WO2007125597A1

WO2007125597A1 - Process for producing resin particulate

Info

Publication number: WO2007125597A1
Application number: PCT/JP2006/308998
Authority: WO
Inventors: Keizo Hayashi; Tomoyuki Yoshimi
Original assignee: Kaneka Corporation
Priority date: 2006-04-28
Filing date: 2006-04-28
Publication date: 2007-11-08

Abstract

A process for producing resin particulates, in which resin particulates are recovered from an aqueous solution containing resin particulates. In particular, it is intended to provide a process for stably producing resin particulates of an isobutylene polymer, especially an isobutylene block copolymer, excelling in transparency and in blocking property. Such a process can be provided by pulverizing a polymer and thereafter adding a colloidal silica of 0.1 to 0.3 μm particle diameter to an aqueous solution containing the resultant resin particulates.

Description

Specification

Method for producing resin powder

Technical field

TECHNICAL FIELD [0001] 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.

Background art

[0002] As a method of separating and recovering rosin powder as a granular material, a method of removing water using various filters and centrifugal dehydrators is generally employed. Many.

[0003] When the resin is a rubber-like polymer, the obtained granular material is soft and irregular in shape, so that often a blocking problem occurs during collection. Addition of a lubricant is the most common method for improving the blocking property of powders. For thermoplastic resin, JP-A 64-26644 (Patent Document 1) describes ethylene bisamide and sorbitan monostearate. A method by adding a lubricant such as a rate is disclosed. Similarly, JP-A-4-300947 (Patent Document 2) and JP-A-7-3106 (Patent Document 3) also disclose a method for adding a hard emulsion polymerization polymer to a thermoplastic resin. ing. For hydrogenated styrene elastomers, Japanese Patent Application Laid-Open No. 10-330404 (Patent Document 4) discloses a method of dusting powdered minerals and organic substances after drying, Japanese Patent Application Laid-Open No. 2002-371136 (Patent Document 5). ) Discloses a method of dusting polypropylene fine particles.

[0004] The blocking property of the product is the same for the isobutylene-based block copolymer. When 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.

[0005] However, in the lubricant addition method, if sufficient blocking property is maintained, the transparency of the product may be impaired, and even if ultrafine particles such as silica are added to maintain transparency, it is efficient. Hasn't established an effective method for adding lubricants, such as not adhering to the surface of the resin? I

[0006] For this reason, when producing a rosin powder granule, particularly when producing a coconut powder granule having an isobutylene block copolymer strength, a product with excellent transparency and high transparency without deterioration in quality. Development of a manufacturing process that stably produces the material has been desired. 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

Disclosure of the invention

Problems to be solved by the invention

[0007] In view of the above-described situation, 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.

Means for solving the problem

[0008] 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.

[0009] 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. .

[0010] A preferred embodiment is a method for producing an isobutylene-based greaves powder, which is a polymer-powered sobutylene-based polymer.

[0011] In a more preferred embodiment, the isobutylene polymer is

(A) a polymer block composed mainly of isobutylene;

(B) a polymer block composed mainly of an aromatic vinyl monomer,

Examples thereof include a method for producing a coconut powder granule, which is a powerful block copolymer. The invention's effect

[0012] According to the production method of the present invention, it is possible to improve the blocking property without deteriorating the quality of the resin particles, particularly without impairing the transparency.

BEST MODE FOR CARRYING OUT THE INVENTION

[0013] In the method according to the present invention, 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.

[0014] Hereinafter, a method for producing an isobutylene polymer will be specifically described.

[0015] 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. Specifically, 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.

[0016] 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. In addition, 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.

[0017] 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.

[0018] 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.

Four

[0019] 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. Preferably, 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.

[0020] 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. . Among these, 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.

[0021] 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.

[0022] As the initiator used in the cationic polymerization, a compound represented by the following formula (I) is preferably used.

[0023] (CR '^ X) R ³ (I)

[Wherein, 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)].

6 4 3 2 2

Propyl) benzene is also called dicumulant mouth ride].

[0024] In the polymerization of the isobutylene block copolymer, an electron donor component may be further present if necessary. Examples of such compounds include pyridines, amines, amides, sulfoxides, esters, or metal compounds having an oxygen atom bonded to a metal atom.

[0025] In carrying out the actual polymerization, 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.

[0026] The number average molecular weight of the isobutylene block copolymer is not particularly limited.

Ability to be 30000-500000 S, preferably 50000-40

Especially preferred to be 0000! /.

[0027] 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.

[0028] 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.

[0029] 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). At the time of granulation, it is desirable that 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. When the dope concentration is low, 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. Further, when the polymer solution concentration is high, it can be adjusted to a desired concentration by diluting with a solvent.

[0030] 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. 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.

[0031] As the surfactant, a nonionic surfactant is preferably used because of its low foaming. Specific examples of 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 glycol. . These may be used alone or in combination of two or more. 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.

[0032] As an apparatus used for liquid-liquid dispersion by stirring and solvent removal, a container equipped with a stirrer is preferably used. Arbitrary blades such as screw blades, probe blades, anchor blades, paddle blades, inclined paddle blades, turbine blades, and large lattice blades can be used. In these, 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.

[0033] 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.

[0034] The obtained aqueous solution containing rosin powder particles is charged with 0.1 to 0.3 / zm of colloidal silica and heated with stirring. 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. In addition, 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. In the case of an isobutylene block copolymer, 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. When the temperature is 70 ° C or lower, colloidal silica does not adhere to the resin efficiently, and the blocking effect is not sufficient. When the temperature is 180 ° C. or higher, fusion between the cocoons becomes remarkable and coarse particles are generated, which is preferable.

[0035] Examples of colloidal silica 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.

[0036] 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.

[0037] Colloidal silica having a particle size of 0.1 to 0.3 µm is used. When 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. When 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.

[0038] 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. In addition, as a continuous method, when one or more aeration and agitation tanks are connected, stripping can be performed by contacting steam and a resin slurry in a shelf manner.

[0039] The aqueous solution containing the rosin powder particles after the steam stripping is dehydrated and dried by the step (3) described below. In order to recover greaves powder granules from aqueous solution containing greaves granules 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.

[0040] 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.

Example

[0041] Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

[0042] The molecular weight and tensile strength of the block copolymer shown in this example were measured by the following methods.

[0043] 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.

[0044] For transparency, a 2 mm thick press sheet was prepared and the transparency was confirmed visually.

[0045] Regarding the blocking property of the obtained rosin powder granules, 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.

[0046] (Production example)

In a 20 L reactor equipped with a stirrer, 1-chlorobutane (dried with molecular sieves) 3.70 kg, hexane (dried with molecular sieves) 1.92 kg, p-dicumyl chloride 2.90 g were charged. After the reaction vessel was cooled to -70 ° C, 2.18 g of N, N-dimethylacetamide and 844 g of isobutylene were added thereto. Furthermore, 85 g of titanium tetrachloride was added to initiate polymerization, and the solution was reacted at −70 ° C. with stirring for 2 hours. Next, 408 g of styrene was added to the reaction solution, and the reaction was further continued for 30 minutes to obtain a polymer solution.

[0047] 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.

[0048] As a result of GPC analysis, the number average molecular weight was 100,000 and the molecular weight distribution was 1.14.

[0049] (Example 1)

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.

[0050] When the temperature in the stirring tank reached 90 ° C, 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.

[0051] This resin slurry was centrifugally dehydrated and dried in a box dryer at 100 ° C for 2 hours to obtain a resin powder.

[0052] As shown in Table 1, the obtained greaves powder granules had good blocking properties and good transparency.

[0053] [Table 1] Procking improver

Colloidal resilient force Average particle size Packing property Transparency

[Parts by weight] [μm]

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 Δ ○ Comparative Example 3 0. 4 5 〇 X

(Note) * 1 ◎: No blocking

〇: Can be loosened immediately by hand.

Δ: Unraveled by hand, but partially coarsened.

X: Completely locked and the resin is fused.

* 2 ○: Good without cloudiness.

X: Cloudy.

[0054] (Example 2)

In 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) The same procedure as in Example 1 was performed except that supplementation was performed.

[0055] As shown in Table 1, the obtained rosin powder granules had good blocking properties and good transparency.

[0056] (Comparative Example 1)

The same procedure as in Example 1 was performed except that in the step (2), colloidal silica was not added.

[0057] As shown in Table 1, the obtained rosin powder granules had poor blocking properties and were fused with each other, and even when loosened by hand, they were completely loose.

[0058] (Comparative Example 2)

In step (2), 12 g of colloidal silica (Nissan Chemical's Snowtex ZL, active ingredient content 40%) with an average particle size of 0.08 μm (the active ingredient content is 0.3 wt. Part

) The same procedure as in Example 1 was carried out except for addition.

[0059] As shown in Table 1, the obtained rosin powder granules had a problem with the transparency of rosin, but the The ability to loosen with a hand with poor king characteristics.

[0060] (Comparative Example 3)

In step (2), colloidal silica with an average particle size of 0.45 μm (MP—

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.

[0061] As shown in Table 1, the obtained resin particles had improved blocking properties, but the transparency of the resin was poor.

Claims

The scope of the claims

[1] When recovering rosin powder particles from an aqueous solution containing rosin particles, the particle size is 0.1-0.

A method for producing a greaves powder granule, comprising adding 3 μm of colloidal silica.

[2] The method for producing a rosin powder granule according to claim 1, wherein the colloidal silica is added in an amount of 0.01 to 5 parts by weight with respect to 100 parts by weight of the polymer in the rosin powder granule.

[3] The method for producing a coconut powder granule according to claim 2, wherein the polymer is an isobutylene polymer.

[4] The isobutylene polymer is

(A) a polymer block composed mainly of isobutylene;

(B) a polymer block composed mainly of an aromatic vinyl monomer,

4. The method for producing a coconut powder granule according to claim 3, wherein the block copolymer is a strong block copolymer.