CN112625171B - Methacrylic resin and preparation method thereof - Google Patents
Methacrylic resin and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of methacrylic resin, which comprises the following steps: dissolving methyl methacrylate, butyl acrylate and 2-methyl-2-adamantyl methacrylate in ethyl acetate, and adding an initiator to form a mixed solution; in protective gas, carrying out polymerization reaction on the mixed solution under the condition of ultrasonic constant temperature; wherein the ultrasonic power under the ultrasonic constant temperature condition is 100-300W, the temperature is 30-75 ℃, and the polymerization reaction time is 1-10 h. Through ultrasonic-assisted polymerization, the reaction time is shortened, methacrylic resins with different molecular weights are obtained under different polymerization conditions, and the polymer in the reaction system has centralized molecular weight and is easy to purify.
Description
Technical Field
The invention belongs to the technical field of chemistry, and particularly relates to methacrylic resin and a preparation method thereof.
Background
Photoresist is a photosensitive material and is a key processing material in the fine processing technology of integrated circuits. The methacrylic resin is used as a part of photoresist composition, determines the quality of the photoresist performance, and is a hotspot of current photoresist material research.
After the resin components are determined, the resins with different molecular weights determine the performance of the photoresist, so in order to meet the requirements of the photoresist, the methacrylic resins with different molecular weights need to be prepared. In the traditional method, an initiator is added into an emulsion or a solution, and the molecular weight of the methacrylic resin is controlled by heating and refluxing in a water bath or an oil bath to perform free radical polymerization reaction. However, the half-life of the initiator is generally long, so that it takes a very long time, usually 20 hours or more, to obtain a polymer having a longer chain length. If the temperature is increased, the decomposition rate of the initiator is accelerated, so that the concentration of free radicals in a reaction system is too high, more short-chain polymers are generated, the molecular weight distribution is wider, and the effect is not ideal. If a low temperature is used, although the initiator can initiate the polymerization for a long period of time, if the temperature is too low, the temperature at the time of polymerization of the monomer may not be reached, resulting in a low monomer conversion and a large amount of small-chain polymer in the reaction system. In conclusion, the conventional method has the technical defects of long reaction time, many small-chain polymers in the reaction system, large amount of solvent required during later precipitation, washing and purification, unsatisfactory synthesis effect and the like.
Disclosure of Invention
The embodiment of the invention provides a preparation method of methacrylic resin, aiming at solving the technical defects of overlong reaction time, a plurality of small-chain polymers in a reaction system, large amount of solvent needed during later precipitation, washing and purification, unsatisfactory synthesis effect and the like of the traditional preparation method.
The embodiment of the invention is realized in such a way that the preparation method of the methacrylic resin comprises the following steps:
dissolving methyl methacrylate, butyl acrylate and 2-methyl-2-adamantyl methacrylate in ethyl acetate, and adding an initiator to form a mixed solution;
in protective gas, carrying out polymerization reaction on the mixed solution under the condition of ultrasonic constant temperature;
wherein the ultrasonic power under the ultrasonic constant temperature condition is 100-300W, the temperature is 30-75 ℃, and the polymerization reaction time is 1-10 h.
In addition, the invention also provides methacrylic resin, which is prepared by the preparation method.
According to the preparation method of the methacrylic resin, a mixed solution obtained by mixing monomers (methyl methacrylate, butyl acrylate and 2-methyl-2-adamantyl methacrylate) and an initiator is subjected to polymerization reaction under the ultrasonic constant-temperature condition. In the initial stage of reaction, the initiator and the monomer are irradiated by ultrasonic energy to release a large amount of free radicals in a short time, so that more primary particles are generated in the initial stage of reaction to form more active centers, the polymerization of the monomer is accelerated, the polymerization time is shortened, and cavitation bubbles are generated in the solution by utilizing the characteristic of ultrasonic cavitation phenomenon, the bubbles are ceaselessly formed and broken under the action of ultrasonic, a solution system is also stirred at a high speed to generate energy, the generated unstable oligomer is activated again to form new free radicals for polymerization, so that the monomer and the oligomer in the solution can be fully utilized to carry out polymerization to form long-chain polymers, thereby forming polymers with narrower molecular weight distribution, the monomer utilization rate is high, after final purification, the amount of residual monomers and the oligomer which need to be washed away is small, and most of the monomers are polymerized, the final yield is also high. Besides, the polymerization degree of the monomer and the molecular weight can be controlled by changing the temperature, the ultrasonic power and the time length.
Drawings
FIG. 1 is a flow chart of a method for preparing a methacrylic resin according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
As shown in fig. 1, an embodiment of the present invention provides a method for preparing a methacrylic resin. The preparation method of the methacrylic resin comprises the following steps:
step S10, dissolving methyl methacrylate, butyl acrylate and 2-methyl-2-adamantyl methacrylate in ethyl acetate, and adding an initiator to form a mixed solution;
and step S20, in protective gas, carrying out polymerization reaction on the mixed solution under the ultrasonic constant temperature condition.
Wherein the ultrasonic power under the ultrasonic constant temperature condition is 100-300W, the temperature is 30-75 ℃, and the polymerization reaction time is 1-10 h. The initiator may be a compound such as dimethyl azodiisobutyrate.
In the initial stage of the reaction, the initiator and the monomers (methyl methacrylate, butyl acrylate and 2-methyl-2-adamantyl methacrylate) are irradiated by ultrasonic energy to release a large amount of free radicals in a short time, so that more primary particles are generated in the initial stage of the reaction, more active centers are formed, the polymerization of the monomers is accelerated, and the polymerization time is shortened. And by utilizing the characteristic of ultrasonic cavitation phenomenon, cavitation bubbles are generated in the solution, and the bubbles are ceaselessly formed and broken under the action of ultrasonic waves, so that the solution system is also stirred at a high speed to generate energy, and the generated unstable oligomer is activated again to form new free radicals for polymerization, so that the monomers and oligomers in the solution can be fully utilized to be polymerized to form long-chain polymers, and the polymers with narrow molecular weight distribution are formed, and the monomer utilization rate is high. Therefore, the degree of polymerization and the polymerization rate of the monomer can be controlled by controlling the irradiation intensity of the ultrasonic waves (ultrasonic power), the polymerization reaction temperature and the polymerization reaction time, thereby obtaining methacrylic resins with different molecular weights.
Generally, the polymerization is carried out for the same time at the same temperature, and the higher the ultrasonic power is, the higher the polymerization degree of the polymerized methacrylamide is; under the condition of the same ultrasonic power and the same polymerization temperature, the longer the polymerization time is, the higher the polymerization degree of the methacrylamide obtained by polymerization is; the polymerization degree of the methacrylamide is higher when the ultrasonic power is the same, the polymerization time is the same, and the temperature is higher.
In another embodiment, the ultrasonic power under the ultrasonic constant temperature condition is 200-300W, the temperature is 50-75 ℃, and the polymerization reaction time is 5-10 h. In another embodiment, the ultrasonic power under the ultrasonic constant temperature condition is 300W, the temperature is 75 ℃, and the polymerization reaction time is 10 h.
In step S10, methyl methacrylate, butyl acrylate, and 2-methyl-2-adamantyl methacrylate are added to a reaction vessel containing ethyl acetate, and after mixing uniformly, an initiator is added, and stirring is performed, and the initiator and the monomers are mixed uniformly to form a mixed solution. Wherein the proportion of the methyl methacrylate, the butyl acrylate and the 2-methyl-2-adamantyl methacrylate is as follows: (1-10) methyl methacrylate, (1-10) butyl acrylate and (1-10) 2-methyl-2-adamantyl methacrylate. The mixing unit is other measurement units such as mass or molar mass. The usage amount of the ethyl acetate is 4 times of the total mass of the monomers, and the usage amount of the initiator is 1 percent of the total mass of the monomers.
After step S10, nitrogen gas was slowly introduced into the reaction vessel for 30min to remove oxygen in the vessel, thereby protecting the reaction system with nitrogen gas.
After the polymerization reaction is finished in step S20, a precipitant is added to the reaction solution after the polymerization reaction to perform precipitation purification treatment of the target product, and after the precipitation purification, the formed suspension is centrifuged, after solid-liquid separation, the solid is taken out and placed in a vacuum oven, and dried overnight at 50-85 ℃ to obtain the final polymerization product. Because the molecular weight distribution of the polymer obtained by ultrasonic-assisted polymerization is narrow, the small-chain polymer in the reaction system is less, and a large amount of solvent is not needed for washing when the precipitant is purified.
In one embodiment, the precipitant is n-hexane, and the amount of the precipitant is 4 times of the mass of the reaction solution. The temperature for overnight drying in the vacuum oven is preferably 80 ℃. The centrifugation speed is 5000rpm, and the centrifugation time is 5-10 min.
The following examples illustrate the preparation of methacrylic resins according to embodiments of the present invention.
Example one
This example provides a method for preparing a base acrylic resin, including the following steps:
(1) 50g of methyl methacrylate, 30g of butyl acrylate and 20g of 2-methyl-2-adamantyl methacrylate are placed in a four-necked flask containing 400g of ethyl acetate, and stirred until the monomers are dissolved;
(2) after the monomers are dissolved, adding an initiator (dimethyl azodiisobutyrate), and stirring until the initiator is dissolved, wherein the using amount of the initiator is 1 g;
(3) placing the four-mouth flask in an ultrasonic constant-temperature pool, slowly introducing nitrogen for 30min, and removing oxygen in the flask;
(4) after the temperature is increased to 75 ℃, when the ultrasonic power is set to 300W, the ultrasonic is started to carry out ultrasonic polymerization;
(5) controlling the ultrasonic time to be 10 hours, and closing the reaction after 10 hours;
(6) pouring the reaction solution into a certain amount of n-hexane for precipitation and purification treatment, wherein the usage amount of the n-hexane is 2000 g;
(7) centrifuging for solid-liquid separation, placing the solid in a vacuum oven, and drying at 80 deg.C overnight;
(8) the dried product was weighed to calculate the yield, molecular weight and molecular weight distribution, and the specific results are shown in table 1.
Example two
This example provides a method for preparing a base acrylic resin, including the following steps:
(1) 50g of methyl methacrylate, 30g of butyl acrylate and 20g of 2-methyl-2-adamantyl methacrylate were put in a four-necked flask containing 400g of ethyl acetate, and stirred until the monomers were dissolved;
(2) after the monomers are dissolved, adding an initiator (dimethyl azodiisobutyrate), and stirring until the initiator is dissolved, wherein the using amount of the initiator is 1 g;
(3) placing the four-mouth flask in an ultrasonic constant-temperature pool, slowly introducing nitrogen for 30min, and removing oxygen in the flask;
(4) after the temperature is increased to 75 ℃, when the ultrasonic power is set to 300W, the ultrasonic is started to carry out ultrasonic polymerization;
(5) controlling the ultrasonic time to be 5 hours, and closing the reaction after 5 hours;
(6) pouring the reaction solution into a certain amount of n-hexane for precipitation and purification treatment, wherein the usage amount of the n-hexane is 2000 g;
(7) centrifuging for solid-liquid separation, placing the solid in a vacuum oven, and drying at 80 deg.C overnight;
(8) the dried product was weighed to calculate the yield, molecular weight and molecular weight distribution, and the specific results are shown in table 1.
EXAMPLE III
This example provides a method for preparing a base acrylic resin, including the following steps:
(1) 50g of methyl methacrylate, 30g of butyl acrylate and 20g of 2-methyl-2-adamantyl methacrylate were put in a four-necked flask containing 400g of ethyl acetate, and stirred until the monomers were dissolved;
(2) after the monomers are dissolved, adding an initiator (dimethyl azodiisobutyrate), and stirring until the initiator is dissolved, wherein the using amount of the initiator is 1 g;
(3) placing the four-mouth flask in an ultrasonic constant-temperature pool, slowly introducing nitrogen for 30min, and removing oxygen in the flask;
(4) after the temperature is increased to 75 ℃, when the ultrasonic power is set to 300W, the ultrasonic is started to carry out ultrasonic polymerization;
(5) controlling the ultrasonic time to be 1h, and closing the reaction after 1 h;
(6) pouring the reaction solution into a certain amount of n-hexane for precipitation and purification treatment, wherein the usage amount of the n-hexane is 2000 g;
(7) centrifuging for solid-liquid separation, placing the solid in a vacuum oven, and drying at 80 deg.C overnight;
(8) the dried product was weighed to calculate the yield, molecular weight and molecular weight distribution, and the specific results are shown in table 1.
Example four
This example provides a method for preparing a base acrylic resin, including the following steps:
(1) 50g of methyl methacrylate, 30g of butyl acrylate and 20g of 2-methyl-2-adamantyl methacrylate were put in a four-necked flask containing 400g of ethyl acetate, and stirred until the monomers were dissolved;
(2) after the monomers are dissolved, adding an initiator (dimethyl azodiisobutyrate), and stirring until the initiator is dissolved, wherein the using amount of the initiator is 1 g;
(3) placing the four-mouth flask in an ultrasonic constant-temperature pool, slowly introducing nitrogen for 30min, and removing oxygen in the flask;
(4) after the temperature is increased to 75 ℃, when the ultrasonic power is set to 200W, the ultrasonic is started to carry out ultrasonic polymerization;
(5) controlling the ultrasonic time to be 10 hours, and closing the reaction after 10 hours;
(6) pouring the reaction solution into a certain amount of n-hexane for precipitation and purification treatment, wherein the usage amount of the n-hexane is 2000 g;
(7) centrifuging for solid-liquid separation, placing the solid in a vacuum oven, and drying at 80 deg.C overnight;
(8) the dried product was weighed to calculate the yield, molecular weight and molecular weight distribution, and the specific results are shown in table 1.
EXAMPLE five
This example provides a method for preparing a base acrylic resin, including the following steps:
(1) 50g of methyl methacrylate, 30g of butyl acrylate and 20g of 2-methyl-2-adamantyl methacrylate were put in a four-necked flask containing 400g of ethyl acetate, and stirred until the monomers were dissolved;
(2) after the monomers are dissolved, adding an initiator (dimethyl azodiisobutyrate), and stirring until the initiator is dissolved, wherein the using amount of the initiator is 1 g;
(3) placing the four-mouth flask in an ultrasonic constant-temperature pool, slowly introducing nitrogen for 30min, and removing oxygen in the flask;
(4) after the temperature is increased to 75 ℃, when the ultrasonic power is set to be 100W, the ultrasonic is started to carry out ultrasonic polymerization;
(5) controlling the ultrasonic time to be 10 hours, and closing the reaction after 10 hours;
(6) pouring the reaction solution into a certain amount of n-hexane for precipitation and purification treatment, wherein the usage amount of the n-hexane is 2000 g;
(7) centrifuging for solid-liquid separation, placing the solid in a vacuum oven, and drying at 80 deg.C overnight;
(8) the dried product was weighed to calculate the yield, molecular weight and molecular weight distribution, and the specific results are shown in table 1.
EXAMPLE six
This example provides a method for preparing a base acrylic resin, including the following steps:
(1) 50g of methyl methacrylate, 30g of butyl acrylate and 20g of 2-methyl-2-adamantyl methacrylate were put in a four-necked flask containing 400g of ethyl acetate, and stirred until the monomers were dissolved;
(2) after the monomers are dissolved, adding an initiator (dimethyl azodiisobutyrate), and stirring until the initiator is dissolved, wherein the using amount of the initiator is 1 g;
(3) placing the four-mouth flask in an ultrasonic constant-temperature pool, slowly introducing nitrogen for 30min, and removing oxygen in the flask;
(4) after the temperature is raised to 50 ℃, when the ultrasonic power is set to 300W, the ultrasonic is started to carry out ultrasonic polymerization;
(5) controlling the ultrasonic time to be 10 hours, and closing the reaction after 10 hours;
(6) pouring the reaction solution into a certain amount of n-hexane for precipitation and purification treatment, wherein the usage amount of the n-hexane is 2000 g;
(7) centrifuging for solid-liquid separation, placing the solid in a vacuum oven, and drying at 80 deg.C overnight;
(8) the dried product was weighed to calculate the yield, molecular weight and molecular weight distribution, and the specific results are shown in table 1.
EXAMPLE seven
This example provides a method for preparing a base acrylic resin, including the following steps:
(1) 50g of methyl methacrylate, 30g of butyl acrylate and 20g of 2-methyl-2-adamantyl methacrylate were put in a four-necked flask containing 400g of ethyl acetate, and stirred until the monomers were dissolved;
(2) after the monomers are dissolved, adding an initiator (dimethyl azodiisobutyrate), and stirring until the initiator is dissolved, wherein the using amount of the initiator is 1 g;
(3) placing the four-mouth flask in an ultrasonic constant-temperature pool, slowly introducing nitrogen for 30min, and removing oxygen in the flask;
(4) after the temperature is raised to 30 ℃, when the ultrasonic power is set to 300W, the ultrasonic is started to carry out ultrasonic polymerization;
(5) controlling the ultrasonic time to be 10 hours, and closing the reaction after 10 hours;
(6) pouring the reaction solution into a certain amount of n-hexane for precipitation and purification treatment, wherein the usage amount of the n-hexane is 4 times of the mass of the reaction solution;
(7) centrifuging for solid-liquid separation, placing the solid in a vacuum oven, and drying at 80 deg.C overnight;
(8) the dried product was weighed to calculate the yield, molecular weight and molecular weight distribution, and the specific results are shown in table 1.
Comparative example 1
This comparative example provides a method for preparing a base acrylic resin, including the steps of:
(1) 50g of methyl methacrylate, 30g of butyl acrylate and 20g of 2-methyl-2-adamantyl methacrylate were put in a four-necked flask containing 400g of ethyl acetate, and stirred until the monomers were dissolved;
(2) after the monomers are dissolved, adding an initiator (dimethyl azodiisobutyrate), and stirring until the initiator is dissolved, wherein the using amount of the initiator is 1 g;
(3) placing the four-mouth flask in an ultrasonic constant-temperature pool, slowly introducing nitrogen for 30min, and removing oxygen in the flask;
(4) heating to 75 deg.c and polymerizing;
(5) controlling the reaction time to be 10h, and closing the reaction after 10 h;
(6) pouring the reaction solution into a certain amount of n-hexane for precipitation and purification treatment, wherein the usage amount of the n-hexane is 2000 g;
(7) centrifuging for solid-liquid separation, placing the solid in a vacuum oven, and drying at 80 deg.C overnight;
(8) the dried product was weighed to calculate the yield, molecular weight and molecular weight distribution, and the specific results are shown in table 1.
Comparative example 2
This comparative example provides a method for preparing a base acrylic resin, including the steps of:
(1) 50g of methyl methacrylate, 30g of butyl acrylate and 20g of 2-methyl-2-adamantyl methacrylate were put in a four-necked flask containing 400g of ethyl acetate, and stirred until the monomers were dissolved;
(2) placing the four-mouth flask in an ultrasonic constant-temperature pool, slowly introducing nitrogen for 30min, and removing oxygen in the flask;
(4) after the temperature is increased to 75 ℃, when the ultrasonic power is set to 300W, the ultrasonic is started to carry out ultrasonic polymerization;
(5) controlling the ultrasonic time to be 10 hours, and closing the reaction after 10 hours;
(6) pouring the reaction solution into a certain amount of n-hexane for precipitation and purification treatment, wherein the usage amount of the n-hexane is 2000 g;
(7) centrifuging for solid-liquid separation, placing the solid in a vacuum oven, and drying at 80 deg.C overnight;
(8) the dried product was weighed to calculate the yield, molecular weight and molecular weight distribution, and the specific results are shown in table 1.
The methacrylic resins prepared in examples 1 to 7 and comparative examples 1 and 2 were weighed and the yields calculated
See table 1 for the ratio, molecular weight and molecular weight distribution, results and experimental conditions:
TABLE 1 preparation results of methacrylic resins
From the results, it can be seen that the use of the ultrasonic method for promoting the polymerization of the methacrylic resin has certain feasibility, and factors influencing the polymerization degree of the polymer are ultrasonic power, polymerization temperature, ultrasonic time and initiator introduction, and have certain regularity.
Specifically, the higher the ultrasonic power, the more energy is provided, the more radicals are generated, the faster the polymerization rate is, and finally the polymer has a higher molecular weight and a narrower molecular weight distribution, and the higher the final yield is due to the high monomer utilization, as shown in the results of example one, example four and example five. When the ultrasonic power is fixed and only the ultrasonic time is changed, the longer the ultrasonic time is, the longer the energy can be continuously supplied to the reaction system, and the monomers and the oligomers can be continuously polymerized to obtain the polymer with large molecular weight and narrow distribution, as shown in the results of the first example, the second example and the third example. The temperature is also an important factor, the initiator has a high decomposition rate due to high temperature, and a lot of free radicals are generated in a short time to carry out free radical polymerization in combination with the monomers, and by utilizing the ultrasonic cavitation characteristic, the chain termination reaction caused by high free radical concentration can be effectively avoided, so that the monomers and oligomers in the reaction liquid are continuously initiated to polymerize, and the polymer with high molecular weight and narrow distribution is obtained. In the comparative example, it can be seen that the conventional radical polymerization reaction was carried out without using ultrasound, and under the same conditions of temperature and polymerization time, the results were very different, first, the reaction system was in a non-ultrasonic state, the initiator in the reaction system was decomposed only by heating to generate radicals for polymerization, the efficiency was low, and second, the reaction time was short, so that the final results also showed that the polymer had a low molecular weight, a large number of small molecules therein, a wide molecular weight distribution, and a low yield, as shown in the results of the comparative example. Under the condition of controlling the ultrasonic power, time and temperature, the method does not add an initiator to directly carry out polymerization reaction, and has poor effect because the step of decomposing the initiator to generate free radicals is lacked, and the method only depends on the ultrasonic to generate monomer free radicals for polymerization, so that the efficiency is lower. The results were also unsatisfactory.
In summary, in the conventional radical polymerization, by applying ultrasonic irradiation, the polymerization efficiency can be further improved, a polymer with high molecular weight and narrow distribution can be obtained, and the molecular weight of the polymer can be effectively controlled by adjusting ultrasonic parameters, so that the method for polymerizing the methacrylic resin by using the ultrasonic method has good practical significance.
Further, the invention also provides a methacrylic resin, and the methacrylic resin is prepared by the preparation method of the embodiment. The methacrylic resin with different molecular weights is obtained by controlling polymerization conditions such as different ultrasonic powers, polymerization temperatures, polymerization durations and the like.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (5)
1. A method for preparing a methacrylic resin, comprising the steps of:
dissolving methyl methacrylate, butyl acrylate and 2-methyl-2-adamantyl methacrylate in ethyl acetate, and adding an initiator to form a mixed solution;
in protective gas, carrying out polymerization reaction on the mixed solution under the condition of ultrasonic constant temperature;
wherein the proportion of the methyl methacrylate, the butyl acrylate and the 2-methyl-2-adamantyl methacrylate is (1-10): (1-10): (1-10); the initiator is dimethyl azodiisobutyrate; the ultrasonic power under the ultrasonic constant temperature condition is 200-300W, the temperature is 50-75 ℃, and the polymerization reaction time is 5-10 h.
2. The method for preparing methacrylic resin according to claim 1, wherein the ultrasonic power under the ultrasonic constant temperature condition is 300W, the temperature is 75 ℃, and the polymerization reaction time is 10 h.
3. The method for preparing a methacrylic resin according to any one of claims 1 to 2, wherein after the polymerization reaction is completed, the method further comprises:
adding a precipitant into the reaction solution after the polymerization reaction, and performing precipitation purification treatment on the target product.
4. The method of claim 3, wherein the precipitant is n-hexane.
5. The method of claim 3, wherein after the precipitation purification treatment of the target product, the method further comprises:
centrifuging the suspension after precipitation and purification, separating solid from liquid, placing the solid in a vacuum oven, and drying at 50-85 ℃ overnight.
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| CN111718439A (en) * | 2020-06-19 | 2020-09-29 | 宁波南大光电材料有限公司 | Methacrylic resin and preparation method and application thereof |
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| CN107674165A (en) * | 2017-11-06 | 2018-02-09 | 重庆大学 | A kind of method for triggering matrix polymerization method synthesizing cationic polyacrylamide using ultrasonic wave |
| CN110669178A (en) * | 2019-10-12 | 2020-01-10 | 江苏景泰玻璃有限公司 | Modified polymethyl methacrylate organic glass raw material and preparation method thereof |
| CN111718439A (en) * | 2020-06-19 | 2020-09-29 | 宁波南大光电材料有限公司 | Methacrylic resin and preparation method and application thereof |
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