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WO2007125597A1 - Procede de production de particules de resine - Google Patents

Procede de production de particules de resine Download PDF

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Publication number
WO2007125597A1
WO2007125597A1 PCT/JP2006/308998 JP2006308998W WO2007125597A1 WO 2007125597 A1 WO2007125597 A1 WO 2007125597A1 JP 2006308998 W JP2006308998 W JP 2006308998W WO 2007125597 A1 WO2007125597 A1 WO 2007125597A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
isobutylene
producing
weight
rosin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2006/308998
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English (en)
Japanese (ja)
Inventor
Keizo Hayashi
Tomoyuki Yoshimi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kaneka Corp
Original Assignee
Kaneka Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kaneka Corp filed Critical Kaneka Corp
Priority to PCT/JP2006/308998 priority Critical patent/WO2007125597A1/fr
Publication of WO2007125597A1 publication Critical patent/WO2007125597A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08J2323/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08J2323/22—Copolymers of isobutene; butyl rubber

Definitions

  • the present invention relates to a method for producing a cocoa powder granule, and more particularly to a method for producing a cocoa powder granule having an isobutylene block copolymer power.
  • Patent Document 4 discloses a method of dusting powdered minerals and organic substances after drying
  • Patent Document 5 discloses a method of dusting polypropylene fine particles.
  • the blocking property of the product is the same for the isobutylene-based block copolymer.
  • the powdered resin is recovered without any surface modifier, there is clogging in the recovery hopper! Blocking occurred and troubles such as inability to pay out occurred, and clogging troubles occurred in the process before dehydration and drying of the powdered resin slurry.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 64-26644
  • Patent Document 2 Japanese Patent Laid-Open No. 4-300947
  • Patent Document 3 Japanese Patent Laid-Open No. 7-3106
  • Patent Document 4 JP-A-10-330404
  • Patent Document 5 JP 2002-371136 A
  • the present invention stably provides a resin particle having excellent blocking properties without deterioration of quality, in particular, transparency, particularly a resin particle of an isobutylene block copolymer.
  • the object is to provide a method that can be manufactured.
  • the present invention relates to a method for producing a coconut powder granule, characterized in that colloidal silica having a particle size of 0.1 to 0.3 m is added to an aqueous solution containing rosin powder particles.
  • a preferred embodiment is a method for producing a rosin powder granule, characterized in that 0.01 to 5 parts by weight of colloidal silica is added to 100 parts by weight of the polymer in the rosin powder granule. .
  • a preferred embodiment is a method for producing an isobutylene-based greaves powder, which is a polymer-powered sobutylene-based polymer.
  • the isobutylene polymer is
  • Examples thereof include a method for producing a coconut powder granule, which is a powerful block copolymer.
  • the invention's effect include a method for producing a coconut powder granule, which is a powerful block copolymer.
  • water is added to a polymer solution obtained by polymerizing one or more monomer components, and then the solution is heated and agitated, whereby the polymer is powdered.
  • the present invention can be widely applied to the manufacturing method of sallow powder granules.
  • the polymer to which the method according to the present invention is applied is not particularly limited, and can be applied to polymers obtained by various polymerization methods such as cationic polymerization, cation polymerization and radical polymerization. In particular, because of its high viscoelasticity, it can be used for isobutylene polymers for which it is difficult to obtain a powder having a good balance between blocking properties and transparency by conventional methods.
  • the isobutylene polymer comprises (A) a polymer block mainly composed of isobutylene, and (B) an isobutylene copolymer composed mainly of a polymer block mainly composed of an aromatic vinyl monomer.
  • a polymer obtained by cationic polymerization of a monomer such as isoprene and an aromatic vinyl monomer together with an initiator in the presence of a Lewis acid catalyst is preferable.
  • the polymer block composed mainly of isobutylene of (A) is usually a polymer block containing 60% by weight or more, preferably 80% by weight or more of isobutylene units.
  • the polymer block composed mainly of the aromatic bulle monomer (B) is usually a polymer containing 60% by weight or more, preferably 80% by weight or more of the aromatic bule monomer unit. It is a block.
  • the aromatic bur monomer is not particularly limited, and examples thereof include styrene, o-, m- or P-methylstyrene, a-methylstyrene, and indene. These may be used alone or in combination of two or more. Of these, styrene, p-methylstyrene, a- methylstyrene or a mixture thereof is particularly preferable from the viewpoint of cost.
  • the Lewis acid catalyst used in the polymerization is not particularly limited as long as it can be used for cationic polymerization, and examples thereof include metal halides such as TiCl, BC1, BF, A1C1, and SnCl. Among these forces, tetrasalt-titanium (TiCl 3) is preferable.
  • the polymerization solvent used in the cationic polymerization is not particularly limited, and a solvent composed of a halogenated hydrocarbon, a non-halogen solvent, or a mixture thereof can be used.
  • a solvent composed of a halogenated hydrocarbon, a non-halogen solvent, or a mixture thereof can be used.
  • it is a mixed solvent of primary and Z or secondary monohalogen hydrocarbons having 3 to 8 carbon atoms and aliphatic and Z or aromatic hydrocarbons.
  • the primary and Z or secondary monohalogenated hydrocarbons having 3 to 8 carbon atoms are not particularly limited, and examples thereof include methyl chloride, methylene chloride, 1 chlorobutane, and black benzene. .
  • 1-chlorobutane is preferable from the standpoint of the solubility of the isobutylene block copolymer, the ease of detoxification by decomposition, the cost, and the like.
  • the aliphatic and Z or aromatic hydrocarbons are not particularly limited, and examples thereof include pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane, and toluene. Can be mentioned. One or more selected from the group consisting of methylcyclohexane, ethylcyclohexane and toluene power are particularly preferred.
  • X represents a halogen atom, an alkoxy group having 1 to 6 carbon atoms or an acyloxy group.
  • R 1 and R 2 are the same or different and each represents a monovalent hydrocarbon group hydrogen atom or 1 to 6 carbon atoms, R 1 and R 2 may be different even in the same.
  • R 3 represents a polyvalent aromatic hydrocarbon group or a polyvalent aliphatic hydrocarbon group.
  • n represents a natural number from 1 to 6.
  • Specific examples of the compound represented by the general formula (I) include 1,4 bis (chloroisopropyl) benzene [C H (C (CH) C1)].
  • Propyl) benzene is also called dicumulant mouth ride.
  • an electron donor component may be further present if necessary.
  • electron donor component examples include pyridines, amines, amides, sulfoxides, esters, or metal compounds having an oxygen atom bonded to a metal atom.
  • each component is cooled, for example, 100 ° C or higher and lower than 0 ° C.
  • Mix at the temperature of In order to balance the energy cost and the stability of the polymerization, it is particularly preferred that the temperature range is from 80 ° C to 1-30 ° C.
  • the number average molecular weight of the isobutylene block copolymer is not particularly limited.
  • the polymer solution obtained by polymerizing the monomer component by a predetermined method is brought into contact with water or alkali water to deactivate the catalyst to stop the reaction, and then washed with water.
  • the catalyst residue extracts and removes metal ions. Thereby, a purified dope can be obtained.
  • the temperature of catalyst deactivation and water washing is not particularly limited, but is preferably in the range of room temperature to 100 ° C. Further, the amount of water used for deactivation and washing is not particularly limited, but the volume ratio of water to the polymer solution is preferably in the range of 1 Z 10 to 10.
  • the purified polymer solution obtained in this manner is subsequently subjected to the powder and granulation step (1) (also referred to as a crumbization step).
  • the concentration of the resin in the polymer solution is 10 to 60% by weight by adding the solvent used for the polymerization as necessary.
  • the concentration can be adjusted to a desired concentration by using one or more evaporators such as flash evaporation, thin film evaporation, stirring tank, and wet wall type.
  • the polymer solution concentration is high, it can be adjusted to a desired concentration by diluting with a solvent.
  • the purified polymer solution thus obtained ie, the catalyst solution deactivated and the polymer solution removed is added with a surfactant and water, and the solution is dispersed in a liquid and liquid state by stirring, and the solvent is removed by heating.
  • a surfactant and water By the step (1) of removing, an aqueous solution containing rosin powder particles can be obtained.
  • the amount of water to be added is not particularly limited, but is preferably added in a volume of 0.5 to 4 times that of the polymer solution in view of liquid-liquid dispersion.
  • a nonionic surfactant is preferably used because of its low foaming.
  • the nonionic surfactant include glycerin fatty acid ester, sorbitan ester, propylene glycol fatty acid ester, Sucrose fatty acid ester, Cenoic acid mono (or di or tri) stearic ester, Pentaerystol fatty acid ester, Trimethylo Propropane fatty acid ester, Polyglycerin fatty acid ester, Polyoxyethylene glycerin fatty acid ester, Polyester, Polyoxyethylene sorbitan fatty acid ester, Polyethylene glycol fatty acid ester, Polypropylene glycol fatty acid ester, Polyoxyethylene glycol fatty alcohol ether, Polyoxyethylene alkyl Examples include phenol ether, N, N bis (2-hydroxyethylene) fattyamine, condensation product of fatty acid and ethanol, block polymer of polyoxyethylene and polyoxypropylene, polyethylene glycol, and polypropylene
  • the amount of the surfactant to be added is not particularly limited, but is preferably 0.05 to 5 parts by weight based on the polymer. If the amount is less than 0.05 parts by weight, the properties as a surfactant cannot be sufficiently exhibited, and particles are not formed. On the other hand, when the amount exceeds 5 parts by weight, the physical properties of the polymer are deteriorated, and the problem of foaming at the time of granulation becomes remarkable.
  • a container equipped with a stirrer is preferably used as an apparatus used for liquid-liquid dispersion by stirring and solvent removal.
  • Arbitrary blades such as screw blades, probe blades, anchor blades, paddle blades, inclined paddle blades, turbine blades, and large lattice blades can be used.
  • liquid-liquid dispersion operation and solvent removal operation can be performed using the same stirring tank, and after the liquid-liquid dispersion operation is performed in advance to form a dispersion, a plurality of solvent removals are subsequently performed. It can also be carried out using a stirring tank.
  • the liquid temperature in the step (1) is not particularly limited, but is preferably equal to or higher than the azeotropic point of the solvent and water. However, even if the azeotropic point is less than that, the solvent can be easily removed by reducing the pressure in the container. Specifically, it is preferably 70 ° C or higher and lower than 130 ° C, more preferably 80 ° C or higher and lower than 110 ° C. If it is 70 ° C or lower, the solvent removal rate is lowered, which is not preferable in terms of production efficiency. If the temperature is 130 ° C or higher, the function of the nonionic surfactant is lost and a stable liquid-liquid dispersion system cannot be formed.
  • the obtained aqueous solution containing rosin powder particles is charged with 0.1 to 0.3 / zm of colloidal silica and heated with stirring.
  • the steam stripping step (2) By passing through the steam stripping step (2), the remaining solvent can be further removed, and at the same time, the added colloidal silica can be efficiently attached to the surface of the resin powder granules. This improves the blocking properties of the powder after dehydration. Therefore, it is possible to perform the dispensing without having to be blocked by a recovery hopper or piping.
  • the dehydrated greaves powder particles are not clogged in the process before being dried, and can be stably produced without deteriorating the quality of the obtained product, in particular, without losing transparency.
  • the heating temperature during the treatment is preferably 70 to 180 ° C. in order to effectively attach colloidal silica to the surface of the resin particle.
  • the temperature is 70 ° C or lower, colloidal silica does not adhere to the resin efficiently, and the blocking effect is not sufficient.
  • the temperature is 180 ° C. or higher, fusion between the cocoons becomes remarkable and coarse particles are generated, which is preferable.
  • colloidal silica examples include colloidal liquid in which silica is dispersed in a solvent. Solvents are good for handling. Dispersed in water is preferred. Silica is preferably nearly spherical.
  • the amount of colloidal silica to be added is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the polymer in the resin particles. Less than 01 parts by weight, the effect as an antiblocking agent is not sufficient. On the other hand, when the amount exceeds 5 parts by weight, the physical properties of the polymer are deteriorated, particularly the mechanical properties such as the tensile strength are markedly reduced.
  • Colloidal silica having a particle size of 0.1 to 0.3 ⁇ m is used.
  • the particle size is 0.1 m or less, the transparency of the resin after drying is good, but the effect of improving the blocking property is insufficient.
  • the particle size is 0.3 m or more, the blocking effect is sufficiently improved, but the transparency of the resin after drying is impaired.
  • the vessel used for the steam stripping step (2) is preferably used as a method for introducing steam into the stirring vessel as in the case of suspension and solvent removal operation, as long as piping for introducing steam is connected.
  • the Further, the steam stripping operation can be performed by ventilating steam in the same tank following the solvent removal, or can be performed by separately providing a stripping tank.
  • stripping can be performed by contacting steam and a resin slurry in a shelf manner.
  • the aqueous solution containing the rosin powder particles after the steam stripping is dehydrated and dried by the step (3) described below.
  • a dehydration operation using various filters, centrifuges, or the like can be used.
  • the water content of the resin particles after dehydration by this operation is not particularly limited, but it should be 10 to 50% by weight. It is effective in terms of energy efficiency in drying.
  • the obtained hydrous greaves powder granulate is a conductive heat transfer dryer such as a grooved stirrer or dryer.
  • the rice cake powder is dried by using a hot air heat receiving dryer such as a fluid dryer, etc. It can be a granule.
  • Molecular weight GPC system manufactured by Waters (column: Shodex K-804 (polystyrene gel) manufactured by Showa Denko KK, mobile phase: black mouth form). The number average molecular weight is expressed in terms of polystyrene.
  • the mortar was dried with a box dryer at 100 ° C, and then filled with 30 g in a cylinder with an inner diameter of 5 cm, and 0.03 MPa was obtained with a piston. After applying a load and storing in an atmosphere of 85 ° C for 2 hours, evaluation was performed by the method of loosening when loosened by hand.
  • the obtained polymer solution was poured into a large amount of water to stop the reaction. After the reaction was stopped, the polymer solution phase and the aqueous phase were separated with a separating funnel. After washing the polymer solution phase twice with the same method, confirm that the aqueous phase is neutral, and then pay off the polymer solution phase in terms of force. A coalesced solution was obtained.
  • a pressure-resistant stirrer with a tank volume of 50 liters and an inner diameter of 30 cm was charged with 12.5 liters of pure water and 12.5 liters of the polymer solution obtained in the production example, and 5. lg of a surfactant (polyethylene glycol monostearate), Added and sealed.
  • the stirrer blade was heated in a jacket while stirring at 400 rpm using a two-stage four-padded paddle with a blade diameter of 15 cm.
  • the solvent gas was introduced into a capacitor attached to the pressure-resistant stirring apparatus, and the solvent was sequentially recovered.
  • the internal pressure was increased or decreased while paying attention to foaming, and the heating and solvent evaporation were stopped when the internal pressure dropped to normal pressure and the stirring tank internal temperature reached 95 ° C.
  • the agitation was stopped after the internal temperature decreased to room temperature, and the resin slurry produced in the agitation tank was recovered (step (1)).
  • the granular material in the collected resin slurry was a good particle having a particle size of 1 to 2 mm.
  • the recovered rosin slurry is returned to the agitation tank again, and 4 g of colloidal silica (Nissan Chemical MP-2040, average particle size 0.19 m, active ingredient content 40%) (0.1 part by weight) was added, sealed and steam stripped (step (2)).
  • the stripping conditions were as follows: steam was blown from the bottom of the stirring tank while maintaining 120 ° C for 60 minutes.
  • This resin slurry was centrifugally dehydrated and dried in a box dryer at 100 ° C for 2 hours to obtain a resin powder.
  • Example 1 0 .1 0 .1 9 ⁇ ⁇ Example 2 0 .3 0 .1 9 ⁇ ⁇ Comparative Example 1 None X ⁇ Comparative Example 2 0 .3 0 .0 8 ⁇ ⁇ Comparative Example 3 0. 4 5 ⁇ X
  • step (2) colloidal silica (MP-2040, Nissan Chemical Co., Ltd., average particle size 0.19 m, active ingredient content 40%) 12 g (0.3 parts by weight of active ingredient relative to rosin)
  • colloidal silica MP-2040, Nissan Chemical Co., Ltd., average particle size 0.19 m, active ingredient content 40%
  • step (2) 12 g of colloidal silica (Nissan Chemical's Snowtex ZL, active ingredient content 40%) with an average particle size of 0.08 ⁇ m (the active ingredient content is 0.3 wt. Part
  • Example 2 The same procedure as in Example 1 was carried out except for addition.
  • step (2) colloidal silica with an average particle size of 0.45 ⁇ m (MP—
  • Example 4540 40% active ingredient content was carried out in the same manner as in Example 1 except that 4 g (the active ingredient content was 0.1 parts by weight relative to rosin) was added.

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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)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

La présente invention concerne un procédé de production de particules de résine, dans lequel les particules de résine sont récupérées dans une solution aqueuse contenant des particules de résine. En particulier, on prévoit de proposer un procédé de production de manière stable de particules de résine d'un polymère d'isobutylène, en particulier d'un copolymère séquencé d'isobutylène, excellent en termes de transparence et de propriété de blocage. On peut proposer un tel procédé en pulvérisant un polymère et en ajoutant ensuite une silice colloïdale de 0,1 à 0,3 μm de diamètre de particules dans une solution aqueuse contenant les particules de résine résultantes.
PCT/JP2006/308998 2006-04-28 2006-04-28 Procede de production de particules de resine Ceased WO2007125597A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/JP2006/308998 WO2007125597A1 (fr) 2006-04-28 2006-04-28 Procede de production de particules de resine

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2006/308998 WO2007125597A1 (fr) 2006-04-28 2006-04-28 Procede de production de particules de resine

Publications (1)

Publication Number Publication Date
WO2007125597A1 true WO2007125597A1 (fr) 2007-11-08

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PCT/JP2006/308998 Ceased WO2007125597A1 (fr) 2006-04-28 2006-04-28 Procede de production de particules de resine

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5049356A (fr) * 1973-09-04 1975-05-02
JPS5224249A (en) * 1975-07-17 1977-02-23 Dunlop Co Ltd Method of manufacturing fluid rubber powder
JPS62240327A (ja) * 1986-04-11 1987-10-21 Tosoh Corp 粉末ゴムの製造方法
JPS6310636A (ja) * 1986-07-01 1988-01-18 Nippon Zeon Co Ltd 粒状ゴムの製造方法
JPS6426644A (en) * 1987-04-13 1989-01-27 Kanegafuchi Chemical Ind Method for improving powder characteristic of synthetic polymer powder
JPH04185646A (ja) * 1990-11-20 1992-07-02 Mitsubishi Rayon Co Ltd 粉体特性改良方法
JPH10330404A (ja) * 1997-05-28 1998-12-15 Jsr Corp ゴム状重合体の取得方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5049356A (fr) * 1973-09-04 1975-05-02
JPS5224249A (en) * 1975-07-17 1977-02-23 Dunlop Co Ltd Method of manufacturing fluid rubber powder
JPS62240327A (ja) * 1986-04-11 1987-10-21 Tosoh Corp 粉末ゴムの製造方法
JPS6310636A (ja) * 1986-07-01 1988-01-18 Nippon Zeon Co Ltd 粒状ゴムの製造方法
JPS6426644A (en) * 1987-04-13 1989-01-27 Kanegafuchi Chemical Ind Method for improving powder characteristic of synthetic polymer powder
JPH04185646A (ja) * 1990-11-20 1992-07-02 Mitsubishi Rayon Co Ltd 粉体特性改良方法
JPH10330404A (ja) * 1997-05-28 1998-12-15 Jsr Corp ゴム状重合体の取得方法

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