CN103360576A - Synthetic method of modified bisphenol A epoxy acrylate - Google Patents
Synthetic method of modified bisphenol A epoxy acrylate Download PDFInfo
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- CN103360576A CN103360576A CN2013103134662A CN201310313466A CN103360576A CN 103360576 A CN103360576 A CN 103360576A CN 2013103134662 A CN2013103134662 A CN 2013103134662A CN 201310313466 A CN201310313466 A CN 201310313466A CN 103360576 A CN103360576 A CN 103360576A
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Abstract
The present invention discloses a synthetic method of modified bisphenol A epoxy acrylate. The synthetic method comprises mixing and heating bisphenol A epoxy resin, polyethylene glycol, a catalyst and a polymerization inhibitor, reacting at 100-120 DEG C for 1-2 hours, adding acrylic acid, incubating at 100-120 DEG C for 3-5 hours to obtain modified bisphenol A epoxy acrylate, wherein the weight of polyethylene glycol is 10-30% of that of bisphenol A epoxy resin, and the weight of acrylic acid is 10%-30% of a total weight of bisphenol A epoxy resin and polyethylene glycol. The modified bisphenol A epoxy acrylate synthesized by the invention significantly helps to improve flexibility and resistance to yellowing of a product, reduce the viscosity of the bisphenol A epoxy acrylate, and expand application areas of the product, and can be used in UV curable inks and plastic coatings.
Description
Technical field
The invention belongs to the synthetic field of resin, be specifically related to a kind of synthetic method of modified bisphenol A epoxy acrylate.
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 20 century 70s.Epoxy acrylate is by commodity Resins, epoxy and acrylic or methacrylic acid esters and get, and is a class photocuring oligopolymer of present domestic photocuring industry internal consumption amount maximum.According to structure type, epoxy acrylate is divided into again bisphenol-a epoxy acrylate, Epoxy Phenolic Acrylates, modified epoxy acrylic ester and epoxy soybean oil acrylate, and is wherein maximum with the bisphenol-a epoxy acrylate consumption again.
Contain aromatic ring and side position hydroxyl in the bisphenol-a epoxy acrylate molecular structure, favourable to improving sticking power; Aromatic ring structure is also given the higher rigidity of resin, tensile strength and thermostability in addition; In general, the principal feature of bisphenol A epoxy acrylate comprises: photocuring reaction speed is very fast, and hardness and tensile strength are large after solidifying, and the rete glossiness is high, and the chemicals-resistant corrosive nature is excellent.Can be widely used as in basic candidate's resin of photo-cured coating, printing ink, tackiness agent.But its main drawback is: the one, bisphenol A epoxy acrylate finished product viscosity is large, substantially at 5000～10000cps(60 ℃), at room temperature mobile very poor, be almost solid-state.Thereby all need baking before using, cause construction inconvenience; The 2nd, the rigid structure of bisphenol A epoxy acrylate causes cured film fragility large, and the snappiness deficiency has limited its consumption and the aspect such as Application Areas; The 3rd, because the catalyzer that adds is tertiary amine or quaternary ammonium salt absolutely mostly, and after finishing, reaction can't go out the yellowing resistance variation that catalyzer makes paint film by effective separation in the process of synthesis of bisphenol A epoxy acrylate.So, requiring the good field of yellowing resistance, such as the plastic cement finish paint, paper glazing wet goods field, bisphenol-a epoxy acrylate can't finely reach requirement.
Therefore, the scientific research personnel has done some effort and trial for above problem is also corresponding.Common methods is improved snappiness as introducing fatty acid modified epoxy acrylate; Or with epoxy soybean oil synthesizing epoxy soybean oil acrylate to reduce viscosity, increase flexible; And use first dibasic acid anhydride (such as Tetra hydro Phthalic anhydride) and Hydroxyethyl acrylate reactant again with the ordinary method such as Resins, epoxy reaction preparation modified epoxy acrylic ester but all can't be more than the fine solution three problems.
Summary of the invention
The object of the present invention is to provide a kind of synthetic method of modified bisphenol A epoxy acrylate, the modified bisphenol A epoxy acrylate that obtains of method has low viscosity and higher anti-yellowing change and snappiness thus.
The present invention realizes that technical scheme that above-mentioned purpose adopts is as follows:
A kind of synthetic method of modified bisphenol A epoxy acrylate, this synthetic method comprises bisphenol A epoxide resin, polyoxyethylene glycol, catalyzer and stopper Hybrid Heating, add vinylformic acid in 100～120 ℃ of lower reactions after 1～2 hour, 100～120 ℃ of lower insulations 3～5 hours, namely obtain modified bisphenol A epoxy acrylate, wherein, the consumption of described polyoxyethylene glycol is 0.1～0.3 times of bisphenol A epoxide resin weight, and described acrylic acid consumption is 10%～30% of bisphenol A epoxide resin and polyoxyethylene glycol gross weight.
Further, described catalyzer is Tetrabutyl amonium bromide.
Further, the consumption of described catalyzer is 0.1%～0.5% of bisphenol A epoxide resin and polyoxyethylene glycol gross weight.
Further, described stopper is MEHQ.
Further, the consumption of described stopper is 0.1%～0.5% of bisphenol A epoxide resin and polyoxyethylene glycol gross weight.
Further, the molecular-weight average of described polyoxyethylene glycol is 400～600.
The present invention carries out modification with polyoxyethylene glycol to bisphenol A epoxy acrylate, a large amount of ehter bond in the polyethylene glycol structures and C-C key are easy to rotation, therefore greatly improved the snappiness of modified bisphenol A epoxy acrylate, simultaneously because molecular structure is easy to rotation, intermolecular reactive force also reduces greatly, and therefore corresponding product viscosity also reduces greatly.The present invention also finds will be much better than with the modified bisphenol A epoxy acrylate yellowing resistance that Tetrabutyl amonium bromide is done the catalyzer gained and adopts triethylamine to make catalyzer.
Modified bisphenol A epoxy acrylate provided by the present invention is compared snappiness, the yellowing resistance that has significantly improved product with existing bisphenol A epoxy acrylate, reduced the viscosity of bisphenol A epoxy acrylate, it is mobile to have improved product, enlarged the Application Areas of this material, as can be applicable to light-curable ink, plastic coating etc.
Embodiment
The present invention is by below in conjunction with specific examples, and is for a more detailed description to the present invention, but it can not be interpreted as limiting protection scope of the present invention.
The preparation of embodiment one bisphenol A epoxy acrylate
First with bisphenol A epoxide resin 660g(epoxy equivalent (weight) 185～195g/eq, available from Jiangsu three lignify worker company limiteds), vinylformic acid 240g, catalyst of triethylamine 2.7g, stopper MEHQ 3g all add in the reactor.Raw material is opened and is stirred after all throwing well, regulates mixing speed at 80～100 rev/mins, and beginning is intensification slowly, is warming up to 115 ℃ in about 1 hour.Then 115～120 ℃ of insulations 5 hours, detect acid number after insulation finishes, treat acid number less than 5mgKOH/g, can open the cooling of water coolant raft, be down to 80 ℃ of blowings.During acid number of the present invention refers to and the mg value of the required potassium hydroxide of 1g sample.
The preparation of embodiment two modified bisphenol A epoxy acrylates
With bisphenol A epoxide resin 470g(epoxy equivalent (weight) 185～195g/eq) and polyoxyethylene glycol 47g(molecular-weight average 400～600) join in the reaction vessel, and adding catalyzer Tetrabutyl amonium bromide 2.1kg, stopper MEHQ 1.2kg, begin to stir and be warming up to 110 ℃ of temperature of reaction, reacted 1～2 hour, after acid number is less than 1, add again 52g vinylformic acid, then 115 ℃ of insulations 3～5 hours, when acid number gets final product less than 5.
The preparation of embodiment three modified bisphenol A epoxy acrylates
With bisphenol A epoxide resin 470g(epoxy equivalent (weight) 185～195g/eq) and polyoxyethylene glycol 140g(molecular-weight average 400～600) join in the reaction vessel, and adding catalyst of triethylamine 2.4kg, stopper MEHQ 1.2kg, begin to stir and be warming up to 100 ℃ of temperature of reaction, reacted 1～2 hour, after acid number is less than 1, add again 170g vinylformic acid, then 100 ℃ of insulations 3～5 hours, when acid number gets final product less than 5.
The preparation of embodiment four modified bisphenol A epoxy acrylates
With bisphenol A epoxide resin 470g(epoxy equivalent (weight) 185～195g/eq) and polyoxyethylene glycol 140g(molecular-weight average 400～600) join in the reaction vessel, and adding catalyzer Tetrabutyl amonium bromide 2.4kg, stopper MEHQ 1.1kg, begin to stir and be warming up to 120 ℃ of temperature of reaction, reacted 1～2 hour, after acid number is less than 1, add again 180g vinylformic acid, then 120 ℃ of insulations 3～5 hours, when acid number gets final product less than 5.
Performance parameter test
1, viscosity test, snappiness test
Detect snappiness according to standard GB/T/T 1731-1993;
Viscosity: use rotational viscosimeter to test 60 ℃.
2, anti-yellowing change test
Testing method
Light trigger (model: 1173, chemical name: 2-hydroxy-methyl phenyl-propane-1-ketone
Proportioning: light trigger (1173): modified bisphenol A epoxy acrylate=3:97(mass ratio)
Base material: white polycarbonate plate
Technique: the mixture of light trigger and modified bisphenol A epoxy acrylate is stirred by above proportioning, with 10 μ m lines rods blade coating on white polycarbonate plate, thickness=10 μ m, place 60 ℃ of thermostatic drying chamber levelling 5min, taking-up is solidified with ultraviolet lamp, colorimetric case ready visual contrast xanthochromia situation.
Illuminate condition: lamp distance: 10cm; Linear speed: 10m/s
Test result
Claims (6)
1. the synthetic method of a modified bisphenol A epoxy acrylate, it is characterized in that: described synthetic method comprises bisphenol A epoxide resin, polyoxyethylene glycol, catalyzer and stopper Hybrid Heating, add vinylformic acid in 100～120 ℃ of lower reactions after 1～2 hour, 100～120 ℃ of lower insulations 3～5 hours, namely obtain modified bisphenol A epoxy acrylate, wherein, the consumption of described polyoxyethylene glycol is 0.1～0.3 times of bisphenol A epoxide resin weight, and described acrylic acid consumption is 10%～30% of bisphenol A epoxide resin and polyoxyethylene glycol gross weight.
2. the synthetic method of modified bisphenol A epoxy acrylate according to claim 1, it is characterized in that: described catalyzer is Tetrabutyl amonium bromide.
3. the synthetic method of modified bisphenol A epoxy acrylate according to claim 1, it is characterized in that: the consumption of described catalyzer is 0.1%～0.5% of bisphenol A epoxide resin and polyoxyethylene glycol gross weight.
4. the synthetic method of modified bisphenol A epoxy acrylate according to claim 1, it is characterized in that: described stopper is MEHQ.
5. the synthetic method of modified bisphenol A epoxy acrylate according to claim 1, it is characterized in that: the consumption of described stopper is 0.1%～0.5% of bisphenol A epoxide resin and polyoxyethylene glycol gross weight.
6. the synthetic method of modified bisphenol A epoxy acrylate according to claim 1, it is characterized in that: the molecular-weight average of described polyoxyethylene glycol is 400～600.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104497696A (en) * | 2014-12-17 | 2015-04-08 | 江苏广信感光新材料股份有限公司 | UV-cured organopolysiloxane resin for ITO touch screen protection sealant |
| CN105400383A (en) * | 2014-09-11 | 2016-03-16 | 洋紫荆油墨（浙江）有限公司 | Flexible ultraviolet-light-curable varnishing oil and preparation method thereof |
| CN106279638A (en) * | 2016-08-16 | 2017-01-04 | 浙江创赢新材料有限公司 | The preparation method of poly-modified by polyacid UV cured epoxy acrylic performed polymer |
| CN111032234A (en) * | 2017-08-16 | 2020-04-17 | 巴斯夫欧洲公司 | Method for producing a matt coating on a sheet-like substrate |
| CN111269638A (en) * | 2020-03-20 | 2020-06-12 | 广州市帝天印刷材料有限公司 | UV (ultraviolet) sun-proof coating varnish and preparation method thereof |
| CN115820187A (en) * | 2022-10-08 | 2023-03-21 | 广东光固新材料有限公司 | High-cohesiveness ultraviolet-curing adhesive and preparation method thereof |
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| JPH1036762A (en) * | 1996-07-23 | 1998-02-10 | Kansai Paint Co Ltd | Aqueous epoxy resin composition |
| CN101928508A (en) * | 2010-08-24 | 2010-12-29 | 华南理工大学 | Polyethylene glycol-modified epoxy acrylate coating and preparation method thereof |
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2013
- 2013-07-24 CN CN2013103134662A patent/CN103360576A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1036762A (en) * | 1996-07-23 | 1998-02-10 | Kansai Paint Co Ltd | Aqueous epoxy resin composition |
| CN101928508A (en) * | 2010-08-24 | 2010-12-29 | 华南理工大学 | Polyethylene glycol-modified epoxy acrylate coating and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105400383A (en) * | 2014-09-11 | 2016-03-16 | 洋紫荆油墨（浙江）有限公司 | Flexible ultraviolet-light-curable varnishing oil and preparation method thereof |
| CN104497696A (en) * | 2014-12-17 | 2015-04-08 | 江苏广信感光新材料股份有限公司 | UV-cured organopolysiloxane resin for ITO touch screen protection sealant |
| CN104497696B (en) * | 2014-12-17 | 2016-04-20 | 江苏广信感光新材料股份有限公司 | A kind of UV of ITO touch screen protective glue solidifies polyorganosiloxane resin |
| CN106279638A (en) * | 2016-08-16 | 2017-01-04 | 浙江创赢新材料有限公司 | The preparation method of poly-modified by polyacid UV cured epoxy acrylic performed polymer |
| CN111032234A (en) * | 2017-08-16 | 2020-04-17 | 巴斯夫欧洲公司 | Method for producing a matt coating on a sheet-like substrate |
| CN111032234B (en) * | 2017-08-16 | 2023-11-03 | 巴斯夫欧洲公司 | Method for producing matt coatings on sheet-like substrates |
| CN111269638A (en) * | 2020-03-20 | 2020-06-12 | 广州市帝天印刷材料有限公司 | UV (ultraviolet) sun-proof coating varnish and preparation method thereof |
| CN115820187A (en) * | 2022-10-08 | 2023-03-21 | 广东光固新材料有限公司 | High-cohesiveness ultraviolet-curing adhesive and preparation method thereof |
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Application publication date: 20131023 |