CN114149387A - Preparation method of butyl glycidyl ether methacrylate - Google Patents
Preparation method of butyl glycidyl ether methacrylate Download PDFInfo
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- CN114149387A CN114149387A CN202111405853.XA CN202111405853A CN114149387A CN 114149387 A CN114149387 A CN 114149387A CN 202111405853 A CN202111405853 A CN 202111405853A CN 114149387 A CN114149387 A CN 114149387A
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- glycidyl ether
- butyl glycidyl
- ether methacrylate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/16—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
- C07D301/30—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms by reaction with carboxyl radicals
Abstract
The invention discloses a preparation method of butyl glycidyl ether methacrylate, which comprises the steps of putting butyl glycidyl ether, methacrylic acid, a catalyst and a polymerization inhibitor into a four-neck flask, heating and stirring to uniformly mix the materials, heating to 105-115 ℃, maintaining the reaction for 5-8 h, measuring the acid value at regular time, finishing the reaction until the acid value is less than 5mgKOH/g, and cooling to room temperature to obtain the butyl glycidyl ether methacrylate. The prepared low-odor and low-volatility butyl glycidyl ether methacrylate has the advantages of low cost, low viscosity, high activity, low toxicity, high boiling point, high flash point, low curing shrinkage, good flexibility and the like, can be widely applied to the fields of environment-friendly insulating paint, light-cured coating, light-cured printing ink, resin composite material and the like, and can better replace the currently widely used styrene with low flash point, high volatility, high toxicity and large brittleness.
Description
Technical Field
The invention belongs to the field of diluents, and particularly relates to a preparation method of butyl glycidyl ether methacrylate.
Background
With the stricter environmental protection policies at home and abroad and the increasing of the environmental protection meanings of people, the use of styrene diluents with low boiling point, low flash point, high saturated vapor pressure, strong odor and high toxicity in the industries of insulating paint, photocuring coating and the like is more and more limited, and methacrylate with the characteristics of high boiling point, low saturated vapor pressure, low melting point, low odor, low toxicity and the like is more and more popular as a substitute environmental protection type active diluent. However, the insulating paint or the light-cured coating prepared by diluting general methacrylate has the defects of large curing shrinkage and large brittleness. The butyl glycidyl ether methacrylate has moderate double bond content and low curing shrinkage, and better flexibility is endowed by longer aliphatic chains in a molecular structure, the existence of hydroxyl improves the compatibility with polar matrix resin and base materials, and is beneficial to improving the diluting capability and the adhesive property of the polar matrix resin. Unfortunately, the method has not been industrially produced in large scale, and the production technology has not been reported in patent. For this reason, the patent production technology of butyl glycidyl ether methacrylate is specifically described in the application document to fill the domestic blank.
Butyl glycidyl ether methacrylate is colorless transparent liquid, is a methacrylate functional monomer with wide application range, and can be used as an active diluent for thermosetting or ultraviolet curing insulating paint, coating, printing ink, composite material and the like. The product has the characteristics of good flexibility, hydrolysis resistance, low volatility, low odor, low toxicity and the like, and can be widely applied to the fields of insulating paint, coating, printing ink, composite materials and the like.
The conventional production of methacrylate in the market at present generally adopts an alkyd esterification method: using excessive acrylic acid, toluene or benzene as a water-carrying agent, and p-toluenesulfonic acid as a catalyst to react to obtain a final product, or using an ester exchange method: under the action of a specific catalyst, methyl acrylate and phenethyl alcohol are subjected to ester exchange reaction. However, the method has the defects of excessive material waste, time-consuming and tedious product separation and purification steps, more discharged waste water and waste organic liquid and the like.
Disclosure of Invention
The invention aims to provide a simple, convenient, efficient and energy-saving preparation method of butyl glycidyl ether methacrylate.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of butyl glycidyl ether methacrylate is a simple preparation method without separation and purification, and comprises the following steps
(1) Adding 390.5 butyl glycidyl ether, 258.3 methacrylic acid, 3.2-3.9 parts of catalyst and 1.9 parts of polymerization inhibitor into a four-neck flask provided with a stirrer, a reflux condenser tube and a temperature control device, and uniformly stirring and mixing;
(2) heating to 105-115 ℃, and maintaining the reaction for 5-7 h;
(3) measuring the acid value at regular time until the acid value is less than 5mgKOH/g, and finishing the reaction;
(4) cooling to room temperature to obtain the finished product of butyl glycidyl ether methacrylate.
According to the preparation method of the butyl glycidyl ether methacrylate, the catalyst is one of triethylamine, N-dimethylethanolamine, N-dimethylaniline, N-dimethylbenzylamine, triphenylphosphine and tetrabutylammonium bromide.
The polymerization inhibitor is one or a combination of more of p-tert-butyl catechol, hydroquinone, p-hydroxyanisole and phenothiazine.
Compared with the prior art, the invention has the beneficial effects that:
the invention prepares an environment-friendly active diluent, namely butyl glycidyl ether methacrylate, by epoxy ring-opening esterification reaction, abandons the traditional alcohol acid esterification method, does not generate water in the reaction process, and the reaction is irreversible reaction (irreversible equilibrium reaction), so a water-carrying agent is not needed to promote the reaction, the odor problem caused by the residual water-carrying agent is further avoided, and the cost of the recovery treatment of the water-carrying agent is also saved.
2, the preparation reaction is a one-pot method, the operation is simple and convenient, the whole operation steps only involve simple feeding, stirring and heating, the complicated and time-consuming treatment processes of alkali washing, water washing, reduced pressure distillation and other separation and purification are not needed, no waste water and waste organic liquid are discharged, and the waste water environmental protection treatment and waste organic liquid recovery treatment cost are saved; the feed ratio is close to the theoretical ratio, the materials are not wasted excessively, the reaction activity is high, the reaction time is short, and the product yield is high. The preparation method is simple and convenient on the whole, high-efficiency, energy-saving, time-saving, labor-saving and money-saving.
3, the invention provides a patent document for reporting a synthesis technology of butyl glycidyl ether methacrylate for the first time in China, provides a feasible technical direction for industrial large-scale production of butyl glycidyl ether methacrylate in the later period, and has a better guiding and revealing effect.
4, the butyl glycidyl ether methacrylate prepared by the invention can be used in ultraviolet and thermal curing technologies, has better performance than common methacrylate monomers, and has good adhesive force with base materials.
5, the butyl glycidyl ether methacrylate prepared by the invention has the advantages of low viscosity, good compatibility, strong diluting capability, high activity, low toxicity, high boiling point, high flash point, good flexibility, lower curing shrinkage rate and the like, is a good environment-friendly active diluent, and can better replace the styrene which is widely used at present and has low flash point, high volatility, high toxicity and large brittleness.
6, the preparation method is simple, low in cost and simple and convenient to operate, and the prepared butyl glycidyl ether methacrylate can be widely applied to the fields of insulating paint, coating, printing ink, resin composite materials and the like.
Detailed Description
The present invention will be further described with reference to the following specific examples.
The preparation method of butyl glycidyl ether methacrylate provided by the invention comprises the following raw materials in parts by weight: 390.5 parts of butyl glycidyl ether, 258.3 parts of methacrylic acid, 3.2-3.9 parts of catalyst and 1.9 parts of polymerization inhibitor. The catalyst is one of triethylamine, N-dimethylethanolamine, N-dimethylaniline, N-dimethylbenzylamine, triphenylphosphine and tetrabutylammonium bromide. The polymerization inhibitor is one of p-tert-butyl catechol, hydroquinone, p-hydroxyanisole and phenothiazine, or a mixture of more than two of the p-tert-butyl catechol, the hydroquinone, the p-hydroxyanisole and the phenothiazine.
In the reaction process of the method, water is not generated, so that a traditional organic solvent water-carrying agent is not needed, and the problem of odor caused by residual water-carrying agent is avoided; the esterification reaction activity of epoxy groups in the butyl glycidyl ether and carboxyl groups of methacrylic acid under the action of a catalyst is high, water is not generated in the reaction, the reaction is irreversible, and the reaction degree is high; the reaction is a one-pot method, the operation is simple and convenient, the whole operation steps only involve simple feeding, stirring and heating, the complicated and time-consuming separation and purification post-treatment processes such as alkali washing, water washing, reduced pressure distillation and the like are not needed, no wastewater is discharged, and the method is time-saving, labor-saving, efficient and energy-saving.
In order to make the objects, technical solutions and advantages of the present invention more clearly understood, the following will explain in detail the preparation method of butyl glycidyl ether methacrylate provided by the present invention with reference to the examples. The experimental procedures in the following examples are conventional unless otherwise specified. 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 experimental materials used in the present invention were all purchased from the market unless otherwise specified.
Example 1
This example provides a method for preparing butyl glycidyl ether methacrylate, which comprises the following steps:
390.5g of butyl glycidyl ether, 258.3g of methacrylic acid, 3.9g of triethylamine and 1.9g of p-tert-butyl catechol are added into a four-neck flask provided with a stirrer, a reflux condenser tube and a temperature control device, condensed water is introduced, stirring is started, and the materials are uniformly mixed; heating to 105 ℃, and maintaining the reaction for 6 hours; after reacting for 6 hours, measuring the acid value of the product every half an hour until the acid value is less than 5 mgKOH/g; cooling to room temperature to obtain the finished product of butyl glycidyl ether methacrylate.
Example 2
This example provides a method for preparing butyl glycidyl ether methacrylate, which comprises the following steps:
390.5g of butyl glycidyl ether, 245.3g of methacrylic acid, 3.8g N, N-dimethylethanolamine and 1.9g of hydroquinone are added into a four-neck flask provided with a stirrer, a reflux condenser tube and a temperature control device, condensed water is introduced, stirring is started, and the materials are uniformly mixed; heating to 110 ℃, and maintaining the reaction for 5 hours; after 5 hours of reaction, measuring the acid value of the product every half an hour until the acid value is less than 5 mgKOH/g; cooling to room temperature to obtain the finished product of butyl glycidyl ether methacrylate.
Example 3
This example provides a method for preparing butyl glycidyl ether methacrylate, which comprises the following steps:
390.5g of butyl glycidyl ether, 258.3g of methacrylic acid, 3.2g N, N-dimethylaniline and 1.9g of p-hydroxyanisole are added into a four-neck flask provided with a stirrer, a reflux condenser tube and a temperature control device, condensed water is introduced, stirring is started, and the materials are uniformly mixed; heating to 110 ℃, and maintaining the reaction for 6 h; after reacting for 6 hours, measuring the acid value of the product every half an hour until the acid value is less than 5 mgKOH/g; cooling to room temperature to obtain the finished product of butyl glycidyl ether methacrylate.
Example 4
This example 4 provides a method for preparing butyl glycidyl ether methacrylate, which comprises the following steps:
390.5g of butyl glycidyl ether, 258.3g of methacrylic acid, 3.9g of 3.9g N, N-dimethylbenzylamine and 1.9g of phenothiazine are added into a four-neck flask provided with a stirrer, a reflux condenser tube and a temperature control device, condensed water is introduced, stirring is started, and the materials are mixed uniformly; heating to 110 ℃, and maintaining the reaction for 5 hours; after 5 hours of reaction, measuring the acid value of the product every half an hour until the acid value is less than 5 mgKOH/g; cooling to room temperature to obtain the finished product of butyl glycidyl ether methacrylate.
Example 5
This example provides a method for preparing butyl glycidyl ether methacrylate, which comprises the following steps:
adding 390.5g of butyl glycidyl ether, 258.3g of methacrylic acid, 3.9g N, N-dimethylbenzylamine and 1.9g of p-hydroxyanisole into a four-neck flask provided with a stirrer, a reflux condenser tube and a temperature control device, introducing condensed water, starting stirring, and uniformly mixing the materials; heating to 115 ℃, and maintaining the reaction for 5 hours; after 5 hours of reaction, measuring the acid value of the product every half an hour until the acid value is less than 5 mgKOH/g; cooling to room temperature to obtain the finished product of butyl glycidyl ether methacrylate.
Example 6
This example provides a method for preparing butyl glycidyl ether methacrylate, which comprises the following steps:
390.5g of butyl glycidyl ether, 258.3g of methacrylic acid, 3.9g of triphenylphosphine and 1.9g of p-hydroxyanisole are added into a four-neck flask provided with a stirrer, a reflux condenser tube and a temperature control device, condensed water is introduced, stirring is started, and the materials are uniformly mixed; heating to 110 ℃, and maintaining the reaction for 7 hours; after 7 hours of reaction, measuring the acid value of the product every half an hour until the acid value is less than 5 mgKOH/g; cooling to room temperature to obtain the finished product of butyl glycidyl ether methacrylate.
Example 7
This example provides a method for preparing butyl glycidyl ether methacrylate, which comprises the following steps:
390.5g of butyl glycidyl ether, 258.3g of methacrylic acid, 3.9g of tetrabutylammonium bromide and 1.9g of p-hydroxyanisole are added into a four-neck flask provided with a stirrer, a reflux condenser tube and a temperature control device, condensed water is introduced, stirring is started, and the materials are uniformly mixed; heating to 115 ℃, and maintaining the reaction for 6 hours; after reacting for 6 hours, measuring the acid value of the product every half an hour until the acid value is less than 5 mgKOH/g; cooling to room temperature to obtain the finished product of butyl glycidyl ether methacrylate.
Example 8
This example provides a method for preparing butyl glycidyl ether methacrylate, which comprises the following steps:
adding 390.5g of butyl glycidyl ether, 258.3g of methacrylic acid, 3.9g N, N-dimethylbenzylamine and 1.9g of p-hydroxyanisole into a four-neck flask provided with a stirrer, a reflux condenser tube and a temperature control device, introducing condensed water, starting stirring, and uniformly mixing the materials; heating to 110 ℃, and maintaining the reaction for 6 h; after reacting for 6 hours, measuring the acid value of the product every half an hour until the acid value is less than 5 mgKOH/g; cooling to room temperature to obtain the finished product of butyl glycidyl ether methacrylate.
The above examples 1 to 8 are preferred embodiments of butyl glycidyl ether methacrylate, but the above embodiments of the present invention do not limit the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.
Claims (3)
1. A preparation method of butyl glycidyl ether methacrylate is characterized in that: comprises the following steps
(1) Adding 390.5 butyl glycidyl ether, 258.3 methacrylic acid, 3.2-3.9 parts of catalyst and 1.9 parts of polymerization inhibitor into a four-neck flask, and stirring and mixing uniformly;
(2) heating to 105-115 ℃, and maintaining the reaction for 5-7 h;
(3) measuring the acid value at regular time until the acid value is less than 5mgKOH/g, and finishing the reaction;
(4) cooling to room temperature to obtain the finished product of butyl glycidyl ether methacrylate.
2. The method according to claim 1, wherein the catalyst is one of triethylamine, N-dimethylethanolamine, N-dimethylaniline, N-dimethylbenzylamine, triphenylphosphine, and tetrabutylammonium bromide.
3. The method for preparing butyl glycidyl ether methacrylate according to claim 1, wherein the polymerization inhibitor is one or more of p-tert-butyl catechol, hydroquinone, p-hydroxyanisole and phenothiazine.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111405853.XA CN114149387A (en) | 2021-11-24 | 2021-11-24 | Preparation method of butyl glycidyl ether methacrylate |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111405853.XA CN114149387A (en) | 2021-11-24 | 2021-11-24 | Preparation method of butyl glycidyl ether methacrylate |
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| CN114149387A true CN114149387A (en) | 2022-03-08 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202111405853.XA Pending CN114149387A (en) | 2021-11-24 | 2021-11-24 | Preparation method of butyl glycidyl ether methacrylate |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3697619A (en) * | 1964-11-13 | 1972-10-10 | Nippon Paint Co Ltd | A coating composition of a copolymer of methyl methacrylate with the polymerizable addition reaction product of an alpha,beta-ethylenically unsaturated acid and an epoxy compound |
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2021
- 2021-11-24 CN CN202111405853.XA patent/CN114149387A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3697619A (en) * | 1964-11-13 | 1972-10-10 | Nippon Paint Co Ltd | A coating composition of a copolymer of methyl methacrylate with the polymerizable addition reaction product of an alpha,beta-ethylenically unsaturated acid and an epoxy compound |
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