CN114805061A - Process for producing isobornyl methacrylate and isobornyl methacrylate - Google Patents
Process for producing isobornyl methacrylate and isobornyl methacrylate Download PDFInfo
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- CN114805061A CN114805061A CN202210577226.2A CN202210577226A CN114805061A CN 114805061 A CN114805061 A CN 114805061A CN 202210577226 A CN202210577226 A CN 202210577226A CN 114805061 A CN114805061 A CN 114805061A
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- polymerization inhibitor
- isobornyl methacrylate
- fractionation
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- naphthoquinone
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- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 title claims abstract description 70
- 229940119545 isobornyl methacrylate Drugs 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims description 10
- 230000008569 process Effects 0.000 title claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 109
- 239000003112 inhibitor Substances 0.000 claims abstract description 100
- 238000005194 fractionation Methods 0.000 claims abstract description 58
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- CRPUJAZIXJMDBK-UHFFFAOYSA-N camphene Chemical compound C1CC2C(=C)C(C)(C)C1C2 CRPUJAZIXJMDBK-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229930192627 Naphthoquinone Natural products 0.000 claims abstract description 27
- 150000002791 naphthoquinones Chemical class 0.000 claims abstract description 27
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 22
- PXRCIOIWVGAZEP-UHFFFAOYSA-N Primaeres Camphenhydrat Natural products C1CC2C(O)(C)C(C)(C)C1C2 PXRCIOIWVGAZEP-UHFFFAOYSA-N 0.000 claims abstract description 17
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229930006739 camphene Natural products 0.000 claims abstract description 17
- ZYPYEBYNXWUCEA-UHFFFAOYSA-N camphenilone Natural products C1CC2C(=O)C(C)(C)C1C2 ZYPYEBYNXWUCEA-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000004925 Acrylic resin Substances 0.000 claims description 13
- 229920000178 Acrylic resin Polymers 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000000047 product Substances 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 238000004508 fractional distillation Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 3
- 241000779819 Syncarpia glomulifera Species 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000001739 pinus spp. Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229940036248 turpentine Drugs 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of isobornyl methacrylate and isobornyl methacrylate. The preparation method of isobornyl methacrylate comprises the following steps of: s001, adding 0.1-0.2 part of catalyst, 1 part of methacrylic acid and 2-2.5 parts of camphene into a reactor, then adding a polymerization inhibitor, and reacting at 40-50 ℃ for 16-24 h under normal pressure; the polymerization inhibitor comprises hydroquinone and naphthoquinone; and S002, fractionating, adding a polymerization inhibitor before condensing the fractionation components, and condensing to obtain a finished product of isobornyl methacrylate. According to the invention, hydroquinone and naphthoquinone are used as polymerization inhibitors to prepare isobornyl methacrylate, so that the polymerization of methacrylic acid and isobornyl methacrylate in the preparation process can be effectively inhibited, and the purity of the product is improved.
Description
Technical Field
The invention relates to the field of isobornyl methacrylate preparation, and particularly relates to an isobornyl methacrylate preparation method and isobornyl methacrylate.
Background
Isobornyl methacrylate is a monomer having good heat resistance, weather resistance, water resistance, abrasion resistance and toxicity resistance, and is widely used in the fields of coating materials, adhesives, optical resins, and the like. Isobornyl methacrylate can be prepared by petrochemical routes, and can also be prepared from natural biomass components.
China has rich turpentine resources, pinene serving as a main component of the turpentine resources can be converted into isomeric camphene, and isobornyl methacrylate can be obtained by esterification reaction of camphene and methacrylic acid. In addition to camphene and methacrylic acid, isobornyl methacrylate production typically requires the addition of a catalyst to facilitate the reaction and increase conversion. During the production process, both the raw material methacrylic acid and the product isobornyl methacrylate are extremely polymerizable monomers, so flocculent impurities are often observed in the obtained product, and the purity of the product is influenced.
It is seen that improvements and enhancements to the prior art are needed.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, the present invention has an object to provide a process for producing isobornyl methacrylate and isobornyl methacrylate, which are intended to improve the production purity of isobornyl methacrylate.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of isobornyl methacrylate comprises the following steps of:
s001, adding 0.1-0.2 part of catalyst, 1 part of methacrylic acid and 2-2.5 parts of camphene into a reactor, then adding a polymerization inhibitor, and reacting at 40-50 ℃ for 16-24 h under normal pressure; the polymerization inhibitor comprises hydroquinone and naphthoquinone;
and S002, fractionating, adding a polymerization inhibitor before condensing the fractionation components, and condensing to obtain a finished product of isobornyl methacrylate.
In the method for producing isobornyl methacrylate, in step S001, a polymerization inhibitor is added so that the concentration of the polymerization inhibitor in the reaction system is at least 50ppm by mass.
The isobornyl methacrylate production process wherein a polymerization inhibitor is added before the fractionation components are condensed, so that the concentration of the polymerization inhibitor in the fractionation components is at least 50 mass ppm.
The preparation method of isobornyl methacrylate comprises the step of adding hydroquinone and naphthoquinone into a polymerization inhibitor, wherein the mass ratio of hydroquinone to naphthoquinone is 1 (2-2.5).
The preparation method of isobornyl methacrylate is characterized in that the catalyst is an acrylic resin catalyst.
In the preparation method of isobornyl methacrylate, in the step S002, vacuum fractionation is adopted, and the vacuum degree is 3KPa to 6 KPa.
In the preparation method of isobornyl methacrylate, in the step S002, the discharge temperature of the fractionation component is 100 to 110 ℃.
Isobornyl methacrylate is prepared by the preparation method of isobornyl methacrylate.
Has the advantages that:
the invention provides a preparation method of isobornyl methacrylate, which adopts hydroquinone and naphthoquinone as polymerization inhibitors, effectively inhibits the polymerization of methacrylic acid and isobornyl methacrylate, and reduces the generation of byproducts. And a polymerization inhibitor is further added before fractionation and cooling, so that a small amount of methacrylic acid in the distillate is prevented from polymerizing, and the purity of the product isobornyl methacrylate is effectively improved.
Detailed Description
The present invention provides a method for producing isobornyl methacrylate, isobornyl methacrylate and a polymerization inhibitor, and the present invention will be further described in detail below with reference to examples in order to make the objects, technical means and effects of the present invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The preparation method of isobornyl methacrylate comprises the following steps of:
s001, adding 0.1-0.2 part of catalyst, 1 part of methacrylic acid and 2-2.5 parts of camphene into a reactor, then adding a polymerization inhibitor, and reacting at 40-50 ℃ for 16-24 h under normal pressure; the polymerization inhibitor comprises hydroquinone and naphthoquinone;
and S002, fractionating, namely adding a polymerization inhibitor before condensing the fractionation components, and condensing to obtain a finished product of isobornyl methacrylate.
Step S001, methacrylic acid and camphene are subjected to esterification reaction, and the purity and the conversion rate of the product can be improved by inhibiting the polymerization reaction in the process. In step S002, during the condensation of the components, the monomers are liquefied and then contacted with each other, and polymerization can be carried out at a suitable temperature, so that a small amount of polymer is produced. Polymer impurities are present in the fractionated product as flocs, which are observed to be less if the product is of high purity and less by-products. Hydroquinone and naphthoquinone as polymerization inhibitors can react with chain radicals to form non-radical species or low-activity radicals which cannot be initiated, thereby terminating the polymerization and effectively inhibiting the polymerization of monomers in the steps S001 and S002.
In the step S001, a polymerization inhibitor is added so that the concentration of the polymerization inhibitor in the reaction system is at least 50 mass ppm. According to the invention, when the addition amount of the polymerization inhibitor is 50ppm or more, the purity of the obtained product is high, and the market requirement is met.
In the step S002, a polymerization inhibitor is added before the fractionation components are condensed, so that the concentration of the polymerization inhibitor in the fractionation components is at least 50 mass ppm.
In the polymerization inhibitor, the mass ratio of hydroquinone to naphthoquinone is 1 (2-2.5). The invention obtains the product with best purity and least floccule in the mass ratio range through experiments.
The catalyst is an acrylic resin catalyst. The acrylic resin catalyst is a solid acid catalyst, has high activity, is easy to separate, and does not influence the purity of the product.
In the step S002, vacuum fractionation is adopted, and the vacuum degree is 3KPa to 6 KPa. The boiling point of the components can be reduced under the vacuum degree, and the energy consumption is reduced.
In the step S002, the discharge temperature of the fractionation components is 100-110 ℃. Isobornyl methacrylate can reach boiling point at 100-110 deg.c under vacuum fractionation to form gaseous matter, which is maintained in the reactor and separated out partial impurity with low boiling point or high boiling point.
Isobornyl methacrylate, prepared by the above method for preparing isobornyl methacrylate.
Example 1
The preparation method of isobornyl methacrylate comprises the following steps of:
s001, adding 0.2 part of catalyst, 1 part of methacrylic acid and 2.5 parts of camphene into a reactor, adding a polymerization inhibitor, and reacting at 50 ℃ under normal pressure for 16 hours; the polymerization inhibitor comprises hydroquinone and naphthoquinone;
and S002, fractionating, adding a polymerization inhibitor before condensing the fractionation components, and condensing to obtain a finished product of isobornyl methacrylate.
In the step S001, a polymerization inhibitor is added so that the concentration of the polymerization inhibitor in the reaction system is 25 mass ppm.
In the step S002, a polymerization inhibitor is added before the fractionation components are condensed, so that the concentration of the polymerization inhibitor in the fractionation components is 25 mass ppm.
In the polymerization inhibitor, the mass ratio of hydroquinone to naphthoquinone is 1: 2.5.
The catalyst is an acrylic resin catalyst.
In the step S002, vacuum fractionation is adopted, and the vacuum degree is 3 KPa.
In the step S002, the discharge temperature of the fractionation components is 110 ℃.
Example 2
The preparation method of isobornyl methacrylate comprises the following steps of:
s001, adding 0.2 part of catalyst, 1 part of methacrylic acid and 2.5 parts of camphene into a reactor, adding a polymerization inhibitor, and reacting at 50 ℃ under normal pressure for 16 hours; the polymerization inhibitor comprises hydroquinone and naphthoquinone;
and S002, fractionating, adding a polymerization inhibitor before condensing the fractionation components, and condensing to obtain a finished product of isobornyl methacrylate.
In the step S001, a polymerization inhibitor is added so that the concentration of the polymerization inhibitor in the reaction system is 50 mass ppm.
In the step S002, a polymerization inhibitor is added before the fractionation components are condensed, so that the concentration of the polymerization inhibitor in the fractionation components is 50 mass ppm.
In the polymerization inhibitor, the mass ratio of hydroquinone to naphthoquinone is 1: 2.5.
The catalyst is an acrylic resin catalyst.
In the step S002, vacuum fractionation is adopted, and the vacuum degree is 3 KPa.
In the step S002, the discharge temperature of the fractionation components is 110 ℃.
Example 3
The preparation method of isobornyl methacrylate comprises the following steps of:
s001, adding 0.2 part of catalyst, 1 part of methacrylic acid and 2 parts of camphene into a reactor, then adding a polymerization inhibitor, and reacting at 50 ℃ under normal pressure for 24 hours; the polymerization inhibitor comprises hydroquinone and naphthoquinone;
and S002, fractionating, adding a polymerization inhibitor before condensing the fractionation components, and condensing to obtain a finished product of isobornyl methacrylate.
In the step S001, a polymerization inhibitor is added so that the concentration of the polymerization inhibitor in the reaction system is 75 mass ppm.
In the step S002, a polymerization inhibitor is added before the fractionation components are condensed, so that the concentration of the polymerization inhibitor in the fractionation components is 75 mass ppm.
In the polymerization inhibitor, the mass ratio of hydroquinone to naphthoquinone is 1: 2.5.
The catalyst is an acrylic resin catalyst.
In the step S002, vacuum fractionation is adopted, and the vacuum degree is 3 KPa.
In the step S002, the discharge temperature of the fractionation components is 110 ℃.
Example 4
The preparation method of isobornyl methacrylate comprises the following steps of:
s001, adding 0.2 part of catalyst, 1 part of methacrylic acid and 2 parts of camphene into a reactor, adding a polymerization inhibitor, and reacting at 50 ℃ for 18h under normal pressure; the polymerization inhibitor comprises hydroquinone and naphthoquinone;
and S002, fractionating, adding a polymerization inhibitor before condensing the fractionation components, and condensing to obtain a finished product of isobornyl methacrylate.
In the step S001, a polymerization inhibitor is added so that the concentration of the polymerization inhibitor in the reaction system is 100 mass ppm.
In the step S002, a polymerization inhibitor is added before the fractionation components are condensed, so that the concentration of the polymerization inhibitor in the fractionation components is 100 mass ppm.
In the polymerization inhibitor, the mass ratio of hydroquinone to naphthoquinone is 1: 2.5.
The catalyst is an acrylic resin catalyst.
In the step S002, vacuum fractionation is adopted, and the vacuum degree is 4 KPa.
In the step S002, the discharge temperature of the fractionation components is 108 ℃.
Comparative example 1
The preparation method of isobornyl methacrylate comprises the following steps of:
s001, adding 0.2 part of catalyst, 1 part of methacrylic acid and 2.5 parts of camphene into a reactor, and reacting at 50 ℃ for 18h under normal pressure;
and S002, fractionating, and condensing to obtain a finished product of isobornyl methacrylate.
The catalyst is an acrylic resin catalyst.
In the step S002, vacuum fractionation is adopted, and the vacuum degree is 4 KPa.
In the step S002, the discharge temperature of the fractionation components is 108 ℃.
Comparative example 2
The preparation method of isobornyl methacrylate comprises the following steps of:
s001, adding 0.2 part of catalyst, 1 part of methacrylic acid and 2.5 parts of camphene into a reactor, adding a polymerization inhibitor, and reacting at 50 ℃ under normal pressure for 16 hours; the polymerization inhibitor comprises hydroquinone and naphthoquinone;
and S002, fractionating, and condensing to obtain a finished product of isobornyl methacrylate.
In the step S001, a polymerization inhibitor is added so that the concentration of the polymerization inhibitor in the reaction system is 50 mass ppm.
In the polymerization inhibitor, the mass ratio of hydroquinone to naphthoquinone is 1: 2.5.
The catalyst is an acrylic resin catalyst.
In the step S002, vacuum fractionation is adopted, and the vacuum degree is 3 KPa.
In the step S002, the discharge temperature of the fractionation components is 110 ℃.
Comparative example 3
The preparation method of isobornyl methacrylate comprises the following steps of:
s001, adding 0.2 part of catalyst, 1 part of methacrylic acid and 2.5 parts of camphene into a reactor, adding a polymerization inhibitor, and reacting at 50 ℃ under normal pressure for 18 h;
and S002, fractionating, adding a polymerization inhibitor before condensing the fractionation components, and condensing to obtain a finished product of isobornyl methacrylate.
The polymerization inhibitor is hydroquinone.
In the step S001, a polymerization inhibitor is added so that the concentration of the polymerization inhibitor in the reaction system is 50 mass ppm.
In the step S002, a polymerization inhibitor is added before the fractionation components are condensed, so that the concentration of the polymerization inhibitor in the fractionation components is 50 mass ppm.
The catalyst is an acrylic resin catalyst.
In the step S002, vacuum fractionation is adopted, and the vacuum degree is 4 KPa.
In the step S002, the discharge temperature of the fractionation components is 108 ℃.
Comparative example 4
The preparation method of isobornyl methacrylate comprises the following steps of:
s001, adding 0.2 part of catalyst, 1 part of methacrylic acid and 2.5 parts of camphene into a reactor, adding a polymerization inhibitor, and reacting at 50 ℃ under normal pressure for 18 h;
and S002, fractionating, adding a polymerization inhibitor before condensing the fractionation components, and condensing to obtain a finished product of isobornyl methacrylate.
The polymerization inhibitor is naphthoquinone.
In the step S001, a polymerization inhibitor is added so that the concentration of the polymerization inhibitor in the reaction system is 50 mass ppm.
In the step S002, a polymerization inhibitor is added before the fractionation components are condensed, so that the concentration of the polymerization inhibitor in the fractionation components is 50 mass ppm.
The catalyst is an acrylic resin catalyst.
In the step S002, vacuum fractionation is adopted, and the vacuum degree is 4 KPa.
In the step S002, the discharge temperature of the fractionation components is 108 ℃.
Comparative example 5
The preparation method of isobornyl methacrylate comprises the following steps of:
s001, adding 0.2 part of catalyst, 1 part of methacrylic acid and 2.5 parts of camphene into a reactor, adding a polymerization inhibitor, and reacting at 50 ℃ under normal pressure for 16 hours; the polymerization inhibitor comprises hydroquinone and naphthoquinone;
and S002, fractionating, adding a polymerization inhibitor before condensing the fractionation components, and condensing to obtain a finished product of isobornyl methacrylate.
In the step S001, a polymerization inhibitor is added so that the concentration of the polymerization inhibitor in the reaction system is 50 mass ppm.
In the step S002, a polymerization inhibitor is added before the fractionation components are condensed, so that the concentration of the polymerization inhibitor in the fractionation components is 50 mass ppm.
In the polymerization inhibitor, the mass ratio of hydroquinone to naphthoquinone is 1: 1.
The catalyst is an acrylic resin catalyst.
In the step S002, vacuum fractionation is adopted, and the vacuum degree is 3 KPa.
In the step S002, the discharge temperature of the fractionation components is 110 ℃.
The purity of the isobornyl methacrylate product distillate obtained in examples 1-4 and comparative examples 1-5 is respectively detected by a visual inspection method, and if the distillate contains obvious floccules, the byproduct is generated in a large amount, and the impurities are obvious; if the fractionated juice is clear, no floc is evident, indicating that the product is of higher purity, wherein the clear product can be further observed by a microscope or a magnifying glass.
The corresponding visual results are as follows:
according to the above results, comparative example 1 was prepared without using a polymerization inhibitor, and the obtained product was observed visually to have a remarkable floc without magnification, indicating that the by-product was abundant and the purity was low. Examples 1-4 are the results of products prepared by adding 25ppm, 50ppm, 75ppm and 100ppm polymerization inhibitors before esterification and cooling by fractional distillation, respectively, and no floc was observed without amplification, indicating that polymerization inhibition was possible and product purity was improved. After the magnification of 50 times, the floccules are observed in the example 1, but the floccules are not observed in the examples 2 to 4, which shows that when the addition amount of the polymerization inhibitor is 50ppm or more, the better polymerization inhibition effect can be achieved, and the purity of the product is better.
In comparative example 2, no polymerization inhibitor was added before the fractional distillation cooling, and the obtained product had obvious floc when observed at 50 times magnification, which indicates that methacrylic acid included in the fractional distillation cooling process was polymerized to produce a part of by-products, resulting in low purity of the product after fractional distillation.
Comparative example 3 only used hydroquinone as the polymerization inhibitor and comparative example 4 only used naphthoquinone as the polymerization inhibitor, and the products obtained in both comparative examples had a small amount of floc when observed at a magnification of 50 times, and the effects were not as good as those of example 2.
Comparative example 5 compared with example 2, the content of naphthoquinone was low, and the obtained product also had a small amount of floc when observed at a magnification of 50 times, and the effect was not as good as that of example 2.
In conclusion, the purity of isobornyl methacrylate can be effectively improved by using hydroquinone and naphthoquinone as a polymerization inhibitor, and the effect is better when the addition amount is 50ppm or more. In addition, the polymerization inhibitor needs to be added during the former esterification reaction and also needs to be added during the latter fractionation reaction, so that the polymerization of a small amount of methacrylic acid during the cooling of the fractionation reaction can be effectively avoided.
It should be understood that equivalents and modifications to the invention as described herein may occur to those skilled in the art, and all such modifications and alterations are intended to fall within the scope of the appended claims.
Claims (8)
1. The preparation method of isobornyl methacrylate is characterized by comprising the following steps of:
s001, adding 0.1-0.2 part of catalyst, 1 part of methacrylic acid and 2-2.5 parts of camphene into a reactor, then adding a polymerization inhibitor, and reacting at 40-50 ℃ for 16-24 h under normal pressure; the polymerization inhibitor comprises hydroquinone and naphthoquinone;
and S002, fractionating, adding a polymerization inhibitor before condensing the fractionation components, and condensing to obtain a finished product of isobornyl methacrylate.
2. The process for producing isobornyl methacrylate as claimed in claim 1, wherein in step S001, a polymerization inhibitor is added so that the concentration of the polymerization inhibitor in the reaction system is at least 50 mass ppm.
3. The process for producing isobornyl methacrylate as claimed in claim 1, wherein in step S002, a polymerization inhibitor is added before the fractionation components are condensed so that the concentration of the polymerization inhibitor in the fractionation components is at least 50 mass ppm.
4. The method for producing isobornyl methacrylate as claimed in claim 2, wherein the mass ratio of hydroquinone to naphthoquinone in the polymerization inhibitor is 1 (2 to 2.5).
5. The method for producing isobornyl methacrylate as claimed in claim 1, wherein the catalyst is an acrylic resin catalyst.
6. The process according to claim 1, wherein in step S002, vacuum fractionation is carried out in a degree of vacuum of 3 to 6 KPa.
7. The method for producing isobornyl methacrylate as claimed in claim 1, wherein in the step S002, the discharge temperature of the fractionated components is 100 to 110 ℃.
8. Isobornyl methacrylate, characterized by being produced by the isobornyl methacrylate production method according to any one of claims 1 to 7.
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| CN202210577226.2A CN114805061A (en) | 2022-05-25 | 2022-05-25 | Process for producing isobornyl methacrylate and isobornyl methacrylate |
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| CN202210577226.2A CN114805061A (en) | 2022-05-25 | 2022-05-25 | Process for producing isobornyl methacrylate and isobornyl methacrylate |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1151395A (en) * | 1995-08-18 | 1997-06-11 | 埃勒夫阿托化学有限公司 | Process for preparation of isobornyl (meth) acrylate |
| US6329543B1 (en) * | 1999-05-06 | 2001-12-11 | Roehm Gmbh & Co Kg | Process for synthesis of isobornyl (Meth) acrylate |
| CN108276281A (en) * | 2018-01-22 | 2018-07-13 | 安徽联化新材料有限公司 | A kind of continuous producing apparatus of isobornyl methacrylate |
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