CN116694188A - High-performance aqueous epoxy resin emulsion and preparation method and application thereof - Google Patents
High-performance aqueous epoxy resin emulsion and preparation method and application thereof Download PDFInfo
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- CN116694188A CN116694188A CN202310790734.3A CN202310790734A CN116694188A CN 116694188 A CN116694188 A CN 116694188A CN 202310790734 A CN202310790734 A CN 202310790734A CN 116694188 A CN116694188 A CN 116694188A
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 83
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 83
- 239000000839 emulsion Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000004945 emulsification Methods 0.000 title description 3
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 24
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004698 Polyethylene Substances 0.000 claims abstract description 15
- 229920000768 polyamine Polymers 0.000 claims abstract description 15
- -1 polyethylene Polymers 0.000 claims abstract description 15
- 229920000573 polyethylene Polymers 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 28
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 230000001105 regulatory effect Effects 0.000 claims description 14
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 9
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003973 paint Substances 0.000 abstract description 13
- 239000000049 pigment Substances 0.000 abstract description 10
- 238000002156 mixing Methods 0.000 abstract description 9
- 150000003839 salts Chemical class 0.000 abstract description 7
- 238000000227 grinding Methods 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 239000011521 glass Substances 0.000 description 12
- 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 8
- 239000000047 product Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- 238000013461 design Methods 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 229940057838 polyethylene glycol 4000 Drugs 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- 230000001804 emulsifying effect Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000004353 Polyethylene glycol 8000 Substances 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 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 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229940085678 polyethylene glycol 8000 Drugs 0.000 description 1
- 235000019446 polyethylene glycol 8000 Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- HPOKESDSMZRZLC-UHFFFAOYSA-N propan-2-one;hydrochloride Chemical compound Cl.CC(C)=O HPOKESDSMZRZLC-UHFFFAOYSA-N 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
Classifications
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
- C08G65/33306—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
-
- 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
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dispersion Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a high-performance water-based epoxy resin emulsion, a preparation method and application thereof, and the high-performance water-based epoxy resin emulsion comprises the following raw materials in parts by weight: 40-60 parts of epoxy resin, 2-2.5 parts of emulsifier, 0.5-4 parts of solvent and 40-60 parts of water; the emulsifier comprises the following raw materials in parts by weight: 100-600 parts of alkanol, 20-250 parts of glycidyl ether epoxy resin, 5-30 parts of alcohol ether and 0.1-3 parts of catalyst; the emulsifier also comprises polyethylene polyamine, the weight ratio of the polyethylene polyamine to the glycidyl ether epoxy resin is 1-2:100, the aqueous epoxy resin emulsion prepared by the invention has excellent mechanical stability and storage stability, compared with the prior art, the aqueous epoxy resin emulsion can be ground together with pigment without demulsification, the problem of inaccurate color mixing caused by grinding together of active pigment and curing agent is avoided, and meanwhile, the formed paint film also has excellent water resistance and salt fog resistance.
Description
Technical Field
The invention belongs to the field of epoxy resin coatings, and particularly relates to a high-performance aqueous epoxy resin emulsion, a preparation method and application thereof.
Background
The benzene ring group contained in the chemical structure of the epoxy resin emulsion has good chemical resistance, corrosion resistance and mechanical property, and the hydroxyl group contained in the epoxy resin emulsion has excellent adhesive force to a metal substrate, can form a compact three-dimensional network polymer film after being matched with a curing agent for reaction, and is widely applied to the fields of anti-corrosion coating, adhesives, industrial floors and the like.
The traditional solvent-based two-component epoxy paint contains a large amount of volatile organic matters, and has great environmental pollution and human body injury, so that the existing two-component epoxy paint is mostly water-based epoxy resin, has the advantages of low VOC and small environmental pollution, and gradually becomes the future development trend of environment-friendly industrial anticorrosive paint.
The two-component epoxy resin paint mostly comprises two components of aqueous epoxy resin emulsion and curing agent, when in use, the two components are firstly mixed and then coated, a paint film is formed after curing, the two-component design of the epoxy resin emulsion and the curing agent mostly needs pigment grinding and color mixing together before mixing, the existing grinding and color mixing operation is generally carried out by mixing with the curing agent, the curing agent can sometimes influence the color appearance of pigment (especially active pigment), but the grinding and color mixing operation cannot be transferred to mixing with the epoxy resin emulsion, because the conventional epoxy resin emulsion can cause demulsification if being ground together with the pigment, the epoxy resin emulsion system is damaged, and the performance of the cured paint film is further influenced.
In summary, the invention aims to provide a high-performance aqueous epoxy resin emulsion which can be ground and tinted together with pigment, does not generate demulsification and further influences the paint film performance, and meanwhile, has excellent water resistance and salt spray resistance.
Disclosure of Invention
Aiming at the problems in the related art, the invention provides a structural design of an emulsifier, and designs a specific emulsion formula and a specific emulsion ratio for the emulsifier, namely a high-performance aqueous epoxy resin emulsion.
The technical scheme of the invention is realized as follows:
a high-performance aqueous epoxy resin emulsion comprises the following raw materials in parts by weight: 40-60 parts of epoxy resin, 2-2.5 parts of emulsifier, 0.5-4 parts of solvent and 40-60 parts of water;
the emulsifier comprises the following raw materials in parts by weight: 100-600 parts of alkanol, 20-250 parts of glycidyl ether epoxy resin, 5-30 parts of alcohol ether and 0.1-3 parts of catalyst;
the emulsifier also comprises polyethylene polyamine, and the weight ratio of the polyethylene polyamine to the glycidyl ether epoxy resin is 1-2:100.
The alkanol is exemplified by polyethylene glycol, and the synthesis reaction is shown in the following figure:
the above-mentioned amphiphilic emulsifier small molecules have a basic emulsifying ability, but in the present invention, in order to obtain a high-potency emulsifier with a low addition amount, a specific design of a certain proportion of polyethylene polyamine is required to graft a plurality of emulsifier small molecules, thereby chain-extending to form a larger molecular emulsifier.
The polyethylene polyamine is exemplified by diethylenetriamine, and the further synthesis reaction is shown in the following figure:
compared with the prior art, the aqueous epoxy resin emulsion prepared by the invention has excellent mechanical stability and storage stability, can be ground together with pigment without demulsification, avoids the problem of inaccurate color mixing caused by grinding together of active pigment and curing agent, and simultaneously forms a paint film with excellent water resistance and salt spray resistance.
Preferably, the average particle size of the aqueous epoxy resin emulsion is 250-450 nm, the D100 particle size is less than 800nm, and the particle size is smaller, so that the agglomeration among emulsion molecules is not easy to occur, and the aqueous epoxy resin emulsion prepared by the invention is not easy to delaminate and a paint film which is cured later has good water resistance and salt spray resistance.
The emulsifier specially developed by the invention can be suitable for most of epoxy resins such as bisphenol A epoxy resin, bisphenol F epoxy resin, phenolic epoxy resin and the like which are sold in the market, but the inventor is proved that the emulsifier is especially suitable for bisphenol A epoxy resin through experiments, the prepared emulsion can keep an emulsion system with small particle size under high-speed shearing of 2000-3000rpm, and the emulsion system and pigment are ground together without coarse thickening or demulsification phenomenon, and preferably, the epoxy resin is bisphenol A epoxy resin; further preferably, the bisphenol a epoxy resin is one or more of E51, E44, E20 and E06 mixed in any proportion.
Preferably, the solvent is one or two of propylene glycol methyl ether and ethylene glycol monobutyl ether which are mixed in any proportion.
Preferably, the polyethylene polyamine is one or more of diethylenetriamine, triethylenetetramine and tetraethylenepentamine which are mixed according to any proportion. The polyethylene polyamine has the function of connecting a plurality of small molecules of the emulsifier to form a larger molecule emulsifier, and meanwhile, the active hydrogen is required to be completely reacted, if the number of functional groups of the polyethylene polyamine is too large, the small molecules of the emulsifier grafted firstly form steric hindrance, so that part of the active hydrogen is difficult to carry out grafting reaction, and the stable epoxy resin emulsion is not beneficial to subsequent preparation.
In addition, compared with other grafts, the polyethylene polyamine selected by the invention has proper and complete interval of functional groups, can effectively complete the reaction and avoid excessive crosslinking, does not need excessive reaction temperature during the design of the preparation process, and can save the production cost and improve the production efficiency to a certain extent.
Preferably, the alkanol is one or two of polyethylene glycol and polypropylene glycol which are mixed according to any proportion. If the methyl in the repeated units is too much, the selected alkanol has adverse effect on the hydrophilicity of the emulsifier, and if the hydroxyl in the repeated units is too much, the hydrophilicity is too strong, so that the emulsifying capacity and the performance of the paint film after curing are affected; in addition, the polyethylene glycol and the polypropylene glycol are low in price, and are beneficial to control of production cost.
Preferably, the molecular weight of the polyethylene glycol is 1000-10000, and the molecular weight of the polypropylene glycol is 1000-5000. More preferably, the polyethylene glycol has a molecular weight of 2000-6000 and the polypropylene glycol has a molecular weight of 2000-3000. The use of alkanol with too large molecular weight can lead to too strong hydrophilicity of the emulsifier prepared by the invention, destroy the hydrophilic and hydrophobic equilibrium state, influence the emulsifying capacity of the invention, and too short hydrophilic chain in the emulsified molecule if alkanol with too small molecular weight is used.
The epoxy resin and the glycidyl ether epoxy resin can be solid, semisolid or liquid, and compared with alkanol, the alcohol ether has better dissolving capacity for the glycidyl ether epoxy resin, so that a certain part of alcohol ether is arranged to fully dissolve the glycidyl ether epoxy resin in a reaction system. Preferably, the alcohol ether is one or more of propylene glycol methyl ether and ethylene glycol monobutyl ether, which are mixed according to any proportion, and both have lower boiling point and saturated vapor pressure, so that subsequent removal is facilitated, and even trace residues can volatilize when a paint film is prepared.
Preferably, the catalyst is HBF 4 Aqueous solutions, triphenylphosphine or triphenylphosphine and HBF 4 The aqueous solutions were added sequentially. More preferably, the catalyst is triphenylphosphine and HBF in a weight ratio of 1:0.5-1 4 The aqueous solution is added successively, the HBF 4 The mass concentration of the aqueous solution is 50-55%, the inventor finds that the reaction is difficult to complete by using a single catalyst in the research and development process, and the problem can be better solved by adding two catalysts sequentially.
Preferably, the glycidyl ether epoxy resin is one or more of bisphenol A epoxy resin, bisphenol F epoxy resin and phenolic epoxy resin which are mixed according to any proportion. More preferably, the glycidyl ether epoxy resin is bisphenol A epoxy resin, and the bisphenol A epoxy resin is one or more of E51, E44, E20 and E06 mixed in any proportion.
The preparation method of the high-performance aqueous epoxy resin emulsion comprises the following steps:
(1) Adding the epoxy resin and the solvent with preset weight parts into a reaction stirring device, adjusting the temperature to 75-95 ℃, and then stirring at constant temperature until all the epoxy resin and the solvent are dissolved, namely the mixture is in a transparent state, and the rotating speed is 50-80rpm;
(2) Regulating the temperature to 85-95 ℃, keeping the temperature, adding the emulsifier with preset weight parts, stirring at least for 20 minutes at the rotating speed of 200-500 rpm;
(3) And (3) regulating the rotating speed to 1800-2200rpm, slowly adding water with preset weight parts to form phase inversion, and converting the mixed material into uniform milky white to prepare the high-performance aqueous epoxy resin emulsion.
Preferably, the preparation method of the emulsifier comprises the following steps:
(1) Adding alkanol and alcohol ether with preset weight parts into a stirring reaction device, wherein the alkanol is unstable at high temperature, the alkanol and the alcohol ether are premixed, so that alkanol molecules are heated uniformly in the heating process and can accelerate the melting process, meanwhile, inert gas is introduced to protect the alkanol, the temperature is raised to 90-130 ℃ and kept at a constant temperature for at least 1 hour to ensure complete melting, and in the reaction process, moisture in a system can be taken away by the continuously introduced inert gas flow together, so that the moisture in the system is prevented from influencing subsequent reactions;
(2) Maintaining the temperature, adding a catalyst with preset weight parts, and stirring at 180-220rpm for at least 5 minutes;
(3) Maintaining the temperature, adding the glycidyl ether epoxy resin with preset weight parts, and stirring at 180-220rpm for reaction for at least 5 hours until the conversion rate is more than or equal to 95%;
(4) Removing the alcohol ether;
(5) Setting the temperature to 100 ℃, stirring at 180-220rpm, adding polyethylene polyamine in a dropwise manner, increasing the dropwise speed to 2-3g/min, heating to 120 ℃ after the dropwise addition is finished, and reacting for at least 3 hours until the reaction is finished;
(6) And (3) cooling to be less than or equal to 90 ℃, preparing a finished product prepared in the step (5) and water according to the weight ratio of 1:0.8-1.2, and slowly adding water into the finished product prepared in the step (5) to prepare the emulsifier. If water is added rapidly, the local water quantity is too large, the self-emulsification of the emulsifier is directly promoted, if water is not added, the emulsifier is solid after cooling, the subsequent mixing preparation of the epoxy resin emulsion is inconvenient, and deionized water is preferably adopted.
The preparation process is continuous and simplified, the prepared finished product of the emulsifier contains widely distributed emulsifier molecules, namely, the emulsifiers with different molecular weights do not need to be produced and mixed respectively, meanwhile, specific preparation steps and parameters are designed for the emulsifier, the process is simplified, the corresponding production line design of production equipment is simpler, the production cost of enterprises is saved, and the production efficiency is improved.
Preferably, in the step (2) of preparing the emulsifier, the specific operation of adding the catalyst is as follows: firstly adding a preset weight part of triphenylphosphine, stirring at 100 ℃ for at least 5 minutes, and then adding a preset weight part of HBF with the mass concentration of 50 percent 4 The aqueous solution was stirred for at least 5 minutes.
Preferably, in the step (4) of preparing the emulsifier, the temperature is set to 120 to 150 ℃, and distillation is performed under reduced pressure to remove alcohol ether.
The application of the high-performance aqueous epoxy resin emulsion comprises the following steps of: 0.1 to 0.3 weight ratio.
Drawings
FIG. 1 is the test results of the water resistance test of example 1;
fig. 2 shows the test results of the salt spray resistance test of example 1.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The raw materials used in this example are all commercially available conventional raw materials, without any particular explanation.
Example 1
A. Preparation of the emulsifier
(1) 400g of polyethylene glycol 4000 and 20g of propylene glycol methyl ether are added into a 1L glass reaction kettle, inert gas is introduced, the temperature is raised to 100 ℃ and kept at the constant temperature for 1 hour, and the mixture is fully dissolved;
(2) Maintaining the temperature, 2g of HBF 4 The aqueous solution (50 wt%), was stirred at 200rpm for 5 minutes;
(3) Maintaining the temperature, adding 52g of glycidyl ether epoxy resin (bisphenol A type E51), and stirring at 200rpm for reaction for 5 hours;
(4) Heating to 120 ℃, and distilling under reduced pressure to remove propylene glycol methyl ether;
(5) Setting the temperature to 100 ℃, stirring at 200rpm, adding 1.0g of diethylenetriamine at a dropping speed of 2g/min, heating to 120 ℃ after the dropping is finished, and reacting for 3 hours;
(6) And (3) cooling to 90 ℃, and slowly adding 450g of deionized water into the finished product prepared in the step (5) to prepare the emulsifier.
B. Preparation of high-performance aqueous epoxy resin emulsion
(1) 450g of E20 solid epoxy resin and 30g of propylene glycol methyl ether are added into a 1L glass reaction kettle, the temperature is regulated to 95 ℃, and then the mixture is stirred at constant temperature until all the mixture is dissolved, namely the mixture is in a transparent state, and the rotating speed is 60rpm;
(2) Then adjusting the temperature to 85 ℃, keeping the temperature constant, adding 20g of emulsifier, stirring for 20 minutes at the rotating speed of 300 rpm;
(3) And (3) regulating the rotating speed to 2000rpm, slowly adding 400g of deionized water to form phase inversion, and converting the mixed material into uniform milky white to prepare the high-performance aqueous epoxy resin emulsion.
Example 2
A. Preparation of the emulsifier
(1) 400g of polyethylene glycol 8000 and 25g of ethylene glycol monobutyl ether are added into a 1L glass reaction kettle, inert gas is introduced, the temperature is raised to 100 ℃ and kept at the constant temperature for 1 hour, and the mixture is fully dissolved;
(2) Maintaining the temperature, adding 1g triphenylphosphine, stirring for 5 min, and adding 0.8g HBF 4 The aqueous solution (50 wt%), was stirred at 200rpm for 5 minutes;
(3) Maintaining the temperature, adding 28g of glycidyl ether epoxy resin (bisphenol A type E51), and stirring at 200rpm for reaction for 5 hours;
(4) Heating to 145 ℃, and distilling under reduced pressure to remove ethylene glycol monobutyl ether;
(5) Setting the temperature to 100 ℃, stirring at 200rpm, adding 0.5g of diethylenetriamine at a dropping speed of 2.5g/min, heating to 120 ℃ after the dropping is finished, and reacting for 3 hours;
(6) And (3) cooling to 90 ℃, and slowly adding 420g of deionized water into the finished product prepared in the step (5) to prepare the emulsifier.
B. Preparation of high-performance aqueous epoxy resin emulsion
(1) 450g of E44 liquid epoxy resin and 10g of propylene glycol methyl ether are added into a 1L glass reaction kettle, the temperature is regulated to 75 ℃, and then the mixture is stirred at constant temperature until all the mixture is dissolved, namely the mixture is in a transparent state, and the rotating speed is 60rpm;
(2) Then adjusting the temperature to 85 ℃, keeping the temperature constant, adding 20g of emulsifier, stirring for 20 minutes at the rotating speed of 300 rpm;
(3) And (3) regulating the rotating speed to 2000rpm, slowly adding 400g of deionized water to form phase inversion, and converting the mixed material into uniform milky white to prepare the high-performance aqueous epoxy resin emulsion.
Example 3
A. Preparation of the emulsifier
(1) 400g of polyethylene glycol 2000, 100g of polypropylene glycol 2000 and 25g of ethylene glycol monobutyl ether are added into a 1L glass reaction kettle, inert gas is introduced, the temperature is raised to 100 ℃ and the temperature is kept constant for 1 hour, and the mixture is fully dissolved;
(2) Maintaining the temperature, adding 1g triphenylphosphine, stirring for 5 min, and adding 0.8g HBF 4 Aqueous solution (50 wt.%) Stirring at 200rpm for 5 minutes;
(3) Maintaining the temperature, adding 211g of glycidyl ether epoxy resin (bisphenol A type E44), and stirring at 200rpm for reaction for 5 hours;
(4) Heating to 120 ℃, and distilling under reduced pressure to remove ethylene glycol monobutyl ether;
(5) Setting the temperature to 100 ℃, stirring at 200rpm, adding 3.7g of diethylenetriamine at a dropping speed of 3g/min, heating to 120 ℃ after the dropping is finished, and reacting for 3 hours;
(6) And (3) cooling to 90 ℃, and slowly adding 720g of deionized water into the finished product prepared in the step (5) to prepare the emulsifier.
B. Preparation of high-performance aqueous epoxy resin emulsion
(1) 450g of E20 liquid epoxy resin and 10g of propylene glycol methyl ether are added into a 1L glass reaction kettle, the temperature is regulated to 75 ℃, and then the mixture is stirred at constant temperature until all the mixture is dissolved, namely the mixture is in a transparent state, and the rotating speed is 60rpm;
(2) Then adjusting the temperature to 85 ℃, keeping the temperature constant, adding 20g of emulsifier, stirring for 20 minutes at the rotating speed of 300 rpm;
(3) And (3) regulating the rotating speed to 2000rpm, slowly adding 400g of deionized water to form phase inversion, and converting the mixed material into uniform milky white to prepare the high-performance aqueous epoxy resin emulsion.
Comparative example 1
A. Preparation of the emulsifier
(1) 400g of polyethylene glycol 4000 and 20g of propylene glycol methyl ether are added into a 1L glass reaction kettle, inert gas is introduced, the temperature is raised to 100 ℃ and kept at the constant temperature for 1 hour, and the mixture is fully dissolved;
(2) Maintaining the temperature, 2g of HBF 4 The aqueous solution (50 wt%), was stirred at 200rpm for 5 minutes;
(3) 52g of bisphenol A epoxy resin (E51) was added while maintaining the temperature, and the reaction was stirred at 200rpm for 5 hours;
(4) Heating to 120deg.C, and distilling under reduced pressure to remove propylene glycol methyl ether to obtain the final product.
B. Preparation of aqueous epoxy resin emulsion
(1) 450g of E20 solid epoxy resin and 30g of propylene glycol methyl ether are added into a 1L glass reaction kettle, the temperature is regulated to 95 ℃, and then the mixture is stirred at constant temperature until all the mixture is dissolved, namely the mixture is in a transparent state, and the rotating speed is 60rpm;
(2) Then adjusting the temperature to 85 ℃, keeping the temperature constant, adding 20g of emulsifier, stirring for 20 minutes at the rotating speed of 300 rpm;
(3) The rotation speed was adjusted to 2000rpm, 400g of deionized water was slowly added to form phase inversion, and the mixture was converted to a uniform milky white color, thus preparing the comparative example.
Comparative example 2
A. Preparation of the emulsifier
(1) 400g of polyethylene glycol 4000 and 40g of propylene glycol methyl ether are added into a 1L glass reaction kettle, inert gas is introduced, the temperature is raised to 100 ℃ and kept at the constant temperature for 1 hour, and the mixture is fully dissolved;
(2) Maintaining the temperature, 2g of HBF 4 The aqueous solution (50 wt%), was stirred at 200rpm for 5 minutes;
(3) 52g of bisphenol A epoxy resin (E51) was added while maintaining the temperature, and the reaction was stirred at 200rpm for 5 hours;
(4) Heating to 120 ℃, and distilling under reduced pressure to remove propylene glycol methyl ether;
(5) Setting the temperature to 100 ℃, stirring at 200rpm, adding 1.3g of diethylenetriamine at a dropping speed of 2g/min, heating to 120 ℃ after the dropping is finished, and reacting for 3 hours;
(6) And (3) cooling to 90 ℃, and slowly adding 450g of deionized water into the finished product prepared in the step (5) to prepare the emulsifier.
B. Preparation of aqueous epoxy resin emulsion
(1) 450g of E20 solid epoxy resin and 30g of propylene glycol methyl ether are added into a 1L glass reaction kettle, the temperature is regulated to 95 ℃, and then the mixture is stirred at constant temperature until all the mixture is dissolved, namely the mixture is in a transparent state, and the rotating speed is 60rpm;
(2) Then adjusting the temperature to 85 ℃, keeping the temperature constant, adding 20g of emulsifier, stirring for 20 minutes at the rotating speed of 300 rpm;
(3) The rotation speed was adjusted to 2000rpm, 400g of deionized water was slowly added to form phase inversion, and the mixture was converted to a uniform milky white color, thus preparing the comparative example.
Comparative example 3
A. Preparation of the emulsifier
(1) 400g of polyethylene glycol 4000 and 20g of propylene glycol methyl ether are added into a 1L glass reaction kettle, inert gas is introduced, the temperature is raised to 100 ℃ and kept at the constant temperature for 1 hour, and the mixture is fully dissolved;
(2) Maintaining the temperature, 2g of HBF 4 The aqueous solution (50 wt%), was stirred at 200rpm for 5 minutes;
(3) Maintaining the temperature, adding 52g of glycidyl ether epoxy resin (bisphenol A type E51), and stirring at 200rpm for reaction for 5 hours;
(4) Heating to 120 ℃, and distilling under reduced pressure to remove propylene glycol methyl ether;
(5) Setting the temperature to 100 ℃, stirring at 200rpm, adding 1.0g of diethylenetriamine at a dropping speed of 2g/min, heating to 120 ℃ after the dropping is finished, and reacting for 3 hours;
(6) And (3) cooling to 90 ℃, and slowly adding 450g of deionized water into the finished product prepared in the step (5) to prepare the emulsifier.
B. Preparation of high-performance aqueous epoxy resin emulsion
(1) 450g of E20 solid epoxy resin and 30g of propylene glycol methyl ether are added into a 1L glass reaction kettle, the temperature is regulated to 95 ℃, and then the mixture is stirred at constant temperature until all the mixture is dissolved, namely the mixture is in a transparent state, and the rotating speed is 60rpm;
(2) Then adjusting the temperature to 100 ℃, keeping the temperature constant, adding 20g of emulsifier, stirring for 20 minutes at 500 rpm;
(3) And (3) regulating the rotating speed to 2000rpm, slowly adding 400g of deionized water to form phase inversion, and converting the mixed material into uniform milky white to prepare the high-performance aqueous epoxy resin emulsion.
1. Determination of epoxy equivalent
The epoxy equivalent refers to the mass of the epoxy resin corresponding to 1mol of epoxy group, and the unit is g/mol, and the invention adopts an acetone hydrochloride method to respectively measure the epoxy equivalent of the step (3) and the step (5) of the step (A) for preparing the emulsifier in the examples 1-3 and the comparative examples 1-2.
2. Determination of particle size distribution
Particle size measurements were performed on examples 1-3 and comparative examples 1-3 by a laser particle sizer.
| Test item | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Average particle diameter/nm | 256 | 612 | 353 | 926 | 622 | 736 |
| D100/nm | 687 | 1128 | 810 | 2054 | 1189 | 1073 |
3. Testing the water solubility of the emulsifier and the storage stability, dilution stability and mechanical stability of the emulsion
(1) The emulsions prepared in examples 1-3 and comparative examples 1-3 were packaged in equal amounts and left to stand at a temperature of 50℃for 2 months.
(2) Equal amounts of the emulsions prepared in examples 1 to 3 and comparative examples 1 to 3 were diluted 2 times and stored at room temperature for 2 months.
(3) The emulsions prepared in examples 1-3 and comparative examples 1-3 were subjected to high shear at 2500rpm for 3 hours in equal amounts.
(4) Equal amounts of the emulsions prepared in examples 1-3 and comparative examples 1-3 were ground 6 times with the powder in a 2500rpm horizontal sand mill.
The emulsions prepared in examples 1-3 and comparative examples 1-3 were mixed with an amine curing agent in an amount of 1: the curing agent is used in a mixed mode according to the weight ratio of 0.2, the basic parameter of the curing agent is that the solid content is 40.5 percent, the viscosity is 35000cP, the equivalent weight is 350, the curing agent is smeared on a tinplate substrate, and after the curing agent is cured into a paint film, the film thickness is 50 mu m, and the following test is carried out.
4. Water and salt spray resistance test
(1) Soaking in constant temperature water bath (40 ℃) for 1 month.
(2) Neutral salt fog is 600 hours.
Variations and modifications to the above would be obvious to persons skilled in the art to which the invention pertains from the foregoing description and teachings. Therefore, the invention is not limited to the specific embodiments disclosed and described above, but some modifications and changes of the invention should be also included in the scope of the claims of the invention. In addition, although specific terms are used in the present specification, these terms are for convenience of description only and do not limit the present invention in any way.
Claims (10)
1. The high-performance aqueous epoxy resin emulsion is characterized by comprising the following raw materials in parts by weight: 40-60 parts of epoxy resin, 2-2.5 parts of emulsifier, 0.5-4 parts of solvent and 40-60 parts of water;
the emulsifier comprises the following raw materials in parts by weight: 100-600 parts of alkanol, 20-250 parts of glycidyl ether epoxy resin, 5-30 parts of alcohol ether and 0.1-3 parts of catalyst;
the emulsifier also comprises polyethylene polyamine, and the weight ratio of the polyethylene polyamine to the glycidyl ether epoxy resin is 1-2:100.
2. The aqueous epoxy resin emulsion of claim 1, wherein the aqueous epoxy resin emulsion has an average particle size of 250nm to 450nm and a d100 particle size of <800nm.
3. The aqueous epoxy resin emulsion of claim 1, wherein the epoxy resin is a bisphenol a epoxy resin.
4. The aqueous epoxy resin emulsion of claim 3, wherein the bisphenol a epoxy resin is one or more of E51, E44, E20, E06 mixed in any proportion.
5. The aqueous epoxy resin emulsion of claim 1, wherein the polyethylene polyamine is one or more of diethylenetriamine, triethylenetetramine and tetraethylenepentamine, and the two or more are mixed according to any proportion.
6. The aqueous epoxy resin emulsion of claim 1, wherein the catalyst is HBF 4 Aqueous solutions, triphenylphosphine or triphenylphosphine and HBF 4 The aqueous solutions were added sequentially.
7. The preparation method of the high-performance aqueous epoxy resin emulsion is characterized by comprising the following steps of:
(1) Adding the epoxy resin and the solvent with preset weight parts into a reaction stirring device, adjusting the temperature to 75-95 ℃, and then stirring at constant temperature until all the epoxy resin and the solvent are dissolved, namely the mixture is in a transparent state, and the rotating speed is 50-80rpm;
(2) Regulating the temperature to 85-95 ℃, keeping the temperature, adding the emulsifier with preset weight parts, stirring at least for 20 minutes at the rotating speed of 200-500 rpm;
(3) And (3) regulating the rotating speed to 1800-2200rpm, slowly adding water with preset weight parts to form phase inversion, and converting the mixed material into uniform milky white to prepare the high-performance aqueous epoxy resin emulsion.
8. The preparation method of claim 7, wherein the preparation method of the emulsifier comprises the following steps:
(1) Adding alkanol and alcohol ether with preset weight parts into a stirring reaction device, introducing inert gas, heating to 90-130 ℃ and keeping the temperature for at least 1 hour;
(2) Maintaining the temperature, adding a catalyst with preset weight parts, and stirring at 180-220rpm for at least 5 minutes;
(3) Maintaining the temperature, adding the glycidyl ether epoxy resin with preset weight parts, and stirring at 180-220rpm for reaction for at least 5 hours;
(4) Removing the alcohol ether;
(5) Setting the temperature to 100 ℃, stirring at 180-220rpm, adding polyethylene polyamine in a dropwise manner, increasing the dropwise speed to 2-3g/min, heating to 120 ℃ after the dropwise addition is finished, and reacting for at least 3 hours;
(6) And (3) cooling to be less than or equal to 90 ℃, preparing a finished product prepared in the step (5) and water according to the weight ratio of 1:0.8-1.2, and slowly adding water into the finished product prepared in the step (5) to prepare the emulsifier.
9. The method according to claim 8, wherein in the step (2) of preparing the emulsifier, the specific operation of adding the catalyst is: firstly adding triphenylphosphine with preset weight parts, stirring at 100 ℃ for at least 5 minutes, and then adding the triphenylphosphine with preset weight partsParts by weight of HBF 4 The aqueous solution was stirred for at least 5 minutes.
10. Use of a high performance aqueous epoxy resin emulsion according to any one of claims 1 to 6 in combination with an amine curing agent in a weight ratio of 1:0.1-0.3.
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