WO2001088021A1 - Procede de production de polymere acrylique - Google Patents

Procede de production de polymere acrylique Download PDF

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Publication number
WO2001088021A1
WO2001088021A1 PCT/JP2001/004153 JP0104153W WO0188021A1 WO 2001088021 A1 WO2001088021 A1 WO 2001088021A1 JP 0104153 W JP0104153 W JP 0104153W WO 0188021 A1 WO0188021 A1 WO 0188021A1
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WO
WIPO (PCT)
Prior art keywords
powder
temperature
latex
dryer
acrylic polymer
Prior art date
Application number
PCT/JP2001/004153
Other languages
English (en)
Japanese (ja)
Inventor
Kouji Matsumura
Akihiro Toritani
Masahiro Oosuka
Seiji Takei
Original Assignee
Mitsubishi Rayon Co., Ltd.
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 Mitsubishi Rayon Co., Ltd. filed Critical Mitsubishi Rayon Co., Ltd.
Publication of WO2001088021A1 publication Critical patent/WO2001088021A1/fr

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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

Definitions

  • the present invention relates to a method for producing an acryl-based polymer powder from an emulsion-polymerized latex containing an acryl-based polymer as a main component.
  • the present invention relates to a method for producing an acryl-based polymer capable of obtaining a powder having good redispersibility when melt-kneaded with a resin.
  • Acrylic polymers used as modifiers for various plastic products such as vinyl chloride resins are generally produced by emulsion polymerization.
  • the acryl-based polymer after the emulsion polymerization is finally melt-kneaded with other resins and used as a powder from the emulsion-polymerized latex (hereinafter simply referred to as latex) after the emulsion polymerization.
  • latex emulsion-polymerized latex
  • the powder characteristics of (1) above are such that the smaller the particle size of the powder and the coarser the structure of the powder, On the contrary, the redispersibility of the above (2) becomes better as the particle size of the powder is smaller and the structure of the powder is coarser.
  • the outlet temperature of a dryer is determined by changing the glass transition temperature of a polymer (hereinafter referred to as Tg). The method is described based on
  • the powder structure cannot be controlled accurately because recent acrylic polymer powders require various performances as modifiers. Therefore, it is considered that the structure is often a multilayer structure, and the T g of such a multilayer structure cannot be generally specified.
  • An object of the present invention is to provide a method for producing an acryl polymer which is obtained by spray-drying an emulsion polymerization latex containing an acrylic polymer as a main component to obtain an acrylic polymer powder.
  • Excellent powder properties such as heat resistance, excellent redispersibility during melt-kneading with other resins, low generation of fish eyes,
  • the purpose is to set the operating conditions of the dryer from which powder suitable as a stick resin modifier is obtained.
  • the present inventors have conducted intensive studies, focusing on the fact that the powder characteristics and redispersibility of an acrylic polymer are greatly affected by the particle size of the powder and the structure of the polymer constituting the powder.
  • the latex is sprayed into the dryer using a spray nozzle to control the particle size of the droplets to be sprayed, and the temperature inside the dryer, particularly the temperature near the outlet of the dryer, is controlled to the minimum latex composition.
  • MFT film temperature
  • an emulsion polymerization latex containing an acrylic polymer as a main component is sprayed into a drier, and a drying gas is sent from an inlet of the drier to obtain the latex. Drying an acrylic polymer powder to obtain an acrylic polymer powder, and collecting the powder from an outlet of the dryer.
  • the temperature of the drying gas near the dryer inlet was set to less than 200 ° C., and the temperature of the drying gas near the dryer outlet was added to the minimum film forming temperature of the emulsion polymerization latex by 30 ° C. The temperature is lower than the temperature.
  • the dryer includes a spray nozzle for spraying at least a latex obtained by emulsion polymerization into a container, an inlet for introducing a drying gas for drying the sprayed latex, a drying gas and after drying. And an outlet portion serving as an outlet for powder.
  • the spray nozzle is provided at the upper part of the dryer, the inlet part is provided at the upper part of the dryer so that a drying gas is applied to the sprayed latex, and the outlet part is provided at the lower part of the dryer. It is preferable to use a type in which the working gas flows from the upper part of the dryer to the lower part.
  • the overall shape of such a dryer is not particularly limited, and its capacity is There is no particular limitation, and any one can be used, from a small-scale one used in a laboratory to a large-scale one used industrially.
  • a pressure nozzle capable of applying a pressure of 0.1 to 20 MPa to the latex and ejecting the latex from the nozzle at a high speed to atomize the latex is preferably used.
  • a pressurizing swirl nozzle that applies a swirl flow to the latex to be sprayed and ejects it is preferable.
  • the particle size of the obtained powder can be adjusted by adjusting the spray pressure when atomizing the latex, so that the desired particle performance can be obtained.
  • the latex can be sprayed.
  • the range of the particle diameter at which the desired powder performance can be obtained depends on the structure of the polymer and the like, and is appropriately adjusted according to the structure of the polymer, the MFT of the latex, and the like. According to such a method, a powder having a large particle diameter can be obtained as compared with the spraying method using a rotating disk as in the conventional example.
  • the temperature of the drying gas near the inlet of the dryer (hereinafter referred to as the inlet temperature) is lower than 200 ° C, preferably lower than 190 ° C. At 200 ° C. or higher, the fusion of the surface portion of the obtained powder proceeds, redispersibility at the time of melt-kneading is reduced, and the amount of generated fish is increased.
  • the lower limit of the inlet temperature is not particularly limited, but is appropriately set so that the temperature in the vicinity of the outlet of the dryer described later falls within a predetermined temperature range, and is preferably 140 ° C. or more. If the above inlet temperature is lower than 140 ° C., the air volume of the drying gas will increase extremely.
  • the gas temperature near the outlet of the dryer (hereinafter referred to as the outlet temperature) is lower than the temperature obtained by adding 30 to the MFT of the latex.
  • the temperature is lower than the temperature obtained by adding 20 ° C to MFT.
  • the latex MFT is the lowest temperature at which a transparent continuous film can be formed when a film is formed from latex, and is a value representative of the Tg of the latex particle surface.
  • MFT correlates with the adhesive force of the latex polymer / particle surface layer, which is a determinant of the powder structure, and serves as an index indicating the adhesive force.
  • the polymer structure of the powder can be controlled, that is, characteristics such as fluidity and redispersibility of the powder can be controlled. Further, even when the polymer has a multilayer structure, the powder properties and redispersibility of the powder can be similarly controlled.
  • the outlet temperature of the dryer is set to a temperature lower than the temperature obtained by adding 30 ° C to the MFT, even when a plurality of latexes having different compositions are dried to obtain a powder, the powder characteristics and redispersibility are good Powder can be obtained.
  • the lower limit of the gas temperature at the outlet of the dryer is not particularly limited, but is preferably higher than 50 ° C. When the temperature is lower than 50 ° C, drying of the powder may be insufficient.
  • a heating device or a cooling device is provided at both ends of a horizontally installed aluminum plate as necessary, so that the aluminum plate has a temperature gradient.
  • the latex is spread uniformly and thinly on the aluminum plate having the temperature gradient, and dried. Then, the lowest temperature at which the latex forms a transparent continuous film is measured, and this is defined as the MFT.
  • the preferred particle size of the powder obtained by drying under the conditions described above cannot be determined unconditionally because it depends on the polymer structure of the powder.
  • particles with low Tg (or MFT) generally have essentially poor powder performance, so it is necessary to set the particle size larger than those with high glass transition temperature (or MFT).
  • MFT glass transition temperature
  • it is preferably between 60 and 300 m, more preferably between 100 and 200 / m. If the particle diameter is less than 60 zm, the handling properties, flowability and blocking resistance of the powder will be reduced due to the increase in fine powder, etc.If it exceeds 300 xm, it will be classified when mixed with resin powder such as vinyl chloride resin. It becomes difficult to mix uniformly.
  • the emulsion polymerization latex containing an acrylic polymer as a main component used in the above production method is not particularly limited, but preferably has an MFT of 20 ° C or more. More preferably, the MFT is above 50 ° C. If MFT is below 20 ° C, dry The temperature at the dryer outlet is 50 ° C or less, resulting in insufficient drying.
  • Such latexes include, specifically, methyl acrylate, ethyl acrylate, butyl acrylate, propyl acrylate, 2-ethylhexyl acrylate, aryl acrylate, glycidyl acrylate, methyl methacrylate, Using one or more acrylic monomers such as ethyl methacrylate, butyl methacrylate, propyl methacrylate, 2-ethylhexyl methacrylate, aryl methacrylate, glycidyl methacrylate, acrylamide, acrylonitrile, etc. Is obtained by copolymerization, seed polymerization, or graft polymerization.
  • acrylic monomers it is also possible to use a small amount of monomers such as styrene, para-methylstyrene, 1,3-butadiene, biel acetate, vinylpyridine, etc. which can be used for emulsion polymerization. It is preferable to contain 50% by mass or more of the acryl-based monomer.
  • cross-linking agent such as divinylbenzene, 1,3-butylenedimethacrylate, arylmethacrylate, and glycidyl methacrylate
  • chain transfer agent such as mercaptans and terpenes.
  • the polymerization initiator used in the emulsion polymerization of the acryl-based polymer is not particularly limited, but water-soluble persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, diisopropylbenzene hydroperoxide, P- Mentane Hydrate Peroxide, cumine hydroperoxide, redox-based initiators containing organic peroxides as one component, such as t-butyl octyl peroxide, can be used.Used for emulsion polymerization of the above acryl-based polymers.
  • the emulsifier is not particularly limited, but one or more alkali metal salts of higher fatty acids such as disproportionated rosin acid, oleic acid, and stearic acid, and alkali metal salts of sulfonic acids such as dodecylbenzenesulfonic acid are combined. Can be used.
  • emulsion polymerization method and emulsion polymerization conditions for the latex used in the above-mentioned production method there is no particular limitation on the emulsion polymerization method and emulsion polymerization conditions for the latex used in the above-mentioned production method, and the method can be carried out by conventionally known methods and conditions.
  • the above latex may be used alone, or may be a mixture of a plurality of latexes. Also, in order to prevent oxidation in the dryer, a suitable antioxidant or additive can be added to the latex to be sprayed and spray dried.
  • inorganic fillers such as silica, talc, calcium carbonate, etc., polyacrylate, polyvinyl alcohol, polyacrylamide, etc. Can be added and spray dried.
  • the emulsion polymerization latex is sprayed by the spray nozzle into the dryer whose temperature is adjusted as described above, and this is dried and collected from the outlet. Thereby, an acryl-based polymer powder having desired powder performance can be obtained.
  • the spray-drying apparatus, method, conditions, etc. are not particularly limited except for the range of the gas temperature at the inlet and outlet of the dryer and the spray method.
  • Air is preferred as the drying gas because of its low cost, but it is also possible to use an inert gas or a mixture of air and an inert gas.
  • the latex is sprayed using the spray nozzle, and the temperature in the dryer is controlled based on the MFT of the latex.
  • the structure of the acrylic polymer can be controlled according to the composition of the acrylic polymer (polymer), and a powder with excellent powder performance can be obtained.
  • the powder has excellent handling properties in handling powder, fluidity, powder properties such as blocking resistance, and dispersibility when melt-kneaded with another resin such as a vinyl chloride resin.
  • An acrylic polymer powder with less generation of fish eyes can be produced.
  • Dryer Table 1 shows the outlet temperature, dryer inlet temperature, and evaluation results.
  • the MFT of the above latex was measured using a minimum film formation temperature measuring device (manufactured by Takabayashi Rika Co., Ltd.).
  • the measurement temperature conditions at this time were 20 ° C on the low temperature side and 180 ° C on the high temperature side.
  • the MFT of the latex was 85.
  • the latex was introduced into a dryer and spray-dried.
  • the dryer used was one with an inner diameter of 3.5 m for the straight body, a height of 4 m for the straight body, and a height of 2.8 m for the cone.
  • the spraying device was a pressurizing nozzle (spray pressure 2.4 Mpa ) Was used. Air was used as the drying gas.
  • Table 1 shows the latex supply speed, heated gas air flow, dryer inlet temperature, and outlet temperature.
  • Table 1 shows the latex feed rate, heated gas flow rate, dryer inlet temperature, and outlet temperature.
  • Example 3 was carried out in the same manner as in Example 3, except that a dryer of a rotating disk spray system (rotation speed: 15000 rpm) was used.
  • the average particle diameter was 50 m, but the fine powder and coarse powder increased and the fluidity decreased.
  • an acrylic polymer having excellent powder properties such as handling properties, fluidity, and blocking resistance, excellent redispersibility at the time of melt-kneading, and having a low fisheye generation amount. Powder can be obtained.
  • Acrylic polymer powders with such excellent powder properties include impact modifiers such as vinyl chloride resin, polystyrene, polycarbonate, ABS resin, acrylic resin, and other various plastics. It can be suitably used as a processability improver.

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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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Cette invention se rapporte à un procédé de production d'une poudre qui possède d'excellentes propriétés de maniabilité, d'aptitude à l'écoulement et d'effet anti-bloquant, qui possède une excellente redispersabilité lors de son malaxage à chaud avec une ou plusieurs autres résines et qui n'engendre guère d'oeil-de-poisson. Ce procédé consiste à pulvériser un latex de polymérisation en émulsion contenant un polymère acrylique comme constituant principal dans une chambre de séchage, à introduire simultanément dans cette chambre un gaz de séchage par l'entrée de la chambre de séchage, pour sécher le latex et former ainsi une poudre du polymère acrylique, et à recueillir la poudre à la sortie de la chambre de séchage. Dans ce procédé, la pulvérisation du latex s'effectue avec une buse de pulvérisation, la température du gaz autour de l'entrée de la chambre de séchage est réglée à un niveau inférieur à 200 °C, et la température du gaz autour de la sortie de la chambre de séchage est réglée à un niveau inférieur à la température supérieure de 30 °C à la température de formation de film minimum du latex de polymérisation en émulsion. Ainsi, on obtient une poudre ayant d'excellentes performances.
PCT/JP2001/004153 2000-05-19 2001-05-18 Procede de production de polymere acrylique WO2001088021A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2000149069A JP2001329067A (ja) 2000-05-19 2000-05-19 アクリル系重合体の製造方法
JP2000-149069 2000-05-19

Publications (1)

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WO2001088021A1 true WO2001088021A1 (fr) 2001-11-22

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005078013A1 (fr) * 2004-02-16 2005-08-25 Mitsubishi Rayon Co., Ltd. Modificateur de résine, composition de résine l'utilisant et article ainsi formé
CN1311006C (zh) * 2002-10-18 2007-04-18 三菱丽阳株式会社 聚合物胶乳的喷雾干燥装置及粉末的回收方法
CN100357006C (zh) * 2002-11-29 2007-12-26 三菱丽阳株式会社 聚合物的回收方法
US20120219694A1 (en) * 2011-02-28 2012-08-30 Basf Se Production Of Pulverulent Coating Compositions For Stable Protective Coatings For Pharmaceutical Dosage Forms
WO2012116941A1 (fr) * 2011-02-28 2012-09-07 Basf Se Production d'agents d'enrobage pulvérulents pour des enrobages de protection stables de formes galéniques

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1235948C (zh) 2001-05-17 2006-01-11 三菱丽阳株式会社 聚合物粒子的制造方法
WO2005030868A1 (fr) * 2003-09-26 2005-04-07 Mitsui Chemicals, Inc. Composition de composite spherique et procede de production d'une composition de composite spherique
KR101306804B1 (ko) * 2008-11-18 2013-09-10 에스케이플래닛 주식회사 전자 종이 입자 및 그 제조 방법

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US4816558A (en) * 1987-02-02 1989-03-28 Rohm Gmbh Method for making redispersible synthetic resin powders
JPH01275637A (ja) * 1988-03-08 1989-11-06 Roehm Gmbh 噴霧乾燥粉末ポリマーの製造法
JPH04145131A (ja) * 1990-10-04 1992-05-19 Japan Synthetic Rubber Co Ltd 中空重合体粒子の製造方法
JPH0718086A (ja) * 1993-06-18 1995-01-20 Basf Ag 水性ポリマー分散液を噴霧乾燥するための助剤及び方法、ポリマー粉末、合成樹脂プラスター、鉱物性結合剤及び合成樹脂プラスター乾燥調合物
JPH08134224A (ja) * 1994-11-15 1996-05-28 Mitsubishi Rayon Co Ltd 再分散可能な樹脂
JPH08231729A (ja) * 1995-02-22 1996-09-10 Mitsubishi Rayon Co Ltd 再分散可能な樹脂の製造方法及びそれで得られる再分散可能な樹脂

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KR0159947B1 (ko) * 1991-03-12 1998-11-16 마사아키 오카와라 분수형 가압 2류체 노즐 장치와 그것을 편입하여 이루어지는 스프레이 드라이어 장치, 및 가압 2류체에 있어서의 액적 경 제어법
CN1035238C (zh) * 1992-08-20 1997-06-25 大川原化工机株式会社 喷雾干燥造粒装置

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4816558A (en) * 1987-02-02 1989-03-28 Rohm Gmbh Method for making redispersible synthetic resin powders
JPH01275637A (ja) * 1988-03-08 1989-11-06 Roehm Gmbh 噴霧乾燥粉末ポリマーの製造法
JPH04145131A (ja) * 1990-10-04 1992-05-19 Japan Synthetic Rubber Co Ltd 中空重合体粒子の製造方法
JPH0718086A (ja) * 1993-06-18 1995-01-20 Basf Ag 水性ポリマー分散液を噴霧乾燥するための助剤及び方法、ポリマー粉末、合成樹脂プラスター、鉱物性結合剤及び合成樹脂プラスター乾燥調合物
JPH08134224A (ja) * 1994-11-15 1996-05-28 Mitsubishi Rayon Co Ltd 再分散可能な樹脂
JPH08231729A (ja) * 1995-02-22 1996-09-10 Mitsubishi Rayon Co Ltd 再分散可能な樹脂の製造方法及びそれで得られる再分散可能な樹脂

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1311006C (zh) * 2002-10-18 2007-04-18 三菱丽阳株式会社 聚合物胶乳的喷雾干燥装置及粉末的回收方法
CN100357006C (zh) * 2002-11-29 2007-12-26 三菱丽阳株式会社 聚合物的回收方法
WO2005078013A1 (fr) * 2004-02-16 2005-08-25 Mitsubishi Rayon Co., Ltd. Modificateur de résine, composition de résine l'utilisant et article ainsi formé
US9206310B2 (en) 2004-02-16 2015-12-08 Mitsubishi Rayon Co., Ltd. Modifier for resin and resin composition using the same and formed article
US20120219694A1 (en) * 2011-02-28 2012-08-30 Basf Se Production Of Pulverulent Coating Compositions For Stable Protective Coatings For Pharmaceutical Dosage Forms
WO2012116941A1 (fr) * 2011-02-28 2012-09-07 Basf Se Production d'agents d'enrobage pulvérulents pour des enrobages de protection stables de formes galéniques
US8865250B2 (en) * 2011-02-28 2014-10-21 Basf Se Production of pulverulent coating compositions for stable protective coatings for pharmaceutical dosage forms

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JP2001329067A (ja) 2001-11-27
CN1429244A (zh) 2003-07-09
CN100341924C (zh) 2007-10-10

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