WO2023200200A1 - Composition de billes polymères et procédé de fabrication de billes polymères l'utilisant - Google Patents

Composition de billes polymères et procédé de fabrication de billes polymères l'utilisant Download PDF

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WO2023200200A1
WO2023200200A1 PCT/KR2023/004804 KR2023004804W WO2023200200A1 WO 2023200200 A1 WO2023200200 A1 WO 2023200200A1 KR 2023004804 W KR2023004804 W KR 2023004804W WO 2023200200 A1 WO2023200200 A1 WO 2023200200A1
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polymer
bead composition
weight
parts
polymer bead
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PCT/KR2023/004804
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Korean (ko)
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배민지
김영신
엄기범
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(주)에이에스피
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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
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • 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
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/02—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of acids, salts or anhydrides
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating

Definitions

  • This specification relates to a polymer bead composition and a method of manufacturing polymer beads using the same.
  • Polymer beads based on polymer materials are highly versatile particles and are used for various purposes in the electrical and electronic fields, as well as in the chemical and bio fields. Currently, it is used as a light diffuser in displays and lighting equipment, and is also widely used as an additive in various industrial fields such as paints, plastic molded products, and cosmetics. Various physical properties are required depending on the intended use.
  • thermal decomposition of polymer beads is divided into chain end unzipping at 250 ⁇ 300°C and unzipping by random scission above 300°C.
  • Thermal decomposition by chain end unzipping at around 300°C is a polymer bead manufactured by suspension polymerization. Due to the nature of radical polymerization, it involves an unequal reaction involving a vinyl group having an unsaturated bond at the end of the polymer chain, which is generated during the termination reaction, and generates radicals, which cause unzipping from the end of the chain and cause thermal decomposition, thereby reducing heat resistance.
  • a chain transfer agent and a silane monomer are added to a composition containing a specific vinyl monomer, the stirring conditions are adjusted to prepare a suspension, and then polymerization is performed using the suspension, resulting in thermogravimetric analysis (TGA: Thermogravimetric Analysis)
  • TGA Thermogravimetric Analysis
  • the above polymer beads had somewhat poor heat resistance at 320°C, and optical properties such as refractive index changed due to copolymerization of silane added to improve heat resistance, resulting in a change in refractive index when applied to an optical film or diffusion plate. Differences in luminance and concealment may occur.
  • the present inventor confirmed that by implementing a polymer bead composition containing a specific monomer, a chain transfer agent, a phenolic compound, and a surface coating agent, a highly heat-resistant polymer bead with low weight loss while improving heat resistance at a temperature of 310 °C or higher was manufactured, , the present invention was completed.
  • Patent Document 1 Korean Patent Publication No. 10-2012-0010366
  • One embodiment of the present invention provides a polymer bead composition and a method of manufacturing polymer beads using the same.
  • One embodiment of the present invention is one or more vinyl-based monomers selected from the group consisting of aromatic vinyl-based monomers, (meth)acrylic acid alkyl ester monomers having 1 to 20 carbon atoms, and (meth)acrylic acid fluoroalkyl ester monomers having 1 to 20 carbon atoms. polymer seeds derived from monomers;
  • a polymer bead composition including a surface coating agent is provided.
  • R is a straight or branched alkyl group having 10 to 30 carbon atoms.
  • an exemplary embodiment of the present invention includes preparing the polymer bead composition described above; and polymerizing the polymer bead composition.
  • One embodiment of the present invention seeks to provide a polymer bead composition that has excellent heat resistance at a temperature of 310 ° C. or higher and has no color change.
  • One embodiment of the present invention seeks to provide a polymer bead composition having a uniform particle size distribution.
  • Another embodiment of the present invention seeks to provide a method of manufacturing polymer beads using the polymer bead composition.
  • Figure 1 shows the particle shape of polymer beads according to Example 2 of the present invention.
  • Figure 2 shows the results of TGA analysis of the polymer beads according to Comparative Example 1.
  • Figures 3 to 6 show the results of TGA analysis of polymer beads according to Examples 1 to 4 of the present invention.
  • the terms comprise, comprises, and comprise mean to include the mentioned article, step, or group of articles, and steps, and any other article. , it is not used in the sense of excluding a step, a group of objects, or a group of steps.
  • (meth)acrylic acid means acrylic acid, methacrylic acid, or a combination thereof.
  • One embodiment of the present invention is one or more vinyl-based monomers selected from the group consisting of aromatic vinyl-based monomers, (meth)acrylic acid alkyl ester monomers having 1 to 20 carbon atoms, and (meth)acrylic acid fluoroalkyl ester monomers having 1 to 20 carbon atoms.
  • polymer seeds derived from monomers A chain transfer agent of Formula 1 below; A phenol-based compound containing the following formula (2) at both ends and the middle chain (3) and (4) below; and a surface coating agent.
  • R is a straight or branched alkyl group having 10 to 30 carbon atoms.
  • polymer beads are prepared by adding a chain transfer agent and a silane monomer to a composition containing a vinyl-based monomer.
  • polymer beads manufactured by conventional manufacturing methods have a particle size of several microns or more, and the particle size distribution is medium-dispersed or higher, and have excellent heat resistance at the film processing temperature, especially when the polymer colloid solution is applied to prevent blocking of films. It must have certain properties, but with conventional methods, heat resistance properties could not be secured, such as physical properties changing or yellowing occurring when processed at high temperatures, and the particle size distribution was not monodisperse, which raised the problem of limiting the scope of application.
  • the present inventors completed the present invention by confirming that when the above-described polymer bead composition has the above composition, the degree of crosslinking is controlled when used to manufacture polymer beads, has excellent heat resistance properties and has a uniform particle size distribution.
  • the vinyl monomer is a group consisting of an aromatic vinyl monomer, a (meth)acrylic acid alkyl ester monomer having 1 to 20 carbon atoms, and a (meth)acrylic acid fluoroalkyl ester monomer having 1 to 20 carbon atoms.
  • an aromatic vinyl monomer a (meth)acrylic acid alkyl ester monomer having 1 to 20 carbon atoms
  • a (meth)acrylic acid fluoroalkyl ester monomer having 1 to 20 carbon atoms.
  • One or more types selected from may be used.
  • the vinyl monomer is methyl methacrylate, divinylbenzene, butyl methacrylate, trimethylolmethane tetraacrylate, trimethylolmethane triacrylate, trimethylolbutane triacrylate, and ethylene. It may contain one or more types selected from the group consisting of glycol dimethacrylate. Preferably, styrene can be used as the vinyl monomer.
  • the polymer seed may include a solvent.
  • the solvent may be an aqueous solvent.
  • the aqueous solvent includes water and the like.
  • the polymer seed may be a mixture of the polymer seed derived from the vinyl monomer and the solvent.
  • the weight of the polymer seed and the solvent may be 40 to 60 parts by weight and 60 to 40 parts by weight, respectively, based on the total weight of the polymer bead composition.
  • the polymer bead composition may further include a styrene compound.
  • the degree of crosslinking is controlled, so heat resistance properties are excellent and uniform particle size distribution can be achieved.
  • the content of the styrene compound may be 10 to 40 parts by weight based on 100 parts by weight of the polymer seed. Preferably, it may be 10 to 35 parts by weight.
  • the degree of crosslinking is adjusted, resulting in excellent heat resistance properties and uniform particle size distribution.
  • the chain transfer agent is represented by Formula 1, and removes radicals generated from the unsaturated bond of the terminal vinyl group, resulting in uneven termination reaction and unreaction of the terminal vinyl group.
  • heat resistance can be improved by removing monomers that decompose at high temperatures.
  • R is a straight or branched alkyl group having 10 to 30 carbon atoms.
  • R may be a straight-chain alkyl group having 10 to 30 carbon atoms.
  • R may be a straight-chain alkyl group.
  • the reactivity of the chain transfer agent is improved, making it easier to induce a chain transfer reaction.
  • Polymer beads manufactured using these chain transfer agents have excellent heat resistance.
  • the chain transfer agent may be one or more selected from the group consisting of 1-dodecanethiol, t-dodecylmercaptan, and t-hexadecylmercaptan.
  • the chain transfer agent may be 1-dodecanethiol.
  • the chain transfer agent may be CAS 112-55-0.
  • the content of the chain transfer agent may be 0.1 to 0.8 parts by weight based on 100 parts by weight of the polymer seed. Preferably, it may be 0.3 to 0.5 parts by weight. If the chain transfer agent is used in excessive amounts, a large amount of polymer with a low molecular weight is produced, thereby increasing the completeness of the reaction, but it has poor solvent resistance, which may cause difficulties in the process when manufacturing an optical film. Therefore, it is important to use an appropriate amount of chain transfer agent to provide heat resistance and solvent resistance. Specifically, within the above numerical range, heat resistance is improved, polymerization stability is maintained, and aggregation of reactants can be prevented.
  • the chain transfer agent is particularly used simultaneously with the phenol-based compound of the present invention, thereby preventing the onset of thermal decomposition above 310°C, improving work efficiency, improving heat resistance, and reducing weight loss. You can.
  • antioxidants such as phosphorus-based, amine-based, hindered amine-based, and sulfur-based compounds instead of the phenol-based compound of the present invention, heat resistance and reactivity tend to decrease.
  • the phenol-based compound may include the following formula (2) at both ends, and the middle chain may include the formula (3) and (4) below. Additionally, the intermediate chain contains 8 to 15 carbon atoms and may be formed as a straight chain.
  • the polymer bead composition includes a phenol-based compound containing the following formula (2) at both ends and the middle chain (3) and (4) below.
  • the phenol-based compound may reduce the reaction when used alone in a polymer bead composition because the OH group of Formula 2 acts as a radical inhibitor, but when used simultaneously with the chain transfer agent, only the peroxide radicals generated during the polymer decomposition reaction are easily captured and removed. Thus, heat resistance can be improved. That is, the phenol-based compound can be used as an antioxidant.
  • the phenol-based compound contains Formula 2 at both ends and Formula 3 and Formula 4 in the middle chain, and the middle chain contains 8 to 15 carbon atoms and has a straight chain structure
  • the polymer from which peroxide radicals generated during the polymer decomposition reaction are removed is located at both ends of the phenolic compound, preventing the onset of thermal decomposition, thereby suppressing fume generation, improving heat resistance, suppressing color change, and weight loss. It is expected.
  • the content of the phenolic compound may be 0.1 to 1 part by weight based on 100 parts by weight of the polymer seed. Preferably, it may be 0.4 to 0.8 parts by weight. Within the above numerical range, heat resistance is improved, polymerization stability is maintained, and aggregation of reactants can be prevented.
  • a representative example of the phenolic compound is antioxidant 245, and its CAS No. is 36443-68-2.
  • the polymer bead composition includes a surface coating agent.
  • the surface coating agent By including the surface coating agent, the stability and dispersibility of the polymer substrate that can be used for various purposes can be improved.
  • the surface coating agent may be at least one selected from the group consisting of acrylate-based compounds, silane-based compounds, silicate-based compounds, phosphonate-based compounds, phosphate-based compounds, and acidic compounds.
  • specific examples of the surface coating agent include 3-trimethoxysilyl propyl methacrylate, silica, tetraethyl orthosilicate, vinyltrimethoxysilane, vinyltriethoxysilane, and allyltrime.
  • the content of the surface coating agent may be 10 to 35 parts by weight based on 100 parts by weight of the polymer seed. Preferably, it may be 18 to 35 parts by weight, 18 to 30 parts by weight, or 20 to 25 parts by weight. Within the above numerical range, the stability and dispersibility of the polymer can be improved.
  • the polymer bead composition may include at least one selected from the group consisting of a crosslinking agent and an initiator.
  • the crosslinking agent may be a compound containing two or more unsaturated carbons.
  • the crosslinking agent is 1,2-ethanediol diacrylate, 1,3-propanediol diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, divinylbenzene, ethylene glycol diacrylate, propylene glycol diacrylate, butylene glycol diacrylate, triethylene glycol diacrylate , polyethylene glycol diacrylate, polypropylene glycol diacrylate, polybutylene glycol diacrylate, allyl acrylate, 1,2-ethanediol dimethacrylate, 1,3-propanediol dimethacrylate, 1, 3-Butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,5-pentanediol dimethacrylate, 1,6
  • the cross-linking agent includes a first cross-linking agent and a second cross-linking agent that are different from each other, and the weight ratio of the first cross-linking agent and the second cross-linking agent may be 1:2 to 2:1.
  • the content of the cross-linking agent may be 15 to 75 parts by weight based on 100 parts by weight of the polymer seed. Preferably, it can be used in an amount of 20 to 72 parts by weight. If the content of the cross-linking agent is less than 15 parts by weight, it cannot be expected to function as a cross-linking agent. If it exceeds 75 parts by weight, it may be difficult to control the heat of reaction. If the degree of cross-linking of the particles increases, the reaction may decrease due to an exothermic reaction.
  • the initiator includes a radical initiator.
  • the radical initiator may be an oil-soluble initiator or a water-soluble initiator.
  • the oil-soluble initiator may include one or more selected from the group consisting of benzoyl peroxide, azobisisobutyronitrile, azobisphenylbutyronitrile, and azobiscyclohexanecarbonitrile.
  • the water-soluble initiator includes at least one selected from the group consisting of potassium sulfate, sodium sulfate, ammonium persulfate, and azo-based water-soluble initiator.
  • the content of the initiator may be 1 to 3 parts by weight based on 100 parts by weight of the polymer seed. If the content of the initiator is less than 0.1 parts by weight, reaction completeness may decrease, and if it exceeds 3 parts by weight, it may be difficult to control the heat of reaction.
  • the particle diameter of the polymer seed may be 100 nm to 1,000 nm. Specifically, it may be 100 nm or more, 200 nm or more, 300 nm or more, 400 nm or more, 500 nm or more, 600 nm or more, 700 nm or more, 800 nm or more, 900 nm or more, and 1000 nm or more. Within the above range, the structural stability of the polymer seed is improved and the particle size distribution can be maintained uniformly.
  • the polymer bead composition may further include a dispersion stabilizer.
  • the dispersion stabilizer may be 1,1-dichloroethane, potassium hydroxide, sodium hydroxide, an adipate-based compound, an amide-based compound, a sulfonate-based compound, or a mixture thereof.
  • the dispersion stabilizer is 1,1-dichloroethane, potassium hydroxide, sodium hydroxide, poly(1,6-hexamethylene adipate), N,N'-dibenzyl -1,6-diaminohexane (N,N'-dibenzyl-1,6-diaminohexane), sodium 4-vinylbenzenesulfonate, or mixtures thereof can be used.
  • the dispersion stabilizer is 1,1-dichloroethane, potassium hydroxide, sodium hydroxide, poly(1,6-hexamethylene adipate), N,N'-dibenzyl-1,6-diaminohexane, sodium 4-vinylbenzenesulfonate, etc. may be used.
  • the content of the dispersion stabilizer may be 0.01 to 1 part by weight based on 100 parts by weight of the polymer seed. Dispersion stability can be improved within the above numerical range.
  • the polymer bead composition may be in a colloidal state.
  • the colloidal state means that the components included in the polymer bead composition exist in nanoparticle sizes (1 micrometer to 100 micrometers).
  • it is derived from one or more vinyl monomers selected from the group consisting of aromatic vinyl monomers, (meth)acrylic acid alkyl ester monomers having 1 to 20 carbon atoms, and (meth)acrylic acid fluoroalkyl ester monomers having 1 to 20 carbon atoms.
  • This means that the polymer seed, chain transfer agent, phenol-based compound, or surface coating agent is nanoparticle-sized and exists in a uniformly spread state in the solvent.
  • One embodiment of the present invention includes preparing the polymer bead composition described above; and polymerizing the polymer bead composition.
  • the step of preparing the polymer bead composition includes an aromatic vinyl monomer, a (meth)acrylic acid alkyl ester monomer having 1 to 20 carbon atoms, and a (meth)acrylic acid fluoroalkyl ester having 1 to 20 carbon atoms. It may include preparing a polymer seed by polymerizing one or more vinyl monomers selected from the group consisting of monomers.
  • At this time, at least one vinyl monomer selected from the group consisting of the vinyl monomer, (meth)acrylic acid alkyl ester monomer having 1 to 20 carbon atoms, and (meth)acrylic acid fluoroalkyl ester monomer having 1 to 20 carbon atoms, and the polymer seed are The content described in the above-described polymer bead composition can be applied.
  • the step of preparing a polymer seed by polymerizing the vinyl monomer may include performing a polymerization reaction at 50°C to 90°C for 5 to 48 hours. Within the above range, the shape of the prepared polymer seed is maintained and the polymerization reaction can be smoothly initiated.
  • the content of each component described above in the polymer bead composition may be applied.
  • the step of polymerizing the polymer bead composition may include conducting a polymerization reaction at 50°C to 90°C for 5 to 48 hours.
  • the polymerization temperature range is 60°C to 80°C, and the polymerization reaction time may be 12 to 30 hours.
  • the temperature of the reactor containing the emulsion is carried out in the above temperature range under a nitrogen atmosphere, so that the chain transfer agent may react before the phenol-based compound during polymerization compared to the case of polymerization while raising the temperature of the reactor. You can. Accordingly, heat resistance can be improved by preventing the onset of thermal decomposition above 310°C.
  • polymerizing the polymer bead composition may include stirring at a stirring speed of 100 rpm to 1,000 rpm.
  • the stirring speed may be 200 rpm to 800 rpm or 300 rpm to 600 rpm. In the above range, polymerization stability is excellent and the physical properties of the produced polymer beads are excellent.
  • a polymer bead composition was prepared by mixing 0.6 parts by weight of nitrile (Azobisisobutyronitrile) and 22.2 parts by weight each of trimethylolpropane triacrylate and divinylbenzene as a crosslinking agent, for a total of 44.4 parts by weight.
  • a polymer bead composition was prepared by mixing 26.2 parts by weight of vinylbenzene for a total of 52.4 parts by weight.
  • Example 2 45 parts by weight of the polystyrene polymer seed prepared in Example 2 and 55 parts by weight of water were mixed. Based on 100 parts by weight of the mixed materials, 13 parts by weight of Styrene, 0.4 parts by weight of CAS 112-55-0 as a chain transfer agent, 0.6 parts by weight of CAS 36443-68-2 as a phenolic compound, and 3-part by weight as a surface coating agent. 14 parts by weight of 3-(trimethoxysilyl) propyl acrylate, 0.6 parts by weight of Azobisisobutyronitrile as an initiator, and Trimethylolpropane triacrylate and dimethylolpropane triacrylate as a crosslinking agent.
  • a polymer bead composition was prepared by mixing 35.7 parts by weight of vinylbenzene for a total of 71.4 parts by weight.
  • Example 2 45 parts by weight of the polystyrene polymer seed prepared in Example 2 and 55 parts by weight of water were mixed. Based on 100 parts by weight of the mixed materials, 32 parts by weight of Styrene, 0.4 parts by weight of CAS 112-55-0 as a chain transfer agent, 0.6 parts by weight of CAS 36443-68-2 as a phenolic compound, and 3-part by weight as a surface coating agent. Mix 14 parts by weight of trimethoxysilyl propyl acrylate, 0.6 parts by weight of Azobisisobutyronitrile as an initiator, and 52.4 parts by weight of Divinylbenzene as a crosslinking agent. A polymer bead composition was prepared.
  • Polymer beads were prepared using the polymer bead compositions of the comparative examples and examples, respectively.
  • polymer beads were prepared by polymerizing each polymer bead composition at 280 rpm at 70°C for 24 hours under a nitrogen atmosphere. Comparison polymer beads and polymer beads 1 to 4, respectively.
  • the polymer beads prepared using the polymer bead compositions of the comparative examples and examples were dried, solid samples were collected, and particle shapes were analyzed through scanning electron microscopy (SEM, COXEM).
  • Figure 1 shows the particle shape of polymer beads according to Example 2 of the present invention. Specifically, it can be confirmed that the polymer beads according to Example 2 of the present invention have a uniform particle size and a smooth surface.
  • thermogravimetric analysis TGA
  • the comparative polymer beads prepared in Comparative Example 1 showed a relatively low thermal decomposition temperature ( Figure 2), but Example 1 ( Figure 3), Example 2 ( Figure 4), Example 3 ( Figure 5), and Example It was confirmed that the thermal decomposition temperature of each of the polymer beads 1 to 4 manufactured in Figure 4 ( Figure 6) was high. Specifically, looking at Figure 2, the comparative polymer beads prepared in Comparative Example 1 undergo thermal decomposition around 307°C, while looking at Figures 3 to 6, the polymer beads 1 to 4 prepared in Examples 1 and 4 undergo thermal decomposition at a temperature of at least 314°C. From the above, it can be confirmed that thermal decomposition proceeds, and in the case of Example 4, it can be confirmed that thermal decomposition proceeds around 330 ° C. In other words, it can be confirmed that the polymer beads according to the present invention have excellent thermal stability, that is, excellent heat resistance.

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Abstract

La présente invention concerne une composition de billes polymères et un procédé de fabrication de billes polymères l'utilisant, la composition de billes polymères comprenant : des germes de polymère dérivés d'au moins un monomère à base de vinyle choisi dans le groupe constitué par un monomère à base de vinyle aromatique, un monomère d'ester d'alkyle d'acide (méth)acrylique de 1 à 20 atomes de carbone, et un monomère d'ester de fluoroalkyle d'acide (méth)acrylique de 1 à 20 atomes de carbone ; un agent de transfert réversible de formule chimique 1 ; un composé à base de phénol comprenant la formule chimique 2 aux deux extrémités et la formule chimique 3 et la formule chimique 4 en milieu de chaîne ; et un agent de revêtement de surface.
PCT/KR2023/004804 2022-04-11 2023-04-10 Composition de billes polymères et procédé de fabrication de billes polymères l'utilisant WO2023200200A1 (fr)

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