CN103664599A - Preparation method for high-purity trimethylolpropane triacrylate - Google Patents
Preparation method for high-purity trimethylolpropane triacrylate Download PDFInfo
- Publication number
- CN103664599A CN103664599A CN201310729394.XA CN201310729394A CN103664599A CN 103664599 A CN103664599 A CN 103664599A CN 201310729394 A CN201310729394 A CN 201310729394A CN 103664599 A CN103664599 A CN 103664599A
- Authority
- CN
- China
- Prior art keywords
- purity
- preparation
- trimethylolpropane
- tmp
- trimethylopropane triacrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 0 CCC(COCC(*=*=C)=O)(COC(CS)=O)CO[N+](C1CC1)[O-] Chemical compound CCC(COCC(*=*=C)=O)(COC(CS)=O)CO[N+](C1CC1)[O-] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method for high-purity trimethylolpropane triacrylate. According to the invention, trimethylolpropane is used as a raw material, and crylic acid, a water-carrying agent, a catalyst and a polymerization inhibitor are added, so that the high-purity trimethylolpropane triacrylate is obtained. The trimethylolpropane triacrylate prepared through the preparation method has the advantages that the purity is more than 98%, and the yield is more than 95%; the reaction is simple, the operation is simple and convenient, the yield is high, energy consumption and cost are low, the product purity is high, the process is green and environmentally friendly, and the preparation method is suitable for large-scale industrial production of the high-purity trimethylolpropane triacrylate.
Description
Technical field
The present invention relates to a kind of high-purity trimethylopropane triacrylate, can be used as the thinner in photo-cured coating.
Background technology
Viscoat 295 is a kind of important fine chemical material, especially can be used as the thinner in photo-cured coating.
Its structural formula is:
Its universal synthesis method is: take TriMethylolPropane(TMP), vinylformic acid is raw material, through esterification, obtains.
University Of Tianjin's journal, 28(3), 403-408,1995 have reported and take D72 large porous strong acid cation exchange resin as catalyzer, take benzene as band aqua, are carried out the method for synthesizing trimethylol propane triacrylate by TriMethylolPropane(TMP) and vinylformic acid.
Fine chemistry industry, 13(3), 22-24,1996 have reported the method for preparing Viscoat 295 with TriMethylolPropane(TMP) and acrylate chloride.
In above-mentioned preparation method, take TriMethylolPropane(TMP) and vinylformic acid carries out esterification as raw material, by the method for benzene band water, because esterification is balanced reaction, so the content of the Viscoat 295 obtaining is not very high, the toxicity of benzene is too large simultaneously, people is injured greatly to not environmental protection.
Directly with TriMethylolPropane(TMP) and acrylate chloride reaction, prepare in Viscoat 295 reaction process and can emit a large amount of hydrogen chloride gas, etching apparatus, contaminate environment, run in the opposite direction with the theory of green chemical industry.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of high-purity trimethylopropane triacrylate, to overcome, product purity in prior art is low, the shortcoming of etching apparatus, contaminate environment.
For achieving the above object, the present invention mainly adopts following technical scheme:
A preparation method for high-purity trimethylopropane triacrylate, is characterized in that, comprises the steps:
1) TriMethylolPropane(TMP), vinylformic acid, band aqua, catalyzer, stopper are mixed in reactor under atmospheric pressure at room, be heated to 80-100 ℃ of backflow, under reflux state, be with water, to no longer there are flowing out, obtain the reaction solution that contains Viscoat 295;
2) remove the band aqua in the reaction solution of step 1) gained under reduced pressure, add solvent, by alkali liquid washing organic phase to pH value, be 7.5-8.5, washing, stratification, collect organic phase decolouring, filter, dry, decompression removes after described solvent, obtains the final product that contains high-purity trimethylopropane triacrylate.
Wherein, step 1) is always consuming time is 5-6h; Step 2), in, utilize circulating water type vacuum pump to remove the band aqua in the reaction solution of step 1) gained under reduced pressure; Utilize the decompression of circulating water type vacuum pump to remove described solvent.
Operational path of the present invention is as follows:
Further, the described alkanes band aqua that is C6～C7 with aqua, is selected from a kind of in following material: hexanaphthene, normal hexane, normal heptane or sherwood oil.Be preferably hexanaphthene.
Again, described catalyzer is selected from a kind of in following material: toluenesulphonic acids, sodium pyrosulfate, silicotungstic acid, phospho-wolframic acid, zinc chloride, tin protochloride, stannous oxalate, copper methanesulfonate, lanthanum methanesulfonate, D002 macropore sulfuric acid resin or PEP-15u molecular sieve.Be preferably PEP-15u molecular sieve.Described PEP-15u molecular sieve buying is from Suzhou Huan Ke novel material company limited.
And described stopper is selected from one or more in following material: Resorcinol, to methoxyl group phenol, biphenyl 3 phenol, thiodiphenylamine, copper sulfate, neutralized verdigris, copper dibutyldithiocarbamate, stopper ZJ701, stopper ZJ705, para benzoquinone or anthraquinone.Be preferably thiodiphenylamine.
Again, the solvent described step 2) is selected from a kind of in following material: ethyl acetate, methyl acetate, trichloromethane or 1,2-ethylene dichloride.Be preferably ethyl acetate.
And described TriMethylolPropane(TMP) and acrylic acid mol ratio are 1:3.0～4.0.Described TriMethylolPropane(TMP) is 1:3.0～5.0 with the weightmeasurement ratio with aqua.The mass ratio of TriMethylolPropane(TMP) and stopper is 100:0.02～0.1.The mass ratio of TriMethylolPropane(TMP) and catalyzer is 20:1～2.TriMethylolPropane(TMP) and step 2) in the weightmeasurement ratio of solvent be 1:3.0～5.0.
In preparation method provided by the present invention, material used is all commercially available.
Compared with prior art, beneficial effect of the present invention is:
The present invention be take TriMethylolPropane(TMP) as raw material, carry out esterification with vinylformic acid, prepare Viscoat 295, can not discharge obnoxious flavour, with alkanes band aqua, replace the benzene of industrial use and toluene aromatic hydrocarbons as refluxing with aqua with the method for water, preparation method's environmental protection;
Low (the 80-100 ℃ of temperature of reaction, lower than 110 ℃ of prior art), energy consumption is also little, in the final product preparing, described Viscoat 295 purity is high, can reach purity more than 98%, and the reached yield of Viscoat 295 is more than 95%, has overcome the defect that current suitability for industrialized production Viscoat 295 purity is low, energy consumption is high, environmental pollution is large.
Embodiment
Below by embodiment, the invention will be further described, but embodiment does not limit the scope of the invention.
Embodiment 1
In the 500mL reaction flask with agitator, thermometer, water trap, reflux condensing tube, add 100mL normal hexane, under stirring, add again 26.8g (0.2mol) TriMethylolPropane(TMP), vinylformic acid 44.7g (0.62mol), tosic acid 2.0g, stopper thiodiphenylamine 0.02g.Heat to the band water that refluxes, until no longer include water out.Reaction finishes, decompression evaporates band aqua normal hexane, add methyl acetate 100mL, by saturated sodium bicarbonate solution washing organic phase, to pH value, be 7.5, then through saturated common salt water washing, deionized water wash, stratification after fully stirring, collect organic phase and arrive reflux decolour with heating activated carbon, cooled and filtered, collects filtrate, dry with Calcium Chloride Powder Anhydrous.Filter out calcium chloride, after decompression desacetoxy methyl esters, obtain Viscoat 295 58.1g, purity 98.2%, yield 96.2%.
Embodiment 2
In the 500mL reaction flask with agitator, thermometer, water trap, reflux condensing tube, add 110mL normal heptane, under stirring, add again 26.8g (0.2mol) TriMethylolPropane(TMP), vinylformic acid 45.4g (0.63mol), stannous oxalate 2.2g, 0.01g stopper thiodiphenylamine, 0.01g stopper ZJ701.Heat to the band water that refluxes, until no longer include water out.Reaction finishes, decompression evaporates band aqua normal heptane, add trichloromethane 110mL, by saturated sodium bicarbonate solution washing organic phase, to pH value, be 8, then through saturated common salt water washing, deionized water wash, stratification after fully stirring, collect organic phase and arrive reflux decolour with heating activated carbon, cooled and filtered, collects filtrate, dry with Calcium Chloride Powder Anhydrous.Filter out calcium chloride, after the de-trichloromethane of decompression, obtain Viscoat 295 57.6g, purity 98.1%, yield 95.3%.
Embodiment 3
In the 500mL reaction flask with agitator, thermometer, water trap, reflux condensing tube, add 120mL hexanaphthene, under stirring, add again 26.8g (0.2mol) TriMethylolPropane(TMP), vinylformic acid 46.1g (0.64mol), PEP-15u molecular sieve 2.4g, 0.012g stopper ZJ705 and stopper thiodiphenylamine 0.013g.Heat to the band water that refluxes, until no longer include water out.Reaction finishes the rear PEP-15u molecular sieve that first filters out, filtrate is reduced pressure and is evaporated band aqua hexanaphthene, in resistates, add ethyl acetate 120mL, by saturated sodium bicarbonate solution washing organic phase, to pH value, be 8.5, then through saturated common salt water washing, deionized water wash, stratification after fully stirring, collect organic phase and arrive reflux decolour with heating activated carbon, cooled and filtered, collects filtrate, dry with Calcium Chloride Powder Anhydrous.Filter out calcium chloride, after decompression desacetoxy ethyl ester, obtain Viscoat 295 58.6g, purity 98.3%, yield 97.2%.
Embodiment 4
In the 500mL reaction flask with agitator, thermometer, water trap, reflux condensing tube, add 110mL sherwood oil, under stirring, add again 26.8g (0.2mol) TriMethylolPropane(TMP), vinylformic acid 46.1g (0.64mol), PEP-15u molecular sieve 2.4g, 0.012g copper dibutyldithiocarbamate and stopper thiodiphenylamine 0.013g.Heat to the band water that refluxes, until no longer include water out.Reaction finishes the rear PEP-15u molecular sieve that first filters out, filtrate is reduced pressure and is evaporated band aqua sherwood oil, in resistates, adding 1,2-ethylene dichloride 110mL, is 8.0 by saturated sodium bicarbonate solution washing organic phase to pH value, again through saturated common salt water washing, deionized water wash, stratification after fully stirring, collects organic phase and arrives reflux decolour, cooled and filtered with heating activated carbon, collect filtrate, dry with Calcium Chloride Powder Anhydrous.Filter out calcium chloride, after de-1, the 2-ethylene dichloride of decompression, obtain Viscoat 295 58.0g, purity 98.2%, yield 96.1%.
It should be noted that, above embodiment is only unrestricted in order to technical scheme of the present invention to be described.Although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can modify or be equal to replacement the technical scheme of invention, and not depart from the scope of technical solution of the present invention, it all should be encompassed within the scope of claim of the present invention.
Claims (10)
1. a preparation method for high-purity trimethylopropane triacrylate, is characterized in that, comprises the steps:
1) TriMethylolPropane(TMP), vinylformic acid, band aqua, catalyzer, stopper are mixed in reactor under atmospheric pressure at room, be heated to 80-100 ℃ of backflow, under reflux state, be with water, to no longer there are flowing out, obtain the reaction solution that contains Viscoat 295;
2) remove the band aqua in the reaction solution of step 1) gained under reduced pressure, add solvent, by alkali liquid washing organic phase to pH value, be 7.5-8.5, washing, stratification, collect organic phase decolouring, filter, dry, decompression removes after described solvent, obtains the final product that contains high-purity trimethylopropane triacrylate.
2. the preparation method of a kind of high-purity trimethylopropane triacrylate according to claim 1, it is characterized in that, the described alkanes band aqua that is C6～C7 with aqua, is selected from a kind of in following material: hexanaphthene, normal hexane, normal heptane or sherwood oil.
3. the preparation method of a kind of high-purity trimethylopropane triacrylate according to claim 1, it is characterized in that, described catalyzer is selected from a kind of in following material: toluenesulphonic acids, sodium pyrosulfate, silicotungstic acid, phospho-wolframic acid, zinc chloride, tin protochloride, stannous oxalate, copper methanesulfonate, lanthanum methanesulfonate, D002 macropore sulfuric acid resin or PEP-15u molecular sieve.
4. the preparation method of a kind of high-purity trimethylopropane triacrylate according to claim 1, it is characterized in that, described stopper is selected from one or more in following material: Resorcinol, to methoxyl group phenol, biphenyl 3 phenol, thiodiphenylamine, copper sulfate, neutralized verdigris, copper dibutyldithiocarbamate, stopper ZJ701, stopper ZJ705, para benzoquinone or anthraquinone.
5. the preparation method of a kind of high-purity trimethylopropane triacrylate according to claim 1, it is characterized in that, described step 2) solvent in is selected from a kind of in following material: ethyl acetate, methyl acetate, trichloromethane or 1,2-ethylene dichloride.
6. the preparation method of a kind of high-purity trimethylopropane triacrylate according to claim 1, is characterized in that, described TriMethylolPropane(TMP) and acrylic acid mol ratio are 1:3.0～4.0.
7. the preparation method of a kind of high-purity trimethylopropane triacrylate according to claim 1, is characterized in that, described TriMethylolPropane(TMP) is 1:3.0～5.0 with the weightmeasurement ratio with aqua.
8. the preparation method of a kind of high-purity trimethylopropane triacrylate according to claim 1, is characterized in that, the mass ratio of TriMethylolPropane(TMP) and stopper is 100:0.02～0.1.
9. the preparation method of a kind of high-purity trimethylopropane triacrylate according to claim 1, is characterized in that, the mass ratio of TriMethylolPropane(TMP) and catalyzer is 20:1～2.
10. the preparation method of a kind of high-purity trimethylopropane triacrylate according to claim 1, is characterized in that, TriMethylolPropane(TMP) and step 2) in the weightmeasurement ratio of solvent be 1:3.0～5.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310729394.XA CN103664599A (en) | 2013-12-26 | 2013-12-26 | Preparation method for high-purity trimethylolpropane triacrylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310729394.XA CN103664599A (en) | 2013-12-26 | 2013-12-26 | Preparation method for high-purity trimethylolpropane triacrylate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103664599A true CN103664599A (en) | 2014-03-26 |
Family
ID=50303493
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310729394.XA Pending CN103664599A (en) | 2013-12-26 | 2013-12-26 | Preparation method for high-purity trimethylolpropane triacrylate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103664599A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262203A (en) * | 2014-09-05 | 2015-01-07 | 张家港威胜生物医药有限公司 | Preparation method of creatine ethyl ester hydrochloride |
| CN106632992A (en) * | 2016-11-15 | 2017-05-10 | 惠州市长润发涂料有限公司 | Ultraviolet light curable epoxy acrylate resin and preparation method |
| CN106748761A (en) * | 2016-11-15 | 2017-05-31 | 惠州市长润发涂料有限公司 | A kind of preparation method of trimethylolpropane trimethacrylate |
| CN108997113A (en) * | 2018-06-25 | 2018-12-14 | 南通百川新材料有限公司 | A kind of preparation method of trimethylolpropane trimethacrylate |
| CN111944339A (en) * | 2020-07-14 | 2020-11-17 | 濮阳展辰新材料有限公司 | Ultraviolet curing monomer and preparation method and application thereof |
| CN112830793A (en) * | 2019-11-22 | 2021-05-25 | 福建臻璟新材料科技有限公司 | Preparation process for preparing high-thermal-conductivity and high-strength aluminum nitride ceramic through gel-process injection molding |
| CN114369024A (en) * | 2021-12-31 | 2022-04-19 | 河南金丹乳酸科技股份有限公司 | PTA and BDO esterification process for PBAT production |
| CN114478255A (en) * | 2022-02-10 | 2022-05-13 | 南通百川新材料有限公司 | Green synthesis process of polyol acrylate by using solid catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1733688A (en) * | 2005-09-05 | 2006-02-15 | 上海华谊丙烯酸有限公司 | A multiple functional group (methyl) acrylate synthesis and purification method |
| CN1907946A (en) * | 2006-08-15 | 2007-02-07 | 张本田 | Method of preparing trimethylolpropane triacrylate |
-
2013
- 2013-12-26 CN CN201310729394.XA patent/CN103664599A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1733688A (en) * | 2005-09-05 | 2006-02-15 | 上海华谊丙烯酸有限公司 | A multiple functional group (methyl) acrylate synthesis and purification method |
| CN1907946A (en) * | 2006-08-15 | 2007-02-07 | 张本田 | Method of preparing trimethylolpropane triacrylate |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262203A (en) * | 2014-09-05 | 2015-01-07 | 张家港威胜生物医药有限公司 | Preparation method of creatine ethyl ester hydrochloride |
| CN106632992A (en) * | 2016-11-15 | 2017-05-10 | 惠州市长润发涂料有限公司 | Ultraviolet light curable epoxy acrylate resin and preparation method |
| CN106748761A (en) * | 2016-11-15 | 2017-05-31 | 惠州市长润发涂料有限公司 | A kind of preparation method of trimethylolpropane trimethacrylate |
| CN106632992B (en) * | 2016-11-15 | 2018-12-28 | 惠州市长润发涂料有限公司 | A kind of ultraviolet cured epoxy acrylic resin and preparation method |
| CN108997113A (en) * | 2018-06-25 | 2018-12-14 | 南通百川新材料有限公司 | A kind of preparation method of trimethylolpropane trimethacrylate |
| CN112830793A (en) * | 2019-11-22 | 2021-05-25 | 福建臻璟新材料科技有限公司 | Preparation process for preparing high-thermal-conductivity and high-strength aluminum nitride ceramic through gel-process injection molding |
| CN111944339A (en) * | 2020-07-14 | 2020-11-17 | 濮阳展辰新材料有限公司 | Ultraviolet curing monomer and preparation method and application thereof |
| CN114369024A (en) * | 2021-12-31 | 2022-04-19 | 河南金丹乳酸科技股份有限公司 | PTA and BDO esterification process for PBAT production |
| CN114369024B (en) * | 2021-12-31 | 2024-01-30 | 河南金丹乳酸科技股份有限公司 | PTA and BDO esterification process for PBAT production |
| CN114478255A (en) * | 2022-02-10 | 2022-05-13 | 南通百川新材料有限公司 | Green synthesis process of polyol acrylate by using solid catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103664599A (en) | Preparation method for high-purity trimethylolpropane triacrylate | |
| CN102675203B (en) | Preparation method of acridine compounds | |
| CN101757950B (en) | Catalyst system and application for leading poly-fluorine phenyl in organic synthesis thereof | |
| CN109232232A (en) | A kind of refining methd of acrylic acid | |
| CN1907945B (en) | Process for preparing trifluoroethyl methacrylate | |
| CN103724320B (en) | The preparation method of 2-isopropyl thioxanthone | |
| CN104513161A (en) | Preparation method of pentaerythritol tetraacrylate mixture | |
| CN103450005B (en) | A kind of preparation method of clopidogrel and the alpha-brominated (2-Chlorophenyl)acetic acid of intermediate and α-thiophene ethamine base substituted acetic acid hydrochlorate | |
| CN103588759B (en) | The preparation technology of 5,6-O-isopropylidene-L-AA | |
| CN102993340A (en) | Photoinitiator for ultraviolet light curing agent and manufacturing method thereof | |
| CN103254073B (en) | Preparation method of high-purity (bi)pentaerythritol crylic acid non-complete esterification product | |
| CN102766088B (en) | Novel process for synchronizing 4,4'-dibromo-2,2'-bipyridyl | |
| CN103709039B (en) | Method for synthesizing methyl (ethyl) gallate through catalysis of Cu-mordenite | |
| CN102731284B (en) | Method for preparing tetrahydro-2-ethyl anthraquinone from working solution for production of hydrogen peroxide by anthraquinone process | |
| CN115124407B (en) | Preparation method of 2,5-ditert octyl hydroquinone | |
| CN102206134B (en) | Preparation method of 2-bromine-3,3,3-trifluoropropene | |
| CN104387252B (en) | A kind of synthetic method of aryl ketones compounds | |
| CN114426525B (en) | White solid photoinitiator and preparation method and application thereof | |
| CN104592115B (en) | Preparation method of acridone N-alkylation derivative | |
| CN109651141A (en) | A kind of synthesis technology of preservative dodecyl nipagin ester | |
| CN105732384A (en) | Preparation method of metacrylic acid ester containing fluoro-alcohol | |
| CN107118088A (en) | A kind of preparation method of m-hydroxy acetophenone | |
| CN108752218B (en) | Route for preparing dolutegravir key intermediate 2, 4-difluorobenzylamine | |
| CN102875415B (en) | Compound and preparation method and application thereof | |
| CN113149827A (en) | Method for synthesizing alkynoic acid by using terminal alkyne and carbon dioxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140326 |
|
| RJ01 | Rejection of invention patent application after publication |