CN111378097B - Epoxy resin for gasoline and salt fog resistant self-extinction 50/50 powder and preparation method thereof - Google Patents
Epoxy resin for gasoline and salt fog resistant self-extinction 50/50 powder and preparation method thereof Download PDFInfo
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- CN111378097B CN111378097B CN202010330821.7A CN202010330821A CN111378097B CN 111378097 B CN111378097 B CN 111378097B CN 202010330821 A CN202010330821 A CN 202010330821A CN 111378097 B CN111378097 B CN 111378097B
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 108
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 108
- 239000000843 powder Substances 0.000 title claims abstract description 39
- 150000003839 salts Chemical class 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 51
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 48
- 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 claims abstract description 44
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000004593 Epoxy Substances 0.000 claims abstract description 27
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims abstract description 18
- ZTVZLYBCZNMWCF-UHFFFAOYSA-N homocystine Chemical compound [O-]C(=O)C([NH3+])CCSSCCC([NH3+])C([O-])=O ZTVZLYBCZNMWCF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011975 tartaric acid Substances 0.000 claims abstract description 18
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 18
- 239000007921 spray Substances 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 13
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims abstract description 12
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004132 cross linking Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 55
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000004321 preservation Methods 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 10
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000005086 pumping Methods 0.000 claims description 5
- 238000005070 sampling Methods 0.000 claims description 5
- 239000010959 steel Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000012360 testing method Methods 0.000 claims description 5
- 238000006011 modification reaction Methods 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims 8
- 239000008346 aqueous phase Substances 0.000 claims 1
- 238000010298 pulverizing process Methods 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 36
- 239000011248 coating agent Substances 0.000 abstract description 33
- 230000007935 neutral effect Effects 0.000 abstract description 11
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 229920001225 polyester resin Polymers 0.000 description 9
- 239000004645 polyester resin Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 230000008033 biological extinction Effects 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000003827 glycol group Chemical group 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
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
- C08G59/308—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/066—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with chain extension or advancing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/12—Polycondensates containing more than one epoxy group per molecule of polycarboxylic acids with epihalohydrins or precursors thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/28—Di-epoxy compounds containing acyclic nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Abstract
The invention belongs to the technical field of epoxy resin preparation, and particularly relates to epoxy resin for gasoline and salt spray resistant self-extinction 50/50 powder, and a preparation method of the epoxy resin. The epoxy resin is prepared by reacting bisphenol A, epichlorohydrin, sodium hydroxide, tartaric acid, octafluoro adipic acid, citric acid, triglycidyl isocyanurate and the like which are mainly used as raw materials, and the epoxy equivalent of the finally obtained epoxy resin is 700-750g/mol, and the acid value is lower than 2 mgKOH/g. The epoxy resin obtained by the invention has higher functionality, so that the crosslinking density of a cured coating is high, the solvent resistance and neutral salt spray resistance of the final coating are excellent, and the self-extinction performance is excellent when the epoxy resin is used in 50/50 powder coating.
Description
Technical Field
The invention belongs to the technical field of epoxy resin preparation, and particularly relates to epoxy resin for gasoline and salt spray resistant self-extinction 50/50 powder, and a preparation method of the epoxy resin.
Background
The common E-12 epoxy resin is obtained by directly reacting bisphenol A and epoxy chloropropane under the action of strong alkali, the molecular structure of the product is single, the branching degree is low, the activity of the terminal epoxy is relatively uniform, and when the product is cured with the mixed 50/50 polyester resin, a coating film with higher gloss is often obtained. And the E-12 epoxy resin has general hydrophobicity and oleophobicity, so that the gasoline resistance and neutral salt spray resistance of the finally cured coating film are insufficient. With the increase of decoration requirements, products requiring 10-20% gloss coating films are more and more on the market. At present, the method is mainly realized by adding a flatting agent, and the prepared powder coating has unstable flatting performance due to poor compatibility and miscibility of the added flatting agent and resin used by the powder coating, such as epoxy resin and polyester resin, so that unqualified powder coating is easy to appear, and great inconvenience is brought to the application in the industry.
CN109749054A provides an epoxy resin for a delustering powder coating, a preparation method and an application thereof, wherein the preparation method comprises the following steps: dissolving: heating and dissolving epoxy chloropropane and bisphenol A under the protection of inert gas, then adding a solvent, and uniformly mixing; and (3) catalytic reaction: adding a catalyst into the mixed solution; separation and purification: comprises the following stages of liquid separation section, neutralization section, water washing section and desolventizing section. The epoxy resin has the characteristics of high epoxy equivalent, low viscosity, low softening point, high content of alpha glycol group and wide range of hydrolytic chlorine, and the low molecular weight n-0 structure has low content, so that the characteristics of low glossiness, good mechanical property, good storage stability and the like of the extinction powder coating can be ensured.
The documents generate a certain amount of emulsion in the production process through the control of a synthesis process, and the emulsion has a matting effect to a certain extent by utilizing the limited compatibility of the emulsion and common epoxy resin, and is superior to common epoxy resin products in the matting effect, but the documents do not pay attention to the performance in the aspects of gasoline resistance and salt mist resistance of the epoxy resin, and a coating prepared by the product is not suitable for being directly used in 50/50 powder coating, and the coating also needs to additionally use a matting curing agent, so that a series of defects of unstable matting performance of the prepared powder coating still exist.
Therefore, the self-extinction epoxy resin for 50/50 powder coating, which has excellent impact property and extinction effect and simultaneously has gasoline resistance and salt fog resistance, needs to be solved.
Disclosure of Invention
Aiming at the problems of the epoxy resin for 50/50 powder coating, the invention uses bisphenol A, epichlorohydrin, sodium hydroxide, tartaric acid, octafluoro adipic acid, citric acid, triglycidyl isocyanurate and the like as raw materials to prepare the epoxy resin for 50/50 powder with excellent gasoline and salt fog resistance and self-extinction property, and the final coating does not need to use an additional extinction agent. The epoxy equivalent of the finally obtained epoxy resin is 750g/mol at 700-.
The invention provides an epoxy resin for gasoline and salt mist resistant self-extinction 50/50 powder, which is prepared from bisphenol A, epichlorohydrin, sodium hydroxide, tartaric acid, octafluoro adipic acid, citric acid and triglycidyl isocyanurate.
Specifically, the epoxy resin comprises the following main raw materials in parts by mole:
5-10 parts of bisphenol A, 20-35 parts of epichlorohydrin, 30-50 parts of sodium hydroxide, 6-12 parts of tartaric acid, 3-7 parts of octafluoro adipic acid, 2-4 parts of citric acid and 7-12 parts of triglycidyl isocyanurate.
The epoxy resin also comprises a catalyst benzyltriethylammonium chloride, and the dosage of the benzyltriethylammonium chloride is 0.1-0.2% of the molar amount of the bisphenol A.
The preparation method of the epoxy resin for the gasoline and salt fog resistant self-extinction 50/50 powder comprises the following steps:
(1) adding triglycidyl isocyanurate into a reaction kettle, heating to melt, stirring, adding citric acid for crosslinking modification, stopping reaction, discharging, cooling to room temperature, and crushing to obtain modified triglycidyl isocyanurate;
(2) pumping a sodium hydroxide solution into a reaction kettle, heating, adding bisphenol A, adding a catalyst benzyltriethylammonium chloride, performing heat preservation reaction, adding epoxy chloropropane, performing heat preservation reaction again, adding tartaric acid and octafluoro adipic acid, and continuing the heat preservation reaction;
(3) after the reaction is stopped, separating out a water phase and an epoxy resin phase, washing the epoxy resin phase with boiling water, and then carrying out reduced pressure dehydration on the epoxy resin to obtain an epoxy resin intermediate;
(4) heating an epoxy resin intermediate, melting at high temperature, adding the modified triglycidyl isocyanurate obtained in the step (1), carrying out chain extension and branching degree reaction, discharging at high temperature when the reaction is stopped, cooling the epoxy resin by using a steel belt with condensed water, crushing and granulating to obtain the epoxy resin for the solvent-resistant, excellent-salt-fog and self-extinction 50/50 powder.
Preferably, in the step (1), the mixture is heated to 100 to 110 ℃ to be melted;
preferably, the reaction is stopped in the step (1) until the acid value of the reacted mixture reaches 60-80 mgKOH/g;
preferably, the particles in the step (1) are crushed to 50-80 μm.
(2) In the method, the solid content of the sodium hydroxide solution is 40-60%, preferably, the solid content of the sodium hydroxide solution is 50%;
preferably, in the step (2), a sodium hydroxide solution is added and then the temperature is kept to 25-35 ℃;
preferably, in the step (2), bisphenol A is added and then the reaction is carried out for 1-2 hours under the condition of heat preservation;
preferably, in the step (2), the catalyst benzyltriethylammonium chloride is added while the bisphenol A is added, and the dosage of the benzyltriethylammonium chloride is 0.1 to 0.2 percent of the molar weight of the bisphenol A;
preferably, (2) adding epoxy chloropropane, and reacting at the temperature of 80-100 ℃;
preferably, epichlorohydrin is added into the step (2), and the reaction is carried out for 2 to 4 hours at the temperature of 80 to 100 ℃;
preferably, tartaric acid and octafluoro adipic acid are added into the mixture obtained in the step (2), and then the mixture is subjected to heat preservation reaction at the temperature of 80-100 ℃;
preferably, tartaric acid and octafluoro adipic acid are added into the reaction solution (2), and then the reaction is continued for 1-3 hours at the temperature of 80-100 ℃.
(3) Sampling to test the epoxy equivalent of the epoxy resin, and stopping the reaction when the epoxy equivalent is 1000-1200 g/mol;
preferably, in the step (3), after the reaction is stopped, separating out a water phase and an epoxy resin phase, and washing the epoxy resin phase with boiling water for 3-5 times;
(3) in the washing with boiling water, the mass of water used each time is one fourth of the mass of the resin.
(4) Heating the epoxy resin intermediate to 120-130 ℃ for high-temperature melting;
preferably, in the step (4), chain extension and branch extension degree reactions are carried out at 120-130 ℃;
preferably, in the step (4), chain extension and branch extension degree reaction is carried out at 120-130 ℃ for 0.5-1.5 h;
preferably, in the step (4), after the chain extension and the chain branching degree reaction, the reaction is stopped when the epoxy equivalent of the resin is 700-750g/mol and the acid value is less than 2 mgKOH/g.
Preferably, the preparation method of the epoxy resin for the gasoline and salt fog resistant self-extinction 50/50 powder comprises the following steps:
(1) adding triglycidyl isocyanurate into a reaction kettle, heating to 100-110 ℃ to melt the triglycidyl isocyanurate, starting stirring, then adding citric acid at one time to perform a crosslinking modification reaction, stopping the reaction when the acid value of a reaction mixture reaches 60-80 mgKOH/g, discharging, cooling to room temperature, and crushing into particles of 50-80 mu m to obtain modified triglycidyl isocyanurate;
(2) pumping a sodium hydroxide solution with a solid content of 40-60% into a reaction kettle, heating to 25-35 ℃, adding bisphenol A, and simultaneously adding a catalyst benzyltriethylammonium chloride, wherein the addition amount of benzyltriethylammonium chloride is 0.1-0.2% of the molar amount of bisphenol A; reacting for 1-2 h under heat preservation, then adding epoxy chloropropane, reacting for 2-4h under heat preservation at 80-100 ℃, finally adding tartaric acid and octafluoro adipic acid, and continuing to react for 1-3 h under heat preservation at 80-100 ℃;
(3) sampling and testing the epoxy equivalent of the epoxy resin, stopping the reaction when the epoxy equivalent is 1000-1200g/mol, separating out a water phase and an epoxy resin phase, washing the epoxy resin phase with boiling water for 3-5 times, wherein the mass of water is one fourth of the mass of the resin each time, and finally performing reduced pressure dehydration on the epoxy resin to obtain an epoxy resin intermediate;
(4) heating the epoxy resin intermediate to 120-130 ℃ for high-temperature melting, then adding modified triglycidyl isocyanurate, carrying out chain extension and chain extension branching degree reaction for 0.5-1.5 h at 120-130 ℃, stopping the reaction when the epoxy equivalent of the resin is 700-750g/mol and the acid value is less than 2mgKOH/g, discharging at high temperature while hot, cooling the epoxy resin by using a steel belt with condensed water, and then crushing and granulating to obtain the epoxy resin for the self-extinction 50/50 powder with excellent solvent resistance and salt fog resistance.
The epoxy resin obtained by the invention has two epoxy groups, such as the epoxy group of the epoxy resin and the epoxy group introduced by triglycidyl isocyanurate, the curing activity of the epoxy group is different, and the epoxy resin also has hydroxyl groups with different activities, and the monohydroxy group introduced by citric acid and the ortho-dihydroxy group introduced by tartaric acid cause different speeds when the epoxy group and the hydroxyl group are cured with the carboxyl group of 50/50 polyester resin, so that the self-extinction phenomenon is generated during curing, and the extinction type coating film with the gloss of 10-20% can be stably obtained without using an extinction agent. Meanwhile, hydrophobic fluorine elements are introduced into the epoxy resin chain segment, and due to the introduction of multifunctional citric acid and triglycidyl isocyanurate, the functionality of a final product of the epoxy resin is higher, so that the crosslinking density of a coating film is high after the epoxy resin is cured with 50/50 polyester resin, and the gasoline resistance and neutral salt fog resistance of the final coating film are excellent.
Detailed Description
In order that those skilled in the art will better understand the present invention, the inventors will further describe and illustrate the present invention by the following specific examples, but do not limit the present invention.
Example 1
The preparation method of the epoxy resin for the gasoline and salt fog resistant self-extinction 50/50 powder comprises the following steps:
(1) adding triglycidyl isocyanurate into a reaction kettle, heating to 105 ℃ to melt the triglycidyl isocyanurate, starting stirring, then adding citric acid at one time to perform crosslinking modification reaction, stopping the reaction when the acid value of the reaction mixture reaches 70mgKOH/g, discharging, cooling to room temperature, and crushing into particles of 70 mu m to obtain modified triglycidyl isocyanurate;
(2) pumping a sodium hydroxide solution with solid content of 50% into a reaction kettle, heating to 30 ℃, adding bisphenol A, and simultaneously adding a catalyst benzyltriethylammonium chloride, wherein the addition amount of benzyltriethylammonium chloride is 0.15% of the molar amount of bisphenol A; keeping the temperature and reacting for 1.5h, then adding epoxy chloropropane, keeping the temperature and reacting for 3h at 90 ℃, finally adding tartaric acid and octafluoro adipic acid, and keeping the temperature and reacting for 2h at 90 ℃;
(3) sampling and testing the epoxy equivalent of the epoxy resin, stopping reaction when the epoxy equivalent is 1100g/mol, separating out a water phase and an epoxy resin phase, washing the epoxy resin phase with boiling water for about 4 times, wherein the water mass is one fourth of the resin mass each time, and finally performing reduced pressure dehydration on the epoxy resin to obtain an epoxy resin intermediate;
(4) heating the epoxy resin intermediate to 125 ℃ for high-temperature melting, then adding modified triglycidyl isocyanurate, carrying out chain extension and branching degree reaction for 1h at 125 ℃, stopping the reaction when the epoxy equivalent of the resin is 700-750g/mol and the acid value is less than 2mgKOH/g, discharging at high temperature while the resin is hot, cooling the epoxy resin by using a steel belt with condensed water, and then crushing and granulating to obtain the epoxy resin for the self-extinction 50/50 powder with excellent solvent resistance and salt spray resistance.
The methods of example 2 and example 3 are the same as example 1, except that the amount of the raw materials is different, and the specific amounts are shown in the following table 1:
TABLE 1 consumption of raw materials for the products of examples 1-4
| Example 1 | Example 2 | Example 3 | Example 4 | |
| Bisphenol A | 8 | 5 | 10 | 8 |
| Epoxy chloropropane | 25 | 24 | 30 | 28 |
| Sodium hydroxide | 40 | 32 | 45 | 42 |
| Tartaric acid | 10 | 9 | 8 | 7 |
| Octafluoroadipic acid | 5 | 4 | 6 | 5 |
| Citric acid | 4 | 2 | 3 | 4 |
| Triglycidyl isocyanurate | 10 | 9 | 8 | 12 |
| Benzyl triethyl ammonium chloride | 0.15 | 0.12 | 0.2 | 0.18 |
The acid values of the products of examples 1-4 were all < 2 mgKOH/g.
TABLE 2 epoxy equivalent and softening point of the products of examples and comparative examples
Comparative example 1: the procedure was repeated as in example 1 except that tartaric acid was replaced with an equimolar amount of succinic acid.
The epoxy equivalent of the prepared epoxy resin is 712g/mol, and the softening point is 100 ℃.
Comparative example 2: the procedure is as in example 2, except that octafluoroadipic acid is replaced by an equimolar amount of adipic acid.
The epoxy equivalent of the prepared epoxy resin is 737g/mol, and the softening point is 99 ℃.
Comparative example 3: the procedure is as in example 3, except that citric acid and triglycidyl isocyanurate are not used.
The epoxy equivalent of the prepared epoxy resin is 1136g/mol, and the softening point is 81 ℃.
Comparative example 4: a comparison was made using a commercially available ordinary E-12 epoxy resin having an epoxy equivalent weight of 870g/mol and a softening point of 88 ℃ available from Hengtai New materials Co., Ltd, Anhui, model No. E-12.
Example 4
The conventional 50/50 mixed powder coating formula is generally as follows in parts by weight:
wherein 50/50 polyester resin is commercially available from Anhui Shenjian New materials GmbH, model SJ 3B.
Preparation of powder coating: the materials are mixed evenly according to the formula of the 50/50 mixed powder coating, extruded, tabletted and crushed by a double-screw extruder (130-135 ℃), and then the tablet is crushed and sieved to prepare the powder coating (180 meshes). The powder coating is sprayed on the galvanized iron substrate after surface treatment by adopting an electrostatic spray gun and is solidified at 180 ℃/15min to obtain a coating layer with the film thickness of 70-80 mu m.
Example 5
Comparison of Performance
The coating index detection is carried out according to GB/T21776-2008 detection standard guidelines for powder coatings and coatings thereof, wherein the gasoline resistance performance test is carried out according to GB/T1734-1993 detection method for gasoline resistance of paint films at part 8.1, and is respectively soaked for 2h and 6h, and the neutral salt spray resistance performance test is carried out according to GB/T1771-2007 determination of performances of colored paint and varnish in neutral salt spray resistance, and the coating performance test results of the epoxy resins prepared by the examples and the comparative examples after the coatings prepared according to the coating formula provided by the invention are shown in the following table 1.
TABLE 3 product Performance test in examples and comparative examples
As can be seen from the comparison of examples 1-4 and comparative examples 1-4 in Table 1, the epoxy resin obtained by the invention and 50/50 polyester resin are mixed to prepare the self-matting powder coating through the mutual matching and synergistic action of the components, no additional matting agent is required to be added, the glossiness of the coating film is basically 10-20%, and the gasoline resistance and the neutral salt fog resistance are excellent.
Comparative example 1 because equal molar amount of tartaric acid was changed to succinic acid, the chain segment of the final product lacked active hydroxyl groups, and the obtained powder coating could not be effectively delustred after curing, and had a high gloss;
in comparative example 2, octafluoro adipic acid is replaced by adipic acid with equal molar quantity, although the technical indexes of the product such as acid value, epoxy equivalent and the like are basically consistent, no fluorine element exists in the chain segment, so that the hydrophobic and oleophobic capabilities of the chain segment are reduced, and after the octafluoro adipic acid and the polyester resin are cured, the gasoline resistance and the neutral salt spray resistance of the chain segment are supported only by high functionality, and the gasoline resistance and the neutral salt spray resistance of the chain segment for a long time are obviously deteriorated;
in comparative example 3, citric acid and triglycidyl isocyanurate with multiple functionalities are not used, and instead, the epoxy resin intermediate is used alone as a product for performance test, and because the epoxy resin intermediate has relatively low molecular weight, low functionality and single activity of epoxy functional groups, the epoxy resin intermediate has an unobvious extinction effect and high gloss after being cured with 50/50 polyester resin; and because of the insufficiency of functionality and crosslinking degree, the shock resistance, the gasoline resistance and the neutral salt spray resistance are all poorer;
in comparative example 4, the commercially available general E-12 epoxy resin has only epoxy groups and single activity, and after being cured with 50/50 polyester resin, the epoxy resin gives a high-gloss coating film without matting effect. The appearance and the shock resistance of the coating film are good, and because the functionality of the common E-12 epoxy resin is low (the functionality is about 2), and the chain segment of the common E-12 epoxy resin does not contain functional elements such as fluorine, the gasoline resistance and the neutral salt spray resistance of the crosslinked coating film are obviously poor.
As can be seen from the data in the table, the epoxy resin obtained by adopting the raw materials and the method of the mixture ratio of the invention has excellent impact resistance, gasoline resistance and neutral salt spray resistance.
Claims (8)
1. The epoxy resin for the gasoline and salt fog resistant self-extinction 50/50 powder is characterized in that the main raw materials of the epoxy resin are bisphenol A, epichlorohydrin, sodium hydroxide, tartaric acid, octafluoro adipic acid, citric acid and triglycidyl isocyanurate; the epoxy resin comprises the following main raw materials in parts by mole: 5-10 parts of bisphenol A, 20-35 parts of epichlorohydrin, 30-50 parts of sodium hydroxide, 6-12 parts of tartaric acid, 3-7 parts of octafluoro adipic acid, 2-4 parts of citric acid and 7-12 parts of triglycidyl isocyanurate;
the preparation method of the epoxy resin for the gasoline and salt fog resistant self-extinction 50/50 powder comprises the following steps:
(1) adding triglycidyl isocyanurate into a reaction kettle, heating until the triglycidyl isocyanurate is molten, stirring, adding citric acid for crosslinking modification, stopping reaction, discharging, cooling to room temperature, and crushing to obtain modified triglycidyl isocyanurate;
(2) pumping a sodium hydroxide solution into a reaction kettle, heating, adding bisphenol A, adding a catalyst benzyltriethylammonium chloride, carrying out heat preservation reaction, adding epichlorohydrin, carrying out heat preservation reaction again, adding tartaric acid and octafluoro adipic acid, and continuing the heat preservation reaction;
(3) after the reaction is stopped, separating out a water phase and an epoxy resin phase, washing the epoxy resin phase with boiling water, and then carrying out reduced pressure dehydration on the epoxy resin to obtain an epoxy resin intermediate;
(4) heating an epoxy resin intermediate, melting at high temperature, adding the modified triglycidyl isocyanurate obtained in the step (1), performing chain extension and branching degree reaction, discharging at high temperature when the reaction is stopped, cooling the epoxy resin by using a steel belt with condensed water, crushing and granulating to obtain epoxy resin for solvent-resistant, excellent-salt-fog and self-extinction 50/50 powder;
in the step (1), stopping the reaction until the acid value of the reacted mixture reaches 60-80 mgKOH/g;
in the step (3), sampling and testing the epoxy equivalent of the epoxy resin, and stopping the reaction when the epoxy equivalent is 1000-1200 g/mol;
in the step (4), after the chain extension and the chain extension branching degree are reacted, the reaction is stopped when the epoxy equivalent of the resin is 700-750g/mol and the acid value is less than 3 mgKOH/g.
2. The epoxy resin for the gasoline and salt fog resistant and self-extinction 50/50 powder, as claimed in claim 1, wherein the dosage of the catalyst benzyltriethylammonium chloride is 0.1-0.2% of the molar weight of bisphenol A.
3. The epoxy resin for the gasoline and salt fog resistant self-extinction 50/50 powder of claim 1, wherein the epoxy equivalent of the epoxy resin is 700-750g/mol, and the softening point is 92-102 ℃.
4. The epoxy resin for the gasoline and salt spray resistant self-extinction 50/50 powder according to claim 1, which is melted by heating to 100-110 ℃ in step (1); pulverizing the mixture to particles of 50-80 μm.
5. The epoxy resin for the gasoline and salt fog resistant self-extinction 50/50 powder, as claimed in claim 1, wherein in the step (2), the solid content of the sodium hydroxide solution is 40-60%; adding a sodium hydroxide solution, and then keeping the temperature to 25-35 ℃; adding bisphenol A, and then carrying out heat preservation reaction for 1-2 h; adding epoxy chloropropane, and reacting for 2-4h at the temperature of 80-100 ℃; and (3) adding tartaric acid and octafluoro adipic acid, and then continuing to perform heat preservation reaction for 1-3 hours at 80-100 ℃.
6. The epoxy resin for the gasoline and salt spray resistant self-extinction 50/50 powder according to claim 1, wherein in the step (3), after the reaction is stopped, an aqueous phase and an epoxy resin phase are separated, and the epoxy resin phase is washed with boiling water for 3-5 times; the mass of water used each time when washing with boiling water is one fourth of the mass of the resin.
7. The epoxy resin for 50/50 powder with gasoline and salt fog resistance and self-extinction as claimed in claim 1, wherein in step (4), the epoxy resin intermediate is heated to 120-130 ℃ for high temperature melting; performing chain extension and branching degree extension reaction at 120-130 ℃ for 0.5-1.5 h.
8. The epoxy resin for the gasoline and salt fog resistant self-extinction 50/50 powder of claim 1, the preparation method comprising the steps of:
(1) adding triglycidyl isocyanurate into a reaction kettle, heating to 100-110 ℃ to melt the triglycidyl isocyanurate, starting stirring, then adding citric acid at one time to perform a crosslinking modification reaction, stopping the reaction when the acid value of a reaction mixture reaches 60-80 mgKOH/g, discharging, cooling to room temperature, and crushing into particles of 50-80 mu m to obtain modified triglycidyl isocyanurate;
(2) pumping a sodium hydroxide solution with the solid content of 40-60% into a reaction kettle, heating to 25-35 ℃, adding bisphenol A, and simultaneously adding a catalyst benzyltriethylammonium chloride, wherein the addition amount of benzyltriethylammonium chloride is 0.1-0.2% of the molar amount of bisphenol A; reacting for 1-2 h under heat preservation, then adding epoxy chloropropane, reacting for 2-4h under heat preservation at 80-100 ℃, finally adding tartaric acid and octafluoro adipic acid, and continuing to react for 1-3 h under heat preservation at 80-100 ℃;
(3) sampling and testing the epoxy equivalent of the epoxy resin, stopping the reaction when the epoxy equivalent is 1000-1200g/mol, separating out a water phase and an epoxy resin phase, washing the epoxy resin phase with boiling water for 3-5 times, wherein the mass of water is one fourth of the mass of the resin each time, and finally performing reduced pressure dehydration on the epoxy resin to obtain an epoxy resin intermediate;
(4) heating the epoxy resin intermediate to 120-130 ℃ for high-temperature melting, then adding modified triglycidyl isocyanurate, carrying out chain extension and chain extension branching degree reaction for 0.5-1.5 h at 120-130 ℃, stopping the reaction when the epoxy equivalent of the resin is 700-750g/mol and the acid value is less than 3mgKOH/g, discharging at high temperature while the resin is hot, cooling the epoxy resin by using a steel belt with condensed water, and then crushing and granulating to obtain the epoxy resin for the self-extinction 50/50 powder with excellent solvent resistance and salt fog resistance.
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| JP2001115086A (en) * | 1999-10-15 | 2001-04-24 | Shikoku Chem Corp | Epoxy/polyester powder coating composition |
| CN108929441A (en) * | 2018-03-05 | 2018-12-04 | 富思特新材料科技发展股份有限公司 | A kind of preparation method from delustring dumb light lotion with Shuangzi structure |
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| DE60017470T2 (en) * | 2000-02-14 | 2005-12-29 | Taiyo Ink Mfg. Co. Ltd. | PHOTO- OR HEAT-HARDENING COMPOSITIONS FOR MAKING MATTER FILMS |
| US7223477B2 (en) * | 2000-12-05 | 2007-05-29 | Alpha Coating Technologies, Llc | Coating powders having enhanced flexability |
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| JP2001115086A (en) * | 1999-10-15 | 2001-04-24 | Shikoku Chem Corp | Epoxy/polyester powder coating composition |
| CN108929441A (en) * | 2018-03-05 | 2018-12-04 | 富思特新材料科技发展股份有限公司 | A kind of preparation method from delustring dumb light lotion with Shuangzi structure |
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Denomination of invention: Epoxy resin and preparation method for gasoline and salt spray resistant, self extinguishing 50/50 powder Granted publication date: 20220722 Pledgee: Huizhou Mount Huangshan rural commercial bank Limited by Share Ltd. Pledgor: Huangshan Yuanrun New Material Technology Co.,Ltd. Registration number: Y2024980009943 |