CN103980114A - Preparation method of dicyclopentadienyl acrylate - Google Patents
Preparation method of dicyclopentadienyl acrylate Download PDFInfo
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- CN103980114A CN103980114A CN201410147625.0A CN201410147625A CN103980114A CN 103980114 A CN103980114 A CN 103980114A CN 201410147625 A CN201410147625 A CN 201410147625A CN 103980114 A CN103980114 A CN 103980114A
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- preparation
- vinylformic acid
- dcpa
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- acid dcpa
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/60—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members
- C07C2603/66—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members containing five-membered rings
- C07C2603/68—Dicyclopentadienes; Hydrogenated dicyclopentadienes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a production preparation method of resin widely used in the field of coatings and adhesives, and in particular relates to a preparation method of excellent performance monomer dicyclopentadienyl acrylate. The method is as follows: under the effect of a catalyst with macroporous microsphere silica as a carrier, controlling the reaction conditions, and respectively and simultaneously dripping a raw material added with a polymerization inhibitor into acrylic acid and dicyclopentadiene with the molar ratio of acrylic acid to dicyclopentadiene of 1.05-1.5:1. The production preparation can effectively reduce the polymerization between the raw material and a product, at the same time, the catalyst has high activity, reaction rate is fast, side reaction is less, and the production preparation can improve the quality of the product , can greatly improve the product yield.
Description
Technical field
The present invention relates to a kind of preparation method that is widely used in the resin of coating and adhesive field, a kind of preparation method of premium properties monomer vinylformic acid DCPA specifically, can effectively reduce the polymerization of raw material and product, catalyst activity is high simultaneously, speed of response is fast, side reaction is few, can improve the quality of products, and also significantly improves product yield.
Background technology
Development along with petrochemical industry, the separation of petroleum cracking product C 5 cuts provides cheap polyester cyclic cpds dicyclopentadiene, the ester generating after itself and vinylformic acid react, this monomer have two can polymerization group---two keys of acrylate and the allyl group on polyester ring, the former can make it carry out radical polymerization, the latter can carry out oxypolymerization in air, polymerization shrinkage is little, polymkeric substance hardness is high, water-intake rate is low, insulating property are high and transparent good, can be widely used in coating, tackiness agent, transparent optical material, optical lens and other synthetic materials.The preparation of this class monomer and application have been carried out to much research abroad, particularly in the application of high-technology field.China starts late to the research and development of this monomer, has its synthetic and application of bibliographical information, but at present without suitability for industrialized production.Document synthesis technique adopts strongly acidic catalyst as the vitriol oil, tosic acid, boron trifluoride ethyl ether complex, catalysis of phosphotungstic acid more, add single-component or two-pack stopper, due to the easy autohemagglutination of vinylformic acid, dicyclopentadiene, the easy oxypolymerization of vinylformic acid DCPA, cause product yield low, of poor quality, and have a large amount of by-product polymerizing things to generate, cause suitability for industrialized production to be difficult to realize.
Summary of the invention
The present invention relates to a kind of preparation method that is widely used in the resin of coating and adhesive field, a kind of preparation method of premium properties monomer vinylformic acid DCPA specifically, can effectively reduce the polymerization of raw material and product, catalyst activity is high simultaneously, speed of response is fast, side reaction is few, can improve the quality of products, and also significantly improves product yield.
In order to realize above object, a kind of preparation method of vinylformic acid DCPA, it is characterized in that: the mol ratio of vinylformic acid and dicyclopentadiene is 1.05～1.5:1, at gross porosity microsphere silica gel, do under the catalyst action of carrier, control reaction conditions, drip respectively the raw material that is added with stopper simultaneously and make.
Described catalyzer is the mixture of phosphoric acid or phosphoric acid salt, tungstate and molybdate, and wherein phosphorus, tungsten, three kinds of element mol ratios of molybdenum are P: W: Mo=0.01～2: 0.01～1: 0.01～0.05.
Described catalyst quality is 0.1%～10% of reaction substrate total mass, is preferably 0.5%～2%.
After selected catalyzer raw material is mixed, be dissolved in the water of 20～100 ℃, and be adjusted to pH value and be less than <3.
In the aqueous solution of selected catalyzer, add gross porosity microsphere silica gel, ageing absorption, after 1～24 hour, is dried activation in 50～500 ℃.
The mean pore size of described gross porosity microsphere silica gel is 125-425um, and its particle size is 40-120 order, needs 100 ℃ of above oven dry 2～24 hours before use.
Described reaction conditions is that controlling temperature of reaction is 40～120 ℃, preferably 60～90 ℃.
Described stopper is MEHQ, p-ten.-butylcatechol and 4-hydroxyl-2,2,6,6-tetramethyl piperidine-1-oxyradical, and above-mentioned any two or three mixes in any proportion.
Accompanying drawing explanation
Fig. 1 is not for being used the gas phase spectrogram of method acrylic acid synthesizing cyclopentadiene ester of the present invention;
Fig. 2 is the gas chromatogram of the product that obtains of embodiment 1;
Fig. 3 is the gas chromatogram of the product that obtains of embodiment 2;
Fig. 4 is the gas chromatogram of the product that obtains of embodiment 3.
Embodiment
Embodiment 1
Catalyzer is made: in the stainless cylinder of steel of 200L, add 100kg deionized water, drop into successively 50kg sodium wolframate, 10kg ammonium molybdate under agitation condition, constantly stir and be warming up to 80 ℃ of insulations.Be incubated after 5 hours, drop into 20kg food phosphates, the mean pore size that 50kg is dried is in advance that 125-425um is of a size of 40-120 object gross porosity microsphere silica gel, and ageing, after 12 hours, is entered 100 ℃ of oven dry of baking oven, more standby in 300 ℃ of activation.
To drop into successively in 500L enamel still 150kg vinylformic acid, 400g MEHQ,, 4-hydroxyl-2 of 200g, proceed to test tank after 2,6,6-tetramethyl piperidine-1-oxyradical stirs.
To drop into successively in 500L enamel still 200kg dicyclopentadiene, 400g MEHQ,, 4-hydroxyl-2 of 200g, proceed to test tank after 2,6,6-tetramethyl piperidine-1-oxyradical stirs.
In 500L enamel still, add the gross porosity microsphere silica gel that contains 3kg catalyzer, be added dropwise to the vinylformic acid and the dicyclopentadiene material that configure simultaneously.Control this temperature of reaction kettle at 100 ℃, dropwise rear liquid chromatograph tracking sampling and detect, the dicyclopentadiene of take reaction is complete is terminal.
Separablely in system go out catalyzer, after solvent elution, can reuse.After in system, unreacted vinylformic acid steams, collect vinylformic acid DCPA 298kg, yield is 96.43%, through gas chromatograph detection level, is 98.16%.
Embodiment 2
Catalyzer making method is identical with embodiment 1.
To 4-hydroxyl-2 of dropping into successively 160kg vinylformic acid, 200g MEHQ, 200g p-ten.-butylcatechol, 200g in 500L enamel still, 2,6,6-tetramethyl piperidine-1-oxyradical, proceeds to test tank after stirring.
In 500L enamel still, drop into successively 200kg dicyclopentadiene, 200g MEHQ, 200g p-ten.-butylcatechol, 200g4-hydroxyl-2,2,6,6-tetramethyl piperidine-1-oxyradical, proceeds to test tank after stirring.
In 500L enamel still, add 3.5kg gross porosity microsphere silica gel to make the catalyzer of carrier, drip material vinylformic acid and the dicyclopentadiene configuring simultaneously, control temperature of reaction at 80 ℃, dropwise rear gas chromatograph tracking sampling and detect.Dicyclopentadiene after completion of the reaction, is isolated catalyzer, steams unreacted vinylformic acid.Collect vinylformic acid DCPA 302kg, yield 97.73%, through gas chromatograph detection level 98.58%;
Embodiment 3
The catalyzer using in this example is for after producing reaction, reclaims and obtains through solvent elution.
To 4-hydroxyl-2 of dropping into successively 150kg vinylformic acid, 500g MEHQ, 250g p-ten.-butylcatechol, 250g in 500L enamel still, 2,6,6-tetramethyl piperidine-1-oxyradical, proceeds to test tank after stirring.
To 4-hydroxyl-2 of dropping into successively 200kg dicyclopentadiene, 500g MEHQ, 250g p-ten.-butylcatechol, 250g in 500L enamel still, 2,6,6-tetramethyl piperidine-1-oxyradical, proceeds to test tank after stirring.
In 500L enamel still, add the gross porosity microsphere silica gel that contains 3.5kg recovery wash-out rear catalyst, drip vinylformic acid and the dicyclopentadiene material configuring simultaneously, control temperature of reaction at 100 ℃.Dropwising rear liquid chromatograph tracking sampling detects.The dicyclopentadiene of take reaction is complete is terminal, isolates catalyzer, steams unreacted vinylformic acid.Collect vinylformic acid DCPA 289kg, yield is 93.52%, through gas chromatograph detection level 98.18%.
The above, be only the specific embodiment of the present invention, it should be pointed out that any those of ordinary skill in the art are in the disclosed technical scope of the present invention, and the variation that can expect easily or replacement, within all should being encompassed in protection scope of the present invention.
Claims (10)
1. the preparation method of a vinylformic acid DCPA, it is characterized in that: the mol ratio of vinylformic acid and dicyclopentadiene is 1.05～1.5:1, at gross porosity microsphere silica gel, do under the catalyst action of carrier, control reaction conditions, drip respectively the raw material that is added with stopper simultaneously and make.
2. the preparation method of a kind of vinylformic acid DCPA as claimed in claim 1, it is characterized in that: described catalyzer is the mixture of phosphoric acid or phosphoric acid salt, tungstate and molybdate, wherein phosphorus, tungsten, three kinds of element mol ratios of molybdenum are P: W: Mo=0.01～2: 0.01～1: 0.01～0.05.
3. the preparation method preparation method of a kind of vinylformic acid DCPA as claimed in claim 1, is characterized in that: described catalyst quality is 0.1%～10% of reaction substrate total mass.
4. the preparation method preparation method of a kind of vinylformic acid DCPA as claimed in claim 1, is characterized in that: described catalyst quality is 0.5%～2% of reaction substrate total mass.
5. the preparation method of a kind of vinylformic acid DCPA as described in claim 2～4 any one, is characterized in that: after selected catalyzer raw material is mixed, be dissolved in the water of 20～100 ℃, and be adjusted to pH value and be less than <3.
6. the preparation method of a kind of vinylformic acid DCPA as described in claim 2～5 any one, is characterized in that: to the aqueous solution of selected catalyzer, add gross porosity microsphere silica gel, ageing absorption, after 1～24 hour, is dried activation in 50～500 ℃.
7. the preparation method of a kind of vinylformic acid DCPA as claimed in claim 1, is characterized in that: the mean pore size of described gross porosity microsphere silica gel is 125-425um, and its particle size is 40-120 order, needs 100 ℃ of above oven dry 2～24 hours before use.
8. the preparation method of a kind of vinylformic acid DCPA as claimed in claim 1, is characterized in that: described reaction conditions is that controlling temperature of reaction is 40～120 ℃.
9. the preparation method of a kind of vinylformic acid DCPA as claimed in claim 8, is characterized in that: described reaction conditions is that controlling temperature of reaction is 60～90 ℃.
10. the preparation method of a kind of vinylformic acid DCPA as claimed in claim 1, it is characterized in that: described stopper is MEHQ, p-ten.-butylcatechol and 4-hydroxyl-2,2,6,6-tetramethyl piperidine-1-oxyradical, above-mentioned any two or three mixes in any proportion.
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| CN201410147625.0A CN103980114B (en) | 2014-04-14 | 2014-04-14 | A kind of preparation method of vinylformic acid DCPA |
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| CN201410147625.0A CN103980114B (en) | 2014-04-14 | 2014-04-14 | A kind of preparation method of vinylformic acid DCPA |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024125138A1 (en) * | 2022-12-14 | 2024-06-20 | 中国石油天然气股份有限公司 | Preparation method for norbornene |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH045257A (en) * | 1990-04-24 | 1992-01-09 | Tosoh Corp | Production of dicyclopentadiene acrylate |
| CN1452511A (en) * | 2000-09-07 | 2003-10-29 | 昭和电工株式会社 | Catalyst for producing lower aliphatic carboxylic acid esters |
| CN103664598A (en) * | 2012-09-25 | 2014-03-26 | 中国石油化工股份有限公司 | Preparation method of dicyclopentadienyl acrylate (DCPA) |
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2014
- 2014-04-14 CN CN201410147625.0A patent/CN103980114B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH045257A (en) * | 1990-04-24 | 1992-01-09 | Tosoh Corp | Production of dicyclopentadiene acrylate |
| CN1452511A (en) * | 2000-09-07 | 2003-10-29 | 昭和电工株式会社 | Catalyst for producing lower aliphatic carboxylic acid esters |
| CN103664598A (en) * | 2012-09-25 | 2014-03-26 | 中国石油化工股份有限公司 | Preparation method of dicyclopentadienyl acrylate (DCPA) |
Non-Patent Citations (1)
| Title |
|---|
| 余华宁 等: "丙烯酸双环戊二烯酯的合成", 《中国胶粘剂》, vol. 21, no. 3, 31 March 2012 (2012-03-31), pages 9 - 12 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024125138A1 (en) * | 2022-12-14 | 2024-06-20 | 中国石油天然气股份有限公司 | Preparation method for norbornene |
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