F44 into the asparagus prepolymer obtained in the step (1), and then reacting for 8 hours at 90 ℃ to obtain an epoxy asparagus hybrid resin product.
Example 4
The epoxy asparagus hybrid resin is obtained by modifying 200 parts by weight of epoxy soybean oil ESO and asparagus prepolymer through a chemical grafting reaction; the aspartic prepolymer is prepared from 230 parts by weight of 4, 4-methylenebis (2-methylcyclohexylamine) and 200 parts by weight of diethyl maleate through a Michael addition reaction.
The preparation method of the epoxy aspartic hybrid resin comprises the following specific steps:
(1) under the protection of nitrogen, 200 parts by weight of diethyl maleate is added dropwise to 230 parts by weight of 4, 4-methylene bis (2-methylcyclohexylamine), the mixture is continuously stirred, the reaction temperature is controlled to be 50 ℃, the dropwise adding time is 0.5h, and then the temperature is kept at 75 ℃ for 15 hours to obtain an asparagus prepolymer;
(2) and (2) adding 200 parts by weight of epoxidized soybean oil ESO into the asparagus prepolymer obtained in the step (1), and then reacting for 15 hours at 80 ℃ to obtain an epoxy asparagus hybrid resin product.
Example 5
The epoxy aspartic hybrid resin is obtained by modifying 50 parts by weight of glycidyl versatate E-10P and an aspartic prepolymer through a chemical grafting reaction; the aspartic prepolymer is obtained by Michael addition reaction of 100 parts by weight of 4, 4-diaminodiphenylmethane, 120 parts by weight of 4, 4-methylenebis (2-methylcyclohexylamine) and 340 parts by weight of diethyl maleate.
The preparation method of the epoxy aspartic hybrid resin comprises the following specific steps:
(1) under the protection of nitrogen, 340 parts by weight of diethyl maleate is added into a mixed solution of 100 parts by weight of 4, 4-diaminodiphenylmethane and 120 parts by weight of 4, 4-methylene-bis (2-methylcyclohexylamine) dropwise, the mixture is continuously stirred, the reaction temperature is controlled at 60 ℃, the dropwise addition time is 2 hours, and then the temperature is kept at 75 ℃ for 12 hours, so that an asparagus prepolymer is obtained;
(2) and (2) adding 50 parts by weight of glycidyl versatate E-10P into the aspartic prepolymer obtained in the step (1), and then reacting for 10h at 80 ℃ to obtain the epoxy aspartic hybrid resin product.
Example 6
The epoxy aspartic hybrid resin is obtained by modifying 80 parts by weight of aliphatic monoglycidyl ether Heloxy-8 and an aspartic prepolymer through a chemical grafting reaction; the aspartyl prepolymer was obtained by a Michael addition reaction of 50 parts by weight of isophorone diamine, 180 parts by weight of 4, 4-methylenebis (2-ethyl) aniline, and 320 parts by weight of diethyl maleate.
The preparation method of the epoxy aspartic hybrid resin comprises the following specific steps:
(1) under the protection of nitrogen, 320 parts by weight of diethyl maleate is added into a mixed solution of 50 parts by weight of isophorone diamine and 180 parts by weight of 4, 4-methylene bis (2-ethyl) aniline, continuously stirred, the reaction temperature is controlled at 60 ℃, added for 1.5 hours, and then kept at 80 ℃ for 10 hours to obtain an asparagus prepolymer;
(2) and (2) adding 80 parts by weight of monoepoxy H-8 into the asparagus prepolymer obtained in the step (1), and then reacting for 10 hours at 100 ℃ to obtain the epoxy asparagus hybrid resin product.
Example 7
The epoxy aspartic hybrid resin of this example is prepared from 300 parts by weight of F44, 100 parts by weight of bisphenol A epoxy resin E-51 and an aspartic prepolymer through a chemical grafting modification reaction; the aspartic prepolymer is obtained by a Michael addition reaction of 100 parts by weight of 4, 4-diaminodicyclohexylmethane, 130 parts by weight of 4, 4-methylenebis (2-methylcyclohexylamine) and 300 parts by weight of diethyl maleate.
The preparation method of the epoxy aspartic hybrid resin comprises the following specific steps:
(1) under the protection of nitrogen, 300 parts by weight of diethyl maleate is added into the mixed solution of 100 parts by weight of 4, 4-diaminodicyclohexylmethane and 130 parts by weight of 4, 4-methylenebis (2-methylcyclohexylamine) dropwise, the mixture is continuously stirred, the reaction temperature is controlled to be 55 ℃, the dropwise addition time is 1.5h, and then the temperature is kept at 75 ℃ for 12h to obtain an asparagus prepolymer;
(2) adding 300 parts by weight of F44 and 100 parts by weight of 128E-51 into the asparagus prepolymer obtained in the step (1), and then reacting for 15h at 80 ℃ to obtain the epoxy asparagus hybrid resin product.
Example 8
The epoxy aspartic hybrid resin is obtained by modifying 150 parts by weight of glycidyl acrylate and an aspartic prepolymer through a chemical grafting reaction; the aspartyl prepolymer was obtained by a Michael addition reaction of 150 parts by weight of 4, 4-diaminodiphenylmethane, 60 parts by weight of bis (4-aminocyclohexyl) ether, and 330 parts by weight of diethyl maleate.
The preparation method of the epoxy aspartic hybrid resin comprises the following specific steps:
(1) under the protection of nitrogen, 330 parts by weight of diethyl maleate is added into the mixed solution of 150 parts by weight of 4, 4-diaminodiphenylmethane and 60 parts by weight of bis (4-aminocyclohexyl) ether, continuously stirred, the reaction temperature is controlled at 50 ℃, the adding time is 2 hours, and then the temperature is kept at 75 ℃ for 15 hours, so as to obtain an asparagus prepolymer;
(2) adding 150 parts by weight of acrylic acid glycerol ether into the obtained asparagus prepolymer in the step (1), and then reacting for 8 hours at 110 ℃ to obtain the epoxy asparagus hybrid resin product.
Example 9
The epoxy aspartic hybrid resin of the embodiment is obtained by modifying 200 parts by weight of F44, 100 parts by weight of glycidyl versatate E-10P and an aspartic prepolymer through a chemical grafting reaction; the aspartic prepolymer is obtained by Michael addition reaction of 40 parts by weight of 4, 4-diaminodiphenylmethane, 200 parts by weight of 4, 4-methylenebis (2-methylcyclohexylamine) and 250 parts by weight of diethyl maleate.
The preparation method of the epoxy aspartic hybrid resin comprises the following specific steps:
(1) under the protection of nitrogen, 250 parts by weight of diethyl maleate is added into the mixed solution of 40 parts by weight of 4, 4-diaminodiphenylmethane and 200 parts by weight of 4, 4-methylene-bis (2-methylcyclohexylamine) dropwise, the mixture is continuously stirred, the reaction temperature is controlled to be 55 ℃, the dropwise addition time is 1h, and then the heat preservation is carried out at 75 ℃ for 12 hours, so as to obtain an asparagus prepolymer;
(2) adding 200 parts by weight of F44 and 100 parts by weight of glycidyl versatate E-10P into the aspartic prepolymer obtained in the step (1), and then reacting for 20 hours at 85 ℃ to obtain an epoxy aspartic hybrid resin product.
TABLE 1 results of tests on the construction pot life, quick drying properties and salt spray properties of the products of examples 1-9
As can be seen from the performance test results of the epoxy-aspartic hybrid resin products in the examples 1-9 listed in the table 1, the epoxy-aspartic hybrid resin provided by the invention has good salt spray resistance, has a long construction adaptation period which can be adjusted from 30min to 120min, can be completely dried within 1h at room temperature without being baked, can greatly reduce energy consumption, and is energy-saving and emission-reducing.
Claims (10)
1. A quick-drying anticorrosion epoxy asparagus hybrid resin is characterized in that the epoxy asparagus hybrid resin is obtained by modifying an epoxy resin and an asparagus prepolymer through a chemical grafting reaction; the epoxy resin is one or more of monoepoxy, diepoxy and polyepoxy; the aspartic prepolymer is obtained by Michael addition reaction of primary organic diamine and unsaturated maleic acid ester.
2. A preparation method of the quick-drying anticorrosive epoxy aspartic hybrid resin as claimed in claim 1, which comprises the following specific steps:
(1) under the protection of nitrogen, dropping unsaturated maleic acid ester into the binary organic primary amine, continuously stirring, controlling the reaction temperature, and performing heat preservation reaction after dropping to obtain an asparagus prepolymer;
(2) and (2) adding epoxy resin into the asparagus prepolymer obtained in the step (1) to perform epoxy ring-opening end-capping reaction, thus obtaining the epoxy asparagus hybrid resin product.
3. The method for preparing the quick-drying anticorrosive epoxy-aspartic hybrid resin according to claim 2, wherein in the step (1), the unsaturated maleic acid ester is one or more of dimethyl maleate, diethyl maleate, diisopropyl maleate, dibutyl maleate and dioctyl maleate.
4. The preparation method of the quick-drying anticorrosive epoxy aspartic hybrid resin according to claim 2 or 3, the method is characterized in that in the step (1), the dibasic organic primary amine is one or more of 4, 4-methylenebis (2-ethyl) aniline, 4-methylenebis (6-methyl-2-ethyl aniline), 4-methylenebis (2, 6-diethyl aniline), 4-diaminodiphenylmethane, 2-bis (4-aminophenyl) propane, 3-dimethyl-4, 4-diaminodiphenylmethane, 4-diaminodicyclohexylmethane, 4-methylenebis (2-methylcyclohexylamine), bis (4-aminocyclohexyl) ether, 4-diaminodiphenyl ether and isophorone diamine; the molar ratio of the primary diamine to the unsaturated maleic acid ester is 1: 1.0 to 1.9, preferably 1: 1.2 to 1.7.
5. The preparation method of the quick-drying anticorrosive epoxy aspartic hybrid resin according to any one of claims 2 to 4, wherein in the step (1), the reaction temperature is 40 to 60 ℃; the dripping time is 0.5-3 h, preferably 1-2 h.
6. The preparation method of the quick-drying anticorrosive epoxy aspartic hybrid resin according to any one of claims 2 to 5, wherein in the step (1), the temperature for heat preservation is 60 to 80 ℃, preferably 65 to 75 ℃; the heat preservation time is 6-15 hours, preferably 10-12 hours.
7. The preparation method of the quick-drying anticorrosive epoxy-aspartic hybrid resin according to any one of claims 2 to 6, wherein in the step (2), the epoxy resin is preferably one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, hydrogenated bisphenol A epoxy resin, cardanol modified epoxy, novolac epoxy, epoxy soybean oil, glycidyl acrylate, glycidyl methacrylate, aliphatic monoglycidyl ether and glycidyl versatate.
8. The preparation method of the quick-drying anticorrosive epoxy-aspartic hybrid resin according to any one of claims 2 to 7, wherein in the step (2), the mass ratio of the aspartic prepolymer to the epoxy resin is 1: 0.1-2.
9. The preparation method of the quick-drying anticorrosive epoxy aspartic hybrid resin according to any one of claims 2 to 8, wherein in the step (2), the reaction temperature is 70 to 120 ℃, preferably 80 to 90 ℃; the reaction time is 6-24 hours, preferably 10-15 hours.
10. An epoxy-aspartic polyurea coating prepared by using the epoxy-aspartic hybrid resin as claimed in claim 1 as raw material.
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| CN115010892A (en) * | 2021-07-13 | 2022-09-06 | 深圳飞扬兴业科技有限公司 | Epoxy modified asparagus polyurea resin composition and weather-resistant material thereof |
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| CN113683775A (en) * | 2021-08-23 | 2021-11-23 | 衡阳拓创聚合新材料有限公司 | Preparation method of aqueous asparagus polyurea resin and aqueous asparagus polyurea resin thereof |
| CN114181599A (en) * | 2021-12-08 | 2022-03-15 | 江苏久诺新材科技股份有限公司 | Preparation method of epoxy modified solvent-free polyurea coating |
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| CN114891160A (en) * | 2022-04-28 | 2022-08-12 | 广东深展实业有限公司 | Asparagus resin and epoxy resin modified waterborne hydroxyl acrylic resin and preparation method and application thereof |
| CN114891160B (en) * | 2022-04-28 | 2024-01-30 | 广东深展实业有限公司 | Asparagus resin and epoxy resin modified water-based resin hydroxy acrylic resin and its preparation method and application |
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