WO2011114585A1 - 残留モノマー除去装置及びポリビニルアルコール樹脂の製造方法 - Google Patents
残留モノマー除去装置及びポリビニルアルコール樹脂の製造方法 Download PDFInfo
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- WO2011114585A1 WO2011114585A1 PCT/JP2010/071792 JP2010071792W WO2011114585A1 WO 2011114585 A1 WO2011114585 A1 WO 2011114585A1 JP 2010071792 W JP2010071792 W JP 2010071792W WO 2011114585 A1 WO2011114585 A1 WO 2011114585A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
- B01D3/343—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances the substance being a gas
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/16—Fractionating columns in which vapour bubbles through liquid
- B01D3/22—Fractionating columns in which vapour bubbles through liquid with horizontal sieve plates or grids; Construction of sieve plates or grids
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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
- C08F118/00—Homopolymers 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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F118/02—Esters of monocarboxylic acids
- C08F118/04—Vinyl esters
- C08F118/08—Vinyl acetate
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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
- C08F216/00—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 alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/02—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 alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
- C08F216/04—Acyclic compounds
- C08F216/06—Polyvinyl alcohol ; Vinyl alcohol
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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
- 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
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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
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
Definitions
- the present invention relates to a residual monomer removing device and a method for producing a polyvinyl alcohol resin using this device. More specifically, the present invention relates to a technique for removing unreacted monomers from a polymerization solution obtained by a polymerization step.
- Polyvinyl alcohol is a water-soluble synthetic resin, and has been used mainly as a raw material for synthetic fibers in the past. In recent years, film materials, emulsifying dispersants, adhesives, and binder resins have been utilized. It is used in various fields. This PVA resin is generally produced by polymerizing a vinyl ester and saponifying the obtained polyvinyl ester in an organic solvent in the presence of a catalyst.
- a demonomer step for removing unreacted monomers from the polymerization solution is performed between the polymerization step and the saponification step.
- the method includes, for example, a method in which a polymerization liquid obtained by a polymerization step is introduced into a demonomer tower having a plurality of shelves and methanol vapor is blown from the bottom of the tower to bring methanol into contact with the polymerization liquid ( (See Patent Documents 1 and 2).
- a perforated plate tower provided with a partition wall has been proposed as a demonomer tower for producing a polyvinyl chloride resin (for example, see Patent Document 3).
- a treatment flow path for a polymerization liquid is formed by a partition wall, thereby adjusting a contact time between the polymerization liquid and water vapor.
- the conventional demonomer method described above has the following problems. That is, in the conventional demonomer tower, a bubble cap tray for a distillation tower is used as a shelf, but the polymerization liquid introduced into the demonomer tower is a high-viscosity fluid exceeding 1 Pa ⁇ s. There is a problem that the flow resistance is large and a liquid depth difference occurs on the tray. Furthermore, if a difference occurs in the depth of the polymerization solution on each tray (shelf plate), gas drift and retention of the polymerization solution occur, so that the monomer removal efficiency decreases.
- the method of forming the processing flow path by providing the partition wall on the shelf plate is a structure in which the liquid pool is easily formed. Has the problem of blockage.
- the present invention provides a residual monomer removing apparatus and a method for producing a polyvinyl alcohol resin that are capable of removing an unreacted monomer efficiently from a polymerization liquid, in which drift of an organic solvent gas and retention of the polymerization liquid hardly occur on the tray.
- the main purpose is to provide.
- the residual monomer removing apparatus has a tower main body and a plurality of gas ejection portions that open only in a direction orthogonal to the flow direction of the polymerization liquid or open toward the downstream side in the flow direction of the polymerization liquid At least, and the trays are arranged in multiple stages in the tower body.
- a valve tray having a gas ejection portion that opens only in a specific direction is used, a drift of an organic solvent gas such as methanol or a stagnation of a polymerization solution hardly occurs on the tray. Thereby, processing efficiency improves and it becomes possible to remove the unreacted monomer equivalent to or higher than the conventional amount with a smaller amount of organic solvent gas.
- the gas ejection part may be configured by a through-hole formed in the bottom surface of the tray and an arch-shaped cover part provided on the through-hole.
- the tray is formed of the gas ejection part. It arrange
- the gas ejection part may be configured by a through-hole formed in the bottom surface of the tray and a cover part provided on the through-hole and opening only in one direction. It arrange
- the tray may be provided with a liquid storage wall on the upstream side and the downstream side in the flow direction of the polymerization liquid. In this case, at least the downstream liquid storage wall is inclined 5 to 45 ° outward. It is desirable that they are disposed in a state where Furthermore, this apparatus can be used in the manufacturing process of polyvinyl alcohol.
- the method for producing a polyvinyl alcohol resin according to the present invention comprises a polymerization step of polymerizing one or more vinyl esters, or copolymerizing a vinyl ester and another monomer copolymerizable therewith, An organic catalyst gas is brought into contact with the polymerization solution obtained by the polymerization step to remove the unreacted monomer, and the solution from which the unreacted monomer has been removed is converted into an alkali catalyst in a solvent containing the organic solvent.
- Unreacted monomer is removed from the polymerization solution by using a residual monomer removing device in which valve trays each having a plurality of gas ejection portions opening toward the downstream side are arranged in multiple stages.
- a residual monomer removing device in which valve trays having gas ejection portions that open only in a specific direction are arranged in multiple stages is used, the processing efficiency is higher than that of the conventional manufacturing method. improves.
- methanol can be used as the organic solvent.
- valve tray that opens only in a specific direction is used, a drift of an organic solvent gas such as methanol and a retention of a polymerization solution hardly occur on the tray, and an unreacted monomer efficiently from the polymerization solution. Can be removed.
- FIG. 1 is a top view which shows the structure of the tray 2 in the residual monomer removal apparatus 1 shown in FIG. 1
- (b) is the shape of the gas ejection part 2a shown in (a)
- (c) is the gas ejection part 2b. It is a perspective view which shows a shape.
- (A) And (b) is a figure which shows the flow analysis result of the polymerization liquid when using the residual monomer removal apparatus of an Example, (a) shows a liquid depth difference, (b) shows pressure distribution. .
- (A) And (b) is a figure which shows the flow analysis result of the polymerization liquid when using the residual monomer removal apparatus of a comparative example, (a) shows a liquid depth difference, (b) shows pressure distribution. .
- valve trays that open in a specific direction are arranged in multiple stages. Use the arranged residual monomer remover.
- a polyvinyl ester is obtained.
- the vinyl ester used herein include vinyl formate, vinyl acetate, vinyl propionate, vinyl valelate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl piperate and vinyl versatate.
- vinyl acetate is particularly preferable from the viewpoint of polymerization stability.
- vinyl esters are not particularly limited.
- ⁇ -olefins such as ethylene and propylene, methyl (meth) acrylate, ethyl (meth) acrylate, (Meth) acrylic acid alkyl esters such as butyl (meth) acrylate and (meth) acrylic acid-2-ethylhexyl, unsaturated amides such as (meth) acrylamide and N-methylolacrylamide, (meth) acrylic acid, croton Unsaturated acids such as acids, maleic acid, itaconic acid and fumaric acid, alkyl esters of unsaturated acids (such as methyl, ethyl, propyl), anhydrides of unsaturated acids such as maleic anhydride, salts of unsaturated acids (sodium Salt, potassium salt, ammonium salt, etc.), allyl glycidyl ether, glycidyl (meta Glycidy
- FIG. 1 is a diagram schematically showing the configuration of a residual monomer removing apparatus used at that time.
- 2 (a) is a plan view showing the tray 2 in the residual monomer removing apparatus 1 shown in FIG. 1
- FIG. 2 (b) shows the shape of the gas ejection part 2a shown in FIG. 2 (a)
- FIG. c) is a perspective view showing the shape of the gas ejection part 2b.
- a plurality of stages of valve trays 2 are arranged at predetermined intervals inside a substantially cylindrical tower body.
- a polymerization liquid inlet for introducing a polymerization liquid is provided at the upper part of the tower body, and a gas inlet for introducing an organic solvent gas obtained by vaporizing an organic solvent such as methanol is provided at the lower part of the tower main body.
- a degassing port for taking out the monomer together with the organic solvent gas is provided at the top of the tower body, and a discharge port for discharging the polymer solution after the demonomer is provided at the bottom of the tower body.
- a plurality of gas jets opened in a direction orthogonal to the flow direction of the polymerization liquid are provided in the valve tray 2 disposed in the tower body.
- the portions 2a are formed in a matrix.
- This gas ejection part 2a can be configured, for example, by forming a through hole on the bottom surface of the tray and providing an arched cover part on the through hole in a side view. Then, by arranging the valve tray 2 so that the longitudinal direction of the cover part of the gas ejection part 2a coincides with the flow direction of the polymerization liquid, as shown in FIG.
- the opening of the gas ejection part 2a can be directed in a direction orthogonal to the direction.
- the gas ejection part 2b that opens toward the downstream side in the flow direction of the polymerization liquid is provided in the valve tray 2.
- the gas ejection part 2b may have a configuration in which a through-hole is formed on the bottom surface of the tray, for example, and a cover part that covers only the other three directions is provided on the through-hole.
- the flow resistance of the polymerization liquid can be reduced by making the cover part incline from the edge of the through hole toward the opening.
- the position at which the gas ejection part 2b is provided is not particularly limited.
- the gas ejection part 2b can be arranged in a line at intervals in the center of the tray in a direction perpendicular to the flow direction of the polymerization liquid 4.
- the flow rate of the polymerization solution is the slowest at the center of the tray, but with this configuration, the flow rate of the polymerization solution can be made uniform.
- the shape of the through-hole in gas ejection part 2a, 2b is not specifically limited, For example, rectangular shape, trapezoid shape, triangular shape, pentagonal shape, hexagonal shape, octagonal shape, circular shape, and elliptical shape by planar view Various shapes can be adopted.
- the heights of the gas ejection portions 2a and 2b are not particularly limited, and can be appropriately set according to the processing conditions such as the viscosity of the polymerization solution. However, if the height of the gas ejection parts 2a, 2b exceeds 30 mm, the flow resistance may increase and the processing efficiency may decrease. Therefore, the height of the gas ejection parts 2a and 2b is desirably 30 mm or less.
- the opening area of the gas ejection parts 2a and 2b can also be appropriately set according to the processing conditions.
- the opening area of the gas ejection parts 2a and 2b is less than 300 mm 2 , the amount of the organic solvent gas blown in is small. Insufficient processing efficiency may be reduced. Therefore, it is desirable that the opening area of the gas ejection portions 2a and 2b be 300 mm 2 or more.
- the opening ratio of the entire valve tray 2 is desirably 3 to 20%. Thereby, the removal efficiency of an unreacted monomer can be improved significantly. If the overall opening ratio is less than 3%, the contact between the organic solvent gas and the polymerization liquid may be insufficient, and unreacted monomers may remain. Further, if the opening ratio exceeds 20%, it may be difficult to maintain a predetermined liquid depth on the valve tray 2.
- the valve tray 2 is provided with a liquid storage wall 2c on the downstream side in the flow direction of the polymerization liquid.
- the liquid reservoir wall 2c is for ensuring a predetermined liquid depth, and the height thereof can be set to 20 to 100 mm, for example.
- the polymerization solution 4 flows into the lower valve tray 2 beyond the liquid storage wall 2 c.
- the liquid storage wall 2c in the valve tray 2 is disposed to be inclined by 5 to 45 ° on the outside. Thereby, the retention of the polymerization liquid at the bottom of the liquid storage wall can be suppressed.
- valve trays 2 described above are arranged alternately, for example, so that the flow direction is reversed for each stage.
- the number of stages at that time is not particularly limited, but is preferably 10 to 50 stages, for example.
- the polymerization solution 4 is introduced from the polymerization can 3 into the upper part of the residual monomer removing apparatus 1 and is allowed to flow over the valve tray 2. Further, an organic solvent gas such as methanol is introduced from the lower part of the residual monomer removing apparatus 1, specifically, the lower side of the lowermost valve tray 2, and the polymerization liquid 4 is introduced from the gas ejection holes 2 a and 2 b of the valve tray 2. Blow toward.
- the polymerization solution 4 comes into contact with the organic solvent gas, and the monomer in the polymerization solution 4 is discharged from the top of the tower together with the organic solvent gas. Further, the polymer solution from which the monomer has been removed is discharged from the bottom of the column and sent to a saponification step described later.
- the temperature is preferably 60 to 100 ° C.
- the concentration of the polymerization solution 4 is preferably 10 to 70% by mass, and the viscosity is preferably 0.001 to 2.0 Pa ⁇ s. Thereby, the demonomer treatment can be performed with high efficiency.
- the kind of organic solvent used when removing a residual monomer from the polymerization liquid 4 is not limited to methanol mentioned above, What is necessary is just to have volatility.
- the organic solvent used here also serves as a solvent for the saponification step described later, it is desirable to use methanol as the organic solvent gas for removing the residual monomer.
- the polymer (polyvinyl ester) solution subjected to the monomer removal treatment is saponified in the presence of a catalyst in a solvent containing the organic solvent described above.
- a solvent containing the organic solvent described above alcohols such as methanol, ethanol, propanol, ethylene glycol, propylene glycol, glycerin and diethylene glycol can be used, and methanol is particularly preferable.
- the saponification catalyst examples include alkali catalysts such as sodium hydroxide, potassium hydroxide, sodium alcoholate and sodium carbonate, and acid catalysts such as sulfuric acid, phosphoric acid and hydrochloric acid.
- alkali catalysts such as sodium hydroxide, potassium hydroxide, sodium alcoholate and sodium carbonate
- acid catalysts such as sulfuric acid, phosphoric acid and hydrochloric acid.
- an alkali catalyst is preferably used, and sodium hydroxide is more preferably used. Thereby, the saponification rate can be increased and the productivity can be improved.
- the degree of saponification of the PVA resin obtained by the saponification step is not particularly limited, and can be appropriately set according to the application.
- a washing step and a drying step for removing impurities such as sodium acetate may be performed as necessary. Good.
- the flow resistance is low, and the direction perpendicular to the flow direction of the polymerization liquid or toward the downstream side of the flow direction. Since a valve tray with an open gas jetting part is used, the polymerization solution has a constant liquid depth and flow resistance is smaller than when a conventional tray is used. The contact time with the liquid can be lengthened. Thereby, processing efficiency improves and the usage-amount of organic solvent gas can be reduced.
- the residual monomer was removed from the polymerization solution using a valve tray (Example) or a bubble cap tray (Comparative Example) shown in Table 1 below, and the processing efficiency was compared.
- interval of each gas ejection part in the bubble tray of an Example was 118.85 mm in the polymerization liquid flow direction, and the direction orthogonal to the polymerization liquid flow direction was 65.86 mm.
- the diameter of the cap in the bubble cap tray of the comparative example was 99 mm
- the diameter of the gas ejection hole was 60 mm
- the gap between the tray bottom and the end of the cap was 8 mm.
- the residual monomer removal apparatus of the example using the valve tray was able to significantly reduce the amount of blown methanol used compared to the conventional apparatus using the bubble cap tray.
- FIGS. 4A and 4B are diagrams showing the flow analysis results of the polymerization liquid when the residual monomer removing apparatus of the example is used, and FIG. 3 (a) shows the liquid depth difference.
- FIGS. 4A and 4B are diagrams showing the flow analysis results of the polymerization liquid when using the residual monomer removing apparatus of the comparative example, and FIG. 4A shows the liquid depth difference.
- (B) shows a pressure distribution.
- the liquid depth difference and the pressure distribution are generated in the flow direction of the polymerization liquid, as shown in FIGS. In the examples, there was no difference in liquid depth and the pressure was uniform.
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Abstract
Description
本発明においては、特定方向にのみ開口するガス噴出部を備えたバルブトレイを使用しているため、トレイ上でメタノールなどの有機溶剤ガスの偏流や重合液の滞留が起こりにくい。これにより、処理効率が向上し、従来よりも少量の有機溶剤ガスで、従来と同等以上の未反応のモノマーを除去することが可能となる。
前記ガス噴出部は、トレイ底面に形成された貫通孔と、該貫通孔上に設けられたアーチ状のカバー部とで構成されていてもよく、その場合、前記トレイは、前記ガス噴出部のカバー部の長手方向と、重合液の通流方向とが一致するように配置される。
又は、前記ガス噴出部は、トレイ底面に形成された貫通孔と、該貫通孔上に設けられ一方向にのみ開口するカバー部とで構成されていてもよく、その場合は、前記トレイは、前記ガス噴出部の開口部が重合液の通流方向下流側に向くように配置される。
また、前記トレイには、重合液の通流方向上流側及び下流側に液溜壁が設けられていてもよく、その場合は、少なくとも下流側の液溜壁は、外側に5~45°傾いた状態で配設されていることが望ましい。
更に、この装置は、ポリビニルアルコールの製造工程で使用することができる。
本発明においては、脱モノマー工程において、特定方向にのみ開口するガス噴出部を備えたバルブトレイを多段に配置した残留モノマー除去装置を使用しているため、従来の製造方法に比べて処理効率が向上する。
この製造方法では、前記有機溶剤として、例えばメタノールを使用することができる。
本実施形態のPVA樹脂の製造方法では、先ず、1種若しくは2種以上のビニルエステルを重合するか、又は、ビニルエステルとこれと共重合可能なその他のモノマー(単量体)とを共重合して、ポリビニルエステルを得る。ここで使用するビニルエステルとしては、例えば、蟻酸ビニル、酢酸ビニル、プロピオン酸ビニル、バレリン酸ビニル、カプリン酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル、安息香酸ビニル、ピパリン酸ビニル及びバーサチック酸ビニルなどが挙げられるが、重合安定性の観点から特に酢酸ビニルが好ましい。
脱モノマー工程では、前述した重合工程後の重合液から、未反応のモノマー(ビニルエステル及びその他のモノマー)を除去する。図1はその際使用する残留モノマー除去装置の構成を模式的に示す図である。また、図2(a)は図1に示す残留モノマー除去装置1におけるトレイ2を示す平面図であり、図2(b)は図2(a)に示すガス噴出部2aの形状、図2(c)はガス噴出部2bの形状を示す斜視図である。
その後、脱モノマー処理したポリマー(ポリビニルエステル)溶液を、前述した有機溶剤を含む溶媒中において、触媒の存在下で鹸化する。ここで使用する溶媒としては、メタノール、エタノール、プロパノール、エチレングリコール、プロピレングリコール、グリセリン及びジエチレングリコールなどのアルコール類を使用することができるが、特に、メタノールが好ましい。
2 トレイ
2a、2b ガス噴出部
2c 液溜壁
3 重合缶
4 重合液
Claims (7)
- 塔本体と、
重合液の通流方向に直交する方向にのみ開口するか、又は、重合液の通流方向下流側に向かって開口する複数のガス噴出部を備えたバルブトレイと、
を少なくとも有し、
前記塔本体内に、前記トレイが多段に配設された残留モノマー除去装置。 - 前記ガス噴出部は、トレイ底面に形成された貫通孔と、該貫通孔上に設けられたアーチ状のカバー部とで構成されており、
前記トレイは、前記ガス噴出部のカバー部の長手方向と、重合液の通流方向とが一致するように配置されていることを特徴とする請求項1に記載の残留モノマー除去装置。 - 前記ガス噴出部は、トレイ底面に形成された貫通孔と、該貫通孔上に設けられ一方向にのみ開口するカバー部とで構成されており、
前記トレイは、前記ガス噴出部の開口部が重合液の通流方向下流側に向くように配置されていることを特徴とする請求項1又は2に記載の残留モノマー除去装置。 - 前記トレイには、重合液の通流方向上流側及び下流側に液溜壁が設けられており、少なくとも下流側の液溜壁は、外側に5~45°傾いた状態で配設されている請求項1乃至3のいずれか1項に記載の残留モノマー除去装置。
- ポリビニルアルコールの製造工程で使用されることを特徴とする請求項1乃至4のいずれか1項に記載の残留モノマー除去装置。
- 1種若しくは2種以上のビニルエステルを重合するか、又は、ビニルエステルとこれと共重合可能なその他のモノマーとを共重合する重合工程と、
該重合工程により得られた重合液に有機溶剤ガスを接触させて、未反応のモノマーを除去する脱モノマー工程と、
未反応のモノマーを除去した溶液を、前記有機溶剤を含む溶媒中において、アルカリ触媒の存在下で鹸化する鹸化工程と、を少なくとも有し、
前記脱モノマー工程は、塔本体内に、重合液の通流方向に直交する方向にのみ開口するか、又は、重合液の通流方向下流側に向かって開口する複数のガス噴出部を備えたバルブトレイを多段に配設した残留モノマー除去装置を使用して、重合液から未反応のモノマーを除去するポリビニルアルコール樹脂の製造方法。 - 前記有機溶剤として、メタノールを使用することを特徴とする請求項6に記載のポリビニルアルコール樹脂の製造方法。
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CN201080065559.2A CN102803305B (zh) | 2010-03-18 | 2010-12-06 | 残留单体去除装置及聚乙烯醇树脂的制造方法 |
EP10847991.6A EP2548896B1 (en) | 2010-03-18 | 2010-12-06 | Residual monomer elimination device and polyvinyl alcohol resin production method |
JP2012505452A JP5759979B2 (ja) | 2010-03-18 | 2010-12-06 | 残留モノマー除去装置及びポリビニルアルコール樹脂の製造方法 |
US13/634,322 US9022362B2 (en) | 2010-03-18 | 2010-12-06 | Residual monomer elimination device and polyvinyl alcohol resin production method |
SG2012067872A SG184050A1 (en) | 2010-03-18 | 2010-12-06 | Residual monomer elimination device and polyvinyl alcohol resin production method |
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JP (1) | JP5759979B2 (ja) |
CN (1) | CN102803305B (ja) |
SG (1) | SG184050A1 (ja) |
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WO (1) | WO2011114585A1 (ja) |
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JP6606666B2 (ja) * | 2013-09-09 | 2019-11-20 | パナソニックIpマネジメント株式会社 | 蓄電デバイスおよびその製造方法およびセパレータ |
CN106117399B (zh) * | 2016-08-17 | 2019-02-26 | 中国石化长城能源化工(宁夏)有限公司 | 一种pva多品种聚合***生产装置 |
CN115947444A (zh) * | 2023-03-13 | 2023-04-11 | 湖南博世科环保科技有限公司 | 一种基于臭氧的深度处理装置及废水深度处理*** |
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- 2010-12-06 JP JP2012505452A patent/JP5759979B2/ja active Active
- 2010-12-06 EP EP10847991.6A patent/EP2548896B1/en active Active
- 2010-12-06 CN CN201080065559.2A patent/CN102803305B/zh active Active
- 2010-12-06 WO PCT/JP2010/071792 patent/WO2011114585A1/ja active Application Filing
- 2010-12-06 SG SG2012067872A patent/SG184050A1/en unknown
- 2010-12-06 US US13/634,322 patent/US9022362B2/en active Active
- 2010-12-22 TW TW099145296A patent/TW201132658A/zh unknown
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Also Published As
Publication number | Publication date |
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CN102803305A (zh) | 2012-11-28 |
TW201132658A (en) | 2011-10-01 |
US9022362B2 (en) | 2015-05-05 |
US20130005906A1 (en) | 2013-01-03 |
SG184050A1 (en) | 2012-10-30 |
EP2548896B1 (en) | 2017-03-08 |
EP2548896A4 (en) | 2014-05-28 |
EP2548896A1 (en) | 2013-01-23 |
JP5759979B2 (ja) | 2015-08-05 |
CN102803305B (zh) | 2015-11-25 |
JPWO2011114585A1 (ja) | 2013-06-27 |
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