WO2010059000A2 - 고분자 입자의 제조 장치 및 제조 방법 - Google Patents

고분자 입자의 제조 장치 및 제조 방법 Download PDF

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Publication number
WO2010059000A2
WO2010059000A2 PCT/KR2009/006881 KR2009006881W WO2010059000A2 WO 2010059000 A2 WO2010059000 A2 WO 2010059000A2 KR 2009006881 W KR2009006881 W KR 2009006881W WO 2010059000 A2 WO2010059000 A2 WO 2010059000A2
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Prior art keywords
tubular reactor
raw material
present
polymer particles
polymerization
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PCT/KR2009/006881
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English (en)
French (fr)
Korean (ko)
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WO2010059000A3 (ko
WO2010059000A9 (ko
Inventor
최재훈
이창훈
서정현
김유석
송인협
최정욱
송광호
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(주)Lg화학
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Application filed by (주)Lg화학 filed Critical (주)Lg화학
Priority to EP09827765.0A priority Critical patent/EP2357036B1/de
Priority to JP2011537368A priority patent/JP5448004B2/ja
Priority to US13/127,012 priority patent/US8378039B2/en
Priority to CN2009801461676A priority patent/CN102215951A/zh
Publication of WO2010059000A2 publication Critical patent/WO2010059000A2/ko
Publication of WO2010059000A9 publication Critical patent/WO2010059000A9/ko
Publication of WO2010059000A3 publication Critical patent/WO2010059000A3/ko

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J14/00—Chemical processes in general for reacting liquids with liquids; Apparatus specially adapted therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
    • B01J19/243—Tubular reactors spirally, concentrically or zigzag wound
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/126—Polymer particles coated by polymer, e.g. core shell structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00788—Three-dimensional assemblies, i.e. the reactor comprising a form other than a stack of plates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00889—Mixing
    • 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
    • C08J2325/00—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 an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/06—Polystyrene
    • 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
    • C08J2333/00—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical

Definitions

  • the present invention relates to a manufacturing apparatus and a manufacturing method of polymer particles.
  • Polymer particles such as polymethyl methacrylate (PMMA) particles or polystyrene (PS) particles, may be used as fillers for flat panel display (FPD), anti-glare coatings, and LC (liquid). It is utilized in various fields, such as a column filler, an anisotropic conductive filler (ACF), a polymerized toner, an e-paper, and a phase change material (PCM).
  • polymer particles are mainly manufactured in a batch process, since it is impossible to continuously synthesize monodisperse polymer particles having a desired size, crosslinking degree, and structure.
  • US Pat. No. 5,863,996 discloses a batch production process for polymer particles.
  • a monomer or a reactant containing the monomer is supplied into a batch reactor, followed by a polymerization reaction, followed by a plurality of processes such as cooling, removing and washing the polymer. Process is required. Accordingly, in the batch process, not only it takes a long time to prepare the polymer particles, but also the manufacturing cost increases significantly.
  • An object of the present invention is to provide an apparatus and method for producing polymer particles.
  • the present invention provides a means for solving the above problems, a raw material mixing device connected to the raw material supply device; And it is provided to be connected to the mixing device and to perform a polymerization reaction of the mixture supplied therefrom, and provides an apparatus for producing polymer particles comprising a tubular reactor having an aspect ratio of 3,000 or more.
  • a method comprising: a first step of inputting a raw material containing a monomer to be polymerized into a raw material mixing device using a raw material supply device and mixing the raw materials in the mixing device; And a second step of introducing the mixture obtained through the first step into a tubular reactor having an aspect ratio of 3,000 or more, and performing a polymerization reaction of the mixture while maintaining the linear velocity of the mixture at 0.5 m / min or more in the reactor. It provides a method for producing a polymer particle comprising a.
  • the present invention provides an apparatus and a method which can efficiently produce polymer particles having excellent monodispersity and uniform physical properties such as crosslinking degree and polymerization degree.
  • particles having a high degree of crosslinking or having a core-shell or core-double shell structure and exhibiting excellent monodispersity within a desired particle size can be effectively produced.
  • the reproducibility of the said polymer particle manufacturing process can be outstandingly maintained.
  • the present invention provides an apparatus and method capable of effectively controlling the particle size, shape, crosslinking degree, degree of polymerization, structure, solid content concentration of the polymerization liquid, and the like according to the purpose.
  • 1-4 is a schematic diagram of the manufacturing apparatus of the polymer particle which concerns on one aspect of this invention.
  • 5 to 12 show SEM pictures of polymer particles prepared in Examples and Comparative Examples of the present invention.
  • the present invention relates to a raw material mixing device connected to a raw material supply device; And it is connected to the mixing device, and is provided to perform the polymerization reaction of the mixture supplied therefrom, and relates to a production apparatus for polymer particles comprising a tubular reactor having an aspect ratio of 3,000 or more.
  • the manufacturing apparatus of this invention can be used as a continuous manufacturing apparatus applied to the process of manufacturing the desired polymer particle continuously.
  • the specific kind of raw material supply apparatus contained in the manufacturing apparatus of this invention is not specifically limited.
  • a supply device a device capable of supplying a raw material to the inside of a raw material mixing device or a tubular reactor by adjusting the input flow rate of the raw material can be used.
  • injection flow rate means the volume of the raw material introduced into the raw material mixing device or the tubular reactor per unit time.
  • a metering pump can be used as the supply device as described above, but the supply device that can be used in the present invention is not limited thereto.
  • the apparatus of the present invention may also include two or more raw material supply devices connected to the raw material mixing device as described above.
  • the raw materials for producing the polymer particles include various components such as monomers, crosslinking agents, polymerization initiators, catalysts, stabilizers or solvents and the like.
  • two or more feed units are used to divide a single component, or two or more raw materials in which two or more components are separately mixed at the same time or sequentially in a mixing apparatus or a tubular reactor, or You can put in multiple places.
  • the apparatus of the present invention includes a raw material mixing device connected with the raw material supply device.
  • the term "B connected to A” means a state in which a flow of a raw material or a reactant thereof is controlled to move from A to B, or B to A.
  • the term includes a case where A and B are directly connected as well as a case where A and B are connected with separate devices (eg A-C-B).
  • the raw material mixing step can be performed before the raw material supplied from the supply device is introduced into the tubular reactor. Accordingly, a uniform mixed state of the raw material or the reactant can be maintained over the raw material inlet and the discharge port in the tubular reactor, whereby polymer particles having uniform physical properties such as crosslinking degree, polymerization degree, shape and particle diameter can be produced.
  • the mixing device installed at the front end of the reactor ensures uniformity in the size of the seed (monesoidal particles) Can be effectively produced.
  • the kind of mixing apparatus that can be used in the present invention is not particularly limited as long as it can mix the input raw materials, and then control the input flow rate to feed the mixture into the tubular reactor.
  • a T mixer for example, a T mixer, a microchannel mixer or a micromixer or a static (in-line) mixer can be used.
  • a microchannel mixer can be used as the mixing device.
  • the microchannel mixer is a form in which fine channels are formed therein, and is preferable for ensuring uniform mixing of raw materials and uniformity of seed particles.
  • the production apparatus of the present invention includes a tubular reactor connected to the mixing apparatus so that a polymerization reaction of the mixture introduced from the apparatus can be performed.
  • the type of polymerization reaction performed in the tubular reactor is not particularly limited, but the reaction is preferably a dispersion polymerization reaction.
  • a method for producing the polymer particles emulsion polymerization, suspension polymerization, dispersion polymerization, and the like are known.
  • the reaction proceeds in a state where the polymerization raw materials having immiscibility with each other are phase separated in the reaction system and polymer particles are prepared. That is, in the case of suspension polymerization, the monomers to be polymerized are incompatible with each other with the solvent (ex. Water) and the initiator.
  • the monomer and the initiator are strongly stirred to prepare a fine suspension, and then a reaction is performed to prepare particles.
  • control of the emulsion particle size in the prepared fine suspension is not easy, It is not easy to secure monodispersity.
  • the monomers and initiators to be polymerized have immiscibility with a solvent (ex. Water).
  • a solvent ex. Water
  • the reaction proceeds in the phase-separated state formed for stirring, and even in this case, it is not easy to ensure the uniformity of the formed micelles (micelles), so it is not easy to secure monodispersity.
  • it is difficult to produce particles having a practical particle size for example, having a particle size of about 1 ⁇ m to 10 ⁇ m and exhibiting monodispersity.
  • the reaction proceeds by decomposition of the initiator or the like in the state where raw materials such as monomers, stabilizers and dispersants are not phase separated, and form a uniform single phase. That is, in dispersion polymerization, a reaction proceeds under a dispersion medium to generate seeds, and particles having monodispersity may be prepared.
  • the aspect ratio of the tubular reactor in which the reaction proceeds may be 3,000 or more, preferably 9,000 or more, more preferably 100,000 or more, and more preferably 150,000 or more.
  • the term "aspect ratio" in the present invention means the ratio (L / D) of the length (L) to the inner diameter (D) of the tubular reactor.
  • the aspect ratio of the tubular reactor by controlling the aspect ratio of the tubular reactor to 3,000 or more, it is possible to prevent the phenomenon that the unit activity of the particles is lowered by the residual monomers in the tubular reactor, whereby the physical properties such as polymer particle size or crosslinking degree are uneven. Can be.
  • the upper limit of the tubular reactor aspect ratio is not particularly limited.
  • the aspect ratio of the tubular reactor is too large, it is difficult to ensure a smooth flow of the raw material inside the reactor, there is a fear that the physical properties of the produced particles may be non-uniform, 3 million or less, preferably 2 million or less, more preferably It can be controlled in the range of 1 million or less.
  • the tubular reactor may have an average inner diameter (D) of 0.5 mm to 10 mm.
  • D average inner diameter
  • the tubular reactor by controlling the average inner diameter of the tubular reactor in the above range, it is possible to prevent the raw material from agglomerating in the reactor, to ensure a smooth flow, and to effectively control the linear velocity in the reactor.
  • the material of the tubular reactor is not particularly limited, and a general material such as stainless may be used.
  • the tubular reactor may be made of a fluorine resin, or the inside thereof may be coated with a fluorine resin.
  • the type of fluorine-based resin that can be used in the present invention is not particularly limited.
  • Teflon specifically, polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP; tetrafluoroethylene-hexafluoropropylene copolymer), tetrafluoroethylene-perfluoroalkylvinylether copolymer (PFA), polyvinylidene fluoride (PVDF) and the like can be used.
  • PTFE polytetrafluoroethylene
  • FEP tetrafluoroethylene-hexafluoropropylene copolymer
  • PFA tetrafluoroethylene-perfluoroalkylvinylether copolymer
  • PVDF polyvinylidene fluoride
  • the tubular reactor may be installed in, for example, a temperature control chamber (eg a constant temperature chamber).
  • a temperature control chamber eg a constant temperature chamber.
  • reaction conditions such as temperature and pressure inside a reactor, can be controlled according to the raw material to be used, a target particle
  • the manufacturing apparatus of the present invention as shown in Figure 1, at least one raw material supply device (1, 1), mixing device 2, such as a microchannel mixer connected to the supply device (1, 1) and the mixing device It may comprise a tubular reactor (3) connected with (2).
  • the mixing device 2 and the tubular reactor 3 as described above may be installed in a suitable constant temperature chamber 4.
  • the tubular reactor 3 can be installed in a coil shape as shown in FIG. 1, but the installation shape of the reactor is not limited to the coil shape in the present invention.
  • the continuous production device of the polymer particles of the present invention may be connected with various additional devices, including existing batch-type devices, as needed. Through this, in the present invention, by performing an additional process to the prepared polymer particles, it is possible to produce particles with various functionalities.
  • 2 is shown as another example of the manufacturing apparatus of the present invention, in which the tubular reactor 3 is connected to a conventional batch apparatus 5.
  • the production apparatus of the present invention may be connected with the production apparatus of additional polymer particles including the tubular reactor 3, as required, as shown in FIG. 3 or 4.
  • the manufacturing apparatus of the present invention may further include a second tubular reactor connected with the above-described tubular reactor (hereinafter sometimes referred to as "first tubular reactor") and a raw material supply device connected with the second tubular reactor.
  • first tubular reactor connected with the above-described tubular reactor
  • raw material supply device connected with the second tubular reactor.
  • the reactants in which the reaction is performed in the first tubular reactor may be introduced back into the second tubular reactor, and further reaction may be performed therein.
  • the raw material supply device connected with the second tubular reactor may inject additional raw material into the second tubular reactor, which may form a shell at the surface of the particles formed in the cross-linking agent or the first tubular reactor. It may be installed to
  • the apparatus also comprises a first tubular reactor (specifically, the outlet of the first tubular reactor), a second tubular reactor (specifically, the second tubular reactor). Inlet of the reactor) and a mixing device connected to the raw material feed device connected to the second tubular reactor.
  • a first tubular reactor specifically, the outlet of the first tubular reactor
  • a second tubular reactor specifically, the second tubular reactor
  • Inlet of the reactor and a mixing device connected to the raw material feed device connected to the second tubular reactor.
  • the manufacturing apparatus of the present invention includes an additional tubular reactor (second tubular reactor), a raw material supply device, a mixing device, or the like as described above, the specific kind thereof is not particularly limited.
  • additional reactors and the like can be appropriately selected depending on the purpose of the reaction within the scope of the above-described tubular reactor, raw material supply device and mixing device.
  • the aspect ratio of the second tubular reactor can be determined according to the thickness of the cell of the polymer particles of the core-cell structure of interest, so that the aspect ratio of the second tubular reactor is the same as the first tubular reactor. Control, or at least about 1/4 level of the first tubular reactor aspect ratio, preferably about 1/2 level, but is not limited thereto.
  • each of the reactors may be installed in the same chamber (ex. Constant temperature chamber) 4 as shown in FIG. 3, and, if necessary, As shown in Figure 4, it may be installed in separate chambers (ex. Constant temperature chamber) (4, 4).
  • polymerization conditions eg, polymerization temperature and pressure, etc.
  • the production apparatus of the present invention may also include two or more tubular reactors or the like as necessary.
  • the manufacturing apparatus of the present invention may further include a third tubular reactor connected to the second tubular reactor and a raw material supply device capable of supplying raw materials into the third tubular reactor.
  • the manufacturing apparatus of the present invention may further include a raw material mixing device connected with the second tubular reactor, the third tubular reactor and the raw material supply device connected with the third tubular reactor.
  • the term “polymer particles having a core-cell structure” includes a core and a cell surrounding the core, as well as a case in which a single core and a single cell surrounding the core are formed in the particle, wherein the cell is composed of two or more layers. It also includes the case where it is formed (ex. Core-shell-shell structure).
  • the apparatus of the present invention may specifically be an apparatus for producing polymer particles having an average diameter of 0.1 ⁇ m to 10 ⁇ m, preferably 0.1 ⁇ m to 5 ⁇ m, more preferably 2 ⁇ m to 5 ⁇ m.
  • the apparatus of the present invention may be, for example, a device for producing polymer particles having a coefficient of variation (CV) value of 5 or less, preferably 4 or less, more preferably about 3.
  • CV coefficient of variation
  • the present invention also provides a method comprising: a first step of inputting a raw material containing a monomer to be polymerized into a raw material mixing device using a raw material supply device, and mixing the raw materials in the mixing device; And introducing a mixture obtained through the first step into a tubular reactor having an aspect ratio of 3,000 or more, and performing a polymerization reaction of the mixture while maintaining the linear velocity of the mixture at 0.5 m / min or more in the reactor. It is related with the manufacturing method of the polymer particle containing.
  • manufacture of the said polymer particle can be performed continuously using the manufacturing apparatus mentioned above, for example (continuous manufacturing method of a polymer particle).
  • a raw material containing a monomer to be polymerized is introduced into a mixing device using a raw material supply device, and raw materials are mixed in the mixing device.
  • the supply apparatus used in the first step of the present invention may be a metering pump that can control the input flow rate of the raw material, and thus, in the first step, the input flow rate of the raw material is about 0.1 mL / min to 80 Can be adjusted to mL / min.
  • the linear velocity of the raw material in the tubular reactor is controlled by controlling the input flow rate of the raw material in the above-described range in consideration of the inner diameter or aspect ratio of the tubular reactor used, and as a result, the residence time or reaction time of the raw material. Can be controlled.
  • the kind of raw material to be added in the first step of the present invention is not particularly limited.
  • the raw material may include components commonly used in the production of polymer particles, for example, the production of polymer particles by dispersion polymerization.
  • the raw material may include a monomer to form the polymer particles.
  • the types of monomers that may be included include alkyl (meth) acrylates, alicyclic (meth) acrylates, (meth) acrylamides, vinyl acetate, alkenyl (meth) acrylates, and aryl (meth) s. ) Acrylate, alkylaryl (meth) acrylate, aralkyl (meth) acrylate, fluoroalkyl (meth) acrylate, nitrogen-containing (meth) acrylate, (meth) acrylic acid, and other vinyl monomers.
  • alkyl (meth) acrylates alicyclic (meth) acrylates, (meth) acrylamides, vinyl acetate, alkenyl (meth) acrylates, and aryl (meth) s.
  • Acrylate alkylaryl (meth) acrylate, aralkyl (meth) acrylate, fluoroalkyl
  • the monomer that can be used in the present invention include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, isobonyl (Meth) acrylate, itaconic acid, glycidyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, Decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl ( Meth)
  • the raw material may also comprise suitable crosslinking agents or crosslinkable monomers for the production of crosslinked polymer particles.
  • suitable crosslinking agents or crosslinkable monomers for the production of crosslinked polymer particles.
  • the kind of crosslinking agent or the like that can be used may also use a general component of the art.
  • crosslinking agents or crosslinkable monomers examples include ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, allyl (meth) acrylate, diethylene glycol di (meth) acrylate, and propylene glycol di (Meth) acrylate, 2,2-dimethylpropane-1,3-di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, Diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) Acrylate, polyethylene glycol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, poly (butanedi
  • the raw material of the first step of the present invention may also include a suitable polymerization initiator, catalyst or stabilizer from the viewpoint of improving the polymerization efficiency, and may also be used as a general component in the art as a polymerization initiator that can be used at this time.
  • a suitable polymerization initiator catalyst or stabilizer from the viewpoint of improving the polymerization efficiency
  • catalyst or stabilizer from the viewpoint of improving the polymerization efficiency
  • a polymerization initiator that can be used at this time.
  • one kind or a mixture of two or more kinds of peroxy ester, dialkyl peroxide, alkyl hydroperoxide, persulfate, azo initiator and redox initiator can be used.
  • the general polymerization initiator, catalyst, or stabilizer of this field can be suitably selected and used.
  • each of the components may be introduced into a tubular reactor dissolved or dispersed in a suitable solvent or dispersion medium.
  • suitable solvent or dispersion medium examples include, but are not limited to, a mixture of one or more kinds of hydrocarbons (ex. Alkanes), fluorinated hydrocarbons, aromatic hydrocarbons, ethers, ketones, esters, alcohols, and water. .
  • each component of the above-described raw materials may be introduced into the mixing apparatus at a time by using a feeding device while all components of the above-mentioned raw materials are dissolved in a predetermined solvent.
  • the separated raw materials may then be introduced simultaneously or sequentially at one or two or more separate locations using two or more feeders.
  • the two kinds of mixtures are preferably injected into the tubular reactor in separate feeders.
  • the raw materials as described above are added to the mixing device, and the mixing step is performed. Accordingly, the raw material introduced into the tubular reactor can maintain a uniform mixed state, thereby effectively producing the desired polymer particles.
  • the dispersion polymerization of the raw material in the second step of the present invention to be described later it is possible to ensure the uniformity of the seed particle size through the mixing process, to ensure the monodispersity of the polymer particles.
  • the raw material mixture mixed in the first step is introduced into a tubular reactor, and a polymerization reaction, for example, a dispersion polymerization reaction, is carried out in the reactor.
  • a polymerization reaction for example, a dispersion polymerization reaction
  • the linear velocity of the raw material in the tubular reactor can be maintained at 0.5 m / min or more, preferably at least 1 m / min, more preferably at least 3 m / min.
  • the term "linear velocity" means a distance in which a raw material or a reactant flows per unit time in a tubular reactor, which can be controlled by controlling the flow rate into the reactor.
  • the linear velocity in the reactor by controlling the linear velocity in the reactor to 0.5 m / min or more, it is possible to ensure a smooth flow of raw materials or reactants in the reactor.
  • the linear velocity plays an important role in connection with the aspect ratio of the tubular reactor.
  • the linear velocity when the linear velocity is too low, there is a fear that the particles generated inside the tubular reactor are precipitated or aggregated so that a smooth reaction does not proceed.
  • the linear velocity if the linear velocity is too high, the amount of residual monomers increases due to the decrease in the residence time in the reactor, and thus the reaction efficiency may also decrease.
  • the upper limit of the linear velocity is not particularly limited, but the linear velocity may be controlled within the range of 50 m / min or less in consideration of the residence time in the reactor of the raw material or the reactant.
  • the internal conditions of the tubular reactor in which the polymerization reaction is carried out may be appropriately selected in consideration of the type of polymerization reaction, the raw materials used and the desired polymer particles.
  • the internal pressure of the tubular reactor in which the polymerization reaction is carried out may be controlled in the range of 0 bar to 50 bar.
  • the internal temperature of the tubular reactor can be controlled in the range of 50 °C to 100 °C.
  • the reaction time or residence time in the tubular reactor can be controlled in the range of about 1 hour to 10 hours.
  • the process of the present invention furthermore feeds the reactants obtained through the second step into the second tubular reactor, if necessary, and into the second tubular reactor using an additional feeder, for example a raw material for forming a cell section. Injecting the third step; And a fourth step of reacting the raw material introduced in the second tubular reactor.
  • the third step may include: (1) injecting the reactant and the raw material into a mixing device, and mixing in the mixing device; And (2) introducing the mixture obtained through step (1) into a second tubular reactor.
  • the raw material input flow rate into the second tubular reactor, the linear velocity in the reactor, the reaction conditions, and the like are not particularly limited.
  • the aspect ratio of the second tubular reactor or the linear velocity in the reactor in the third or fourth step it is possible to adjust the thickness, shape or physical properties of the cell portion. For example, when the input flow rate of the raw material into the second tubular reactor is adjusted to lower the linear velocity in the reactor, particles having a corrugated surface of the cell portion may be manufactured. On the contrary, by adjusting the input flow rate, it is possible to increase the linear velocity in the reactor and to obtain particles having a smooth shape without wrinkles on the surface.
  • the fifth step may also include: (a) introducing reactants and raw materials into a mixing device, and mixing in the mixing device; And (b) injecting the mixture obtained through step (a) into a third tubular reactor.
  • Each of the aforementioned polymer particles produced in the method of the present invention may have an average diameter of, for example, 0.1 ⁇ m to 10 ⁇ m, preferably 0.1 ⁇ m to 5 ⁇ m, more preferably 2 ⁇ m to 5 ⁇ m.
  • the particles produced according to the present invention may have a CV (Coefficient of variation) value of 5 or less, preferably 4 or less, more preferably about 3.
  • the present invention it is possible to effectively control the physical properties of the size, shape, crosslinking degree, polymerization degree and structure of the polymer particles by installing an additional tubular reactor in the apparatus, or by controlling the aspect ratio or linear velocity.
  • physical properties such as solid content concentration of the reaction solution finally discharged can be effectively controlled by adjusting the composition of the raw material introduced into the tubular reactor.
  • Polystyrene polymer particles were prepared using the apparatus for preparing polymer particles as shown in FIG. 1. Specifically, the first raw material mixture (Feed 1) comprising 9.0 parts by weight of styrene, 36.5 parts by weight of ethanol and 4.4 parts by weight of a stabilizer; And a second raw material mixture including 0.5 part by weight of 2,2'-azobis (2-methylpropionitrile), 41.5 parts by weight of ethanol, and 8.1 parts by weight of water (Feed 2). ) was prepared. Subsequently, the first raw material mixture was introduced into the mixer (microchannel mixer) 2 using the first metering pump 1 and the second raw material mixture using the second metering pump 1.
  • the mixer microchannel mixer
  • the obtained mixture was introduced to maintain a linear speed of about 3 m / min in the tubular reactor (aspect ratio: 600,000) 3. Thereafter, in a reactor, dispersion polymerization was performed to prepare polymer particles. At this time, the polymerization reaction was carried out at a pressure of 15 bar and a temperature of 70 °C. Through this step, the average diameter of the produced polystyrene polymer particles was about 3 ⁇ m.
  • a crosslinked polystyrene particle (average diameter: 3.5 ⁇ m) was prepared by a continuous reaction process using an apparatus for preparing polymer particles having two tubular reactors connected in series.
  • the first raw material mixture (Feed 1) comprising 8.9 parts by weight of styrene, 18.3 parts by weight of ethanol and 2.1 parts by weight of a stabilizer
  • a second raw material mixture (Feed 2) comprising 0.5 parts by weight of 2,2-azobis (2-methylpropionnitrile), 41.2 parts by weight of ethanol and 8.5 parts by weight of water
  • a third raw material mixture (Feed 3) including 0.5 parts by weight of divinyl benzene (DVB) and 19.7 parts by weight of ethanol was prepared, respectively.
  • the first raw material mixture was introduced into the mixer (microchannel mixer) 2 using the first metering pump 1 and the second raw material mixture 1 using the second metering pump 1, and the first and second raw materials introduced were After the mixture was mixed, it was fed into a first tubular reactor (aspect ratio: 600,000) 3. Thereafter, while maintaining the linear velocity in the first tubular reactor at about 3 m / min, dispersion polymerization (polymerization pressure: 15 bar; polymerization temperature: 70 °C) was carried out to prepare polymer particles. Subsequently, the prepared polymer particles were introduced into a second mixer (microchannel mixer) 2, and a third raw material mixture was introduced into the second mixer 2 using a third metering pump 1.
  • polystyrene particles (average diameter: 3.5 ⁇ m) cross-linked by a continuous reaction process were prepared using an apparatus for producing polymer particles in which two tubular reactors each installed in separate constant temperature chambers were connected in series. Prepared.
  • the first raw material mixture comprising 8.9 parts by weight of styrene, 2.1 parts by weight of stabilizer and 18.3 parts by weight of ethanol
  • a second raw material mixture comprising 0.5 parts by weight of 2,2'-azobis (2-methylpropionnitrile), 41.2 parts by weight of ethanol and 8.5 parts by weight of water
  • a third raw material mixture including 0.3 parts by weight of pentaerythritol triacrylate (PETA) and 19.4 parts by weight of ethanol was prepared.
  • PETA pentaerythritol triacrylate
  • the first raw material mixture was introduced into the mixer (microchannel mixer) 2 using the first metering pump 1 and the second raw material mixture 1 using the second metering pump 1, and the first and second mixtures introduced were After mixing, it was fed into a first tubular reactor (aspect ratio: 600,000) 3. Thereafter, dispersion polymerization (polymerization pressure: 15 bar; polymerization temperature: 70 ° C.) was performed in a tubular reactor while maintaining the linear velocity at about 3 m / min to prepare polymer particles. Subsequently, the prepared polymer particles were introduced into a second mixer (microchannel mixer) 2, and the third raw material mixture was introduced into the second mixer 2 using a third metering pump 1.
  • the mixture After mixing the polymer particles and the third raw material mixture in the second mixer (2), the mixture is introduced into a second tubular reactor (aspect ratio: 200,000) (3), and in the second tubular reactor (3)
  • the reaction pressure: 15 bar; temperature: 75 °C was carried out to prepare cross-linked polystyrene particles.
  • Polymer particles were prepared in the same manner as in Example 2, except that the linear velocity of the raw material was maintained at about 0.5 m / min in the second tubular reactor.
  • Polymer particles were prepared in the same manner as in Example 2, except that the linear velocity of the raw material was maintained at about 3 m / min in the second tubular reactor.
  • a third tubular reactor (aspect ratio: 200,000), a fourth raw material supply device and a third mixing device are further installed, and the third mixing device is the second tubular reactor 3.
  • crosslinked polystyrene particles were prepared using an apparatus for producing polymer particles arranged to be connected to a third tubular reactor and a fourth raw material feed device.
  • the reaction up to the second tubular reactor 3 is carried out under the same conditions as in Example 2, but the reactant of the second tubular reactor 3 is introduced into a third mixing device (microchannel mixer), and the metering pump
  • a fourth raw material mixture (Feed 4) containing 0.3 parts by weight of pentaerythritol triacrylate (PETA) and 19.4 parts by weight of ethanol was introduced into a third mixer (microchannel mixer) using the (fourth raw material supply device).
  • the mixture was mixed and injected into the third tubular reactor to proceed with the reaction.
  • the input flow rate of the mixture mixed in the third mixer to the third tubular reactor was controlled to about 5 ml / min.
  • the reaction pressure in the third tubular reactor was about 15 bar
  • the temperature was controlled to about 75 °C to proceed with the reaction to prepare cross-linked polystyrene particles.
  • Crosslinked polystyrene particles were prepared using an apparatus in which a tubular reactor and a continuous stirred tank reactor were connected in series.
  • the first raw material mixture (Feed 1) comprising 8.9 parts by weight of styrene, 2.1 parts by weight of stabilizer and 18.3 parts by weight of ethanol;
  • a second raw material mixture (Feed 2) comprising 0.5 parts by weight of 2,2'-azobis (2-methylpropionnitrile), 41.2 parts by weight of ethanol and 8.5 parts by weight of water;
  • a third raw material mixture (Feed 3) including 0.5 parts by weight of pentaerythritol triacrylate (PETA) and 19.7 parts by weight of ethanol was prepared.
  • the first raw material mixture is introduced into a mixer (microchannel mixer) using a first metering pump and a second raw material mixture using a second metering pump, and the first and second mixtures introduced are mixed, and then the first raw material mixture is mixed.
  • a mixer microchannel mixer
  • a second raw material mixture using a second metering pump
  • the first and second mixtures introduced are mixed, and then the first raw material mixture is mixed.
  • Charged into a tubular reactor (aspect ratio: 600,000).
  • dispersion polymerization polymerization pressure: 15 bar; polymerization temperature: 70 ° C.
  • the prepared polymer particles were supplied to the continuous stirred tank reactor, and the prepared third mixture was also supplied to the continuous stirred tank reactor through a metering pump.
  • the synthesized polymer particles and the third raw material mixture were simultaneously injected into the continuous stirred tank reactor, and the stirrer installed in the continuous stirred tank reactor was operated (stirring speed: 300 rpm).
  • the reaction was carried out in a continuous stirred tank reactor for 2 hours to produce crosslinked polystyrene particles, which were discharged through a pump connected to the outlet of the continuous stirred tank reactor.
  • a first raw material mixture comprising 8 parts by weight of styrene and 80 parts by weight of ethanol;
  • a second raw material mixture comprising 4 parts by weight of 2,2-azobis (2-methylpropionnitrile) and 6.4 parts by weight of water, and 1.6 parts by weight of divinylbenzene (DVB) as a crosslinking agent, were prepared by conventional conventional batch reaction.
  • DVB divinylbenzene
  • Polymer particles were prepared in the same manner as in Example 1, except that a reactor having an aspect ratio of 2,500 was used as the tubular reactor.

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PCT/KR2009/006881 2008-11-21 2009-11-23 고분자 입자의 제조 장치 및 제조 방법 WO2010059000A2 (ko)

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US13/127,012 US8378039B2 (en) 2008-11-21 2009-11-23 Method and apparatus for manufacturing polymer particle
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US20110263800A1 (en) 2011-10-27
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EP2357036A2 (de) 2011-08-17
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TWI432457B (zh) 2014-04-01
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