CN101205290B - Isocyanate modified epoxy acrylic ester and preparation thereof - Google Patents
Isocyanate modified epoxy acrylic ester and preparation thereof Download PDFInfo
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- CN101205290B CN101205290B CN200710031800XA CN200710031800A CN101205290B CN 101205290 B CN101205290 B CN 101205290B CN 200710031800X A CN200710031800X A CN 200710031800XA CN 200710031800 A CN200710031800 A CN 200710031800A CN 101205290 B CN101205290 B CN 101205290B
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Abstract
The invention discloses a preparation method for isocyanate-modified epoxy acrylate, which comprises the following steps that: the epoxy resin and the inhibitor are added in a reaction vessel and the mixtures are stirred at a speed ranging from 150 to 250r/min so as to raise the temperature to 90 to 100 DEG C; then the mixtures of the acylic acid and the catalysts are added in drop by drop and the obtained mixtures are stirred to carry out a reaction for 3 to 4 hours at a speed ranging from 250 to 350r/min with controlling the temperature to rang 110 to120 DEG C so as to obtain the epoxy acrylate; the temperature of the mixtures in the reactor vessel is lowered to 50 to 60 DEG C and then the isocyanate is added in the mixtures drop by drop, and the mixtures are stirred to conduct the reaction for 0.5 to 2 hours at a speed ranging from 250 to 350r/min so as to obtain the modified epoxy acrylate. The light-cured resin obtained through the method of the invention has lower viscosity and excellent flexibility.
Description
Technical field
The present invention relates to a kind of resin and preparation method thereof, particularly a kind of isocyanate-modified epoxy acrylate and preparation method thereof.
Background technology
In recent years, world's environmental regulation is perfect day by day, require harsh day by day, traditional solvent based coating has been because the discharging of volatile organic matter (VOC) has been subjected to great impact, and is that the environment-friendly coating of representative becomes that people pay close attention to and the focus of research with ultraviolet-curing paint (UVCC), water-borne coatings, high solid coating and powder coating.Compare with the coating of other types, the UVCC curing speed is fast, solidification value is low, environmental protection and energy saving, coating performance excellence, can be used for the coating of thermo-sensitivity grounds such as plastics, paper and timber.Annual growth has surpassed 25% since 1998, and the annual growth of estimating the coming years still can not be lower than 25%.
UVCC is made up of light-cured resin, reactive monomer, light trigger and various additives.Contain the C=C unsaturated double-bond in the light-cured resin, kind commonly used at present has unsaturated polyester, epoxy acrylate, urethane acrylate, polyester acrylate, polyenoid/mercaptan system, polyether acrylate etc.
Wherein, the epoxy acrylate strong adhesion, chemical resistance is good, hardness of film is high, price is cheap, is the maximum and most widely used floodlight cured resin of present consumption.
The epoxy acrylate that prior art is produced, the resin viscosity height is semi-solid, needs to add a large amount of reactive thinners and regulates viscosity.Because reactive thinner all has special irritating smell and higher toxicity, and local environment is had pollution, and there is injury in operator; And reactive thinner costs an arm and a leg, and product cost is increased.Its fragility height of filming of coating, poor in flexibility, easy to crack by the epoxy acrylate preparation influence decorative effect.
Owing to adopt the excessive mode of Resins, epoxy during the synthesizing epoxy acrylate at present, cause epoxide group more in the product to exist, so the package stability of resin be relatively poor; Traditional preparation process technology often adopts higher temperature of reaction, causes side reaction easily, causes resin viscosity to rise and degradation.
In sum, existing prescription and the existing shortcoming of preparation technology thereof of producing epoxy acrylate, cause shorter resin storage period, over-all properties not high, need mix more reactive monomer.Therefore epoxy acrylate is carried out modification, prolong the storage period of resin, under the situation of mixing reactive monomer less, improve the over-all properties of filming, have positive meaning reducing resin cost and toxicity.
Summary of the invention
The objective of the invention is provides a kind of isocyanate-modified epoxy acrylate and preparation method thereof in order to solve the deficiency that prior art exists.Light-cured resin by this method preparation has lower viscosity and excellent flexibility.
The preparation method of isocyanate-modified epoxy acrylate of the present invention comprises the steps:
(1) in reaction vessel, adds Resins, epoxy and stopper, be warming up to 90-100 ℃ with 150-250 rev/min of speed stirring, the mixed solution of dropwise addition of acrylic acid and catalyzer, temperature control 110-120 ℃ with 250-350 rev/min of speed stirring reaction 3-4 hour, obtain epoxy acrylate;
(2) reaction vessel with step (1) is cooled to 50-60 ℃, and to wherein dripping vulcabond, with 250-350 rev/min of speed stirring reaction 0.5-2 hour, obtains modified epoxy acrylic ester.
The consumption mass fraction of above-mentioned raw materials is as follows:
Resins, epoxy 39.2～42.4
Vinylformic acid 7.3～7.6
Diisocyanate based 1.68～5.88
Catalyzer 0.27～0.51
Stopper 0.024～0.059.
The consumption mass fraction of described raw material is preferably as follows:
Resins, epoxy 39.2～39.5
Vinylformic acid 7.3～7.4
Diisocyanate based 1.90～4.55
Catalyzer 0.30～0.45
Stopper 0.024～0.035.
Described Resins, epoxy is bisphenol A type epoxy resin, preferred E-51 or E-44.
Described stopper is Resorcinol and/or MEHQ.
Described catalyzer is triphenyl phosphorus and/or Tetrabutyl amonium bromide.
Described vulcabond is one or more in tolylene diisocyanate, diphenylmethanediisocyanate, the isophorone diisocyanate.
The dropwise addition of acrylic acid of described step (1) and the mixed solution of catalyzer were added dropwise to complete in 30-60 minute, were added dropwise to complete in preferred 35-45 minute.
The dropping isocyanic ester of described step (2) was added dropwise to complete in 10-50 minute, preferably was added dropwise to complete in 15-40 minute.
The isocyanate-modified epoxy acrylate that utilizes preparation method of the present invention to obtain is that the vinylformic acid by excessive slightly (mol ratio) reacts with Resins, epoxy under catalyzer, stopper existence condition, product and isocyanic ester continue reaction, the gained resin viscosity is 5000-7000mPa.s (70 ℃), be about about 1/2 of existing commercially available prod, snappiness is 2-5mm (normal temperature), improves greatly than currently available products.
The present invention adopts the excessive slightly prescription condition of vinylformic acid for guaranteeing the abundant reaction of epoxide group, makes the synthetic resin that good stability be arranged, but can not excessive too many (being no more than 5%), in order to avoid excessive vinylformic acid causes detrimentally affect to ground.
The first step reaction of the present invention is adopted first low temperature, back pyritous processing condition.Elder generation's low temperature (90-100 ℃) is for reacting balance being carried out, avoid the generation of side reaction, but can not low excessively (being lower than 90 ℃), in order to avoid decomposition induction time is long, the end reaction time lengthening increases possibility of double-bond polymerization, viscosity rising; Back high temperature (110-120 ℃) is in order to increase speed of response in the reaction later stage, to reduce the reaction times.Adopt first low temperature, back pyritous technology makes the resin of preparation that lower viscosity be arranged.
The beneficial effect of isocyanate-modified epoxy acrylate of the present invention is: the polyurethane chain of the pendant hydroxyl group of isocyanic ester and epoxy acrylate reaction formation itself promptly has high snappiness on the one hand; This modified-reaction has been introduced the carbamate segment at the epoxy acrylic ester side chain on the other hand, its spatial volume is increased, changed the molecular structure of resin, make the molecular resin motion flexibly, snappiness strengthens, and has consumed a part of hydroxyl simultaneously, has reduced the degree that forms hydrogen bond, and making molecular resin in conjunction with no longer so tight, viscosity also reduces widely.
Embodiment
For better understanding the present invention, below in conjunction with embodiment the present invention is done detailed description further, but the scope of protection of present invention is not limited to the scope that embodiment represents.
Embodiment 1
The first step adds the MEHQ of epoxy resin E-44 and the 0.024g of 39.2g in reaction vessel, be warming up to 90 ℃ with 150 rev/mins of speed stirrings, the mixed solution of the triphenyl phosphorus of the vinylformic acid of dropping 7.3g and 0.27g in 30 minutes, temperature control 118 ℃ and stir with 250 rev/mins of speed under reaction 3 hours, epoxy acrylate;
Second step was cooled to 50 ℃ with the described reaction system of the first step, and temperature control also dripped the tolylene diisocyanate TDI/80 of 1.68g in container in 15 minutes, with 250 rev/mins of speed stirring reactions 0.5 hour, modified epoxy acrylic ester I-1.
Embodiment 2
The first step adds the Resins, epoxy E-20 of 39.5g and the Resorcinol of 0.035g in reaction vessel, be warming up to 100 ℃ with 200 rev/mins of speed stirrings, the mixed solution of the Tetrabutyl amonium bromide of the vinylformic acid of dropping 7.4g and 0.30g in 60 minutes, temperature control 120 ℃ and stir with 350 rev/mins of speed under reaction 4 hours, epoxy acrylate;
Second step was cooled to 60 ℃ with the described reaction system of the first step, and temperature control also dripped the diphenylmethanediisocyanate of 1.90g in container in 10 minutes, with 350 rev/mins of speed stirring reactions 2 hours, modified epoxy acrylic ester I-2.
Embodiment 3
The first step adds the Resins, epoxy E-51 of 42.4g and MEHQ and the Resorcinol of 0.035g in reaction vessel, be warming up to 95 ℃ with 250 rev/mins of speed stirrings, in 40 minutes, drip vinylformic acid and the triphenyl phosphorus of 0.51g and the mixed solution of Tetrabutyl amonium bromide of 7.6g, temperature control is at 120 ℃ and with 300 rev/mins of speed stirring reactions 3.5 hours, epoxy acrylate;
Second step was cooled to 55 ℃ with the described reaction system of the first step, temperature control and in 30 minutes in container the isophorone diisocyanate TDI/80 of Dropwise 5 .88g, with 300 rev/mins of speed stirring reactions 1 hour, modified epoxy acrylic ester I-3.
Embodiment 4
The first step adds the MEHQ of epoxy resin E-44 and the 0.035g of 40g in reaction vessel, be warming up to 98 ℃ with 250 rev/mins of speed stirrings, the mixed solution of the triphenyl phosphorus of the vinylformic acid of dropping 7.5g and 0.45g in 30 minutes, temperature control is at 110 ℃ and with 250 rev/mins of speed stirring reactions 3.5 hours, epoxy acrylate;
Second step was cooled to 60 ℃ with the described reaction system of the first step, temperature control also dripped isophorone diisocyanate IPDI and the diphenylmethanediisocyanate of 4.55g in container in 40 minutes, with 350 rev/mins of speed stirring reactions 2 hours, modified epoxy acrylic ester I-4.
Embodiment 5
The first step adds the Resins, epoxy E-51 of 39.2g and the Resorcinol of 0.05g in reaction vessel, be warming up to 100 ℃ with 200 rev/mins of speed stirrings, the mixed solution of the Tetrabutyl amonium bromide of the vinylformic acid of dropping 7.4g and 0.5g Resins, epoxy massfraction 1.0% in 30 minutes, temperature control 115 ℃ and in 50 minutes with 350 rev/mins of speed stirring reactions 3 hours, epoxy acrylate;
Second step was cooled to 50 ℃ with the described reaction system of the first step, temperature control also drips isophorone diisocyanate IPDI, tolylene diisocyanate TDI/80 and the diphenylmethanediisocyanate of 1.68g in container, with 330 rev/mins of speed stirring reactions 1 hour, modified epoxy acrylic ester I-5.
Embodiment 6
The first step adds the Resins, epoxy E-12 of 42g and the Resorcinol of 0.059g in reaction vessel, be warming up to 90 ℃ with 220 rev/mins of speed stirrings, the mixed solution of the Tetrabutyl amonium bromide of the vinylformic acid of dropping 7.4g and 0.45g in 45 minutes, temperature control 1120 ℃ and in 30 minutes with 250 rev/mins of speed stirring reactions 4 hours, epoxy acrylate;
Second step was cooled to 58 ℃ with the described reaction system of the first step, and temperature control also drips the tolylene diisocyanate 2 of 0.024g in container, 4-TDI, with 255 rev/mins of speed stirring reactions 1.5 hours, modified epoxy acrylic ester I-6.
Embodiment 7
The first step adds the Resins, epoxy E-51 of 39.5g and the MEHQ of 0.035g in reaction vessel, be warming up to 100 ℃ with 230 rev/mins of speed stirrings, the mixed solution of the triphenyl phosphorus of the vinylformic acid of dropping 7.5g and 0.51g in 35 minutes, temperature control 110C and in 30 minutes with 250 rev/mins of speed stirring reactions 4 hours, epoxy acrylate;
Second step was cooled to 55 ℃ with the described reaction system of the first step, and temperature control also drips the diphenylmethanediisocyanate MDI of 4.55g in container, with 350 rev/mins of speed stirring reactions 2 hours, modified epoxy acrylic ester I-7.
Embodiment 8
Modified epoxy acrylic ester of the present invention and product that existing market is sold are carried out package stability relatively, and the result is: when modified epoxy acrylic ester of the present invention, room temperature are six months following storage period, do not have tangible viscosity rising phenomenon, good fluidity; And product viscosity that sell in market rises, retrogradation, mobile variation.Prove that modified epoxy acrylic ester of the present invention has better package stability, sees table 1 for details.
Embodiment 9
Modified epoxy acrylic ester of the present invention and product that existing market is sold are carried out viscosity test relatively, the result is: modified epoxy acrylic ester of the present invention, viscosity is about about 1/2 of product that existing market is sold, prove that modified epoxy acrylic ester of the present invention has lower viscosity, sees table 1 for details.
Embodiment 10
Modified epoxy acrylic ester of the present invention and product that existing market is sold are cured the snappiness test comparison of filming, see table 1 for details.
Table 1
| Sample | Package stability | Viscosity (mPa.s/70 ℃) | Snappiness (mm) |
| I-1 | Excellent, no considerable change | 5800 | 5 |
| I-2 | Excellent, no considerable change | 6200 | 4 |
| I-3 | Excellent, no considerable change | 5400 | 3 |
| I-4 | Excellent, no considerable change | 5100 | 2 |
| I-5 | Excellent, no considerable change | 4850 | 2 |
| I-6 | Excellent, no considerable change | 6500 | 4 |
| Sample | Package stability | Viscosity (mPa.s/70 ℃) | Snappiness (mm) |
| I-7 | Excellent, no considerable change | 5650 | 3 |
| The commercially available prod | Retrogradation, mobile variation | 10500 | ＞10 |
Table 1 result shows: modified epoxy acrylic ester cured coating film snappiness of the present invention is 2-5mm, and products solidifying that sell in the market snappiness of filming is 15mm, proves that modified epoxy acrylic ester of the present invention has excellent flexibility.
Claims (9)
1. the preparation method of an isocyanate-modified epoxy acrylate is characterized in that, comprises the steps:
(1) in reaction vessel, adds Resins, epoxy and stopper, be warming up to 90-100 ℃ with 150-250 rev/min of speed stirring, the mixed solution of dropwise addition of acrylic acid and catalyzer, temperature control is at 110-120 ℃, with 250-350 rev/min of speed stirring reaction 3-4 hour, obtain epoxy acrylate;
(2) reaction vessel with step (1) is cooled to 50-60 ℃, and to wherein dripping vulcabond, with 250-350 rev/min of speed stirring reaction 0.5-2 hour, obtains modified epoxy acrylic ester;
The consumption mass fraction of above-mentioned raw materials is as follows:
Resins, epoxy 39.2～42.4
Vinylformic acid 7.3～7.6
Vulcabond 1.68～5.88
Catalyzer 0.27～0.51
Stopper 0.024～0.059.
2. preparation method according to claim 1 is characterized in that, the consumption mass fraction of described raw material is preferably as follows:
Resins, epoxy 39.2～39.5
Vinylformic acid 7.3～7.4
Vulcabond 1.90～4.55
Catalyzer 0.30～0.45
Stopper 0.024～0.035.
3. preparation method according to claim 1 is characterized in that, described Resins, epoxy is bisphenol A type epoxy resin.
4. preparation method according to claim 1 is characterized in that, described stopper is Resorcinol and/or MEHQ.
5. preparation method according to claim 1 is characterized in that, described catalyzer is triphenyl phosphorus and/or Tetrabutyl amonium bromide.
6. preparation method according to claim 1 is characterized in that, described vulcabond is one or more in tolylene diisocyanate, diphenylmethanediisocyanate, the isophorone diisocyanate.
7. preparation method according to claim 1 is characterized in that, the dropwise addition of acrylic acid of described step (1) and the mixed solution of catalyzer were added dropwise to complete in 30-60 minute.
8. preparation method according to claim 1 is characterized in that, the dropping vulcabond of described step (2) was added dropwise to complete in 10-50 minute.
9. the isocyanate-modified epoxy acrylate that obtains of the described preparation method of one of claim 1-8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN200710031800XA CN101205290B (en) | 2007-11-30 | 2007-11-30 | Isocyanate modified epoxy acrylic ester and preparation thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710031800XA CN101205290B (en) | 2007-11-30 | 2007-11-30 | Isocyanate modified epoxy acrylic ester and preparation thereof |
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| CN101205290A CN101205290A (en) | 2008-06-25 |
| CN101205290B true CN101205290B (en) | 2010-04-21 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101942072A (en) * | 2010-09-30 | 2011-01-12 | 烟台德邦科技有限公司 | Synthetic method of epoxy acrylate |
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| CN101928379A (en) * | 2010-08-24 | 2010-12-29 | 华南理工大学 | Ultraviolet-cured low-viscosity epoxy acrylate and preparation method thereof |
| CN102827342B (en) * | 2012-02-03 | 2014-06-04 | 黑龙江省科学院石油化学研究院 | Epoxy group contained isocyanated acrylate monomer, and preparation method and application thereof |
| CN102702480B (en) * | 2012-06-29 | 2015-06-03 | 惠州市长润发涂料有限公司 | Modified epoxy acrylate and preparation method thereof |
| CN102702479A (en) * | 2012-06-29 | 2012-10-03 | 惠州市长润发涂料有限公司 | Method for synthesizing modified epoxy acrylate |
| CN103013414B (en) * | 2012-12-20 | 2014-01-08 | 东华大学 | Alpha-cyanogroup-beta-ethyl ethoxyacrylate modified epoxy resin adhesive and preparation method thereof |
| CN105885013B (en) * | 2016-04-26 | 2018-05-08 | 深圳市姿彩科技有限公司 | A kind of preparation method for the low viscosity epoxy acrylic resin that can be used for spraying |
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| CN110483743A (en) * | 2019-06-28 | 2019-11-22 | 广东博兴新材料科技有限公司 | A kind of modified epoxy acrylic ester resin, preparation method and its preparing the application in conductive adhesive |
| CN113150245B (en) * | 2021-04-30 | 2022-01-21 | 华南农业大学 | Modified vinyl ester resin and preparation method thereof, toughened and modified vinyl ester resin with good air-drying property and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1081187A (en) * | 1992-07-06 | 1994-01-26 | 上海新华树脂厂 | Isocyanate-modified vinyl ester resin |
| CN1810847A (en) * | 2006-01-17 | 2006-08-02 | 江苏三木集团有限公司 | Improved epoxy acrylic ester and its prepn |
-
2007
- 2007-11-30 CN CN200710031800XA patent/CN101205290B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1081187A (en) * | 1992-07-06 | 1994-01-26 | 上海新华树脂厂 | Isocyanate-modified vinyl ester resin |
| CN1810847A (en) * | 2006-01-17 | 2006-08-02 | 江苏三木集团有限公司 | Improved epoxy acrylic ester and its prepn |
Non-Patent Citations (4)
| Title |
|---|
| Stefan Oprea, et al.Epoxy urethane acrylate.European Polymer Journal 36.2000,(36),373-378. |
| Stefan Oprea, et al.Epoxy urethane acrylate.European Polymer Journal 36.2000,(36),373-378. * |
| 王锋，涂伟萍.UV固化环氧丙烯酸酯涂料研究进展.热固性树脂22 4.2007,22(4),36-40. * |
| 王锋，胡剑青，涂伟萍.UV固化低聚物及其涂料研究进展.热固性树脂22 3.2007,22(3),41-46. * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101942072A (en) * | 2010-09-30 | 2011-01-12 | 烟台德邦科技有限公司 | Synthetic method of epoxy acrylate |
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Assignee: Jiangmen Paint Factory Co., Ltd. Assignor: South China University of Technology Contract record no.: 2010440001521 Denomination of invention: Isocyanate modified epoxy acrylic ester and preparation thereof Granted publication date: 20100421 License type: Exclusive License Open date: 20080625 Record date: 20101215 |
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