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WO2017002651A1 - Polymère de farnesène et son procédé de production - Google Patents

Polymère de farnesène et son procédé de production Download PDF

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Publication number
WO2017002651A1
WO2017002651A1 PCT/JP2016/068257 JP2016068257W WO2017002651A1 WO 2017002651 A1 WO2017002651 A1 WO 2017002651A1 JP 2016068257 W JP2016068257 W JP 2016068257W WO 2017002651 A1 WO2017002651 A1 WO 2017002651A1
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WIPO (PCT)
Prior art keywords
farnesene
polymer
mol
farnesene polymer
molecular weight
Prior art date
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Ceased
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PCT/JP2016/068257
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English (en)
Japanese (ja)
Inventor
久保　敬次
敦 稲富
社地　賢治
大輔 香田
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Kuraray Co Ltd
Amyris Inc
Original Assignee
Kuraray Co Ltd
Amyris Inc
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Priority to JP2017526292A priority Critical patent/JP6741297B2/ja
Publication of WO2017002651A1 publication Critical patent/WO2017002651A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • 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
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/22—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having three or more carbon-to-carbon double bonds

Definitions

  • the present invention relates to a farnesene polymer and a method for producing the same. More specifically, the present invention relates to a farnesene polymer having a high molecular weight and excellent fluidity and moldability and a method for producing the same.
  • Patent Document 1 Since the farnesene polymer exhibits rubber elasticity by being crosslinked, it is known that a rubber composition containing the farnesene polymer is crosslinked and used as a tire (Patent Document 1). In general, it is known that in a polymer that exhibits rubber elasticity by crosslinking, the molecular weight is increased (high molecular weight) in order to improve the mechanical properties (mechanical strength, rubber elasticity, etc.) of the crosslinked product. However, when the polymer has a high molecular weight, there is a problem that fluidity and molding processability are lowered.
  • Patent Document 2 a rubber composition containing a low-viscosity ethylene copolymer, a high-viscosity ethylene copolymer, and a crosslinking agent is known (Patent Document 2).
  • Patent Document 2 the mechanical properties of a crosslinked product obtained by crosslinking the rubber composition are still insufficient, and it is desired to increase the molecular weight while maintaining excellent fluidity and molding processability.
  • the present invention has been made in view of the above-described present situation, and an object thereof is to provide a farnesene polymer having a high molecular weight and high fluidity and excellent molding processability, and a method for producing the same.
  • the present invention it is possible to provide a farnesene polymer having a high molecular weight, high fluidity, and excellent moldability, and a method for producing the same.
  • the farnesene polymer of the present invention is a farnesene polymer containing a farnesene-derived monomer unit (a), which is obtained by the SEC-MALS method and has a radius of inertia ( ⁇ r g 2 >) in a dilute solution of THF. 1/2 ) and the absolute molecular weight (M) are polymers satisfying the following formula (1).
  • the “dilute solution” refers to a solution having a concentration of 1 g / dl or less obtained by dissolving a farnesene polymer in THF.
  • the farnesene polymer of the present invention is a mixture having a molecular weight distribution and containing polymers of different absolute molecular weights (M). Therefore, the absolute molecular weight represented by M in the above formula (1) is determined from the viewpoint of measuring without differentiating molecular weights of polymers having different absolute molecular weights, and from the viewpoint of measuring the absolute molecular weights of high molecular weight polymers. Measured by the MALS method.
  • the polymer chain constituting the polymer compound is spread in various forms in the solution, and the average of the spread state of the polymer chain is expressed as an inertia radius ⁇ r g 2 > 1/2 .
  • the radius of inertia represented by ⁇ r g 2 > 1/2 is measured by the SEC-MALS method from the viewpoint of directly measuring the polymers having different absolute molecular weights without fractionating the molecular weight.
  • the inertia radius ⁇ r g 2 > 1/2 represents the average of the spread state of the polymer chain. Therefore, ⁇ ′, which is a parameter indicating the degree of increase in the radius of inertia ⁇ r g 2 > 1/2 accompanying the increase in the absolute molecular weight (M), is the absolute molecular weight of the polymer compound and the polymer chain in the dilute solution. Represents the relationship with the spread state. For example, ⁇ ′ is 1 if the spread state of the polymer chain is linear, and the inertia radius ⁇ r g 2 > 1/2 is directly proportional to the absolute molecular weight (M) of the polymer compound. It becomes about 0.6, and becomes smaller as it gets closer to a sphere.
  • ⁇ ′ in the dilute THF solution of the farnesene polymer of the present invention is a positive constant ⁇ of less than 0.5, ie, the absolute molecular weight (M) and the radius of inertia ( ⁇ r g 2 ) of the farnesene polymer of the present invention. > 1/2 ) satisfies the following formula (1).
  • ⁇ in the formula (1) is an absolute molecular weight (M) obtained by a SEC-MALS method and a radius of inertia ⁇ r g 2 > 1/2 using a dilute solution of farnesene polymer in THF. Obtained from a log-log plot, the absolute molecular weight (M) is calculated from the slope of the straight line in the range of 500,000 to 20,000,000.
  • ⁇ in the formula (1) is preferably 0.4 or less from the viewpoint of fluidity of the farnesene polymer, and 0.3 or more is preferable from the viewpoint of ease of production.
  • the absolute molecular weight (Mt) at the peak top of the chromatogram obtained by the SEC-MALS method of the farnesene polymer of the present invention is preferably 1 million or more, more preferably 2 million or more, from the viewpoint of enhancing the mechanical properties of the crosslinked product. More preferably, it is 2.5 million or more. From the viewpoint of fluidity of the farnesene polymer, 20 million or less is preferable, 10 million or less is more preferable, 5 million or less is further preferable, and 4 million or less is even more preferable.
  • the absolute molecular weight (Mt) of the peak top of a chromatogram is calculated
  • the farnesene polymer of the present invention contains farnesene-derived monomer units (a) (hereinafter simply referred to as “monomer units (a)”).
  • the monomer unit (a) may be a monomer unit derived from ⁇ -farnesene, or may be a monomer unit derived from ⁇ -farnesene represented by the following formula (I): Although it may contain a monomer unit derived from ⁇ -farnesene and a monomer unit derived from ⁇ -farnesene, it is preferable to contain a monomer unit derived from ⁇ -farnesene from the viewpoint of ease of production.
  • the content of the monomer unit derived from ⁇ -farnesene is preferably 80 mol% or more, more preferably 90 mol% or more, and more preferably 100 mol% in the monomer unit (a) from the viewpoint of ease of production. That is, it is more preferable that all of the monomer units (a) are ⁇ -farnesene-derived monomer units.
  • the content of the monomer unit (a) in the farnesene polymer of the present invention is preferably in the range of more than 50 mol% and 100 mol% or less, more preferably in the range of 60 mol% or more and 100 mol% or less, and 65 mol%. The range of 100 mol% or less is more preferable, and the range of 70 mol% or more and 100 mol% or less is still more preferable.
  • the farnesene polymer of the present invention may further contain a monomer unit (b) derived from another monomer other than farnesene (hereinafter simply referred to as “monomer unit (b)”).
  • monomer unit (b) derived from another monomer other than farnesene
  • Other monomers that can form the monomer unit (b) are not particularly limited as long as they can be radically copolymerized with farnesene.
  • aromatic vinyl compounds, conjugated dienes, acrylic acid and derivatives thereof examples include methacrylic acid and derivatives thereof, acrylamide and derivatives thereof, methacrylamide and derivatives thereof, and acrylonitrile.
  • aromatic vinyl compound examples include styrene, ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-tert-butylstyrene, 4-cyclohexylstyrene, 4- Dodecylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, N, N-diethyl-4 -Styrene derivatives such as aminoethylstyrene, 4-methoxystyrene, monochlorostyrene, dichlorostyrene; 1-vinylnaphthalene, 2-vinylnaphthalene, vinylanthracene, vinylpyridine and
  • conjugated dienes examples include butadiene, isoprene, 2,3-dimethylbutadiene, 2-phenylbutadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-octadiene, Examples include conjugated dienes other than farnesene such as 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octatriene, myrcene, chloroprene and the like.
  • acrylic acid derivatives examples include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, isononyl acrylate, lauryl acrylate, Stearyl acrylate, cyclohexyl acrylate, isobornyl acrylate, dicyclopentenyloxyethyl acrylate, tetraethylene glycol acrylate, tripropylene glycol acrylate, 4-hydroxybutyl acrylate, 3-hydroxy-1-adamantyl acrylate, acrylic Examples include tetrahydrofurfuryl acid, methoxyethyl acrylate, N, N-dimethylaminoethyl acrylate, and the like.
  • methacrylic acid derivatives examples include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, Cyclohexyl methacrylate, isobornyl methacrylate, dicyclopentanyl methacrylate, benzyl methacrylate, dicyclopentenyloxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxy-1-adamantyl methacrylate Tetrahydrofurfuryl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, glycidyl methacrylate, etc. It is.
  • acrylamide derivatives examples include dimethylacrylamide, acryloylmorpholine, isopropylacrylamide, diethylacrylamide, dimethylaminopropylacrylamide, dimethylaminopropylacrylamide methyl chloride quaternary salt, hydroxyethylacrylamide, 2-acrylamido-2-methylpropanesulfonic acid, and the like. Can be mentioned.
  • methacrylamide derivatives examples include dimethylmethacrylamide, methacryloylmorpholine, isopropylmethacrylamide, diethylmethacrylamide, dimethylaminopropylmethacrylamide, hydroxyethylmethacrylamide and the like.
  • aromatic vinyl compounds are preferable, styrene and derivatives thereof are more preferable, and one or more selected from styrene and ⁇ -methylstyrene are more preferable.
  • aromatic vinyl compounds are preferable, styrene and derivatives thereof are more preferable, and one or more selected from styrene and ⁇ -methylstyrene are more preferable.
  • These other monomers may be used alone or in combination of two or more.
  • the content of the monomer unit (b) derived from another monomer other than farnesene in the farnesene polymer of the present invention is preferably in the range of 0 mol% or more and less than 50 mol%, and preferably 1 mol% or more and 50 mol%.
  • the range of less than 5 mol% is more preferable, the range of 5 mol% to 40 mol% is more preferable, the range of 8 mol% to 35 mol% is still more preferable, the range of 10 mol% to 30 mol% is still more preferable. .
  • the farnesene polymer of the present invention can be obtained by polymerizing the monomer (X) containing farnesene.
  • the polymerization method of the monomer (X) is not particularly limited, but a radical polymerization method is preferable from the viewpoint of industrial productivity, and an emulsion polymerization method is more preferable from the viewpoint of increasing the molecular weight of the obtained polymer.
  • the farnesene-containing monomer (X) is emulsion-polymerized so that the polymerization rate is 60% or more.
  • the higher the polymerization rate the more the branched structure based on the chain transfer of radicals to the unsaturated residue of the farnesene polymer, so the value of ⁇ can be reduced.
  • the polymerization rate is 60% or more, preferably 70% or more, more preferably 80% or more, and further preferably 90% or more.
  • a polymerization rate is calculated
  • the farnesene contained in the monomer (X) used in the production method of the present invention may be ⁇ -farnesene, may be ⁇ -farnesene represented by the formula (I), and ⁇ - A mixture of farnesene and ⁇ -farnesene may be used.
  • the farnesene used in the production method of the present invention preferably contains ⁇ -farnesene from the viewpoint of ease of production, and the content of ⁇ -farnesene in the total amount of the farnesene is preferably 80 mol% or more, and 90 mol%. The above is more preferable, and 100 mol% is still more preferable.
  • the content of farnesene in the monomer (X) used in the production method of the present invention is preferably in the range of more than 50 mol% to 100 mol%, more preferably in the range of 60 mol% to 100 mol%, more preferably 65 mol % Or more and 100 mol% or less is still more preferable, and 70 mol% or more and 100 mol% or less is still more preferable.
  • the monomer (X) may further contain a monomer other than farnesene. Examples of such other monomers include monomers capable of forming the monomer unit (b) described above.
  • the content of the other monomer in the monomer (X) used in the production method of the present invention is preferably in the range of 0 mol% or more and less than 50 mol%, more preferably in the range of 1 mol% or more and less than 50 mol%.
  • the range of 5 mol% or more and 40 mol% or less is more preferable, the range of 8 mol% or more and 35 mol% or less is more preferable, and the range of 10 mol% or more and 30 mol% or less is still more preferable.
  • the emulsion polymerization according to the production method of the present invention is performed in a latex in which the monomer (X) is dispersed in water.
  • the amount of the monomer (X) used with respect to 100 parts by mass of water is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and still more preferably 40 parts by mass or more from the viewpoint of productivity.
  • the amount of the monomer (X) is preferably 200 parts by mass or less, more preferably 100 parts by mass or less, and 80 parts by mass. The following is more preferable.
  • an emulsifier is usually used.
  • the emulsifier include anionic surfactants such as sodium alkylbenzene sulfonate, higher fatty acid sodium and rosin soap; nonionic surfactants such as alkyl polyethylene glycol and nonylphenol ethoxylate; distearyldimethylammonium chloride, benzalkco chloride Cationic surfactants such as nium; amphoteric surfactants such as cocamidopropyl betaine and cocamidopropylhydroxysultain can be used.
  • anionic surfactants such as sodium alkylbenzene sulfonate, higher fatty acid sodium and rosin soap
  • nonionic surfactants such as alkyl polyethylene glycol and nonylphenol ethoxylate
  • distearyldimethylammonium chloride benzalkco chloride Cationic surfactants
  • amphoteric surfactants such as cocamidopropyl betaine and co
  • a radical polymerization initiator (hereinafter simply referred to as “polymerization initiator”) is usually used.
  • polymerization initiators include water-soluble inorganic initiators, water-soluble azo initiators, oil-soluble azo initiators, and organic peroxides.
  • water-soluble inorganic initiator examples include hydrogen peroxide, sodium persulfate, and potassium persulfate.
  • Water-soluble azo initiators include 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) Propane] disulfate dihydrate, 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate, 2, , 2′-azobis [2- (2-imidazolin-2-yl) propane], 2-2′-azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride, 2,2′-azobis [ 2-methyl-N- (2-hydroxyethyl) propionamide] and the like.
  • oil-soluble azo initiators examples include 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′- Azobis (isobutyronitrile), 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl) Azo] formamide, 2,2′-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2′-azobis (N-butyl-2-methylpropionamide), dimethyl 2,2- And azobis (isobutyrate).
  • Organic peroxides include diacyl peroxides such as bis-3,5,5-trimethylhexanoyl peroxide, dilauroyl peroxide, and dibenzyl peroxide; 1,1,3,3-tetramethylbutyl hydroperoxide , Cumene hydroperoxide, hydroperoxide such as t-butyl hydroperoxide; dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,3-bis (t Dialkyl peroxides such as -butylperoxyisopropyl) benzene, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3; 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, 1,1-di-t-butyl
  • water-soluble azo initiators 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis [2- (2-imidazolin-2-yl) ) Propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate, 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2, 2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate, 2,2′-azobis [2- (2-imidazolin-2-yl) propane], and 2,2′- One or more kinds selected from azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride are preferred,
  • Rokishiechiru) propionamide is more preferable.
  • organic peroxides hydroperoxide is preferable, and cumene hydroperoxide is more preferable.
  • the amount of the polymerization initiator used is preferably 0.01 to 1 part by mass, more preferably 0.05 to 0.5 part by mass with respect to 100 parts by mass of water.
  • a reducing agent with the said polymerization initiator.
  • the reducing agent include iron compounds such as ferrous chloride and ferrous sulfate; sodium salts such as sodium hydrogen sulfate, sodium bisulfite, sodium sulfite, sodium hydrogen sulfite, and sodium hydrogen carbonate; ascorbic acid, longgarit, diiotin
  • organic reducing agents such as sodium acid, triethanolamine, glucose, fructose, glyceraldehyde, lactose, arabinose, and maltose.
  • the amount of the reducing agent used is preferably in the range of 0.001 to 0.2 parts by mass, more preferably in the range of 0.005 to 0.1 parts by mass with respect to 100 parts by mass of water.
  • the amount of the iron compound used is preferably 0.001 to 0.05 parts by mass, and 0.001 to 0.01 parts by mass with respect to 100 parts by mass of water.
  • the amount of the organic reducing agent used is preferably 0.005 to 0.1 parts by mass, more preferably 0.01 to 0.05 parts by mass with respect to 100 parts by mass of water.
  • additives such as ethylenediaminetetraacetic acid-2 sodium salt and potassium pyrophosphate can be used as necessary.
  • a chain transfer agent may be added to the emulsion polymerization system as necessary.
  • chain transfer agents include mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, hexadecyl mercaptan and n-octadecyl mercaptan; mercaptoacetic acid, 2-ethylhexyl mercaptoacetate, methoxybutyl mercaptoacetate, ⁇ -mercapto Thiols such as propionic acid, methyl ⁇ -mercaptopropionate, 2-ethylhexyl ⁇ -mercaptopropionate, 3-methoxybutyl ⁇ -mercaptopropionate, mercaptoethanol, 3-mercapto-1,2-propanediol; ⁇ -methyl Hydrocarbon compounds having a large chain transfer constant
  • a thickening inhibitor may be added to the emulsion polymerization system as necessary.
  • the thickening inhibitor include potassium chloride, sodium chloride, sodium acetate and the like.
  • the use amount of the thickening inhibitor is 20 parts by mass or less with respect to 100 parts by mass of the emulsifier from the viewpoint of the stability of micelles in the latex. Is preferably 10 parts by mass or less, more preferably 5 parts by mass or less.
  • the emulsion polymerization according to the production method of the present invention is performed by polymerizing in the latex containing the monomer (X), water, and, if necessary, the above-described emulsifier, reducing agent, additive, chain transfer agent, and thickening inhibitor. It is preferable to carry out by adding an initiator. It is preferable to sufficiently remove oxygen in the latex before adding the polymerization initiator.
  • the addition time is preferably 6 hours or less, and more preferably 4 hours or less.
  • the total addition time including the time not added is preferably 8 hours or less, more preferably 6 hours or less, and the interval between the addition times is preferably 2 hours or less to ensure the polymerization rate. From the viewpoint of the above, 1 hour or less is more preferable.
  • a water-soluble polymerization initiator When using a water-soluble polymerization initiator, it may be added as an aqueous solution, but when using a polymerization initiator that is sparingly soluble in water, an emulsion of the polymerization initiator is prepared in advance using water and an emulsifier, and this is used. It may be added. In this case, the emulsifier used may be the same as or different from that used in the emulsion polymerization. Two or more emulsifiers may be combined.
  • the polymerization temperature for emulsion polymerization is usually preferably in the range of 0 to 100 ° C., and preferably from 50 to 90 ° C. from the viewpoint of increasing the polymerization rate.
  • the farnesene polymer can be recovered from the emulsion-polymerized latex by a known method such as salting out, aciding out, freezing, or addition of a solvent.
  • the farnesene polymer thus recovered may be further purified by a known method such as washing, reprecipitation or steam stripping.
  • an antioxidant may be added from the viewpoint of suppressing the deterioration of the farnesene polymer.
  • the anti-aging agent may be subjected to a recovery process or a purification process for the farnesene polymer after being added to the latex after the emulsion polymerization from the viewpoint of suppressing deterioration in the recovery process and the purification process for the farnesene polymer after the polymerization reaction. .
  • the anti-aging agent may be removed in the recovery or purification treatment of the farnesene polymer. It is desirable to add it again later.
  • hydroquinone hydroquinone monomethyl ether, 2,5-di-t-butylphenol, 2,6-di (t-butyl) -4-methylphenol, mono (or di, or tri) ( ⁇ -methylbenzyl)
  • Phenolic compounds such as phenol; 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-thiobis Bisphenol compounds such as (3-methyl-6-t-butylphenol); benzimidazole compounds such as 2-mercaptobenzimidazole and 2-mercaptomethylbenzimidazole; 6-ethoxy-1,2-dihydro-2,2, 4-trimethylquinoline, reaction product of diphenylamine and acetone, 2,2,4-trimethyl-1 Amine-ketone compounds such as 2-dihydroquinoline polymers; N-phenyl-1-n
  • Anionic surfactant Rosin soap [Disproportionated rosin soap, trade name “Longis K-25” (solid content 25% by mass), manufactured by Arakawa Chemical Industries, Ltd.]
  • Water-soluble azo initiator 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] [trade name: VA-086, manufactured by Wako Pure Chemical Industries, Ltd.]
  • Hydroperoxide cumene hydroperoxide (reducing agent)
  • Iron compounds Ferrous sulfate (7 hydrate)
  • Organic reducing agent Rongalite (additive) ⁇ Ethylenediaminetetraacetic acid-2sodium salt ⁇ Potassium pyrophosphate (thickening inhibitor) ⁇ Potassium chloride (anti-aging agent) ⁇ 2,6-di (t-butyl) -4-methylphenol (BHT) [manufactured by Honshu Chemical Industry Co., Ltd.]
  • Example 1 Manufacture of farnesene polymer
  • ion-exchange water 186.5 g
  • emulsifier 18 g
  • 100 g of ⁇ -farnesene 100 g
  • thickening inhibitor potassium chloride
  • VA-086 0.25 g
  • VA-086 a water-soluble azo initiator
  • the obtained emulsion was put into acetone to precipitate and recover the polymer, 0.1 g of BHT was added, kneaded, and dried. The dried polymer was dissolved in THF to form a 5% by mass solution, which was added dropwise to about 5 times mass of methanol to reprecipitate. 0.1 g of BHT was added to the obtained polymer, kneaded, and then dried at 200 Pa and 25 ° C. for 48 hours to obtain a farnesene polymer (hereinafter also referred to as “polymer 1”). About the obtained polymer 1, it evaluated by the method mentioned later. The results are shown in Table 1.
  • Example 2 Preparation of polymerization initiator emulsion 0.17 g of a polymerization initiator (cumene hydroperoxide) and 0.11 g of an emulsifier (Longis K-25) were added to 5.96 g of ion-exchanged water and emulsified to obtain a polymerization initiator emulsion.
  • a polymerization initiator cumene hydroperoxide
  • an emulsifier Longis K-25
  • the polymerization initiator emulsion was added at a constant rate over 4 hours using a feed pump. After completion of the addition, the mixture was driven at 80 ° C. for 1 hour and polymerized for a total of 5 hours, and then cooled to 40 ° C. to complete the reaction, whereby an emulsion was obtained.
  • the obtained emulsion was put into acetone to recover the polymer, 0.1 g of BHT was added, kneaded, and dried. The dried polymer was dissolved in THF to form a 5% by mass solution, which was added dropwise to about 5 times mass of methanol to reprecipitate.
  • Example 3 Manufacture of farnesene polymer
  • polymer 3 a farnesene polymer (hereinafter referred to as “polymer 3”) was prepared in the same manner as in Example 2 except that instead of 100 g of ⁇ -farnesene, a mixture of 82 g of ⁇ -farnesene and 18 g of styrene was used. Obtained). The obtained polymer 3 was evaluated by the method described later. The results are shown in Table 1.
  • Comparative Example 1 Manufacture of farnesene polymer
  • a pressure-resistant container that has been purged with nitrogen and dried is charged with 1490 g of cyclohexane as a solvent and 1.24 g of sec-butyllithium (10.5 mass% cyclohexane solution) as a polymerization initiator, heated to 50 ° C., and then 300 g prepared in advance.
  • a mixture of butadiene and 1200 g of ⁇ -farnesene was added at 10 ml / min and polymerized for 1 hour. After adding 0.65 g of methanol to the obtained polymerization reaction liquid to stop the polymerization, the polymerization reaction liquid was washed with 1500 g of water.
  • polymer 4 The polymerization reaction solution after washing and water were separated and dried at 70 ° C. for 12 hours to obtain a farnesene polymer (hereinafter also referred to as “polymer 4”).
  • the obtained polymer 4 was evaluated by the method described later. The results are shown in Table 1.
  • Comparative Example 2 Manufacture of farnesene polymer
  • a pressure-resistant container purged with nitrogen and dried was charged with 1790 g of cyclohexane as a solvent and 0.9 g of sec-butyl lithium (10.5% by mass cyclohexane solution) as a polymerization initiator, heated to 50 ° C., and then added with 3 g of THF.
  • a mixture of 276 g of styrene and 924 g of ⁇ -farnesene prepared in advance was added at 10 ml / min and polymerized for 1 hour.
  • polymer 5 After adding 0.47 g of methanol to the obtained polymerization reaction solution to stop the polymerization, the polymerization reaction solution was washed with 1800 g of water. The polymerization reaction solution after washing and water were separated and dried at 70 ° C. for 12 hours to obtain a farnesene polymer (hereinafter also referred to as “polymer 5”). The obtained polymer 5 was evaluated by the method described later. The results are shown in Table 1.
  • Example 3 Manufacture of farnesene polymer
  • polymer 6 a farnesene polymer (hereinafter also referred to as “polymer 6”) was obtained in the same manner as in Example 3 except that the polymerization was performed at 5 ° C. The obtained polymer 6 was evaluated by the method described later. The results are shown in Table 1.
  • a solution obtained by filtering the diluted solution with a filter having a pore size of 0.45 ⁇ m was used as a measurement sample, and an SEC-MALS (size exclusion chromatography-multi-angle light scattering) apparatus [HPLC system (manufactured by Waters, “Allians Separation Module 2695”), Using a multi-angle light scattering detector (manufactured by Wyatt Technology, “DAWN E”), column (manufactured by Showa Denko KK, “LKF-806L” (two-wire connection))], analysis was performed under the following conditions. After determining the baseline correction and peak range, the absolute molecular weight (M) and the radius of inertia ⁇ r g 2 > 1/2 were determined.
  • SEC-MALS size exclusion chromatography-multi-angle light scattering
  • Mooney viscosity As an index of the molding processability of the rubber composition, the Mooney viscosity (after 1 minute of preheating and 4 minutes after the start of rotation) of the obtained farnesene polymer at 100 ° C. was measured according to JIS K6300. The smaller the value, the better the moldability.
  • Table 1 shows that Examples 1 to 3 each have an ⁇ value of less than 0.5, while Comparative Examples 1 to 3 have an ⁇ value of 0.5 or more. .
  • Examples 1 to 3 have a low Mooney viscosity and high fluidity, although they have a high molecular weight, compared with Comparative Examples 1 to 3. Therefore, according to the present invention, since the balance between molecular weight and viscosity is excellent, good moldability can be obtained.
  • the polymer of the present invention has a high molecular weight and high fluidity and is excellent in moldability, it can be suitably used for rubber compositions such as tires.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne : un polymère de farnesène qui comprend un motif monomère (a) dérivé du farnesène, pour lequel le rayon de giration (<rg 2>1/2) et la masse moléculaire absolue (M) dans une solution diluée de tétrahydrofurane, obtenus par une méthodologie de chromatographie d'exclusion diffusion-diffusion de lumière multi-angles, satisfont à la formule (1); et un procédé de production dudit polymère de farnesène par polymérisation en émulsion du monomère (X) comprenant le farnesène, de sorte que la vitesse de polymérisation soit supérieure ou égale à 60 %. log{<rg 2>1/2} = αlog(M) + β (1) (Dans la formule (1), α est une constante positive inférieure à 0,5 et β est une constante).
PCT/JP2016/068257 2015-06-30 2016-06-20 Polymère de farnesène et son procédé de production Ceased WO2017002651A1 (fr)

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WO2014157624A1 (fr) * 2013-03-29 2014-10-02 株式会社クラレ Polymère, son procédé de production et composition de résine contenant ledit polymère

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