CN102516326A - Method for synthesizing tannin-based hyperbranched acrylic acid ester - Google Patents
Method for synthesizing tannin-based hyperbranched acrylic acid ester Download PDFInfo
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- CN102516326A CN102516326A CN2011104067473A CN201110406747A CN102516326A CN 102516326 A CN102516326 A CN 102516326A CN 2011104067473 A CN2011104067473 A CN 2011104067473A CN 201110406747 A CN201110406747 A CN 201110406747A CN 102516326 A CN102516326 A CN 102516326A
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- acid ester
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- propenoic acid
- tannin
- hyperbranched propenoic
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Abstract
A method for synthesizing tannin-based hyperbranched acrylic acid ester contains the following preparation steps of: dissolving tannic acid, a catalyst and a polymerization inhibitor in a reaction solvent at normal pressure; heating the mixed system to 80-90 DEG C while stirring, adding dropwisely into an epoxy monomer within 0.5-1h; sealing the reaction container, keeping stirring, heating the temperature of the mixed liquor to 90-100 DEG C, and reacting under insulation for 45-50 hours to obtain a dark brown sticky product after the reaction. The dark brown sticky product is the tannin-based hyperbranched acrylic acid ester. The synthesis technology provided by the invention has advantages of simple condition, renewable raw materials, green and environmental protection, and can satisfy requirements of sustainable development.
Description
Technical field
The present invention relates to ultraviolet light polymerization and polymerization technique field, especially relate to a kind of tannin base that utilizes and carry out acrylate hyperbranched method.
Background technology
Because the research of most coating and industrialization product thereof all are to be main raw material(s) with the petroleum chemicals, when consuming the bulk petroleum resource also with some poisonous petroleum chemicalss of inevasible release.And petroleum resources is progressively exhausted; Rising steadily of price; And more and more stricter legislations of environmental protection will have influence on the Sustainable development of coatings industry; So coatings industry day by day transforms to green industry through introducing more alternative starting material and green technology (like ultraviolet light polymerization, high solids content and water-borne coatings technology etc.).
UV-curing technology has energy-saving and environmental protection, economic dispatch advantage, and development is comparatively rapid in current coating industry; Renewable resources is owing to wide material sources, with low cost and renewable, environmental protection; In coatings industry, has very application prospects, so utilize the alternative petroleum base resin of renewable raw materials synthesising biological base light-cured resin that the Sustainable development of coatings industry is had great importance.
The bio-based UV-cured resin; Especially the development of light-cured resin that with the vegetables oil is presoma is very rapid; Investigators have carried out a large amount of work and have developed a series of commercial bio-based light-cured resins (like the Ebecryl860 of UCB chemical company); The research of other renewable resources such as starch, rosin and verivate simultaneously is also flourish, and obtained bigger progress, in the resin of radical photoinitiator curing system and cation photocuring system synthesizes, application arranged all.Though the development of these bio-based light-cured resins is very fast; But because the development time in this field is shorter at present; The restriction of renewable resources that is utilized and verivate kind thereof, and the reasons such as constitutional features of renewable resources and verivate, the bio-based UV-cured resin that is obtained also is short of in the performance of aspects such as photocuring activity, cured film mechanical property, mechanical property to some extent; And kind is also less, thereby has limited further developing of bio-based photo-cured coating.
Summary of the invention
To the problems referred to above that prior art exists, the applicant provides a kind of preparation method and use of tannin base hyperbranched propenoic acid ester.Synthetic technological condition of the present invention is simple, regenerated raw materials, and environmental protection more can be satisfied the requirement of Sustainable development.
Technical scheme of the present invention is following:
A kind of compound method of tannin base hyperbranched propenoic acid ester, preparation process is following: under condition of normal pressure, Weibull, catalyzer and stopper are dissolved in the reaction solvent; Under whipped state, mixed system is heated to 80 ~ 90 ℃ after, dropwise splash into epoxy monomer, drip off in 0.5 ~ 1h; Sealed reaction vessel keeps stirring, and mixeding liquid temperature is risen to 90 ~ 100 ℃ of following insulation reaction 45 ~ 50 hours; Reaction obtains the thick product of dark-brown after finishing, and is tannin base hyperbranched propenoic acid ester;
Said catalyzer is a kind of in triphenylphosphine, Tetrabutyl amonium bromide, 4 bromide, the triethylamine, catalyst consumption be Weibull and epoxy monomer quality and 0.5 ~ 1.5%.Said stopper is MEHQ, Resorcinol, Resorcinol, 2, a kind of in the 6-di-t-butyl p-ethyl phenol, the consumption of stopper be Weibull and epoxy monomer quality and 0.05 ~ 0.15%.Said reaction solvent is N, any one in dinethylformamide, water, ETHYLE ACETATE, ethanol, butylacetate, the acetone or their mutual mixtures, and the consumption of reaction solvent is 20 ~ 60% of a reaction system total mass;
Said epoxy monomer reaches the epoxy monomer that does not contain photosensitive pair of key by the epoxy monomer that contains photosensitive pair of key to be formed, and the amount of substance that wherein contains the epoxy monomer of photosensitive pair of key is 20 ~ 100% of total epoxy monomer.The said epoxy monomer that contains photosensitive pair of key is a kind of in SY-Monomer G, glycidyl allyl ether, the glycidyl acrylate; The said epoxy monomer that does not contain photosensitive pair of key is a kind of in tertiary carbonic acid glycidyl ester, n-butyl glycidyl ether, octyl glycidyl ether, Racemic glycidol butyl ester, the ethylene glycol diglycidylether.Said Weibull and epoxy monomer are pressed the mole group of phenolic hydroxyl group and epoxy group(ing) than being 1:2 to 2:1.
Beneficial technical effects of the present invention is:
The present invention is a main raw material with the Weibull that contains the polyphenol hydroxyl structure; Under the basic catalyst condition, carry out opening through phenolic hydroxyl group on the Weibull and the epoxy monomer that contains active epoxy group(ing); Introduce the vinyl that can carry out ultraviolet light polymerization simultaneously and (have vinyl on the epoxy monomer; Be photosensitive pair of key), the content of introducing vinyl is controlled.This propenoate can be used the ultraviolet-curing paint of the high bio-based content of preparation with existing plant oil based light-cured resin, can improve the over-all properties of cured film simultaneously.
Description of drawings
Fig. 1 is infrared (FTIR) spectrogram of this tannin base hyperbranched propenoic acid ester.
Fig. 2 be this tannin base hyperbranched propenoic acid ester nuclear-magnetism (
1H-NMR) spectrogram.
Embodiment
Be equipped with TM, mechanical stirring, reflux exchanger there-necked flask in add the deionized water of 17.012g (10.00mmol) Weibull, 0.788g triphenylphosphine, 0.079g MEHQ, 13.138g, slow stirring heating mixture to 90 ℃; Dropwise splash into 35.538g (250.00mmol) SY-Monomer G with tap funnel, the control rate of addition drips off in the 1h; Sealed reaction vessel rises to solution temperature and continues stirring until reaction 45h under 95 ℃ and finish the postcooling cooling, is bio-based hyperbranched propenoic acid ester---tannin acidic group hyperbranched propenoic acid ester.
Be equipped with TM, mechanical stirring, reflux exchanger there-necked flask in add ethanol/n-butyl acetate mixed solvent of 17.012g (10.00mmol) Weibull, 0.491g 4 bromide, 0.049g Resorcinol, 49.127g, slow stirring heating mixture to 80 ℃; Dropwise splash into 22.800g (200.00mmol) glycidyl acrylate and 9.315g (50.00mmol) octyl glycidyl ether with tap funnel, the control rate of addition drips off in 0.5; Sealed reaction vessel rises to solution temperature and continues stirring until reaction 48h under 90 ℃ and finish the postcooling cooling, is bio-based hyperbranched propenoic acid ester---tannin acidic group hyperbranched propenoic acid ester.
Be equipped with TM, mechanical stirring, reflux exchanger there-necked flask in add the ethyl acetate and butyl acetate mixed solvent of 25.518g (15.00mmol) Weibull, 0.278g triphenylphosphine, 0.028g Resorcinol, 37.309g, slow stirring heating mixture to 90 ℃; Dropwise splash into 17.121g (150.00mmol) glycidyl allyl ether and 13.019g (100.00mmol) n-butyl glycidyl ether with tap funnel, the control rate of addition drips off in 0.5; Sealed reaction vessel rises to solution temperature and continues stirring until reaction 50h under 100 ℃ and finish the postcooling cooling, is bio-based hyperbranched propenoic acid ester---tannin acidic group hyperbranched propenoic acid ester.
Be equipped with TM, mechanical stirring, reflux exchanger there-necked flask in add the acetone/butyl acetate mixed solvent of 34.024g (20.00mmol) Weibull, 0.600g Tetrabutyl amonium bromide, 0.040g MEHQ, 100.575g, slow stirring heating mixture to 85 ℃; Dropwise splash into 11.400g (100.00mmol) glycidyl acrylate and 21.626g (150.00mmo) Racemic glycidol butyl ester with tap funnel, the control rate of addition drips off in 0.5; Sealed reaction vessel rises to solution temperature and continues stirring until reaction 48h under 95 ℃ and finish the postcooling cooling, is bio-based hyperbranched propenoic acid ester---tannin acidic group hyperbranched propenoic acid ester.
Be equipped with TM, mechanical stirring, reflux exchanger there-necked flask in add 17.012g (10.00mmol) Weibull, 0.472g Tetrabutyl amonium bromide, 0.071g MEHQ, 14.740gN; Dinethylformamide, slowly stirring heating mixture to 85 ℃; Dropwise splash into 7.108g (50.00mmol) SY-Monomer G and 34.840g (200.00mmol) ethylene glycol diglycidylether with tap funnel, the control rate of addition drips off in 0.5; Sealed reaction vessel rises to solution temperature and continues stirring until reaction 48h under 95 ℃ and finish the postcooling cooling, is bio-based hyperbranched propenoic acid ester---tannin acidic group hyperbranched propenoic acid ester.
Be equipped with TM, mechanical stirring, reflux exchanger there-necked flask in add the deionized water of 17.012g (10.00mmol) Weibull, 1.476g triphenylphosphine, 0.098g MEHQ, 24.593g, slow stirring heating mixture to 80 ℃; Dropwise splash into 56.860g (400.00mmol) SY-Monomer G and 24.500g (100.00mmol) tertiary carbonic acid glycidyl ester with tap funnel, the control rate of addition drips off in the 1h; Sealed reaction vessel rises to solution temperature and continues stirring until reaction 48h under 95 ℃ and finish the postcooling cooling, is bio-based hyperbranched propenoic acid ester---tannin acidic group hyperbranched propenoic acid ester.
The chemical reagent that above embodiment adopted is the commercially available prod.Carry out structure detection in the face of embodiment 1 resulting tannin acidic group hyperbranched propenoic acid ester down, detected result is as depicted in figs. 1 and 2; The structure detection of the product that all the other embodiment 2 ~ 6 obtain is similar with embodiment 1.
Can find out from the infrared spectrum (Fig. 1) of novel tannin base hyperbranched propenoic acid ester: 3410cm
-1The place is the hydroxyl of Weibull and the formation of epoxy monomer generation ring-opening reaction, 715cm
-1The place is C=O stretching vibration absorption peak, 1600 cm
-1, 1540 cm
-1The place is the skeleton stretching vibration of phenyl ring, 1760cm
-1Be the out-of-plane deformation vibration of phenyl ring, 2900 cm
-1~ 2965cm
-1The place is the methyl in the epoxy monomer, the C-H stretching vibration absorption peak of methylene radical, 1636cm
-1, 810cm
-1The place is the stretching vibration of C=C in the vinyl of introducing, 908 cm
-1The epoxy absorption peak of place's methyl propenoic acid glycidyl ether disappears.
The test (Fig. 2) of the proton nmr spectra through tannin base hyperbranched propenoic acid ester; The kind of clear each the pairing hydrogen in peak of figure acceptance of the bid; Consistent with the title product structure, therefore can judge the tannin base hyperbranched propenoic acid ester that has successfully synthesized the title product uV curable.
More than two kinds of signs proved that all we have synthesized tannin base hyperbranched propenoic acid ester.The foregoing description is used for the present invention that explains, rather than limits the invention, and in the protection domain of spirit of the present invention and claim, any modification and change to the present invention makes all fall into protection scope of the present invention.
Claims (7)
1. the compound method of a tannin base hyperbranched propenoic acid ester is characterized in that preparation process is following: under condition of normal pressure, Weibull, catalyzer and stopper are dissolved in the reaction solvent; Under whipped state, mixed system is heated to 80 ~ 90 ℃ after, dropwise splash into epoxy monomer, drip off in 0.5 ~ 1h; Sealed reaction vessel keeps stirring, and mixeding liquid temperature is risen to 90 ~ 100 ℃ of following insulation reaction 45 ~ 50 hours; Reaction obtains the thick product of dark-brown after finishing, and is tannin base hyperbranched propenoic acid ester.
2. the compound method of tannin base hyperbranched propenoic acid ester according to claim 1; It is characterized in that; Said catalyzer is a kind of in triphenylphosphine, Tetrabutyl amonium bromide, 4 bromide, the triethylamine, catalyst consumption be Weibull and epoxy monomer quality and 0.5 ~ 1.5%.
3. the compound method of tannin base hyperbranched propenoic acid ester according to claim 1; It is characterized in that; Said stopper is MEHQ, Resorcinol, Resorcinol, 2; A kind of in the 6-di-t-butyl p-ethyl phenol, the consumption of stopper be Weibull and epoxy monomer quality and 0.05 ~ 0.15%.
4. the compound method of tannin base hyperbranched propenoic acid ester according to claim 1; It is characterized in that; Said reaction solvent is N; In dinethylformamide, water, ETHYLE ACETATE, ethanol, butylacetate, the acetone any one or their mutual mixtures, the consumption of reaction solvent is 20 ~ 60% of a reaction system total mass.
5. the compound method of tannin base hyperbranched propenoic acid ester according to claim 1; It is characterized in that; Said epoxy monomer reaches the epoxy monomer that does not contain photosensitive pair of key by the epoxy monomer that contains photosensitive pair of key to be formed, and the amount of substance that wherein contains the epoxy monomer of photosensitive pair of key is 20 ~ 100% of total epoxy monomer.
6. the compound method of tannin base hyperbranched propenoic acid ester according to claim 5 is characterized in that, the said epoxy monomer that contains photosensitive pair of key is a kind of in SY-Monomer G, glycidyl allyl ether, the glycidyl acrylate; The said epoxy monomer that does not contain photosensitive pair of key is a kind of in tertiary carbonic acid glycidyl ester, n-butyl glycidyl ether, octyl glycidyl ether, Racemic glycidol butyl ester, the ethylene glycol diglycidylether.
7. according to the compound method of claim 1 and 5 described tannin base hyperbranched propenoic acid esters, it is characterized in that said Weibull and epoxy monomer press the mole group of phenolic hydroxyl group and epoxy group(ing) than being 1:2 to 2:1.
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Cited By (12)
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| CN102796441A (en) * | 2012-09-12 | 2012-11-28 | 江南大学 | Novel polyphenol photocuring antibacterial paint |
| CN104650341A (en) * | 2013-11-19 | 2015-05-27 | 江南大学 | Preparation of multi-arm photosensitive resin with tannic acid as core |
| CN105602111A (en) * | 2016-01-31 | 2016-05-25 | 桂林理工大学 | Preparation method of modified PP/CaCO3 composite material |
| CN105694019A (en) * | 2016-01-31 | 2016-06-22 | 桂林理工大学 | Preparation method of poly(12-hydroxystearate) grafted tannic acid compatilizer |
| CN106634089A (en) * | 2016-09-18 | 2017-05-10 | 江南大学 | Ultraviolet curing paint based on carbon nanotubes and preparation method of ultraviolet curing paint |
| WO2017117826A1 (en) * | 2016-01-05 | 2017-07-13 | 江南大学 | Triazine-containing photocurable resin and preparation method thereof |
| CN108929459A (en) * | 2018-08-01 | 2018-12-04 | 张陈钇衡 | A kind of preparation method of the polymer foaming expandable microspheres for decorative wall paper |
| CN111019060A (en) * | 2019-12-12 | 2020-04-17 | 贵州师范学院 | Preparation method of tannic acid base star-shaped polycarboxylate superplasticizer |
| CN111875648A (en) * | 2020-07-16 | 2020-11-03 | 华北科技学院 | Bio-based macromolecular flame retardant and preparation method and application thereof |
| CN112126076A (en) * | 2020-09-28 | 2020-12-25 | 长春工业大学 | Preparation method of tannin grafted dangling double bond |
| CN114316333A (en) * | 2022-01-12 | 2022-04-12 | 江苏怡丽科姆新材料股份有限公司 | Wear-resistant antifouling hardened film and preparation method thereof |
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Cited By (16)
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| CN102796441B (en) * | 2012-09-12 | 2014-12-24 | 江南大学 | Novel polyphenol photocuring antibacterial paint |
| CN102796441A (en) * | 2012-09-12 | 2012-11-28 | 江南大学 | Novel polyphenol photocuring antibacterial paint |
| CN104650341A (en) * | 2013-11-19 | 2015-05-27 | 江南大学 | Preparation of multi-arm photosensitive resin with tannic acid as core |
| WO2017117826A1 (en) * | 2016-01-05 | 2017-07-13 | 江南大学 | Triazine-containing photocurable resin and preparation method thereof |
| US9969703B2 (en) | 2016-01-05 | 2018-05-15 | Jiangnan University | Triazine-containing photocurable resin and preparation method thereof |
| CN105694019A (en) * | 2016-01-31 | 2016-06-22 | 桂林理工大学 | Preparation method of poly(12-hydroxystearate) grafted tannic acid compatilizer |
| CN105602111B (en) * | 2016-01-31 | 2017-12-12 | 桂林理工大学 | A kind of MODIFIED PP/CaCO3The preparation method of composite |
| CN105602111A (en) * | 2016-01-31 | 2016-05-25 | 桂林理工大学 | Preparation method of modified PP/CaCO3 composite material |
| CN106634089A (en) * | 2016-09-18 | 2017-05-10 | 江南大学 | Ultraviolet curing paint based on carbon nanotubes and preparation method of ultraviolet curing paint |
| CN106634089B (en) * | 2016-09-18 | 2019-01-29 | 江南大学 | A kind of ultraviolet-curing paint and preparation method thereof based on carbon nanotube |
| CN108929459A (en) * | 2018-08-01 | 2018-12-04 | 张陈钇衡 | A kind of preparation method of the polymer foaming expandable microspheres for decorative wall paper |
| CN111019060A (en) * | 2019-12-12 | 2020-04-17 | 贵州师范学院 | Preparation method of tannic acid base star-shaped polycarboxylate superplasticizer |
| CN111875648A (en) * | 2020-07-16 | 2020-11-03 | 华北科技学院 | Bio-based macromolecular flame retardant and preparation method and application thereof |
| CN112126076A (en) * | 2020-09-28 | 2020-12-25 | 长春工业大学 | Preparation method of tannin grafted dangling double bond |
| CN114316333A (en) * | 2022-01-12 | 2022-04-12 | 江苏怡丽科姆新材料股份有限公司 | Wear-resistant antifouling hardened film and preparation method thereof |
| CN115466567A (en) * | 2022-09-29 | 2022-12-13 | 东莞市汉普森工业材料有限公司 | LED-UV gloss oil and preparation method thereof |
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