CN113234207B - Preparation method of acid-resistant solvent-free epoxy resin curing agent and application of curing agent - Google Patents
Preparation method of acid-resistant solvent-free epoxy resin curing agent and application of curing agent Download PDFInfo
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- CN113234207B CN113234207B CN202110560549.6A CN202110560549A CN113234207B CN 113234207 B CN113234207 B CN 113234207B CN 202110560549 A CN202110560549 A CN 202110560549A CN 113234207 B CN113234207 B CN 113234207B
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 111
- 239000002253 acid Substances 0.000 title claims abstract description 49
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 41
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 238000000576 coating method Methods 0.000 claims description 88
- 239000011248 coating agent Substances 0.000 claims description 69
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 48
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 16
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical group CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 12
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 239000000853 adhesive Substances 0.000 claims description 7
- 230000001070 adhesive effect Effects 0.000 claims description 7
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000003292 glue Substances 0.000 claims description 4
- 239000011440 grout Substances 0.000 claims description 4
- 239000004570 mortar (masonry) Substances 0.000 claims description 4
- 239000004575 stone Substances 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- 239000004848 polyfunctional curative Substances 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 18
- -1 alicyclic diamine Chemical class 0.000 abstract description 17
- 239000006087 Silane Coupling Agent Substances 0.000 abstract description 16
- 239000012745 toughening agent Substances 0.000 abstract description 15
- 239000004593 Epoxy Substances 0.000 abstract description 10
- 230000002195 synergetic effect Effects 0.000 abstract description 6
- 238000012360 testing method Methods 0.000 description 24
- 239000000047 product Substances 0.000 description 21
- 239000000463 material Substances 0.000 description 18
- 230000007797 corrosion Effects 0.000 description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 9
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 9
- 239000003973 paint Substances 0.000 description 8
- 125000002723 alicyclic group Chemical group 0.000 description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 238000005187 foaming Methods 0.000 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 description 3
- 239000000843 powder Substances 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- 239000000080 wetting agent Substances 0.000 description 3
- 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
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 description 2
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-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
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- ZDWQSEWVPQWLFV-UHFFFAOYSA-N C(CC)[Si](OC)(OC)OC.[O] Chemical compound C(CC)[Si](OC)(OC)OC.[O] ZDWQSEWVPQWLFV-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5026—Amines cycloaliphatic
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Abstract
The application relates to the field of epoxy curing agents, in particular to a preparation method of an acid-resistant solvent-free epoxy resin curing agent and application of the curing agent. The preparation method comprises the following steps: s1, adding 25-50 parts by weight of toughening agent into 30-60 parts by weight of alicyclic diamine for more than 2 times, and stirring and dispersing uniformly to form transparent liquid; s2, adding 0-5 parts of accelerator into the product dispersed in the step S1, and stirring and dispersing uniformly to form transparent liquid; s3 adding 0.1-0.6 weight part of silane coupling agent into the dispersed product of the step S2, stirring and dispersing uniformly to form transparent liquid. The proportion of each component is controlled through the synergistic effect of the toughening agent, the alicyclic diamine and the silane coupling agent, and the anti-corrosion performance of the curing agent is greatly improved by matching with the preparation method, and the prepared curing agent has stable performance.
Description
Technical Field
The application relates to the field of epoxy curing agents, in particular to a preparation method of an acid-resistant solvent-free epoxy resin curing agent and application of the curing agent.
Background
The epoxy resin is a high molecular polymer and is a generic name of a polymer containing more than two epoxy groups in a molecule. The excellent physical mechanical and electrical insulation properties of epoxy resins, their adhesion to various materials, and their flexibility in the process of use are not available with other thermosets. Therefore, the adhesive can be made into adhesives, coatings, composite materials, casting materials, mould pressing materials and injection molding materials, and can be widely applied to various fields of national economy.
The epoxy resin curing agent is an additive which reacts with epoxy resin to form a reticular three-dimensional polymer, and the composite material aggregate is enveloped in a reticular body to change linear resin into tough body-type solid. Therefore, the performance of the epoxy resin curing agent directly influences the performance of the epoxy resin, and the acid resistance of the solvent-free epoxy curing agent in the current market cannot pass the standard of GB/T22374-2018 terrace coating material, so that the application of the epoxy resin is limited; in particular, in industrial production of petroleum, chemical industry and smelting, concentrated sulfuric acid is often required to be prepared, and terraces of production sites are easy to corrode, so that the acid resistance of the epoxy resin curing agent needs to be improved.
Disclosure of Invention
In order to improve the acid resistance of the epoxy resin curing agent, the application provides a preparation method and application of the acid-resistant solvent-free epoxy resin curing agent.
In a first aspect, the preparation method of the acid-resistant solvent-free epoxy resin curing agent provided by the application adopts the following technical scheme:
a preparation method of an acid-resistant solvent-free epoxy resin curing agent comprises the following steps:
s1, adding 25-50 parts by weight of toughening agent into 30-60 parts by weight of alicyclic diamine for more than 2 times, and stirring and dispersing uniformly to form transparent liquid;
s2, adding 0-5 parts of accelerator into the product dispersed in the step S1, and stirring and dispersing uniformly to form transparent liquid;
s3 adding 0.1-0.6 weight part of silane coupling agent into the dispersed product of the step S2, stirring and dispersing uniformly to form transparent liquid.
Experiments show that the proportion of the components is controlled through the synergistic effect of the toughening agent, the alicyclic diamine and the silane coupling agent, and the corrosion resistance of the curing agent is greatly improved by matching with the preparation method, and the prepared curing agent has stable performance. The curing agent is used for floor coating materials, can also greatly improve the acid resistance, has stronger corrosion resistance, completely meets the standard of GB/T22374 plus 2018 floor coating materials, and simultaneously ensures that the cured substance prepared by the curing agent has good toughness and high hardness. The toughening agent is mixed with the alicyclic diamine for more than 2 times, so that heat release can be better controlled, the stirring and the dispersing are uniform and faster, the product stability of the curing agent can be ensured, the dispersing time can be shortened, and the dispersing efficiency can be improved.
The accelerator is beneficial to improving the reaction speed of the curing agent and the epoxy resin, reducing the curing temperature, saving more energy and preventing a cured product prepared from the curing agent from being embrittled.
Preferably, the cycloaliphatic diamine in step S1 is a cycloaliphatic primary diamine; preferably 4, 4-diaminodicyclohexylmethane or 3, 3-dimethyl-4, 4-diaminodicyclohexylmethane.
Tests show that the curing agent selects alicyclic binary primary amine, especially 4, 4-diaminodicyclohexyl methane or 3, 3-dimethyl-4, 4-diaminodicyclohexyl methane, and is used for the colorless transparent epoxy curing agent, so that the corrosion resistance of the curing agent can be improved, and the effects of toughening, strengthening and weather resistance are achieved.
Preferably, the toughening agent in the step S1 is benzyl alcohol or cardanol; in step S2, the accelerator is DMP-30.
Benzyl alcohol and cardanol can be better cooperated with alicyclic diamine and a silane coupling agent, the toughness of the curing agent is improved, the hardness of a cured product prepared from the curing agent is guaranteed, meanwhile, the viscosity can be reduced, stirring and dispersion are facilitated, benzyl alcohol is easy to obtain, and large-scale industrial production is facilitated. The DMP-30 can greatly reduce the curing temperature of the curing agent and improve the curing efficiency; the compatibility of DMP-30 with other components is also good.
Preferably, the stirring speed in steps S1, S2 and S3 is 400-600 rpm, and the stirring time is 20-50 minutes.
The stirring speed is adopted, so that the splashing is not easy, the dispersion efficiency can be ensured, and the quality of the prepared curing agent is more stable.
Preferably, 5 to 10 parts by weight of alkylphenol is added before the silane coupling agent is added to the dispersed product of step S1, and the mixture is stirred and dispersed uniformly to form a transparent liquid.
Through test tests, the alkylphenol improves the water-white resistance of a cured product, and can keep good processability of the curing agent by controlling the addition amount of the alkylphenol.
Preferably, the alkylphenol is added into the dispersed product of the step S1, the stirring speed is 400-600 r/min, and the stirring time is 20-50 min.
The stirring speed is adopted, so that splashing is not easy to occur, the dispersion efficiency can be ensured, and the quality of the prepared curing agent is more stable.
Preferably, the weight ratio of the alicyclic diprimary amine to the toughening agent is 1.2-1.3, and the weight ratio of the alicyclic diprimary amine to the silane coupling agent is 100-300.
Tests show that the acid resistance of the curing agent is better within the range of the mixture ratio.
In a second aspect, the acid-resistant solvent-free epoxy resin curing agent provided by the application adopts the following technical scheme:
an acid-resistant solvent-free epoxy resin curing agent comprises the following components in parts by weight:
30-60 parts of alicyclic diamine
25-50 parts of toughening agent
0.1 to 0.6 portion of silane coupling agent
0 to 5 portions of accelerant
Tests show that the proportion of each component is controlled by the synergistic action of the toughening agent, the alicyclic diamine and the silane coupling agent, and the corrosion resistance of the curing agent is greatly improved by matching with the preparation method. The accelerator is beneficial to improving the reaction speed of the curing agent and the epoxy resin, reducing the curing temperature, saving more energy and preventing a cured product prepared from the curing agent from being embrittled.
Preferably, the alicyclic diamine is alicyclic primary diamine; preferably 4, 4-diaminodicyclohexylmethane or 3, 3-dimethyl-4, 4-diaminodicyclohexylmethane.
Tests show that the curing agent selects alicyclic binary primary amine, especially 4, 4-diaminodicyclohexyl methane or 3, 3-dimethyl-4, 4-diaminodicyclohexyl methane, and is used for the colorless transparent epoxy curing agent, so that the corrosion resistance of the curing agent can be improved, and the effects of toughening, strengthening and weather resistance are achieved.
Preferably, the toughening agent is benzyl alcohol; in step S2, the accelerator is DMP-30.
The benzyl alcohol can be better cooperated with the alicyclic diamine and the silane coupling agent, the toughness of the curing agent is improved, the hardness of a cured product prepared from the curing agent is ensured, meanwhile, the viscosity can be reduced, the stirring and the dispersion are convenient, the benzyl alcohol is also easily obtained, and the large-scale industrial production is convenient. The DMP-30 can greatly reduce the curing temperature of the curing agent and improve the curing efficiency; the compatibility of DMP-30 with other components is also good.
Preferably, 5 to 10 parts by weight of nonyl phenol is also included.
Nonyl phenol improves water-white resistance of a cured product, and can keep good processability of a curing agent by controlling the addition amount of the nonyl phenol.
In a third aspect, the solvent-free coating provided by the application adopts the following technical scheme:
the solvent-free coating comprises 15-18 wt% of the acid-resistant solvent-free epoxy resin curing agent and other components, wherein the other components comprise the following components in parts by weight:
e-5138-42 parts
3-6 parts of benzyl alcohol
0.1 to 0.3 portion of dispersant
0.1 to 0.3 portion of wetting agent
0.2 to 0.4 portion of flatting agent
0.2 to 0.4 portion of defoaming agent
33-37 parts of barium sulfate
17-21 parts of quartz powder
Preferably, the weight ratio of the curing agent to the other components is 1: 5.
The solvent-free coating prepared by the formula has stronger acid resistance and corrosion resistance, completely meets the standard of GB/T22374 plus 2018 terrace coating material, and simultaneously ensures that a cured product prepared by the curing agent has good toughness and high hardness.
Preferably, the other components comprise the following components in parts by weight:
e-5140 parts
5 parts of benzyl alcohol
0.2 part of dispersant
0.2 portion of wetting agent
0.3 part of flatting agent
0.3 portion of defoaming agent
35 portions of barium sulfate
19 parts of quartz powder
The solvent-free coating prepared by the formula has stronger acid resistance and corrosion resistance, particularly has better concentrated sulfuric acid corrosion resistance, and can be used in some special occasions.
In a fourth aspect, the application of the curing agent provided by the present application adopts the following technical scheme:
the curing agent prepared by the preparation method of the acid-resistant solvent-free epoxy resin curing agent is applied to anticorrosive floor coatings, self-leveling and stripe paint floor coatings, chemical resistance energy storage tank lining coatings, mortar and grout, decorative tile glue, permeable adhesive stones and colored pavements.
In summary, the present application has at least the following beneficial effects:
1. experiments show that the coupling agent mainly enhances the adhesive force, and alicyclic amines have no atom with large electronegativity except amino groups and cannot form intermolecular hydrogen bonds with an object to be coated, so that the adhesive strength of a cured product of the alicyclic amines is influenced, and the alicyclic amines are limited in use. According to the curing agent, the proportioning of each component is controlled through the synergistic effect of the toughening agent, the alicyclic diamine and the silane coupling agent, the corrosion resistance of the curing agent is greatly improved, the curing agent is used for floor coating materials, the acid resistance of the curing agent can also be greatly improved, the corrosion resistance is stronger, the curing agent completely meets the standard of GB/T22374 and 2018 floor coating materials, and meanwhile, the curing agent prepared from the curing agent has good toughness and high hardness. The toughening agent is mixed with the alicyclic diamine for more than 2 times, so that heat release can be better controlled, the stirring and the dispersing are uniform and faster, the product stability of the curing agent can be ensured, the dispersing time can be shortened, and the dispersing efficiency can be improved.
2. The accelerator is beneficial to improving the reaction speed of the curing agent and the epoxy resin, reducing the curing temperature, saving more energy and preventing a cured product prepared from the curing agent from being embrittled.
3. Tests show that the curing agent selects alicyclic binary primary amine, especially 4, 4-diaminodicyclohexyl methane or 3, 3-dimethyl-4, 4-diaminodicyclohexyl methane, and is used for the colorless transparent epoxy curing agent, so that the corrosion resistance of the curing agent can be improved, and the effects of toughening, strengthening and weather resistance are achieved.
4. Through test tests, the alkylphenol improves the water-white resistance of the cured product, and the good processability of the curing agent can be kept by controlling the addition amount of the alkylphenol.
5. The curing agent has excellent corrosion resistance, can be used for anticorrosive floor coatings, self-leveling and stripe paint floor coatings, chemical resistance storage tank lining coatings, mortar and grout, decorative tile glue, permeable adhesive stone and colored pavements, greatly expands the application scenes of the curing agent, and has industrial value.
6. The solvent-free coating prepared by the method has stronger acid resistance and corrosion resistance, completely meets the standard of GB/T22374 plus 2018 terrace coating material, has the final Shore D hardness of more than 78 basically, has the compressive strength of more than 85MPa basically, is more substantial in price and is more beneficial to industrial popularization.
Drawings
FIG. 1 is a schematic representation of the curing agents prepared in example 5 and comparative example 7.
Detailed Description
The acid resistance of the solvent-free epoxy curing agent in the current market can not pass the standard of GB/T22374 plus 2018 terrace coating material, thereby limiting the application of the epoxy resin; in particular, in industrial production of petroleum, chemical industry and smelting, concentrated sulfuric acid is often required to be prepared, and terraces of production sites are easy to corrode, so that the acid resistance of the epoxy resin curing agent needs to be improved. The applicant researches a lot of formulas and preparation methods of curing agents, and surprisingly discovers that the synergistic effect of the toughening agent, the alicyclic diamine and the silane coupling agent, the corrosion resistance of the curing agent is greatly improved by controlling the proportion of the components and matching with the corresponding preparation method, the prepared curing agent has stable performance, can be used for floor coating materials, also greatly improve the acid resistance of the curing agent, has stronger corrosion resistance, completely accords with the standard of GB/T22374 and 2018 floor coating materials, and simultaneously ensures that a cured substance prepared from the curing agent has good toughness and high hardness.
In order to facilitate understanding of the technical solution of the present application, the preparation method of the acid-resistant solvent-free epoxy resin curing agent of the present application is described in further detail below, but is not intended to limit the scope of the present application.
The present application is further described in detail below with reference to tables and examples.
The reagents used in the examples are all commercially available.
DMP-30 is an abbreviation for 2, 4, 6-tris (dimethylaminomethyl) phenol. In the following table, the alkylphenol is nonylphenol and the silane coupling agent is gamma-glycidoxypropyltrimethoxysilane.
The E-type epoxy resin is a linear polymer prepared by polycondensation of bisphenol A (2, 2-bis (4-hydroxyphenyl) propane) and epichlorohydrin in an alkaline medium, and E-51 is a trade mark and represents an average epoxy value (51/100=0.51, and the epoxy value N/100 is 0.48-0.54), and the product mark is 618.
The 120# solvent oil is also called industrial heptane, commonly called white spirit and white alcohol, and the distillation range is collected at 80-120 ℃.
An acid-resistant solvent-free epoxy resin curing agent comprises the following components in parts by weight shown in Table 1
TABLE 1 formulation tables for examples 1-7 and comparative examples 1-4
The method for preparing the acid-resistant solvent-free epoxy resin curing agent of examples 1 to 7 and comparative examples 1 to 4 in the above table 1 comprises the steps of:
s1, dividing benzyl alcohol into 3 equal parts, adding the 3 equal parts into 4, 4-diaminodicyclohexyl methane for 3 times, and stirring and dispersing uniformly to form transparent liquid;
s2, adding DMP-30 into the product dispersed in the step S1, and stirring and dispersing uniformly to form transparent liquid;
s3 adding silane coupling agent into the dispersed product of the step S2, stirring and dispersing uniformly to form light-colored transparent liquid.
And (4) adding nonyl phenol before adding the silane coupling agent into the dispersed product of the step S1, and stirring and dispersing uniformly to form transparent liquid. In the steps S1, S2, S3 and the step of adding nonylphenol, the stirring speed was 500 rpm and the stirring time was 35 minutes. The stirring time can be flexibly adjusted according to the dispersion condition of each component.
In order to better and more quickly detect the acid and alkali resistance of the curing agent, the applicant prepares the curing agents prepared in the above examples and comparative examples into solvent-free coating, wherein the solvent-free coating comprises the acid-resistant solvent-free epoxy resin curing agent described in any one of examples 1-7 and comparative examples 1-4 and other components, and the other components comprise the following components in parts by weight:
40 parts of E-51 epoxy resin
5 parts of benzyl alcohol
0.2 part of dispersant
0.2 portion of wetting agent
0.3 part of flatting agent
0.3 portion of defoaming agent
35 portions of barium sulfate
19 parts of quartz powder
Wherein the weight ratio of the curing agent to other components is 1: 5.
The corresponding relationship between the solvent-free coatings A-G prepared by the formula and the curing agent is shown in the following table 2:
TABLE 2 comparative tables of curing agents and solventless coating materials prepared in examples 1-7 and comparative examples 1-4
The chemical resistance of the coating A-K is tested according to the standard of GB/T22374-2018 terrace coating material, in order to save the test cost, the test is carried out according to the sequence of acid resistance, alkali resistance and oil resistance, if one of the test results is not in accordance with the requirement, the subsequent test is stopped, and the test results are as follows in the following table 3:
as is clear from Table 3 below, the acid resistance, alkali resistance and oil resistance of the coatings A to G were all good, whether at 10% H by mass 2 SO 4 The corrosion resistance is greatly improved because the solution is soaked for 48 hours, the solution is soaked for 72 hours in NaOH solution with the mass fraction of 20 percent, and the solution is soaked for 72 hours in No. 120 solvent oil without foaming and peeling. The curing agents added in the coatings A-G have high gloss,the viscosity is moderate (the viscosity at 25 ℃ is 120-200 mPa & S), and the processability is good. Nonyl phenol is not added into the coatings A-C, slight color change is caused in the test process, but the use is not influenced. The relative nonyl phenol content in coating G was higher, the viscosity was greatest in coatings A-G, and the processability was slightly inferior to that of coatings D, E and F, so coatings D, E and F had better processability. The DMP-30 has the main functions of greatly reducing the curing temperature of the curing agent and improving the curing efficiency; therefore, coating E, F is preferred for further investigation.
The gamma-glycidoxypropyltrimethoxysilane is not added in the coating H, so that the acid resistance is greatly reduced, and the coating H is peeled off in a large area after being soaked in a sulfuric acid solution and cannot be used for actual production.
The paint I is not added with benzyl alcohol, so that the acid resistance is obviously reduced, a large amount of bubbles and peeling are generated, in addition, the viscosity of the curing agent is large in the preparation process, and the processing performance of the mixture with other components is obviously reduced. The coating H was also brittle after drying and could not be used in actual production.
The amount of benzyl alcohol in the coating J is too much, the viscosity of the coating is reduced more, the construction difficulty is increased, and the acid resistance is higher than that of the coating I but does not meet the requirement. The coating J is soaked in sulfuric acid with the mass fraction of 10% for 48 hours, has obvious foaming and obvious shedding, and cannot be used for terraces on special occasions.
The amount of benzyl alcohol in the coating K is too small, the viscosity of the coating is reduced, the construction process is relatively difficult, obvious bubbles are generated when the coating K is soaked in sulfuric acid with the mass fraction of 10% for 48 hours, the large-area coating is easy to peel off, and the coating K cannot be used for terraces in special occasions.
TABLE 3 Corrosion resistance test chart for coatings A-K
It can also be seen from the above table that benzyl alcohol, 4-diaminodicyclohexylmethane and gamma-glycidoxypropyltrimethoxysilane have a very good synergistic effect, and the absence of either component can seriously affect the acid resistance of the coating. Too much or too little benzyl alcohol can also affect the acid resistance of the coating.
In order to better verify the acid resistance of the coating D, E and F, the coating D, E and F are soaked in sulfuric acid with the mass fraction of 50% for 48 hours, and the coating E and F still do not foam, peel off or change color obviously after soaking is finished. Paint G had a small amount of bubbles and was slightly less acid resistant than paints E and F. Tests show that the weight ratio of the 4, 4-diaminodicyclohexyl methane to the benzyl alcohol is controlled to be 1.2-1.3, and the weight ratio of the 4, 4-diaminodicyclohexyl methane to the gamma-glycidyl ether oxygen propyl trimethoxy silane is better to improve the acid resistance of the curing agent at 100-300.
The present application also investigated the preparation of epoxy resin curing agents.
Example 8
Example 8 differs from example 5 in that S1 divides the toughening agent into 2 equal portions, adds it in 2 portions, and stirs it while adding, with a stirring speed of 600 rpm and a stirring time of 20 minutes. S1 the whole process is carried out in a thermostatic chamber at 16-20 ℃. Paint L was prepared using the curing agent prepared in example 8.
Comparative example 5
The difference between the comparative example 5 and the example 5 is that the toughening agent S1 is added into the 4, 4-diaminodicyclohexyl methane at one time, a large amount of heat is released in the reaction, the stirring is difficult to be accelerated, and the heat has certain loss to stirring equipment, so that the requirement on the heat resistance of a reaction vessel is higher. Coating M was made using the curing agent prepared in comparative example 5.
Comparative example 6
Comparative example 6 is different from example 5 in that DMP-30, nonylphenol and a silane coupling agent were mixed and then added together to the transparent liquid obtained in S1. Paint N was prepared using the curing agent prepared in comparative example 6.
The chemical resistance of the coating L-N is tested according to the standard of GB/T22374-2018 terrace coating material, in order to save the test cost, the test is carried out according to the sequence of acid resistance, alkali resistance and oil resistance, if one of the test results is not in accordance with the requirement, the subsequent test is stopped, and the test results are as shown in the following table 4:
TABLE 4 Corrosion-resisting property test table for coating L-N
As can be seen from the above Table 4, the acid resistance, alkali resistance and oil resistance of the coating L are excellent, and the acid resistance of the coatings M and N can not meet the standard of GB/T22374-.
In order to better satisfy the requirement of terrace coating material, this application has also made the test to other performances of coating E. The gel time of coating E was 25min at 25 ℃; the surface drying time is 3 hours, which is much faster than the surface drying time required by GB/T22374-2018 floor coating material which is less than 8 hours, thereby greatly improving the construction efficiency. The surface of the coating film of the coating E is flat, and no obvious phenomena of shrinkage, flooding, blooming, wrinkling, pinholes or cracking are caused; the final shore D hardness was 83. The compressive strength of the coating E is also as high as 94.5MPa, which is improved by one time compared with 45MPa required by the national standard. The tensile bonding strength, the impact resistance and the skid resistance of the coating E are all superior to the national standard. The artificial climate aging resistance can also achieve no foaming, no peeling, no crack, no pulverization and no obvious color change after 500 hours.
The coating E can resist 50% of sulfuric acid by mass, and can also be used as a lining coating of a chemical-resistant storage tank, so that the application range of the coating is further expanded.
Comparative example 7
The solvent-free epoxy curing agent 2280 of the scientific research gas in the United states has excellent acid resistance, and the coating O prepared according to the formula of the coating does not foam, peel off and have no obvious color change after being soaked in sulfuric acid with the mass fraction of 10% for 48 hours, but slightly foams after being soaked in sulfuric acid with the mass fraction of 50% for 48 hours. In addition, the product cost is very high, 70-80 yuan is needed for each kilogram, the cost of the curing agent prepared by the method is only 20-30 yuan for each kilogram, the cost is greatly reduced, and the industrial popularization and application are facilitated. The final Shore D hardness of the coating O is 70, the final Shore D hardness of the coating is basically over 78, particularly the Shore D hardness of the coating E is 83, and the coating is still greatly improved compared with the coating O. The compressive strength of the coating O is 50MPa, the compressive strength of the coating is basically over 85MPa, and particularly the compressive strength of the coating E is 94.5MPa, and the difference is very large.
As is also clear from a comparison of FIG. 1, the curing agent 2110 prepared in example 5 contained in the left beaker is clear in color and can be used for light-colored epoxy resins; the right beaker was filled with the curing agent of comparative example 7, which was extremely dark in color and could not be used at all for light colored epoxy resins.
Excellent performance based on this application curing agent can be used to anticorrosive terrace coating, from the level and stripe paint terrace coating, chemical resistance can storage tank inside lining coating, mortar and grout, decorative ceramic tile glue, the gluing stone that permeates water, colored road surface.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (7)
1. The preparation method of the acid-resistant solvent-free epoxy resin curing agent is characterized by comprising the following steps:
s1, adding 25-50 parts by weight of benzyl alcohol into 30-60 parts by weight of 4, 4-diaminodicyclohexyl methane for more than 2 times, and stirring and dispersing uniformly to form transparent liquid; the weight ratio of the 4, 4-diaminodicyclohexyl methane to the benzyl alcohol is 1.2-1.3;
s2, adding 0-5 parts of accelerator into the product dispersed in the step S1, and stirring and dispersing uniformly to form transparent liquid;
s3 adding 0.1-0.6 weight part of gamma-glycidoxypropyltrimethoxysilane into the dispersed product of S2, and stirring to disperse uniformly to form transparent liquid.
2. The method for preparing the acid-resistant solventless epoxy resin curing agent according to claim 1, wherein: in step S2, the accelerator is DMP-30.
3. The method for preparing the acid-resistant solventless epoxy resin curing agent according to claim 1, wherein: in the steps S1, S2 and S3, the stirring speed is 400-600 rpm, and the stirring time is 20-50 minutes.
4. The method for preparing an acid-resistant solvent-free epoxy resin hardener as claimed in any one of claims 1 to 3, wherein: in the dispersed product of the step S1, 5-10 parts by weight of alkylphenol is added before the gamma-glycidoxypropyltrimethoxysilane is added in the step S3, and the mixture is stirred and dispersed uniformly to form transparent liquid.
5. The method for preparing the acid-resistant solventless epoxy resin curing agent according to claim 4, wherein: in the step of adding the alkylphenol to the dispersed product in the step S1, the stirring speed is 400-600 r/min, and the stirring time is 20-50 min.
6. The method for preparing the acid-resistant solventless epoxy resin curing agent according to claim 1, wherein: the weight ratio of the 4, 4-diaminodicyclohexylmethane to the gamma-glycidoxypropyltrimethoxysilane is 100-300.
7. Use of the curing agent obtained by the method for producing an acid-resistant solventless epoxy resin curing agent according to any one of claims 1 to 6, characterized in that: the coating is used for anticorrosive floor coatings, self-leveling or mottle floor coatings, chemical resistance storage tank lining coatings, mortar, grout, decorative tile glue, permeable adhesive stone and colored pavements.
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| CN102321423A (en) * | 2011-10-27 | 2012-01-18 | 中国海洋石油总公司 | Heavy-duty anti-corrosion phenolic epoxy coating |
| CN113045955A (en) * | 2021-03-25 | 2021-06-29 | 河北涂铠新材料科技有限公司 | Low-surface-treatment heavy-duty anticorrosive paint and preparation method and application thereof |
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| WO2006016625A1 (en) * | 2004-08-10 | 2006-02-16 | Chugoku Marine Paints, Ltd. | High-solid anticorrosive coating composition, high-solid rapidly-curable anticorrosive coating composition, method of coating ship or the like, high-solid anticorrosive film and rapidly cured high-solid anticorrosive film obtained, and coated ship and underwater structure coated with these coating films |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102321423A (en) * | 2011-10-27 | 2012-01-18 | 中国海洋石油总公司 | Heavy-duty anti-corrosion phenolic epoxy coating |
| CN113045955A (en) * | 2021-03-25 | 2021-06-29 | 河北涂铠新材料科技有限公司 | Low-surface-treatment heavy-duty anticorrosive paint and preparation method and application thereof |
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