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WO1999002572A1 - Granules de chlorure de vinyle pour le traitement de pate et leur procedes de production - Google Patents

Granules de chlorure de vinyle pour le traitement de pate et leur procedes de production Download PDF

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Publication number
WO1999002572A1
WO1999002572A1 PCT/JP1998/003047 JP9803047W WO9902572A1 WO 1999002572 A1 WO1999002572 A1 WO 1999002572A1 JP 9803047 W JP9803047 W JP 9803047W WO 9902572 A1 WO9902572 A1 WO 9902572A1
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WO
WIPO (PCT)
Prior art keywords
vinyl chloride
chloride resin
granules
resin granules
bulk density
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/JP1998/003047
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English (en)
Japanese (ja)
Inventor
Yoshimitu Nagatomo
Tatsuya Ozaki
Shousuke Kondou
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.)
Shin Dai Ichi Vinyl Corp
Original Assignee
Shin Dai Ichi Vinyl 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 Shin Dai Ichi Vinyl Corp filed Critical Shin Dai Ichi Vinyl Corp
Priority to JP50843899A priority Critical patent/JP4059929B2/ja
Publication of WO1999002572A1 publication Critical patent/WO1999002572A1/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
    • C08J3/122—Pulverisation by spraying
    • 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
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/02—Monomers containing chlorine
    • C08F14/04—Monomers containing two carbon atoms
    • C08F14/06—Vinyl chloride
    • 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
    • C08F6/001—Removal of residual monomers by physical means
    • C08F6/003—Removal of residual monomers by physical means from polymer solutions, suspensions, dispersions or emulsions without recovery of the polymer therefrom
    • 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
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride

Definitions

  • the present invention has a high bulk density, powder flowability, and open-package, which are used for processing a paste produced from an aqueous dispersion of a vinyl chloride resin obtained by fine suspension polymerization or emulsion polymerization.
  • the present invention relates to vinyl chloride resin granules having improved dust-preventing properties and plasticizer dispersibility, and a method for producing the same. Background art
  • polyvinyl chloride resin for paste processing has been manufactured as follows. That is, usually, vinyl chloride having a primary particle size of 0.1 to 5 m obtained by emulsion polymerization or fine suspension polymerization of vinyl chloride or a monomer mixture mainly composed of vinyl chloride in the presence of a surfactant. If necessary, 5 to 30% by weight of particles having a primary particle size of 0.2 to 2 zm of a surfactant or a polymer of the same type is added to the aqueous dispersion of the polymer, and then spray drying is performed. And dry.
  • paste processing is usually performed by classifying and removing aggregates of resin granules and fragments of sediment on the wall surface of a dryer from the combined and mixed powder and granules, and then pulverizing.
  • Plasticizer and, if necessary, heat It was mixed with compounding agents such as stabilizers and fillers to form plastisols (pastes).
  • the powder properties of the vinyl chloride resin for paste processing are governed by its shape.
  • the above-mentioned pulverizing step can be omitted, and as a result, dust generated when the bag packing the resin is opened is reduced.
  • the method of improving the deterioration of the work environment due to the generation of the resin and enabling the automatic metering and supply of the same resin powder, which has been difficult in the past, is disclosed in Japanese Patent Publication No. 3-7814, No. 6-5. It has been proposed in Japanese Patent Publication No. 831 and Japanese Patent Publication No. 6-712169.
  • the vinyl chloride resin powder still contains fine particles collected by a cyclone or a bag filter or a combination thereof in the spray drying method as described above. Problems remain, such as dust being generated at the time of opening the bag and deteriorating the work environment. Moreover, the vinyl chloride resin granules produced by the proposed production method have insufficient plasticizer dispersibility, so that further improvement has been desired.
  • the prepared paste sol removes the resin granules and aggregates that are not dispersed in the plasticizer by means of a strainer or the like, and is heated and gelled through a process such as coating. Processed and made into a product. Resin granules are less dispersible in plasticizers than pulverized paste processing resins.Therefore, when preparing plastisols, it is necessary to take measures such as increasing the kneading strength or lengthening the kneading time compared to pulverized products. Was. There were also dangers such as the strainer clogging due to undispersed material and the incorporation of coarse particles into the coating sol.
  • An object of the present invention is to provide a powder having a large bulk density, powder flowability, dust prevention at the time of bag opening, and
  • An object of the present invention is to provide a vinyl chloride resin granule for paste processing with improved dispersibility of a plasticizer.
  • the spherical granules are aggregates of primary particles of vinyl chloride resin, the angle of repose of which is 30 to 38 degrees, and the ratio of spherical granules having a diameter of 20 m or more is 60% by weight.
  • vinyl chloride resin granules for paste processing characterized by having an average particle size of 35 to 200 / m and a bulk density (loose) of 0.59 to 0.65 g Zcc. Is performed.
  • the above vinyl chloride resin granules for paste processing preferably have an undispersed particle ratio of 0.30% by weight or less.
  • an aqueous vinyl chloride polymer obtained by emulsion polymerization or fine suspension polymerization of vinyl chloride or a monomer mixture mainly containing vinyl chloride in the presence of a surfactant is used.
  • the dispersion is spray-dried to recover the salted polyvinyl resin granules
  • the vinyl chloride resin fine particles accompanying the exhaust air are removed.
  • the spherical granules are separated and removed independently of the granules, the angle of repose is 30 to 38 degrees, the ratio of the spherical granules having a diameter of 20 or more is 60% by weight or more, and the average particle size is 35
  • a method for producing bi-chloride resin granules for paste processing which comprises collecting bi-chlor chloride resin granules having a bulk density (looseness) of 0.59 to 0.65 g / cc up to 200 m. Is provided.
  • FIG. 1 is a flowchart showing a drying step of vinyl chloride resin granules in a process for producing a salted vinyl resin granule for paste processing of the present invention.
  • 2A and 2B are a side view and a front view, respectively, showing a stirring blade of a stirring device used for measuring an undispersed particle ratio.
  • the vinyl chloride resin granules of the present invention are aggregates of polymer particles having a primary particle size of 0.1 to 5 obtained by emulsion polymerization, fine suspension polymerization, etc. It has powder fluidity.
  • the proportion of spherical granules having a diameter of 20 m or more is 60 wt% or more, preferably 85 wt% or more, and the proportion of spherical granules having a diameter of 40 m or more is more than 60 wt%, particularly It is preferably at least 80% by weight and has an average particle size of 35 to 200 m, preferably 50 to 150 m.
  • the term “spherical” is not limited to a true sphere, but also refers to a spheroid or a spheroid with a ratio of the major axis to the minor axis in the range of 1: 1 to 1: 0.8. This concept is included.
  • the term “diameter” refers to the circular equivalent diameter (haywood diameter) and the sieving diameter, which can be determined in a methanol solvent using a laser diffraction particle sizer, or a sieving method using a JIS standard sieve. It is measured by.
  • the vinyl chloride resin granules of the present invention have an angle of repose of 30 to 38 degrees, preferably 32 to 35 degrees, and a bulk density (loose) of 0.59 to 0.658 (::, preferably 0.60 to 0.638 f).
  • the resin granules preferably have an undispersed particle ratio of 0.3% by weight or less, more preferably 0.2% by weight or less, based on the measurement method described below.
  • the vinyl chloride resin granules having the above properties have the following advantages.
  • the vinyl chloride polymer used in the production of the vinyl chloride resin granules of the present invention is a monomer mixture comprising vinyl chloride or vinyl chloride as a main component and an unsaturated monomer copolymerizable therewith.
  • emulsion polymerization including seeded emulsion polymerization
  • fine suspension polymerization including seeded fine suspension polymerization
  • the emulsion polymerization or the fine suspension polymerization may be performed by a known method, and is not particularly limited.
  • An aqueous dispersion of a vinyl chloride polymer is obtained by these methods, but the concentration is not particularly limited.
  • composition of the vinyl chloride-based polymer is not particularly limited, but in the case of a copolymer, 50% by weight of a monoethylenically unsaturated monomer unit copolymerizable with 50% by weight or more of vinyl chloride units. What consists of the following is preferable.
  • Monoethylenically unsaturated monomers that can be copolymerized with chlorovinyl include, for example, olefinic compounds such as ethylene and propylene; vinyl esters such as vinyl acetate and vinyl propionate; acrylic acid and methacrylic acid; Unsaturated monocarboxylic acids: methyl acrylate, ethyl acrylate, _n-butyl acrylate, 2-hydroxyethyl acrylate, methyl methacrylate, methyl ethyl methacrylate, mono N, N-dimethyl methacrylate Unsaturated monocarboxylic acid esters such as aminoethyl; unsaturated amides such as acrylamide and methacrylamide; unsaturated nitriles such as acrylonitrile and methacrylonitrile; unsaturated dicarboxylic acids such as maleic acid and fumaric acid; Esters and their anhydrides; N-substituted maleimides; Methyl ether,
  • emulsion polymerization water is used as a medium, an anionic or nonionic surfactant, an emulsifier, and a water-soluble polymerization initiator are used. Sharp within the range of 0.05 to 0.5 m in diameter A microspherical polymer latex with a particle size distribution is obtained.
  • the seeding emulsion polymerization method is a polymerization method in which a polymer obtained by emulsion polymerization is used as a seed and is enlarged by polymerization of a monomer in an aqueous medium.
  • the anionic surfactant for stabilizing the polymer particles is added in harmony with the progress of the polymerization reaction so that the amount does not exceed the amount required to cover the surface of the polymer particles. Is polymerized with a polymerization initiator.
  • the resulting polymerization system usually contains, in addition to the enlarged main polymer particles having an average particle size of 0.9 to 1.3 m, a relatively small amount of an average particle size of 0.1 to 0.3 m. By-product polymer particles are mixed.
  • the fine suspension polymerization method is a method in which monomers are homogenized with an anionic surfactant using a homogenizer or the like in an aqueous medium in the presence of an oil-soluble polymerization initiator, and then polymerized under relatively gentle stirring. .
  • spherical polymer particles having a broad normal distribution-like particle size distribution of usually from 0.05 to about 2 im of primary particles are obtained.
  • the anionic surfactant used in the polymerization is not particularly limited.
  • examples thereof include alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate; alkyl sulfates such as sodium lauryl sulfate and sodium tetradecyl sulfate; Sulfosuccinates such as sodium silicate and sodium dihexyl sulfosuccinate; Fatty acid salts such as sodium laurate and potassium potassium semi-hardened tallow fatty acid; Sodium polyoxyethylene lauryl ether sulfate; Polyoxyethylene nonylphenyl sulfate Ethoxysulfate salts of alkane sulfonates; alkyl ether phosphate esters; and the like.
  • the amount of the anionic surfactant used depends on the polymerization method to be used, but is usually selected from the range of 0.2 to 2.5 parts by weight per 100 parts by weight of the monomer.
  • polyoxyethylene nonylphenyl ether may be appropriately used in combination.
  • a lipophilic auxiliary emulsifier such as a higher alcohol or sorbyster stearyl ester in emulsion polymerization, fine suspension polymerization and the like.
  • the polymerization initiator may be water-soluble or oil-soluble.
  • Water-soluble polymerization examples of the initiator include water-soluble compounds such as potassium persulfate, ammonium persulfate, and hydrogen peroxide; these initiators or sodium peroxysulfite in a hydroperoxide described later, sodium ethylenediaminetetraacetate complex of ferrous ion, Redox initiators in combination with reducing agents such as ammonium sulfite, ascorbic acid and ferrous pyrophosphate are exemplified.
  • oil-soluble polymerization initiators examples include acetyl chloride, 3,5,5-trimethylhexanoyl parkioside, lauroyl peroxide, benzoyl peroxide, and diacylpoxide such as naphthoyl baroxide; Ketone peroxides such as tyl ketone peroxide; cumene hydroperoxide, p-cymene hydroperoxide, diisopropyl benzene hydroperoxide, t-butyl hydroperoxide, t-pentyl hydroperoxide, P-mensperoxide Hydroperoxides such as hydroperoxides; peroxyesters such as t-butylperoxybivalte; veroxydicarbonates such as diisopropyl veroxydicarbonate and getylhexylperoxydicarbonate; Ki Organic peroxides such as sulfonyl peroxides such as silsulfonyl peroxide
  • the vinyl chloride resin fine particles accompanying the exhaust air are separated and removed independently of the vinyl chloride resin granules, so that the desired vinyl chloride resin spherical shape is obtained. Collect the granules.
  • the process of recovering spherical vinyl resin granules by spray drying will be described with reference to FIG.
  • the dispersion of the vinyl chloride polymer is supplied to the chamber 1 of the spray dryer by the pump 4 and spray-dried.
  • the spray dryer may be a well-known spray dryer used for a vinyl chloride resin for paste.
  • the spray type may be any type such as a rotary disk type atomizer, a two-fluid nozzle type, and a pressurized nozzle type. May be. Drying air Can be collected from the atmosphere, and there is no particular need to adjust humidity.
  • the temperature and air volume of the inlet and outlet of the drying air introduced into the chamber 1 of the dryer by the blower 7 may be the same conditions as those usually used for drying the aqueous dispersion of the vinyl chloride polymer.
  • the degree of drying is such that the moisture contained in the dried granules is 0.05 to 1.5% by weight, preferably 0.01 to 1.0% by weight.
  • the supply of the vinyl chloride polymer aqueous dispersion should be adjusted so that the drying inlet temperature is 100 to 190 ° C and the outlet hot air temperature is 50 to 70 ° C. I just need.
  • This drying usually gives a powder having an average particle size of 20 to 100 m.
  • the resin granules having a large particle diameter fall into the cone below the chamber 1 of the spray drier, and are guided by the blower 8 from the bottom of the chamber to the bag filter 3 or a cyclone (not shown) through the empty pipe A, Drops and is collected in the lower discharge pipe D.
  • the fine resin particles accompanying the exhaust air from the spray dryer are guided to the bag filter 2 or a cyclone (not shown) via the exhaust pipe B, fall, and are collected in the lower exhaust pipe C.
  • the resin granules having a large particle diameter recovered from the discharge pipe D and the resin fine particles recovered from the discharge pipe C are each independently produced without being combined.
  • the ratio of spherical granules having a repose angle of 30 to 38 degrees and a diameter of 20 or more in the total mass is 60% by weight or more, and Spherical granules having a particle size of 35 to 120 / m and a bulk density (looseness) of 0.59 to 0.65 gZc, preferably an undispersed particle ratio of 0.30% by weight or less are obtained.
  • the bulk density (looseness) of the spherical granules collected from the discharge pipe D below the bag filter 3 is the same as that of the damper 5 provided in the exhaust pipe B while maintaining the internal pressure of the spray dryer constant.
  • the opening can be adjusted by adjusting the opening of the damper 6 provided in the empty pipe A below the chamber of the spray dryer, and adjusting the air volume of the empty pipe A and the exhaust pipe B.
  • the bulk density (looseness) can be reduced by opening the damper 5 so that the air volume in the exhaust pipe B increases.
  • PVC Make sure that more fine particles of NIR ⁇ fat are collected on the exhaust pipe B side.
  • the bulk density of the vinyl chloride resin granules can also be adjusted by changing other operating conditions of the spray dryer.
  • the temperature of the inlet of hot air blown into the chamber of the spray dryer is increased, and an aqueous dispersion of a vinyl chloride polymer is used.
  • a method such as increasing the spray pressure can be adopted.
  • vinyl chloride resin granules having the above-mentioned desired properties can be collected from the lower part of the chamber of the spray dryer.
  • the diameter and average particle diameter of the resin fine particles are not limited, but those having a diameter of about 50 xm or less and an average particle diameter of about 10 to 30 m are typical.
  • the resin fine particles can be used in a different manner from the vinyl chloride resin granules of the present invention. For example, it can be used as it is or pulverized for thickening adjustment to be added to a low-viscosity first sol, or shipped to small-lot users.
  • the spray dryer used in the present invention has a repose angle of 30 to 38 when the vinyl chloride resin granules collected from the lower part of the chamber via baggage piping A through bagging pipe A or bag outlet pipe outlet.
  • the ratio of spherical granules having a diameter of 20 m or more is 60% by weight or more, the average particle size is 35 to 200 m, and the bulk density (relaxing) power SO.59 to 0.65 g / It is sufficient that the granules have a structure that can be independently commercialized as granules having an undispersed particle ratio of preferably not more than 0.3% by weight.
  • fine resin particles accompanying exhaust air from a spray dryer are used. Are independently separated and removed to obtain vinyl chloride resin granules having the above-mentioned desired characteristics.
  • the resin granules having a large particle diameter recovered from the discharge pipe D and the fine resin particles recovered from the discharge pipe C were combined into a final product.
  • Such conventional products have a smaller angle of repose, a smaller proportion of spherical granules having a diameter of 20 m or more, a smaller average particle size, and a lower bulk density than the resin granules of the present invention.
  • the above-mentioned conventional products have a large undispersed particle ratio and are inferior in plasticizer dispersibility compared to the resin granules of the present invention.
  • the fine resin particles generally 5 to 15 m in diameter
  • the particles in the spray droplets are well packed with each other, and only the resin granules having a high bulk density and a large particle diameter are collected independently of the above resin fine particles. That's why.
  • Average particle size of granules Measure the cumulative particle size distribution in a methanol solvent using a laser one-light diffraction particle sizer (Malvern Co., Ltd., Mass Spectrometer), and determine the average particle size equivalent to 50% by weight. Diameter (unit: m).
  • Compressibility Calculated by the following formula. The larger the value of the degree of compression (%), the greater the blocking property.
  • Compressibility (%) [bulk density (hard) One bulk density (loose)]
  • Undispersed particle ratio It is indicated by the remaining amount (%) on a 250 mesh sieve.
  • 100 g of the sample powder and 60 g of octyl phthalate are placed in a cylindrical container having an inner diameter of 85 mm.
  • a petal-shaped flat blade 12 with a blade length a of 35 mm from the rotation axis center, a horizontal blade width b of 20 mm, and a thickness c of 0.7 mm shown in Figs.2A and 2B is shown.
  • An agitating blade 11 consisting of four cruciforms arranged in a fixed ring 9 (ring height d is 14 mm, outer dimension e is 13 mm) at the lower end of an agitating shaft 10 with a diameter of 8 mm 5 mm from the center.
  • the plastisol obtained by stirring and mixing by rotating the stirring blade 11 at a rotation speed of 500 pm for 5 minutes is diluted with 100 g of mineral spirit, filtered through a JIS 62 standard sieve (250 mesh), and treated with methanol. Wash off on a Petri dish of known weight. Methanol is volatilized to obtain the weight on the dish, and the result is expressed as a percentage of 100 g of the sample powder. The smaller the value of the undispersed particles (%), the better the sol dispersibility.
  • Seeding emulsion polymerization of vinyl chloride was carried out according to a conventional method, and 92 parts of a particle component having a mode particle size of 1.2 z / m and a mode particle size of 0.2; 100 parts of a vinyl chloride resin composed of 8% of a um particle component and 100 parts of sodium dodecylbenzenesulfonate A 46% solids aqueous dispersion containing 1.0 part of A rotary disk type atomizer (diameter 12 cm) (not shown) in the top of the spray dryer 1 having a chamber consisting of a cylindrical section and a conical section, and an insert attached to the cylindrical section to discharge exhaust air 8 OA exhaust pipe B, Under the chamber 1, a spray drier 1 with air carrying pipes A for collecting particles having a large particle size not entrained by the exhaust air is used.
  • the inlet hot air temperature is 130 ° C
  • the outlet hot air temperature is 55 ° C
  • the aqueous dispersion was dried at 18,000
  • the openings of the damper 5 of the exhaust pipe B and the damper 6 of the empty pipe A were opened 70% and 80%, respectively.
  • the average particle size of salt vinyl resin granules obtained from sampling pipe D is 72 ⁇ m, bulk density (loose) «0.61 gZc c, angle of repose is 34 degrees, dispersity is 18.5%, undispersed particle rate is 16.4% there were.
  • Example 2 Using the same aqueous dispersion spray-drying apparatus as in Example 1, the same drying temperature conditions were used, and only the number of revolutions was reduced to 12000 rpm, and the same aqueous dispersion of biel chloride resin was dried.
  • the opening of damper 6 for pipe 5 and pipe A was 70% open and 80% open, respectively.
  • the average particle size of the resin granules obtained from sampling pipe D was 85, the bulk density (loose) was 0.63 g / cc, the angle of repose was 33 degrees, the dispersity was 20.3%, and the undispersed particle ratio was 0.19%.
  • the opening of damper 6 for pipe 5 and pipe A was 70% open and 80% open, respectively.
  • the average particle size of the resin granules obtained from sampling pipe D was 85, the bulk density (loose) was 0.63 g / cc, the angle of repose was 33 degrees, the dispersity was 20.3%, and the undispersed particle ratio was 0.1
  • the vinyl chloride aqueous resin dispersion was dried in the same manner as in Example 1. However, the average particle size of the vinyl chloride resin granules collected by Bagfill 1 and obtained from the collection pipe C was 32 m, The density (loose) was 0.41 gZc c, the angle of repose was 42 degrees, the dispersity was 55.6%, and the undispersed particle ratio was 0.53%.
  • the vinyl chloride resin aqueous dispersion was dried in the same manner as in Example 2. However, the average particle size of the vinyl chloride resin granules collected at Bagfill 1 and obtained from the collection pipe C was 36 m, and the bulk density ( The looseness was 0.46 g / cc, the angle of repose was 46 degrees, the dispersity was 48.5%, and the undispersed particle ratio was 0.62%.
  • Example 4 The whole amount of the granules collected in the collection pipes C and D of Example 1 and Comparative Example 1 was mixed, and the average particle diameter was 40 m, the bulk density (loose) was 0.48 g / cc, and the angle of repose was 43 degrees. A vinyl chloride resin granule having a dispersity of 50.4% and an undispersed particle ratio of 0.44% was obtained. Comparative Example 4
  • the drying conditions were as follows: Humidity 0.01 kg water Zkg air air, hot air inlet temperature 80 ° C, outlet hot air temperature 45, and the damper 5 for pipe B and damper 6 for pipe A were opened 90% and 60, respectively.
  • the aqueous dispersion of the salted vinyl resin was spray-dried in the same manner as in Example 1 except that it was opened at%, and the whole amount of the granules collected by the collection pipes C and D was mixed.
  • the obtained vinyl chloride resin granules have an average particle size of 45 m and bulk density.
  • Table 1 summarizes the results obtained in Examples 1 and 2 and Comparative Examples 1 to 5.
  • an aqueous dispersion of a vinyl chloride resin obtained by emulsion polymerization or fine suspension polymerization is spray-dried, and if necessary, the opening degree of the damper of the exhaust pipe and the damper of the empty granule pipe is adjusted.
  • the vinyl chloride resin granules collected from the lower part of the dryer chamber and captured by the bag filter 3 via the air carrying pipe A and collected are granules with a repose angle of 30 to 38 degrees and a diameter of 20 m or more.
  • the powder has extremely low dusting properties and excellent sol dispersibility (Examples 1 and 2).
  • the fine particles accompanying the exhaust air discharged from the pipe B installed in the middle part of the dryer chamber are collected by the bag filter 12 and the particles with a repose angle of 42 and 46 degrees and a diameter of 20 ⁇ or more are collected. 75% and 78% by weight, average particle size 32 m and 36 m, bulk density (loose) 0.41 g / cc and 0.46 g, cc, undispersed particle ratio 0.53% by weight and 0.62% by weight, powder
  • the fluidity is extremely poor, the degree of dispersion is extremely large, the dusting time is very long due to the long flouring time, and the sol dispersibility is poor (Comparative Examples 1 and 2).
  • the granules collected in the lower piping A of the dryer chamber and the fine powder in the exhaust air from the piping B in the middle part of the chamber are obtained by the conventional method of spraying and drying the powdered polyvinyl chloride for paste processing.
  • the characteristics of the powders obtained by mixing with the following are also: angle of repose 43 degrees, ratio of granules with a diameter of 20 m or more 84% by weight and 85% by weight, average particle size 40 ⁇ and 45 m, and bulk density (loose) 0.488 / 0.49 g / cc, undispersed particle ratio 0.44% by weight and 0.53% by weight. Poor powder flowability, high degree of dispersion, and considerably long dusting time.
  • Comparative Example 5 the opening degree of dampers 5 and 6 is adjusted within the range of the general manufacturing method of resin granules by a conventional spray dryer, and the bulk density of the integrated granules collected in piping C and piping D is increased.
  • the results of Comparative Example 5 thus obtained were as follows: the angle of repose was 34 degrees, the ratio of granules having a diameter of 20 zzm or more was 82% by weight, the average particle size was 45, and the bulk density (loose) was 0.55 g.
  • the vinyl chloride resin granules of the present invention have a smaller angle of repose, a larger proportion of spherical granules having a diameter of 20 / m or more, and a larger average particle size, as compared with vinyl chloride resin granules prepared by a conventional method.
  • the bulk density (looseness) is large, and preferably, the undispersed particle ratio is small. Therefore, the vinyl chloride resin granules of the present invention have good flow properties, low dusting properties, good blocking properties, and preferably excellent plasticizer dispersibility.
  • the vinyl chloride resin granules of the present invention are excellent particularly for paste processing.

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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)
  • Dispersion Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention porte sur des granulés de chlorure de vinyle destinés à être utilisés dans le traitement de pâte. Ces granulés sont des agglomérats sphériques de particules de résine de chlorure de vinyle primaire qui ont un angle de repos compris entre 30 et 38°, une partie de ces granulés sphériques, au moins 60 % en poids, ayant un diamètre non inférieur à 20 νm, le diamètre moyen des particules étant compris entre 35 et 200 νm, et une masse volumique apparente (en vrac) comprise entre 0,59 et 0,65 g/cc. De préférence, la teneur des particules non dispersibles dans les granulés est de 0,30 % au plus. Les granulés de résine sont produits par un procédé consistant à sécher par atomisation une dispersion polymère aqueuse de chlorure de vinyle, obtenue par polymérisation en émulsion ou polymérisation en suspension fine, et à récupérer le polymère. Les particules fines entraînées par l'air d'évacuation au cours du séchage par atomisation sont retirées séparément des granulés de résine ayant un plus grand diamètre de particule.
PCT/JP1998/003047 1997-07-07 1998-07-07 Granules de chlorure de vinyle pour le traitement de pate et leur procedes de production Ceased WO1999002572A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP50843899A JP4059929B2 (ja) 1997-07-07 1998-07-07 ペースト加工用塩化ビニル樹脂顆粒およびその製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP19646897 1997-07-07
JP9/196468 1997-07-07

Publications (1)

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WO1999002572A1 true WO1999002572A1 (fr) 1999-01-21

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PCT/JP1998/003047 Ceased WO1999002572A1 (fr) 1997-07-07 1998-07-07 Granules de chlorure de vinyle pour le traitement de pate et leur procedes de production

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WO2001000713A1 (fr) * 1999-06-24 2001-01-04 Dynea Chemicals Oy Pigment polymere applicable a sec
JP2004339349A (ja) * 2003-05-15 2004-12-02 Tosoh Corp ペースト加工用ポリ塩化ビニル系樹脂顆粒及びその製造方法
JP2007119791A (ja) * 2007-02-08 2007-05-17 Shin Dai-Ichi Vinyl Corp ペースト加工用塩化ビニル樹脂顆粒
CN114274405A (zh) * 2021-12-30 2022-04-05 无锡市佳尔新材料科技有限公司 一种高强度耐腐蚀pvc粒子的制备装置及工艺

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KR102774254B1 (ko) * 2019-07-30 2025-02-27 주식회사 엘지화학 염화비닐계 중합체의 제조방법 및 이로부터 제조된 염화비닐계 중합체

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JPS62149726A (ja) * 1985-08-21 1987-07-03 Mitsubishi Rayon Co Ltd 粉粒状重合体およびその製造方法
JPS6395204A (ja) * 1986-09-12 1988-04-26 アトケム プラスチゾルを形成可能な塩化ビニルホモ重合体及び共重合体の製造方法
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001000713A1 (fr) * 1999-06-24 2001-01-04 Dynea Chemicals Oy Pigment polymere applicable a sec
JP2004339349A (ja) * 2003-05-15 2004-12-02 Tosoh Corp ペースト加工用ポリ塩化ビニル系樹脂顆粒及びその製造方法
JP2007119791A (ja) * 2007-02-08 2007-05-17 Shin Dai-Ichi Vinyl Corp ペースト加工用塩化ビニル樹脂顆粒
CN114274405A (zh) * 2021-12-30 2022-04-05 无锡市佳尔新材料科技有限公司 一种高强度耐腐蚀pvc粒子的制备装置及工艺

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