CN101602858A - A kind of water soluble acrylic acid epoxy resin and preparation method thereof - Google Patents
A kind of water soluble acrylic acid epoxy resin and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of water soluble acrylic acid epoxy resin and preparation method thereof, it is the catalytic esterification product neutralization of acrylic resin and Resins, epoxy, the emulsion that self-emulsifying forms, and 6 months-4 glasss of viscosity that are coated with of emulsion storage change less than 5%; The epoxy equivalent (weight) of Resins, epoxy is 180～5000g/mol, and Resins, epoxy accounts for 10%～80% in Resins, epoxy and acrylic resin gross weight; Acrylic resin is to cause hydroxy acryl acid with superoxide, contains carboxy acrylic, and other vinylformic acid and styrene monomer are polymerized, and its acid value is 50～500mgKOH/g, and number-average molecular weight is 5000～60000g/mol; The Resins, epoxy of epoxy equivalent (weight)＜1300g/mol need not the dihydroxyphenyl propane chain extension, and is simple to operate, is convenient to the Resins, epoxy proportion; Can make the water soluble acrylic acid epoxy resin of Resins, epoxy proportion broad, stable storing with the inventive method.
Description
Technical field
The present invention relates to a kind of water soluble acrylic acid epoxy resin and preparation method thereof.
Background technology
Water-borne coatings is with water to replace organic solvent, can reduce the use of coating industry organic solvent to a great extent, and its validity, cost and environmental acceptability are conspicuous, therefore, more and more is subjected to people's favor.
As water-base resin of the main film forming matter of water-borne coatings and preparation method thereof is the technology emphasis of water-borne coatings.The preparation method who is used as the water soluble acrylic acid epoxy resin of film forming matter at present roughly has physical blending and chemical modification two classes.But the water soluble acrylic acid epoxy resin ubiquity problems of stability in storage of physical blending, and the water soluble acrylic acid epoxy resin of chemical modification, its performance is then different with chemical modification method institute, for example: the water soluble acrylic acid epoxy resin that adopts the preparation of free radical grafting method, because of percentage of grafting lower, the actual product that finally obtains still is mixture, comprising the grafts of not grafted Resins, epoxy, acrylic resin and Resins, epoxy, free polyacrylic resin etc., so the resin stability in storage still has problems; Another method is to utilize the epoxy group(ing) of Resins, epoxy and the carboxyl of acrylic resin etc. to pass through esterification, acrylic resin and Resins, epoxy are combined together to form new macromole, because Resins, epoxy has bifunctional, acrylic resin has polyfunctional group, when both carry out esterification, be easy to occur the gel phenomenon, though find to adopt a large amount of tertiary amines as catalyzer, can effectively avoid the gel phenomenon, but, Resins, epoxy as starting raw material is that epoxy equivalent (weight) is the small molecules Resins, epoxy of 180～200g/mol, after dihydroxyphenyl propane chain extension to epoxy equivalent (weight) is 750～5000g/mol, carry out esterification with acrylic resin again, complex operation, and be difficult to regulate and control as required Resins, epoxy shared proportion in whole water soluble acrylic acid epoxy resin, therefore, the kind of the water soluble acrylic acid epoxy resin that makes is few, and then has limited its range of application.
Summary of the invention
First purpose of the present invention is: provide that a kind of shelf characteric is stable, Resins, epoxy proportion broad, can give the water soluble acrylic acid epoxy resin of the superperformance of filming.
The technical scheme that realizes first purpose of the present invention is: a kind of water soluble acrylic acid epoxy resin, it is the catalytic esterification product of acrylic resin and Resins, epoxy, through the emulsion that the water self-emulsifying that neutralizes, adds forms, 6 months-4 glasss of viscosity that are coated with of emulsion storage change less than 5%;
The epoxy equivalent (weight) of described Resins, epoxy is 180～5000g/mol;
Described Resins, epoxy accounts for 10%～80% in Resins, epoxy and acrylic resin gross weight;
Described acrylic resin acid value is 50～500mgKOH/g, and number-average molecular weight is 5000～60000g/mol;
Described acrylic resin is the radical polymerization product of following component, each component and consumption thereof are as follows: in weight part per-cent, hydroxy acryl acid class monomer 5%～15%, contain carboxy acrylic class monomer 5%～20%, other acrylic monomers 10%～25%, styrene monomer 10%～25%, peroxide initiator 1%～5%, pure ethers solubility promoter 40%～60%;
The catalyst levels of described catalytic esterification is described Resins, epoxy in 5%～30% of the weight part of solid.
In the above-mentioned water soluble acrylic acid epoxy resin, described acrylic resin acid value is 80～250mgKOH/g, and number-average molecular weight is 8000～20000g/mol.
In the above-mentioned water soluble acrylic acid epoxy resin, the catalyzer of described catalytic esterification is tertiary amine, quaternary amine or mineral alkali; The neutralizing agent that described neutralization is used is one or more in dimethylethanolamine, triethylamine, the ammoniacal liquor.
In the above-mentioned water soluble acrylic acid epoxy resin, as the component of described acrylic resin, its hydroxy acryl acid class monomer is one or more in Propylene glycol monoacrylate, Hydroxyethyl acrylate, the caprolactone; Its contain carboxy acrylic class monomer be in the acrylic or methacrylic acid one or both; Its other acrylic monomers are one or more in methyl methacrylate, butyl methacrylate, methyl acrylate, the butyl acrylate; Its styrene monomer is one or more in vinylbenzene, a vinyl toluene, the p-methylstyrene.
In the above-mentioned water soluble acrylic acid epoxy resin, as the component of described acrylic resin, its peroxide initiator is one or both in the peroxidation tert-butyl ester, peroxidation two tert-pentyl esters; Its pure ethers solubility promoter is one or several in propylene glycol monomethyl ether, butyl glycol ether, the ethylene glycol ethyl ether.
Second purpose of the present invention is: provide that a kind of simple, easy-operating preparation shelf characteric is stable, Resins, epoxy proportion broad, can give the water soluble acrylic acid epoxy resin method of the superperformance of filming.
The technical scheme that realizes second purpose of the present invention is: a kind of preparation method of water soluble acrylic acid epoxy resin, and its preparation process is specific as follows:
(1) preparation acrylic resin
1. prepare each component raw material by following proportioning
Each ingredients weight parts per-cent is as follows: hydroxy acryl acid class monomer 5%～15%, contain carboxy acrylic class monomer 5%～20%, other acrylic monomers 10%～25%, styrene monomer 10%～25%, peroxide initiator 1%～5%, pure ethers solubility promoter 40%～60%;
2. preparation
The pure ethers solubility promoter that in reaction vessel, adds the part formula ratio, stirring is warming up to temperature of reaction, under this temperature, drip the mixture of forming by the peroxide initiator of all monomers of whole formula ratios and part formula ratio, the dropping time is 4～5h, after dropwising, be incubated 0.5h at least in temperature of reaction, drip the mixture of remaining peroxide initiator and remaining pure ethers solubility promoter again, after dropwising, again at temperature of reaction insulation reaction 2～3h, the cooling stopped reaction, making acid number is 50～500mgKOH/g, number-average molecular weight is the acrylic resin of 5000～60000g/mol, and is standby;
(2) preparation epoxy resin solution
1. prepare Resins, epoxy and solvent thereof, aminating agent according to following calculated amount
Calculating epoxy equivalent (weight) by the solids constituent of epoxy resin solution is the commercially available Resins, epoxy of 1300g/mol to 5000g/mol and the consumption of solvent thereof;
To calculate epoxy equivalent (weight) be 180g/mol calculates aminating agent consumption to the＜commercially available Resins, epoxy of 1300g/mol and the consumption of solvent thereof and by this Resins, epoxy 50% epoxy group(ing) of amination by the solids constituent of epoxy resin solution;
2. prepare epoxy resin solution
The commercially available Resins, epoxy that with epoxy equivalent (weight) is 1300g/mol to 5000g/mol is with solvent is heated to dissolving evenly in container after, and is standby;
Perhaps being 180g/mol with epoxy equivalent (weight) is heated to dissolving evenly with partial solvent to the commercially available Resins, epoxy of＜1300g/mol in reactor, under heating, the mixture that drips aminating agent and residual solvent carries out amination then, drip, insulation to reaction finishes again, and cooling is standby;
(3) preparation water soluble acrylic acid epoxy resin
1. prepare raw material
In Resins, epoxy and acrylic resin gross weight, account for 10%～80% proportioning by Resins, epoxy, take by weighing the epoxy resin solution that acrylic resin that step () makes and step (two) make respectively;
5%～30% of (2) contained solid epoxy weight part of epoxy resin solution of making prepare the catalyzer that catalytic esterification is used set by step;
Prepare an amount of neutralizing agent;
2. preparation
The epoxy resin solution that takes by weighing is put into reactor, add the acrylic resin that takes by weighing, after heated and stirred is even, slowly drip the catalytic esterification catalyzer that takes by weighing, be warming up to temperature of reaction and carry out catalytic esterification in this temperature, reaction finishes and is cooled to 80 ℃～90 ℃, it is 8.0～9.0 that the following adding of stirring neutralizing agent is neutralized to the pH value, be cooled to 60～70 ℃ after stirring, slowly drip deionized water and carry out self-emulsifying, the discharging that stirs promptly makes water soluble acrylic acid epoxy resin of the present invention, its outward appearance is a slightly transparent emulsion of oyster white, and 6 months-4 glasss of viscosity that are coated with of emulsion storage change less than 5%.
Above-mentioned water soluble acrylic acid epoxy resin preparation method, the hydroxy acryl acid class monomer that its step () preparation acrylic resin uses is one or more in Propylene glycol monoacrylate, Hydroxyethyl acrylate, the caprolactone; Use contain carboxy acrylic class monomer be in the acrylic or methacrylic acid one or both; Other acrylic monomers that use are one or more in methyl methacrylate, butyl methacrylate, methyl acrylate, the butyl acrylate; The styrene monomer that uses is one or more in vinylbenzene, a vinyl toluene, the p-methylstyrene; The pure ethers solubility promoter that uses is one or several in propylene glycol monomethyl ether, butyl glycol ether, the ethylene glycol ethyl ether; The peroxide initiator that uses is one or both in the peroxidation tert-butyl ester, peroxidation two tert-pentyl esters.
Above-mentioned water soluble acrylic acid epoxy resin preparation method, the commercially available Resins, epoxy that its step (two) preparation epoxy resin solution uses is bisphenol A-type; The Resins, epoxy solvent that uses is pure ether solvent; The aminating agent that uses is a hydramine.
Above-mentioned water soluble acrylic acid epoxy resin preparation method, the catalyzer that its step (three) preparation water soluble acrylic acid epoxy resin uses is tertiary amines, quaternary ammonium salts or inorganic base.
Above-mentioned water soluble acrylic acid epoxy resin preparation method, neutralizing agent described in its step (three) is one or more in dimethylethanolamine, triethylamine, the ammoniacal liquor.
Technique effect of the present invention is: water soluble acrylic acid epoxy resin 1. of the present invention is a kind of resin of chemical modification, and it is by acrylic resin with suitable acid value and the Resins, epoxy with appropriate epoxy equivalent (weight), combines through catalytic esterification.Because the used acrylic resin acid value of esterification is suitable, contains hydroxyl and carboxyl simultaneously, both can play hydrophilic interaction, can play solidification again, need add emulsifying agent and just can form emulsion and emulsion stable storing by self-emulsifying.Each monomer collocation as the used acrylic resin component of esterification is appropriate, and wherein an amount of styrene monomer makes to have excellent dryness, hardness, gloss, fullness ratio and water tolerance after the resin film forming; The used acrylic resin of esterification is with the superoxide free radical polyalcohol that causes as initiator of peroxidation two tert-pentyl esters particularly, the hydrogen-taking capacity that its peroxidation two tert-pentyl esters decompose the free radical that produces a little less than, what cause in the monomer polymerization process is crosslinked less, therefore, the viscosity of the acrylic resin that obtains is less, and resin is also more even; Because the used Resins, epoxy of esterification has appropriate epoxy equivalent (weight), it just can obtain the water soluble acrylic acid epoxy resin of Resins, epoxy proportion broad (10～80%) with the acrylic resin with suitable acid value by catalytic esterification; When 2. preparing resin of the present invention, used Resins, epoxy is that epoxy equivalent (weight) is the resin solution of the commercially available bisphenol A type epoxy resin preparation of 180～5000g/mol, when its epoxy equivalent (weight) is 1300～5000g/mol, can directly prepare resin solution, when its epoxy equivalent (weight) is 180g/mol to＜1300g/mol, as long as carry out the part amination with heating, just can effectively reduce the functionality of epoxy group(ing), small molecules Resins, epoxy does not need to pass through dihydroxyphenyl propane chain extension step again, therefore, simplified preparation manipulation greatly, also be convenient to Resins, epoxy proportion in whole acrylic acid epoxy resin, thereby obtain the water soluble acrylic acid epoxy resin of Resins, epoxy proportion broad (10～80%); 3. water soluble acrylic acid epoxy resin of the present invention Resins, epoxy proportion wherein is in 10～80% scopes, it and suitable amino resin curing agents are used the baking-type coating of preparation, its film all have the hardness height, good, alkaline-resisting, the anti-solvent of snappiness and good antiseptic property (seeing Table 6), can be suitable for the different user requirement.
Embodiment
Below in conjunction with embodiment the present invention is further described, but is not limited thereto.
The raw materials used coating commercially available product that is among the embodiment, the raw material consumption is the weight part in gram.
Embodiment 1 preparation acrylic resin (abbreviation A1～A3)
(1) prescription: each ingredients weight parts per-cent is as follows: hydroxy acryl acid class monomer 5%～15%, contain carboxy acrylic class monomer 5%～20%, other acrylic monomers 10%～25%, styrene monomer 10%～25%, peroxide initiator 1%～5%, alcohol ethers solubility promoter 40%～60% is pressed the concrete prescription of table 1 and is prepared raw material.
Table 1
| Component | Raw material | Consumption A1 | Consumption A2 | Consumption A3 |
| Hydroxy acryl acid class monomer | Propylene glycol monoacrylate | 92.7 | 92.7 | 92.7 |
| Contain carboxy acrylic class monomer | Vinylformic acid | 51.3 | 102.7 | 160.5 |
| Other acrylic monomers | Butyl acrylate | 186 | 164.3 | 141.8 |
| Styrene monomer | Vinylbenzene | 155 | 120 | 90 |
| Peroxide initiator | Peroxidation two tert-pentyl esters | 15 | 15 | 15 |
| Alcohol ethers solubility promoter | The butyl glycol ether propylene glycol monomethyl ether | 273 60 | 273 60 | 273 60 |
Annotate: the preparation acrylic resin is raw materials used not to be subjected to the raw materials used restriction of table 1, can select for use from the kind of aforementioned list.
(2) preparation:
Press the formula ratio of table 1,198 weight parts alcohol ethers solubility promoter butyl glycol ether and 60 weight part propylene glycol monomethyl ethers are joined thermometer is housed, in the 1000ml four-hole boiling flask of whipping appts and condensing works, start to stir and be warming up to 145 ℃ of temperature of reaction, all monomers of whole formula ratios and the mixture of 12 weight part peroxidation, two tert-pentyl esters are stirred, slowly be added drop-wise in the above-mentioned four-hole boiling flask then, drip about 4h, after dropwising, keep 0.5h for 145 ℃ in temperature of reaction, drip 3 weight part oxidations, two tert-pentyl esters remained and the mixture of remaining 75 weight part butyl glycol ethers again, about 1h of dropping time, at 145 ℃ of insulation reaction 2h of temperature of reaction, the cooling stopped reaction makes acrylic resin A1 respectively at last, A2 and A3, its solids constituent is 60 weight %, and acid value and number-average molecular weight see Table 2.
Table 2
| Acrylic resin | Acid value (mgKOH/g) | Number-average molecular weight (g/mol) |
| A1 | 80 | 35081 |
| A2 | 160 | 29195 |
| A3 | 250 | 37820 |
Embodiment 2 preparation epoxy resin solutions (solid is divided into 60%, abbreviation E1～E3)
(1) prescription
Calculating epoxy equivalent (weight) by the solids constituent of epoxy resin solution is the commercially available Resins, epoxy of 1300g/mol to 5000g/mol and the consumption of solvent thereof;
To calculate epoxy equivalent (weight) be 180g/mol calculates aminating agent consumption to the＜commercially available Resins, epoxy of 1300g/mol and the consumption of solvent thereof and by this Resins, epoxy 50% epoxy group(ing) of amination by the solids constituent of epoxy resin solution, and concrete prescription sees Table 3.
Table 3
Annotate 1: the raw materials used table 3 that is not limited to of preparation Resins, epoxy is raw materials used, can select for use from aforementioned qualification kind;
Annotate 2: the aminating agent consumption is calculated as follows
Aminating agent consumption=(100 ÷ epoxy equivalent (weight)) * 50% * aminating agent molecular weight
(2) preparation
Preparation E1 resin solution: press the formula ratio in the table 3, commercially available E-03 Resins, epoxy and solvent ethylene glycol butyl ether are joined in the 500ml four-hole boiling flask that thermometer, whipping appts and condensing works are housed, it is evenly standby to be heated to 120 ℃ of dissolvings;
Preparation E2 and E3 resin solution: press the formula ratio in the table 3, commercially available E-12 or E-20 Resins, epoxy and 40 weight part butyl glycol ethers are joined respectively in the 500ml four-hole boiling flask that thermometer, whipping appts and condensing works are housed, be heated to 120 ℃ of dissolvings evenly, carry out amination in 120 ℃ of mixtures that drip aminating agent diethanolamine and remaining butyl glycol ether down, 1h drips, and is incubated the 2h reaction again and finishes cooling, make epoxy resin solution E2 and E3 respectively, standby;
Embodiment 3 preparation water soluble acrylic acid epoxy resins (abbreviation 1#～9#)
(1) prescription
In Resins, epoxy and acrylic resin gross weight, account for 10%～80% proportioning by Resins, epoxy, take by weighing the epoxy resin solution that acrylic resin that embodiment 2 makes and embodiment 2 make respectively;
5%～30% of the contained solid epoxy weight part of epoxy resin solution that makes by embodiment 2 is prepared the catalyzer that catalytic esterification is used, and concrete prescription sees Table 4.
Table 4
(2) preparation
Thermometer is being housed, in the 1000ml four-hole boiling flask of whipping appts and condensing works, press table 4 formula ratio and add acrylic resin, epoxy resin solution, be heated to 80 ℃, stir, slowly drip dimethyl ethanolamine catalyst again, be warming up to 120 ℃ of temperature of reaction and carry out catalytic esterification 3h in this temperature, reaction finishes, be cooled to 85 ℃, stir and add neutralizing agent organic alcohol amine (for example dimethylethanolamine) neutralization down, make the pH value of system be controlled at 8.0～9.0, be cooled to 60～70 ℃ after stirring, slowly drip deionized water and carry out self-emulsifying, fully stir the 30min discharging then, making outward appearance respectively is slightly transparent emulsion of oyster white, and the emulsion particle diameter is water soluble acrylic acid epoxy resin 1#～9# of 200～600nm, and the salient features of each resin sees Table 5
Table 5
| Salient features | 1# | 2# | 3# | 4# | 5# | 6# | 7# | 8# | 9# |
| The pH value | 8.5 | 8.5 | 8.3 | 8.8 | 8.3 | 8.6 | 8.6 | 8.6 | 8.5 |
| Solids constituent, % | 38 | 35 | 35 | 40 | 40 | 30 | 35 | 28 | 30 |
| Be coated with-4 glasss of viscosity, s | 165 | 124 | 109 | 225 | 256 | 153 | 198 | 110 | 128 |
| Store and be coated with-4 glasss of viscosity, s after 6 months | 171 | 125 | 114 | 227 | 265 | 155 | 201 | 109 | 130 |
By the data of table 5 as can be seen, after water soluble acrylic acid epoxy resin of the present invention stores 6 months, be coated with-4 glasss of viscosity and change, and-4 glasss of viscosity that are coated with of the water soluble acrylic acid epoxy resin that similar physics is mixed are changed to about 10% all less than 5%.As seen the stability in storage of water soluble acrylic acid epoxy resin of the present invention is improved.
In order to show the film performance of the water soluble acrylic acid epoxy resin that makes with the inventive method, water soluble acrylic acid epoxy resin 1#～9# with embodiment 3 preparations is basic film-forming resin, general formulation by the amino Baking Paint of existing water-based, allocate preparation watersoluble baking lacquers such as suitable amino curing agent, defoamer, flow agent, color stuffing into, press coatings industry concerned countries standard detection film performance.
Preparation detects used model: plate size 10cm * 5cm, and the surface sprays the coating of 1#～9# resins respectively after oil removing, polishing, first surface drying 20min, again in 180 ℃ of baking 30min, build 20 ± 2 μ m, detected result is listed in table 6.
Table 6
| Project | 1# | 2# | 3# | 4# | 5# | 6# | 7# | 8# | 9# |
| Sticking power, level | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| Impact Kg.cm | 50 | 40 | 40 | 50 | 50 | 40 | 40 | 40 | 40 |
| Snappiness, mm | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
| Gloss, 60 ° | 88 | 89 | 89 | 88 | 88 | 94 | 89 | 92 | 92 |
| Pencil hardness | 2H | 3H | 3H | 2H | 2H | 3H | 3H | 3H | 3H |
| Anti-butanone wiping, inferior | 200 | 200 | 200 | 100 | 100 | 200 | 200 | 200 | 200 |
| Alkaline-resisting (10% sodium hydroxide solution), day | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 |
| Salt spray resistance, hour | 120 | 240 | 240 | 120 | 120 | 240 | 240 | 240 | 240 |
Table 6 detected result can illustrate, the watersoluble baking lacquer of the water soluble acrylic acid epoxy resin of the present invention preparation that makes with the inventive method, its hardness of film, snappiness, alkaline-resisting, anti-solvent, alkali resistance, performances such as salt spray resistance can be fit to different working conditionss, 1# for example, 4#, 5# more is applicable to and requires the more occasion of high impact properties, 6#, 8#, 9# more is applicable to the occasion that requires high gloss, thereby illustrate with the simple method of the present invention and can make Resins, epoxy proportion broad (10～80%), the water soluble acrylic acid epoxy resin that stability in storage improves is more conducive to the popularization of water-base resin.
Claims (10)
1, a kind of water soluble acrylic acid epoxy resin is characterized in that, it is the catalytic esterification product of acrylic resin and Resins, epoxy, and through the emulsion that the water self-emulsifying that neutralizes, adds forms, 6 months-4 glasss of viscosity that are coated with of emulsion storage change less than 5%;
The epoxy equivalent (weight) of described Resins, epoxy is 180～5000g/mol;
Described Resins, epoxy accounts for 10%～80% in Resins, epoxy and acrylic resin gross weight;
Described acrylic resin acid value is 50～500mgKOH/g, and number-average molecular weight is 5000～60000g/mol;
Described acrylic resin is the radical polymerization product of following component, each component and consumption thereof are as follows: in weight part per-cent, hydroxy acryl acid class monomer 5%～15%, contain carboxy acrylic class monomer 5%～20%, other acrylic monomers 10%～25%, styrene monomer 10%～25%, peroxide initiator 1%～5%, pure ethers solubility promoter 40%～60%;
The catalyst levels of described catalytic esterification is described Resins, epoxy in 5%～30% of the weight part of solid.
2, water soluble acrylic acid epoxy resin according to claim 1 is characterized in that, described acrylic resin acid value is 80～250mgKOH/g, and number-average molecular weight is 8000～20000g/mol.
3, water soluble acrylic acid epoxy resin according to claim 1 is characterized in that, the catalyzer of described catalytic esterification is tertiary amine, quaternary amine or mineral alkali; The neutralizing agent that described neutralization is used is one or more in dimethylethanolamine, triethylamine, the ammoniacal liquor.
4, water soluble acrylic acid epoxy resin according to claim 1 is characterized in that, as the component of described acrylic resin, its hydroxy acryl acid class monomer is one or more in Propylene glycol monoacrylate, Hydroxyethyl acrylate, the caprolactone; Its contain carboxy acrylic class monomer be in the acrylic or methacrylic acid one or both; Its other acrylic monomers are one or more in methyl methacrylate, butyl methacrylate, methyl acrylate, the butyl acrylate; Its styrene monomer is one or more in vinylbenzene, a vinyl toluene, the p-methylstyrene.
5, water soluble acrylic acid epoxy resin according to claim 1 is characterized in that, as the component of described acrylic resin, its peroxide initiator is one or both in the peroxidation tert-butyl ester, peroxidation two tert-pentyl esters; Its pure ethers solubility promoter is one or several in propylene glycol monomethyl ether, butyl glycol ether, the ethylene glycol ethyl ether.
6, a kind of preparation method of water soluble acrylic acid epoxy resin is characterized in that, preparation process is specific as follows:
(1) preparation acrylic resin
1. prepare each component raw material by following proportioning
Each ingredients weight parts per-cent is as follows: hydroxy acryl acid class monomer 5%～15%, contain carboxy acrylic class monomer 5%～20%, other acrylic monomers 10%～25%, styrene monomer 10%～25%, peroxide initiator 1%～5%, pure ethers solubility promoter 40%～60%;
2. preparation
The pure ethers solubility promoter that in reaction vessel, adds the part formula ratio, stirring is warming up to temperature of reaction, under this temperature, drip the mixture of forming by the peroxide initiator of all monomers of whole formula ratios and part formula ratio, the dropping time is 4～5h, after dropwising, be incubated 0.5h at least in temperature of reaction, drip the mixture of remaining peroxide initiator and remaining pure ethers solubility promoter again, after dropwising, again at temperature of reaction insulation reaction 2～3h, the cooling stopped reaction, making acid number is 50～500mgKOH/g, number-average molecular weight is the acrylic resin of 5000～60000g/mol, and is standby;
(2) preparation epoxy resin solution
1. prepare Resins, epoxy and solvent thereof, aminating agent according to following calculated amount
Calculating epoxy equivalent (weight) by the solids constituent of epoxy resin solution is the commercially available Resins, epoxy of 1300g/mol to 5000g/mol and the consumption of solvent thereof;
To calculate epoxy equivalent (weight) be 180g/ol calculates aminating agent consumption to the＜commercially available Resins, epoxy of 1300g/mol and the consumption of solvent thereof and by this Resins, epoxy 50% epoxy group(ing) of amination by the solids constituent of epoxy resin solution;
2. prepare epoxy resin solution
The commercially available Resins, epoxy that with epoxy equivalent (weight) is 1300g/mol to 5000g/mol is with solvent is heated to dissolving evenly in container after, and is standby;
Perhaps being 180g/mol with epoxy equivalent (weight) is heated to dissolving evenly with partial solvent to the commercially available Resins, epoxy of＜1300g/mol in reactor, under heating, the mixture that drips aminating agent and residual solvent carries out amination then, drip, insulation to reaction finishes again, and cooling is standby;
(3) preparation water soluble acrylic acid epoxy resin
1. prepare raw material
In Resins, epoxy and acrylic resin gross weight, account for 10%～80% proportioning by Resins, epoxy, take by weighing the epoxy resin solution that acrylic resin that step () makes and step (two) make respectively;
5%～30% of (2) contained solid epoxy weight part of epoxy resin solution of making prepare the catalyzer that catalytic esterification is used set by step;
Prepare an amount of neutralizing agent;
2. preparation
The epoxy resin solution that takes by weighing is put into reactor, add the acrylic resin that takes by weighing, after heated and stirred is even, slowly drip the catalytic esterification catalyzer that takes by weighing, be warming up to temperature of reaction and carry out catalytic esterification in this temperature, reaction finishes and is cooled to 80 ℃～90 ℃, it is 8.0～9.0 that the following adding of stirring neutralizing agent is neutralized to the pH value, be cooled to 60～70 ℃ after stirring, slowly drip deionized water and carry out self-emulsifying, the discharging that stirs promptly makes water soluble acrylic acid epoxy resin of the present invention, its outward appearance is a slightly transparent emulsion of oyster white, and 6 months-4 glasss of viscosity that are coated with of emulsion storage change less than 5%.
7, water soluble acrylic acid epoxy resin preparation method according to claim 6 is characterized in that, the hydroxy acryl acid class monomer that step () preparation acrylic resin uses is one or more in Propylene glycol monoacrylate, Hydroxyethyl acrylate, the caprolactone; Use contain carboxy acrylic class monomer be in the acrylic or methacrylic acid one or both; Other acrylic monomers that use are one or more in methyl methacrylate, butyl methacrylate, methyl acrylate, the butyl acrylate; The styrene monomer that uses is one or more in vinylbenzene, a vinyl toluene, the p-methylstyrene; The pure ethers solubility promoter that uses is one or several in propylene glycol monomethyl ether, butyl glycol ether, the ethylene glycol ethyl ether; The peroxide initiator that uses is one or both in the peroxidation tert-butyl ester, peroxidation two tert-pentyl esters.
8, water soluble acrylic acid epoxy resin preparation method according to claim 6 is characterized in that, the commercially available Resins, epoxy that step (two) preparation epoxy resin solution uses is bisphenol A-type; The Resins, epoxy solvent that uses is pure ether solvent; The aminating agent that uses is a hydramine.
9, water soluble acrylic acid epoxy resin preparation method according to claim 6 is characterized in that, the catalyzer that step (three) preparation water soluble acrylic acid epoxy resin uses is tertiary amines, quaternary ammonium salts or inorganic base.
10, water soluble acrylic acid epoxy resin preparation method according to claim 6 is characterized in that, neutralizing agent described in the step (three) is one or more in dimethylethanolamine, triethylamine, the ammoniacal liquor.
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Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101817930A (en) * | 2010-04-28 | 2010-09-01 | 常州市科祥化工有限公司 | Waterborne epoxy modified acrylic resin specific for tape measure and preparation method thereof |
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| CN102964535B (en) * | 2012-11-22 | 2014-12-10 | 上海涂料有限公司技术中心 | Preparation method and application of composite emulsion for alkali-resistant wine label coating |
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| CN103910825A (en) * | 2014-03-28 | 2014-07-09 | 江门市三木化工有限公司 | Novel resin and preparation method thereof |
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| CN104877086B (en) * | 2015-05-29 | 2017-11-28 | 佛山市华立龙科技有限公司 | A kind of high-performance environment protection type soluble epoxide acrylic resin |
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| CN107163256A (en) * | 2017-06-02 | 2017-09-15 | 广东深展实业有限公司 | Epoxy modified aqueous acrylic acid resin and the aqueous vacuum coating priming paint prepared with it |
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| CN109294407A (en) * | 2018-09-14 | 2019-02-01 | 广东华科新材料研究院有限公司 | A kind of water-based anticorrosive paint and preparation method thereof |
| CN113698838A (en) * | 2021-08-13 | 2021-11-26 | 成都杰晟蜀邦新材料科技有限公司 | Resin for water-based glass baking varnish and preparation method thereof |
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Correction item: Patentee|Address|Co-patentee Correct: China Marine Petroleum & Chemical Co., Ltd. | 100010 Beijing City Higashiro-ku, Chaoyoang Kitakami-shi No. 25 4705 Shinkansen|CNOOC Changzhou coatings chemical research institute CNOOC energy development Limited by Share Ltd False: CNOOC Changzhou Paint & Coatings Industry Research Institute|213016 Changzhou Zhong Road, Jiangsu Province, No. 22 Longjiang Road Number: 15 Volume: 27 |
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Correction item: Patentee|Address|Co-patentee Correct: China Marine Petroleum & Chemical Co., Ltd. | 100010 Beijing City Higashiro-ku, Chaoyoang Kitakami-shi No. 25 4705 Shinkansen|CNOOC Changzhou coatings chemical research institute CNOOC energy development Limited by Share Ltd False: CNOOC Changzhou Paint & Coatings Industry Research Institute|213016 Changzhou Zhong Road, Jiangsu Province, No. 22 Longjiang Road Number: 15 Page: The title page Volume: 27 |
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Free format text: CORRECT: PATENTEE; ADDRESS; CO-PATENTEE; FROM: CNOOC CHANGZHOU PAINT + COATINGS INDUSTRY RESEARCH INSTITUTE;213016 NO. 22, LONGJIANG MIDDLE ROAD, ZHONGLOU DISTRICT, CHANGZHOU CITY, JIANGSU PROVINCE TO: CHINA MARINE PETROLEUM GENERAL CO.;100010 MAILBOX 4705, NO. 25, CHAOYANGMEN NORTH STREET, DONGCHENG DISTRICT, BEIJING; CNOOC CHANGZHOU PAINT + COATINGS INDUSTRY RESEARCH INSTITUTE CNOOC ENERGY DEVELOPMENT CO., LTD. |
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Address after: 100010 Dongcheng District, Chaoyangmen, North Street, No. 4705, No. 25, box office, Beijing Patentee after: China National Offshore Oil Corporation Patentee after: CNOOC CHANGZHOU PAINT CHEMICAL RESEARCH INSTITUTE CO., LTD. Patentee after: CNOOC Energy Development Co., Ltd. Address before: 100010 Dongcheng District, Chaoyangmen, North Street, No. 4705, No. 25, box office, Beijing Patentee before: China National Offshore Oil Corporation Patentee before: CNOOC Changzhou Paint & Coatings Industry Research Institute Patentee before: CNOOC Energy Development Co., Ltd. |
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Effective date of registration: 20161227 Address after: 213016 Changzhou Zhong Road, Jiangsu Province, No. 22 Longjiang Road Patentee after: CNOOC CHANGZHOU PAINT CHEMICAL RESEARCH INSTITUTE CO., LTD. Patentee after: CNOOC Energy Technology Co., Ltd. Address before: 100010 Dongcheng District, Chaoyangmen, North Street, No. 4705, No. 25, box office, Beijing Patentee before: China National Offshore Oil Corporation Patentee before: CNOOC CHANGZHOU PAINT CHEMICAL RESEARCH INSTITUTE CO., LTD. Patentee before: CNOOC Energy Technology Co., Ltd. |