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WO1993023441A1 - Procede de fluoration directe de resines polymeres - Google Patents

Procede de fluoration directe de resines polymeres Download PDF

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Publication number
WO1993023441A1
WO1993023441A1 PCT/CA1992/000200 CA9200200W WO9323441A1 WO 1993023441 A1 WO1993023441 A1 WO 1993023441A1 CA 9200200 W CA9200200 W CA 9200200W WO 9323441 A1 WO9323441 A1 WO 9323441A1
Authority
WO
WIPO (PCT)
Prior art keywords
carrier fluid
range
fluorine
dense carrier
dense
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CA1992/000200
Other languages
English (en)
Inventor
Gregorio Tarancon
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Linde Canada Inc
Original Assignee
Liquid Carbonic Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US07/545,277 external-priority patent/US5149744A/en
Application filed by Liquid Carbonic Inc filed Critical Liquid Carbonic Inc
Priority to AU17435/92A priority Critical patent/AU1743592A/en
Publication of WO1993023441A1 publication Critical patent/WO1993023441A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C08F8/18—Introducing halogen atoms or halogen-containing groups
    • C08F8/20—Halogenation
    • C08F8/22—Halogenation by reaction with free halogens
    • 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
    • B01J19/20—Stationary reactors having moving elements inside in the form of helices, e.g. screw 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
    • B01J8/10—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles moved by stirrers or by rotary drums or rotary receptacles or endless belts
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1881—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with particles moving downwards while fluidised
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • B01J8/26—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with two or more fluidised beds, e.g. reactor and regeneration installations
    • 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
    • B01J2219/18—Details relating to the spatial orientation of the reactor
    • B01J2219/185—Details relating to the spatial orientation of the reactor vertical
    • 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
    • B01J2219/18—Details relating to the spatial orientation of the reactor
    • B01J2219/187—Details relating to the spatial orientation of the reactor inclined at an angle to the horizontal or to the vertical plane

Definitions

  • This invention relates to the direct fluorination of polymeric resins and, more particularly, relates to the direct fluorination of polymeric resins in particulate or product form which are capable of being fluorinated by contact with elemental fluorine and a dense carrier fluid.
  • Fluorination of polymeric resins is usually carried out with carriers in the gas phase or in the liquid phase.
  • the temperature of operation is generally lower than room temperature and the fluorine concentration is lower than 2 mole per cent.
  • the temperature of operation is above the room temperature and the fluorine concentration generally is higher than 2 mole per cent.
  • Gaseous carrier fluids essentially are ideal gases with low heat capacity per unit of volume, low polarizability or ability to induce dipole moment, and low critical temperature as well as a cryogenic boiling point.
  • fluorine reacts with solid particles of polymeric resin, such as polyolefin resins including polyethylene
  • hydrogen in the polymer molecule combines with fluorine atoms to form hydrogen fluoride.
  • the reaction is exothermic and, in order to prevent deterioration of the resin during fluorination due to local overheating, generated heat must be dissipated.
  • ⁇ t is a principal object of the present invention to provide a process for the fluorination of polymeric resins quickly, consistently and safely by the use of elemental fluorine in a vapour phase with a dense carrier fluid which effectively functions as a heat sink.
  • the process of the present invention comprises fluorinating polymer material capable of being fluorinated by contacting said polymeric material with elemental fluorine and a dense carrier fluid having a critical temperature higher than ambient temperature, a boiling point lower than ambient temperature minus 60 celcius degrees, and a molecular weight greater than the molecular weight of elemental fluorine.
  • the dense carrier fluid preferably has a molecular weight in the range of about 40 to about 200.
  • the polymeric material preferably is in the form of solid particles but may be in the form of products of hydrocarbon polymers capable of being fluorinated by contact with elemental fluorine. DESCRIPTION OF THE PREFERRED EMBODIMENT
  • the dense carrier fluids of the present invention are neither gases nor liquids but function, under the conditions of the process of the invention, as vapours, which are dense compared to ideal gases but sufficiently remote from the dew point not be classified as liquids.
  • Dense carrier fluids of the invention are vapours with molecular weights greater than the molecular weight of fluorine, critical temperatures higher than ambient temperature, i.e. room temperature, and a boiling point lower than room temperature minus 60 celcius degrees. Ambient or room temperature is defined to be about 24°C.
  • the carrier fluid of the invention has a critical temperature higher than room temperature and a boiling point lower than room temperature minus 60 celcius degrees, a vaporous condition outside of the dew point is established in the temperature range of the process of a maximum of 60 celcius degrees above room temperature and a minimum of 60 celcius degrees below room temperature, i.e. about -36°C to about 84°C (237°K to about 357°K).
  • the dense carrier fluid has a molecular weight in the range of from about 40 to 200, preferably about 44 to 188, which is greater than the molecular weight of fluorine, to provide a carrier fluid having a density greater than the density of fluorine.
  • the selection of dense carrier fluid is based on its reactiveness with fluorine at the operating temperature and fluorine concentration while being compatible with the fluorine.
  • Dense carrier fluids which meet the above criteria and are suited for the process of the invention are typified by perfluoropropane, chloropentafluoroethane, sulphurtetrafluoride, sulphur hexafluoride, tetrafluoroethylene, hexafluorothane, carbon dioxide, chlorotrifluoromethane, bromotrifluoromethane, and trifluoro ethane.
  • the dense carrier fluids have advantages compared with liquids and ideal gases. Liquids are difficult to totally remove from the reactor and represent hazardous environmental problem.
  • the dense fluids approach the heat capacity of the liquids but can be extracted from the reactor in the same way as ideal gases which have low heat capacity that permits easy elevation of the temperature in the reactor.
  • Liquid fluids have the critical temperature higher than the room temperature and the boiling point higher than the room temperature minus 60 celcius degrees.
  • Gas fluids (ideal gases) have the critical temperature lower than the room temperature minus 60 celcius degrees and the boiling point lower than the room temperature minus 60 celcius degrees, as shown in Table 1.
  • Vapor carrier fluids having a molecular weight of 40 to 200 have a range of density of 1.8 to 9 g/1 and a range of heat capacity of 9 cal/mole ⁇ C to 45 cal/mole ⁇ C.
  • the partial pressure of fluorine during the process of the invention is in the range of about 12 to about 120 torr and the total pressure is in the range of about 12 to 12,000 torr, preferably about 25 to about 2500 torr.
  • the fluorine concentration in the carrier fluid is in the range of about 2 to about 15% by volume, preferably about 3 to about 12% by volume.
  • the reactor had an internal volume of about 35 litres with a lower reaction zone of 15 cm diameter and a height of 80 cm and an upper contiguous phase separation zone of 25 cm diameter and a height of 40 cm.
  • a supply tank had an internal volume of 200 litres and a working pressure of about 3300 torr.
  • the reactor was charged with 5 kg of polyethylene resin and the fluorination process took place at room temperature.
  • the dwell time was 60 minutes and the pressure in the reaction was maintained at 800 torr.
  • the method of fluorination was flow through at a flow rate of 11 1/minute with a carrier fluid of carbon dioxide.
  • Fluorine concentration in the supply tank was 5% by volume.
  • the initial pressure in the supply tank was 3200 torr.
  • the fluorine incorporated was about 0.5% by weight.
  • Example 2 The conditions were the same as Example 1 except for a charge of 2.5 kg of polyethylene resin. No agglomeration, colour change or, bulk density change was observed. The fluorine incorporated was about 1.0% by weight.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention décrit un procédé de fluoration directe de résines polymères dans lequel un polymère pouvant être fluoruré est mis en contact avec le fluor élémentaire et un fluide porteur dense ayant une température critique plus grande que la température ambiante, un point d'ébullition plus bas que la température ambiante moins 60 °C et un poids moléculaire plus grand que le poids moléculaire du fluor élémentaire. De préférence, le fluide porteur dense a un poids moléculaire situé dans une plage d'environ 40 à 200.
PCT/CA1992/000200 1990-06-28 1992-05-08 Procede de fluoration directe de resines polymeres Ceased WO1993023441A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU17435/92A AU1743592A (en) 1992-05-08 1992-05-08 Process for the direct fluorination of polymeric resins

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US07/545,277 US5149744A (en) 1990-06-28 1990-06-28 Process for the direct fluorination of polymeric resins

Publications (1)

Publication Number Publication Date
WO1993023441A1 true WO1993023441A1 (fr) 1993-11-25

Family

ID=24175581

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CA1992/000200 Ceased WO1993023441A1 (fr) 1990-06-28 1992-05-08 Procede de fluoration directe de resines polymeres

Country Status (1)

Country Link
WO (1) WO1993023441A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1197527A3 (fr) * 2000-10-13 2002-04-24 Messer Griesheim Gmbh Matières plastiques de charge modifiées

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3445445A (en) * 1966-06-13 1969-05-20 Universal Oil Prod Co Modification of polyolefinic resins
US4144374A (en) * 1974-12-12 1979-03-13 Massachusetts Institute Of Technology Perfluorinated functionalized materials
EP0113428A2 (fr) * 1982-12-11 1984-07-18 PVI Patent-Verwertungs- und Innovations-Gesellschaft mbH Procédé pour fluorer la surface d'un article formé de matière plastique
EP0132407A1 (fr) * 1983-07-25 1985-01-30 Massachusetts Institute Of Technology Fluoration de surfaces polymères assistée par de la lumière ultraviolette
US4994308A (en) * 1988-05-31 1991-02-19 Tarancon Corporation Direct fluorination of polymeric materials by using dioxifluorine fluid (mixture of CO2 and F2)

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3445445A (en) * 1966-06-13 1969-05-20 Universal Oil Prod Co Modification of polyolefinic resins
US4144374A (en) * 1974-12-12 1979-03-13 Massachusetts Institute Of Technology Perfluorinated functionalized materials
EP0113428A2 (fr) * 1982-12-11 1984-07-18 PVI Patent-Verwertungs- und Innovations-Gesellschaft mbH Procédé pour fluorer la surface d'un article formé de matière plastique
EP0132407A1 (fr) * 1983-07-25 1985-01-30 Massachusetts Institute Of Technology Fluoration de surfaces polymères assistée par de la lumière ultraviolette
US4994308A (en) * 1988-05-31 1991-02-19 Tarancon Corporation Direct fluorination of polymeric materials by using dioxifluorine fluid (mixture of CO2 and F2)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1197527A3 (fr) * 2000-10-13 2002-04-24 Messer Griesheim Gmbh Matières plastiques de charge modifiées

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