CN103360575A - Aqueous organic salt modified epoxy ester resin, and preparation method and application thereof - Google Patents
Aqueous organic salt modified epoxy ester resin, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to an aqueous organic salt modified epoxy ester resin, and a preparation method and an application thereof. The modified epoxy ester resin is prepared by using the following raw materials, by mass, 7-9% of an epoxy resin, 26-34% of vegetable oil fatty acid, 3-5% of organic sulfonate, 9-16% of diol, 5-10% of polyol, 17-21% of diacid, 1.5-3.0% of polyacid, 0.06-0.08% of an esterification catalyst, 16-18% of a cosolvent and 0.3-0.5% of amine or ammonia. The invention also relates to the preparation method of the aqueous organic salt modified epoxy ester resin, and the application of the aqueous organic salt modified epoxy ester resin. The aqueous organic salt modified epoxy ester resin has a good water soluble stability and a good salt spray resistance.
Description
Technical field
The present invention relates to a kind of water-based organic salt modified epoxy ester resin and preparation method thereof and application.
Background technology
The water-base epoxy ester paint is because its excellent rustless property and the feature of environmental protection have splendid use value in the metal rust preventing field.The epoxy ester resin Water-borne modification adopts salt forming method usually, namely synthesizes first the epoxy ester resin that also has carboxyl, uses in the alkali and formation salt again, reaches water-soluble purpose.
CN101851396A discloses a kind of water-base epoxy ester resin composition and preparation method thereof on October 06th, 2010, it is with the vinyl monomer modified epoxy ester resin, with in the ammonia and after add water-dispersion and obtain water-base epoxy ester resin.The method residual vinyl monomer is more, and smell is heavy, and resinous acid value is higher, in and alkali number larger, ester bond facile hydrolysis fracture under alkaline environment, stable resin is not good enough.
CN102757551A discloses a kind of waterborne epoxy modified Synolac and preparation method thereof on October 31st, 2012, and it prepares the high acid value epoxy alkyd resin with trimellitic acid 1,2-anhydride, to obtain ammonium salt with resin in the ammonia.The equally ester linkage hydrolyzing fracture in alkaline environment of this resin, profit layering in the storage process, relatively poor with the standby coating of this resin salt fog resistance of filming.
CN102391439A disclosed a kind of preparation method of epoxy ester modified water-based alkyd resin in 03 month on the 28th in 2012, the method prepares first the epoxy ester modified alkyd resin, make the water-soluble epoxy ester modified alkyd resin with the addition reaction under the initiator effect of 2-acrylamide-2-methyl propane sulfonic again, the difficult control of the method technological process, the easy gel of resin.
Summary of the invention
Technical problem to be solved by this invention is, a kind of water-soluble good stability is provided, and water-based organic salt modified epoxy ester resin that salt fog resistance is good and preparation method thereof utilizes epoxy ester resin of the present invention can prepare bottom surface unification rust proof paint.
The technical solution adopted for the present invention to solve the technical problems is:
The present invention's water-based organic salt modified epoxy ester resin, raw material by following mass percent is made: Resins, epoxy 7～9%, vegetable fatty acids 26～34%, organic sulfonate 3～5%, dibasic alcohol 9～16%, polyvalent alcohol 5～10%, diprotic acid 17～21%, polyprotonic acid 1.5～3.0%, esterifying catalyst 0.06～0.08%, solubility promoter 16～18%, amine or ammonia 0.3～0.5%.
Further, described Resins, epoxy is one or more the mixture in E-06 Resins, epoxy, E-12 Resins, epoxy, the E-20 Resins, epoxy.
Further, described vegetable fatty acids is one or more the mixture in linolenic acid, dehydrated castor oleic acid, soy(a)-bean oil fatty acid, inferior eleostearic acid, cocinic acid, oleic acid, the ready denier oil acid.
Further, described organic sulfonate is the functional monomer that contains sulphonate-base, is selected from one or more the mixture in sodiosulfoisophthalic acid, terephthaldehyde's disulfonate acid, sulfonic group para Toluic Acid, the sulfonic group o-benzoic acid.
Further, described dibasic alcohol is one or more the mixture in ethylene glycol, propylene glycol, neopentyl glycol, 1,3-PD, the 1,3 butylene glycol.
Further, described polyvalent alcohol is one or more the mixture in glycerine, tetramethylolmethane, TriMethylolPropane(TMP), the trimethylolethane.
Further, described diprotic acid is one or more the mixture in m-phthalic acid, terephthalic acid, phthalic acid, Tetra hydro Phthalic anhydride, hexanodioic acid, tetrahydrophthalic anhydride, MALEIC ANHYDRIDE, the pentanedioic acid.
Further, described polyprotonic acid is trimellitic acid 1,2-anhydride.
Further, described esterifying catalyst is one or more the mixture in zinc oxide, lithium hydroxide, dodecyl tin laurate, n-butylstannoic acid, the isocaprylic acid tin.
Further, described solubility promoter is one or more the mixture in butyl glycol ether, propandiol butyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propyl carbinol, isopropylcarbinol, the 1-Methoxy-2-propyl acetate.
The preparation method of the present invention's water-based organic salt modified epoxy ester resin may further comprise the steps:
(1) takes by weighing raw material by following quality per distribution ratio: Resins, epoxy 7～9%, vegetable fatty acids 26～34%, organic sulfonate 3～5%, dibasic alcohol 9～16%, polyvalent alcohol 5～10%, diprotic acid 17～21%, polyprotonic acid 1.5～3%, esterifying catalyst 0.06～0.08%, solubility promoter 16～18%, amine or ammonia 0.3～0.5%;
(2) preparation of organic sulfonate carboxylate: with organic sulfonate, the dibasic alcohol that is equivalent to organic sulfonate treble amount, the esterifying catalyst of formula ratio 1/3rd adds in the reactor, after stirring is warming up to 160 ± 5 ℃, be warming up to 200～210 ℃ with 5 ± 1 ℃/15 minutes speed, insulation reaction to acid number less than 2mgKOH/g, obtain the organic sulfonate carboxylate;
(3) epoxy ester semi-loop reactant preparation: the esterifying catalyst of Resins, epoxy, vegetable fatty acids and formula ratio 1/3rd is added in the reactor, be warming up to 130 ± 5 ℃ and begin to stir, continue to be warming up to 180～185 ℃, reaction 1.0～1.5h;
(4) esterifying catalyst of the dibasic alcohol of adding organic sulfonate carboxylate, remainder, polyvalent alcohol, diprotic acid, remainder in step (3) gained reactant, stirring is warming up to 160～165 ℃, then be warmed up to 225～230 ℃ with 5 ± 1 ℃/15 minutes speed, insulation is until reactant is transparent;
(5) detect acid number, when acid number is that 18～20mgKOH/g(then continues to reflux as being higher than this scope, can suitably replenish dimethylbenzene) time, be cooled to 180～185 ℃, add polyprotonic acid, at 180～185 ℃ of insulation 1.0～1.5h, cool to 155～150 ℃, add solubility promoter, speed with 300～500r/min stirs, and is cooled to 80～75 ℃, discharging, its solid acid number is 20～25mgKOH/g, and solid part is 80 ± 2%;
(6) this resin adds amine or ammonia to regulate pH value is 7.0～7.5, and the adding deionized water stirs with the speed of 300～500r/min, and obtaining solid part is that 40%(described " % " is mass percent) water-base epoxy ester resin.
The preparation method of the present invention's water-based organic salt modified epoxy ester resin adopts organic sulfonate to participate in reaction, introduces sulfonate groups at the epoxy ester resin molecule, improves the water-dilutable of resin.Its preparating mechanism is as follows: (1) organic sulfonate carries out esterification with dibasic alcohol first and generates the small molecules carboxylate that is rich in sulfonate; (2) Resins, epoxy and vegetable fatty acids carry out first the half ester reaction, carry out condensation reaction with diprotic acid, polyvalent alcohol, sulfonate carboxylate, polyprotonic acid again, after acid number is qualified, add solubility promoter, namely obtain water-based organic salt modified epoxy ester resin, this resin has water-dilutable owing to containing sulfonate groups, synthetic epoxy ester resin acid number is lower, do not need to add too many amine neutralization, ester bond is not easy hydrolytic cleavage, stability and water-tolerant.
The application of the present invention's water-based organic acid salt modified epoxy ester resin: can prepare the environment-friendly type industrial antirust coating, be widely used in various metal steel structure protection against corrosions aspect.
Compared with prior art, the present invention has the following advantages:
(1) introduce sulfonate groups in the resin, a small amount of sulfonate groups has resin under the condition of pH value 7.0-7.5 good water-soluble, and the resistant to hydrolysis ability of water-base resin improves, the coating shelf-stable;
(2) do not need to add reflux solvent in the resin building-up process, only need to add a small amount of solubility promoter, and the poisonous organic solvent such as containing benezene not, can prepare the environmentally friendly rust proof paint of low VOC;
(3) resin provides water-soluble by a small amount of sulfonate, the amine of interpolation seldom, the water resistance of filming is good; Adopt diprotic acid (m-phthalic acid), polyvalent alcohol (TriMethylolPropane(TMP)) modified epoxy ester resin in the resin preparation process simultaneously, can improve the salt spray resistance of filming;
(4) resin is water-soluble good, good mechanical stability, can with rust-stabilising pigment, filler together direct grinding distribution, the pigment of interpolation, wetting agent, dispersion agent seldom further improve water tolerance and the salt fog resistance of rust proof paint;
(5) this rust-proofing primer with water as thinner, the poisonous organic solvent such as containing benezene not, there is not the danger of burning, blast, poisoning and contaminate environment in VOC content (not moisture)≤160g/L; The water-base epoxy ester paint is selected anticorrosive pigment of environmental protection, and the product technology standard reaches solvent type epoxy ester priming paint regulation, paint film salt spray resistance 〉=300h; Water-base epoxy ester paint product room temperature storage 1 year, stable performance.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
The water-based organic salt modified epoxy ester resin of the present embodiment, component raw material by following quality is made: E-20 Resins, epoxy 71.7g, ready denier oil acid 334g, sodiosulfoisophthalic acid 33g, neopentyl glycol 126g, TriMethylolPropane(TMP) 57.4g, m-phthalic acid 178g, trimellitic acid 1,2-anhydride 28.6g, n-butylstannoic acid 0.75g, butyl glycol ether 171g, triethylamine 4g.
The preparation method may further comprise the steps:
(1) takes by weighing raw material: E-20 Resins, epoxy 71.7g, ready denier oil acid 334g, sodiosulfoisophthalic acid 33g, neopentyl glycol 126g, TriMethylolPropane(TMP) 57.4g, m-phthalic acid 178g, trimellitic acid 1,2-anhydride 28.6g, n-butylstannoic acid 0.75g, butyl glycol ether 171g, triethylamine 4g;
(2) preparation of organic sulfonate carboxylate: sodiosulfoisophthalic acid 33g, neopentyl glycol 99g, n-butylstannoic acid 0.25g are added in the four-hole boiling flask, stirring is warming up to 160 ℃, then be warming up to 200 ℃ with 5 ℃/15 minutes speed, insulation reaction to acid number less than 2mgKOH/g, get the organic sulfonate carboxylate, for subsequent use;
(3) epoxy ester semi-loop reactant preparation: E-20 Resins, epoxy 71.7g, ready denier oil acid 334g, n-butylstannoic acid 0.25g are added reactor, be warming up to 130 ℃ and begin to stir, continue to be warming up to 180 ℃, insulation reaction 1 hour;
(4) in step (3) gained reactant, add organic sulfonate carboxylate 126g, neopentyl glycol 27g, TriMethylolPropane(TMP) 57.4g, m-phthalic acid 178g, n-butylstannoic acid 0.25g, stirring is warming up to 160 ℃, then be warmed up to 225 ℃ with 5 ℃/15 minutes speed, insulation is until reactant is transparent;
(5) detect acid number, acid number is 18mgKOH/g, is cooled to 180 ℃, adds trimellitic acid 1,2-anhydride 28.6g, at 180 ℃ of insulation 1.5h, be cooled to 155 ℃, add butyl glycol ether 171g, stir with 400r/min speed, be cooled to 80 ℃, discharging, obtaining acid number is 22mgKOH/g, solid part is 80% organic salt modified epoxy ester resin;
(6) add triethylamine (4g) at above-mentioned organic acid salt modified epoxy ester resin, regulating the pH value is 7.0, then adds deionized water 851g, stirs with the speed of 400r/min, obtains solid part and be 40% water-based organic acid salt modified epoxy ester resin A.
Embodiment 2
The water-based organic salt modified epoxy ester resin of the present embodiment, component raw material by following each quality is made: E-12 Resins, epoxy 77g, inferior eleostearic acid 264g, sodiosulfoisophthalic acid 33g, neopentyl glycol 132g, TriMethylolPropane(TMP) 78g, m-phthalic acid 204g, trimellitic acid 1,2-anhydride 18g, n-butylstannoic acid 0.75g, butyl glycol ether 177g, N, N-dimethylethanolamine 3g.
The preparation method may further comprise the steps:
(1) takes by weighing raw material: E-12 Resins, epoxy 77g, inferior eleostearic acid 264g, sodiosulfoisophthalic acid 33g, neopentyl glycol 132g, TriMethylolPropane(TMP) 78g, m-phthalic acid 204g, trimellitic acid 1,2-anhydride 18g, n-butylstannoic acid 0.75g, butyl glycol ether 177g, N, N-dimethylethanolamine 3g;
(2) preparation of organic sulfonate carboxylate: sodiosulfoisophthalic acid 33g, neopentyl glycol 99g, n-butylstannoic acid 0.25g are added in the reactor, stirring is warming up to 160 ℃, then be warming up to 200 ℃ with 5 ℃/15 minutes speed, insulation reaction to acid number less than 2mgKOH/g, get the organic acid salt carboxylate, for subsequent use;
(3) epoxy ester semi-loop reactant preparation: E-12 Resins, epoxy 77g, inferior eleostearic acid 264g, n-butylstannoic acid 0.25g are added reactor, be warming up to 135 ℃ and begin to stir, continue to be warming up to 180 ℃, insulation reaction 1.0 hours;
(4) in step (3) gained reactant, add organic sulfonate carboxylate 132g, neopentyl glycol 33g, TriMethylolPropane(TMP) 78g, m-phthalic acid 204g, n-butylstannoic acid 0.25g, stirring is warming up to 160 ℃, then be warmed up to 225 ℃ with 5 ± 1 ℃/15 minutes speed, insulation is until reactant is transparent;
(5) detect acid number, acid number is 20mgKOH/g, is cooled to 180 ℃, adds trimellitic acid 1,2-anhydride 18g, at 185 ℃ of insulation 1h, be cooled to 150 ℃, add butyl glycol ether 177g, stir with the speed of 500r/min, be cooled to 80 ℃, discharging, obtaining acid number is 25mgKOH/g, solid part is 80% organic salt modified epoxy ester resin;
(6) add N at above-mentioned organic acid salt modified epoxy ester resin, N-dimethylethanolamine (3g), regulating the pH value is 7.2, then adds deionized water 852g, speed with 500r/min stirs, and obtains solid part and be 40% water-based organic acid salt modified epoxy ester resin B.
Embodiment 3
The water-based organic salt modified epoxy ester resin of the present embodiment, component raw material by following each quality is made: E-06 Resins, epoxy 71g, soy(a)-bean oil fatty acid 296g, sodiosulfoisophthalic acid 31g, neopentyl glycol 124g, TriMethylolPropane(TMP) 93g, Tetra hydro Phthalic anhydride 184g, trimellitic acid 1,2-anhydride 27g, n-butylstannoic acid 0.75g, butyl glycol ether 180g, ammoniacal liquor 3.1g.
The preparation method may further comprise the steps:
(1) takes by weighing raw material: E-06 Resins, epoxy 71g, soy(a)-bean oil fatty acid 296g, sodiosulfoisophthalic acid 31g, neopentyl glycol 124g, TriMethylolPropane(TMP) 93g, Tetra hydro Phthalic anhydride 184g, trimellitic acid 1,2-anhydride 27g, n-butylstannoic acid 0.75g, butyl glycol ether 180g, ammoniacal liquor 3.1g;
(2) preparation of organic acid salt carboxylate: sodiosulfoisophthalic acid 31g, neopentyl glycol 93g, n-butylstannoic acid 0.25g are added in the reactor, stirring is warming up to 160 ℃, then to rise 5 ℃ temperature rise rate in per 15 minutes, be warming up to 200 ℃, insulation reaction to acid number less than 2mgKOH/g, get the organic acid salt carboxylate, for subsequent use;
(3) epoxy ester semi-loop reactant preparation: E-06 Resins, epoxy 71g, soy(a)-bean oil fatty acid 296g, n-butylstannoic acid 0.25g are added reactor, be warming up to 135 ℃ and begin to stir, continue to be warming up to 180 ℃, insulation reaction 1 hour;
(4) in step (3) gained reactant, add organic sulfonate carboxylate 120g, neopentyl glycol 31g, TriMethylolPropane(TMP) 93g, Tetra hydro Phthalic anhydride 184g, n-butylstannoic acid 0.25g, stir, after being warming up to 160 ℃, be warmed up to 225 ℃ with 5 ± 1 ℃/15 minutes speed, insulation is until reactant is transparent;
(5) detect acid number, acid number is 20mgKOH/g, is cooled to 180 ℃, add trimellitic acid 1,2-anhydride 27g, 185 ℃ the insulation 1h, to acid number be 25mgKOH/g, lower the temperature 150 ℃, add butyl glycol ether 180g, speed with 500r/min stirs, and is cooled to 80 ℃, discharging, obtaining acid number is 25mgKOH/g, and solid part is 80% organic acid salt modified epoxy ester resin;
(4) add ammoniacal liquor (3.1g) at above-mentioned organic acid salt modified epoxy ester resin, regulating the pH value is 7.2, then adds deionized water 850g, stirs with the speed of 400r/min, obtains solid part and be 40% water-based organic acid salt modified epoxy ester resin C.
A, B, the C of above-mentioned water-base epoxy ester resin are deployed into water-base epoxy ester rust proof paint by the described proportioning of table 1, and its performance sees Table 2.
Table 1 water-based organic salt modified epoxy ester rust proof paint proportioning
Table 2 water-based organic salt modified epoxy ester rust proof paint performance
Claims (10)
1. water-based organic salt modified epoxy ester resin, it is characterized in that, made by the raw material of following mass percent: Resins, epoxy 7～9%, vegetable fatty acids 26～34%, organic sulfonate 3～5%, dibasic alcohol 9～16%, polyvalent alcohol 5～10%, diprotic acid 17～21%, polyprotonic acid 1.5～3.0%, esterifying catalyst 0.06～0.08%, solubility promoter 16～18%, amine or ammonia 0.3～0.5%.
2. water-based organic salt modified epoxy ester resin according to claim 1 is characterized in that: described Resins, epoxy is one or more the mixture in E-06 Resins, epoxy, E-12 Resins, epoxy, the E-20 Resins, epoxy.
3. water-based organic salt modified epoxy ester resin according to claim 1 and 2 is characterized in that: described vegetable fatty acids is one or more the mixture in linolenic acid, dehydrated castor oleic acid, soy(a)-bean oil fatty acid, paulownia linolic acid, cocinic acid, oleic acid, the ready denier oil acid.
4. water-based organic salt modified epoxy ester resin according to claim 1 and 2, it is characterized in that: described organic sulfonate is the functional monomer that contains sulphonate-base, is selected from one or more the mixture in sodiosulfoisophthalic acid, terephthaldehyde's disulfonate acid, sulfonic group para Toluic Acid, the sulfonic group o-benzoic acid.
5. water-based organic salt modified epoxy ester resin according to claim 1 and 2 is characterized in that: described dibasic alcohol is one or more the mixture in ethylene glycol, propylene glycol, neopentyl glycol, 1,3-PD, the 1,3 butylene glycol.
6. water-based organic salt modified epoxy ester resin according to claim 1 and 2 is characterized in that: described polyvalent alcohol is one or more the mixture in glycerine, tetramethylolmethane, TriMethylolPropane(TMP), the trimethylolethane.
7. water-based organic salt modified epoxy ester resin according to claim 1 and 2 is characterized in that: described diprotic acid is one or more the mixture in m-phthalic acid, terephthalic acid, phthalic acid, Tetra hydro Phthalic anhydride, hexanodioic acid, tetrahydrophthalic anhydride, maleic anhydride, the pentanedioic acid.
8. water-based organic salt modified epoxy ester resin according to claim 1 and 2, it is characterized in that: described polyprotonic acid is trimellitic acid 1,2-anhydride.
9. the preparation method of a water-based organic salt modified epoxy ester resin as claimed in claim 1 is characterized in that, comprises the following steps:
(1) takes by weighing raw material by following quality per distribution ratio: Resins, epoxy 7～9%, vegetable fatty acids 26～34%, organic sulfonate 3～5%, dibasic alcohol 9～16%, polyvalent alcohol 5～10%, diprotic acid 17～21%, polyprotonic acid 1.5～3%, esterifying catalyst 0.06～0.08%, solubility promoter 16～18%, amine or ammonia 0.3～0.5%;
(2) preparation of organic sulfonate carboxylate: with organic sulfonate, the dibasic alcohol that is equivalent to organic sulfonate treble amount, the esterifying catalyst of formula ratio 1/3rd adds in the reactor, after stirring is warming up to 160 ± 5 ℃, be warming up to 200～210 ℃ with 5 ± 1 ℃/15 minutes speed, insulation reaction to acid number less than 2mgKOH/g, obtain the organic sulfonate carboxylate;
(3) epoxy ester semi-loop reactant preparation: the esterifying catalyst of Resins, epoxy, vegetable fatty acids and formula ratio 1/3rd is added in the reactor, be warming up to 130 ± 5 ℃ and begin to stir, continue to be warming up to 180～185 ℃, reaction 1.0～1.5h;
(4) esterifying catalyst of the dibasic alcohol of adding organic sulfonate carboxylate, remainder, polyvalent alcohol, diprotic acid, remainder in step (3) gained reactant, stirring is warming up to 160～165 ℃, then be warmed up to 225～230 ℃ with 5 ± 1 ℃/15 minutes speed, insulation is until reactant is transparent;
(5) detect acid number, when acid number is 18～20mgKOH/g, be cooled to 180～185 ℃, add polyprotonic acid, at 180～185 ℃ of insulation 1.0～1.5h, cool to 155～150 ℃, add solubility promoter, stir with the speed of 300～500r/min, be cooled to 80～75 ℃, discharging, its solid acid number is 20～25mgKOH/g, solid part is 80 ± 2%;
(6) this resin adds amine or ammonia to regulate pH value is 7.0～7.5, and the adding deionized water stirs with the speed of 300～500r/min, obtains solid part and be 40% water-base epoxy ester resin.
10. a water-based organic salt modified epoxy ester resin as claimed in claim 1 is in the application of environment-friendly type industrial antirust coating.
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| CN107540819A (en) * | 2017-09-04 | 2018-01-05 | 山东奔腾漆业股份有限公司 | Dispersible epoxy ester resin and preparation method thereof in a kind of water |
| CN108690466A (en) * | 2018-06-06 | 2018-10-23 | 长木（宁波）新材料科技有限公司 | A kind of water-base epoxy ester and preparation method thereof based on bio-based materials |
| CN108690466B (en) * | 2018-06-06 | 2020-07-24 | 长木（宁波）新材料科技有限公司 | Waterborne epoxy ester based on bio-based material and preparation method thereof |
| CN110183678B (en) * | 2019-06-14 | 2022-01-25 | 长沙学院 | Water-based hyperbranched polyester resin and preparation method and application thereof |
| CN110183678A (en) * | 2019-06-14 | 2019-08-30 | 长沙学院 | A kind of aqueous hyperbranched polyester resin and its preparation method and application |
| KR20220016535A (en) * | 2020-08-03 | 2022-02-10 | (주)디어스아이 | Synthesis method of epoxy ester resin for food coating |
| KR102417469B1 (en) * | 2020-08-03 | 2022-07-12 | (주)디어스아이 | Synthesis method of epoxy ester resin for food coating |
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