CN117701102A - Composite flame-retardant waterborne epoxy resin, preparation method thereof and coating - Google Patents
Composite flame-retardant waterborne epoxy resin, preparation method thereof and coating Download PDFInfo
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- CN117701102A CN117701102A CN202311622937.8A CN202311622937A CN117701102A CN 117701102 A CN117701102 A CN 117701102A CN 202311622937 A CN202311622937 A CN 202311622937A CN 117701102 A CN117701102 A CN 117701102A
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- retardant
- phosphorus
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 169
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 169
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000003063 flame retardant Substances 0.000 title claims abstract description 85
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000011248 coating agent Substances 0.000 title claims description 12
- 238000000576 coating method Methods 0.000 title claims description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 49
- 239000011574 phosphorus Substances 0.000 claims abstract description 49
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 47
- 150000002367 halogens Chemical class 0.000 claims abstract description 47
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 38
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- IXAZNYYEGLSHOS-UHFFFAOYSA-N 2-aminoethanol;phosphoric acid Chemical compound NCCO.OP(O)(O)=O IXAZNYYEGLSHOS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000004945 emulsification Methods 0.000 claims abstract description 19
- 238000010992 reflux Methods 0.000 claims abstract description 19
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 17
- 229960000583 acetic acid Drugs 0.000 claims abstract description 16
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 16
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 15
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 12
- GJOWSEBTWQNKPC-UHFFFAOYSA-N 3-methyloxiran-2-ol Chemical compound CC1OC1O GJOWSEBTWQNKPC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 24
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 15
- 238000009775 high-speed stirring Methods 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 9
- JRAFOWMFDBBVPB-UHFFFAOYSA-N 5,6,7,7a-tetrabromo-3ah-2-benzofuran-1,3-dione Chemical compound BrC1=C(Br)C(Br)=CC2C(=O)OC(=O)C21Br JRAFOWMFDBBVPB-UHFFFAOYSA-N 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 3
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 claims description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 3
- FLBJFXNAEMSXGL-UHFFFAOYSA-N het anhydride Chemical compound O=C1OC(=O)C2C1C1(Cl)C(Cl)=C(Cl)C2(Cl)C1(Cl)Cl FLBJFXNAEMSXGL-UHFFFAOYSA-N 0.000 claims description 3
- 239000004843 novolac epoxy resin Substances 0.000 claims description 3
- AUHHYELHRWCWEZ-UHFFFAOYSA-N tetrachlorophthalic anhydride Chemical compound ClC1=C(Cl)C(Cl)=C2C(=O)OC(=O)C2=C1Cl AUHHYELHRWCWEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003973 paint Substances 0.000 abstract description 18
- 238000003860 storage Methods 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 12
- 239000011159 matrix material Substances 0.000 abstract description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 20
- 229910052801 chlorine Inorganic materials 0.000 description 20
- 239000000460 chlorine Substances 0.000 description 20
- 239000000839 emulsion Substances 0.000 description 20
- 239000004593 Epoxy Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 239000002245 particle Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- VOOLKNUJNPZAHE-UHFFFAOYSA-N formaldehyde;2-methylphenol Chemical compound O=C.CC1=CC=CC=C1O VOOLKNUJNPZAHE-UHFFFAOYSA-N 0.000 description 7
- 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 7
- 239000006185 dispersion Substances 0.000 description 6
- 239000005944 Chlorpyrifos Substances 0.000 description 5
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 5
- -1 chlorpyrifos anhydride Chemical class 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
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- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229920006334 epoxy coating Polymers 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
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- 230000002195 synergetic effect Effects 0.000 description 2
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- VPBZZPOGZPKYKX-UHFFFAOYSA-N 1,2-diethoxypropane Chemical compound CCOCC(C)OCC VPBZZPOGZPKYKX-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
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Landscapes
- Epoxy Resins (AREA)
Abstract
The invention relates to the technical field of water-based paint, in particular to a composite flame-retardant water-based epoxy resin, a preparation method thereof and paint. The preparation method comprises the following steps: (a) Heating and reacting halogen-containing anhydride with epoxypropanol to obtain an intermediate, and then heating and reacting with epoxy resin A to obtain halogen-containing epoxy resin; (b) Reflux reacting epoxy resin B, polyethylene glycol diglycidyl ether and monoethanolamine phosphate in a solvent, cooling, and adding glacial acetic acid for reaction to obtain a phosphorus-containing emulsifier; (c) Mixing halogen-containing epoxy resin, a phosphorus-containing emulsifier and water for phase inversion emulsification to obtain composite flame-retardant aqueous epoxy resin; the mass ratio of the epoxy resin A to the intermediate is (40-120) to 1. The invention can greatly reduce the consumption of halogen type flame-retardant raw materials by preparing the phosphorus-containing emulsifier, and can improve the compatibility of the matrix and the mechanical property and storage stability of the matrix while greatly reducing the production cost.
Description
Technical Field
The invention relates to the technical field of water-based paint, in particular to a composite flame-retardant water-based epoxy resin, a preparation method thereof and paint.
Background
The waterborne epoxy coating has excellent self-performance, excellent corrosion resistance and adhesion, and particularly excellent performance in the primer of an industrial coating system. It is suitable for almost all substrate surfaces and is an indispensable important paint variety. But they are extremely flammable, emit a lot of heat when burned and release toxic fumes, which are potentially dangerous to the life and property safety of people. The fire hazard of the water-based epoxy paint limits the application of the water-based epoxy paint in the field with high flame retardant requirements, in particular to the industries of aerospace, rail transit, electric and electronic and the like. Therefore, the development of the flame-retardant epoxy resin has important significance. And with the development of new energy automobile industry, new energy automobile motor epoxy paint meets the opportunity. The stability and reliability of the flame-retardant system are important guarantees for safe operation and use of the motor. The driving motor of the new energy automobile is usually frequently started, changed in speed and changed in torque in the running process, so that the driving motor has high working temperature and strong mechanical vibration, and the coating for the new energy automobile has higher requirements on the performance of the coating for the motor of the new energy automobile, and has higher mechanical strength, heat resistance and heat conductivity.
The application proportion of the novel phosphorus-containing flame retardant developed by DOPO and the derivatives thereof in the flame retardant field is obviously improved in recent years, however, the novel phosphorus-containing flame retardant has the remarkable characteristics of low toxicity, low smoke, environmental friendliness and the like, but also has the defects of low phosphorus content, high water absorbability, high cost and the like, and greatly limits the application range.
In practical application, in order to achieve a good flame retardant effect, more flame retardant raw materials need to be introduced, and the defects of poor compatibility with a resin system can occur while the production cost is increased. And after the emulsion is prepared by the reverse rotation method, the defects of poor fineness and poor storage property and mechanical property of the emulsion can be overcome, and the requirements of industrial production can not be met. Therefore, how to stably add the flame-retardant raw material into the epoxy resin and meet the requirement of industrial production is a difficult problem to be solved in the field.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a preparation method of a composite flame-retardant waterborne epoxy resin, which aims to solve the problems of insufficient flame retardance, insufficient stability and the like of the flame-retardant waterborne epoxy resin in the prior art.
Another object of the present invention is to provide a composite flame retardant waterborne epoxy resin.
It is yet another object of the present invention to provide a coating comprising a composite flame retardant waterborne epoxy.
In order to achieve the above object of the present invention, the present invention provides a method for preparing a composite flame retardant waterborne epoxy resin, comprising the steps of:
(a) Heating and reacting halogen-containing anhydride with epoxypropanol to obtain an intermediate, and then heating and reacting with epoxy resin A to obtain halogen-containing epoxy resin;
(b) Reflux reacting epoxy resin B, polyethylene glycol diglycidyl ether and monoethanolamine phosphate in a solvent, cooling, and adding glacial acetic acid for reaction to obtain a phosphorus-containing emulsifier;
(c) Mixing the halogen-containing epoxy resin, the phosphorus-containing emulsifier and water for phase inversion emulsification to obtain the composite flame-retardant waterborne epoxy resin;
the mass ratio of the epoxy resin A to the intermediate is (40-120) to 1.
In a specific embodiment of the present invention, in step (a), the molar ratio of the halogen-containing anhydride to the epoxypropanol is 1: (0.8-1.2). Further, in the heating reaction of the halogen-containing anhydride and the epoxypropanol, the heating temperature is 60-80 ℃, and the reaction time is 3-4 hours.
In a specific embodiment of the present invention, in the step (a), the heating reaction with the epoxy resin a is performed at a temperature of 100 to 120 ℃ for 2 to 3 hours.
In a specific embodiment of the present invention, the epoxy resin a comprises bisphenol a type epoxy resin and/or novolac epoxy resin.
In a specific embodiment of the present invention, the halogen-containing anhydride comprises at least one of 1,4,5, 6-tetrabromophthalic anhydride, tetrachlorophthalic anhydride, and chlorendic anhydride.
In a specific embodiment of the present invention, in the step (B), the mass ratio of the epoxy resin B, the polyethylene glycol diglycidyl ether, and the monoethanolamine phosphate is (7 to 8)/(6 to 7)/(2 to 4).
In a specific embodiment of the present invention, in the step (B), the solvent is used in an amount of 15% to 30% of the mass of the epoxy resin B; the dosage of the glacial acetic acid is 0.5 to 1.5 times of the mass of the monoethanolamine phosphate.
In a specific embodiment of the present invention, in the step (b), the temperature of the reflux reaction is 80 to 90 ℃, and the time of the reflux reaction is 3 to 5 hours.
In a specific embodiment of the present invention, the epoxy resin B is a bisphenol a type epoxy resin.
In a specific embodiment of the present invention, the solvent includes at least one of propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol monobutyl ether, methyl isobutyl ketone, and ethylene glycol butyl ether.
In a specific embodiment of the present invention, in the step (c), the mass ratio of the halogen-containing epoxy resin, the phosphorus-containing emulsifier and the water is (46 to 49): (3.8 to 5): (45 to 48).
In a specific embodiment of the present invention, the temperature of the system in the phase inversion emulsification is 50 to 70 ℃. Further, in the phase inversion emulsification, high-speed stirring is performed; the stirring speed is 2000-4000 r/min.
The invention further provides the composite flame-retardant waterborne epoxy resin prepared by the preparation method of any one of the composite flame-retardant waterborne epoxy resins.
In yet another aspect, the invention provides a coating comprising any one of the above-described composite flame retardant waterborne epoxy resins.
Compared with the prior art, the invention has the beneficial effects that:
(1) Compared with DOPO type epoxy resin which is used in large quantity at present, the halogen-containing anhydride modified epoxy resin has the advantages of wide sources of flame retardant elements, less raw material consumption, simple preparation process and higher cost performance; meanwhile, no solvent is added in the preparation process of the halogen-containing anhydride modified epoxy resin, so that the cost is saved, and the market demand of low VOC emission is met;
(2) According to the invention, monoethanolamine phosphate is introduced into the emulsifier, and the synergistic flame retardant effect of the monoethanolamine phosphate and halogen flame retardant elements in the halogen-containing epoxy resin is good, so that the flame retardance of the resin is obviously improved;
(3) The invention can greatly reduce the consumption of halogen type flame-retardant raw materials by preparing the phosphorus-containing emulsifier, and can improve the compatibility of the matrix and the mechanical property and storage stability of the matrix while greatly reducing the production cost.
Detailed Description
The technical solution of the present invention will be clearly and completely described in conjunction with the specific embodiments, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative only and should not be construed as limiting the scope of the present invention. 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 specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The invention provides a preparation method of a composite flame-retardant waterborne epoxy resin, which comprises the following steps:
(a) Heating and reacting halogen-containing anhydride with epoxypropanol to obtain an intermediate, and then heating and reacting with epoxy resin A to obtain halogen-containing epoxy resin;
(b) Reflux reacting epoxy resin B, polyethylene glycol diglycidyl ether and monoethanolamine phosphate in a solvent, cooling, and adding glacial acetic acid for reaction to obtain a phosphorus-containing emulsifier;
(c) Mixing halogen-containing epoxy resin, a phosphorus-containing emulsifier and water for phase inversion emulsification to obtain composite flame-retardant aqueous epoxy resin;
the mass ratio of the epoxy resin A to the intermediate is (40-120) to 1.
According to the invention, the monoethanolamine phosphate is introduced into the emulsifier to obtain the phosphorus-containing emulsifier, the phosphorus-containing emulsifier has good synergistic flame retardant effect with halogen in halogen-containing epoxy resin, and the flame retardance of the resin is obviously improved. Meanwhile, due to the introduction of the phosphorus-containing emulsifier, the consumption of halogen-type flame-retardant raw materials can be reduced, the compatibility of a matrix can be obviously improved, the mechanical property and storage stability of the matrix can be improved, and the like.
Meanwhile, in the preparation of the halogen-containing epoxy resin, no solvent is added, so that the cost is saved, and the market demand of low VOC emission is met.
In various embodiments, the mass ratio of the epoxy resin A to the intermediate may be 40:1, 50:1, 60:1, 70:1, 80:1, 90:1, 100:1, 110:1, 120:1 or a range of any two thereof, such as (45-95):1.
Due to the introduction of the phosphorus-containing emulsifier, the halogen-containing epoxy resin can realize excellent flame retardant property by only introducing a small amount of halogen.
In a specific embodiment of the present invention, in step (a), the molar ratio of halogen-containing anhydride to epoxypropanol is 1: (0.8-1.2).
As in the various embodiments, in step (a), the molar ratio of halogen-containing anhydride to epoxypropanol may be in the range of 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, or any two thereof.
In the specific embodiment of the invention, in the heating reaction of halogen-containing anhydride and glycidol, the heating temperature is 60-80 ℃ and the reaction time is 3-4 h.
In the heating reaction of the halogen-containing anhydride with the glycidol, as in the various embodiments, the heating temperature may be 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ or a range of any two thereof; the reaction time can be 3h, 3.5h or 4h, and the specific reaction time can be adjusted according to actual conditions.
In a specific embodiment of the present invention, in the step (a), the epoxy resin A is heated and reacted for 2 to 3 hours at a temperature of 100 to 120 ℃.
As in the different embodiments, in the heating reaction of the intermediate with the epoxy resin a in step (a), the heating temperature may be 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃ or a range of any two thereof; the reaction time can be 2h, 2.5h or 3h, and the specific reaction time can be adjusted according to actual conditions.
In a specific embodiment of the present invention, epoxy resin a comprises bisphenol a type epoxy resin and/or novolac epoxy resin. Further, the epoxy equivalent of the bisphenol A type epoxy resin is 180-350 g/eq; the epoxy equivalent of the phenolic epoxy resin is 170-180 g/eq, and the functionality of the phenolic epoxy resin is 2.5-3.5.
As in the different embodiments, in epoxy resin a, the epoxy equivalent of the bisphenol a type epoxy resin may be 180g/eq, 200g/eq, 220g/eq, 250g/eq, 280g/eq, 300g/eq, 320g/eq, 350g/eq or a range of any two of these; the epoxy equivalent weight of the phenolic epoxy resin may be 170g/eq, 172g/eq, 175g/eq, 178g/eq, 180g/eq or any two of these ranges of composition, the functionality of the phenolic epoxy resin may be 2.5, 3, 3.5, etc.
In a specific embodiment of the present invention, the halogen-containing anhydride comprises at least one of 1,4,5, 6-tetrabromophthalic anhydride, tetrachlorophthalic anhydride, and chlorendic anhydride.
In a specific embodiment of the present invention, in the step (B), the mass ratio of the epoxy resin B, the polyethylene glycol diglycidyl ether, and the monoethanolamine phosphate is (7 to 8): (6 to 7): (2 to 3).
In the different embodiments, in the step (B), the mass ratio of the epoxy resin B, the polyethylene glycol diglycidyl ether and the monoethanolamine phosphate may be 7:6:3, 7.5:6:3, 8:6:3, 7:6:2, 7:6.5:2, 7:7:2, 7:6:2.5 or a range composed of any two of them.
In a specific embodiment of the present invention, in step (B), the amount of solvent is 15 to 30wt% based on the mass of the epoxy resin B; the consumption of the glacial acetic acid is 0.5 to 1.5 times of the mass of the monoethanolamine phosphate.
As in the various embodiments, in step (B), the amount of solvent may be 15wt%, 18wt%, 20wt%, 22wt%, 25wt%, 28wt%, 30wt% or a range consisting of any two thereof, of the mass of epoxy resin B; the glacial acetic acid may be used in an amount ranging from 0.5 times, 0.8 times, 1 time, 1.2 times, 1.5 times, or any two of the mass of the monoethanolamine phosphate.
In a specific embodiment of the present invention, in step (b), the temperature of the reflux reaction is 80 to 90 ℃ and the time of the reflux reaction is 3 to 5 hours.
As in the various embodiments, in step (b), the temperature of the reflux reaction may be 80 ℃, 82 ℃, 85 ℃, 88 ℃, 90 ℃, or a range of any two of these; the time of the reflux reaction may be 3 hours, 4 hours, 5 hours, etc. The temperature of the reflux reaction can be adjusted conventionally according to different solvents and systems.
In the specific embodiment of the invention, in the step (B), the epoxy resin B and the polyethylene glycol diglycidyl ether are stirred and dissolved in a solvent, and then the monoethanolamine phosphate is added for reaction.
In a specific embodiment of the invention, in step (b), the temperature is reduced to 45-50 ℃; adding glacial acetic acid for reaction for 2-3 h.
In various embodiments, in step (b), the temperature may be reduced to 45 ℃, 48 ℃, 50 ℃, or the like; after the glacial acetic acid is added, the reaction time can be 2 hours, 2.5 hours or 3 hours, etc.
In a specific embodiment of the present invention, epoxy resin B is a bisphenol a type epoxy resin. Further, the epoxy equivalent of the epoxy resin B is 190 to 600g/eq.
As in the different embodiments, the epoxy equivalent of the bisphenol a type epoxy resin in epoxy resin B may be 190g/eq, 200g/eq, 250g/eq, 300g/eq, 350g/eq, 400g/eq, 450g/eq, 500g/eq, 550g/eq, 600g/eq, or a range of any two of these compositions.
In a specific embodiment of the present invention, the solvent comprises at least one of propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol monobutyl ether, methyl isobutyl ketone, and ethylene glycol butyl ether.
In a specific embodiment of the present invention, in step (c), the mass ratio of the halogen-containing epoxy resin, the phosphorus-containing emulsifier and the water is (46 to 49)/(3.8 to 5)/(45 to 48).
In the different embodiments, in the step (c), the mass ratio of the halogen-containing epoxy resin, the phosphorus-containing emulsifier and the water may be 46:3.8:45, 47:3.8:45, 48:3.8:45, 49:3.8:45, 46:4:45, 46:5:45, 46:3.8:46, 46:3.8:47, 46:3.8:48 or a range composed of any two of them.
In a specific embodiment of the invention, the temperature of the system in the phase inversion emulsification is 50-70 ℃. Further, in the phase inversion emulsification, high-speed stirring is performed; the stirring speed is 2000-4000 r/min.
As in the various embodiments, in step (c), the temperature of the system may be controlled to be 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃ or a range of any two of these.
During phase inversion emulsification, high-speed stirring and shearing are carried out, and the stirring speed can be 2000r/min, 2500r/min, 3000r/min, 3500r/min, 4000r/min or a range formed by any two of the above materials.
In practice, in step (c), water is added dropwise to the mixture of halogen-containing epoxy resin and phosphorus-containing emulsifier at a rate of from 2 to 5 drops/s.
The invention further provides the composite flame-retardant waterborne epoxy resin prepared by the preparation method of any one of the composite flame-retardant waterborne epoxy resins.
The composite flame-retardant waterborne epoxy resin prepared by the method has the flame-retardant element content of about 1-5 wt% in the emulsion, the fineness of 20-35 mu m, the particle size of 300-430 nm, the UL 94 grade of V-0 grade and the LOI of 25.2-28%.
In yet another aspect, the invention provides a coating comprising any of the above-described composite flame retardant waterborne epoxy resins.
In a specific embodiment of the invention, the coating is a two-component coating comprising component a and component B; the component A comprises composite flame-retardant waterborne epoxy resin, pigment and auxiliary agent; component B includes a curing agent.
Wherein, in the component A, the usage amount of the composite flame-retardant waterborne epoxy resin is 38 to 42 weight percent, and the usage amount of the pigment can be 54 to 58 weight percent. The adjuvants may include any one or more of solvents, wetting agents, defoamers, leveling agents and rheology adjuvants; the curing agent may include an epoxy curing agent. Wherein, the pigment, the auxiliary agent and the curing agent can be used in the conventional composition of the existing paint.
In a specific embodiment of the invention, the composite flame-retardant waterborne epoxy resin in the component A and the curing agent in the component B are prepared into paint according to the molar ratio of epoxy in the composite flame-retardant waterborne epoxy resin to amine hydrogen in the curing agent of 1: (0.75-0.85), such as 1:0.8.
In actual operation, the application method of the coating comprises the following steps: after mixing the component A and the component B, spraying under certain temperature and humidity conditions, leveling for 30-40 min at room temperature, and then baking for 1.5-2.5 h at 75-85 ℃.
Example 1
The embodiment provides a preparation method of a composite flame-retardant waterborne epoxy resin, which comprises the following steps:
(1) 59.34g of chlorpyrifos anhydride and 11.85g of glycidol are added into a 100mL reaction kettle provided with a stirring device and a thermometer, and the temperature is raised to 60 ℃ and the temperature is kept for 3 hours to obtain a chlorine-containing flame-retardant intermediate; subsequently, 3.84g of a chlorine-containing flame-retardant intermediate and 360g of an o-cresol formaldehyde epoxy resin (molecular weight: 1800, functionality: 3.33, EEW:180 g/eq) were added to a 500mL reaction vessel equipped with a stirring device and a thermometer, and the temperature was raised to 110℃and kept for 2 hours, to obtain a chlorine-containing epoxy resin.
(2) 50g of epoxy resin E51 and 43.55g of polyethylene glycol diglycidyl ether (molecular weight 330) are dissolved in 13.75g of propylene glycol methyl ether, and the mixture is added into a 250mL reaction kettle equipped with a stirring device and a thermometer, and the temperature is raised to 60 ℃ for 30min for dispersion; then 23.9g of monoethanolamine phosphate is added, the temperature is raised to 80 ℃ for reflux reaction for 4 hours, 15.62g of glacial acetic acid is added after the temperature is reduced to 50 ℃, and the reaction is carried out for 2 hours at 50 ℃ to obtain the phosphorus-containing emulsifier.
(3) 29.11g of the phosphorus-containing emulsifier prepared in the step (2) is added into the chlorine-containing epoxy resin prepared in the step (1) and mixed for 30min at 110 ℃, then the temperature is reduced to 60 ℃, 348.47g of deionized water is slowly added for emulsification under the condition of high-speed stirring (3000 rpm) for 15min, and the phosphorus-containing halogen-containing waterborne epoxy resin is obtained, the solid content of the phosphorus-containing halogen-containing waterborne epoxy resin is 53%, the average particle size of the phosphorus-containing halogen-containing waterborne epoxy resin is 430nm, the fineness of the phosphorus-containing halogen-containing waterborne epoxy resin is 20 mu m, and the emulsion is milky blue.
Example 2
The embodiment provides a preparation method of a composite flame-retardant waterborne epoxy resin, which comprises the following steps:
(1) 59.34g of chlorpyrifos anhydride and 11.85g of glycidol are added into a 100mL reaction kettle provided with a stirring device and a thermometer, and the temperature is raised to 60 ℃ and the temperature is kept for 3 hours to obtain a chlorine-containing flame-retardant intermediate; then, 7.68g of the chlorine-containing flame-retardant intermediate and 360g of an o-cresol formaldehyde epoxy resin (molecular weight: 1800, functionality: 3.33, EEW:180 g/eq) were added to a 500mL reaction vessel equipped with a stirring device and a thermometer, and the temperature was raised to 120℃and kept for 2 hours, to obtain a chlorine-containing epoxy resin.
(2) 50g of epoxy resin E51 and 43.55g of polyethylene glycol diglycidyl ether (molecular weight 330) are dissolved in 13.75g of propylene glycol methyl ether, and the mixture is added into a 250mL reaction kettle equipped with a stirring device and a thermometer, and the temperature is raised to 60 ℃ for 30min for dispersion; then 23.9g of monoethanolamine phosphate is added, the temperature is raised to 80 ℃ for reflux reaction for 4 hours, 15.62g of glacial acetic acid is added after the temperature is reduced to 50 ℃, and the reaction is carried out for 2 hours at 50 ℃ to obtain the phosphorus-containing emulsifier.
(3) Adding 29.42g of the phosphorus-containing emulsifier prepared in the step (2) into the chlorine-containing epoxy resin prepared in the step (1), mixing for 30min at 110 ℃, cooling to 60 ℃, slowly adding 352.15g of deionized water for emulsification under the condition of high-speed stirring (3000 rpm) for 15min to obtain the phosphorus-containing halogen-containing waterborne epoxy resin, wherein the solid content is 53%, the average particle size is 320nm, the fineness is 20 mu m, and the emulsion is milky blue.
Example 3
The embodiment provides a preparation method of a composite flame-retardant waterborne epoxy resin, which comprises the following steps:
(1) 74.18g of 1,4,5, 6-tetrabromophthalic anhydride and 11.85g of epoxy propanol are added into a 200mL reaction kettle provided with a stirring device and a thermometer, and the temperature is raised to 65 ℃ and the temperature is kept for 3 hours to obtain a bromine-containing flame-retardant intermediate; then, 4.64g of a bromine-containing flame-retardant intermediate and 228g of an epoxy resin E44 (molecular weight 456) were added to a 500mL reaction vessel equipped with a stirring device and a thermometer, and the temperature was raised to 110℃and kept for 2 hours to obtain a bromine-containing epoxy resin.
(2) 50g of epoxy resin E51 and 43.55g of polyethylene glycol diglycidyl ether (molecular weight 330) are dissolved in 13.75g of propylene glycol diethyl ether, and the mixture is added into a 250mL reaction kettle equipped with a stirring device and a thermometer, and the temperature is raised to 60 ℃ for 30min for dispersion; then 23.9g of monoethanolamine phosphate is added, the temperature is raised to 80 ℃ for reflux reaction for 4 hours, 15.62g of glacial acetic acid is added after the temperature is reduced to 50 ℃, and the reaction is carried out for 2 hours at 50 ℃ to obtain the phosphorus-containing emulsifier.
(3) Adding 18.61g of the phosphorus-containing emulsifier prepared in the step (2) into the bromine-containing epoxy resin prepared in the step (1), mixing for 30min at 110 ℃, cooling to 60 ℃, slowly adding 222.80g of deionized water for emulsification under the condition of high-speed stirring (3000 rpm) for 15min to obtain the phosphorus-containing halogen-containing waterborne epoxy resin, wherein the solid content is 53%, the average particle size is 360nm, the fineness is 30 mu m, and the emulsion is milky blue.
Example 4
The embodiment provides a preparation method of a composite flame-retardant waterborne epoxy resin, which comprises the following steps:
(1) 59.34g of chlorpyrifos anhydride and 11.85g of glycidol are added into a 100mL reaction kettle provided with a stirring device and a thermometer, and the temperature is raised to 60 ℃ and the temperature is kept for 3 hours to obtain a chlorine-containing flame-retardant intermediate; 15.36g of the chlorine-containing flame-retardant intermediate and 360g of o-cresol formaldehyde epoxy resin (molecular weight 1800, functionality 3.33, EEW:180 g/eq) were then added to a 500mL reaction vessel equipped with a stirring device, thermometer, and the temperature was raised to 110℃and maintained for 2 hours, to obtain the chlorine-containing epoxy resin.
(2) 50g of epoxy resin E51 and 43.55g of polyethylene glycol diglycidyl ether (molecular weight 330) are dissolved in 13.75g of propylene glycol methyl ether, and the mixture is added into a 250mL reaction kettle equipped with a stirring device and a thermometer, and the temperature is raised to 60 ℃ for 30min for dispersion; then 23.9g of monoethanolamine phosphate is added, the temperature is raised to 80 ℃ for reflux reaction for 4 hours, 15.62g of glacial acetic acid is added after the temperature is reduced to 50 ℃, and the reaction is carried out for 2 hours at 50 ℃ to obtain the phosphorus-containing emulsifier.
(3) Adding 37.54g of the phosphorus-containing emulsifier prepared in the step (2) into the chlorine-containing epoxy resin prepared in the step (1), mixing for 30min at 110 ℃, cooling to 60 ℃, slowly adding 366.16g of deionized water for emulsification under the condition of high-speed stirring (3000 rpm) for 15min to obtain the phosphorus-containing halogen-containing waterborne epoxy resin, wherein the solid content is 53%, the average particle size is 350nm, the fineness is 35 mu m, and the emulsion is milky blue.
Comparative example 1
Comparative example 1 provides a method for preparing an aqueous epoxy resin comprising the steps of:
(1) 59.34g of chlorpyrifos anhydride and 11.85g of glycidol are added into a 100mL reaction kettle provided with a stirring device and a thermometer, and the temperature is raised to 60 ℃ and the temperature is kept for 3 hours to obtain a chlorine-containing flame-retardant intermediate; then, 7.68g of the chlorine-containing flame-retardant intermediate and 360g of an o-cresol formaldehyde epoxy resin (molecular weight: 1800, functionality: 3.33, EEW:180 g/eq) were added to a 500mL reaction vessel equipped with a stirring device and a thermometer, and the temperature was raised to 110℃and kept for 2 hours, to obtain a chlorine-containing epoxy resin.
(2) Adding 22.06g of a commercial emulsifier (Nantong Xinbao source LAE-4) into the chlorine-containing epoxy resin prepared in the step (1), mixing for 30min at 110 ℃, cooling to 60 ℃, slowly adding 345.62g of deionized water for emulsification under the condition of high-speed stirring (3000 rpm) for 15min to obtain the halogen-containing waterborne epoxy resin, wherein the solid content is 53%, the average particle size is 490nm, the fineness is 40 mu m, and the emulsion is milky.
Comparative example 2
Comparative example 2 provides a method for preparing an aqueous epoxy resin comprising the steps of:
(1) 59.34g of chlorpyrifos anhydride and 11.85g of glycidol are added into a 100mL reaction kettle provided with a stirring device and a thermometer, and the temperature is raised to 60 ℃ and the temperature is kept for 3 hours to obtain a chlorine-containing flame-retardant intermediate; then, 30.72g of a chlorine-containing flame-retardant intermediate and 360g of an o-cresol formaldehyde epoxy resin (molecular weight: 1800, functionality: 3.33, EEW:180 g/eq) were added to a 500mL reaction vessel equipped with a stirring device and a thermometer, and the temperature was raised to 120℃and kept for 2 hours, to obtain a chlorine-containing epoxy resin.
(2) 50g of epoxy resin E51 and 43.55g of polyethylene glycol diglycidyl ether (molecular weight 330) are dissolved in 13.75g of propylene glycol methyl ether, and the mixture is added into a 250mL reaction kettle equipped with a stirring device and a thermometer, and the temperature is raised to 60 ℃ for 30min for dispersion; then 23.9g of monoethanolamine phosphate is added, the temperature is raised to 80 ℃ for reflux reaction for 4 hours, 15.62g of glacial acetic acid is added after the temperature is reduced to 50 ℃, and the reaction is carried out for 2 hours at 50 ℃ to obtain the phosphorus-containing emulsifier.
(3) Adding 50.79g of the phosphorus-containing emulsifier prepared in the step (2) into the chlorine-containing epoxy resin prepared in the step (1), mixing for 30min at 110 ℃, cooling to 60 ℃, slowly adding 390.99g of deionized water for emulsification under the condition of high-speed stirring (3000 rpm) for 15min to obtain the water-based epoxy resin, wherein the solid content is 53%, the average particle size is 500nm, the fineness is 45 mu m, and the emulsion is milky.
Comparative example 3
Comparative example 3 provides a method for preparing an aqueous epoxy resin comprising the steps of:
(1) 360g of an o-cresol formaldehyde epoxy resin (molecular weight: 1800, functionality: 3.33, EEW:180 g/eq) and 25.9g of DOPO were charged into a 500mL reaction vessel equipped with a stirring device and a thermometer, followed by addition of 23.15g of propylene glycol methyl ether, heating to 120℃to liquefy the mixed raw materials, then heating to 130℃to add 1.16g of triphenylphosphine, and preserving heat for 5 hours to obtain a phosphorus-containing epoxy resin.
(2) 50g of epoxy resin E51 and 43.55g of polyethylene glycol diglycidyl ether (dissolved in 13.75g of propylene glycol methyl ether, added into a 250mL reaction kettle equipped with a stirring device and a thermometer, heated to 60 ℃ for 30min for dispersion, then 23.9g of monoethanolamine phosphate is added, heated to 80 ℃ for reflux reaction for 4h, cooled to 50 ℃ for reaction for 2h, and 15.62g of glacial acetic acid is added for reaction at 50 ℃ to obtain the phosphorus-containing emulsifier.
(3) Adding 30.87g of the phosphorus-containing emulsifier prepared in the step (2) into the phosphorus-containing epoxy resin prepared in the step (1), mixing for 30min at 110 ℃, cooling to 60 ℃, slowly adding 370.36g of deionized water for emulsification under the condition of high-speed stirring (3000 rpm) for 15min to obtain the phosphorus-containing waterborne epoxy resin, wherein the solid content is 53%, the average particle size is 400nm, the fineness is 35 mu m, and the emulsion is milky blue.
Comparative example 4
Comparative example 4 provides a method for preparing an aqueous epoxy resin comprising the steps of:
(1) 360g of an o-cresol formaldehyde epoxy resin (molecular weight: 1800, functionality: 3.33, EEW:180 g/eq) and 65.41g of DOPO were charged into a 500mL reaction vessel equipped with a stirring device and a thermometer, followed by 25.52g of propylene glycol methyl ether, heating to 120℃to liquefy the mixed raw material, then heating to 130℃to 1.28g of tetramethyl ammonium bromide, and preserving heat for 5 hours to obtain a phosphorus-containing epoxy resin.
(2) 34.03g of commercial aqueous epoxy film forming material emulsifier (Nantong Xinbao source LAE-4) is added into the phosphorus-containing epoxy resin prepared in the step (1) and mixed for 30min at 110 ℃, then the temperature is reduced to 60 ℃, 407.43g of deionized water is slowly added for emulsification under the condition of high-speed stirring (3000 rpm) for 15min, and the phosphorus-containing aqueous epoxy resin is obtained, the solid content of the phosphorus-containing aqueous epoxy resin is 53%, the average particle size is 500nm, the fineness is 40 mu m, and the emulsion is milky.
Experimental example 1
The aqueous epoxy resins of examples 1 to 4 and comparative examples 1 to 4 were tested, and the test results are shown in Table 1.
The following test results refer to the following test methods or criteria:
the particle size of the epoxy resin is tested by using a PSS particle sizer in the United states, and the fineness of the emulsion GB/T1724-1979 is tested;
UL-94 values were measured using a CZF-6 vertical burn tester according to ASTM D-3801 test standard;
LOI value is tested according to GB/T2046 standard by adopting JF-5 type oxygen index tester;
the test method for thermal storage stability comprises the following steps: and (3) taking a proper amount of the prepared aqueous epoxy resin, placing the aqueous epoxy resin in a thermal storage bottle, and placing the thermal storage bottle in a 50 ℃ oven for storage stability acceleration experiments. And observing whether the emulsion in the hot storage bottle has the phenomena of layering, soft sedimentation, thickening, demulsification, large particle size and the like every two days. No abnormalities were noted as passing within 30 days.
TABLE 1 test results of different waterborne epoxy resins
Experimental example 2
The aqueous epoxy resins of examples 1 to 4 and comparative examples 1 to 4 were respectively prepared into a paint including a component A and a component B. Component A was formulated according to the composition of Table 2, and component B was an AQUAC-3126 epoxy hardener (Jiangsu Fuqisen) which was diluted with a mixed solvent (propylene glycol methyl ether to water mass ratio 1:1) to a solids content of 30%. The composition of the pigment-filler slurry is shown in table 3.
TABLE 2 composition of component A
| Raw material name | Mass percent (%) |
| Water-based epoxy resin | 40.0 |
| Pigment and filler slurry (specific formulation is as follows) | 56.6 |
| Cosolvent (TEGO 902W, german Digao) | 2.0 |
| Defoaming agent BYK015 (Pick chemistry) | 0.3 |
| Base wetting agent TEGO270 (German Digao) | 0.5 |
| Rheology assistant XS-83 (French Gaotai) | 0.4 |
| Leveling agent BYK301 (Pick chemistry) | 0.2 |
| Total amount of | 100 |
TABLE 3 composition of pigment and filler slurries
The preparation method of the coating comprises the following steps: component A was prepared according to the composition of Table 2, and after mixing uniformly, a lacquer was prepared with component B according to a molar ratio of epoxy in the aqueous epoxy resin to amine hydrogen in the curing agent of 1:0.8. And then spraying the prepared paint on the polished tinplate and the cold-rolled steel plate to prepare a paint film, standing and leveling the paint film after construction for 30min, and then placing the paint film in an oven at 80 ℃ for curing for 2h. Performance testing was performed after 24h of standing. Among them, the cold rolled steel sheet was used for hot water resistance and neutral salt spray resistance tests, and other tests were performed by a tinplate, and the test results are shown in table 4.
Table 4 test results of different waterborne epoxy coatings
| Test item | Adhesion force | Hardness of | Flexibility/mm | Impact resistance/cm | Water/d resistance at 40 DEG C | Neutral salt fog/h resistance |
| Example 1 | Level 0 | 3H | 2mm | 50 | ＞30d | 408h |
| Example 2 | Level 0 | 2H | 3mm | 40 | ＞30d | 360h |
| Example 3 | Level 0 | 2H | 2mm | 40 | ＞30d | 360h |
| Example 4 | Level 0 | 2H | 2mm | 30 | ＞30d | 360h |
| Comparative example 1 | Level 0 | HB | 2mm | 30 | 20d | 312h |
| Comparative example 2 | Level 1 | HB | 2mm | 30 | 15d | 288h |
| Comparative example 3 | Level 1 | HB | 2mm | 30 | 20d | 312h |
| Comparative example 4 | Level 1 | HB | 2mm | 30 | 20d | 312h |
Wherein the test results are referenced to the following test methods or criteria:
the adhesion was determined by the cross-hatch method, GB/T9286-1998;
the pencil hardness of the paint film is measured, GB/T6739-1996;
the flexibility of the paint film is measured, GB/T1731-1993;
the impact resistance of the paint film is measured GB/T1973-1993;
measuring 40 ℃ water resistance, GB/T1733-1993;
and (3) measuring neutral salt fog resistance, and GB/T1771-2007.
From the test results, the composite flame-retardant waterborne epoxy resin prepared by the invention greatly reduces the consumption of flame-retardant raw materials after using the corresponding phosphorus-containing emulsifier, saves the production cost, improves the compatibility of a matrix, ensures that the composite flame-retardant waterborne epoxy resin has excellent flame-retardant effect, obtains excellent fineness and storage stability, and improves the problem of poor mechanical property. As is clear from the comparison of examples 1 to 4, the emulsion has good flame retardance and is stable in storage and excellent in mechanical property when the content of the flame retardant element in the emulsion is 2.2%. While too much or too little flame retardant content in the emulsion can have an effect on flame retardancy and storage stability. As can be seen from the comparison of comparative examples 1 to 4, the use of commercially available emulsifiers is expected to achieve good flame retardant effect, more flame retardant raw materials are required, and the problems of poor compatibility and poor emulsion stability are obvious while the production cost is extremely high. Compared with the common DOPO type flame-retardant emulsion in the market, the flame-retardant epoxy resin disclosed by the invention has the advantages of less consumption of flame-retardant raw materials, lower cost and better flame-retardant effect and resistance than the DOPO type flame-retardant epoxy resin.
In conclusion, the composite flame-retardant waterborne epoxy resin prepared by the invention has new breakthrough in epoxy resin modification and emulsifier modification, reduces the production cost, improves the flame-retardant property of emulsion, and simultaneously improves the storage stability and mechanical property of the emulsion, thereby meeting the requirements of industrial production.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. The preparation method of the composite flame-retardant waterborne epoxy resin is characterized by comprising the following steps:
(a) Heating and reacting halogen-containing anhydride with epoxypropanol to obtain an intermediate, and then heating and reacting with epoxy resin A to obtain halogen-containing epoxy resin;
(b) Reflux reacting epoxy resin B, polyethylene glycol diglycidyl ether and monoethanolamine phosphate in a solvent, cooling, and adding glacial acetic acid for reaction to obtain a phosphorus-containing emulsifier;
(c) Mixing the halogen-containing epoxy resin, the phosphorus-containing emulsifier and water for phase inversion emulsification to obtain the composite flame-retardant waterborne epoxy resin;
the mass ratio of the epoxy resin A to the intermediate is (40-120) to 1.
2. The method for producing a composite flame-retardant waterborne epoxy resin according to claim 1, wherein in the step (a), the molar ratio of the halogen-containing anhydride to the epoxypropanol is 1: (0.8-1.2);
preferably, in the heating reaction of the halogen-containing anhydride and the epoxypropanol, the heating temperature is 60-80 ℃, and the reaction time is 3-4 hours.
3. The method for preparing a composite flame-retardant waterborne epoxy resin according to claim 1, wherein in the step (a), in the heating reaction with the epoxy resin A, the heating temperature is 100-120 ℃, and the reaction time is 2-3 hours;
preferably, the epoxy resin a comprises bisphenol a type epoxy resin and/or novolac epoxy resin.
4. The method for preparing a composite flame-retardant waterborne epoxy resin according to claim 1, wherein the halogen-containing anhydride comprises at least one of 1,4,5, 6-tetrabromophthalic anhydride, tetrachlorophthalic anhydride and chlorendic anhydride.
5. The method for producing a composite flame-retardant waterborne epoxy resin according to claim 1, wherein in the step (B), the mass ratio of the epoxy resin B, the polyethylene glycol diglycidyl ether and the monoethanolamine phosphate is (7-8)/(6-7)/(2-4);
preferably, in the step (B), the solvent is used in an amount of 15 to 30% of the mass of the epoxy resin B;
preferably, the glacial acetic acid is used in an amount of 0.5 to 1.5 times the mass of the monoethanolamine phosphate.
6. The method for preparing a composite flame-retardant waterborne epoxy resin according to claim 1, wherein in the step (b), the temperature of the reflux reaction is 80-90 ℃, and the time of the reflux reaction is 3-5 h;
preferably, the epoxy resin B is bisphenol A type epoxy resin;
preferably, the solvent includes at least one of propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol monobutyl ether, methyl isobutyl ketone, and ethylene glycol butyl ether.
7. The method of producing a composite flame retardant waterborne epoxy resin according to claim 1, wherein in the step (c), the mass ratio of the halogen-containing epoxy resin, the phosphorus-containing emulsifier and the water is (46 to 49)/(3.8 to 5)/(45 to 48).
8. The method for preparing the composite flame-retardant waterborne epoxy resin according to claim 1, wherein in the phase inversion emulsification, the temperature of a system is 50-70 ℃;
preferably, in the phase inversion emulsification, high-speed stirring is performed; the stirring speed is 2000-4000 r/min.
9. The composite flame-retardant waterborne epoxy resin prepared by the preparation method of the composite flame-retardant waterborne epoxy resin of any one of claims 1 to 8.
10. A coating comprising the composite flame retardant waterborne epoxy resin of claim 9.
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