CN101914171B - Sulfonic acid ultraviolet (UV)-cured aqueous epoxy emulsion and preparation method thereof - Google Patents
Sulfonic acid ultraviolet (UV)-cured aqueous epoxy emulsion and preparation method thereof Download PDFInfo
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Abstract
The invention discloses sulfonic acid ultraviolet (UV)-cured aqueous epoxy emulsion and a synthetic method thereof. The method comprises the following steps of: performing an ring-opening esterification reaction on an epoxy resin and maleic anhydride under the action of a catalyst at the temperature of between 90 and 120 DEG C for 3 to 5 hours and ending the reaction after an acid value falls to 40 to 60 percent of an original acid value to obtain an epoxy maleic acid ester; heating the epoxy maleic acid ester to 50 to 90 DEG C, adding phosphorus trichloride serving as an acyl chlorinating agent dropwise, reacting at the temperature of between 50 and 90 DEG C for 2 to 3 hours to obtain epoxy fumarylchloride; and adjusting the pH value of sulfamic acid to be between 8 and 10 with alcoholic solution of NaOH, reacting the sulfamic acid and the epoxy fumarylchloride and adding water to disperse the reaction product so as to obtain the UV-cured aqueous epoxy emulsion. A product obtained by the method has the advantages of bright luster, high storage stability, high coating performance and the like and can be applied in the field of aqueous UV-cured coatings.
Description
Technical field
The present invention relates to a kind of aqueous epoxy emulsion, particularly relate to a kind of sulfonic acid ultraviolet (UV)-cured aqueous epoxy emulsion and compound method thereof.
Background technology
Photocuring is a kind of fast development " green " new technology.From the seventies in 20th century so far, radiation curing technology is more and more universal in the application of developed country, has been widely used in fields such as various coating, printing ink and sizing agent.Wherein, development of UV curing (ultraviolet light polymerization) technology is rapider.China's photo-curing material exploitation starts from early 1970s, begins suitability for industrialized production to the nineties, has become at present to be only second to the U.S. and the photocuring starting material of Japan and the big producing country of product.Though photocuring technology and material have had very fast development, also there are some problems in it, and application and the popularization, particularly reactive thinner and the volatile organic matter that have influenced it are to the infringement of human body and the pollution of environment.The aqueous photo-curing system can overcome these disadvantages.Waterborne radiation curable coating is to have combined the coating material solidified characteristics separately with water-borne coatings of traditional UV; Compare following advantage with traditional oiliness UV coating: (1) water is that most convenient obtains, the most cheap raw material; Water replaces reactive thinner dilution oligopolymer; Be easy to regulate viscosity, can realize the non-activity diluent formulation; (2), just there are not problems such as VOC, pungency and stink without reactive thinner; (3) applicable various coating equipment is especially to spraying safety; (4) can avoid because with the caused curing volumetric shrinkage of reactive thinner; (5) can realize the shallow layer coating, reduce cost; (6) coating equipment and container can clean by the use scavenging solution.In addition also solved the contradiction between hardness of film and the suppleness.
The water-based oligopolymer is the coating material solidified important component part of water-based UV, has determined the physical and mechanical propertiess such as hardness, snappiness, intensity and wear resistance of cured film, and has influenced laser curing velocity.The water-based oligopolymer sees from structure, and one will have and can carry out photopolymerisable group, like acryloxy, methacryloxy, vinyl, allyl group etc. because the acryloxy curing speed is the fastest, think the principal item of all kinds of vinyl resins.Two want to contain on the molecular chain hydrophilic radical of some amount; Like carboxyl, hydroxyl, amino, quaternary ammonium group, ether, carboxamido-group, sulfonic group etc.; The water-based oligopolymer that uses at present mainly contains propenoate, unsaturated polyester, urethane acrylate and epoxy acrylate etc.; These water-based oligopolymer mainly are to be hydrophilic radical with the carboxylate salt, and sulfonic acid type water-based oligopolymer is report and few at present.
Current; Epoxy acrylate is the maximum photocuring oligopolymer of consumption; There is research to generate epoxy acrylate, introduces carboxyl with the MALEIC ANHYDRIDE esterification again, with disperseing to obtain water-based UV cured epoxy acrylated oligomer with the back in the alkali with bisphenol A epoxide resin and vinylformic acid ring-opening reaction; Also available vinylformic acid and epoxy resin reacting epoxy propenoate again with the MALEIC ANHYDRIDE esterification by ring opening, are introduced carboxyl and unsaturated group, add the alkali neutralization, form UV curable water-borne aqueous epoxy emulsion.These methods all are to be hydrophilic radical with the carboxyl in the cis-butenedioic anhydride, compare with sulfonic acid group, the carboxyl electronegativity a little less than, the epoxy oligomer wetting ability that forms relatively poor, the stability in storage in later stage is also relatively poor.
Summary of the invention
The present invention will solve the problems of the technologies described above and be to provide a kind of sulfonic acid ultraviolet (UV)-cured aqueous epoxy resin emulsion and preparation method thereof, and its product has advantages such as color and luster is good, and stability in storage is good, and film performance is excellent.
In order to achieve the above object, the present invention adopts following technical scheme:
A kind of preparation method of sulfonic acid ultraviolet (UV)-cured aqueous epoxy emulsion may further comprise the steps:
(1) with epoxy resin and MALEIC ANHYDRIDE esterification by ring opening reaction under the effect of catalyzer; Epoxy resin and MALEIC ANHYDRIDE mol ratio are 1: 2～2.1; At 90～120 ℃ of reaction 3～5h, acid number is reduced to 40 of initial acid value～60% o'clock end reaction, and reaction obtains the epoxy maleic acid ester;
(2) the epoxy maleic acid ester is heated to 50～90 ℃, drips the acyl chlorinating agent phosphorus trichloride, the mol ratio of epoxy maleic acid ester and phosphorus trichloride is 1: 0.5～2, and 50～90 ℃ of reactions 2～3 hours, reaction obtained the epoxy fumaryl chloride;
(3) thionamic acid is regulated pH value to 8～10 with the NaOH alcoholic solution; React 1～3h with epoxy fumaric acid acyl chlorides at 50～80 ℃ then; The mol ratio of epoxy fumaric acid acyl chlorides and thionamic acid is 1: 2～2.1, adds water-dispersion and can obtain UV Curing Waterborne Epoxy Resin emulsion.
Epoxy resin is bisphenol A type epoxy resin E51 or E44 in the said step (1).
Thionamic acid is Sulphanilic Acid, N methyl taurine or taurine in the said step (3).
The mass concentration of described NaOH alcoholic solution is preferably 5%～10%.
Acid number is measured by following method in the said step (1):
(0.5～1g) places the 100mL Erlenmeyer flask to sample thief, adds the 25ml volume ratio and is 1: 1 ethanol and acetone mixing solutions sample is dissolved fully, drips the 0.1ml phenolphthalein indicator, with KOH-ethanol standard solution titration to pink till, counts;
Do blank test, the blank test method: get the 25ml volume ratio and be 1: 1 ethanol and acetone mixing solutions, drip the 0.1ml phenolphthalein indicator, with KOH-ethanol standard solution titration to pink till, count;
Acid number=56.1 * [(V-V
0) c/m]
In the formula: the KOH volume that V-titration sample is consumed, unit/ml;
V
0The blank KOH volume that is consumed of-titration, unit/ml; The m-sample mass, the g of unit;
The volumetric molar concentration of c-KOH vs, the mol/mL of unit.
A kind of sulfonic acid ultraviolet (UV)-cured aqueous epoxy emulsion is by method for preparing.
The preparation method of a kind of sulfonic acid ultraviolet (UV)-cured aqueous epoxy emulsion of the present invention can realize through following concrete steps:
(1) with epoxy resin and the reaction of MALEIC ANHYDRIDE esterification by ring opening, reaction obtains the epoxy maleic acid ester.
(2) above-mentioned epoxy maleic acid ester is heated to 50～90 ℃, drips the acyl chlorinating agent phosphorus trichloride, should obtain the epoxy fumaryl chloride.
(3) thionamic acid is regulated pH value to 8～10 with the NaOH alcoholic solution, again with the epoxy fumaryl chloride 50～80 ℃ of reactions.
(4) cooling adds water-dispersion and obtains UV curable water-borne epoxy emulsion.
The present invention is an initial feed with epoxy resin, along Succinic anhydried and Sulphanilic Acid, through esterification by ring opening, chloride and condensation, adds water-dispersion and obtains the finished product.
With respect to prior art, beneficial effect of the present invention is following:
(1) at first can improve the molecular reaction activity, introduce thionamic acid easily through chloride.
(2) synthetic route is simple, and side reaction is less, and is pollution-free, need not in the reaction process to purify to have the product of applications well performance with regard to passable obtaining.
(3) the present invention makes its epoxy resin that wetting ability arranged through introducing sulfonic acid group, through introducing acryloxy with the maleic acid anhydride reactant, can carry out photopolymerization reaction.
(4) to compare color and luster better for sulfonic acid ultraviolet (UV)-cured aqueous epoxy emulsion and carboxylic acid type, and stability in storage is more excellent.
(5) all there is electron-withdrawing group-carbonyl two key both sides in the made UV cured epoxy resin, make two keys more active, participate in reaction more easily, and photocuring takes place.
Embodiment
Below in conjunction with embodiment the present invention is described further, but the scope that the present invention requires to protect is not limited to the scope that embodiment explains.
Embodiment 1
(1) is 1: 2 in molar ratio, epoxy resin E51 and MALEIC ANHYDRIDE are mixed that initial acid value is the 190.6mg/g resin, behind 90 ℃ of reaction 1h, be warming up to 120 ℃, continue reaction.When acid number was reduced to the 96mg/g resin, stopped reaction promptly obtained the epoxy maleic acid ester.Acid number is measured by following method:
Sample thief (0.5～1g) places the 100mL Erlenmeyer flask, and the ethanol and the acetone mixing solutions that add the 25ml volume ratio and be 1: 1 dissolve sample fully,, drip the 0.1ml phenolphthalein indicator, with KOH-ethanol standard solution titration to pink till, count.Do blank test simultaneously.Blank test method: get the 25ml volume ratio and be 1: 1 ethanol and acetone mixing solutions, drip the 0.1ml phenolphthalein indicator, with KOH-ethanol standard solution titration to pink till, count.
Acid number=56.1 * [(V-V
0) c/m]
In the formula: the KOH volume that V-titration sample is consumed, ml;
V
0The blank KOH volume that is consumed of-titration, ml; The m-sample mass, g;
The volumetric molar concentration of c-KOH vs, mol/mL.
(2) the epoxy maleic acid ester is heated to 50 ℃, drips the chloride reagent phosphorus trichloride, the mol ratio of epoxy maleic acid ester and phosphorus trichloride is 1: l, and dropwise continued and react 2h down at 50 ℃, finish reaction.Obtaining product is the epoxy fumaryl chloride.
(3) under 60 ℃; It is that 5% NaOH alcoholic solution is regulated pH value to 8 that Sulphanilic Acid is used mass concentration, dropping epoxy fumaryl chloride, and 1～2h dropwises; The mol ratio of aniline sulfonic acid and epoxy fumaryl chloride is 2: 1; Dropwise the back and continue reaction 1h down, promptly obtain title product, add water-dispersion and obtain UV curable water-borne epoxy emulsion at 60 ℃.
Embodiment 2
(1) is 1: 2.1 in molar ratio, epoxy resin E51 and MALEIC ANHYDRIDE are mixed that initial acid value is the 178.4mg/g resin, behind 100 ℃ of reaction 1h, be warming up to 120 ℃, continue reaction.When acid number was reduced to the 89mg/g resin, stopped reaction promptly obtained the epoxy maleic acid ester.The measuring method of acid number is with embodiment 1.
(2) the epoxy maleic acid ester is heated to 90 ℃, drips the chloride reagent phosphorus trichloride, the mol ratio of epoxy maleic acid ester and phosphorus trichloride is 1: 0.5, dropwises continued and reacts 2h down at 90 ℃, finishes reaction.Obtaining product is the epoxy fumaryl chloride.
(3) be cooled under 80 ℃; Use mass concentration to regulate pH value to 9 as the 10%NaOH alcoholic solution Sulphanilic Acid, drip the epoxy fumaryl chloride, 1～2h dropwises; The mol ratio of aniline sulfonic acid and epoxy fumaryl chloride is 2.1: 1; Dropwise the back and continue reaction 1h down, promptly obtain title product, add water-dispersion and obtain UV curable water-borne epoxy emulsion at 80 ℃.
Embodiment 3
(1) is 1: 2 in molar ratio, epoxy resin E44 and MALEIC ANHYDRIDE are mixed that initial acid value is the 172.4mg/g resin, behind 100 ℃ of reaction 1h, be warming up to 120 ℃, continue reaction.When acid number was reduced to the 87mg/g resin, stopped reaction promptly obtained the epoxy maleic acid ester.The measuring method of acid number is with embodiment 1.
(2) the epoxy maleic acid ester is heated to 70 ℃, drips the chloride reagent phosphorus trichloride, the mol ratio of epoxy maleic acid ester and phosphorus trichloride is 1: 2, dropwises continued and reacts 2h down at 70 ℃, finishes reaction.Obtaining product is the epoxy fumaryl chloride.
(3) under 80 ℃; Use mass concentration to regulate pH value to 10 as the 5%NaOH alcoholic solution taurine, drip the epoxy fumaryl chloride, 1～2h dropwises; The mol ratio of taurine and epoxy fumaryl chloride is 2: 1; Dropwise the back and continue reaction 1h down, promptly obtain title product, add water-dispersion and obtain UV curable water-borne epoxy emulsion at 80 ℃.
Embodiment 4
(1) is 1: 2.1 in molar ratio, epoxy resin E44 and MALEIC ANHYDRIDE are mixed that initial acid value is the 178.4mg/g resin, behind 100 ℃ of reaction 1h, be warming up to 120 ℃, continue reaction.When acid number was reduced to the 89mg/g resin, stopped reaction promptly obtained the epoxy maleic acid ester.The measuring method of acid number is with embodiment 1.
(2) the epoxy maleic acid ester is heated to 70 ℃, drips the chloride reagent phosphorus trichloride, the mol ratio of epoxy maleic acid ester and phosphorus trichloride is 1: 1, dropwises continued and reacts 2h down at 70 ℃, finishes reaction.Obtaining product is the epoxy fumaryl chloride.
(3) under 70 ℃; Use mass concentration to regulate pH value to 9 as the 10%NaOH alcoholic solution N methyl taurine, drip the epoxy fumaryl chloride, 1～2h dropwises; The mol ratio of N methyl taurine and epoxy fumaryl chloride is 2: 1; Dropwise the back and continue reaction 1h down, promptly obtain title product, add water-dispersion and obtain UV curable water-borne epoxy emulsion at 70 ℃.
In the prior art, have and utilize that epoxy resin and cis-butenedioic anhydride esterification single stage method under the effect of tertiary amine catalyst is synthetic to have the UV Curing Waterborne Epoxy Resin of unsaturated group and hydrophilic radical, its oligopolymer component structure formula is:
Its concrete preparation technology is: the E-44 resin of adding 45.45 in the four-hole boiling flask that TM, prolong, tap funnel are housed; Make thinner with 5g acetone, after stirring is dissolved epoxy resin fully, add 19.6g MALEIC ANHYDRIDE and 0.65g triphenyl phosphorus; Recording initial acid value is the 160mgKOH/g resin; Be warming up to 100 ℃, when isothermal reaction to acid number will be for the 80mgKOH/g resin, stopped reaction.Be cooled to 50 ℃, add the 70g mass concentration and be in 6% the NaOH aqueous solution and disperse, obtain title product.
Make comparison sample with this, as shown in table 1 with the emulsion property index contrast of various embodiments of the present invention.Compare with the present invention; The difference of comparison sample mainly is a hydrophilic radical, but all there are gap in gained emulsion and film performance and products obtained therefrom of the present invention, as: emulsion appearance, appearance of film, stability in storage, hardness, sticking power, wear resistance and shock resistance etc.; Especially stability in storage aspect; In the embodiment of the invention 1～4, storage surpasses 6 months does not all have demixing phenomenon, and demixing phenomenon just appears in the contrast product storage time of sample above one month.The present invention has shown huge meliority especially.
Each embodiment of table 1 obtains emulsion property
Claims (4)
1. the preparation method of a sulfonic acid ultraviolet (UV)-cured aqueous epoxy emulsion is characterized in that may further comprise the steps:
(1) with epoxy resin and MALEIC ANHYDRIDE esterification by ring opening reaction under the effect of catalyzer; Epoxy resin and MALEIC ANHYDRIDE mol ratio are 1: 2～2.1; At 90～120 ℃ of reaction 3～5h, acid number is reduced to 40 of initial acid value～60% o'clock end reaction, and reaction obtains the epoxy maleic acid ester;
(2) the epoxy maleic acid ester is heated to 50～90 ℃, drips the acyl chlorinating agent phosphorus trichloride, the mol ratio of epoxy maleic acid ester and phosphorus trichloride is 1: 0.5～2, and 50～90 ℃ of reactions 2～3 hours, reaction obtained the epoxy fumaryl chloride;
(3) thionamic acid is regulated pH value to 8～10 with the NaOH alcoholic solution; React 1～3h with epoxy fumaric acid acyl chlorides at 50～80 ℃ then; The mol ratio of epoxy fumaric acid acyl chlorides and thionamic acid is 1: 2～2.1, adds water-dispersion and can obtain UV Curing Waterborne Epoxy Resin emulsion;
Epoxy resin is bisphenol A type epoxy resin E51 or E44 in the said step (1);
Thionamic acid is Sulphanilic Acid, N methyl taurine or taurine in the said step (3).
2. the preparation method of sulfonic acid ultraviolet (UV)-cured aqueous epoxy emulsion according to claim 1, it is characterized in that: the mass concentration of described NaOH alcoholic solution is 5%～10%.
3. the preparation method of sulfonic acid ultraviolet (UV)-cured aqueous epoxy emulsion according to claim 1 is characterized in that: acid number is measured by following method in the said step (1):
Sample thief 0.5～1g places the 100mL Erlenmeyer flask, and the ethanol and the acetone mixing solutions that add the 25ml volume ratio and be 1: 1 dissolve sample fully, drips the 0.1ml phenolphthalein indicator, with KOH-ethanol standard solution titration to pink till, counts;
Do blank test, the blank test method: get the 25ml volume ratio and be and be ethanol and acetone mixing solutions at 1: 1, drip the 0.1ml phenolphthalein indicator, till KOH-ethanol standard solution titration to pink, count;
Acid number=56.1 * [(V-V
0) c/m]
In the formula: the KOH volume that V-titration sample is consumed, unit/ml;
V
0The blank KOH volume that is consumed of-titration, unit/ml; The m-sample mass, the g of unit;
The volumetric molar concentration of c-KOH vs, the mol/mL of unit.
4. a sulfonic acid ultraviolet (UV)-cured aqueous epoxy emulsion is characterized in that by the said method preparation of claim 1.
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| CN104945974A (en) * | 2015-06-18 | 2015-09-30 | 成都纳硕科技有限公司 | UV-curable rust-proof environment-friendly coating |
| CN113861802A (en) * | 2020-06-30 | 2021-12-31 | 中国石油化工股份有限公司 | Liquid water-based epoxy resin, preparation method and application thereof, composition, coating product and preparation method thereof |
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| EP1647584A1 (en) * | 2004-10-13 | 2006-04-19 | Cytec Surface Specialties Austria GmbH | Aqueous epoxy resin systems |
| CN100412068C (en) * | 2006-08-18 | 2008-08-20 | 中国科学院广州化学研究所 | 2-amino ethyl sulfonic acid modified water epoxy resin and its preparation method and water epoxy emulsion prepared from said water epoxy resin |
| CN101200527B (en) * | 2007-11-30 | 2011-04-13 | 江南大学 | Liquid rubber modified epoxy acrylic ester prepolymer and use for preparation of ultraviolet curing paint |
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