WO2020235673A1 - Copolymère méthacrylique, procédé de production associé et article moulé correspondant - Google Patents

Copolymère méthacrylique, procédé de production associé et article moulé correspondant Download PDF

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WO2020235673A1
WO2020235673A1 PCT/JP2020/020290 JP2020020290W WO2020235673A1 WO 2020235673 A1 WO2020235673 A1 WO 2020235673A1 JP 2020020290 W JP2020020290 W JP 2020020290W WO 2020235673 A1 WO2020235673 A1 WO 2020235673A1
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mass
unit derived
methacrylic copolymer
meth
monomer unit
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PCT/JP2020/020290
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Japanese (ja)
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伸崇 平岡
洋太 瀧華
英孝 田村
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株式会社クラレ
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Priority to JP2021520874A priority Critical patent/JP7422753B2/ja
Publication of WO2020235673A1 publication Critical patent/WO2020235673A1/fr

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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
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids

Definitions

  • the present invention relates to a methacrylic copolymer, a method for producing the same, and a molded product. More specifically, the present invention relates to a methacrylic copolymer having excellent fluidity during heat molding and less mold stain, a method for producing the same, and a molded product having high heat resistance and high mechanical strength.
  • Methacrylic resin has high transparency and is useful as a material for molded products used for optical members, lighting members, signboard members, decorative members and the like. In some fields where molded products of methacrylic resin are used, there is a demand for weight reduction or thinning of molded products. In order to obtain a thin-walled molded product, it is necessary for the methacrylic resin to have high fluidity when melted. As a measure for increasing the fluidity of the resin, it is generally known to lower the softening temperature or the glass transition temperature, lower the molecular weight, widen the molecular weight distribution, and the like. However, when these measures are applied to methacrylic resin, the heat resistance is lowered and the mechanical strength is lowered. In consideration of such a situation, Cited Documents 1 to 3 propose various methacrylic resins and methods for producing the same.
  • An object of the present invention is to provide a methacrylic copolymer having excellent fluidity during heat molding and less mold stain, a method for producing the methacrylic copolymer, and a molded product having high heat resistance and high mechanical strength.
  • [4] A pellet-shaped molding material containing the methacrylic copolymer according to any one of [1] to [3].
  • [5] A molded product containing the methacrylic copolymer according to any one of [1] to [3].
  • [6] The molded product according to [5], which is in the form of a plate having a thickness of 0.5 mm or less.
  • the polymerization reaction was carried out at 110 to 140 ° C. at a polymerization conversion rate of 35 to 65% without using a solvent. It then comprises removing unreacted monomers by heating and devolatile at 220-260 ° C.
  • the methacrylic copolymer of the present invention has excellent fluidity and is unlikely to cause molding defects such as silver streaks, cracks, sink marks, flow marks, resin burns, gas stains, and coloring.
  • the molding material containing the methacrylic copolymer of the present invention is suitable for injection molding.
  • the molding material containing the methacrylic copolymer of the present invention is suitable for obtaining a thin-walled molded product, for example, a plate having a thickness of 0.5 mm or less.
  • the molded product containing the methacrylic copolymer of the present invention has high heat resistance and mechanical strength, and has no appearance defects such as coloring.
  • the molding material containing the methacrylic copolymer of the present invention has low heat generation due to shearing during injection molding, and can be injection-molded at a low temperature and at a high injection pressure, so that the appearance of the obtained molded product is good.
  • the methacrylic copolymer of the present invention is a monomer unit derived from methyl methacrylate, which is a (meth) acrylic acid ester represented by the formula (1) (hereinafter, may be referred to as a monomer (I)). It is composed of a monomer unit derived from the monomer unit and a monomer unit derived from methyl acrylate.
  • the content of the monomer unit derived from methyl methacrylate is 85 to 93.5% by mass, preferably 87.5 to 93.5% by mass, and more preferably 88 to 93.5% by mass.
  • the content of the monomer unit derived from the (meth) acrylic acid ester represented by the formula (1) is 0.3 to 2.0% by mass, preferably 0.3 to 1.5% by mass, more preferably. Is 0.3 to 1.2% by mass.
  • the content of the monomer unit derived from methyl acrylate is 5.0 to 13% by mass, preferably 5.0 to 12.0% by mass, and more preferably 5.5 to 10% by mass.
  • the total of the monomer unit derived from methyl methacrylate, the monomer unit derived from monomer (I), and the monomer unit derived from methyl acrylate is It is preferably 99% by mass or more, and more preferably 100% by mass.
  • R 2 represents a hydrogen atom or a methyl group.
  • R 1 represents an acyclic alkyl group having 8 to 24 carbon atoms, preferably an acyclic alkyl group having 10 to 22 carbon atoms, and more preferably an acyclic alkyl group having 10 to 18 carbon atoms. From the viewpoint of improving fluidity, in the formula (1), R 1 is preferably a linear alkyl group having 8 to 24 carbon atoms, more preferably a linear alkyl group having 10 to 22 carbon atoms, and further preferably 10 carbon atoms. ⁇ 18 linear alkyl groups.
  • Examples of the monomer (I) include n-octyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-undecyl (meth) acrylate, and (meth).
  • the methacryl copolymer of the present invention is a monomer other than the monomer unit derived from methyl methacrylate, the monomer unit derived from monomer (I), and the monomer unit derived from methyl acrylate.
  • Such monomers may have units, such as ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, and the like.
  • the methacrylic copolymer of the present invention has a weight average molecular weight Mw of 48,000 to 59000, preferably 48,000 to 55,000, and more preferably 49000 to 53000. Further, in the methacrylic copolymer of the present invention, the ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn is 2.1 or less, preferably 1.7 or more and 2.0 or less.
  • the weight average molecular weight Mw and the number average molecular weight Mn are values obtained by converting the chart measured by gel permeation chromatography into the molecular weight of standard polystyrene.
  • the methacrylic copolymer of the present invention preferably has a Tg / R ratio of a glass transition temperature Tg of 230 ° C. and a melt flow rate R to a melt flow rate R of 4.0 to 1.5 ° C. for 10 minutes / g. Is 3.5 to 1.5 ° C. for 10 minutes / g, more preferably 3.3 to 1.5 ° C. for 10 minutes / g.
  • the glass transition temperature is once raised to 230 ° C. using a differential scanning calorimetry device (manufactured by Shimadzu Corporation, DSC-50 (product number)) in accordance with JIS K7121, then cooled to room temperature, and then to room temperature.
  • the DSC curve was measured under the condition that the temperature was raised from 1 to 230 ° C. at 10 ° C./min. It is an intermediate point glass transition temperature (Tmg) determined based on the DSC curve measured at the time of the second temperature rise.
  • Tmg intermediate point glass transition temperature
  • the melt flow rate is a value measured under the conditions of 230 ° C., 3.8 kg load, and 10 minutes in accordance with JIS K7210.
  • the lower limit of the melt flow rate R of the methacrylic copolymer of the present invention measured at 230 ° C. and a load of 3.8 kg is preferably 15 g / 10 minutes, more preferably 25 g / 10 from the viewpoint of moldability, toughness and the like. Minutes, with an upper limit of preferably 60 g / 10 minutes.
  • the methacrylic copolymer of the present invention has a sulfur bond amount of preferably 0.40 mol% or less, more preferably 0.30 to 0.38 mol%, still more preferably 0.30 mol% or less, based on a monomer unit derived from methyl methacrylate. It is 0.31 to 0.36 mol%.
  • the amount of sulfur bond is related to imparting good moldability, low mold stain, and high fluidity to the methacrylic copolymer.
  • the amount of bound sulfur atom is a value S p which is determined as follows. The methacrylic copolymer is dissolved in chloroform to obtain a solution. This solution is added to n-hexane to give a precipitate. The precipitate is dried at 80 ° C.
  • An appropriate amount of the obtained dried product is precisely weighed, set in a sulfur combustion device, decomposed in a reactor having a temperature of 400 ° C., and the generated gas is passed through a furnace having a temperature of 900 ° C. Absorb with.
  • the obtained liquid (decomposed gas aqueous solution) is appropriately diluted with pure water, and sulfate ions are quantified by ion chromatography (ICS-1500 manufactured by DIONEX, column: AS12A). From the mass W p (mass%) of sulfur atoms per mass of the dried product, the amount of bound sulfur atoms (mol%) with respect to the monomer unit derived from methyl methacrylate is calculated.
  • the method for producing the methacrylic copolymer of the present invention is not particularly limited.
  • it can be produced by a known polymerization reaction such as a radical polymerization reaction or an anionic polymerization reaction.
  • a radical polymerization reaction is preferable.
  • the polymerization reaction can be carried out by a suspension polymerization method, a bulk polymerization method, a solution polymerization method, or an emulsion polymerization method.
  • the massive polymerization method is preferable because it contains less impurities.
  • the polymerization conversion rate is preferably 35 to 65%.
  • the bulk polymerization method is preferably carried out by a continuous flow method. In the continuous flow type massive polymerization method, the average residence time in the reactor is preferably 1.5 to 3 hours.
  • the method for producing the methacrylic copolymer used in the present invention is a monomer containing methyl methacrylate, monomer (I) and methyl acrylate, preferably methyl methacrylate 79.0 to 93.2% by mass, simply. It is preferable that a monomer containing 0.3 to 2.0% by mass of the amount (I) and 6.5 to 19.0% by mass of methyl acrylate is polymerized by a massive polymerization method.
  • (Meta) Acrylic acid acyclic alkyl esters and methyl acrylates are involved in imparting high fluidity and low glass transition temperatures to methacrylic copolymers.
  • the polymerization reaction is carried out using a polymerization initiator, a predetermined monomer, and if necessary, a chain transfer agent or the like.
  • the temperature at the time of polymerization is preferably 100 to 150 ° C, more preferably 110 to 140 ° C, and even more preferably 120 to 140 ° C. The lower the polymerization temperature, the higher the heat resistance of the methacrylic copolymer of the present invention tends to be.
  • the polymerization initiator used in the present invention is not particularly limited.
  • an azo-based polymerization initiator such as azobisisobutyronitrile
  • a peroxide-based polymerization initiator such as t-hexyl peroxyisopropyl monocarbonate and the like
  • the polymerization initiator used in the present invention preferably has a half-life of 1 second to 1 minute at the temperature at the time of polymerization. When the amount of the polymerization initiator used is small, the methacrylic copolymer of the present invention tends to have less mold stain.
  • azobisisobutyronitrile is preferably 0.02 parts by mass or less, more preferably 0 parts by mass, based on a total of 100 parts by mass of the monomers to be polymerized. It can be used in an amount of .002 parts by mass or more and 0.01 parts by mass or less.
  • the chain transfer agent used in the present invention is not particularly limited.
  • mercaptan chain transfer agents such as n-octyl mercaptan and n-dodecyl mercaptan; ⁇ -methylstyrene dimer; terpinolene and the like can be mentioned.
  • the amount of the chain transfer agent used is preferably 0.42 to 0.52 parts by mass with respect to a total of 100 parts by mass of the monomers to be polymerized. As the amount of the mercaptan chain transfer agent used increases, the amount of sulfur bound to the monomer unit derived from methyl methacrylate increases.
  • n-octyl mercaptan is preferably 0.3 parts by mass or more and 0.6 parts by mass or less, more preferably 0.41 parts by mass or more and 0. It can be used in an amount of 50 parts by mass or less.
  • the unreacted monomer is preferably removed by a thermal devolatile method at a temperature of 220 to 260 ° C.
  • the molding material of the present invention contains the methacrylic copolymer of the present invention.
  • the molding material of the present invention is an antioxidant, a heat deterioration inhibitor, an ultraviolet absorber, a light stabilizer, a lubricant, a mold release agent, a polymer processing aid, an antistatic agent, as long as the effects of the present invention are not impaired.
  • Additives such as flame retardant, dye pigment, light diffusing agent, organic dye, matting agent, impact resistance modifier, and phosphor may be further contained.
  • the antioxidant is effective in preventing oxidative deterioration of the resin by itself in the presence of oxygen.
  • phosphorus-based antioxidants hindered phenol-based antioxidants, thioether-based antioxidants, and the like can be mentioned.
  • phosphorus-based antioxidants and hindered phenol-based antioxidants are preferable from the viewpoint of the effect of preventing deterioration of optical properties due to coloring, and the combined use of phosphorus-based antioxidants and hindered phenol-based antioxidants is more preferable. preferable.
  • a phosphorus-based antioxidant and a hindered phenol-based antioxidant are used in combination, it is recommended to use a phosphorus-based antioxidant / hindered phenol-based antioxidant in a mass ratio of 0.2 / 1 to 2/1. It is preferably used at 0.5 / 1/1 to 1/1, more preferably.
  • Phosphorus antioxidants include 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite (manufactured by ADEKA; trade name: ADEKA STAB HP-10), tris (2,4-di-).
  • ADEKA ADEKA STAB HP-10
  • t-Butylphenyl) Phosphite manufactured by BASF; trade name: IRUGAFOS168
  • 3,9-bis (2,6-di-t-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa 3 , 9-Diphosphaspiro [5.5] Undecan (manufactured by ADEKA; trade name: ADEKA STAB PEP-36) and the like.
  • pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by BASF; trade name IRGANOX1010), octadecyl-3- (3,5-Di-t-Butyl-4-hydroxyphenyl) propionate (manufactured by BASF; trade name IRGANOX1076) and the like are preferable.
  • the heat deterioration of the resin can be prevented by capturing the polymer radicals generated when exposed to high heat under a substantially oxygen-free state.
  • the heat deterioration inhibitor include 2-t-butyl-6- (3'-t-butyl-5'-methyl-hydroxybenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd .; trade name: Sumilyzer GM).
  • 2,4-dit-amyl-6- (3', 5'-di-t-amyl-2'-hydroxy- ⁇ -methylbenzyl) phenylacrylate (manufactured by Sumitomo Chemical Co., Ltd .; trade name Sumilyzer GS) and the like are preferable. ..
  • the ultraviolet absorber is a compound having an ability to absorb ultraviolet rays, and is said to have a function of mainly converting light energy into heat energy.
  • the ultraviolet absorber include benzophenones, benzotriazoles, triazines, benzoates, salicylates, cyanoacrylates, oxalic acid anilides, malonic acid esters, formamidines and the like.
  • benzotriazoles, triazines, and ultraviolet absorbers having a maximum molar extinction coefficient ⁇ max of 100 dm 3 ⁇ mol -1 cm -1 or less at a wavelength of 380 to 450 nm are preferable.
  • Benzotriazoles are highly effective in suppressing deterioration of optical properties such as coloring due to ultraviolet exposure, and are therefore preferable as an ultraviolet absorber used when the molded product of the present invention is applied to optical applications.
  • benzotriazoles include 2- (2H-benzotriazole-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (manufactured by BASF; trade name TINUVIN329), 2- (2H-).
  • Benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (manufactured by BASF; trade name: TINUVIN234), 2,2'-methylenebis [6- (2H-benzotriazole-2) -Il) -4-t-octylphenol] (manufactured by ADEKA; LA-31) and the like are preferable.
  • an ultraviolet absorber having a maximum molar extinction coefficient ⁇ max of 1200 dm 3 ⁇ mol -1 cm -1 or less at a wavelength of 380 to 450 nm can suppress discoloration of the obtained molded product.
  • examples of such an ultraviolet absorber include 2-ethyl-2'-ethoxy-oxalanilide (manufactured by Clariant Japan Co., Ltd .; trade name: Sandeuboa VSU).
  • benzotriazoles are preferably used from the viewpoint of suppressing resin deterioration due to UV exposure.
  • a triazine-type ultraviolet absorber is preferably used.
  • examples of such an ultraviolet absorber include 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine (manufactured by ADEKA; LA-F70).
  • examples thereof include hydroxyphenyltriazine-based ultraviolet absorbers (manufactured by BASF; TINUVIN 477 and TINUVIN 460), which are related thereto.
  • the maximum value ⁇ max of the molar extinction coefficient of the ultraviolet absorber is measured as follows. 10.00 mg of an ultraviolet absorber is added to 1 L of cyclohexane and dissolved so that there is no undissolved substance by visual observation. This solution is injected into a quartz glass cell of 1 cm ⁇ 1 cm ⁇ 3 cm, and the absorbance at a wavelength of 380 to 450 nm and an optical path length of 1 cm is measured using a U-3410 spectrophotometer manufactured by Hitachi, Ltd.
  • the light stabilizer is a compound that is said to have a function of capturing radicals mainly generated by oxidation by light.
  • Suitable light stabilizers include hindered amines such as compounds having a 2,2,6,6-tetraalkylpiperidine skeleton.
  • the lubricant examples include stearic acid, behenic acid, stearoamic acid, methylene bisstearoamide, hydroxystearic acid triglyceride, paraffin wax, ketone wax, octyl alcohol, and hydrogenated oil.
  • the melt flow rate R of the methacrylic resin composition of the present invention tends to be increased to increase the fluidity.
  • the mold release agent is a compound having a function of facilitating separation of a molded product from a mold.
  • the release agent include higher alcohols such as cetyl alcohol and stearyl alcohol; and glycerin higher fatty acid esters such as stearic acid monoglyceride and stearic acid diglyceride.
  • higher alcohols and glycerin fatty acid monoester in combination as a release agent.
  • the mass ratio of the higher alcohols / glycerin fatty acid monoester is preferably in the range of 2.5 / 1 to 3.5 / 1, 2.8. It is more preferable to use it in the range of / 1 to 3.2 / 1.
  • polymer particles having a particle size of 0.05 to 0.5 ⁇ m can be used.
  • the polymer particles may be single-layer particles composed of polymers having a single composition ratio and a single ultimate viscosity, or multilayer particles composed of two or more kinds of polymers having different composition ratios or ultimate viscosities. You may. Among these, particles having a two-layer structure having a polymer layer having a low ultimate viscosity in the inner layer and a polymer layer having a high ultimate viscosity of 5 dl / g or more in the outer layer are preferable.
  • the polymer processing aid preferably has an ultimate viscosity of 3 to 6 dl / g.
  • the amount of the polymer processing aid used is preferably 0.1 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the methacrylic resin. Good processing characteristics are obtained when the amount of the polymer processing aid used is 0.1 parts by mass or more, and surface smoothness is good when the amount of the polymer processing aid used is 5 parts by mass or less.
  • the impact resistance modifier examples include a core-shell type modifier containing acrylic rubber or diene rubber as a core layer component; and a modifier containing a plurality of rubber particles.
  • the organic dye a compound having a function of converting ultraviolet rays, which are considered to be harmful to the resin, into visible light is preferably used.
  • the light diffusing agent and the matting agent include glass fine particles, polysiloxane-based crosslinked fine particles, crosslinked polymer fine particles, talc, calcium carbonate, barium sulfate and the like.
  • the phosphor include fluorescent pigments, fluorescent dyes, fluorescent white dyes, fluorescent whitening agents, and fluorescent bleaching agents.
  • additives may be used alone or in combination of two or more. These additives may be added at the time of producing the methacrylic copolymer, or may be added to the produced methacrylic copolymer.
  • the total amount of the additives is preferably 1% by mass or less, more preferably 0.8% by mass or less, still more preferably 0.5% by mass, based on the methacrylic copolymer from the viewpoint of suppressing poor appearance of the molded product. % Or less.
  • the methacrylic copolymer or molding material of the present invention can be in any form such as pellets, granules, and powder in order to enhance convenience such as transportation and storage.
  • the molded product of the present invention can be obtained by molding the methacrylic copolymer or molding material of the present invention. Molding can be performed by a known method such as an injection molding method, a compression molding method, an extrusion molding method, a vacuum forming method, or a cast molding method. Of these, the injection molding method is preferable.
  • the methacrylic copolymer of the present invention can provide a thin-walled and wide-area molded product with little residual strain and almost no coloring even when injection-molded at a low cylinder temperature and a high injection pressure with high production efficiency. it can.
  • the maximum value of the ratio of the resin flow length to the thickness of the mold that can be used in injection molding is preferably 450 or more.
  • the methacrylic copolymer of the present invention is suitable for producing a thin-walled molded product.
  • the molded product of the preferred form of the present invention has a plate shape, and the thickness thereof is preferably 0.5 mm or less, more preferably 0.45 mm or less, particularly preferably 0.4 mm or less, and most preferably 0.35 mm or less. Is.
  • Examples of the molded product of the present invention include signboard parts such as advertising towers, stand signs, sleeve signs, column signboards, and rooftop signs; display parts such as showcases, dividers, and store displays; fluorescent lamp covers, mood lighting covers, etc.
  • Lighting parts such as lamp shades, light ceilings, light walls, chandeliers; Interior parts such as pendants and mirrors; Building parts such as doors, dome, safety window glass, partitions, staircase wainscots, balcony wainscots, roofs of leisure buildings Transport equipment related parts such as aircraft windshields, pilot visors, motorcycles, motor boat windshields, bus shading plates, automobile side visors, rear visors, head wings, headlight covers; audiovisual nameplates, stereo covers, TV protective masks, Electronic equipment parts such as vending machines; Medical equipment parts such as incubators and roentgen parts; Equipment-related parts such as machine covers, instrument covers, experimental equipment, rulers, dials, observation windows; LCD protective plates, light guide plates, guides Optical components such as optical films, frennel lenses, lenticular lenses, front plates of various displays, diffusers, polarizer protective films, polarizing plate protective films, retardation films; road signs, guide plates, curved mirrors, soundproof walls, etc.
  • methacrylic copolymer of the present invention is suitable for an optical member, and among the optical members, it is suitable for a light guide.
  • the light guide is used, for example, as a member of the backlight of the liquid crystal display element. It guides the light from the light source on the side or back so that the light can be radiated uniformly from the entire plate surface.
  • the plate surface of the light guide may be provided with micron-sized irregularities for uniformly radiating light.
  • ODMA unit ⁇ Unit derived from n-octadecyl methacrylate (ODMA unit)>
  • X ODMA methylene group hydrogen adjacent to the ester oxygen of methacrylic acid-n octadecyl in the copolymer
  • W ODMA (wt%) of the unit derived from n-octadecyl methacrylate was calculated by the following formula.
  • a ODMA [(X ODMA / 2) / ((X ODMA / 2) + 100)] x 100
  • W ODMA [(A ODMA x 338.58) / ((100-A ODMA ) x 100.14 + A ODMA x 338.58)] x 100 ⁇ Unit derived from n-dodecyl acrylate (DDA unit)>
  • the integral value of the peak of 3.98 ppm methylene group hydrogen adjacent to the ester oxygen of n-dodecyl acrylate in the copolymer was defined as X DDA .
  • the ratio of units derived from n-dodecyl acrylate WDDA (wt%) was calculated by the following formula.
  • ODA The integral value of the peak of 3.95 ppm (methylene group hydrogen adjacent to the ester oxygen of n-octadecyl acrylate in the copolymer) was defined as X ODA .
  • the ratio of units derived from n-octadecyl acrylate W ODA (wt%) was calculated by the following formula.
  • the integral value of the peak of 3.99 ppm methylene group hydrogen adjacent to the ester oxygen of n-butyl methacrylate in the copolymer
  • the ratio WBMA (wt%) of the unit derived from n-butyl methacrylate was calculated by the following formula.
  • a BMA [(X BMA / 2) / ((X BMA / 2) + 100)] x 100
  • W BMA [(A BMA x 142.20) / ((100-A BMA ) x 100.14 + A BMA x 142.20)] x 100
  • the methacrylic copolymer is dissolved in chloroform to obtain a solution. This solution is added to n-hexane to give a precipitate. The precipitate is dried at 80 ° C. for 12 hours or longer under vacuum. An appropriate amount of the obtained dried product is precisely weighed, set in a sulfur combustion device, decomposed in a reactor having a temperature of 400 ° C., and the generated gas is passed through a furnace having a temperature of 900 ° C., and then 0.3% hydrogen peroxide solution is used. Absorb with.
  • the obtained liquid (decomposed gas aqueous solution) is appropriately diluted with pure water, and sulfate ions are quantified by ion chromatography (ICS-1500 manufactured by DIONEX, column: AS12A).
  • ICS-1500 manufactured by DIONEX, column: AS12A.
  • Glass transition temperature Tg Glass transition temperature Tg
  • DSC-50 product number
  • injection moldability Using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd .: SE-180DU-HP), injection molding is performed in a cylinder temperature of 280 ° C., a mold temperature of 75 ° C., and a molding cycle of 1 minute, and the long side is 205 mm and the short side is 160 mm.
  • a flat plate S having a thickness of 0.4 mm was manufactured.
  • the appearance of the flat plate S was observed and evaluated by the following indexes. ⁇ : There are no cracks or sink marks. ⁇ : There is a sink mark. ⁇ : There is a crack.
  • Examples 1 to 4 and Comparative Examples 1 to 8 Purified methyl methacrylate (MMA), n-dodecyl acrylate (DDA), n-octadecyl acrylate (ODA), n-octadecyl methacrylate (ODMA), n-butyl methacrylate units in autoclave A with a stirrer. (BMA) and methyl acrylate (MA), and 2,2'-azobis (2-methylpropionitrile) (AIBN) and n-octyl mercaptan (n-OM) in the proportions listed in Tables 1 and 2. And uniformly dissolved to obtain a polymerization raw material.
  • MMA methyl methacrylate
  • DDA n-dodecyl acrylate
  • ODA n-octadecyl acrylate
  • ODMA n-octadecyl methacrylate
  • BMA methyl acrylate
  • AIBN 2,2
  • the polymerization raw material is continuously supplied from the autoclave A to a tank reactor controlled at a temperature of 140 ° C. at 1.5 kg / hr, and the polymerization reaction is carried out by a massive polymerization method with an average residence time of 120 minutes.
  • the liquid containing the methacrylic copolymer was continuously discharged from the water.
  • the polymerization conversion rate was 57% by mass.
  • the liquid discharged from the reactor was heated to 230 ° C. and supplied to a twin-screw extruder controlled to 240 ° C. In the twin-screw extruder, the volatile matter containing the unreacted monomer as a main component was removed, and the methacrylic copolymer was extruded as a strand.
  • the strands were cut with a pelletizer to obtain resin pellets.
  • resin pellets measure weight average molecular weight Mw, molecular weight distribution Mw / Mn, ratio of each monomer unit, amount of bound sulfur atom (bond S), glass transition temperature Tg, melt flow rate R, and bending strength. did.
  • injection moldability, fluidity, and mold stains were evaluated using resin pellets. The results are shown in Tables 1 and 2.
  • “pts.” And “%” in a table are "part by mass” and "% by mass”.
  • the polymers obtained in Examples 1 to 4 had high fluidity, excellent injection moldability, and did not cause mold stains. As a result, the molded products obtained in Examples 1 to 4 were excellent in transparency, heat resistance, mechanical strength, appearance and the like. On the other hand, the polymers obtained in Comparative Examples 1 to 8 had low fluidity, poor injection moldability, and mold stains. As a result, the molded products obtained in Comparative Examples 1 to 8 were inferior in at least one of heat resistance, mechanical strength, and appearance.

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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un copolymère méthacrylique qui contient 85,0 à 93,5 % en masse d'un motif monomère dérivé de méthacrylate de méthyle, 0,3 à 2,0 % en masse d'un motif monomère dérivé d'un ester d'acide (méth)acrylique représenté par la formule (1), et 5,0 à 13,0 % en masse d'un motif monomère dérivé d'acrylate de méthyle, et qui présente un poids moléculaire moyen en poids (Mw) de 4 000 à 59 000, un rapport du poids moléculaire moyen en poids (Mw) au poids moléculaire moyen en nombre (Mn), à savoir Mw/Mn, de 2,1 ou moins, et un rapport de la température de transition vitreuse (Tg) au débit de fusion (R) à 230 °C sous une charge de 3,8 kg, à savoir Tg/R, allant de 4,0 °C∙10 minutes/g à 1,5 °C∙10 minutes/g. (Dans La formule (1), R1 représente un groupe alkyle acyclique comprenant 8 à 24 atomes de carbone ; et R2 représente un atome d'hydrogène ou un groupe méthyle.)
PCT/JP2020/020290 2019-05-22 2020-05-22 Copolymère méthacrylique, procédé de production associé et article moulé correspondant WO2020235673A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59122509A (ja) * 1982-12-28 1984-07-16 Mitsubishi Rayon Co Ltd 低吸湿性メタクリル系樹脂
WO2014002504A1 (fr) * 2012-06-29 2014-01-03 株式会社クラレ Procédé de fabrication d'une composition de résine (méth)acrylique
WO2016104701A1 (fr) * 2014-12-26 2016-06-30 株式会社クラレ Procédé de fabrication d'une composition de résine (méth)acrylique
WO2016136930A1 (fr) * 2015-02-27 2016-09-01 株式会社クラレ Procédé de production d'une composition de résine (méth)acrylique
WO2019004083A1 (fr) * 2017-06-28 2019-01-03 株式会社クラレ Copolymère méthacrylique et article moulé

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59122509A (ja) * 1982-12-28 1984-07-16 Mitsubishi Rayon Co Ltd 低吸湿性メタクリル系樹脂
WO2014002504A1 (fr) * 2012-06-29 2014-01-03 株式会社クラレ Procédé de fabrication d'une composition de résine (méth)acrylique
WO2016104701A1 (fr) * 2014-12-26 2016-06-30 株式会社クラレ Procédé de fabrication d'une composition de résine (méth)acrylique
WO2016136930A1 (fr) * 2015-02-27 2016-09-01 株式会社クラレ Procédé de production d'une composition de résine (méth)acrylique
WO2019004083A1 (fr) * 2017-06-28 2019-01-03 株式会社クラレ Copolymère méthacrylique et article moulé

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