WO2014136699A1 - Procédé pour refroidir une solution réactionnelle contenant un monomère d'ester de méthacrylate - Google Patents

Procédé pour refroidir une solution réactionnelle contenant un monomère d'ester de méthacrylate Download PDF

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Publication number
WO2014136699A1
WO2014136699A1 PCT/JP2014/055201 JP2014055201W WO2014136699A1 WO 2014136699 A1 WO2014136699 A1 WO 2014136699A1 JP 2014055201 W JP2014055201 W JP 2014055201W WO 2014136699 A1 WO2014136699 A1 WO 2014136699A1
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WIPO (PCT)
Prior art keywords
temperature
polymerization
reactor
pipe
raw material
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PCT/JP2014/055201
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English (en)
Japanese (ja)
Inventor
真吾 山内
康彦 森
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住友化学株式会社
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Publication date
Application filed by 住友化学株式会社 filed Critical 住友化学株式会社
Publication of WO2014136699A1 publication Critical patent/WO2014136699A1/fr

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    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/02—Polymerisation in bulk
    • 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
    • B01J19/1862—Stationary reactors having moving elements inside placed in series
    • 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
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • B01J2219/00094—Jackets
    • 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
    • C08F20/00—Homopolymers and 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 a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols
    • C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids

Definitions

  • the present invention relates to a method of cooling a reaction liquid containing a raw material monomer by passing it through a pipe during a continuous bulk polymerization process for producing a methacrylic acid ester-based polymer using a methacrylic acid ester-based monomer.
  • methacrylic acid ester polymers have been widely used in various fields because of their excellent transparency and processability.
  • the stirrers 14 and 24 are for bringing the inside of the reactor into a substantially complete mixed state.
  • These agitators may be equipped with any appropriate agitating blade, such as a MIG wing, a Max blend wing (registered trademark, manufactured by Sumitomo Heavy Industries, Ltd.), a paddle wing, a double helical ribbon wing, a full zone. Wings (registered trademark, manufactured by Shinko Environmental Solution Co., Ltd.) may be provided.
  • a baffle in the reactor.
  • the polymerization apparatus of the present embodiment is not limited thereto, and may have any appropriate configuration in place of the stirrers 14 and 24 as long as the inside of the reactor can be substantially completely mixed.
  • the second reactor 20 is preferably connected to a polymerization initiator tank 17 (a supply source of a new polymerization initiator and optionally a raw material monomer) via a pump 19.
  • the supply source of the new polymerization initiator is the polymerization initiator tank 17, but the number of supply sources of the new polymerization initiator and the mode of the polymerization initiator (for example, the composition in the case of a mixture)
  • the polymerization initiator tank 17 may be connected to the supply port 21a of the reactor 20 in the connection line 15 via the pump 19 as shown in FIG.
  • another supply port 21c is provided in the second reactor 20, and this supply port 21c is connected to the polymerization initiator tank 17 via a pump 19, for example, as shown by a dotted line in FIG. Good.
  • the temperature is stored in the ROM based on the set temperature data of the cooler 40 and the temperature in the connection line 15 in the vicinity of the supply port 21a of the second reactor 20 and in other places when actually measured.
  • the set temperature of the jacket 16 of the connection line 15 or the cooler 40 may be adjusted by executing the program (which may be a part of the program or a program different from the program).
  • higher fatty acid esters include, for example, methyl laurate, ethyl laurate, propyl laurate, butyl laurate, octyl laurate, methyl palmitate, ethyl palmitate, propyl palmitate, butyl palmitate, and palmitate.
  • the supply flow rate A of the raw material monomer from the raw material monomer tank 1 Kg / h
  • a feed flow rate B kg / h
  • the ratio A: B to h) is preferably adjusted to be in the range of 80:20 to 98: 2.
  • continuous polymerization can be performed in a state where the reactor is filled with the reaction mixture and substantially no gas phase is present (hereinafter referred to as “full liquid state”).
  • This is particularly suitable for continuous bulk polymerization. Due to this full liquid state, there is a problem that the gel adheres to the inner wall surface of the reactor and grows, and the problem that the quality of the finally obtained polymer composition is deteriorated when this gel is mixed into the reaction mixture. Can be prevented in advance. Furthermore, this full liquid state can effectively utilize the entire volume of the reactor in the reaction space, and thus high production efficiency can be obtained.
  • the full liquid state is simple by simply supplying and extracting the first reactor 10 continuously by positioning the extraction port 11b of the first reactor 10 at the top of the reactor as in this embodiment. Can be realized.
  • the position of the outlet at the top of the reactor is particularly suitable for continuous polymerization of methacrylate monomers.
  • Polymerization heat and stirring heat generated in the first reactor 10 are usually carried away when the intermediate composition is extracted from the first reactor 10.
  • the amount of heat that the intermediate composition takes away is determined by the flow rate of the intermediate composition, the specific heat, and the temperature of the polymerization reaction.
  • the pressure of continuous polymerization in the first polymerization step is understood as the pressure in the first reactor 10.
  • This pressure is set to a pressure equal to or higher than the vapor pressure of the raw material monomer at the temperature in the reactor so that no gas of the raw material monomer is generated in the reactor, and is usually about 1.0 to 2.0 MPa in gauge pressure. .
  • the intermediate composition is continuously extracted from the extraction port 11 b of the first reactor 10.
  • the obtained intermediate composition contains the produced polymer and unreacted raw material monomers, and may further contain an unreacted polymerization initiator, a polymerization initiator decomposition product, and the like.
  • the dissolved oxygen concentration in the intermediate composition can be adjusted by bubbling nitrogen gas into the raw material monomer in a raw material tank and then bubbling it and then storing it in a nitrogen atmosphere. Note that when the treatment step is downstream from the pump, the solution is full, so the dissolved oxygen concentration does not change during the process.
  • a dissolved oxygen meter may be provided at an arbitrary position of the reactor 10 to measure or monitor the dissolved oxygen concentration of the intermediate composition flowing into the connection line 15.
  • connection line 15 it is preferable to provide a mixing means in the connection line 15.
  • the mixing means By providing the mixing means, the intermediate composition flowing in the connection line 15 is uniformly mixed, the temperature distribution is likely to be uniform, and blockage of the connection line 15 by the intermediate composition can be suppressed.
  • a static mixer or a dynamic mixer may be provided in the connection line 15.
  • the second polymerization step will be described mainly with respect to differences from the first polymerization step, and the same description as the first polymerization step will be applied unless otherwise specified.
  • the adiabatic state can be realized by making the temperature inside the second reactor 20 substantially equal to the temperature of its outer wall surface. Specifically, the temperature of the outer wall surface of the second reactor 20 set with respect to the jacket (temperature adjusting means) 23 and the temperature sensor (temperature detecting means) using the above-described control means (not shown). ) Feed monomers and polymerization initiator to the second reactor 20 are fed to pumps 5 and 7 and, if present, so that the temperature in the second reactor 20 detected by T matches. This can be realized by adjusting the operation of the pump 19. If the temperature of the outer wall surface of the reactor is set too high as compared with the temperature in the reactor, it is not preferable because extra heat is applied in the reactor. It is preferable that the temperature difference between the inside of the reactor and the outer wall surface of the reactor is as small as possible. Specifically, it is preferable to adjust the temperature difference within a range of about ⁇ 5 ° C.
  • the continuous polymerization apparatus and the polymer composition that is, the methacrylic ester polymer used in the present invention have been described in detail.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un procédé dans lequel, pendant un procédé continu de polymérisation en masse, on fait passer une solution réactionnelle contenant un monomère d'ester de méthacrylate au travers d'un tuyau et elle est mise en contact avec les surfaces de la paroi interne dudit tuyau afin de refroidir ladite solution réactionnelle. La température de la solution réactionnelle s'écoulant dans le tuyau est d'au moins 110°C, la température des surfaces de la paroi interne du tuyau qui sont en contact avec la solution réactionnelle est d'au plus 105°C et la concentration en oxygène dissous de la solution réactionnelle refroidie par le contact avec les surfaces de la paroi interne du tuyau est située entre 0,01 et 10 ppm, valeurs extrêmes incluses.
PCT/JP2014/055201 2013-03-08 2014-02-25 Procédé pour refroidir une solution réactionnelle contenant un monomère d'ester de méthacrylate WO2014136699A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013047061A JP2014173009A (ja) 2013-03-08 2013-03-08 メタクリル酸エステル系モノマーを含む反応液の冷却方法
JP2013-047061 2013-03-08

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WO2014136699A1 true WO2014136699A1 (fr) 2014-09-12

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WO (1) WO2014136699A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016021694A1 (fr) * 2014-08-06 2016-02-11 株式会社クラレ Procédé de production de composition de résine (méth)acrylique
CN107001511A (zh) * 2014-12-26 2017-08-01 株式会社可乐丽 (甲基)丙烯酸类树脂组合物的制造方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6657846B2 (ja) * 2015-11-24 2020-03-04 三菱ケミカル株式会社 半導体リソグラフィー用重合体の製造方法、レジスト組成物の製造方法、およびパターンが形成された基板を製造する方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03111408A (ja) * 1989-09-27 1991-05-13 Kuraray Co Ltd メタクリル系ポリマーの製造方法
JPH07126307A (ja) * 1993-11-04 1995-05-16 Sekisui Chem Co Ltd アクリル系重合体の製造方法
JP2000159818A (ja) * 1998-11-24 2000-06-13 Mitsubishi Rayon Co Ltd メタクリル系重合体の製造方法及びプラスチック光ファイバの製造方法
JP2003002912A (ja) * 2001-06-21 2003-01-08 Mitsubishi Rayon Co Ltd メタクリル系重合体の製造方法
WO2011125980A1 (fr) * 2010-04-06 2011-10-13 三菱レイヨン株式会社 Appareil et procédé pour la production de polymère méthacrylique

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03111408A (ja) * 1989-09-27 1991-05-13 Kuraray Co Ltd メタクリル系ポリマーの製造方法
JPH07126307A (ja) * 1993-11-04 1995-05-16 Sekisui Chem Co Ltd アクリル系重合体の製造方法
JP2000159818A (ja) * 1998-11-24 2000-06-13 Mitsubishi Rayon Co Ltd メタクリル系重合体の製造方法及びプラスチック光ファイバの製造方法
JP2003002912A (ja) * 2001-06-21 2003-01-08 Mitsubishi Rayon Co Ltd メタクリル系重合体の製造方法
WO2011125980A1 (fr) * 2010-04-06 2011-10-13 三菱レイヨン株式会社 Appareil et procédé pour la production de polymère méthacrylique

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016021694A1 (fr) * 2014-08-06 2016-02-11 株式会社クラレ Procédé de production de composition de résine (méth)acrylique
US10030081B2 (en) 2014-08-06 2018-07-24 Kuraray Co., Ltd. Method for producing (meth)acrylic resin composition
CN107001511A (zh) * 2014-12-26 2017-08-01 株式会社可乐丽 (甲基)丙烯酸类树脂组合物的制造方法
EP3239191A4 (fr) * 2014-12-26 2018-08-29 Kuraray Co., Ltd. Procédé de fabrication d'une composition de résine (méth)acrylique

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