CN101585766A - Epoxy acrylate containing alicyclic structure and preparation method thereof - Google Patents
Epoxy acrylate containing alicyclic structure and preparation method thereof Download PDFInfo
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- CN101585766A CN101585766A CNA2009100629826A CN200910062982A CN101585766A CN 101585766 A CN101585766 A CN 101585766A CN A2009100629826 A CNA2009100629826 A CN A2009100629826A CN 200910062982 A CN200910062982 A CN 200910062982A CN 101585766 A CN101585766 A CN 101585766A
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Abstract
The invention relates to epoxy acrylate containing an alicyclic structure and a preparation method thereof, the structural formula thereof (shown in Figure) comprises that: epoxy resin containing the alicyclic structure is put into a reaction vessel to be agitated and heated up to 80-90 DEG C, evenly-mixed acrylic acid or methacrylic acid and catalyst, inhibitor solution are instilled into the reaction vessel, after the instilling is completed, reaction liquid in the reaction vessel is heated up to 100-110 DEG C, heat preservation is carried out for 2-4 hours to obtain mixed solution; acid value of the mixed solution is measured, when the acid value is reduced to 5mg/LOH/g, the reaction is ceased and the solution is cooled to room temperature, in the end, discharging is implemented to obtain the epoxy acrylate containing the alicyclic structure. The inventive epoxy acrylate containing the alicyclic structure has the characteristics of excellent ultraviolet resistance and weathering resistance, relatively low viscosity, good fluidity and outstanding yellowing resistance, and can overcome the defects of bisphenol A epoxy resin such as high acid ester viscosity and inferior aging resistance and yellowing resistance.
Description
Technical field
The present invention relates to a kind of UV-cured resin and preparation method, particularly a kind of epoxy acrylate that contains alicyclic structure and preparation method thereof.
Background technology
The synthetic of epoxy acrylate just has patent report as far back as the 1950's, but, just is applied to the photocuring field to the seventies in 20th century.Epoxy acrylate is by commodity Resins, epoxy and acrylic or methacrylic acid estersization and get, and is a class photocuring oligopolymer of present domestic photocuring industry internal consumption amount maximum.Wherein commonly used with bisphenol-a epoxy acrylate again, consumption is also maximum.The major advantage of bisphenol-a epoxy acrylate comprises: photocuring reaction speed is very fast, and hardness and tensile strength are big after solidifying, coating gloss height, chemicals-resistant corrosive nature excellence.Be widely used as basic candidate's resin of photo-cured coating, printing ink, sizing agent, but its shortcoming is that the cured film flexibility is not enough, the fragility height, viscosity is big, and is ageing-resistant, and performances such as anti-xanthochromia are not good, and therefore outdoor use is restricted.
Summary of the invention
Problem to be solved by this invention is to provide a kind of epoxy acrylate that contains alicyclic structure at above-mentioned prior art, and it has good UV resistant and weathering resistance, and ratio of viscosities is lower, good fluidity, and yellowing resistance can be good.
The present invention for the solution that problem adopts of the above-mentioned proposition of solution is: a kind of epoxy acrylate that contains alicyclic structure, and its general structure is:
Wherein R is H or CH
3
The technical scheme that the epoxy acrylate preparation method who contains alicyclic structure of the present invention is adopted is: contain the preparation method of the epoxy acrylate of alicyclic structure, it is characterized in that including following steps:
1) gets material, get Resins, epoxy 90-110, acrylic or methacrylic acid 60-80, catalyzer 0.05-5.5, the stopper 0.2-2 that contains alicyclic structure according to mass fraction; The acrylic or methacrylic acid of being got is mixed with catalyzer, stopper;
2) Resins, epoxy that will contain alicyclic structure is put in the reaction vessel that agitator, thermometer, dropping funnel are housed, stirring is warming up to 80 ℃-90 ℃, the acrylic or methacrylic acid that mixes in the step 1) is added drop-wise in the reaction vessel with catalyzer, inhibitor solution, dropwised in 40-60 minute, the structural formula of the above-mentioned Resins, epoxy that contains alicyclic structure is:
3) reaction solution in the reaction vessel is warming up to 100-110 ℃, is incubated 2-4 hour, obtain mixing solutions;
4) determination step 3) acid number of gained mixing solutions, reduce to stopped reaction when acid number less than 5mgKOH/g, be cooled to room temperature, discharging promptly obtains containing the epoxy acrylate of alicyclic structure.
Press such scheme, described determination of acid value is measured by GB2895-82 " mensuration of unsaturated polyester resin acid number ".
Press such scheme, described catalyzer is the 2-picoline, triphenylphosphine, antimony triphenyl, any one in the triphenylarsine or multiple.
Press such scheme, described stopper is a Resorcinol, 2, and 5-dimethyl Resorcinol, 2, any one in the 6-toluene di-tert-butyl phenol or multiple.
For guaranteeing that epoxide group transforms fully, it is excessive slightly that acrylic or methacrylic acid contains the epoxide group of Resins, epoxy of alicyclic structure relatively.Because the residual epoxy base is being subjected under the thermal conditions for a long time in the system, or in the room temperature storage process, cause the polymerization of residual epoxy group probably, viscosity increases severely, and is rotten until producing gel.
The epoxy acrylate that contains alicyclic structure of the present invention has good UV resistant and weathering resistance, and viscosity ratio is lower, good fluidity, the characteristics that the yellowing resistance energy is good, can effectively overcome bisphenol-a epoxy acrylate viscosity height, ageing-resistant, yellowing resistance can be not good etc. shortcoming.
Embodiment
Further introduce the present invention below by embodiment, but embodiment can not be construed as limiting the invention.
Embodiment 1
(a) with 60.21g vinylformic acid and 0.09g triphenylphosphine, the 0.33g Resorcinol mixes;
(b) in the reaction vessel that agitator, thermometer, dropping funnel are housed, add the Resins, epoxy that 90.80g contains alicyclic structure, stir and be warming up to 80 ℃, the solution that mixes in (a) was dropwised in 40 minutes; The structural formula of the above-mentioned Resins, epoxy that contains alicyclic structure is (down together):
(c) reacting liquid temperature in the reaction vessel is warming up to 100 ℃, is incubated 2 hours;
(d) measure the solution acid number, its acid number is 4.71mgKOH/g, and this moment, stopped reaction was cooled to the room temperature discharging, must contain alicyclic structure epoxy acrylate 1-1, and its structural formula is
Embodiment 2
(a) with 66.35g vinylformic acid and 0.17g triphenylphosphine, the 0.67g Resorcinol mixes;
(b) in the reaction vessel that agitator, thermometer, dropping funnel are housed, add 100.10g and contain alicyclic structure Resins, epoxy, stir and be warming up to 80 ℃, the solution that mixes in (a) was dropwised in 40 minutes;
(c) reacting liquid temperature in the reaction vessel is warming up to 100 ℃, is incubated 3 hours;
(d) measure the solution acid number, its acid number is 4.84mgKOH/g, and this moment, stopped reaction was cooled to the room temperature discharging, must contain alicyclic structure epoxy acrylate 1-2, and its structural formula is with embodiment 1.
Embodiment 3
(a) with 66.37g vinylformic acid and 0.35g triphenylarsine, 1.01g2,5-dimethyl Resorcinol mixes;
(b) in the reaction vessel that agitator, thermometer, dropping funnel are housed, add 100.04g and contain alicyclic structure Resins, epoxy, stir and be warming up to 85 ℃, the solution that mixes in (a) was dropwised in 50 minutes;
(c) reacting liquid temperature in the reaction vessel is warming up to 105 ℃, is incubated 3 hours;
(d) measure the solution acid number, its acid number is 4.77mgKOH/g, and this moment, stopped reaction was cooled to the room temperature discharging, must contain alicyclic structure epoxy acrylate 1-3, and its structural formula is with embodiment 1.
Embodiment 4
(a) with 66.34g vinylformic acid and 0.83g2-picoline, 1.33g2,5-dimethyl Resorcinol mixes;
(b) in the reaction vessel that agitator, thermometer, dropping funnel are housed, add 100.03g and contain alicyclic structure Resins, epoxy, stir and be warming up to 85 ℃, the solution that mixes in (a) was dropwised in 50 minutes;
(c) reacting liquid temperature in the reaction vessel is warming up to 105 ℃, is incubated 3 hours;
(d) measure the solution acid number, its acid number is 4.63mgKOH/g, and this moment, stopped reaction was cooled to the room temperature discharging, must contain alicyclic structure epoxy acrylate 1-4, and its structural formula is with embodiment 1.
Embodiment 5
(a) with 66.32g vinylformic acid and 1.67g2-picoline, the 1.66g Resorcinol mixes;
(b) in the reaction vessel that agitator, thermometer, dropping funnel are housed, add 100.07g and contain alicyclic structure Resins, epoxy, stir and be warming up to 90 ℃, the solution that mixes in (a) was dropwised in 60 minutes;
(c) reacting liquid temperature in the reaction vessel is warming up to 110 ℃, is incubated 4 hours;
(d) measure the solution acid number, its acid number is 4.55mgKOH/g, and this moment, stopped reaction was cooled to the room temperature discharging, must contain alicyclic structure epoxy acrylate 1-5, and its structural formula is with embodiment 1.
Embodiment 6
(a) with 75.47g methacrylic acid and 2.63g triphenylphosphine, 0.44g2, the 6-toluene di-tert-butyl phenol mixes;
(b) in the reaction vessel that agitator, thermometer, dropping funnel are housed, add 100.04g and contain alicyclic structure Resins, epoxy, stir and be warming up to 80 ℃, the solution that mixes in (a) was dropwised in 40 minutes;
(c) reacting liquid temperature in the reaction vessel is warming up to 100 ℃, is incubated 2 hours;
(d) measure the solution acid number, its acid number is 4.89mgKOH/g, and this moment, stopped reaction was cooled to the room temperature discharging, must contain alicyclic structure epoxy acrylate 1-6, and its structural formula is
Embodiment 7
(a) with 75.44g methacrylic acid and 3.50g antimony triphenyl, 0.88g2, the 6-toluene di-tert-butyl phenol mixes;
(b) in the reaction vessel that agitator, thermometer, dropping funnel are housed, add 100.06g and contain alicyclic structure Resins, epoxy, stir and be warming up to 80 ℃, the solution that mixes in (a) was dropwised in 50 minutes;
(c) reacting liquid temperature in the reaction vessel is warming up to 100 ℃, is incubated 3 hours;
(d) measure the solution acid number, its acid number is 4.66mgKOH/g, and this moment, stopped reaction was cooled to the room temperature discharging, must contain alicyclic structure epoxy acrylate 1-7, and its structural formula is with embodiment 6.
Embodiment 8
(a) with 75.46g methacrylic acid and 4.38g triphenylarsine, 1.31g2,5-dimethyl Resorcinol mixes;
(b) in the reaction vessel that agitator, thermometer, dropping funnel are housed, add 100.01g and contain alicyclic structure Resins, epoxy, stir and be warming up to 85 ℃, the solution that mixes in (a) was dropwised in 50 minutes;
(c) reacting liquid temperature in the reaction vessel is warming up to 105 ℃, is incubated 3 hours;
(d) measure the solution acid number, its acid number is 4.85mgKOH/g, and this moment, stopped reaction was cooled to the room temperature discharging, must contain alicyclic structure epoxy acrylate 1-8, and its structural formula is with embodiment 6.
Embodiment 9
(a) with 75.40g methacrylic acid and 5.26g triphenylphosphine, the 1.75g Resorcinol mixes;
(b) in the reaction vessel that agitator, thermometer, dropping funnel are housed, add 100.01g and contain alicyclic structure Resins, epoxy, stir and be warming up to 80 ℃, the solution that mixes in (a) was dropwised in 60 minutes;
(c) reacting liquid temperature in the reaction vessel is warming up to 110 ℃, is incubated 4 hours;
(d) measure the solution acid number, its acid number is 4.53mgKOH/g, and this moment, stopped reaction was cooled to the room temperature discharging, must contain alicyclic structure epoxy acrylate 1-9, and its structural formula is with embodiment 6.
Realize by following steps during the realization of the mensuration of the weathering resistance in the table 1:
1. the light trigger 1-hydroxyl-ring ethyl benzophenone that adds its quality 3% in the epoxy acrylate that contains alicyclic structure that will make mixes and films, and photocuring is 15 seconds in medium pressure mercury lamp.
2. carry out weathering resistance by paint film weatherability assay method GB1767-79 and measure measurement result such as table 1.
Table 1
| Sample | Package stability | Color | Viscosity (mPa.s/25 ℃) | Weathering resistance |
| 1-1 | Excellent, no considerable change | Yellow | 815 | One-level |
| 1-2 | Excellent, no considerable change | Yellow | 802 | One-level |
| 1-3 | Excellent, no considerable change | Yellow | 853 | One-level |
| 1-4 | Excellent, no considerable change | Yellow | 920 | One-level |
| 1-5 | Excellent, no considerable change | Yellow | 916 | One-level |
| 1-6 | Excellent, no considerable change | Yellow | 955 | One-level |
| 1-7 | Excellent, no considerable change | Yellow | 971 | One-level |
| 1-8 | Excellent, no considerable change | Yellow | 924 | One-level |
| 1-9 | Excellent, no considerable change | Yellow | 902 | One-level |
As shown in Table 1, the epoxy acrylate that contains the ester ring structure of the present invention has the characteristics than low viscosity, good weatherability.
Each cited raw material of the present invention can both be realized the present invention, and the bound value of each raw material, interval value can both realize the present invention; Do not enumerate embodiment one by one at this.Bound value, the interval value of processing parameter of the present invention (as temperature, time etc.) can both be realized the present invention, do not enumerate embodiment one by one at this.
Claims (5)
1, a kind of epoxy acrylate that contains alicyclic structure, its general structure is:
Wherein R is H or CH
3
2, the described preparation method who contains the epoxy acrylate of alicyclic structure of claim 1 is characterized in that including following steps:
1) gets material, get Resins, epoxy 90-110, acrylic or methacrylic acid 60-80, catalyzer 0.05-5.5, the stopper 0.2-2 that contains alicyclic structure according to mass fraction; The acrylic or methacrylic acid of being got is mixed with catalyzer, stopper;
2) Resins, epoxy that will contain alicyclic structure is put in the reaction vessel that agitator, thermometer, dropping funnel are housed, stirring is warming up to 80 ℃-90 ℃, the acrylic or methacrylic acid that mixes in the step 1) is added drop-wise in the reaction vessel with catalyzer, inhibitor solution, dropwised in 40-60 minute, the structural formula of the above-mentioned Resins, epoxy that contains alicyclic structure is:
3) reaction solution in the reaction vessel is warming up to 100-110 ℃, is incubated 2-4 hour, obtain mixing solutions;
4) determination step 3) acid number of gained mixing solutions, reduce to stopped reaction when acid number less than 5mgKOH/g, be cooled to room temperature, discharging promptly obtains containing the epoxy acrylate of alicyclic structure.
3,, it is characterized in that described determination of acid value measures by GB2895-82 " mensuration of unsaturated polyester resin acid number " by the described preparation method who contains the epoxy acrylate of alicyclic structure of claim 2.
4,, it is characterized in that described catalyzer is the 2-picoline, triphenylphosphine, antimony triphenyl, any one in the triphenylarsine or multiple by claim 2 or the 3 described preparation methods that contain the epoxy acrylate of alicyclic structure.
5, by claim 2 or the 3 described preparation methods that contain the epoxy acrylate of alicyclic structure, it is characterized in that described stopper is a Resorcinol, 2,5-dimethyl Resorcinol, 2, any one in the 6-toluene di-tert-butyl phenol or multiple.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584578A (en) * | 2012-01-06 | 2012-07-18 | 南昌大学 | Preparation method and application of 1,4-cyclohexanedimethanol diglycidyl ether diacrylate |
| CN102993010A (en) * | 2012-11-17 | 2013-03-27 | 南昌大学 | Method for preparing para-tertiary butyl phenol glycidyl ether acrylate |
| CN103030559A (en) * | 2012-12-17 | 2013-04-10 | 南昌大学 | Method for synthesizing ultraviolet curable photosensitive diluent-2-ethyl hexyl glycidyl ether acrylate |
| CN104327248A (en) * | 2014-10-23 | 2015-02-04 | 招远鸿瑞印染有限公司 | Preparation process of photocuring material |
| CN104558522A (en) * | 2013-10-23 | 2015-04-29 | 湖南岁丰新材料科技发展有限公司 | Ultraviolet-curing modified epoxy acrylic resin and preparation method thereof |
| CN107828050A (en) * | 2017-11-16 | 2018-03-23 | 广州日高新材料科技有限公司 | Modified epoxy acrylate resin and preparation method thereof |
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2009
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584578A (en) * | 2012-01-06 | 2012-07-18 | 南昌大学 | Preparation method and application of 1,4-cyclohexanedimethanol diglycidyl ether diacrylate |
| CN102993010A (en) * | 2012-11-17 | 2013-03-27 | 南昌大学 | Method for preparing para-tertiary butyl phenol glycidyl ether acrylate |
| CN103030559A (en) * | 2012-12-17 | 2013-04-10 | 南昌大学 | Method for synthesizing ultraviolet curable photosensitive diluent-2-ethyl hexyl glycidyl ether acrylate |
| CN104558522A (en) * | 2013-10-23 | 2015-04-29 | 湖南岁丰新材料科技发展有限公司 | Ultraviolet-curing modified epoxy acrylic resin and preparation method thereof |
| CN104327248A (en) * | 2014-10-23 | 2015-02-04 | 招远鸿瑞印染有限公司 | Preparation process of photocuring material |
| CN107828050A (en) * | 2017-11-16 | 2018-03-23 | 广州日高新材料科技有限公司 | Modified epoxy acrylate resin and preparation method thereof |
| CN109181494A (en) * | 2018-08-10 | 2019-01-11 | 久盛地板有限公司 | Ground heating solid wooden floor board crack resistence paint and preparation method thereof |
| CN109181494B (en) * | 2018-08-10 | 2021-01-22 | 久盛地板有限公司 | Anti-cracking paint for floor heating solid wood floor and preparation method thereof |
| CN113004772A (en) * | 2021-02-26 | 2021-06-22 | 山东硕力新材料科技有限公司 | Environment-friendly long-acting water-based antirust agent and preparation method thereof |
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|---|---|
| CN101585766B (en) | 2012-10-10 |
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