CN101037497A - Preparation method of special epoxy resin for aqueous ultraviolet solidifying coating - Google Patents
Preparation method of special epoxy resin for aqueous ultraviolet solidifying coating Download PDFInfo
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- CN101037497A CN101037497A CN 200710034856 CN200710034856A CN101037497A CN 101037497 A CN101037497 A CN 101037497A CN 200710034856 CN200710034856 CN 200710034856 CN 200710034856 A CN200710034856 A CN 200710034856A CN 101037497 A CN101037497 A CN 101037497A
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Abstract
A method of preparing special epoxy resin for water ultraviolet light curing coating includes steps: a) using bisphenol A type epoxy resin and acrylic acid as raw material, adding catalyst of triethylamine and inhibitor of p-hydroxyanisole, reacting at 70-100 DEG C, after mass concentration of acrylic acid lower than 40-50%, raising temperature to 110-120 DEG C until acid value of the system lower than 5mgKOH/100g and generating epoxy acrylate; b) mixing the maleic anhydride and the epoxy acrylate according mole ratio of 0.8:1.05-0.8:1.05 and reacting water epoxy acrylate, adding catalyst triethylamine and inhibitor of p-hydroxyanisole under temperature of 60-100 DEG C and reacting for 1-3 h, adding dimethlyethanolamine to neutralizing, adding water and obtaining water epoxy acrylate with certain solid content.
Description
Technical field
The present invention relates to a kind of preparation method of special epoxy resin for UV-curable waterborne coatings.
Background technology
Resins, epoxy because have that cohesiveness height, shrinking percentage are low, characteristic such as good stability, physical strength height, processing characteristics are good, be widely used in the every field of national economy.But traditional epoxypaint is generally solvent type, be subjected to the restriction of aspects such as environmental pollution, construction safety, and aqueous epoxide resin paint has volatile organic compounds (VOC) but content is low, smell is less, the construction safety electrophoresis applies, can wash by water etc. advantage, application in the general industry paint field enlarges day by day, has substituted many habitual solvent based coatings.Advantages such as the coating material solidified special-purpose aqueous Resins, epoxy of UV (UV-light) is because of having cured film hardness height, and sticking power is good, and the high and chemical proofing of glossiness is good and being favored have become the focus of waterborne ultraviolet curing resin.
Epocryl synthetic traditional technology is introduced the photosensitive acryloyl group with the epoxy reaction in vinylformic acid and the Resins, epoxy, promptly makes Epocryl.All adopt the technology of nitrogen protection, dropwise addition of acrylic acid monomer, low-temp reaction, thereby this is because vinylformic acid thermopolymerization very easily takes place causes whole system gel under the situation of being heated.Yet the traditional technology condition exists obvious defects: 1. low temperature reaction down, and speed of response is slow, and the vinylformic acid transformation efficiency is low; 2. catalyzer and stopper consumption are big, and not only cost increases, and the more important thing is that the catalyzer that remains in the product can slowly cause the ring-opening polymerization of residual epoxide base at normal temperatures, has a strong impact on the shelf characteric of product; 3. adopt nitrogen protection easily volatile some starting material to be taken out of, influence reaction conversion ratio.The mode of 4. original process using dropwise addition of acrylic acid, the bad control of dropping process.
Summary of the invention
It is simpler that purpose of the present invention aims to provide a kind of technological process, can reduce cost, and the product color and luster is good, and viscosity is low, and storage stability is good, the preparation method of a kind of special epoxy resin for UV-curable waterborne coatings of more favourable industrial application.
The objective of the invention is to realize by following manner:
Technology of the present invention is: a, bisphenol A type epoxy resin and vinylformic acid are that raw material is 0.95～1.05 by epoxy group(ing) and acrylic acid mol ratio: 0.95～1.05 feeds intake, add catalyst of triethylamine and stopper MEHQ, reaction is 0.5～2 hour in the time of 70～100 ℃, behind vinylformic acid mass concentration decline 40-50%, be warming up to 110～120 ℃ of reactions 3～8 hours then, being lower than 5mgKOH/g to the system acid number is terminal point, generates epoxy acrylate;
B, be 0.8: 1.05～0.8: 1.05 water generation reaction epoxy acrylate in molar ratio with maleic anhydride and epoxy acrylate, add catalyst of triethylamine and stopper MEHQ, temperature of reaction should be 60～100 ℃.Reaction times added the dimethylethanolamine neutralization at 1-3 hour, added the water-based epoxy acrylic ester that pure water promptly gets certain solid content.
The catalyst consumption that a, b added in the step accounts for the total reaction system quality than 2-8 ‰; It is 2-6 ‰ that stopper accounts for the reaction system mass ratio.
The present invention has considered to influence the factors of Resins, epoxy and vinylformic acid reaction emphatically, and the inhibition that utilizes air adopts disposable feeding intake simultaneously to reduce the add-on of catalyzer and stopper, does not need dropwise addition of acrylic acid again, makes that reaction process is easier to be controlled.Traditional technology adopts the N2 protection, mainly is in order to protect stopper, can to make color and luster generation xanthochromia after the stopper oxidation that has.This synthesis technique does not need the N2 protection by selecting suitable stopper, can reach the color and luster requirement yet.Add the inhibition of oxygen, can suitably reduce the consumption of stopper.
Traditional technology adopts the method for dropwise addition of acrylic acid, is because the reaction of vinylformic acid and Resins, epoxy is very violent, easily polymerization reaction take place.Why we can disposablely feed intake, because we suitably improve temperature after being reacted to earlier material concentration decline 40～50% at a lower temperature again, thereby have overcome easy polymeric problem.
Technology of the present invention is also adjusted temperature of reaction and time.And its technology is optimized, make whole process operation simple, the time shortens, and reduces the input of stopper and catalytic amount, need not nitrogen protection.
Below optimize the research trial process of technology for the present invention.
One, the preparation of Epocryl
1.1 the selection of catalyst type
Also esterification can take place between the hydroxyl of Resins, epoxy and the vinylformic acid, therefore must select appropriate catalyst, make reaction help the reaction of carboxylic acid and epoxy group(ing).Selecting catalyst must be considered together with temperature of reaction, because the reaction of catalysis carboxyl and epoxide group effectively at high temperature of some catalyzer; And some catalyzer is just effective when low temperature, but can take place to decompose or catalyze side reactions when high temperature.The catalyst activity difference is different to the influence of indexs such as reaction times, terminal point balance acid number, product viscosity, colourity, product stability in storage.If reaction not exclusively, the residual epoxy group is being heated down for a long time in the system, and perhaps in the room temperature storage process, because catalyst action causes the residual epoxy polymerization probably, viscosity increases severely, even it is rotten to produce gel.
Catalyzer as carboxylic acid and epoxy reaction mainly is a bases, as tertiary amine, quaternary ammonium salt, KOH etc., is example with the triethylamine, and its catalytic mechanism is as follows:
That is: the lone-pair electron on the nitrogen-atoms of triethylamine have nucleophilicity, with the carbon of the mode attack epoxy group(ing) band portion positive charge of SN2, make epoxy ring-opening generate inner salt.Investigate triethylamine, KOH, three kinds of representational catalyzer of tetramethyl ammonium chloride in the test respectively, find that by a large amount of experiments in these several catalyzer, the catalytic effect of KOH is the poorest, be reacted to 5 hours after the system acid number still far away apart from reaction end; The tetramethyl ammonium chloride good catalytic activity, reacting balance, product is light, but the tetramethyl ammonium chloride price is expensive, and easily the moisture absorption stores difficulty; Triethylamine is cheap and easy to get, and is the liquid material, and is reinforced convenient, but its boiling point is lower, need be to vapor condensation to prevent its volatilization during reaction.Take all factors into consideration, select triethylamine as catalyst for reaction.
1.2 the selection of stopper
Stopper mainly contains Resorcinol, MEHQ etc.The present invention mainly investigates the polymerization inhibition effect of Resorcinol, two kinds of stoppers of MEHQ.Add-on is identical, no N
2Under the situation of protection, two kinds of stoppers are as shown in the table to the influence of synthetic epoxy acrylate:
Table 1 stopper is to the influence of synthetic epoxy acrylate
| Stopper | The gel situation | The product outward appearance |
| The Resorcinol MEHQ | Easily or not of gelling | Deep yellow is light yellow to Vandyke brown |
Stopper can be promptly and elementary free radical and the effect of chain free radical, and transfer reaction is stopped.As seen from Table 1, at no N
2Under the protection, when making stopper with Resorcinol, synthetic product color is that deep yellow is to Vandyke brown; this is because the easy oxidation of Resorcinol; MEHQ then is difficult for oxidation, and the synthetic color of resin is more shallow, therefore selects MEHQ better as stopper.
1.3 determining of reaction times
At the reaction initial period, the acid number of system descends very fast, and after reaction proceeded to certain hour, the acid number of system descended slower.This is because of initial reaction stage, the monomer concentration height, and system viscosity is little, and molecular diffusion is fast, the effective collision frequency height, reaction is carried out easily; After being reacted to certain hour, the epoxy group(ing) and the acrylic acid groups quantity that participate in reaction reduce, and system viscosity increases, the diffusion difficulty, and the molecule effective collision frequency descends, and speed of response descends.Reaction is 0.5～2 hour when therefore being chosen in 70～100 ℃, is warming up to 110～120 ℃ of reactions 3～8 hours then, and (preferred 3-6 hour), the system acid number is reduced to below the 5mgKOH/g, and the product color is yellowish transparent.
Two, the water-based epoxy acrylic ester is synthetic
2.1 Temperature Influence
When temperature is too low, speed of response is too slow, thereby the acid anhydrides transformation efficiency is too low, but temperature is when too high, because reaction is thermopositive reaction, cause the heat radiation difficulty, be unfavorable for that reaction carries out towards the esterification direction, and too high temperature can cause also two keys of system to be opened, the generation thermopolymerization, by repeatedly experiment, find that suitable temperature range is 60～100 ℃; Preferred 80-90 ℃.
2.2 the influence of catalyst type
The reaction of cis-butenedioic anhydride and Epocryl will could be carried out in the presence of appropriate catalyst smoothly.The present invention has investigated the catalytic effect of triethylamine, tetramethyl ammonium chloride two kinds of catalyzer.Reaction conditions is mol ratios such as hydroxyl and cis-butenedioic anhydride, and MEHQ is a stopper, and add-on is 5 ‰ (wt), reacts 90 minutes down at 80 ℃.The results are shown in Table 2.
Different as shown in Table 2 catalyzer does not have significant difference to the catalytic effect of synthetic water-based epoxy acrylic ester reaction, and from the cost consideration of raw materials for production, it is good adopting triethylamine.
Table 2 different catalysts is to the influence of cis-butenedioic anhydride transformation efficiency
| Catalyzer | 90min acid number (mgKOH/g) | Cis-butenedioic anhydride transformation efficiency (%) |
| The triethylamine tetramethyl ammonium chloride | 115.6 115.3 | 96.3 96.6 |
2.3 different neutralizing agents are to the xanthochromia influence of water-based system
Different neutralizing agents are very big to the xanthochromia influence of water-based epoxy acrylic ester, and some neutralizing agent can make coating that xanthochromia takes place gradually, influence the storage time of coating and the performance of filming.Triethylamine, trolamine and the dimethylethanolamine coating as neutralizing agent has been studied in this experiment respectively, places air three months, investigates the influence of three kinds of neutralizing agents to coating appearance.The results are shown in Table 3.
Table 3 neutralizing agent is to the influence of water-based epoxy acrylic ester xanthochromia
| Neutralizing agent | The time of in air, putting | Outward appearance |
| Triethylamine trolamine dimethylethanolamine | Individual month of two months one Wednesday | Slight xanthochromia, the serious xanthochromia of poor stability is xanthochromia not |
As can be seen from Table 3, when making neutralizing agent with triethylamine and dimethylethanolamine, the xanthochromia degree of coating is lighter, and trolamine is when making neutralizing agent, and xanthochromia is serious.This is because trolamine easily oxidation in air.Use simultaneously in the triethylamine and after, therefore the water-based system less stable adopts the neutralizing agent of dimethylethanolamine as water-base resin.
Embodiment
Embodiment 1
The technology of present embodiment is: a, be raw material by epoxy group(ing) and acrylic acid mol ratio by proportioning bisphenol A type epoxy resin and vinylformic acid be to feed intake at 0.95～1.05: 0.95～1.05, the bisphenol A type epoxy resin epoxy equivalent (weight) is 186g/eq.Add catalyst of triethylamine reaction 1.5 hours when accounting for 6 ‰, 90 ℃ of reaction system mass ratio 8 ‰ and stopper MEHQ, be reacted to vinylformic acid mass concentration decline 40-50% after, be warming up to 110 ℃ of reactions 5.5 hours then, generate epoxy acrylate;
B, be 0.8: 1.0 water generation reaction epoxy acrylate in molar ratio, add catalyst of triethylamine and account for reaction system mass ratio 8 ‰ and stopper MEHQ 6 ‰ that temperature of reaction is 80 ℃ with maleic anhydride and epoxy acrylate.Reaction times added the dimethylethanolamine neutralization, degree of neutralization 60% at 60 minutes.The adding pure water is made into the water-based epoxy acrylic ester of solid content 50%.
Gained water-based epoxy acrylic ester index is:
Outward appearance: colourless or yellowish transparent liquid
Rotary viscosity: 887mPas (25 ℃)
Acid number: 68.9mgKOH/g
Embodiment 2
The technology of present embodiment is: a, be raw material by epoxy group(ing) and acrylic acid mol ratio by proportioning bisphenol A type epoxy resin and vinylformic acid be to feed intake at 0.95～1.05: 0.95～1.05, the bisphenol A type epoxy resin epoxy equivalent (weight) is 189g/eq.Add catalyst of triethylamine reaction 1.5 hours when accounting for 5 ‰, 100 ℃ of reaction system mass ratio 5 ‰ and stopper MEHQ, after being reacted to the vinylformic acid mass concentration and dropping to 40-50%, be warming up to 115 ℃ of reactions 5.5 hours then, generate epoxy acrylate;
B, be 0.9: 1.0 water generation reaction epoxy acrylate in molar ratio, add catalyst of triethylamine and account for reaction system mass ratio 5 ‰ and stopper MEHQ 5 ‰ that temperature of reaction is 80 ℃ with maleic anhydride and epoxy acrylate.Reaction times added the dimethylethanolamine neutralization, degree of neutralization 85% at 90 minutes.The adding pure water is made into the water-based epoxy acrylic ester of solid content 50%.
Gained water-based epoxy acrylic ester index is:
Outward appearance: colourless or yellowish transparent liquid
Rotary viscosity: 900mPas (25 ℃)
Acid number: 72.5mgKOH/g
Embodiment 3
The technology of present embodiment is: a, be that raw material is 0.95～1.05 by epoxy group(ing) and acrylic acid mol ratio by proportioning bisphenol A type epoxy resin and vinylformic acid: 0.95～1.05 feeds intake.Add catalyst of triethylamine reaction 2 hours when accounting for 4 ‰, 100 ℃ of reaction system mass ratio 3 ‰ and stopper MEHQ, after being reacted to the vinylformic acid mass concentration and dropping to 40-50%, be warming up to 115 ℃ of reactions 5 hours then, generate epoxy acrylate;
B, be 1.0: 1.05 water generation reaction epoxy acrylates in molar ratio, add catalyst of triethylamine and account for reaction system mass ratio 3 ‰ and stopper MEHQ 4 ‰ that temperature of reaction is 85 ℃ with maleic anhydride and epoxy acrylate.Reaction times added the dimethylethanolamine neutralization at 90 minutes.The adding pure water is made into the water-based epoxy acrylic ester of solid content 50%.
Claims (2)
1, a kind of preparation method of special epoxy resin for UV-curable waterborne coatings, it is characterized in that: a, bisphenol A type epoxy resin and vinylformic acid are that raw material is 0.95～1.05 by epoxy group(ing) and acrylic acid mol ratio: 0.95～1.05 feeds intake, add catalyst of triethylamine and stopper MEHQ, reaction is 0.5～2 hour in the time of 70～100 ℃, after being reacted to the vinylformic acid mass concentration and dropping to 40-50%, be warming up to 110～120 ℃ of reactions 3～8 hours then, being lower than 5mgKOH/100g to the system acid number is terminal point, generates epoxy acrylate;
B, be 0.8～1.05: 0.8～1.05 water generation reaction epoxy acrylate in molar ratio with maleic anhydride and epoxy acrylate, add catalyst of triethylamine and stopper MEHQ, temperature of reaction should be 60～100 ℃, reaction times was at 1-3 hour, add the dimethylethanolamine neutralization, add the water-based epoxy acrylic ester that pure water promptly gets certain solid content.
2, the preparation method of a kind of special epoxy resin for UV-curable waterborne coatings according to claim 1 is characterized in that: the catalyst consumption that a, b added in the step accounts for reaction system mass ratio 2-8 ‰; It is 2-6 ‰ that stopper accounts for the reaction system mass ratio.
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