WO2012056939A1 - Granulé de copolymère séquencé hydrogéné et procédé pour sa production - Google Patents

Granulé de copolymère séquencé hydrogéné et procédé pour sa production Download PDF

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WO2012056939A1
WO2012056939A1 PCT/JP2011/073909 JP2011073909W WO2012056939A1 WO 2012056939 A1 WO2012056939 A1 WO 2012056939A1 JP 2011073909 W JP2011073909 W JP 2011073909W WO 2012056939 A1 WO2012056939 A1 WO 2012056939A1
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crumb
block copolymer
mass
hydrogenated block
drying
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PCT/JP2011/073909
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English (en)
Japanese (ja)
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伸明 久保
孝夫 山口
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日本エラストマー株式会社
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Priority to CN201180051908.XA priority Critical patent/CN103189406B/zh
Priority to JP2012540785A priority patent/JP5591346B2/ja
Priority to SG2013030341A priority patent/SG189956A1/en
Publication of WO2012056939A1 publication Critical patent/WO2012056939A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/06—Treatment of polymer solutions
    • C08F6/12—Separation of polymers from solutions
    • 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
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes

Definitions

  • the present invention relates to a hydrogenated block copolymer crumb and a method for producing the same.
  • a hydrogenated block copolymer which is a hydrogenated product of a block copolymer composed of a vinyl aromatic hydrocarbon and a conjugated diene, has excellent resilience and low-temperature properties. It is used as a modifier to improve impact resistance, low temperature characteristics, workability, and the like.
  • the composition of the hydrogenated block copolymer and the thermoplastic resin is widely used in the fields of electric / electronic parts, automobile parts, various industrial parts, daily necessities and the like.
  • the high molecular weight hydrogenated block copolymer is excellent in mechanical properties in addition to the various properties described above, and therefore, by combining with a liquid softener such as oil, a plasticizer and a thermoplastic resin such as polypropylene, It is used as a material for various industrial parts such as electric cables and automobile parts.
  • the above-mentioned high molecular weight hydrogenated block copolymer is generally handled in the form of porous dry crumbs, not pellets, in order to improve kneadability with oil and the like during compounding.
  • Many proposals have hitherto been made regarding methods for obtaining such porous dry crumbs of hydrogenated block copolymers.
  • the water content is 1% by mass by further dehydrating and drying with an extrusion dehydrator.
  • Methods for obtaining the following polymer crumb are known (see, for example, Patent Documents 1 and 2).
  • the operating temperature of the extruder for dehydrating the hydrogenated block copolymer crumb and the water content of the slurry before charging the extruder were adjusted.
  • Dehydration / drying method using an extrusion dehydrator for example, see Patent Document 3
  • a method for drying a hydrogenated block copolymer crumb with a hot air dryer under a specific temperature condition for example, see Patent Document 4
  • Patent Document 4 a specific temperature condition
  • Patent Documents 1 and 2 are preferable as a method for obtaining a low molecular weight hydrogenated block copolymer crumb, but for high molecular weight hydrogenated block copolymer crumbs, oil absorption during compounding is preferred. In terms of sex, sufficient characteristics have not yet been obtained.
  • the high molecular weight hydrogenated block copolymer crumb obtained by the methods disclosed in Patent Documents 3 and 4 does not uniformly disperse oil throughout the crumb when compounded with a thermoplastic resin or oil. Furthermore, there is a problem that the compound processability is still unstable, for example, the crumb does not completely melt and remains as an unmelted polymer.
  • the present inventor in a compound of a high molecular weight hydrogenated block copolymer crumb and a softening agent such as a thermoplastic resin or process oil, the oil is uniformly dispersed throughout the crumb and the residual amount of unmelted polymer is suppressed.
  • a high molecular weight hydrogenated block copolymer comprising a vinyl aromatic hydrocarbon and a conjugated diene having a specific range of crumb specific surface area and particle size distribution. It has been found that a method for producing crumb and its hydrogenated block copolymer crumb comprising a specific dehydration / drying step can solve the above-mentioned problems of the prior art, and has completed the present invention. That is, the present invention is as follows.
  • a hydrogenated block copolymer crumb comprising a hydrogenated product of a block copolymer of a vinyl aromatic hydrocarbon and a conjugated diene and satisfying the following (1) to (4): (1) Main peak molecular weight is 200,000 to 600,000 (2) Moisture content is 1% by mass or less (3) Specific surface area is 0.3 to 1.0 m 2 / g (4) A component that passes through a sieve having an opening of 3.35 mm and does not pass through a sieve having an opening of 0.425 mm is 80% by mass or more of the total crumb [2] A method for producing a hydrogenated block copolymer crumb according to [1] above, comprising the following ⁇ Step 1> to ⁇ Step 3>.
  • ⁇ Step 1> An aqueous slurry containing a hydrogenated block copolymer crumb is dehydrated, and all crumb components that have a moisture content of more than 60% by mass and not more than 80% by mass and do not pass through a sieve having an opening of 3.35 mm are included. Obtaining a crumb that is 60% by weight or more of the crumb.
  • ⁇ Step 2> A step of dehydrating and drying the crumb obtained in ⁇ Step 1> to obtain a crumb having a water content of 3 to 30% by mass.
  • ⁇ Step 3> A step of drying the crumb obtained in ⁇ Step 2> to obtain a crumb having a moisture content of 1% by mass or less.
  • a hydrogenated block copolymer having an excellent compound processability such as a uniform dispersion of oil throughout the crumb, good oil absorbability (oil retention), and reduction of unmelted polymer.
  • a crumb is obtained.
  • the hydrogenated block copolymer crumb of this embodiment is a crumb made of a hydrogenated block copolymer of vinyl aromatic hydrocarbon and conjugated diene, and satisfies the following (1) to (4).
  • Main peak molecular weight is 200,000 to 600,000
  • Water content is 1% by mass or less
  • Specific surface area is 0.3 to 1.0 m 2 / g (4)
  • a component that passes through a sieve having an opening of 3.35 mm and does not pass through a sieve having an opening of 0.425 mm is 80% by mass or more of the total crumb.
  • the hydrogenated block copolymer crumb in this embodiment is obtained by adding hydrogen to a block copolymer consisting of a vinyl aromatic hydrocarbon and a conjugated diene as described above, and as shown in the above (1),
  • the main peak molecular weight is 200,000 or more from the viewpoint of mechanical strength and impact resistance when a predetermined polymer composition is used, and 600,000 or less from the viewpoint of workability and compatibility with a high-molecular substance such as a thermoplastic resin. It is.
  • the main peak molecular weight is preferably 230,000 to 500,000, more preferably 250,000 to 450,000.
  • the molecular weight of the main peak of the hydrogenated block copolymer can be measured using GPC (gel permeation chromatography) measurement and a calibration curve obtained from measurement of commercially available standard polystyrene. Specifically, it can measure by the method as described in the Example mentioned later.
  • GPC gel permeation chromatography
  • the hydrogenated block copolymer crumb of the present embodiment has a water content of 1% by mass or less as shown in (2) above. Thereby, when it is compounded with a predetermined thermoplastic resin to obtain a thermoplastic resin composition, it is possible to prevent poor appearance due to foaming, generation of silver or the like.
  • the hydrogenated block copolymer crumb of this embodiment preferably has a moisture content of 0.9% by mass or less, and more preferably 0.8% by mass or less.
  • the hydrogenated block copolymer crumb of this embodiment has a specific surface area of 0.3 to 1.0 m 2 / g, preferably 0.35 to 0.8 m 2 / g, as shown in (3) above. Preferably, it is 0.4 to 0.7 m 2 / g.
  • the hydrogenated block copolymer crumb of the present embodiment has a crumb size that passes through a sieve having an opening of 3.35 mm and does not pass through a sieve having an opening of 0.425 mm, as shown in (4) above. It is assumed that the component is 80% by mass or more, preferably 82% by mass or more, more preferably 85% by mass or more of the total crumb.
  • the oil absorbability becomes good, the oil absorption unevenness can be suppressed, the plastic can be uniformly plasticized at the time of compound preparation, and the number of unmelted polymers can be reduced. Can do.
  • the water content, specific surface area, and size of the hydrogenated block copolymer crumb can be determined by the method described in the examples described later.
  • a hydrogenated block copolymer is prepared, and then a predetermined treatment is performed to obtain a hydrogenated block copolymer crumb.
  • a block copolymer of a vinyl aromatic hydrocarbon and a conjugated diene compound is obtained by a polymerization reaction, and then a hydrogenation reaction is performed to obtain a hydrogenated block copolymer.
  • the block copolymer can be produced by polymerizing vinyl aromatic hydrocarbon and conjugated diene in a hydrocarbon solvent using an organolithium compound as a polymerization initiator.
  • vinyl aromatic hydrocarbon examples include styrene, ⁇ -methylstyrene, p-methylstyrene, 2-vinylnaphthalene, divinylbenzene and the like.
  • conjugated diene examples include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3 butadiene, 1,3-pentadiene, 1,3-heptadiene, and the like.
  • the vinyl aromatic hydrocarbon content of the block copolymer is preferably 90% by mass or less, more preferably 60% by mass or less, and still more preferably 40% by mass or less, from the viewpoint of improving the impact resilience. .
  • Examples of the method for producing the block copolymer include Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-171979, Japanese Patent Publication No. 46-32415, Japanese Patent Publication No. 49-36957, and Japanese Patent Publication No. 48-2423. Examples thereof include the methods described in Japanese Patent Publication Nos. 48-4106, 51-49567, and 59-166518.
  • Examples of the structure of the block copolymer include those represented by general formulas (AB) n , (AB) n -A, and B- (AB) n .
  • A is a polymer block mainly composed of vinyl aromatic hydrocarbons
  • B is a polymer block mainly composed of conjugated diene. The boundary between the A block and the B block does not necessarily have to be clearly distinguished.
  • N is an integer of 1 or more, preferably an integer of 1 to 5.
  • the polymer block A mainly composed of vinyl aromatic hydrocarbons contains 50% by mass or more of vinyl aromatic hydrocarbons, preferably 70% by mass or more of vinyl aromatic hydrocarbons and conjugated dienes. These copolymer blocks and / or vinyl aromatic hydrocarbon homopolymer blocks are shown.
  • the polymer block B mainly composed of a conjugated diene contains a conjugated diene in an amount exceeding 50% by mass, preferably a copolymer block of a conjugated diene and a vinyl aromatic hydrocarbon containing 60% by mass or more, and And / or a conjugated diene homopolymer block.
  • the polymer block A and the polymer block B are a copolymer block of a vinyl aromatic hydrocarbon and a conjugated diene, even if the vinyl aromatic hydrocarbon in the copolymer block is uniformly distributed, It may be distributed in a tapered shape.
  • a plurality of portions where the vinyl aromatic hydrocarbons are uniformly distributed and / or a portion where the portions are distributed in a tapered shape may coexist. Further, a plurality of portions having different vinyl aromatic hydrocarbon contents may coexist in the copolymer block portion.
  • the block copolymer constituting the hydrogenated block copolymer crumb of this embodiment may be any mixture of block copolymers represented by the above general formula.
  • the ratio of the vinyl aromatic hydrocarbon polymer block incorporated in the block copolymer before hydrogenation to the total vinyl aromatic hydrocarbon (of vinyl aromatic hydrocarbon) is preferably 50% by mass or more, and more preferably 70 to 98% by mass.
  • the block ratio of vinyl aromatic hydrocarbons is measured by a method of oxidatively decomposing a block copolymer with tertiary butyl peroxide using osmium tetroxide as a catalyst (IM KOLTHOFF, et al., J. Polym. Sci). .1,429 (1946)).
  • the microstructure (ratio of cis, trans, vinyl) of the conjugated diene polymer incorporated in the block copolymer before hydrogenation can be arbitrarily changed by using a polar compound described later.
  • the 1,2-vinyl bond content of the block copolymer before hydrogenation is preferably 10 to 80%, more preferably 25 to 75%.
  • the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds is 3 to 80%. Preferably, it is 5 to 70%.
  • the microstructure of the conjugated diene polymer incorporated in the block copolymer is that the block copolymer before hydrogenation is a carbon disulfide solution, and the infrared spectrum is in the range of 600 to 1000 cm ⁇ 1 using a solution cell. And can be determined according to the calculation formula of the method of Hampton (styrene-butadiene copolymer) by the absorbance at a predetermined wave number.
  • Hydrocarbon solvents used for the production of block copolymers include aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane, octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, etc.
  • An alicyclic hydrocarbon or an aromatic hydrocarbon solvent such as benzene, toluene, ethylbenzene or xylene can be used. These may be used alone or in combination of two or more.
  • the organolithium compound used as a polymerization initiator for the polymerization of the block copolymer is a compound in which one or more lithium atoms are bonded in the molecule, for example, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium. Sec-butyl lithium, tert-butyl lithium, hexamethylene lithium, butadienyl dilithium, isoprenyl dilithium, and the like. These may be used alone or in combination of two or more. Further, the organolithium compound may be added in portions during the polymerization in the production of the block copolymer.
  • a predetermined polar compound can be used for the purpose of adjusting the polymerization rate, changing the microstructure of the polymerized conjugated diene moiety, and the like.
  • polar compounds include ethers such as tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxybenzene, and 2,2-bis (2-oxolanyl) propane; Tertiary amine compounds such as methylethylenediamine, dipiperidinoethane, trimethylamine, triethylamine, pyridine, quinuclidine; alkali metal alkoxide compounds such as potassium tert-amylate, potassium tert-butylate, sodium tert-butylate, sodium amylate A phosphine compound such as triphenylphosphin
  • the polymerization temperature for producing the block copolymer is preferably ⁇ 10 to 150 ° C., more preferably 30 to 120 ° C.
  • the time required for the polymerization varies depending on the conditions, but is preferably within 48 hours, more preferably 0.5 to 10 hours.
  • the polymerization atmosphere is preferably an inert gas atmosphere such as nitrogen gas.
  • the polymerization pressure is not particularly limited as long as it is carried out within a range of pressure sufficient to maintain the monomer and solvent in a liquid phase within the above polymerization temperature range.
  • impurities that inactivate the catalyst and the living polymer for example, water, oxygen, carbon dioxide gas, and the like are not mixed in the polymerization system.
  • the hydrogenation catalyst is not particularly limited and is conventionally known
  • a so-called Ziegler type hydrogenation catalyst using an organic acid salt such as Ni, Co, Fe, Cr or a transition metal salt such as acetylacetone salt and a reducing agent such as organic aluminum (3) Ti, Ru Homogeneous hydrogenation catalysts such as so-called organometallic complexes such as organometallic compounds such as Rh and Zr are used.
  • Specific examples of the hydrogenation catalyst include Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No.
  • the hydrogenation catalyst described in JP-B-2-9041 can be used.
  • Preferred hydrogenation catalysts include a mixture with a titanocene compound and / or a reducing organometallic compound.
  • the titanocene compound compounds described in JP-A-8-109219 can be used.
  • (substituted) cyclopentadidi such as biscyclopentadienyl titanium dichloride and monopentamethylcyclopentadienyl titanium trichloride.
  • Examples thereof include compounds having at least one ligand having an enyl skeleton, an indenyl skeleton, or a fluorenyl skeleton.
  • Examples of the reducing organometallic compound include organic alkali metal compounds such as organolithium, organomagnesium compounds, organoaluminum compounds, organoboron compounds, and organozinc compounds.
  • the hydrogenation reaction is preferably carried out in the temperature range of 0 to 200 ° C, more preferably 30 to 150 ° C.
  • the hydrogen pressure used for the hydrogenation reaction is preferably 0.1 to 15 MPa, more preferably 0.2 to 10 MPa, and still more preferably 0.3 to 5 MPa.
  • the hydrogenation reaction time is preferably 3 minutes to 10 hours, more preferably 10 minutes to 5 hours.
  • the hydrogenation reaction can be any of a batch process, a continuous process, or a combination thereof.
  • the total hydrogenation rate after hydrogenation of the unsaturated double bond based on the conjugated diene compound incorporated in the block copolymer before hydrogenation can be arbitrarily selected according to the purpose and is not particularly limited.
  • 70% or more, more preferably 80% or more, and still more preferably 95% or more of the unsaturated double bond based on the conjugated diene compound in the block copolymer may be hydrogenated, and only a part is water. It may be attached.
  • the hydrogenation rate is preferably 10% or more and less than 70%, more preferably 15% or more and less than 65%, and further preferably 20% or more and less than 60%.
  • the hydrogenation rate of the hydrogenated block copolymer is measured by a nuclear magnetic resonance apparatus (NMR).
  • the hydrogenated block copolymer constituting the hydrogenated block copolymer crumb of this embodiment has a main peak molecular weight of 200,000 to 600,000.
  • the main peak molecular weight can be controlled by adjusting the amount of the polymerization initiator.
  • a crumbing agent may be used, and as the crumbing agent, an anionic surfactant, a cationic surfactant, or a nonionic surfactant is generally used.
  • the surfactant as the crumbing agent is generally added in an amount of 0.1 to 3000 ppm with respect to the water in the stripping zone.
  • water-soluble salts of metals such as Li, Na, K, Mg, Ca, Al, and Zn can also be used as a crumb dispersion aid.
  • ⁇ Step of recovering hydrogenated block copolymer crumb> As described above, an aqueous slurry obtained by dispersing a hydrogenated block copolymer crumb in water obtained by a steam stripping step is subjected to dehydration and drying treatments through the following steps to obtain a hydrogenated block copolymer crumb. Can be recovered. In the recovery step of the hydrogenated block copolymer crumb, ⁇ Step 1> dehydration treatment, ⁇ Step 2> dehydration treatment and drying treatment, and ⁇ Step 3> drying treatment described later are performed.
  • the dehydration process and the drying process may be performed by independent devices, each having a dehydration process unit and a drying process unit, and a so-called integrated type having a structure in which these units communicate with each other. You may perform using the following extrusion-type dryer.
  • the aqueous slurry is dehydrated to obtain a crumb having a moisture content of more than 60% by mass and 80% by mass or less and a crumb component not passing through a sieve having an opening of 3.35 mm is 60% by mass or more of the total crumbs.
  • the water content of the crumb after ⁇ Step 1> is preferably 62% by mass to 80% by mass, and more preferably 65% by mass to 75% by mass.
  • the crumb component which does not pass a sieve with a mesh opening of 3.35 mm after passing through ⁇ process 1> is 70 mass% or more of all crumbs, and it is more preferable that it is 80 mass% or more.
  • the dehydration treatment in ⁇ Step 1> can be performed by, for example, a rotary screen, a vibrating screen, a centrifugal dehydrator, or the like.
  • a decrease in polymer fluidity in the extruder in ⁇ Step 2> to be described later can be suppressed, and when the water content is 80% by mass or less, in Step 2 to be described later
  • the heat load on the polymer crumb in the extruder can be suppressed.
  • the dehydration and drying treatment in ⁇ Step 2> described later can be performed stably, and the desired crumb Specific surface area and particle size distribution can be obtained, and excellent compound workability can be achieved.
  • the crumb that has been dehydrated in ⁇ Step 1> and has a predetermined moisture content is made into a crumb having a moisture content of 3 to 30% by mass by performing the dehydration treatment and the drying treatment in ⁇ Step 2> It transfers to ⁇ process 3> mentioned later.
  • the water content of the crumb after the ⁇ Step 2> is preferably 3 to 25% by mass, and more preferably 3.2 to 20% by mass.
  • the dehydration treatment and the drying treatment may be performed by independent devices, but a so-called integrated extrusion dryer having a structure in which the dehydration treatment means and the drying treatment means are communicated with each other is used. You may go.
  • the extrusion dryer is a device that performs a dehydration process and a drying process, and includes a dehydration process unit and a drying process unit.
  • the dehydration process unit includes an extruder (an extruder-type water squeezer) and a drying process unit.
  • a kneader type dryer, a screw type expander type dryer or the like is employed.
  • the dehydrating means includes a single screw or twin screw multi-screw extruder and the drying means includes a screw dryer.
  • a combination of a single screw extruder and a screw dryer is particularly preferable.
  • a dehydrating apparatus and a drying apparatus for performing ⁇ Step 2> an extrusion dryer in which the dehydrating means and the drying means are integrated, specifically, a screw-type extruder,
  • the screw-type dryer, the integrated screw extruder-type dryer, and the like may be provided with a vent mechanism and a dewatering slit according to the purpose of use.
  • the moisture content of the crumb By setting the moisture content of the crumb to 3% by mass or more by ⁇ Step 2>, it is possible to prevent the crumb from gelling and / or decomposing by the shearing force of the extruder, and the moisture content is set to 30% by mass or less. Thus, it is possible to easily control the moisture content of the crumb obtained by ⁇ Step 3> described later to 1% by mass or less.
  • the outlet temperature of the apparatus that performs the drying process in ⁇ Step 2> that is, when the dehydration process and the drying process are performed separately, the outlet temperature of the apparatus that performs the dehydration process is set to 120 ° C. or less and the drying process is performed. It is preferable that the outlet temperature of the apparatus for performing the above is 135 to 175 ° C. More preferably, the outlet temperature of the apparatus for performing the dehydration treatment is 120 ° C. or less, the outlet temperature of the apparatus for performing the drying treatment is 138 to 172 ° C., and more preferably, the outlet temperature of the apparatus for performing the dehydration treatment is 118 ° C.
  • the outlet temperature of the drying apparatus is set to 140 to 172 ° C.
  • the temperature at the first stage outlet is set to 120 ° C. or lower, and the temperature at the second stage outlet. Is preferably 135 to 175 ° C. More preferably, the temperature at the first stage outlet is 120 ° C. or lower, the temperature at the second stage outlet is 138 to 172 ° C., more preferably the temperature at the first stage outlet is 118 ° C. or lower, and The temperature is 140-172 ° C.
  • the crumb obtained in ⁇ Step 2> is dried with a hot air dryer to obtain a crumb having a moisture content of 1% by mass or less.
  • the water content of the crumb after the ⁇ Step 3> is 1% by mass or less, preferably 0.95% by mass or less, and more preferably 0.9% by mass or less.
  • the aqueous slurry is dehydrated by ⁇ Step 1>, and the crumb component that has a moisture content of more than 60% by mass and not more than 80% by mass and does not pass through a sieve having an opening of 3.35 mm is 60% by mass of the total crumbs.
  • the crumb component that has a moisture content of more than 60% by mass and not more than 80% by mass and does not pass through a sieve having an opening of 3.35 mm is 60% by mass of the total crumbs.
  • the water content and size of the hydrogenated block copolymer crumb can be determined by the method described in the examples described later.
  • the crumb size and moisture content in the above ⁇ Step 1> and further defining the outlet temperature in the apparatus and the moisture content of the crumb at the outlet through ⁇ Step 1> to ⁇ Step 3>,
  • the pulsating flow in the device is also suppressed, and fine crumbs (passing through a sieve with an opening of 0.425 mm, sandy hard crumb) and large particle crumbs (passing through a sieve with an opening of 3.35 mm) Uniform crumbs with less foaming) are obtained.
  • the hydrogenated block copolymer crumb of this embodiment has a specific surface area of 0.3 to 1.0 m 2 / g. Moreover, the component which passes a sieve with an opening of 3.35 mm and does not pass a sieve with an opening of 0.425 mm is 80 mass% or more of the total crumbs. In order to obtain such a crumb, it is particularly effective to adjust the size and moisture content of the crumb before entering ⁇ Process 2> and optimize the dehydration and drying conditions in ⁇ Process 2>. is there. Specifically, if the water content of the crumb after passing through ⁇ Step 1> is too small as 60% or less, it will be dehydrated too much in ⁇ Step 2> and the fluidity will decrease.
  • ⁇ Step 2> if the water content is too high (over 80%) or the crumb size is too small to pass through a sieve having an opening of 3.35 mm, the dehydration and drying process can be stably performed in ⁇ Step 2>. It is not possible to obtain good fluidity.
  • ⁇ Step 2> if the water content of crumb is too high, the load in ⁇ Step 3> increases, and if the water content of crumb is too low, the fluidity of the crumb is lowered and foaming becomes uneven. The crumb size is uneven.
  • the outlet temperature of the apparatus in the drying process is set to 135 to 175 ° C. in ⁇ Step 2>. It is preferable. Therefore, as described above, in ⁇ Step 1>, the moisture content of the crumb is adjusted to be more than 60% by mass and 80% by mass or less, and the crumb component that does not pass through the sieve having a mesh size of 3.35 mm is 60% by mass of the total crumbs As described above, it is effective to control the water content of crumb to be 3 to 30% by mass in ⁇ Step 2>.
  • the hydrogenated block copolymer crumb of the present embodiment is prepared by using a predetermined thermoplastic resin or a softening agent such as process oil to produce a thermoplastic composition that can be used for various applications described later. it can.
  • a compound with a thermoplastic resin such as propylene and a softening agent such as process oil various additives can be blended depending on the purpose.
  • the type of additive is not particularly limited as long as it is generally used for blending thermoplastic resins and rubber-like polymers.
  • inorganic fillers such as metal hydroxides, silica-based inorganic fillers, metal oxides, organic fillers, antioxidants, UV absorbers and light stabilizers, stearic acid, behenic acid, zinc stearate, stear With lubricants such as calcium phosphate, magnesium stearate, ethylene bisstearamide, mold release agent, paraffin, plasticizer, flame retardant, antistatic agent, organic fiber, carbon fiber, metal whisker and other reinforcing materials, pigments, colorants, etc. is there.
  • lubricants such as calcium phosphate, magnesium stearate, ethylene bisstearamide, mold release agent, paraffin, plasticizer, flame retardant, antistatic agent, organic fiber, carbon fiber, metal whisker and other reinforcing materials, pigments, colorants, etc. is there.
  • additives may be added to the hydrogenated block copolymer crumb solution, or may be added in the dehydration step and / or the drying step, or may be added after the drying step.
  • the hydrogenated block copolymer crumb of this embodiment includes various thermoplastic resin modifiers, footwear materials, adhesive / adhesive materials, asphalt modifiers, industrial parts such as electric cables, automobile parts, and medical use. It can be used as a material for appliance materials, home appliances and parts thereof, electronic devices and parts thereof, household goods, toys and the like.
  • ⁇ Vinyl bond content> A carbon disulfide solution of a sample for measurement (a block copolymer produced according to Production Example 1 below) is prepared, and an infrared spectrum is 600 to 1000 cm ⁇ 1 using an infrared spectrophotometer (Spectraum 100 manufactured by PerkinElmer Japan). And the absorbance at a predetermined wave number was determined according to the formula for the method of Hampton (styrene-butadiene copolymer).
  • the hydrogenation rate of the hydrogenated block copolymer was measured using a nuclear magnetic resonance apparatus (DPX-400 manufactured by BRUCKER).
  • paraffinic process oil Diaffinic process oil (Diana Process Oil PW90 manufactured by Idemitsu Petrochemical Co., Ltd.) colored by dropping ink, and stirred so that the process oil was distributed throughout the crumb. Allowed to stand for 10 minutes. The image of the entire crumb after standing was binarized, and the area ratio of the colored portion (the ratio of the crumb that absorbed oil) was calculated.
  • paraffinic process oil colored with ink Diana Process Oil PW90 manufactured by Idemitsu Petrochemical Co., Ltd.
  • Oil holding power mass of paraffinic process oil (10 g) / [crumb total mass (10 g) ⁇ mass of crumb not colored with ink (g)]
  • the oil retention force is high, it means that the oil has accumulated above the crumb, and a certain amount of oil could be held with a small amount of crumb.
  • An unmelted polymer refers to a polymer in which crumbs are not completely melted and remain in the compound.
  • 24.57 g of paraffinic process oil (Diana Process Oil PW90 manufactured by Idemitsu Petrochemical Co., Ltd.) was added to 16.38 g of the hydrogenated block copolymer crumb and stirred so that the process oil spread evenly. Next, it was allowed to stand for 20 minutes at room temperature to absorb oil.
  • FIG. 1 shows a cross-sectional photograph of a sheet having the fish eye (unmelted polymer, diameter A). Actually, the fish eyes were observed as dots on the surface. The difference in the number of fish eyes (unmelted polymer) after 3 minutes (compound becomes uniform but unmelted polymer remains) and after 20 minutes (all unmelted polymer melts) is unmelted in the compound. The number of polymers.
  • 68 parts by mass of butadiene is supplied for polymerization, and finally, 16 parts by mass of styrene is supplied for polymerization to block the block copolymer of the SBS structure (S is a polystyrene block and B is a polybutadiene block). Coalescence was obtained.
  • the resulting block copolymer had a styrene content of 32% by mass, a main peak molecular weight of 280,000, and a vinyl bond content of the butadiene portion of 36%.
  • the steam stripping was carried out by adding the amount of styrene-maleic anhydride copolymer Na salt (hereinafter referred to as “crumbing agent A”) shown in Table 1 as a crumbing agent.
  • concentration of the hydrogenated block copolymer crumb in the obtained aqueous slurry was 5% by mass.
  • the aqueous slurry containing the hydrogenated block copolymer crumb obtained above is sent to a vibrating screen having a mesh opening of 1 mm and subjected to dehydration treatment ( ⁇ Step 1>), and then the method of (4) above
  • the water content of the hydrogenated block copolymer crumb that had undergone ⁇ Step 1> was measured, and the crumb size was measured by the method of (6) above.
  • Table 1 below shows the water content (% by mass) and the crumb size (ratio of components that do not pass through a sieve having an opening of 3.35 mm) (% by mass) of the hydrogenated block copolymer crumb obtained by ⁇ Step 1>. .
  • the crumbs of Examples 1 to 4 have good oil absorption uniformity, high oil retention, and the number of unmelted polymers in the compound is 10 or less, while the crumbs of Comparative Examples 1 to 4 are practical. Good oil absorption uniformity was not obtained, the oil retention was low, and the number of unmelted polymers in the compound was 15 or more.
  • Table 2 below shows the water content (% by mass) and the crumb size (ratio of components that do not pass through a sieve having an opening of 3.35 mm) (% by mass) of the hydrogenated block copolymer crumb obtained by ⁇ Step 1>.
  • the hydrogenated block copolymer crumb is supplied to a two-stage single-screw extruder in which a dehydrating means (first stage) and a drying means (second stage) are integrated, and the screw speed is about 80 rpm. Then, dehydration treatment and drying treatment were performed (first step and second step of ⁇ Step 2>).
  • the used two-stage single-screw extruder has a slit in the first-stage dewatering treatment means, but in order to keep the water in the crumb up to the second-stage drying treatment means, the slit is fully closed.
  • Table 2 below shows the respective outlet temperatures (first-stage outlet temperature, second-stage outlet temperature) of the dehydration treatment means and the drying treatment means, and the moisture content of the crumb obtained from the outlet of the drying treatment means.
  • the hydrogenated block copolymer crumb obtained above was dried with hot air of about 90 ° C. using a vibration transport dryer to obtain a dried crumb ( ⁇ Step 3>).
  • the water content, specific surface area, crumb size, oil absorption uniformity, oil retention, and number of unmelted polymers in the compound of the finally obtained hydrogenated block copolymer crumb are shown in Table 2 below.
  • the crumbs of Examples 5 to 8 have good oil absorption uniformity, high oil retention, and the number of unmelted polymers in the compound is 10 or less, while the crumbs of Comparative Examples 5 to 8 are practical. Good oil absorption uniformity was not obtained, oil retention was low, and the number of unmelted polymers in the compound was 15 or more. Moreover, the comparative example 9 had too much water content of the crumb, and could not be put into a dryer, and it was impossible to perform a dehydration process and a drying process.
  • Table 2 below shows the moisture content (% by mass) and the crumb size (ratio of components that do not pass through a sieve having an opening of 3.35 mm) (% by mass) of the crumb obtained in ⁇ Step 1>.
  • This crumb was subjected to a drying treatment with hot air of about 90 ° C. using a vibration transport dryer without performing the above-described ⁇ Step 2> to obtain a dried crumb ( ⁇ Step 3>).
  • the water content, specific surface area, crumb size, oil absorption uniformity, oil retention, and number of unmelted polymers in the compound of the finally obtained hydrogenated block copolymer crumb are shown in Table 2 below.
  • the crumb of Comparative Example 11 did not have a practically good oil absorption uniformity, had a low oil retention, and had 15 or more unmelted polymers in the compound.
  • Comparative Example 10 is an example in which ⁇ Step 3> was not performed after ⁇ Step 1> and ⁇ Step 2> under the same conditions as Comparative Example 8, and the crumb after ⁇ Step 2> was performed. The characteristics were shown. Moreover, in Table 2, Comparative Example 11 showed the characteristics of crumbs after performing ⁇ Step 3> without performing ⁇ Step 2> after performing ⁇ Step 1>.
  • the hydrogenated block copolymer crumb of the present invention is used industrially as a material for medical instrument materials, home appliances and parts thereof, electronic devices and parts thereof, various industrial parts such as electric cables, automobile parts, toys and the like. there is a possibility.

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

L'invention vise à produire un granulé de copolymère séquencé hydrogéné qui peut présenter d'excellentes propriétés de formation de mélange, y compris la dispersion homogène d'une huile dans tout le granulé lors de la formation d'un mélange avec l'huile, la diminution de granulés non fondus et similaire. Le granulé de copolymère séquencé hydrogéné de l'invention comprend un produit hydrogéné d'un copolymère séquencé d'un hydrocarbure vinylique aromatique et d'un diène conjugué et qui satisfait aux exigences (1) à (4) suivantes : (1) la masse moléculaire du pic principal de la distribution de la masse moléculaire est de 200 000 à 600 000 ; (2) la teneur en eau est inférieure ou égale à 1 % en masse ; (3) la surface spécifique est de 0,3-1,0 m2/g ; et (4) un composant qui passe à travers un tamis ayant une ouverture de maille de 3,35 mm mais qui ne passe pas à travers un tamis ayant une ouverture de maille de 0,425 mm est contenu en une quantité supérieure ou égale à 80 % en masse par rapport à la quantité totale de tous les granulés.
PCT/JP2011/073909 2010-10-28 2011-10-18 Granulé de copolymère séquencé hydrogéné et procédé pour sa production WO2012056939A1 (fr)

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JP2016222760A (ja) * 2015-05-27 2016-12-28 日本エラストマー株式会社 ブロック共重合体クラム及びその製造方法
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EP4265646B1 (fr) 2022-04-18 2024-10-16 Japan Elastomer Co., Ltd. Chapelure de copolymère séquencé ou produit hydrogéné de celle-ci et composition d'asphalt

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JP2015044909A (ja) * 2013-08-27 2015-03-12 サンノプコ株式会社 クラム脱水工程用喰込み性改良剤及びゴム状重合体の製造方法
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WO2015108139A1 (fr) * 2014-01-17 2015-07-23 旭化成ケミカルズ株式会社 Polymère et composition d'asphalte
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JPWO2015108139A1 (ja) * 2014-01-17 2017-03-23 旭化成株式会社 重合体及びアスファルト組成物
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KR101789003B1 (ko) 2014-05-20 2017-11-15 아사히 가세이 가부시키가이샤 블록 공중합체의 크럼 및 점접착제 조성물
CN106459250B (zh) * 2014-05-20 2018-09-28 旭化成株式会社 嵌段共聚物的屑粒和粘着粘结剂组合物
JPWO2015178260A1 (ja) * 2014-05-20 2017-04-20 旭化成株式会社 ブロック共重合体のクラム及び粘接着剤組成物
WO2015178260A1 (fr) * 2014-05-20 2015-11-26 旭化成ケミカルズ株式会社 Granule de copolymère séquencé et composition adhésive
CN106459250A (zh) * 2014-05-20 2017-02-22 旭化成株式会社 嵌段共聚物的屑粒和粘着粘结剂组合物
KR20160147831A (ko) 2014-05-20 2016-12-23 아사히 가세이 가부시키가이샤 블록 공중합체의 크럼 및 점접착제 조성물
RU2647856C1 (ru) * 2014-05-20 2018-03-21 Асахи Касеи Кабусики Кайся Крошка блок-сополимера и чувствительная к давлению клеевая композиция
WO2016052279A1 (fr) * 2014-09-29 2016-04-07 株式会社クラレ Procédé de production d'un complexe de tebbe
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JPWO2016052279A1 (ja) * 2014-09-29 2017-07-27 株式会社クラレ テッベ錯体の製造方法
JP2016186049A (ja) * 2015-03-27 2016-10-27 日本エラストマー株式会社 ブロック共重合体組成物、粘接着剤組成物及びこれらの製造方法
JP2016222760A (ja) * 2015-05-27 2016-12-28 日本エラストマー株式会社 ブロック共重合体クラム及びその製造方法
JP2019131810A (ja) * 2018-02-02 2019-08-08 旭化成株式会社 共役ジエン系重合体のクラム及びベール成形体
KR20190094110A (ko) * 2018-02-02 2019-08-12 아사히 가세이 가부시키가이샤 공액 디엔계 중합체의 크럼 및 베일 성형체
KR102336847B1 (ko) * 2018-02-02 2021-12-09 아사히 가세이 가부시키가이샤 공액 디엔계 중합체의 크럼 및 베일 성형체
JP7333695B2 (ja) 2018-02-02 2023-08-25 旭化成株式会社 共役ジエン系重合体のクラム及びベール成形体

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