Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
  • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
  • C07C69/732—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids of unsaturated hydroxy carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
  • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
  • C07C69/54—Acrylic acid esters; Methacrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
  • C07C39/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with no unsaturation outside the aromatic ring
  • C07C39/08—Dihydroxy benzenes; Alkylated derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
  • C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
  • C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
  • C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
  • C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
  • C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol
  • C07C39/16—Bis-(hydroxyphenyl) alkanes; Tris-(hydroxyphenyl)alkanes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
  • C07C39/205—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic, containing only six-membered aromatic rings as cyclic parts with unsaturation outside the rings
  • C07C39/21—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic, containing only six-membered aromatic rings as cyclic parts with unsaturation outside the rings with at least one hydroxy group on a non-condensed ring
• • 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
  • C08F20/00—Homopolymers and 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
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/20—Esters of polyhydric alcohols or polyhydric phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
• • 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
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/04—Reduction, e.g. hydrogenation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/13—Phenols; Phenolates
  • C08K5/134—Phenols containing ester groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Definitions

• the present invention relates to a phenol compound, a resin composition and a method for producing the same, and a molded product.
• a production process in which a polymer solution containing a polymerization solvent is heat-treated under reduced pressure and high temperature conditions may be carried out.
• the polymer solution is usually treated at a temperature considerably higher than the boiling point of the polymerization solvent for the purpose of removing the polymerization solvent, so that the polymer obtained by the heat treatment is thermally deteriorated or colored. Problems sometimes occurred. Therefore, an additive has been developed that can reduce problems such as thermal deterioration caused by heat treatment by adding to the resin composition.
• Patent Document 1 proposes a phenolic compound capable of preventing thermal deterioration and coloring of a polymer when it is treated at a high temperature to separate the polymer from the polymer solution during the production of a butadiene polymer. ..
• the resin that is, the polymer
• the resin that is, the polymer
• the polymer is decomposed, whereby the polymer is produced. May deteriorate due to heat. Therefore, in the production of the resin composition, an additive capable of sufficiently suppressing the decomposition of the resin is required even when the heat treatment is performed under low pressure and high temperature conditions.
• the additive it is necessary that the additive not only has the ability to suppress the decomposition of the resin, but also that the additive itself does not easily volatilize even when exposed to high temperature conditions.
• the present inventors have conducted diligent studies for the purpose of solving the above problems. Then, the present inventors are excellent in the ability to suppress the decomposition of the resin under reduced pressure and high temperature conditions without easily volatilizing the phenol compound satisfying a specific structure even when exposed to high temperature conditions. This was newly found and the present invention was completed.
• the present invention aims to solve the above problems advantageously, and the phenol compound of the present invention has the following general formula (I): [In the general formula (I), R 1 and R 2 each independently represent a hydrogen atom or an alkyl group. ] Is represented by.
• the phenol compound having the above-mentioned predetermined structure does not easily volatilize even when exposed to high temperature conditions, and the resin decomposition inhibitory ability under reduced pressure and high temperature conditions is sufficiently high. Therefore, by blending such a phenol compound into the resin composition, decomposition of the resin can be sufficiently suppressed even when exposed to treatment under low pressure and high temperature conditions.
• the phenolic compound of the present invention it is preferable that R 1 and R 2 of the general formula (I) are hydrogen atoms, respectively.
• the phenolic compound of the present invention is preferably a bisphenol monoacrylate compound.
• the phenolic compound of the present invention is preferably a bisphenol monomethacrylate compound.
• the present invention is intended to advantageously solve the above problems, and the resin composition of the present invention is characterized by containing either a resin or the above-mentioned phenol compound. If the resin composition contains at least one of the above-mentioned phenolic compounds, the resin can be sufficiently decomposed even when the resin composition is exposed to the treatment under reduced pressure and high temperature conditions. It can be suppressed.
• the resin is a thermoplastic polymer.
• a thermoplastic polymer as a resin and a phenol compound as described above in a resin composition, the ability to suppress decomposition of the resin under reduced pressure and high temperature conditions can be more effectively exhibited. ..
• the present invention aims to solve the above problems advantageously, and the molded product of the present invention is characterized in that the above-mentioned resin composition is molded.
• the molded product obtained by molding the above-mentioned resin composition has excellent properties.
• the present invention also aims to advantageously solve the above problems, and the method for producing a resin composition of the present invention is to prepare a mixture containing the resin and the phenol compound at 200 ° C. or higher and under reduced pressure. It is characterized by including a heating step of heating with. By reducing the pressure and heating the mixture containing the resin and the predetermined phenol compound under predetermined conditions, a resin composition having good properties can be efficiently produced.
• under reduced pressure means an environment in which the absolute pressure is 50 kPa or less.
• the present invention it is possible to provide a phenol compound which does not easily volatilize even when exposed to high temperature conditions and has a sufficiently high ability to suppress decomposition of the resin under reduced pressure and high temperature conditions. Further, according to the present invention, it is possible to provide a resin composition containing the above-mentioned phenol compound and an efficient production method thereof. Further, according to the present invention, it is possible to provide a molded product made of the above resin composition.
• the phenol compound of the present invention does not easily volatilize even when exposed to high temperature conditions, and has a sufficiently high ability to suppress decomposition of the resin under reduced pressure and high temperature conditions. It can be suitably blended for resin compositions that can be exposed to treatment under reduced pressure and high temperature conditions during time and molding. Then, the resin composition of the present invention can be efficiently produced by the method for producing the resin composition of the present invention. Further, the resin composition of the present invention can be suitably used as a material for the molded product of the present invention.
• the phenolic compound of the present invention is a phenolic compound represented by the following general formula (I).
• R 1 and R 2 each independently represent a hydrogen atom or an alkyl group.
• the phenolic compound of the present invention satisfies the structure represented by the predetermined general formula (I), it does not easily volatilize even when exposed to high temperature conditions, and suppresses decomposition of the resin under high temperature and reduced pressure conditions. The ability is high enough. Therefore, by blending such a phenol compound with the resin composition, decomposition of the resin can be sufficiently suppressed even when exposed to treatment under reduced pressure and high temperature conditions.
• the alkyl groups of R 1 and R 2 can be independently, for example, alkyl groups having 1 to 6 carbon atoms.
• the alkyl group having 1 to 6 carbon atoms is not particularly limited, and for example, a linear, branched chain or cyclic structure such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group or a cyclohexyl group can be used. Examples thereof include alkyl groups having.
• R 1 and R 2 are independently hydrogen atoms or methyl groups, respectively. More specifically, the phenol compound satisfying the structure represented by the general formula (I) is preferably a phenol compound represented by either the following formula (I-1) or (I-2).
• the phenol compound of the present invention preferably has a melting point of 30 ° C. or higher, more preferably 40 ° C. or higher, preferably 200 ° C. or lower, more preferably 150 ° C. or lower, 100. More preferably, it is below ° C.
• the melting point of the phenol compound is at least the above lower limit, it becomes a solid at room temperature, so that the compound can be handled excellently.
• the melting point of the phenol compound is not more than the above upper limit value, it tends to be lower than the drying temperature, the concentration temperature, and the molding temperature of the resin, and the phenol compound is easily sufficiently melted during the production of the molded product using the resin composition. , The transparency of the obtained molded product can be enhanced.
• the melting point of the phenol compound can be measured according to the method described in Examples.
• the resin composition of the present invention contains a resin and the above-mentioned phenol compound. Since the resin composition of the present invention contains the above-mentioned phenol compound, it is possible to sufficiently suppress the decomposition of the resin even when it is exposed to the treatment under reduced pressure and high temperature conditions.
• the resin composition may optionally contain a solvent and additives.
• the resin composition may be a solution in which the resin is dissolved in a solvent under normal temperature and pressure (25 ° C., 1 atm) conditions, or a solid substance (for example, resin pellets) containing a resin in a solid state. It may be.
• the content ratio of the predetermined phenol compound in the resin composition is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, and preferably 10 parts by mass or less, with the content of the resin being 100 parts by mass. , 1.0 part by mass or less is more preferable.
• any known polymer can be used depending on the intended use.
• examples of such polymers include various polymers listed as component a) in JP-A-3-207788.
• Monoolefin and diolefin polymers such as polypropylene, polyisobutylene, polybutene, polymethylpentene, polyisoprene or polybutadiene, and cycloolefin polymers such as cyclopentene or norbornene, dicyclopentadiene and tetracyclododecene polymers, polyethylene (which). Is non-crosslinked or may be crosslinked), such as high density polyethylene (HDPE), low density polyethylene (LDPE) and linear low density polyethylene (LLDPE). 2. 2. 2.
• Monoolefin and diolefin polymers such as polypropylene, polyisobutylene, polybutene, polymethylpentene, polyisoprene or polybutadiene, and cycloolefin polymers such as cyclopentene or norbornene, dicyclopentadiene and tetracyclododecene polymers, polyethylene (which). Is non-
• a mixture of polymers according to 1 above such as a mixture of polypropylene and polyisobutylene, a mixture of polypropylene and polyethylene (eg PP / HDPE and PP / LDPE) and a mixture of different types of polyethylene (eg LDPE / HDPE).
• Hydrocarbon resin for example, 5 to 9 carbon atoms.
• Vinyl aromatic polymers such as polystyrene, poly- (p-methylstyrene), poly- ( ⁇ -methylstyrene), polyvinylnaphthalene, polydiphenylethylene. 5.
• Copolymers of styrene or other vinyl aromatics with diene or acrylic derivatives such as styrene / butadiene, styrene / isoprene, styrene / acrylonitrile, styrene / alkylmethacrylate, styrene / methylstyrene, styrene / vinylnaphthalene, styrene / methylstyrene / Isoprene, styrene / vinylnaphthalene / isoprene, styrene / butadiene / alkyl acrylate, styrene / maleic anhydride, styrene / acrylonitrile / methyl acrylate, styrene copolymers and other polymers such as polyacrylates, diene polymers or ethylene / blobylene / buter
• Impact resistant mixtures made from and block copolymers of styrene, such as styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene. 6.
• styrene such as styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene.
• Graft copolymers of styrene or ⁇ -methylstyrene such as styrene graft copolymers for polybutadiene, styrene graft copolymers for polybutadiene / styrene or polybutadiene / acrylonitrile, styrene and acrylonitrile (or acrylonitrile) graft copolymers for polybutadiene, styrene and styrene for polybutadiene and Graft copolymer of maleic anhydride or maleimide, styrene to polybutadiene, acrylonitrile and graft copolymer of maleic anhydride or maleimide, graft copolymer of acrylonitrile and methylmethacrylate for polybutadiene ⁇ Graft copolymer of styrene and alkylacrylate or methacrylate for polybutadiene,
• halogenated polymers such as polychloroprene, chlorinated rubber, chlorinated or sulfonated polyethylene, copolymers of ethylene with chlorinated ethylene, epichlorohydrin monos and
• Polymers derived from unsaturated alcohols and amines or acyl derivatives or their acetals such as polyvinyl alcohol, polyvinyl acetate, vinyl polystearate, vinyl polybenzoate, vinyl polymaleate, vinyl polybutyrate, allyl polyphthalate or polyallyl polyphthalate. Melamine; as well as the olefins described in 1 above and copolymers thereof. 11. Homopolymers and copolymers of cyclic ethers. Copolymers thereof with, for example, polyalkylene glycols, polyethylene oxides, polypropylene oxides or bisglycidyl ethers. 12. Polyacetal.
• polyoxymethylene and their polyoxymethylene containing ethylene oxide as a comonomer polyacetal modified with thermoplastic polyurethane, acrylate or MBS.
• Polyamides or copolyamides derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or equivalent lactams such as polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12 and 4 / 6, Polyamide 11, Polyamide 12, m-Aromatic polyamide obtained by condensation of xylene diamine and adipic acid; Elastomer is used or used as a modifier from hexamethylenediamine and isophthalic acid and / or terephthalic acid.
• Polyesters derived from dicarboxylic acids and diols and / or from hydrokincarboxylic acids or equivalent lactones such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, polyhydroxybenzoate and hydroxyl-terminated polyether Brock-copolyether ester derived from; and further modified polyester with polycarbonate or MBS. 18.
• Polyblends of the aforementioned polymers, such as PP / EPDM, polyamide 6 / EPDM or ABS, PVC / EVA, PVS / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylate, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / acrylate, POM / MBS, PPE / HIPS, PPE / PA6.6 and copolymers, PA / HDPE, PA / PP, PA / PPE. 23. The hydrogenated modified product of the polymer according to 1 to 22 above.
• the resin contained in the resin composition of the present invention is preferably a thermoplastic polymer.
• the thermoplastic polymer contains at least one of a vinyl aromatic polymer or a hydrogenated modified product thereof; a copolymer of styrene or other vinyl aromatic and a diene; and a block copolymer of styrene. ..
• the "thermoplastic polymer” in the present specification is a polymer capable of exhibiting fluidity to the extent that it can be molded by heating, and at least one of a glass transition point and a melting point can be detected and a glass transition can be detected. It means a polymer that softens when heated to a temperature above the point or melting point.
• the above-mentioned polymer is not particularly limited, and can be polymerized by adopting any known polymerization method suitable for the monomer used for forming the polymer. Furthermore, as the polymer, it is of course possible to use a commercially available polymer.
• the weight average molecular weight of the polymer is preferably 10,000 or more, more preferably 50,000 or more, and preferably 1,000,000 or less.
• the weight average molecular weight of the polymer is 10,000 or more, the heat resistance and mechanical strength of the molded product formed from the resin composition can be enhanced.
• the weight average molecular weight of the polymer is 1,000,000 or less, the moldability of the resin composition can be improved.
• the weight average molecular weight of the polymer can be measured according to the method described in Examples.
• the solvent that can be arbitrarily contained in the resin composition of the present invention is not particularly limited, and examples thereof include saturated hydrocarbon solvents such as cyclohexane and aromatic hydrocarbon solvents such as toluene.
• the content of the solvent in the resin composition can be appropriately set.
• the content of the solvent in the resin composition may be zero, that is, the solvent may not be substantially contained in the resin composition.
• additives such as thermal deterioration inhibitors, various antioxidants, ultraviolet absorbers, light stabilizers such as hindered amine light stabilizers (HALS), lubricants, and products are added to the resin composition of the present invention.
• a nucleating agent, an antistatic agent, an inorganic filler, a pigment and the like may be blended. Specific examples of some of these additives are given below.
• heat deterioration inhibitor examples include 2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl (Sumilizer GM) and 1'-hydroxy acrylate [ 2,2'-Etilidenebis [4,6-bis (1,1-dimethylpropyl) benzene]] -1-yl (Sumilizer GS) can be mentioned.
• the antioxidant is not particularly limited, and examples thereof include a phenol-based antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant.
• phenolic antioxidants include butyl hydroxytoluene (BHT), 2,2'-methylenebis (6-tert-butyl-p-cresol) (Sumilizer MDP-S), and 4,4'-thiobis (6-tert).
• phosphorus-based antioxidants include tris (2,4-di-tert-butylphenyl) (Irgafos 168), 4,4', 4'', 4''-[[(1,1). '-Biphenyl-4,4'-diyl) bis (phosphintriyl)] tetrakisoxy] tetrakis (1,3-di-tert-butylbenzene) (Sandostab P-EPQ), 3,9-bis (2,4) -Di-tert-butylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] Undecane (Ultranox 626), 3,9-bis (2,6-di-tert-butyl-4) -Methylphenoxy) -2,4,8,10-Tetraoxa-3,9-Diphospaspiro [5.5] Undecane (Adekastab PEP-36),
• sulfur-based antioxidants examples include dilauryl 3,3'-thiodipropionate (Sumilizer TPL-R), ditetradecyl 3,3'-thiodipropionate (Sumilizer TPM), and distearyl-3,3-thio.
• Dipropionate Sumilizer TPS
• metal inactivating agent examples include N, N'-bis ⁇ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl ⁇ hydrazine (Irganox MD1024), [2,2-oxamidbis. Ethyl, 3 (3,5-di-tert-butyl-hydroxyphenyl) propionate] (Naugard LX-1) and the like.
• UV absorber examples include drometrizole (Tinuvin P), bumetrizole (Tinuvin 326), 4,6-bis (1,1-dimethylpropyl) -2- (2H-benzotriazole-2-yl) phenol (Tinuvin).
• HALS includes, for example, bis sebacate (2,2,6,6-tetramethyl-4-piperidyl) (Tinuvin770), 2-[[3,5-bis (1,1-dimethylethyl) -4-hydroxy). Phenyl] methyl] -2-butylpropane diate bis [1,2,2,6,6-pentamethyl-4-piperidinyl] (Tinuvin 144), decanediate bis [2,2,6,6-tetramethyl- 1- (octyloxy) piperidine-4-yl] (Tinuvin123), 1,5,8,12-tetrakis [4,6-bis (N-butyl-N-1,2,2,6,6-pentamethyl) -4-Piperidylamino) -1,3,5-triazin-2-yl] -1,5,8,12-tetraazadodecane (Tinuvin 119), dimethyl 1- (2 hydroxyethyl) succinate-4- Hydroxy-2,2,6,6
• the method for producing a resin composition of the present invention is characterized by comprising a heating step of heating a mixture containing the above-mentioned resin and the above-mentioned phenol compound at 200 ° C. or higher and under reduced pressure.
• the heating step removes impurities unavoidably contained in the mixture and at least a part of a solvent that can be optionally blended in the mixture from the mixture to dry and dry the mixture. It may be a step of concentrating to obtain a solution or solid resin composition.
• the heating temperature in the heating step needs to be 200 ° C. or higher, and can be 400 ° C. or lower.
• the absolute pressure in the heating step is preferably 50 kPa or less, and more preferably 20 kPa or less. In other words, in the heating step, it is preferable to carry out an operation of heating the mixture to 200 ° C. or higher under a pressure condition of 50 kPa or lower.
• the heating step is not particularly limited as long as the above temperature and pressure conditions are satisfied, and known devices such as a centrifugal thin film continuous evaporator, a scratch surface heat exchange type continuous reactor type evaporator, and a high viscosity reactor device are used.
• the direct heat drying method using the above can be carried out.
• a step of mixing the above-mentioned resin and the above-mentioned phenol compound to obtain a mixture can be performed.
• the mixing method is not particularly limited, and examples thereof include a method of adding a predetermined phenol compound to a solution in which the resin is dissolved and mixing by a known method.
• a pelletizing step may be carried out in which the melt containing the resin and the predetermined phenol compound is pelletized to form a pellet-shaped resin composition.
• the molded product of the present invention is formed by molding the above-mentioned resin composition. Since the molded product of the present invention contains a resin and the above-mentioned specific phenol compound, decomposition of the resin (polymer) does not easily proceed even when exposed to reduced pressure and high temperature conditions, and the mechanical strength is high. It is possible to maintain good properties such as. Then, the molded product of the present invention can be advantageously used as, for example, an optical lens or the like.
• the molded product of the present invention can be molded into a film or a molded product having various shapes through a known molding method suitable for a desired shape.
• the molding method is not particularly limited, and examples thereof include an injection molding method, an extrusion molding method, and a blow molding method.
• a molding method a method of processing into a non-woven fabric or a fiber by melt spinning such as a span bond method or a melt blow method can be mentioned.
• the molding conditions can be appropriately set according to the equipment used at the time of molding, the desired shape of the molded product, and the like.
• the melting point of the phenol compound is 20 ° C at the measurement start temperature and 200 ° C at the measurement end temperature using a melting point measuring device (manufactured by METTLER TOLEDO, product name "MP70"). The measurement was carried out at a heating rate of 5 ° C./min. In this way, the melting point of the phenol compound produced according to Production Examples 1 and 2 was obtained.
• (2) Weight average molecular weight (Mw) The weight average molecular weight (Mw) was determined as a standard polystyrene-equivalent value by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent.
• Example 1 ⁇ Thermoplastic resin preparation process (polymerization-hydrogenation)> 231 parts of dehydrated cyclohexane, 100 parts of dehydrated styrene, and 0.39 part of dibutyl ether were placed in a reactor provided with a stirrer and whose inside was sufficiently nitrogen-substituted. While stirring the whole volume at 60 ° C., 0.53 part of n-butyllithium (15% cyclohexane solution) was added to initiate polymerization. Subsequently, the whole volume was stirred at 60 ° C. for 60 minutes. Then, 0.18 part of isopropyl alcohol was added to stop the reaction to obtain a polystyrene solution.
• the polystyrene solution is transferred to a pressure resistant reactor equipped with a stirrer, and 10 parts of a diatomaceous earth-supported nickel catalyst (manufactured by Nikki Catalyst Kasei Co., Ltd., product name "E22U", nickel-supported amount 60%) is added as a hydrogenation catalyst. Then, the mixture was stirred for 0.1 hour. The inside of the reactor was replaced with hydrogen gas, hydrogen was further supplied while stirring the solution, and a hydrogenation reaction was carried out at a temperature of 180 ° C. and a pressure of 4.6 MPa for 7 hours. As a result, a reaction solution containing polystyrene hydride as a polymer to be blended in the resin composition was obtained.
• a diatomaceous earth-supported nickel catalyst manufactured by Nikki Catalyst Kasei Co., Ltd., product name "E22U", nickel-supported amount 60%
• the weight average molecular weight (Mw0) of the obtained polystyrene hydride was 90,000. 0.5 part of the phenol compound 1 (bisphenol monoacrylate compound) obtained in Production Example 1 was added to the reaction solution and dissolved. This solution is filtered under pressure at a pressure of 0.35 MPa using diatomaceous earth (manufactured by Showa Kagaku Kogyo Co., Ltd., product name "Radiolite (registered trademark) # 500”) as a filtration bed ("Fundaback filter” manufactured by Ishikawajima Harima Heavy Industries, Ltd.). Then, the hydrogenation catalyst was removed to obtain a colorless and transparent hydride polystyrene solution.
• diatomaceous earth manufactured by Showa Kagaku Kogyo Co., Ltd., product name "Radiolite (registered trademark) # 500"
• Redaback filter manufactured by Ishikawajima Harima Heavy Industries, Ltd.
• the polystyrene hydride solution was heated to 200 ° C. under a nitrogen atmosphere and continuously supplied to a thin film evaporator (manufactured by Hitachi, Ltd., product name controller) at a pressure of 3 MPa.
• the operating conditions of the thin film evaporator were that the temperature of the concentrated polymer solution inside was 200 ° C. under a pressure of 13.4 kPa.
• the concentrated solution was continuously derived from the thin film evaporator and further supplied to the thin film evaporator of the same type at a pressure of 1.6 MPa.
• the operating conditions were a pressure of 0.5 kPa and a temperature of 260 ° C.
• ⁇ Pelterizing process> A composition containing a molten polymer is continuously derived from a thin film evaporator, extruded from a die at 200 ° C. in a class 100 clean room, cooled with water, and then pelletized (product name "OSP-2", Nagata Seisakusho Co., Ltd.). The pellet was obtained as a resin composition containing phenol compound 1 (bisphenol monoacrylate compound) and polystyrene hydride as a polymer. When the pellet was dissolved in cyclohexane again and Mw1 was measured, Mw1 was 86,000. ⁇ Molding process> Pellets are kneaded and melted for 1 minute at 260 ° C.
• Example 2 Pellets and flat plates were subjected to the same operations as in Example 1 except that 0.5 part of phenol compound 2 (bisphenol monomethacrylate compound) was added to the reaction solution containing polystyrene hydride as a thermoplastic resin. Got The Mw1 of the pellet was 85,500. The haze of the flat plate was 0.4%. Based on the various measured values obtained, various evaluations were performed according to the above. The results are shown in Table 1.
• Example 1 (Comparative Example 1) Various operations similar to those in Example 1 were carried out except that the phenol compound 1 was not added after the hydrogenation reaction, to obtain pellets and flat plates as molded products. The Mw1 of the pellet was 60,000. The haze of the flat plate was 1.1%. Based on the various measured values obtained, various evaluations were performed according to the above. The results are shown in Table 1.
• the additive having a structure similar to that of the bisphenol monoacrylate compound used in Example 1 but not satisfying the general formula (I) has an ability to suppress the decomposition of the resin under reduced pressure and high temperature conditions. It can be seen that there was a tendency for volatilization to occur easily when exposed to high temperature conditions. Furthermore, from Comparative Example 4, the antioxidant (Irganox 1010), which has a significantly different structure from the bisphenol monoacrylate compound used in Example 1, is difficult to volatilize under high temperature conditions, but is a resin under reduced pressure and high temperature conditions. It can be seen that the ability to suppress decomposition of was insufficient. Then, in Examples 1 and 2, all the evaluation results of transparency were "A" evaluations. From this, according to the bisphenol monoacrylate compound and the bisphenol monomethacrylate compound having a predetermined structure satisfying the general formula (I), it was possible to satisfactorily suppress the coloring of the resin when exposed to high temperature conditions. I understand.
• the present invention it is possible to provide a phenol compound which does not easily volatilize even when exposed to high temperature conditions and has a sufficiently high ability to suppress decomposition of the resin under reduced pressure and high temperature conditions. Further, according to the present invention, it is possible to provide a resin composition containing the above-mentioned phenol compound and an efficient production method thereof. Further, according to the present invention, it is possible to provide a molded product made of the above resin composition.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• General Chemical & Material Sciences (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Macromonomer-Based Addition Polymer (AREA)

Priority Applications (5)

Applications Claiming Priority (2)

Publications (1)

Family

ID=74228584

Family Applications (1)

Country Status (7)

Families Citing this family (1)

Citations (4)

Family Cites Families (9)

• 2020
  • 2020-07-15 US US17/597,702 patent/US12030851B2/en active Active
  • 2020-07-15 CN CN202080036904.3A patent/CN113840872B/zh active Active
  • 2020-07-15 EP EP20847854.5A patent/EP4006092B1/en active Active
  • 2020-07-15 KR KR1020227001520A patent/KR102879917B1/ko active Active
  • 2020-07-15 WO PCT/JP2020/027523 patent/WO2021020133A1/ja not_active Ceased
  • 2020-07-15 JP JP2021536921A patent/JP7521533B2/ja active Active
  • 2020-07-17 TW TW109124272A patent/TWI828931B/zh active

Patent Citations (4)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events