CN113845616B - PMMA copolymerized functional resin and preparation method thereof - Google Patents
PMMA copolymerized functional resin and preparation method thereof Download PDFInfo
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- CN113845616B CN113845616B CN202111302368.XA CN202111302368A CN113845616B CN 113845616 B CN113845616 B CN 113845616B CN 202111302368 A CN202111302368 A CN 202111302368A CN 113845616 B CN113845616 B CN 113845616B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
Abstract
The invention discloses a PMMA copolymerization functional resin and a preparation method thereof, wherein methyl methacrylate, glycidyl methacrylate, an auxiliary agent and water are mixed, heated to react and then cured to obtain the PMMA copolymerization functional resin; specifically, an initiator and a chain transfer agent are dissolved in a monomer, a dispersant is added into reaction medium water, and then the initiator and the dispersant are added into a reaction kettle to be mixed and subjected to suspension polymerization. After separation, cleaning and drying, the bead-shaped functional copolymer microspheres are obtained. The invention adopts a low-temperature suspension polymerization process, improves the stability of a reaction system, reduces the gel effect, simultaneously leads the polymerization rate of the reaction system to be moderate through the adjustment of a unique formula process, and greatly increases the suspension polymerization stability of the methyl methacrylate matrix functional copolymer resin.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to PMMA copolymerized functional resin and a preparation method thereof, and specifically relates to binary copolymer resin prepared by copolymerizing methyl methacrylate monomer and glycidyl methacrylate monomer and a preparation process thereof.
Background
Polymethyl methacrylate (PMMA), also known as acrylic or organic glass, is a transparent material with superior properties. PMMA is also a very beautiful material, has good processing performance, and is widely applied to the fields of aviation, buildings, optical instruments, medical consumables and the like. However, PMMA needs to be blended and modified with other materials, such as PC, ABS and the like, in some application places because of poor impact resistance of PMMA. Because PMMA is incompatible with most polymers, the mechanical property or the apparent property of PMMA is difficult to improve by direct blending modification, and therefore, a functional copolymer resin is required to be directly added as a compatilizer in the process of blending the polymers so as to improve the comprehensive performance of the product.
The polymerization mainly based on methyl methacrylate monomer has a remarkable characteristic of gel effect. When the monomer reaches about 20% during the polymerization of MMA, the polymerization rate increases significantly and the viscosity rises so rapidly that local overheating, even "implosion", occurs. The gel effect occurs in the polymerization process of a plurality of monomers, but the gel effect is obvious in the bulk polymerization of MMA, the polymerization reaction rate is obviously increased due to the characteristic, the automatic acceleration effect is generated, and the molecular weight distribution is widened.
In addition, the free radical polymerization production technology comprises bulk polymerization, suspension polymerization, solution polymerization, emulsion polymerization and the like, wherein the investment of bulk polymerization equipment is large; the solution polymerization adopts a solvent, and the post-treatment is complex; emulsion polymerization contains a large amount of emulsifier, and washing water consumption is large; conventional suspension polymerization, in order to control the exotherm, has a large water ratio and a low single pot productivity of the apparatus.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a PMMA copolymerized functional resin and a preparation method thereof. The P (MMA-co-GMA) copolymer resin is prepared by adopting a low-temperature suspension method, the production process is simple, the relatively low reaction temperature of 68-72 ℃ is adopted, the water ratio can be controlled within 2, the heat release of the polymerization reaction is stable, and on one hand, the single-kettle yield can be improved, and meanwhile, the industrial production 'implosion' is avoided; on the other hand, the reaction temperature is controlled stably, and the molecular weight distribution of the prepared finished product is narrow. In the invention, a small amount of GMA functional group is copolymerized with MMA monomer to synthesize P (MMA-co-GMA). P (MMA-co-GMA) can be used in PMMA/PC alloy, a small amount of GMA functional groups can react with carboxyl or hydroxyl on PC or polyester, and the PC-PMMA graft polymer is generated by in-situ reaction, so that the compatibility of the PMMA/PC alloy is improved.
The purpose of the invention is realized by the following technical scheme:
a preparation method of PMMA copolymerized functional resin comprises the following steps of mixing methyl methacrylate, glycidyl methacrylate, an auxiliary agent and water, reacting for 2-5 hours at the temperature of 68-72 ℃, and then curing to obtain the PMMA copolymerized functional resin.
In the invention, methyl methacrylate and glycidyl methacrylate are taken as monomers, and the sum of the weight of the methyl methacrylate and the weight of the glycidyl methacrylate is 100 percent, wherein the weight of the methyl methacrylate is 90 to 99.5 percent; the weight of the water is 100-200%; the weight of the auxiliary agent is 0.2-5%.
The preparation method of the functional copolymer resin provided by the invention is a low-temperature suspension polymerization process, and can be carried out at normal pressure; the method specifically comprises the following steps: taking the total weight of the monomers as 100 percent as a reference, mixing 90 to 99.5 weight percent of methyl methacrylate monomer, 0.5 to 10 weight percent of glycidyl methacrylate monomer, 0.2 to 0.5 weight percent of initiator, 0.2 to 2 weight percent of molecular weight regulator, 0.01 to 2 weight percent of dispersant and deionized water with the total weight ratio of the monomers of (1 to 2) to 1 in a reaction kettle, reacting for 2 to 5 hours at 68 to 72 ℃ under conventional stirring, and then heating to 85 to 110 ℃ for curing for 0.5 to 2 hours; then discharging, filtering, cleaning, and drying the obtained particles at 85-110 ℃ to obtain the PMMA copolymerized functional resin.
Preferably, the ratio of the deionized water to the total weight of the monomers is 1.5, which can improve the single kettle productivity by 1 time compared with 3.
Preferably, the temperature of the reaction is 70 ℃.
Preferably, the temperature of the aging is 95 ℃.
In the invention, the auxiliary agent comprises an initiator, a molecular weight regulator and a dispersant; preferably, the initiator is an azo-type initiator, preferably Azobisisobutyronitrile (AIBN). Preferably, the molecular weight regulator is a thiol molecular weight regulator or an alpha-methylstyrene dimer molecular weight regulator; wherein the molecular weight regulator of the mercaptan is preferably dodecyl mercaptan. Preferably, the dispersant is an inorganic dispersant or an organic dispersant; the inorganic dispersant comprises active calcium phosphate (TPC); the organic dispersant comprises hydroxyethyl cellulose (CMC), polyvinyl alcohol (PVA); preferably, the organic dispersant is used in an amount of 0.01 to 0.5wt% based on the total weight of the monomers.
The suspension polymerization process generally comprises the steps of dispersing monomers into liquid drops under the shearing action, stably suspending the liquid drops in a dispersant aqueous solution, and polymerizing the liquid drops by adopting an oil-soluble initiator, wherein the suspension polymerization generally requires lower requirements than other polymerizations in the aspect of requirements on a reactor. The specific operations such as stirring, discharging, filtering and cleaning related to the invention are conventional in the prior art.
The reaction temperature of the invention is 68-72 ℃, the preferable reaction temperature is 70 ℃, and the corresponding reaction period is 2-5 hours. Under the condition of controlling the reaction rate, the reaction rate is not reduced, the polymerization time is shortened, and the reaction is not out of control and is not exploded; and the water consumption is small, and the molecular weight distribution of the product is narrow.
Drawings
FIG. 1 is an IR spectrum of the product of example 1.
FIG. 2 is a photograph of a product of example 1.
FIG. 3 is a photograph of a product of example 2.
FIG. 4 is a GPC curve of the product of example 1.
FIG. 5 is a GPC curve of the product of example 2.
FIG. 6 is a GPC curve of the product of comparative example 2.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention. The raw materials of the invention are all the existing commercial products, the specific operation method and the test method are all the conventional technologies, the temperature control of the reaction kettle is the prior art, and all the operations are carried out under the conventional environment without special description. The percentages in the following examples are based on methyl methacrylate monomer + glycidyl methacrylate monomer = 100%. The structure analysis was performed by infrared spectroscopy (IR method). Yield = amount of product after drying/total weight of monomer charged; methyl methacrylate and glycidyl methacrylate are taken as monomers, and the sum of the weights of the methyl methacrylate and the glycidyl methacrylate is the total weight of the monomers.
Example 1
Mixing methyl methacrylate accounting for 99.5 percent of the total amount of the monomers, glycidyl methacrylate accounting for 0.5 percent of the total amount of the monomers, all oil-soluble initiator azobisisobutyronitrile accounting for 0.3 percent of the total amount of the monomers, all molecular weight regulator dodecyl mercaptan accounting for 1 percent of the total amount of the monomers, all dispersant active calcium phosphate accounting for 1.5 percent of the total amount of the monomers and deionized water accounting for 1.5 times of the total amount of the monomers in a reaction kettle, reacting for 3 hours at 70 ℃ under conventional stirring, and then heating to 95 ℃ for curing for 1 hour; and then discharging the materials into a storage tank, conventionally filtering and washing the materials by using deionized water, and then drying the obtained product at 90 ℃ to constant weight to obtain the final product of PMMA functional copolymer resin.
FIG. 1 shows the IR spectrum of a PMMA-copolymerized GMA functional resin of example 1, in the range of 1620 cm to 1680cm -1 The absence of a characteristic peak in the region indicates the absence of a C = C double bond in the polymerization product, which on the one hand proves that the polymerization is complete and on the other hand proves that GMA is also reacted with double bonds at 1720cm -1 The presence of an ester group was confirmed at 1269cm -1 (symmetrical vibration absorption Peak of epoxy group) 911cm -1 And 840cm -1 (two absorption peaks of the asymmetric vibration of the epoxy group), indicating the presence of the epoxy group.
Example 2
Mixing methyl methacrylate accounting for 90% of the total amount of the monomers, glycidyl methacrylate accounting for 10% of the total amount of the monomers, all oil-soluble initiator azobisisobutyronitrile accounting for 0.3% of the total amount of the monomers, all molecular weight regulator dodecyl mercaptan accounting for 1% of the total amount of the monomers, all dispersant active calcium phosphate accounting for 1.5% of the total amount of the monomers and deionized water accounting for 1.5 times of the total amount of the monomers in a reaction kettle, reacting for 4 hours at 70 ℃ under conventional stirring, and then heating to 95 ℃ for curing for 1 hour; and then discharging the material into a storage tank, conventionally filtering and washing the material with deionized water, and then drying the obtained product at 90 ℃ to constant weight to obtain the final product, namely the functional copolymer resin.
Comparative example 1
Methyl methacrylate accounting for 99.5 percent of the total amount of the monomers, glycidyl methacrylate accounting for 0.5 percent of the total amount of the monomers, all oil-soluble initiator azobisisobutyronitrile accounting for 0.3 percent of the total amount of the monomers, all molecular weight regulator dodecyl mercaptan accounting for 1 percent of the total amount of the monomers, all dispersant active calcium phosphate accounting for 1.5 percent of the total amount of the monomers and deionized water accounting for 1.5 times of the total amount of the monomers are mixed in a reaction kettle and react at 75 ℃ under conventional stirring to generate implosion. It can be seen that, on the basis of example 1, comparative example 1 is only the reaction temperature is raised and implosion occurs. Similarly, the reaction temperature was raised to 75 ℃ on the basis of example 2, and implosion occurred.
Comparative example 2
Methyl methacrylate accounting for 99.5 percent of the total amount of the monomers, glycidyl methacrylate accounting for 0.5 percent of the total amount of the monomers, all oil-soluble initiator azobisisobutyronitrile accounting for 0.3 percent of the total amount of the monomers, all molecular weight regulator dodecyl mercaptan accounting for 1 percent of the total amount of the monomers, all dispersant active calcium phosphate accounting for 1.5 percent of the total amount of the monomers and deionized water accounting for 3 times of the total weight of the monomers are mixed in a reaction kettle, reacted for 3 hours at 75 ℃ under conventional stirring, and then heated to 95 ℃ for curing for 1 hour. And then discharging the material into a storage tank, conventionally filtering and washing the material with deionized water, and then drying the obtained product at 90 ℃ to constant weight to obtain the final product, namely the functional copolymer resin.
FIGS. 2 and 3 are photographs of products of examples 1 and 2; FIG. 4, FIG. 5, and FIG. 6 are GPC curves of the products of example 1, example 2, and comparative example 2, respectively. The formulations and results of examples 1 to 2 and comparative examples 1 and 2 are shown in Table 1. The results in Table 1 show that, under the same equipment conditions, when the reaction temperature is set at 70 ℃, the reaction processes of the examples are stable and the molecular weight distribution of the obtained polymer is narrow. Comparative examples 1-2, in which the reaction temperature was set at 75 ℃, the reaction process was unstable, resulting in "implosion" of comparative example 1, and comparative example 2, although the molecular weight distribution of the product was too broad due to the high water ratio without "implosion", and the single pot yield was too low and the water consumption was large. The reaction temperature is set at a lower temperature and the formula is limited, so that the reaction rate is controlled, and the PMMA-based functional resin is easier to implement and control in a suspension polymerization system.
Example 3
Mixing methyl methacrylate accounting for 98% of the total amount of the monomers, glycidyl methacrylate accounting for 2% of the total amount of the monomers, all oil-soluble initiator azobisisobutyronitrile accounting for 0.35% of the total amount of the monomers, all molecular weight regulator dodecyl mercaptan accounting for 1% of the total amount of the monomers, all dispersant active calcium phosphate accounting for 1.1% of the total amount of the monomers and deionized water accounting for 1.5 times of the total amount of the monomers in a reaction kettle, reacting for 3 hours at 71 ℃ under conventional stirring, and heating to 95 ℃ for curing for 1 hour; and then discharging the materials into a storage tank, conventionally filtering and washing the materials by using deionized water, and then drying the obtained product at 90 ℃ to constant weight to obtain the final product of PMMA functional copolymer resin.
Example 4
Mixing methyl methacrylate accounting for 92% of the total amount of the monomers, glycidyl methacrylate accounting for 8% of the total amount of the monomers, all oil-soluble initiator azobisisobutyronitrile accounting for 0.25% of the total amount of the monomers, all molecular weight regulator dodecyl mercaptan accounting for 1% of the total amount of the monomers, all dispersant active calcium phosphate accounting for 0.8% of the total amount of the monomers and deionized water accounting for 1 time of the total amount of the monomers in a reaction kettle, reacting for 5 hours at 69 ℃ under conventional stirring, and then heating to 95 ℃ for curing for 1 hour; and then discharging the material into a storage tank, conventionally filtering and washing the material with deionized water, and then drying the obtained product at 90 ℃ to constant weight to obtain the final product, namely the functional copolymer resin.
Example 5
Mixing methyl methacrylate accounting for 95% of the total amount of the monomers, glycidyl methacrylate accounting for 5% of the total amount of the monomers, all oil-soluble initiator azobisisobutyronitrile accounting for 0.3% of the total amount of the monomers, all molecular weight regulator dodecyl mercaptan accounting for 1.2% of the total amount of the monomers, all dispersant active calcium phosphate accounting for 1.5% of the total amount of the monomers and deionized water accounting for 1.5 times of the total amount of the monomers in a reaction kettle, reacting for 3.5 hours at 71 ℃ under conventional stirring, and then heating to 95 ℃ for curing for 1 hour; and discharging the material into a storage tank, conventionally filtering and washing the material by using deionized water, and drying the obtained product at 90 ℃ to constant weight to obtain the final product, namely the PMMA functional copolymer resin.
The product yield of the examples 3 to 5 exceeds 97 percent, and the molecular weight distribution is between 2.1 and 2.2.
Comparative example 3
Mixing methyl methacrylate accounting for 100% of the total amount of the monomers, all oil-soluble initiator azodiisobutyronitrile accounting for 0.3% of the total amount of the monomers, all molecular weight regulator dodecyl mercaptan accounting for 1% of the total amount of the monomers, all dispersant active calcium phosphate accounting for 1.5% of the total amount of the monomers and deionized water accounting for 1.5 times of the total amount of the monomers in a reaction kettle, reacting for 3 hours at 70 ℃ under conventional stirring, and then heating to 95 ℃ for curing for 1 hour; and then discharging the product into a storage tank, conventionally filtering and washing the product by using deionized water, and then drying the obtained product at 90 ℃ to constant weight to obtain a final product, wherein the yield is 97%, and the molecular weight distribution is 2.6.
Comparative example 4
Mixing methyl methacrylate accounting for 85% of the total amount of the monomers, glycidyl methacrylate accounting for 15% of the total amount of the monomers, all oil-soluble initiator azobisisobutyronitrile accounting for 0.3% of the total amount of the monomers, all molecular weight regulator dodecyl mercaptan accounting for 1% of the total amount of the monomers, all dispersant active calcium phosphate accounting for 1.5% of the total amount of the monomers and deionized water accounting for 1.5 times of the total amount of the monomers in a reaction kettle, reacting for 3 hours at 70 ℃ under conventional stirring, and then heating to 95 ℃ for curing for 1 hour; and then discharging the product into a storage tank, conventionally filtering and washing the product by using deionized water, and then drying the obtained product at 90 ℃ to constant weight to obtain the final product, namely the functional copolymer resin, wherein the yield is 89%, the molecular weight distribution is 2.38, and the transparency is slightly poor when the product is applied at downstream.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (8)
1. The preparation method of the PMMA copolymerized functional resin is characterized by comprising the following steps of mixing methyl methacrylate, glycidyl methacrylate, an auxiliary agent and water, reacting for 2-5 hours at 68-72 ℃, and curing to obtain the PMMA copolymerized functional resin; the weight sum of methyl methacrylate and glycidyl methacrylate is 100 percent, wherein the weight sum of methyl methacrylate is 90 to 99.5 percent; the weight of the water is 100-200%; the weight of the auxiliary agent is 0.2-5%; the auxiliary agent comprises an initiator, a molecular weight regulator and a dispersant; the weight sum of methyl methacrylate and glycidyl methacrylate is 100 percent, wherein the weight of the initiator is 0.2 to 0.5 weight percent, the weight of the molecular weight regulator is 0.2 to 2 weight percent, and the weight of the dispersant is 0.01 to 2 weight percent.
2. The PMMA copolymerized functional resin of claim 1, wherein the initiator is azo initiator; the molecular weight regulator is a thiol molecular weight regulator or an alpha-methyl styrene dimer molecular weight regulator; the dispersant is an inorganic dispersant or an organic dispersant.
3. The method for preparing a PMMA copolymerized functional resin as claimed in claim 1, which comprises the steps of mixing methyl methacrylate, glycidyl methacrylate, an auxiliary agent, and water, reacting at 68-72 ℃ for 2-5 hours, and then curing to obtain the PMMA copolymerized functional resin.
4. The method for preparing PMMA copolymerized functional resin according to claim 3, characterized in that the reaction temperature is 70 ℃; the curing temperature is 95 ℃ and the curing time is 0.5 to 2 hours.
5. The method for preparing PMMA copolymerized functional resin according to claim 3, characterized in that after curing, discharging, filtering, cleaning and drying are carried out to obtain the PMMA copolymerized functional resin.
6. The method for preparing PMMA copolymer functional resin according to claim 3, wherein the reaction is carried out under normal pressure.
7. The use of the PMMA copolymerized functional resin of claim 1 in the preparation of alloy plastic.
8. Use of the PMMA copolymerized functional resin according to claim 1 for preparing transparent plastic.
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| CN110105489A (en) * | 2019-05-31 | 2019-08-09 | 高密浩翰木塑材料科技有限公司 | A kind of high solids content super high molecular weight Acrylate copolymerical emulsion production method |
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| GB853886A (en) * | 1958-09-18 | 1960-11-09 | Du Pont | Improvements relating to methacrylate polymers |
| GB1313653A (en) * | 1969-06-30 | 1973-04-18 | Canadian Ind | Coating compositions based on esterified methyl methacrylate glycidyl acrylate or methacrylate copolymers |
| GB1313652A (en) * | 1969-06-30 | 1973-04-18 | Canadian Ind | Copolymers of methyl methacrylate and glycidyl acrylate or methacrylate esterified with aliphatic acids and coating compositions containing same |
| JP3637794B2 (en) * | 1998-11-27 | 2005-04-13 | 住友化学株式会社 | Method for producing methyl methacrylate polymer beads |
| CN105254789B (en) * | 2015-10-20 | 2019-02-05 | 佳易容相容剂江苏有限公司 | A kind of copolymerzation with cross-linking resin and preparation method thereof |
| CN106554456A (en) * | 2016-12-05 | 2017-04-05 | 陕西高新实业有限公司 | The method that precipitation polymerization prepares glycidyl methacrylate type polyacrylate |
| CN108239234B (en) * | 2016-12-27 | 2019-11-19 | 金发科技股份有限公司 | A kind of graft copolymer and its application containing epoxy group |
| CN112266438B (en) * | 2020-11-04 | 2022-11-15 | 三棵树(上海)新材料研究有限公司 | Methyl methacrylate polymer and preparation method and application thereof |
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