WO2013090941A1 - Polymérisation de monomères vinyliques fluorés dans des solutions aqueuses de sels - Google Patents

Polymérisation de monomères vinyliques fluorés dans des solutions aqueuses de sels Download PDF

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Publication number
WO2013090941A1
WO2013090941A1 PCT/US2012/070202 US2012070202W WO2013090941A1 WO 2013090941 A1 WO2013090941 A1 WO 2013090941A1 US 2012070202 W US2012070202 W US 2012070202W WO 2013090941 A1 WO2013090941 A1 WO 2013090941A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
reactor
fluorinated
vinyl fluoride
mpa
Prior art date
Application number
PCT/US2012/070202
Other languages
English (en)
Inventor
Brian D. Mather
Mark Brandon Shiflett
Nicole M. Reinartz
Ronald Earl Uschold
Original Assignee
E. I. Du Pont De Nemours And Company
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
Application filed by E. I. Du Pont De Nemours And Company filed Critical E. I. Du Pont De Nemours And Company
Publication of WO2013090941A1 publication Critical patent/WO2013090941A1/fr

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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
    • C08F14/00—Homopolymers and 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 a halogen
    • C08F14/18—Monomers containing fluorine
    • 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
    • C08F114/00—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 a halogen
    • C08F114/18—Monomers containing fluorine
    • C08F114/20—Vinyl fluoride
    • 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
    • C08F2/04—Polymerisation in solution
    • C08F2/10—Aqueous solvent

Definitions

  • Fluorinated vinyl monomers such as vinyl fluoride and vinylidene fluoride
  • vinyl fluoride and vinylidene fluoride are widely used to make polymers and copolymers that are useful in many applications.
  • poly (vinyl fluoride) finds wide use as a protective or
  • hydroperoxide and acetyl hydroperoxide water-soluble salts of inorganic peracids such as ammonium persulfate, potassium persulfate, potassium perphosphate , and potassium percarbonate ; and azo compounds such as -azoisobutryamidine hydrochloride, 2 , 2 ' -diguanyl-2 , 2 ' -azopropane dihydrochloride, 4 , 4-azobis ( 4- cyanovaleric acid), 2 , 2 ' -diguanyl-2 , 2 ' -azobutane
  • the concentration of the water-soluble salt in the aqueous salt solution is typically greater than about 20 wt% .
  • the upper concentration limit is determined by the aqueous solubility of the salt.
  • the concentration of the water-soluble salt in the aqueous salt solution is about 40 wt% to about 90 wt% . In another embodiment, the
  • Preferred halogen-free surfactants are nonionic surfactants having polymeric blocks of alkylene oxide units, for example, ethylene oxide and propylene oxide units .
  • Exemplary nonionic surfactants include without limitation the Pluronic® series and the Pluronic® R series from BASF (Florham Park, NJ) , such as Pluronic® 31R1.
  • the surfactant, if used, is typically present in the reaction mixture at a concentration less than or equal to about 0.1 t% based on the total weight of the reaction mixture.
  • the unreacted vinyl fluoride was vented into a fume hood, and the product was decanted into a sample jar.
  • the product was an opaque white sludge.
  • the polymer was obtained by removing the water by evaporation at room
  • the autoclave was also equipped with a
  • VF feed was resumed to maintain the pressure at 700 psi (4.83 MPa) using an Isco 1000D syringe pump.
  • the addition of VF continued for 81 min, until 35 g of VF had been added.
  • the VF and initiator feeds were then stopped.
  • the heating was turned off and cooling was turned on until the temperature dropped to 80 °C and then the excess VF was vented.
  • the reactor reached 44 °C, it was purged three times with 80 psi (0.55 MPa) nitrogen while stirring at 100 rpm.
  • the product which was a thick white sludge, was then discharged from the reactor into a pre-weighed jar.
  • the product was filtered and then divided into two fractions.
  • To one product fraction (319.40 g) was added 640 mL of deionized water and the resulting suspension was mixed at 250 rpm for 20 min using an overhead mixer

Landscapes

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

Abstract

L'invention concerne un procédé perfectionné pour la polymérisation d'un monomère vinylique fluoré pour produire un polymère fluoré. Le procédé de polymérisation comprend la polymérisation par radicaux libres d'un monomère vinylique fluoré dans une solution aqueuse de sel, qui contient un sel soluble dans l'eau ayant un cation métallique et un anion fluoré. Le sel soluble dans l'eau augmente la solubilité du monomère vinylique fluoré dans la solution aqueuse, permettant ainsi de réduire la pression requise pour la polymérisation.
PCT/US2012/070202 2011-12-16 2012-12-17 Polymérisation de monomères vinyliques fluorés dans des solutions aqueuses de sels WO2013090941A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201161576406P 2011-12-16 2011-12-16
US61/576,406 2011-12-16

Publications (1)

Publication Number Publication Date
WO2013090941A1 true WO2013090941A1 (fr) 2013-06-20

Family

ID=48613291

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2012/070202 WO2013090941A1 (fr) 2011-12-16 2012-12-17 Polymérisation de monomères vinyliques fluorés dans des solutions aqueuses de sels

Country Status (1)

Country Link
WO (1) WO2013090941A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106496371A (zh) * 2016-09-30 2017-03-15 中国科学院上海有机化学研究所 2‑氟丙烯‑甲基丙烯酸共聚物

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3475396A (en) * 1966-07-06 1969-10-28 Diamond Shamrock Corp Process for polymerizing vinylidene fluoride
US4025709A (en) * 1974-09-24 1977-05-24 Produits Chimiques Ugine Kuhlmann Process for the polymerization of vinylidene fluoride
US20040225053A1 (en) * 2003-05-06 2004-11-11 Atofina Chemicals, Inc. Polymerization of fluoromonomers using a 3-allyloxy-2-hydroxy-1-propanesulfonic acid salt as surfactant
US20080114143A1 (en) * 2006-11-09 2008-05-15 E. I. Du Pont De Nemours And Company Aqueous Polymerization of Fluorinated Monomers Using Polymerization Agent Comprising Fluoropolyether Acid or Salt and Siloxane Surfactant
US20080269408A1 (en) * 2006-11-09 2008-10-30 E. I. Du Pont De Nemours And Company Aqueous Polymerization of Fluorinated Monomer Using Polymerization Agent Comprising Fluoropolyether Acid or Salt and Short Chain Fluorosurfactant

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3475396A (en) * 1966-07-06 1969-10-28 Diamond Shamrock Corp Process for polymerizing vinylidene fluoride
US4025709A (en) * 1974-09-24 1977-05-24 Produits Chimiques Ugine Kuhlmann Process for the polymerization of vinylidene fluoride
US20040225053A1 (en) * 2003-05-06 2004-11-11 Atofina Chemicals, Inc. Polymerization of fluoromonomers using a 3-allyloxy-2-hydroxy-1-propanesulfonic acid salt as surfactant
US20080114143A1 (en) * 2006-11-09 2008-05-15 E. I. Du Pont De Nemours And Company Aqueous Polymerization of Fluorinated Monomers Using Polymerization Agent Comprising Fluoropolyether Acid or Salt and Siloxane Surfactant
US20080269408A1 (en) * 2006-11-09 2008-10-30 E. I. Du Pont De Nemours And Company Aqueous Polymerization of Fluorinated Monomer Using Polymerization Agent Comprising Fluoropolyether Acid or Salt and Short Chain Fluorosurfactant

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106496371A (zh) * 2016-09-30 2017-03-15 中国科学院上海有机化学研究所 2‑氟丙烯‑甲基丙烯酸共聚物

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