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WO2025053025A1 - Copolymère séquencé - Google Patents

Copolymère séquencé Download PDF

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Publication number
WO2025053025A1
WO2025053025A1 PCT/JP2024/030757 JP2024030757W WO2025053025A1 WO 2025053025 A1 WO2025053025 A1 WO 2025053025A1 JP 2024030757 W JP2024030757 W JP 2024030757W WO 2025053025 A1 WO2025053025 A1 WO 2025053025A1
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Prior art keywords
block
mass
units
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block copolymer
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English (en)
Japanese (ja)
Inventor
純平 高橋
淳也 鈴木
冬木 大田
晃純 木村
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Denka Co Ltd
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Denka Co Ltd
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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
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • 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
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer

Definitions

  • This disclosure relates to block copolymers.
  • thermoplastic resin compositions which are made by blending rubber components with thermoplastic resins containing acrylonitrile, styrene, etc., are used in a variety of fields.
  • Patent Document 1 describes that a block copolymer having a block of a random copolymer of methyl methacrylate/naphthyl methacrylate and a block of an elastomer can provide a thermoplastic resin composition whose transparency does not decrease when mixed with a thermoplastic resin.
  • Patent Document 2 describes that an acrylonitrile-based diblock copolymer can similarly provide a thermoplastic resin composition that is excellent in transparency, etc.
  • the transparency of the thermoplastic resin composition is improved by improving the compatibility between the matrix resin and the block copolymer.
  • thermoplastic resin compositions containing rubber components One of the reasons why transparency decreases in thermoplastic resin compositions containing rubber components is the large difference in refractive index between the rubber component and the matrix resin. It is believed that transparency can be improved if the refractive indexes of the rubber component and matrix resin can be made uniform.
  • (meth)acrylic acid alkyl ester rubber has a low refractive index of about 1.40 to 1.48.
  • the objective of the present invention is to provide a new block copolymer that can achieve a high refractive index of 1.50 or more.
  • a block copolymer comprising a first block including a vinyl cyanide unit and an aromatic vinyl unit, and a second block including a (meth)acrylic acid ester unit.
  • a block copolymer according to [1] wherein the proportion of the second block is more than 50% by mass and less than 75% by mass with respect to the total amount of the first block and the second block.
  • a block copolymer containing at least a first block containing vinyl cyanide units and aromatic vinyl units, and a second block containing (meth)acrylic acid ester units can achieve a high refractive index.
  • the present invention provides a block copolymer that can achieve a high refractive index of 1.50 or more.
  • the first block contains a vinyl cyanide unit and an aromatic vinyl unit.
  • the vinyl cyanide constituting the vinyl cyanide unit include acrylonitrile, methacrylonitrile, and ethacrylonitrile.
  • the first block may contain one or more types of vinyl cyanide units. From the viewpoint of further improving compatibility or dispersibility with MS resin, AS resin, and the like, the vinyl cyanide unit may contain an acrylonitrile unit.
  • AS and the like refers to a polymer (or copolymer) component contained in the block copolymer.
  • AS resin polymer
  • MS resin and the like refers to a matrix resin.
  • Aromatic vinyls constituting styrene-based units include, for example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, ⁇ -methylstyrene, ⁇ -methylstyrene, 2,6-dimethylstyrene, 2,4-dimethylstyrene, ⁇ -methyl-o-methylstyrene, ⁇ -methyl-m-methylstyrene, ⁇ -methyl-p-methylstyrene, ⁇ -methyl-o-methylstyrene, ⁇ -methyl-m-methylstyrene, ⁇ -methyl-p-methylstyrene, 2,4,6-trimethylstyrene, ⁇ -methyl-2,6-dimethylstyrene, ⁇ -methyl-2,4-dimethylstyrene, ⁇ -methyl-2,6-dimethylstyrene, ⁇ -methyl-2,
  • styrene examples include o-chlorostyrene, ⁇ -chloro-m-chlorostyrene, ⁇ -chloro-p-chlorostyrene, ⁇ -chloro-o-chlorostyrene, ⁇ -chloro-m-chlorostyrene, ⁇ -chloro-p-chlorostyrene, 2,4,6-trichlorostyrene, ⁇ -chloro-2,6-dichlorostyrene, ⁇ -chloro-2,4-dichlorostyrene, ⁇ -chloro-2,6-dichlorostyrene, ⁇ -chloro-2,4-dichlorostyrene, o-t-butylstyrene, m-t-butylstyrene, p-t-butylstyrene, o-methoxystyrene, m-methoxystyrene, p-meth
  • the aromatic vinyl unit may be an aromatic vinyl unit other than a styrene-based unit.
  • the aromatic vinyl constituting the aromatic vinyl unit other than a styrene-based unit may be indene, vinylnaphthalene, or vinylanthracene.
  • the aromatic vinyl may be at least one selected from the group consisting of styrene, ⁇ -methylstyrene, and p-methylstyrene.
  • the first block may be composed only of vinyl cyanide units and aromatic vinyl units, or may be composed only of acrylonitrile units and styrene-based units, in order to further improve compatibility or dispersibility.
  • the first block may contain units derived from other monomer units (1) other than vinyl cyanide units and aromatic vinyl units.
  • the other monomers (1) constituting the other monomer units (1) are not particularly limited as long as they do not inhibit the effects of the present invention and are copolymerizable with vinyl cyanide and aromatic vinyl.
  • Examples of the other monomers (1) include (meth)acrylic acid esters, maleic anhydride, N-substituted maleimide, acrylic acid, methacrylic acid, acrylamide, and methacrylamide.
  • Examples of the (meth)acrylic acid esters include the same as the (meth)acrylic acid esters in the second block described below.
  • the first block may contain one or more types of units derived from other monomers (1).
  • the proportion of aromatic vinyl units may be 60% by mass or more relative to all monomer units constituting the first block, and from the viewpoint of easier control of polymerization, may be 65% by mass or more, 70% by mass or more, or 80% by mass or more.
  • the proportion of aromatic vinyl units may be 95% by mass or less relative to all monomer units constituting the first block, and from the viewpoint of easier control of polymerization, may be 90% by mass or less.
  • the mass ratio of vinyl cyanide units to vinyl aromatic units in the first block may be 0.05 or more, or 0.10 or more, and may be 0.50 or less, 0.40 or less, 0.30 or less, or 0.20 or less.
  • the first block may be a block in which vinyl cyanide units and vinyl aromatic units are randomly or alternately copolymerized (random copolymer or alternating polymer).
  • the first block may preferably be a random copolymer.
  • the proportion of the first block may be 10% by mass or more, more than 10% by mass, 20% by mass or more, more than 20% by mass, 25% by mass or more, more than 25% by mass, 30% by mass or more, or more than 30% by mass, based on the total amount of the first block and the second block.
  • the proportion of the first block may be 60% by mass or less, less than 60% by mass, 55% by mass or less, less than 55% by mass, 50% by mass or less, less than 50% by mass, 49% by mass or less, less than 49% by mass, 48% by mass or less, or less than 48% by mass, based on the total amount of the first block and the second block.
  • the weight average molecular weight (hereinafter, weight average molecular weight will be referred to as "Mw”) of the first block may be 10,000 or more, or may be 20,000 or more.
  • the Mw of the first block may be 180,000 or less, or may be 100,000 or less.
  • the Mw and number average molecular weight (hereinafter referred to as "Mn") of each block or block copolymer can be measured using GPC (for example, product name "HLC-8320" manufactured by Tosoh Corporation) under the following conditions. ⁇ Measurement conditions> Column: TSKgel Three GMHHR-H in series Temperature: 40°C Detection: Differential refractive index Solvent: THF Calibration curve: Prepared using standard polystyrene (PS).
  • the second block includes (meth)acrylic acid ester units.
  • (meth)acrylic acid ester includes one or both of an acrylic acid ester and a methacrylic acid ester.
  • Examples of (meth)acrylic acid esters that constitute the (meth)acrylic acid ester units include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, amyl methacrylate, isoamyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, lauryl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, and phenyl methacrylate.
  • the second block may contain one or more units derived from a (meth)acrylic acid ester.
  • the (meth)acrylic acid ester unit may contain a (meth)acrylic acid alkyl ester unit having an alkyl group with a carbon number of 1 to 4, and may contain an n-butyl acrylate unit.
  • the second block may contain other monomer units (2) other than the (meth)acrylic acid ester units.
  • the other monomers (2) constituting the other monomer units (2) are not particularly limited as long as they do not inhibit the effects of the present invention and can be copolymerized with the (meth)acrylic acid ester.
  • Examples of the other monomers (2) include aromatic vinyl, vinyl cyanide, maleic anhydride, N-substituted maleimide, methacrylic acid, acrylamide, methacrylamide, etc.
  • Examples of the aromatic vinyl and vinyl cyanide include the same ones as the aromatic vinyl and vinyl cyanide in the first block, respectively. However, a block containing both aromatic vinyl units and vinyl cyanide units is classified as the first block described above.
  • the second block may contain one or more types of other monomer units (2).
  • the proportion of (meth)acrylic acid ester units may be 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, or 95% by mass or more, or may be 100% by mass, based on the total monomer units constituting the second block.
  • the (meth)acrylic acid ester units may be only (meth)acrylic acid alkyl ester units having an alkyl group with 1 to 4 carbon atoms.
  • the second block may be a block consisting only of n-butyl acrylate units (poly n-butyl acrylate (PBA) block).
  • the proportion of the second block may be 40% by mass or more, more than 40% by mass, 45% by mass or more, more than 45% by mass, 50% by mass or more, more than 50% by mass, 51% by mass or more, more than 51% by mass, 52% by mass or more, or more than 52% by mass, based on the total amount of the first block and the second block.
  • the proportion of the second block may be 75% by mass or less, less than 75% by mass, 74% by mass or less, less than 74% by mass, 73% by mass or less, less than 73% by mass, 72% by mass or less, less than 72% by mass, 71% by mass or less, less than 71% by mass, 70% by mass or less, less than 70% by mass, 65% by mass or less, less than 65% by mass, 60% by mass or less, or less than 60% by mass.
  • the Mw of the second block may be 12,000 or more and 180,000 or less.
  • the block copolymer may be a diblock copolymer consisting of only a first block and a second block, from the viewpoint of excellent compatibility or dispersibility in MS resins and AS resins.
  • the block copolymer according to the present embodiment may further include a third block in addition to the first block and the second block.
  • the third block may be a block containing an aromatic vinyl unit. Examples of the aromatic vinyl constituting the aromatic vinyl unit include the same aromatic vinyl as that in the first block.
  • the third block may be a block consisting of only aromatic vinyl units, or may be a polystyrene block consisting of only styrene units.
  • the proportion of the third block may be 1% by mass or more, 5% by mass or more, or 10% by mass or more, and may be 36% by mass or less, or 30% by mass or less, based on the total amount of all blocks constituting the block copolymer.
  • the proportion of the vinyl cyanide units may be 1% by mass or more, 3% by mass or more, or 5% by mass or more, and 20% by mass or less, 18% by mass or less, or 16% by mass or less, based on the total monomer units constituting the block copolymer.
  • the proportion of the aromatic vinyl units may be 10% by mass or more, 15% by mass or more, or 20% by mass or more, based on the total monomer units constituting the block copolymer, and from the viewpoint of making it easier to achieve a high refractive index, may be 30% by mass or more, 32% by mass or more, 34% by mass or more, 35% by mass or more, or 38% by mass or more.
  • the proportion of the aromatic vinyl units may be 45% by mass or less, 40% by mass or less, or 35% by mass or less, based on the total monomer units constituting the block copolymer.
  • the proportion of the (meth)acrylic acid ester units may be 40% by mass or more or 45% by mass or more, based on the total monomer units constituting the block copolymer.
  • the proportion of the (meth)acrylic acid ester units may be 90% by mass or less, 80% by mass or less, or 70% by mass or less, based on the total monomer units constituting the block copolymer, and from the viewpoint of making it easier to achieve a high refractive index, may be 65% by mass or less, 60% by mass or less, or 55% by mass or less.
  • the block copolymer according to this embodiment may be further crosslinked with a crosslinking agent.
  • a crosslinking agent is a compound having two or more polymerizable groups. By being crosslinked with a crosslinking agent, the block copolymer according to this embodiment tends to become a stronger resin.
  • the block copolymer is produced as polymer particles by, for example, the method described below, the particle shape of the polymer particles obtained after crosslinking tends to be maintained.
  • the polymerizable group examples include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group.
  • the crosslinking agent may be a compound having two or more ethylenically unsaturated groups, a compound having two or more (meth)acryloyl groups, or an aromatic polyene.
  • (meth)acryloyl group includes either an acryloyl group or a methacryloyl group, or both.
  • the crosslinking agent may be one type or two or more types.
  • Examples of compounds having two or more (meth)acryloyl groups include polyfunctional (meth)acrylic acid esters obtained by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid; caprolactone-modified polyfunctional (meth)acrylic acid esters; alkylene oxide-modified polyfunctional (meth)acrylic acid esters; polyfunctional urethane (meth)acrylic acid esters obtained by reacting a (meth)acrylic acid ester having a hydroxyl group with a polyfunctional isocyanate; and polyfunctional (meth)acrylic acid esters having a carboxyl group obtained by reacting a (meth)acrylic acid ester having a hydroxyl group with an acid anhydride.
  • the compound having two or more (meth)acryloyl groups may be a polyfunctional (meth)acrylic acid ester obtained by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid, or may be a bifunctional (meth)acrylic acid ester.
  • bifunctional (meth)acrylic acid esters include diol diacrylates such as 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, and 1,10-decanediol diacrylate; ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol diacrylate.
  • diol diacrylates such as 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, and 1,10-decanediol diacrylate
  • ethylene glycol diacrylate diethylene glycol diacrylate
  • triethylene glycol diacrylate triethylene glycol diacrylate
  • diacrylate examples include glycol diacrylates such as neopentyl glycol diacrylate, diacrylates of diols obtained by adding at least one of ethylene oxide and propylene oxide to neopentyl glycol, and caprolactone-modified hydroxypivalic acid neopentyl glycol diacrylate; diacrylates of EO adducts of bisphenol A, diacrylates of PO adducts of bisphenol A, tricyclodecane dimethanol diacrylate, hydrogenated dicyclopentadienyl diacrylate, and diacrylates having a cyclic structure such as cyclohexyl diacrylate.
  • the bifunctional (meth)acrylic acid ester may be one or two types.
  • the aromatic polyene may have 10 to 30 carbon atoms, two or more double bonds (vinyl groups), and one or more aromatic groups.
  • the aromatic polyene may be o-divinylbenzene, p-divinylbenzene, m-divinylbenzene, 1,4-divinylnaphthalene, 3,4-divinylnaphthalene, 2,6-divinylnaphthalene, 1,2-divinyl-3,4-dimethylbenzene, 1,3-divinyl-4,5,8-tributylnaphthalene, etc.
  • the aromatic polyene may be one type or two or more types.
  • the average particle size of the block copolymer may be 50 nm or more or 100 nm or more, and may be 1000 nm or less or 500 nm or less.
  • the average particle size can be measured by a dynamic light scattering method (for example, product name "ELSZ-2000ZS” manufactured by Otsuka Electronics Co., Ltd.).
  • the block copolymer according to the present embodiment can be polymerized in an aqueous dispersion according to the production method described below, for example, to obtain a copolymer having a narrow molecular weight distribution (Mw/Mn) and a high molecular weight.
  • Mw/Mn narrow molecular weight distribution
  • Mc critical molecular weight
  • Mc critical molecular weight
  • the critical molecular weight is a molecular weight corresponding to the molecular chain length required for entanglement of molecules in an undiluted polymer. If the Mw of the polymer exceeds Mc, the viscosity increases rapidly.
  • Mc varies depending on the type and composition of the polymer (e.g., the monomer composition of each block that forms a block copolymer). Mc is given in many publications. For example, but not limited to, it has been reported that the Mc of acrylonitrile-styrene copolymer is 24,000, and the Mc of polystyrene is 31,200.
  • a conventionally known method can be used as a method for measuring Mc of the block copolymer according to this embodiment.
  • a method for experimentally deriving Mc by determining the point (critical point) where the slope of a logarithmic graph (horizontal axis: log(Mw), vertical axis: log(viscosity)) showing the relationship between Mw and viscosity of the block copolymer changes from 1.0 to 3.4 (for example, a method described in JP-A-2010-506002, etc.), or a method for confirming whether a rubber-like flat region appears when the storage modulus is measured by viscoelasticity measurement, can be used.
  • the Mw and Mn of the block copolymer can be values measured under the above-mentioned conditions.
  • the block copolymer according to the present embodiment may not dissolve in a solvent in some cases.
  • the Mw of the finally obtained block copolymer may be determined to be equal to or greater than Mc by measuring the Mc of the block copolymer by the above-mentioned viscoelasticity measurement or by confirming that the Mw of the block copolymer is equal to or greater than Mc in the production method described below.
  • the block copolymer according to the present embodiment is a block copolymer having a first block and a second block, and thus can achieve a refractive index similar to that of thermoplastic resins such as MS resins and AS resins.
  • thermoplastic resins such as MS resins and AS resins.
  • the block copolymer does not contain a vinyl group in the structure, it is considered that the weather resistance is also good. Therefore, it can be used by being contained in a thermoplastic resin as a rubber component having a higher refractive index than conventional acrylic rubbers.
  • the method for producing the block copolymer according to the present embodiment is not particularly limited as long as it is a method for polymerizing each monomer so as to include the above-mentioned first block and second block.
  • the block copolymer may be produced by a method for constituting each block by living radical polymerization.
  • Living radical polymerization methods include the NMP method (nitroxide-mediated radical polymerization method), the ATRP method (atom transfer radical polymerization method), the TERP method (radical polymerization method using an organotellurium compound), and the RAFT polymerization method (reversible addition-fragmentation chain transfer polymerization method).
  • the RAFT polymerization method is preferred because it allows the polymerization reaction to proceed under mild conditions and is compatible with a variety of monomers.
  • An example of the production of the block copolymer of this embodiment by the RAFT polymerization method is described below.
  • the manufacturing method includes a step (i) of polymerizing a monomer mixture (M1) containing a vinyl cyanide monomer and an aromatic vinyl monomer in water containing a RAFT agent, an emulsifier, and a polymerization initiator to obtain a latex (L1) containing a copolymer (P1) of a vinyl cyanide monomer and an aromatic vinyl monomer, and a step (ii) of mixing and reacting a monomer mixture (M2) containing a (meth)acrylic acid ester monomer with the latex (L1) to obtain a latex (L2) containing a block copolymer (P2) of the copolymer (P1) and the monomer mixture (M2).
  • Step (i) is a step of polymerizing a vinyl cyanide monomer and an aromatic vinyl monomer to obtain a copolymer (P1).
  • a polymerization initiator is mixed into a mixture containing a vinyl cyanide monomer, an aromatic vinyl monomer, a RAFT agent, water, and an emulsifier to obtain a latex (L1) containing seed particles (S1) made of a copolymer (P1) having a structure derived from the RAFT agent at its end.
  • the copolymer (P1) and the seed particles (S1) contain a polymer that constitutes the first block in the finally obtained block copolymer.
  • the vinyl cyanide monomer may be one or more selected from the vinyl cyanides in the vinyl cyanide units of the first block.
  • the aromatic vinyl monomer may be one or more selected from the aromatic vinyls constituting the aromatic vinyl units of the first block.
  • the proportion of the vinyl cyanide monomer in the monomer mixture (M1) may be 5% by mass or more or 10% by mass or more, and 40% by mass or less, 35% by mass or less, 30% by mass or less, or 20% by mass or less, based on the total amount of the monomer mixture (M1).
  • the proportion of the vinyl aromatic monomer in the monomer mixture (M1) may be 60% by mass or more, 65% by mass or more, 70% by mass or more, or 80% by mass or more, and 95% by mass or less, or 90% by mass or less, based on the total amount of the monomer mixture (M1).
  • the mixture of monomers (M1) may further comprise other monomers (1) as described above.
  • the water used in step (i) may be pure water, and the content of pure water may be 100% by mass or more and 400% by mass or less based on the total amount of vinyl cyanide monomer and vinyl aromatic monomer.
  • the RAFT agent is a compound used in a RAFT polymerization reaction, and may be a compound having a structure represented by the following formula (1):
  • the RAFT agent may be, for example, a thiocarbonyl compound such as dithiobenzoate, trithiocarbamate, dithiocarbamate, or xanthate.
  • examples of the RAFT agent represented by formula (1) include dithiocarbamates, dithioesters, and trithiocarbamates.
  • examples of the RAFT agent represented by formula (1) include benzyl 1-pyrrole carbodithioate (common name: benzyl 1-pyrrole dithiocarbamate), benzyl phenyl carbodithioate, 1-benzyl-N,N-dimethyl-4-aminodithiobenzoate, 1-benzyl-4-methoxydithiobenzoate, 1-phenylethyl imidazole carbodithioate (common name: 1-phenylethyl imidazole dithiocarbamate), benzyl-1-(2-pyrrolidinone) carbodithioate) (common name: benzyl-1-(2-pyrrolidinone) dithiocarbamate), Benzyl phthalimidyl carbodithioate, (common name: benzyl phthalimi
  • the emulsifier is not particularly limited, and examples thereof include anionic surfactants, nonionic surfactants, and amphoteric surfactants. More specifically, examples of the emulsifier include anionic surfactants such as sulfate esters of higher alcohols (e.g., alcohols having 6 to 30 carbon atoms), alkylbenzenesulfonates, fatty acid sulfonates, phosphate salts (e.g., ammonium monoglyceride phosphate), fatty acid salts (e.g., dipotassium alkenyl succinate), and amino acid derivative salts; nonionic surfactants such as alkyl esters, alkyl ethers, and alkylphenyl ethers of polyethylene glycol; and amphoteric surfactants having carboxylates, sulfates, sulfonates, and phosphate salts in the anion portion and amine salts, quaternary ammonium salts,
  • the emulsifier may be one or more kinds. From the viewpoint of emulsion stability and ease of handling, the emulsifier may be anionic surfactants, alkylbenzenesulfonates, or sodium dodecylbenzenesulfonate.
  • the proportion of the emulsifier may be 1% by mass or more and 10% by mass or less based on the total amount of all the monomers used in steps (i) and (ii).
  • Polymerization initiator examples include persulfates, sodium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, and azo compounds.
  • the polymerization initiator may be an azo compound from the viewpoint of suppressing side reactions derived from the initiator.
  • the proportion of the polymerization initiator may be 10 mol % or more and 50 mol % or less based on the substance amount of the RAFT agent used.
  • azo compounds examples include 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl)azo]formamide, 4,4'-azobis(4-cyanovaleric acid), dimethyl 2,2'-azobis(2 -methylpropionate), dimethyl 1,1'-azobis(1-cyclohexanecarboxylate), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2'-azobis(N-cyclohexyl-2-methylpropionamide), 2,2'-azobis[2-(2-imidiol)-but
  • the polymerization temperature in step (i) may be 10° C. or more or 20° C. or more, and 100° C. or less or 80° C. or less.
  • the polymerization time in step (i) may be 1 hour or more or 2 hours or more, and 20 hours or less or 10 hours or less.
  • the monomer conversion in step (i) may be 70% or more or 80% or more, and 100% or less.
  • Step (ii) is a step of reacting the copolymer (P1) obtained in step (i) with a (meth)acrylic acid ester monomer to obtain a block copolymer (P2).
  • this step is a step of mixing the latex (L1) with a monomer mixture (M2) and seed-polymerizing the monomer mixture (M2) with the structure derived from the RAFT agent at the end of the seed particle (S1) to obtain a latex (L2) containing a polymer particle (S2) made of a block copolymer (P2).
  • the block copolymer (P2) and the polymer particle (S2) contain a block copolymer containing a first block and a second block according to this embodiment.
  • the (meth)acrylic acid ester monomer may be one or more selected from the (meth)acrylic acid esters in the (meth)acrylic acid ester unit described above.
  • the proportion of the (meth)acrylic acid ester monomer in the monomer mixture (M2) may be 90 mass% or more, 95 mass% or more, or 100 mass% based on the total amount of the monomer mixture (M2).
  • the mixture of monomers (M2) may contain other monomers (2).
  • a crosslinking agent may be mixed into the monomer mixture (M2). By mixing the crosslinking agent into the monomer mixture (M2), the second block is crosslinked.
  • the crosslinking agent may be 10% by mass or less based on the total amount of the monomer mixture (M2).
  • the polymerization temperature in step (ii) may be 10°C or more or 20°C or more, and 100°C or less or 80°C or less.
  • the polymerization time in step (ii) may be 1 hour or more or 2 hours or more, and 20 hours or less or 10 hours or less.
  • the monomer conversion in step (ii) may be 70% or more or 80% or more, and 100% or less.
  • the block copolymer (P2) may contain a structure derived from the RAFT agent at its terminal. Since the structure exhibits high reactivity, a step (step (iii)) of treating the terminal of the block copolymer may be included after the step (ii).
  • step (iii) Various techniques are known for step (iii). These techniques can be suitably used in the present invention. Suitable techniques include, for example, those described in Chongetal, Macromolecules 2007, 40, 4446-4455; Chongetal, Aust. J. Chem. 2006, 59, 755-762; Postmaetal, Macromolecules 2005, 38, 5371-5374; Moadetal, Polymer International 60, no. 1, 2011, 9-25; and Wilcocketal, Polym. Chem. , 2010, 1, 149-157.
  • the polymerization rate of the block copolymer may be 50% or more, 60% or more, or 100% or less.
  • the refractive index of the block copolymer may be adjusted by removing unreacted monomers while adjusting the polymerization rate.
  • a polymerization inhibitor may be mixed. By mixing a polymerization inhibitor, the polymerization reaction can be stopped and the polymerization rate can be adjusted.
  • polymerization inhibitors include oil-soluble polymerization inhibitors such as thiodiphenylamine, 4-tert-butylcatechol, and 2,2-methylenebis-4-methyl-6-tert-butylphenol, and water-soluble polymerization inhibitors such as diethylhydroxylamine.
  • unreacted monomers may be removed by a known method such as vacuum distillation.
  • Methods for recovering the block copolymer after removing the unreacted monomers include, for example, (1) a method in which latex (L2) containing block copolymer (P2) is poured into hot water in which a coagulant is dissolved, and the block copolymer (P2) is coagulated into a slurry state to recover the block copolymer (P2) (wet method), and (2) a method in which latex (L2) containing block copolymer (P2) is sprayed into a heated air atmosphere to recover the block copolymer (P2) (spray drying method).
  • Coagulants include, but are not limited to, inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, and nitric acid, and metal salts such as calcium chloride, calcium acetate, aluminum sulfate, and magnesium sulfate.
  • inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, and nitric acid
  • metal salts such as calcium chloride, calcium acetate, aluminum sulfate, and magnesium sulfate.
  • Methods for obtaining a dry block copolymer (P2) from a slurry of block copolymer (P2) include (3) a method in which the emulsifier residues and coagulant residues remaining in the slurry are dissolved in water by washing, and then the slurry is dehydrated in a centrifugal dehydrator or press dehydrator, and further dried in an air flow dryer or the like, and (4) a method in which the slurry is simultaneously dehydrated and dried in a squeeze dehydrator, extruder, or the like.
  • Example 1 A diblock copolymer consisting of a first block and a second block was produced by the following method.
  • ⁇ Manufacture of the first block 9.4 parts by mass of sodium dodecylbenzenesulfonate and 2.0 parts by mass of sodium hydrogen carbonate were dissolved in 219 parts by mass of deionized water substituted with nitrogen, and the solution was charged into a polymerization vessel equipped with a stirrer. Then, while stirring the liquid in the polymerization vessel, 85 parts by mass of styrene, 15 parts by mass of acrylonitrile, and 0.89 parts by mass of butylbenzyltrithiocarbonate were added, and the temperature in the vessel was set to 70°C.
  • Example 2 A triblock copolymer consisting of a third block, a first block and a second block was produced by the following method.
  • ⁇ Manufacture of the third block 9 parts by mass of sodium dodecylbenzenesulfonate and 2 parts by mass of sodium hydrogen carbonate were dissolved in 220 parts by mass of deionized water substituted with nitrogen, and the solution was charged into a polymerization vessel equipped with a stirrer. Then, while stirring the liquid in the polymerization vessel, 1.3 parts by mass of butylbenzyltrithiocarbonate was dissolved in 100 parts by mass of styrene in advance, and the temperature in the vessel was set to 80°C.
  • the monomer conversion was 84%, the Mw was 38,400, the Mn was 33,900, and the molecular weight distribution (Mw/Mn) was 1.1. At this time, it was confirmed that the Mw of the diblock (third block-first block) copolymer was equal to or greater than the Mc (24,000) of the acrylonitrile-styrene copolymer.
  • n-butyl acrylate 14 parts by mass of 1,9-nonanediol diacrylate, 95 parts by mass of deionized water, and 4 parts by mass of sodium dodecylbenzenesulfonate were added to obtain a triblock copolymer latex in which the second block consisting of n-butyl acrylate units was copolymerized with the diblock copolymer.
  • the monomer conversion was 90%, and the average particle size of the triblock copolymer was 250 nm.
  • Examples 3 to 5 diblock copolymers were obtained in the same manner as in Example 1, except that the content ratio of each monomer unit was changed as shown in Table 1.
  • the refractive index of each of the resulting block copolymers was evaluated according to the following procedure. The results are shown in Table 1.
  • a sheet having a thickness of 2 mm was prepared by recovering polymer components from the latexes of the block copolymers of Examples 1 to 5.
  • the refractive index of the obtained sheet was measured using an Abbe refractometer (multi-wavelength Abbe refractometer, manufactured by Atago Co., Ltd., product name "DR-M2”) at a measurement wavelength of 589 nm and a measurement temperature of 23°C.
  • Abbe refractometer multi-wavelength Abbe refractometer, manufactured by Atago Co., Ltd., product name "DR-M2

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Abstract

L'invention concerne un copolymère séquencé qui contient : une première séquence contenant à son tour une unité cyanure de vinyle et une unité vinyle aromatique ; et une seconde séquence contenant à son tour une unité ester d'acide (méth)acrylique.
PCT/JP2024/030757 2023-09-05 2024-08-28 Copolymère séquencé Pending WO2025053025A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003096150A (ja) * 2001-07-16 2003-04-03 Kanegafuchi Chem Ind Co Ltd ブロック共重合体
WO2003037945A1 (fr) * 2001-10-29 2003-05-08 Kaneka Corporation Copolymere sequence a base d'acrylonitrile et compositions de resines thermoplastiques
JP2004099722A (ja) * 2002-09-09 2004-04-02 Mitsubishi Rayon Co Ltd Ａｂｓ樹脂用流動性向上剤及びこれを含む熱可塑性樹脂組成物並びにａｂｓ樹脂用流動性向上剤の製造方法
JP2010235715A (ja) * 2009-03-30 2010-10-21 Ps Japan Corp 耐薬品性に優れるスチレン系樹脂組成物
JP2022015394A (ja) * 2020-07-09 2022-01-21 テクノＵｍｇ株式会社 無機充填剤分散剤、無機充填剤マスターバッチ、樹脂組成物、その製造方法及び成形品

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003096150A (ja) * 2001-07-16 2003-04-03 Kanegafuchi Chem Ind Co Ltd ブロック共重合体
WO2003037945A1 (fr) * 2001-10-29 2003-05-08 Kaneka Corporation Copolymere sequence a base d'acrylonitrile et compositions de resines thermoplastiques
JP2004099722A (ja) * 2002-09-09 2004-04-02 Mitsubishi Rayon Co Ltd Ａｂｓ樹脂用流動性向上剤及びこれを含む熱可塑性樹脂組成物並びにａｂｓ樹脂用流動性向上剤の製造方法
JP2010235715A (ja) * 2009-03-30 2010-10-21 Ps Japan Corp 耐薬品性に優れるスチレン系樹脂組成物
JP2022015394A (ja) * 2020-07-09 2022-01-21 テクノＵｍｇ株式会社 無機充填剤分散剤、無機充填剤マスターバッチ、樹脂組成物、その製造方法及び成形品

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