CN103980114B - A kind of preparation method of vinylformic acid DCPA - Google Patents
A kind of preparation method of vinylformic acid DCPA Download PDFInfo
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- CN103980114B CN103980114B CN201410147625.0A CN201410147625A CN103980114B CN 103980114 B CN103980114 B CN 103980114B CN 201410147625 A CN201410147625 A CN 201410147625A CN 103980114 B CN103980114 B CN 103980114B
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- vinylformic acid
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- dcpa
- silica gel
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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 present invention relates to a kind of preparation method being widely used in the resin of coating and adhesive field, a kind of preparation method of premium properties monomeric acrylic DCPA specifically: the mol ratio of vinylformic acid and dicyclopentadiene is 1.05 ~ 1.5:1, do the catalyst action of carrier at gross porosity microsphere silica gel under, control reaction conditions, drip the raw material being added with stopper respectively simultaneously and obtain.The present invention effectively can reduce the polymerization of raw material and product, and catalyst activity is high simultaneously, and speed of response is fast, and side reaction is few, can improve the quality of products, also significantly improve product yield.
Description
Technical field
The present invention relates to a kind of preparation method being widely used in the resin of coating and adhesive field, a kind of preparation method of premium properties monomeric acrylic DCPA specifically, effectively can 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, also significantly improve product yield.
Background technology
Along with the development of petrochemical industry, the separation of petroleum cracking product C 5 cut provides cheap polyester cyclic cpds dicyclopentadiene, the ester generated after itself and vinylformic acid react, this monomer has two groups that can be polymerized---the allyl group on the double bond of acrylate and polyester ring, the former can make it carry out radical polymerization, the latter can carry out oxypolymerization in atmosphere, polymerization shrinkage is little, polymkeric substance hardness is high, water-intake rate is low, insulating property are high and transparent good, coating can be widely used in, tackiness agent, transparent optical material, optical lens and other synthetic materials.Much research is carried out, particularly in the application of high-technology field to the preparations and applicatio of this kind of monomer abroad.The research and development of China to this monomer are started late, and have its synthesis of bibliographical information and application, but at present without suitability for industrialized production.Document synthesis technique many employings strongly acidic catalyst is as the vitriol oil, tosic acid, boron trifluoride ethyl ether complex, catalysis of phosphotungstic acid, 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 thing 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 being widely used in the resin of coating and adhesive field, a kind of preparation method of premium properties monomeric acrylic DCPA specifically, effectively can 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, also significantly improve 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, do the catalyst action of carrier at gross porosity microsphere silica gel under, control reaction conditions, drip the raw material being added with stopper respectively simultaneously and obtain.
Described catalyzer is the mixture of phosphoric acid or phosphoric acid salt, tungstate and molybdate, and wherein phosphorus, tungsten, molybdenum three kinds of elemental mole ratios 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%.
Be dissolved in after the mixing of selected catalyzer raw material in the water of 20 ~ 100 DEG C, and be adjusted to pH value and be less than <3.
To in the aqueous solution of selected catalyzer, add gross porosity microsphere silica gel, ageing absorption, after 1 ~ 24 hour, dries activation in 50 ~ 500 DEG C.
The mean pore size of described gross porosity microsphere silica gel is 125-425um, and its particle size is 40-120 order, needs more than 100 DEG C to dry before using 2 ~ 24 hours.
Described reaction conditions is, controlling temperature of reaction is 40 ~ 120 DEG C, preferably 60 ~ 90 DEG C.
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 the gas phase spectrogram not using method acrylic acid synthesizing cyclopentadiene ester of the present invention;
Fig. 2 is the gas chromatogram of the product that embodiment 1 obtains;
Fig. 3 is the gas chromatogram of the product that embodiment 2 obtains;
Fig. 4 is the gas chromatogram of the product that embodiment 3 obtains.
Embodiment
Embodiment 1
Catalyzer makes: in the stainless cylinder of steel of 200L, add 100kg deionized water, drop into 50kg sodium wolframate, 10kg ammonium molybdate under agitation condition successively, constantly stirs and is warming up to 80 DEG C 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, enters the oven dry of 100 DEG C, baking oven, more for subsequent use in 300 DEG C of activation.
Drop into successively in 500L enamel still 150kg vinylformic acid, 400g MEHQ, proceed to test tank after 4-hydroxyl-2,2,6, the 6-tetramethyl piperidine-1-oxyradical of 200g stirs.
Drop into successively in 500L enamel still 200kg dicyclopentadiene, 400g MEHQ, proceed to test tank after 4-hydroxyl-2,2,6, the 6-tetramethyl piperidine-1-oxyradical of 200g stirs.
In 500L enamel still, add the gross porosity microsphere silica gel containing 3kg catalyzer, be added dropwise to the vinylformic acid and dicyclopentadiene material that configure simultaneously.Control this temperature of reaction kettle at 100 DEG C, dropwise rear liquid chromatograph tracking sampling and detect, complete for terminal with dicyclopentadiene reaction.
In system separable go out catalyzer, can reuse after solvent elution.After being steamed by vinylformic acid unreacted in system, collect vinylformic acid DCPA 298kg, yield is 96.43%, is 98.16% through gas chromatograph detection level.
Embodiment 2
Catalyzer making method is identical with embodiment 1.
In 500L enamel still, drop into 4-hydroxyl-2,2,6, the 6-tetramethyl piperidine-1-oxyradical of 160kg vinylformic acid, 200g MEHQ, 200g p-ten.-butylcatechol, 200g successively, after stirring, proceed to test tank.
In 500L enamel still, drop into 200kg dicyclopentadiene, 200g MEHQ, 200g p-ten.-butylcatechol, 200g4-hydroxyl-2,2,6,6-tetramethyl piperidine-1-oxyradical successively, after stirring, proceed to test tank.
In 500L enamel still, add the catalyzer that 3.5kg gross porosity microsphere silica gel does carrier, drip the material vinylformic acid and dicyclopentadiene that configure simultaneously, control temperature of reaction at 80 DEG C, dropwise rear gas chromatograph tracking sampling and detect.Dicyclopentadiene after completion of the reaction, isolates catalyzer, steams unreacted vinylformic acid.Collect vinylformic acid DCPA 302kg, yield 97.73%, through gas chromatograph detection level 98.58%;
Embodiment 3
The catalyzer used in this example, for after producing reaction, reclaims and to obtain through solvent elution.
In 500L enamel still, drop into 4-hydroxyl-2,2,6, the 6-tetramethyl piperidine-1-oxyradical of 150kg vinylformic acid, 500g MEHQ, 250g p-ten.-butylcatechol, 250g successively, after stirring, proceed to test tank.
In 500L enamel still, drop into 4-hydroxyl-2,2,6, the 6-tetramethyl piperidine-1-oxyradical of 200kg dicyclopentadiene, 500g MEHQ, 250g p-ten.-butylcatechol, 250g successively, after stirring, proceed to test tank.
In 500L enamel still, add the gross porosity microsphere silica gel reclaiming wash-out rear catalyst containing 3.5kg, drip the vinylformic acid and dicyclopentadiene material that configure simultaneously, control temperature of reaction at 100 DEG C.Dropwise rear liquid chromatograph tracking sampling to detect.Isolate catalyzer so that dicyclopentadiene reaction is complete for terminal, steam 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 technical scope disclosed by the present invention, the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.
Claims (5)
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, do the catalyst action of carrier at gross porosity microsphere silica gel under, control reaction conditions, drip the raw material being added with stopper respectively simultaneously and obtain;
Described catalyzer is the mixture of phosphoric acid or phosphoric acid salt, tungstate and molybdate, and wherein phosphorus, tungsten, molybdenum three kinds of elemental mole ratios are P: W: Mo=0.01 ~ 2: 0.01 ~ 1: 0.01 ~ 0.05;
Described catalyst quality is 0.5% ~ 2% of reaction substrate total mass;
Be dissolved in after the mixing of selected catalyzer raw material in the water of 20 ~ 100 DEG C, and be adjusted to pH value and be less than 3; To the aqueous solution of selected catalyzer, add gross porosity microsphere silica gel, ageing absorption, after 1 ~ 24 hour, dries activation in 50 ~ 500 DEG C.
2. 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 125-425 μm, and its particle size is 40-120 order, needs more than 100 DEG C to dry before using 2 ~ 24 hours.
3. the preparation method of a kind of vinylformic acid DCPA as claimed in claim 1, is characterized in that: described reaction conditions is, controlling temperature of reaction is 40 ~ 120 DEG C.
4. the preparation method of a kind of vinylformic acid DCPA as claimed in claim 1, is characterized in that: described reaction conditions is, controlling temperature of reaction is 60 ~ 90 DEG C.
5. 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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| CN103980114B true CN103980114B (en) | 2016-01-20 |
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| CN118184479A (en) * | 2022-12-14 | 2024-06-14 | 中国石油天然气股份有限公司 | Process for the preparation of norbornene |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH045257A (en) * | 1990-04-24 | 1992-01-09 | Tosoh Corp | Production of dicyclopentadiene acrylate |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
|---|
| 丙烯酸双环戊二烯酯的合成;余华宁 等;《中国胶粘剂》;20120331;第21卷(第3期);9-12 * |
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