US20050004337A1 - Process for producing a polyfluoroalkyl (meth) acrylate - Google Patents

Process for producing a polyfluoroalkyl (meth) acrylate Download PDF

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Publication number
US20050004337A1
US20050004337A1 US10/859,213 US85921304A US2005004337A1 US 20050004337 A1 US20050004337 A1 US 20050004337A1 US 85921304 A US85921304 A US 85921304A US 2005004337 A1 US2005004337 A1 US 2005004337A1
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United States
Prior art keywords
meth
acrylate
polyfluoroalkyl
process according
tert
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Abandoned
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US10/859,213
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English (en)
Inventor
Shoji Furuta
Taiki Hoshino
Ryuji Seki
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AGC Inc
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Asahi Glass Co Ltd
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Assigned to ASAHI GLASS COMPANY, LIMITED reassignment ASAHI GLASS COMPANY, LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HOSHINO, TAIKI, FURUTA, SHOJI, SEKI, RYUJI
Publication of US20050004337A1 publication Critical patent/US20050004337A1/en
Priority to US12/350,502 priority Critical patent/US7723439B2/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/88—Post-polymerisation treatment
    • C08G63/90—Purification; Drying
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/10—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes

Definitions

  • the present invention relates to a process for producing a polyfluoroalkyl (meth)acrylate.
  • a fluorinated copolymer obtained by copolymerizing a polyfluoroalkyl (meth)acrylate (hereinafter referred to also as a fluorinated compound) with a monomer polymerizable with a fluorinated compound, is useful as a raw material for a water and oil repellent for fibers.
  • a polyfluoroalkyl acrylate and a polyfluoroalkyl (meth)acrylate will be generally referred to as a polyfluoroalkyl (meth)acrylate, and the same applies also to a metal (meth)acrylate or the like.
  • a method for producing such a fluorinated compound a method of taking out the fluorinated compound by distilling a suspension of a metal iodide and the fluorinated compound obtained by reacting the corresponding polyfluoroalkyl iodide with a metal (meth)acrylate in a solvent such as tert-butanol, by means of a distillation apparatus as shown in FIG. 2 , or a method of filtering such a suspension and then taking out the fluorinated compound by distillation by means of one distillation apparatus, as shown in FIG. 3 , is known (e.g. JP-A-2001-19663).
  • the present invention provides a process for producing a polyfluoroalkyl (meth)acrylate, which comprises isolating, from a reaction mixture containing a polyfluoroalkyl (meth)acrylate obtained by reacting a polyfluoroalkyl iodide of the formula C n F 2n+1 (CH 2 ) m I (wherein n is an integer of from 2 to 7, and m is an integer of from 1 to 4) with a metal (meth)acrylate in tert-butanol, said polyfluoroalkyl (meth)acrylate by the following steps (1) to (3):
  • FIG. 1 is a diagrammatical view showing an example of the apparatus which is useful for carrying out the process of the present invention.
  • FIG. 2 is a diagrammatical view showing an example of the apparatus which was used for carrying out a conventional process.
  • FIG. 3 is a diagrammatical view showing another example of the apparatus which was used for carrying out a conventional process.
  • FIG. 1 the process shown in FIG. 1 is an example, and the present invention is by no means limited to FIG. 1 .
  • n is preferably from 4 to 6, more preferably 4 or 6, and m is preferably from 2 to 4, more preferably 2.
  • the metal (meth)acrylate is preferably a compound of the formula CH 2 ⁇ CXCOOM (wherein M is a monovalent metal ion, and X is a hydrogen atom or a methyl group).
  • the monovalent metal is preferably an alkali metal or an alkaline earth metal.
  • the metal (meth)acrylate is preferably an alkali metal salt such as a lithium salt, a sodium salt or a potassium salt, particularly preferably a potassium salt.
  • the fluorinated compound is preferably a compound of the formula C n F 2n+ 1 (CH 2 ) m OCOCX ⁇ CH 2 . Further, by this reaction, a metal iodide will be formed.
  • the reaction temperature is preferably from 130 to 220° C., more preferably from 140 to 180° C., most preferably from 145 to 175° C. Within such a temperature range, the conversion will be high, and formation of by-products in the reaction will be suppressed.
  • the reaction time the optimum time may suitably be selected depending upon the reaction temperature to be employed, and in the case of from 160 to 180° C., the reaction time is preferably from 4 to 12 hours, more preferably from 6 to 10 hours. Within such a range, the conversion will be high, and formation of by-products in the reaction can be suppressed.
  • the step of taking out a crude liquid from the reaction mixture containing the fluorinated compound obtained by the reaction, by solid-liquid separation, is carried out by means of a separation apparatus 1.
  • a separation apparatus a pressure filtration apparatus, a reduced pressure filtration apparatus or a centrifugal separation apparatus, may, for example, be mentioned.
  • a centrifugal separation machine a batch type centrifugal separator or a continuous type centrifugal separator may, for example, be mentioned.
  • the separation apparatus is preferably provided with a heater to prevent solidification of tert-butanol.
  • the temperature at the time of the separation is preferably from 20 to 60° C., more preferably from 30 to 40° C., to prevent solidification of tert-butanol and to prevent a polymerization reaction of the fluorinated compound.
  • the step (2) is carried out by means of a distillation apparatus 2.
  • the distillation apparatus has a heating tank and a distillation column.
  • the crude liquid obtained in the step (1) is introduced into the distillation column, and compound group A of compounds having a lower boiling point than the fluorinated compound is separated as a distillate, and compound group B of the fluorinated compound and compounds having a higher boiling point than the fluorinated compound, is separated as the bottoms.
  • the distillation in the step (2) is preferably a continuous distillation operation.
  • the compound group A includes a polyfluoroalkyleneolefin of the formula C n F 2n+1 (CH 2 ) m ⁇ 2 CH ⁇ CH 2 as a by-product in the reaction in a case where m is at least 2, tert-butanol, water, etc.
  • the above compound group B includes, in addition to the fluorinated compound as the desired product, compounds of the formulae C n F 2n+1 (CH 2 ) m OCOCHXCH 2 OC(CH 3 ) 3 , C n F 2n+1 (CH 2 ) m OCOCHXCH 2 OCOCHX ⁇ CH 2 , and C n F 2n+1 (CH 2 ) m OCOCHXCH 2 O(CH 2 ) m C n F 2n+1 (wherein n, m and X are as defined above).
  • the distillation operation in the step (2) may be carried out under atmospheric pressure or under reduced pressure.
  • Compound group A has a boiling point of at most about 100° C. under atmospheric pressure, and in order to take out compound group A as a distillate, the degree of reduced pressure is preferably from 6.67 ⁇ 10 3 to 66.7 ⁇ 10 3 Pa (from 50 to 500 mmHg), more preferably from 26.7 ⁇ 10 3 to 40.0 ⁇ 10 3 Pa (from 200 to 300 mmHg).
  • the step (2) in order to prevent a polymerization reaction of the fluorinated compound in the distillation column and the heating tank, it is preferred to carry out the distillation in an atmosphere containing oxygen gas.
  • the oxygen gas is usually diluted and supplied as an oxygen-containing gas.
  • the supply location is not particularly limited and is preferably in the heating tank in the case of a batch type distillation operation, and preferably at the lowest portion of the distillation column in the case of a continuous distillation operation. Further, the supply location is preferably more than one.
  • the content of the oxygen gas in the oxygen-containing gas to be supplied as described above is preferably from 0.01 to 5%, more preferably from 0.02 to 3%, based on the amount of vapor (by volume calculated as in the standard state) generated in the heating tank.
  • the effect for preventing the polymerization reaction is sufficient, and the increase in the amount of vapor to be carried by the oxygen-containing gas is small, and in a case where the distillation is carried out under reduced pressure, the load to the vacuuming apparatus is little.
  • the step (2) is preferably conducted in the presence of a polymerization inhibitor to prevent the polymerization reaction of the fluorinated compound.
  • a polymerization inhibitor may be one added during the reaction, which still remains, or may be added afresh in the step (2).
  • Such a polymerization inhibitor is preferably the same compound as the above-mentioned polymerization inhibitor, and the amount thereof is preferably from 0.001 to 0.05 mol, more preferably from 0.01 to 0.03 mol, per mol of the fluorinated compound.
  • the step (3) is carried out by means of a distillation apparatus 4 in such a manner that the compound group B obtained in the step (2) is introduced into a distillation column, and the fluorinated compound is taken out as a distillate from the distillation column.
  • the distillation operation in the step (3) may be carried out under atmospheric pressure or under reduced pressure.
  • the compound group B has a boiling point of at least about 150° C. under atmospheric pressure (for example, the boiling point of C 6 F 13 (CH 2 ) 2 OCOC(CH 3 ) ⁇ CH 2 is about 230° C.
  • the pressure is preferably from 0.13 ⁇ 10 3 to 3.33 ⁇ 10 3 Pa (from 1 to 25 mmHg), more preferably from 0.13 ⁇ 10 3 ⁇ 1.33 ⁇ 10 3 Pa (from 1 to 10 mmHg).
  • the step (3) it is preferred to carry out the distillation in an atmosphere containing oxygen gas in order to prevent the polymerization reaction of the fluorinated compound.
  • the oxygen gas is usually diluted and supplied as an oxygen-containing gas.
  • the supply location is not particularly limited and is preferably in the heating tank. The supply location is preferably more than one.
  • the content of the oxygen gas in the oxygen-containing gas to be supplied as described above is preferably from 0.01 to 5%, more preferably from 0.02 to 3%, based on the amount of vapor (by volume calculated as in the standard state) generated in the heating tank.
  • the effect for preventing the polymerization reaction is sufficient, the increase of the amount of vapor to be carried by the oxygen-containing gas is small, and when distillation is carried out under reduced pressure, the load to the vacuuming apparatus is little.
  • the step (3) is carried out in the presence of a polymerization inhibitor in order to prevent the polymerization reaction of the fluorinated compound.
  • a polymerization inhibitor may be one added during the reaction or in the step (2), which still remains, or may be added afresh in the step (3).
  • the polymerization inhibitor is preferably the same compound as the above-mentioned polymerization inhibitor, and the amount thereof is preferably from 0.001 to 0.05 mol, more preferably from 0.01 to 0.03 mol, per mol of the fluorinated compound.
  • step (4) of distilling the compound group A obtained in the step (2) and taking out tert-butanol as a distillate from the distillation column is preferred.
  • Such a step can be carried out by means of a distillation apparatus 3 .
  • the distillation operation in the step (4) may be carried out under atmospheric pressure or under reduced pressure. In order to increase the efficiency for recovery of tert-butanol, it is preferred to carry out the distillation under atmospheric pressure or under slightly reduced pressure.
  • a perfluoroalkylolefin contained in the compound group A may sometimes form an azeotropic mixture with tert-butanol depending upon the carbon number of its perfluoroalkyl group (C n F 2n+1 ).
  • the perfluoroalkylolefin is C 6 F 13 CH ⁇ CH 2 (boiling point: 106° C./1.01 ⁇ 10 6 Pa)
  • it forms an azeotropic mixture of about 60 mass % (boiling point: about 78° C./1.01 ⁇ 10 6 Pa) with tert-butanol (boiling point: 82.5° C./1.01 ⁇ 10 6 Pa).
  • step (4) it is possible to recover tert-butanol obtaining substantially no water.
  • Water contained in a very small amount in the compound group A is mainly one included during the separation operation in the step (1) or during the transfer operation of the separated liquid. Water forms a 22% azeotropic mixture (boiling point: 80° C./1.01 ⁇ 10 6 Pa) with tert-butanol. Accordingly, water present in a very small amount in the compound group A may be azeotropically boiled with tert-butanol and can be removed as an initial distillate at the initial stage of the step.
  • the recovered tert-butanol is preferably utilized as a solvent for the reaction or for washing the solid phase after the separation operation in the step (1).
  • a polyfluoroalkylolefin such as C 6 F 13 CH ⁇ CH 2 taken out as a distillate in the step (4) can be converted to a polyfluoroalkyl alcohol such as C 6 F 13 CH 2 CH 2 CH 2 OH by a reaction with methanol or ethanol in the presence of a radical initiator. Further, such a polyfluoroalkyl alcohol may be led to a fluorinated compound by an esterification reaction with (meth)acrylic acid, whereby the selectivity and the yield of the reaction can be improved.
  • FMA C q F 2q+1 C 2 H 4 OCOCCH 3 ⁇ CH 2 ,
  • the solid phase containing potassium iodide was washed a few times by means of tert-butanol with stirring and then dried under reduced pressure, whereupon the fluorine content in the solid phase was measured.
  • the tert-butanol solution used for washing the solid phase and the liquid phase (the filtrate) were put together to obtain a crude liquid. The results are shown in Table 2.
  • Solid-liquid separation was carried out under the conditions as shown in Table 2 by means of a centrifugal filtration apparatus provided with a jacket (manufactured by Sanyo Rikagaku Kiki K. K.) instead of the pressure filtration apparatus in Example 10.
  • the solid phase was washed a few times by means of tert-butanol and then dried under reduced pressure, whereupon the fluorine content in the solid phase was measured.
  • the tert-butanol solution used for washing the solid phase and the liquid phase were put together to obtain a crude liquid. The results are shown in table 2.
  • Solid-liquid separation was carried out under the conditions shown in Table 2 by means of a reduced pressure filtration apparatus provided with a jacket (1.5 liters, manufactured by ADVANTEC TOYO KAISHA, LTD.) instead of the pressure filtration apparatus in Example 10.
  • the solid phase was washed a few times with tert-butanol with stirring and then dried under reduced pressure, whereupon the fluorine content in the solid phase was measured.
  • the tert-butanol solution used for washing the solid phase and the liquid phase were put together to obtain a crude liquid. The results are shown in Table 2.
  • Solid-liquid separation was carried out under the conditions shown in Table 2 by means of a centrifugal separator (cooled high speed centrifugal separator H-9R, manufactured by KOKUSAN Corporation) instead of the pressure filtration apparatus in Example 10.
  • the liquid phase was obtained by decantation, and then, to wash the solid phase, tert-butanol was put and stirred, whereupon centrifugal separation and decantation were carried out again.
  • the obtained liquid phases were put together to obtain a crude liquid.
  • the washed solid phase was dried under reduced pressure, whereupon the fluorine content contained in the solid phase was measured. The results are shown in Table 2.
  • Example 2 The reaction mixture obtained in Example 1 was put in an autoclave (10 liters) equipped with double helical vanes and heated under atmospheric pressure to 120° C., whereby tert-butanol and C 6 F 13 CH ⁇ CH 2 (boiling point: 106° C./1.01 ⁇ 10 6 Pa) were recovered. Then, the pressure was stepwisely lowered to about 1.3 ⁇ 10 3 Pa (10 mmHg), and the temperature was raised to 160° C. with stirring to evaporate a liquid component. The fluorine content in the solid phase remaining in the autoclave was measured. The results are shown in Table 2.
  • the distillation residue was 300 g, the main components of the residue were C 6 F 13 (CH 2 ) 2 OCOC(CH 3 ) ⁇ CH 2 and phenothiazine, and no polymer was formed.
  • the obtained crude product and 2 g of hydroquinone were put into a glass container (1 liter) having a heating device, equipped with a distillation column (inner diameter: 35 mm, height: 600 mm) having a theoretical plate number of 30 plates, and distillation was carried out (pressure: 1.33 ⁇ 10 3 Pa (10 mmHg), temperature: 110 to 140° C.) while introducing air from the bottom of the glass container so that oxygen would be 3 volume % based on the amount of vapor generated in the glass container. 402 g of C 6 F 13 (CH 2 ) 3 OCOC(CH 3 ) ⁇ CH 2 having a purity of 99.5%, was obtained as a distillate.
  • a fluorinated compound having a high purity can be obtained in good yield.
  • the recovery rate of tert-butanol as the solvent can be made high, no polymerization reaction of the fluorinated compound will take place, and the fluorine content in the recovered metal iodide is little, whereby iodine can readily be recovered from the metal iodide.
  • the polymerization reaction of the fluorinated compound can be prevented, the number of removal operations can be reduced since the polymer formed in the distillation column is little, and the process is excellent in the purification operation efficiency of the fluorinated compound and excellent in the productivity.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
US10/859,213 2003-06-05 2004-06-03 Process for producing a polyfluoroalkyl (meth) acrylate Abandoned US20050004337A1 (en)

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US12/350,502 US7723439B2 (en) 2003-06-05 2009-01-08 Process for producing a polyfluoroalkyl (meth)acrylate

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JP2003-160885 2003-06-05
JP2003160885A JP2004359616A (ja) 2003-06-05 2003-06-05 （メタ）アクリル酸ポリフルオロアルキルエステルの製造方法

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EP (1) EP1486482B1 (ko)
JP (1) JP2004359616A (ko)
KR (1) KR100934893B1 (ko)
CN (1) CN100368376C (ko)
AT (1) ATE520641T1 (ko)
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070123712A1 (en) * 2005-11-29 2007-05-31 Balakrishnan Ganesan Methods for increasing the mean particle size of 2-hydrocarbyl-3,3-bis(hydroxyaryl)phthalimidines
US20070249876A1 (en) * 2005-04-20 2007-10-25 Asahi Glass Company, Limited Fluoroalkyl iodide and its production process
US7579498B2 (en) 2005-11-29 2009-08-25 E. I. Du Pont De Nemours And Company Process for preparing fluorinated alkyl carboxylate esters
US9834633B2 (en) 2006-03-30 2017-12-05 Asahi Glass Company, Limited Liquid repellent composition, liquid repellent processing method, and article having liquid repellent film

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CN100579950C (zh) * 2004-04-26 2010-01-13 大金工业株式会社 含氟(甲基)丙烯酸酯的制造方法
JPWO2005102984A1 (ja) * 2004-04-26 2008-03-13 ダイキン工業株式会社 含フッ素アクリル酸エステルの製造方法
JP5260826B2 (ja) * 2005-12-12 2013-08-14 東ソー株式会社 高純度含フッ素（メタ）アクリル酸エステルの製造方法
CN104672055B (zh) * 2013-11-29 2016-03-30 四川西艾氟科技有限公司 从全氟烷基乙基丙烯酸酯粗产物中分离全氟烷基乙烯的方法
JP7360856B2 (ja) 2019-09-05 2023-10-13 東ソー・ファインケム株式会社 含フッ素（メタ）アクリル酸エステル類の製造方法
US10807063B1 (en) 2019-12-31 2020-10-20 Industrial Technology Research Institute Device and method for continuously manufacturing acrylate compound

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US3239557A (en) * 1962-01-18 1966-03-08 Du Pont Process for converting halides to esters

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JPS3918112B1 (ko) 1963-01-17 1964-08-28
JP3787261B2 (ja) * 1999-04-16 2006-06-21 株式会社日本触媒 易重合性化合物の重合防止方法
JP4649689B2 (ja) * 1999-07-09 2011-03-16 ダイキン工業株式会社 ポリフルオロアルキルエステル類の製造方法およびこのエステルを用いる含フッ素アクリル共重合体の製造方法
JP4048953B2 (ja) * 2001-02-07 2008-02-20 ダイキン工業株式会社 フルオロアルキルアイオダイドテロマー混合物の製造方法および含フッ素（メタ）アクリル酸エステル混合物の製造方法

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US3239557A (en) * 1962-01-18 1966-03-08 Du Pont Process for converting halides to esters

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070249876A1 (en) * 2005-04-20 2007-10-25 Asahi Glass Company, Limited Fluoroalkyl iodide and its production process
US8729321B2 (en) 2005-04-20 2014-05-20 Asahi Glass Company, Limited Fluoroalkyl iodide and its production process
US8957264B2 (en) 2005-04-20 2015-02-17 Asahi Glass Company, Limited Fluoroalkyl iodide and its production process
US20070123712A1 (en) * 2005-11-29 2007-05-31 Balakrishnan Ganesan Methods for increasing the mean particle size of 2-hydrocarbyl-3,3-bis(hydroxyaryl)phthalimidines
US7579498B2 (en) 2005-11-29 2009-08-25 E. I. Du Pont De Nemours And Company Process for preparing fluorinated alkyl carboxylate esters
US9834633B2 (en) 2006-03-30 2017-12-05 Asahi Glass Company, Limited Liquid repellent composition, liquid repellent processing method, and article having liquid repellent film

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TWI332946B (en) 2010-11-11
TW200502214A (en) 2005-01-16
KR20040108565A (ko) 2004-12-24
CN100368376C (zh) 2008-02-13
KR100934893B1 (ko) 2010-01-06
ATE520641T1 (de) 2011-09-15
EP1486482B1 (en) 2011-08-17
JP2004359616A (ja) 2004-12-24
US20090118433A1 (en) 2009-05-07
US7723439B2 (en) 2010-05-25
EP1486482A1 (en) 2004-12-15
CN1572783A (zh) 2005-02-02

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