CN116082647A - Water-soluble polyester modified epoxy resin and preparation method thereof - Google Patents
Water-soluble polyester modified epoxy resin and preparation method thereof Download PDFInfo
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- CN116082647A CN116082647A CN202310142146.9A CN202310142146A CN116082647A CN 116082647 A CN116082647 A CN 116082647A CN 202310142146 A CN202310142146 A CN 202310142146A CN 116082647 A CN116082647 A CN 116082647A
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 107
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 107
- 229920000728 polyester Polymers 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims description 13
- 239000002253 acid Substances 0.000 claims abstract description 52
- 239000000203 mixture Substances 0.000 claims abstract description 44
- 229920001225 polyester resin Polymers 0.000 claims abstract description 31
- 239000004645 polyester resin Substances 0.000 claims abstract description 31
- 239000000539 dimer Substances 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims description 28
- 150000007519 polyprotic acids Polymers 0.000 claims description 19
- 239000006184 cosolvent Substances 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229920005862 polyol Polymers 0.000 claims description 4
- 150000003077 polyols Chemical class 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- 239000003973 paint Substances 0.000 abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- 238000000576 coating method Methods 0.000 abstract description 13
- 239000011248 coating agent Substances 0.000 abstract description 11
- 239000007787 solid Substances 0.000 abstract description 10
- 150000003839 salts Chemical class 0.000 abstract description 8
- 239000006185 dispersion Substances 0.000 abstract description 7
- 239000000853 adhesive Substances 0.000 abstract description 6
- 230000001070 adhesive effect Effects 0.000 abstract description 6
- 238000005054 agglomeration Methods 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 5
- 238000001879 gelation Methods 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000007711 solidification Methods 0.000 abstract description 3
- 230000008023 solidification Effects 0.000 abstract description 3
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 3
- 239000010935 stainless steel Substances 0.000 abstract description 3
- 239000005028 tinplate Substances 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 16
- 238000001035 drying Methods 0.000 description 9
- 239000000839 emulsion Substances 0.000 description 8
- 150000005846 sugar alcohols Polymers 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical group CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000005711 Benzoic acid Substances 0.000 description 3
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 3
- 235000010233 benzoic acid Nutrition 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000007689 inspection Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 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 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000002562 thickening agent 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block 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
- C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C09D187/005—Block or graft polymers not provided for in groups C09D101/00 - C09D185/04
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
Abstract
The invention provides a water-soluble polyester modified epoxy resin, which comprises, by weight, 36-38 parts of a water-soluble polyester mixture, 38-42 parts of an epoxy resin, 9-11 parts of a dimer acid mixture, 0.3-0.5 part of a catalyst and 10-12 parts of a solvent. The water-soluble polyester modified epoxy resin can enhance dispersion stability and improve the solid content of the water-based epoxy resin by using a specific water-soluble polyester resin mixture; effectively improves the thickness of the disposable coating and greatly reduces the use amount of the coating and the amount of organic volatile matters. Meanwhile, the prepared water-soluble polyester modified epoxy resin has the characteristics of low VOC and high solid content through the combined action of the epoxy resin and the components such as the dimer acid mixture in the system, and has the advantages of excellent adhesive force of paint films on metal substrates such as stainless steel plates, galvanized plates, electroplated plates and tinplate, quick solidification, thick coating, good paint film flexibility, good water resistance, excellent salt fog resistance, good stability, difficult agglomeration, gelation and the like.
Description
Technical Field
The invention belongs to the field of epoxy resin materials, and particularly relates to water-soluble polyester modified epoxy resin and a preparation method thereof.
Background
Due to the rapid development of society, consumers have higher and higher requirements on living environment, the coating industry is faced with industrial upgrading, the oily products are transformed into water-based low-VOC products, environment-friendly coatings are popular, and market share of the environment-friendly coatings is larger and larger.
The traditional aqueous epoxy emulsion has the characteristics of excellent technological properties, such as good adhesive force after curing, high paint film hardness, good salt spray resistance and the like. However, the method has the defects of low solid content, no thick coating film, low drying rate and the like.
Chinese patent CN114805744A discloses a waterborne polyurethane modified epoxy resin, a preparation method and application thereof, wherein epoxy groups are introduced through glycidol, the glycidol is adopted as a monomer to synthesize the polyurethane modified epoxy resin, and isocyanate monomers are firstly adopted to react with polyalcohol during preparation, so that isocyanate prepolymer containing-NCO is prepared; then introducing a hydrophilic modifier, and then reacting glycidol with the rest-NCO, wherein compared with the traditional preparation method, the epoxy resin has high epoxy equivalent, and excellent flexibility, elongation at break and impact resistance of a paint film are endowed after curing, the corrosion resistance is equivalent to that of the epoxy resin, the flexibility is as low as 1mm, and the adhesive force level is 1 grade; the elongation at break reaches 88-125%, and the impact resistance is more than 50cm. Chinese patent CN113512159A discloses a water-based single-component modified epoxy resin, a preparation method and application thereof, wherein the water-based single-component modified epoxy resin comprises epoxy resin, a modifier, an adhesion promoter, a catalyst, an initiator, a hydrophilic monomer, a cosolvent and a neutralizer, and the water-based single-component modified epoxy resin has the advantages of convenient use, long service life, quick drying, high gloss, good salt spray resistance, good adhesion to difficult-to-adhere substrates such as galvanized plates and aluminum plates, wide universality and environmental friendliness. However, the prepared epoxy resin still has the problems of low curing rate, poor thick coating usability, low solid content and the like.
Disclosure of Invention
Aiming at the problems, the water-soluble polyester modified epoxy resin provided by the invention has the characteristics of low VOC and high solid content, has good paint film adhesive force when in use, has excellent adhesive force to metal substrates such as stainless steel plates, galvanized plates, electroplated plates, tinplate and the like, has the advantages of quick solidification, thick coating, good paint film flexibility, good water resistance, excellent salt fog resistance, good stability, difficult agglomeration, gelation and the like.
The invention provides a water-soluble polyester modified epoxy resin, which comprises, by weight, 36-38 parts of a water-soluble polyester mixture, 38-42 parts of an epoxy resin, 9-11 parts of a dimer acid mixture, 0.3-0.5 part of a catalyst and 10-12 parts of a solvent.
Preferably, the water-soluble polyester mixture comprises, by weight, 12-14 parts of polybasic acid, 2-4 parts of maleic anhydride, 42-44 parts of monobasic acid, 17-19 parts of polyol, 2-4 parts of solvent and 17-20 parts of cosolvent.
The polyester resin can enhance dispersion stability and improve the solid content of emulsion. In the prior art, the solid content of the common epoxy emulsion is not more than 50%, and if the solid content is too high, the dispersion is uneven, and the dispersion stability is affected. In the present invention, however, the addition of a specific polyester resin can effectively enhance the dispersion stability. The inventor analyzes that the polyester resin is probably because the polyester resin is a linear macromolecular material, the molecular weight distribution is uniform, after being combined with the epoxy resin, the polyester resin can be uniformly dispersed in a system and form macromolecular crosslinking, so that the stability of the polyester resin is enhanced, and the polyester resin with specific molecular weight has better wettability, so that the polyester resin is more favorable for spreading a paint film.
Preferably, the number average molecular weight of the polyester resin in the water-soluble polyester resin mixture is 700 to 800; the hydroxyl percentage is less than 2 percent, and the acid value is 30 to 35mgKOH/g.
In order to effectively increase the curing and drying rate of the epoxy resin, it is further preferable that the hydroxyl group percentage of the polyester resin is 1%.
The inventors found that the aqueous polyester resin modified epoxy resin produced has an excellent drying rate only when the hydroxyl group percentage is less than 2%. The inventors analyzed that, probably due to the use of the polyester resin as a raw material for the preparation of the epoxy resin in the present invention, it was only used as an intermediate for the reaction. The prepared aqueous polyester resin modified epoxy resin is mainly cured of epoxy resin when cured, the curing agent is crosslinked with the epoxy resin, the intermediate only has an auxiliary effect, and if the hydroxyl content in the polyester resin is too high, the crosslinking of the epoxy resin is affected, the curing effect is poor, and the drying rate of the epoxy resin used as a paint film is affected.
Preferably, the polybasic acid is one or two of adipic acid or phthalic anhydride.
Preferably, the monoacid is one or more of benzoic acid and lauric acid.
Further preferably, the monoacid is benzoic acid.
Further preferably, the mass ratio of the polybasic acid to the monobasic acid is (1-1.5): (4-4.5).
Further preferably, the mass ratio of the polybasic acid to the monobasic acid is 1.3:4.3.
the inventors found that when a polybasic acid and a monobasic acid are used together, particularly when the mass ratio of the polybasic acid to the monobasic acid is (4 to 4.5): (1-1.5), the polyurethane resin obtained has a suitable degree of crosslinking and molecular weight. The inventor analyzes that only through the cooperation of polybasic acid and monoacid, the polyester resin with the number average molecular weight of 700-800, the hydroxyl percentage of less than 2% and the acid value of 25-30 mgKOH/g can be effectively prepared, and meanwhile, the prepared polyester resin has more branched chains due to the fact that the polybasic acid has more branched chains, the subsequent crosslinking during the reaction of the polyester resin and the epoxy resin is facilitated, and the stability of the epoxy resin is enhanced. However, the inventors found that when the amount of the polybasic acid is too large, the polyester resin has too large molecular weight, poor wettability, difficulty in dispersion in emulsion during use, and too high crosslinking degree with the epoxy resin, on one hand, the synthetic reaction is unstable and difficult to control, and at the same time, the emulsion is gelled due to excessive crosslinking, so that the use of the emulsion is seriously affected.
Preferably, the polyol is one or two of glycerol or trimethylolpropane.
Preferably, the solvent is xylene.
Preferably, the cosolvent is ethylene glycol monobutyl ether.
Preferably, the water-soluble polyester mixture is prepared by the following steps:
1) Mixing: putting polybasic acid, maleic anhydride, monobasic acid, polyalcohol and solvent into a reaction kettle, and introducing nitrogen for 5-15min;
2) Heating: heating is started, the temperature is raised to 200-220 ℃ in sections, heat preservation and reflux are carried out, and the acid value is 30-35 mgKOH/g;
3) And (3) cooling: cooling to 190-195 deg.c, vacuum pumping, cooling to below 120 deg.c, cooling to obtain water soluble polyester resin, and adding cosolvent to obtain the water soluble polyester mixture.
Further preferably, the specific steps of the sectional heating are as follows: (1) Heating to 145-150 ℃ for 1-2h, starting dehydration reflux, and preserving heat for 1-2h; (2) Heating to 155-165 ℃ for 0.5-1.5 h, and preserving heat for 1-2h; (3) heating to 175-185 ℃ for 1.5-2 h, and preserving heat for 1-2h; (4) Heating to 200-220 ℃ for 1.5-2.5h, maintaining the temperature and reflux, and reacting until the acid value AV is 30-35 mgKOH/g.
Further preferably, the water-soluble polyester mixture is prepared by the following steps:
1) Mixing: putting polybasic acid, maleic anhydride, monobasic acid, polyalcohol and solvent into a reaction kettle, and introducing nitrogen for 10min;
2) Heating: (1) Heating to 145-150 ℃ for 1-2h, starting dehydration reflux, and preserving heat for 1h; (2) heating to 160 ℃ for 1h, and preserving heat for 1h; (3) heating to 180 ℃ for 1.5-2 h, and preserving heat for 1h; (4) Heating to 200-210 ℃ for 2h, maintaining the temperature and reflux, and reacting until the acid value AV is 30-35 mgKOH/g.
3) And (3) cooling: cooling to 190-195 ℃, vacuumizing until the xylene content in the reaction kettle is less than or equal to 0.5%, cooling to below 120 ℃, cooling to obtain water-soluble polyester resin, and adding a cosolvent to obtain the water-soluble polyester mixture.
Preferably, the epoxy resins are epoxy resin E51 and epoxy resin E20.
Further preferably, the mass ratio of the epoxy resin E51 to the epoxy resin E20 is (2.4-2.6): (1.4-1.6).
Further preferably, the mass ratio of the epoxy resin E51 to the epoxy resin E20 is 2.5:1.5.
when two specific epoxy resin components are used together, particularly when the mass ratio of the epoxy resin E51 to the epoxy resin E20 is (2.4 to 2.6): (1.4-1.6), the epoxy resin formed has excellent curing rate and stability, good flexibility, good water resistance and excellent salt spray resistance when used as a paint film. If the epoxy resin E51 is too much, the hardness of a paint film becomes poor and the drying rate becomes slow, and if the epoxy resin E20 is too much, the prepared emulsion is easy to cause the problems of agglomeration, gelation and the like, and the use of the product is affected. The inventors analyzed that it is possible that the epoxy equivalent of the epoxy resin E51 is small, and if the content is too large, the paint film becomes soft; on the other hand, if the epoxy resin E20 has a large epoxy equivalent, excessive crosslinking tends to occur when the polyester resin is used for modifying the resin, and agglomeration and gelation are caused.
Preferably, the dimer acid mixture has a viscosity of 7500-8000 mPa.s/25 ℃.
Further preferably, the dimer acid mixture comprises a mono-acid, a dimer acid, a poly-acid.
Further preferably, the dimer acid mixture comprises, in weight percent: 4% or less of monopolyacid, 75-85% of dimer acid and 14-18% of poly acid.
Further preferably, the dimer acid mixture comprises, in weight percent: 2.7% of monopolyacid, 80.4% of dimer acid and 16.9% of poly acid.
Preferably, the catalyst is one or more of calcium isooctanoate and DMP-30.
Further preferably, the catalyst is calcium isooctanoate.
Preferably, the solvent is ethylene glycol monobutyl ether.
The second aspect of the invention provides a preparation method of water-soluble polyester modified epoxy resin, which comprises the following specific steps:
s1: adding the water-soluble polyester mixture, the epoxy resin, the dimer acid mixture and the catalyst into a reaction kettle, introducing nitrogen and heating;
s2: heating to 120-140 deg.C, and maintaining for 20-40min; and then heating to 170-180 ℃, preserving heat until the acid value is 30-35 mgKOH/g, cooling, and adding a cosolvent to obtain the water-soluble polyester modified epoxy resin.
Preferably, the preparation method of the water-soluble polyester modified epoxy resin comprises the following specific steps:
s1: adding the water-soluble polyester mixture, the epoxy resin, the dimer acid mixture and the catalyst into a reaction kettle, introducing nitrogen and heating;
s2: heating to 130 ℃, and preserving heat for 30min; and then heating to 170-180 ℃, preserving heat until the acid value is 25-30 mgKOH/g, cooling, and adding a cosolvent to obtain the water-soluble polyester modified epoxy resin. Compared with the prior art, the invention has the following beneficial effects:
the water-soluble polyester modified epoxy resin can enhance dispersion stability and improve the solid content of emulsion by using a specific water-soluble polyester resin mixture; the curing and drying rate of the epoxy resin is effectively improved. Meanwhile, the prepared water-soluble polyester modified epoxy resin has the characteristics of low VOC and high solid content through the combined action of the epoxy resin and the components such as the dimer acid mixture in the system, and has the advantages of excellent adhesive force of paint films on metal substrates such as stainless steel plates, galvanized plates, electroplated plates and tinplate, quick solidification, thick coating, good paint film flexibility, good water resistance, excellent salt fog resistance, good stability, difficult agglomeration, gelation and the like.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other.
Examples
Example 1
In one aspect, the embodiment provides a water-soluble polyester modified epoxy resin, which comprises, by weight, 37 parts of a water-soluble polyester mixture, 39 parts of an epoxy resin, 10 parts of a dimer acid mixture, 0.4 part of a catalyst and 11 parts of a solvent.
The water-soluble polyester mixture comprises, by weight, 13 parts of polybasic acid, 3 parts of maleic anhydride, 43 parts of monobasic acid, 18 parts of polyhydric alcohol, 3 parts of solvent and 18 parts of cosolvent.
The polybasic acid is adipic acid; the monobasic acid is benzoic acid; the polyalcohol is glycerol; the solvent is dimethylbenzene; the cosolvent is ethylene glycol monobutyl ether.
The preparation method of the water-soluble polyester mixture comprises the following steps:
1) Mixing: putting polybasic acid, maleic anhydride, monobasic acid, polyalcohol and solvent into a reaction kettle, and introducing nitrogen for 10min;
2) Heating: (1) Heating to 145 ℃ for 1h, starting dehydration reflux, and preserving heat for 1h; (2) heating to 160 ℃ for 1h, and preserving heat for 1h; (3) heating to 180 ℃ for 1.5h, and preserving heat for 1h; (4) The temperature was raised to 200℃over 2 hours, the reflux was maintained at a constant temperature, and the reaction was carried out until the acid value AV was 30mgKOH/g.
3) And (3) cooling: cooling to 190 ℃, vacuumizing until the xylene content in the reaction kettle is less than or equal to 0.5%, cooling to below 120 ℃, cooling to obtain water-soluble polyester resin, and adding a cosolvent to obtain the water-soluble polyester mixture.
The mass ratio of the epoxy resin is 2.5:1.5 epoxy resin E51 and epoxy resin E20, available from Shanghai Yuan Pont chemical Co., ltd.
The dimer acid mixture comprises the following components in percentage by weight: 2.7% of monopolyacid, 80.4% of dimer acid and 16.9% of poly acid. Purchased from Anhui Hongtai New Material Co., ltd., brand number is HY-17
The catalyst is calcium isooctanoate. The cosolvent is ethylene glycol monobutyl ether.
The second aspect of the embodiment provides a preparation method of water-soluble polyester modified epoxy resin, which comprises the following specific steps:
s1: adding the water-soluble polyester mixture, the epoxy resin, the dimer acid mixture and the catalyst into a reaction kettle, introducing nitrogen and heating;
s2: heating to 130 ℃, and preserving heat for 30min; and then heating to 170 ℃, preserving heat until the acid value is 25mgKOH/g, cooling, and adding a cosolvent to obtain the water-soluble polyester modified epoxy resin.
Example 2
In one aspect, the embodiment provides a water-soluble polyester modified epoxy resin, which comprises, by weight, 37 parts of a water-soluble polyester mixture, 39 parts of an epoxy resin, 10 parts of a dimer acid mixture, 0.4 part of a catalyst and 11 parts of a solvent.
The water-soluble polyester mixture comprises, by weight, 13 parts of polybasic acid, 3 parts of maleic anhydride, 43 parts of monobasic acid, 18 parts of polyhydric alcohol, 3 parts of solvent and 18 parts of cosolvent.
The specific sources of the raw materials in this example are the same as those in example 1.
In a second aspect of this embodiment, a method for preparing a water-soluble polyester modified epoxy resin is provided, and the specific steps are the same as in embodiment 1.
Example 3
In one aspect, the embodiment provides a water-soluble polyester modified epoxy resin, which comprises, by weight, 37 parts of a water-soluble polyester mixture, 39 parts of an epoxy resin, 10 parts of a dimer acid mixture, 0.4 part of a catalyst and 11 parts of a solvent.
The water-soluble polyester mixture comprises, by weight, 13 parts of polybasic acid, 3 parts of maleic anhydride, 43 parts of monobasic acid, 18 parts of polyhydric alcohol, 3 parts of solvent and 18 parts of cosolvent.
The specific sources of the raw materials in this example are the same as those in example 1.
In a second aspect of this embodiment, a method for preparing a water-soluble polyester modified epoxy resin is provided, and the specific steps are the same as in embodiment 1.
Example 4
In one aspect, the embodiment of the present invention provides a water-soluble polyester modified epoxy resin, which is similar to embodiment 1, and is different from embodiment 1 in that the mass ratio of the epoxy resin is 2.4:1.6 epoxy resin E51 and epoxy resin E20.
In a second aspect of this embodiment, a method for preparing a water-soluble polyester modified epoxy resin is provided, and the specific steps are the same as in embodiment 1.
Comparative example 1
In one aspect, the embodiment of the water-soluble polyester modified epoxy resin is the same as that of the embodiment 1, and the difference between the embodiment 1 and the embodiment 1 is that the polybasic acid is 20 parts.
In a second aspect of this embodiment, a method for preparing a water-soluble polyester modified epoxy resin is provided, and the specific steps are the same as in embodiment 1.
Comparative example 2
In one aspect, the embodiment of the present invention provides a water-soluble polyester modified epoxy resin, which is similar to embodiment 1, and is different from embodiment 1 in that the epoxy resin is epoxy resin E51.
In a second aspect of this embodiment, a method for preparing a water-soluble polyester modified epoxy resin is provided, and the specific steps are the same as in embodiment 1.
Comparative example 3
In one aspect, the present embodiment provides a water-soluble polyester modified epoxy resin, which is different from embodiment 1 in that the polyester resin is a commercially available polyester resin with a hydroxyl group percentage of 3%.
In a second aspect of this embodiment, a method for preparing a water-soluble polyester modified epoxy resin is provided, and the specific steps are the same as in embodiment 1.
Comparative example 4
In one aspect, the present embodiment provides a water-soluble polyester modified epoxy resin, which is similar to embodiment 1, and is different from embodiment 1 in that the polyester resin is a commercially available polyester resin with a molecular weight of 1500.
In a second aspect of this embodiment, a method for preparing a water-soluble polyester modified epoxy resin is provided, and the specific steps are the same as in embodiment 1.
Performance testing
1. Adhesion test: the test was carried out according to GBT 1720-1979 paint film adhesion assay.
2. Fineness: the tests were carried out according to GB 1724-1979 coating fineness determination.
3. Pencil hardness: the test was carried out according to GB 6739-1996 pencil test for hardness of coating film.
4. Drying rate: the tests were carried out according to GB 1728-1979 method for measuring drying time of coating putty film.
5. Water resistance: the test was carried out according to GBT 9274-1988 determination of liquid medium resistance of paints and varnishes.
6. Salt spray resistance: the test was carried out according to GBT 1765-1979, method for preparing paint film for measuring resistance to damp-heat, salt fog and weather (artificially accelerated).
7. Impact resistance: the test was performed according to GBT 20624.1-2006 section 1 drop hammer test (large area punch) for quick deformation (impact resistance) test of paints and varnishes.
8. Bending properties: the tests were carried out according to GB 1731-1993 paint film flexibility assay.
9. Drawing: the test was performed according to GBT 5210-2006, adhesion test by paint and varnish pull-off method.
And (3) preparing paint: the water-soluble polyester modified epoxy resins of examples 1 to 4 and comparative examples 1 to 4 were subjected to lacquer making,
the production process comprises the following steps:
and (3) a component A: weighing deionized water according to a formula, starting stirring, slowly adding a dispersing agent, a defoaming agent and bentonite, dispersing at a high speed for 15min, adding pigment and filler, continuously dispersing for 20 min, and grinding to obtain the product with fineness less than 30 mu m. Adding the water-based epoxy resin into the ground front slurry, starting stirring at a rotating speed of 500RPM/min, adding the cosolvent, the flatting agent, the anti-flash rust agent and the thickening agent, dispersing for 30min for inspection, and filtering and packaging by adopting a 120-mesh filter screen after passing the inspection.
And the component B comprises the following components: weighing the curing agent and deionized water according to the formula, starting stirring, dispersing at high speed for 5min, adding the anti-flash rust agent, dispersing for 15min for carrying out inspection, and filtering and packaging by adopting a 120-mesh filter screen after the curing agent and the deionized water are qualified.
The paint film prepared in example 1 was subjected to adhesion test, and the data obtained are shown in Table 1 below.
TABLE 1
The paint films prepared in examples 1 to 4 and comparative examples 1 to 4 were subjected to the performance tests of items 2 to 9 described above, and the data were obtained as shown in Table 2 below.
TABLE 2
Claims (10)
1. The water-soluble polyester modified epoxy resin is characterized in that the preparation raw materials comprise, by weight, 36-38 parts of a water-soluble polyester mixture, 38-42 parts of an epoxy resin, 9-11 parts of a dimer acid mixture, 0.3-0.5 part of a catalyst and 10-12 parts of a solvent.
2. The water-soluble polyester modified epoxy resin according to claim 1, wherein the water-soluble polyester mixture comprises, by weight, 12-14 parts of polybasic acid, 2-4 parts of maleic anhydride, 42-44 parts of monobasic acid, 17-19 parts of polyol, 2-4 parts of solvent and 17-20 parts of cosolvent.
3. The water-soluble polyester-modified epoxy resin according to claim 1, wherein the number average molecular weight of the polyester resin in the water-soluble polyester resin mixture is 700 to 800; the hydroxyl percentage is less than 2 percent, and the acid value is 25 to 30mgKOH/g.
4. The water-soluble polyester modified epoxy resin according to claim 2, wherein the mass ratio of the polybasic acid to the monobasic acid is (1-1.5): (4-4.5).
5. A water-soluble polyester modified epoxy resin according to claim 2, wherein said polyol is one or a mixture of two of glycerol or trimethylolpropane.
6. The water-soluble polyester modified epoxy resin according to claim 1, wherein the epoxy resin is an epoxy resin E51 and an epoxy resin E20.
7. The water-soluble polyester modified epoxy resin according to claim 6, wherein the mass ratio of the epoxy resin E51 to the epoxy resin E20 is (2.4-2.6): (1.4-1.6).
8. The water-soluble polyester modified epoxy resin according to claim 1, wherein the dimer acid mixture has a viscosity of 7500 to 8000 mPa-s/25 ℃.
9. The water-soluble polyester modified epoxy resin according to claim 1, wherein the catalyst is one or more of calcium isooctanoate and DMP-30.
10. The method for preparing a water-soluble polyester modified epoxy resin according to any one of claims 1 to 9, characterized by comprising the following specific steps:
s1: adding the water-soluble polyester mixture, the epoxy resin, the dimer acid mixture and the catalyst into a reaction kettle, introducing nitrogen and heating;
s2: heating to 120-140 deg.C, and maintaining for 20-40min; and then heating to 170-180 ℃, preserving heat until the acid value is 25-30 mgKOH/g, cooling, and adding a cosolvent to obtain the water-soluble polyester modified epoxy resin.
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