CN102516326B - 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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- CN102516326B CN102516326B CN201110406747.3A CN201110406747A CN102516326B CN 102516326 B CN102516326 B CN 102516326B CN 201110406747 A CN201110406747 A CN 201110406747A CN 102516326 B CN102516326 B CN 102516326B
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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 research and the industrialization product thereof of most coating are all take petroleum chemicals as main raw material(s), in consuming bulk petroleum resource also by 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, by introducing more alternative starting material and green technology (as ultraviolet light polymerization, high solids content and water-borne coatings technology etc.), day by day transforms to green industry.
UV-curing technology has energy-saving and environmental protection, economic dispatch advantage, and in current coating industry, development is comparatively rapid; Renewable resources is due to wide material sources, with low cost and renewable, environmental protection, in coatings industry, there is application prospect very widely, so utilize renewable raw materials synthesising biological base light-cured resin petroleum replacing base resin to have great importance to the Sustainable development of coatings industry.
Bio-based UV-cured resin, especially the development of the light-cured resin take vegetables oil as 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 (as the Ebecryl860 of UCB chemical company), the research of other renewable resourcess such as while starch, rosin and derivative is also flourish, and obtained larger progress, in synthesizing, the resin of radical UV curing system and cation photocuring system has application.Although the development of these bio-based light-cured resins is very fast, but because the development time in current this field is shorter, the restriction of the renewable resources utilizing and derivative kind thereof, and the reason such as the constitutional features of renewable resources and derivative, the bio-based UV-cured resin obtaining is also short of to some extent in the performance of the aspects such as photocuring activity, cured film mechanical property, mechanical property, and kind is also less, thereby limit further developing of bio-based photo-cured coating.
Summary of the invention
The problems referred to above that exist for prior art, the applicant provides a kind of preparation method and use of tannin-based hyperbranched acrylic acid ester.Synthetic technological condition of the present invention is simple, and raw material is renewable, and environmental protection more can meet the requirement of Sustainable development.
Technical scheme of the present invention is as follows:
A synthetic method for tannin-based hyperbranched acrylic acid ester, preparation process is as follows: under condition of normal pressure, Weibull, catalyzer and stopper are dissolved in reaction solvent; Under whipped state, mixed system is heated to, after 80 ~ 90 ℃, dropwise splash into epoxy monomer, in 0.5 ~ 1h, drip off; Sealed reaction vessel, keeps stirring, and mixeding liquid temperature is risen at 90 ~ 100 ℃ to insulation reaction 45 ~ 50 hours; After reaction finishes, obtain the thick product of dark-brown, be tannin-based hyperbranched acrylic acid ester;
Described catalyzer is the one in triphenylphosphine, Tetrabutyl amonium bromide, 4 bromide, triethylamine, the consumption of catalyzer be Weibull and epoxy monomer quality and 0.5 ~ 1.5%.Described stopper is MEHQ, Resorcinol, Resorcinol, 2, the one in 6-di-t-butyl p-ethyl phenol, the consumption of stopper be Weibull and epoxy monomer quality and 0.05 ~ 0.15%.Described reaction solvent is any one or their the mutual mixture in DMF, water, ethyl acetate, ethanol, butylacetate, acetone, and the consumption of reaction solvent is 20 ~ 60% of reaction system total mass;
Described epoxy monomer is by containing the epoxy monomer of photosensitive pair of key and do not form containing the epoxy monomer of photosensitive pair of key, is wherein total epoxy monomer containing the amount of substance of the epoxy monomer of photosensitive pair of key 20 ~ 100%.The described epoxy monomer containing photosensitive pair of key is the one in glycidyl methacrylate, glycidyl allyl ether, glycidyl acrylate; Described is not the one in tertiary carbonic acid glycidyl ester, n-butyl glycidyl ether, octyl glycidyl ether, Racemic glycidol butyl ester, ethylene glycol diglycidylether containing the epoxy monomer of photosensitive pair of key.It is 1:2 to 2:1 with a mole group ratio for epoxy group(ing) that described Weibull is pressed phenolic hydroxyl group with epoxy monomer.
The technique effect that the present invention is useful is:
The present invention is take the Weibull that contains polyphenol hydroxyl structure as main raw material, under basic catalyst condition, carry out opening by phenolic hydroxyl group on Weibull and the epoxy monomer that contains active epoxy group(ing), the vinyl that introducing simultaneously can be carried out ultraviolet light polymerization (has vinyl on epoxy monomer, be photosensitive pair of key), the content of introducing vinyl is controlled.This acrylate can be used in conjunction with existing plant oil based light-cured resin the ultraviolet-curing paint of the high bio-based content of preparation, can improve the over-all properties of cured film simultaneously.
Accompanying drawing explanation
Fig. 1 is infrared (FTIR) spectrogram of this tannin-based hyperbranched acrylic acid ester.
Fig. 2 be this tannin-based hyperbranched acrylic acid ester nuclear-magnetism (
1h-NMR) spectrogram.
Embodiment
Be equipped with thermometer, mechanical stirring, reflux exchanger there-necked flask in add 17.012g(10.00mmol) deionized water of Weibull, 0.788g triphenylphosphine, 0.079g MEHQ, 13.138g, slowly stirring heating mixture to 90 ℃; Dropwise splash into 35.538g(250.00mmol with dropping funnel) glycidyl methacrylate, control rate of addition, in 1h, drip off; Sealed reaction vessel, rises to solution temperature at 95 ℃ and continues stirring until after reaction 45h finishes and cool, and is bio-based hyperbranched propenoic acid ester---tannin acidic group hyperbranched propenoic acid ester.
Be equipped with thermometer, mechanical stirring, reflux exchanger there-necked flask in add 17.012g(10.00mmol) ethanol/n-butyl acetate mixed solvent of Weibull, 0.491g 4 bromide, 0.049g Resorcinol, 49.127g, slowly stirring heating mixture to 80 ℃; Dropwise splash into 22.800g(200.00mmol with dropping funnel) glycidyl acrylate and 9.315g(50.00mmol) octyl glycidyl ether, control rate of addition, drip off in 0.5; Sealed reaction vessel, rises to solution temperature at 90 ℃ and continues stirring until after reaction 48h finishes and cool, and is bio-based hyperbranched propenoic acid ester---tannin acidic group hyperbranched propenoic acid ester.
Be equipped with thermometer, mechanical stirring, reflux exchanger there-necked flask in add 25.518g(15.00mmol) the ethyl acetate and butyl acetate mixed solvent of Weibull, 0.278g triphenylphosphine, 0.028g Resorcinol, 37.309g, slowly stirring heating mixture to 90 ℃; Dropwise splash into 17.121g(150.00mmol with dropping funnel) glycidyl allyl ether and 13.019g(100.00mmol) n-butyl glycidyl ether, control rate of addition, drip off in 0.5; Sealed reaction vessel, rises to solution temperature at 100 ℃ and continues stirring until after reaction 50h finishes and cool, and is bio-based hyperbranched propenoic acid ester---tannin acidic group hyperbranched propenoic acid ester.
Be equipped with thermometer, mechanical stirring, reflux exchanger there-necked flask in add 34.024g(20.00mmol) the acetone/butyl acetate mixed solvent of Weibull, 0.600g Tetrabutyl amonium bromide, 0.040g MEHQ, 100.575g, slowly stirring heating mixture to 85 ℃; Dropwise splash into 11.400g(100.00mmol with dropping funnel) glycidyl acrylate and 21.626g(150.00mmo) Racemic glycidol butyl ester, control rate of addition, drip off in 0.5; Sealed reaction vessel, rises to solution temperature at 95 ℃ and continues stirring until after reaction 48h finishes and cool, and is bio-based hyperbranched propenoic acid ester---tannin acidic group hyperbranched propenoic acid ester.
Be equipped with thermometer, 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 with dropping funnel) glycidyl methacrylate and 34.840g(200.00mmol) ethylene glycol diglycidylether, control rate of addition, drip off in 0.5; Sealed reaction vessel, rises to solution temperature at 95 ℃ and continues stirring until after reaction 48h finishes and cool, and is bio-based hyperbranched propenoic acid ester---tannin acidic group hyperbranched propenoic acid ester.
Be equipped with thermometer, mechanical stirring, reflux exchanger there-necked flask in add 17.012g(10.00mmol) deionized water of Weibull, 1.476g triphenylphosphine, 0.098g MEHQ, 24.593g, slowly stirring heating mixture to 80 ℃; Dropwise splash into 56.860g(400.00mmol with dropping funnel) glycidyl methacrylate and 24.500g(100.00mmol) tertiary carbonic acid glycidyl ester, control rate of addition, in 1h, drip off; Sealed reaction vessel, rises to solution temperature at 95 ℃ and continues stirring until after reaction 48h finishes and cool, and is bio-based hyperbranched propenoic acid ester---tannin acidic group hyperbranched propenoic acid ester.
The chemical reagent that above embodiment adopts is commercially available prod.The tannin acidic group hyperbranched propenoic acid ester below embodiment 1 being obtained carries out structure detection, and detected result as depicted in figs. 1 and 2; The structure detection of the product that all the other embodiment 2 ~ 6 obtain is similar to embodiment 1.
Can find out from the infrared spectrum (Fig. 1) of novel tannin-based hyperbranched acrylic acid ester: 3410cm
-1place is the hydroxyl of Weibull and the formation of epoxy monomer generation ring-opening reaction, 715cm
-1place is C=O stretching vibration absorption peak, 1600 cm
-1, 1540 cm
-1place is the skeleton stretching vibration of phenyl ring, 1760cm
-1for the out-of-plane deformation vibration of phenyl ring, 2900 cm
-1~ 2965cm
-1place is the methyl in epoxy monomer, the C-H stretching vibration absorption peak of methylene radical, 1636cm
-1, 810cm
-1place 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 by tannin-based hyperbranched acrylic acid ester, figure acceptance of the bid understands the kind of the corresponding hydrogen in each peak, consistent with target product structure, therefore can judge the tannin-based hyperbranched acrylic acid ester that has successfully synthesized target product uV curable.
Above two kinds of signs have all proved that we have synthesized tannin-based hyperbranched acrylic acid ester.Above-described embodiment 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 that the present invention is made, all fall into protection scope of the present invention.
Claims (2)
1. a synthetic method for tannin-based hyperbranched acrylic acid ester, is characterized in that preparation process is as follows: under condition of normal pressure, Weibull, catalyzer and stopper are dissolved in reaction solvent; Under whipped state, mixed system is heated to, after 80 ~ 90 ℃, dropwise splash into epoxy monomer, in 0.5 ~ 1h, drip off; Sealed reaction vessel, keeps stirring, and mixeding liquid temperature is risen at 90 ~ 100 ℃ to insulation reaction 45 ~ 50 hours; After reaction finishes, obtain the thick product of dark-brown, be tannin-based hyperbranched acrylic acid ester;
Described catalyzer is the one in triphenylphosphine, Tetrabutyl amonium bromide, 4 bromide, triethylamine, the consumption of catalyzer be Weibull and epoxy monomer quality and 0.5 ~ 1.5%;
Described stopper is MEHQ, Resorcinol, Resorcinol, 2, the one in 6-di-t-butyl p-ethyl phenol, the consumption of stopper be Weibull and epoxy monomer quality and 0.05 ~ 0.15%;
Described reaction solvent is any one or their the mutual mixture in DMF, water, ethyl acetate, ethanol, butylacetate, acetone, and the consumption of reaction solvent is 20 ~ 60% of reaction system total mass;
Described epoxy monomer is by containing the epoxy monomer of photosensitive pair of key and do not form containing the epoxy monomer of photosensitive pair of key, is wherein total epoxy monomer containing the amount of substance of the epoxy monomer of photosensitive pair of key 20 ~ 100%;
The described epoxy monomer containing photosensitive pair of key is the one in glycidyl methacrylate, glycidyl acrylate; Described is not the one in tertiary carbonic acid glycidyl ester, n-butyl glycidyl ether, octyl glycidyl ether, Racemic glycidol butyl ester, ethylene glycol diglycidylether containing the epoxy monomer of photosensitive pair of key.
2. the synthetic method of tannin-based hyperbranched acrylic acid ester according to claim 1, is characterized in that, it is 1:2 to 2:1 with a mole group ratio for epoxy group(ing) that described Weibull is pressed phenolic hydroxyl group with epoxy monomer.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101280045A (en) * | 2008-05-06 | 2008-10-08 | 华南理工大学 | Branched polyphenol hydroxyl polymer and preparation thereof |
| CN101735176A (en) * | 2008-11-26 | 2010-06-16 | 建滔化工集团有限公司 | Synthesis method of four-functional group epoxy resin and prepared epoxy resin |
| CN102030884A (en) * | 2010-10-26 | 2011-04-27 | 华南理工大学 | High-solid-content UV (Ultraviolet)-curing aqueous urethane acrylate dispersion liquid and preparation method thereof |
| CN102234268A (en) * | 2011-01-04 | 2011-11-09 | 南京工业大学 | Preparation method of UV-cured polyisocyanate modified hyperbranched epoxy acrylate |
-
2011
- 2011-12-09 CN CN201110406747.3A patent/CN102516326B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101280045A (en) * | 2008-05-06 | 2008-10-08 | 华南理工大学 | Branched polyphenol hydroxyl polymer and preparation thereof |
| CN101735176A (en) * | 2008-11-26 | 2010-06-16 | 建滔化工集团有限公司 | Synthesis method of four-functional group epoxy resin and prepared epoxy resin |
| CN102030884A (en) * | 2010-10-26 | 2011-04-27 | 华南理工大学 | High-solid-content UV (Ultraviolet)-curing aqueous urethane acrylate dispersion liquid and preparation method thereof |
| CN102234268A (en) * | 2011-01-04 | 2011-11-09 | 南京工业大学 | Preparation method of UV-cured polyisocyanate modified hyperbranched epoxy acrylate |
Non-Patent Citations (2)
| Title |
|---|
| 大孔球形纤维素载体固定化单宁的制备及其对蛋白质的吸附性能;王玉恒 等;《离子交换与吸附》;20070831;第23卷(第4期);360-367 * |
| 王玉恒 等.大孔球形纤维素载体固定化单宁的制备及其对蛋白质的吸附性能.《离子交换与吸附》.2007,第23卷(第4期),360-367. |
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