WO2001019582A1 - Technique de stabilisation de copolymere fluore - Google Patents

Technique de stabilisation de copolymere fluore Download PDF

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Publication number
WO2001019582A1
WO2001019582A1 PCT/JP2000/006080 JP0006080W WO0119582A1 WO 2001019582 A1 WO2001019582 A1 WO 2001019582A1 JP 0006080 W JP0006080 W JP 0006080W WO 0119582 A1 WO0119582 A1 WO 0119582A1
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WO
WIPO (PCT)
Prior art keywords
stabilizing
copolymer
fluorine
fluorinated copolymer
main chain
Prior art date
Application number
PCT/JP2000/006080
Other languages
English (en)
Japanese (ja)
Inventor
Hiroyuki Imanishi
Yoshiyuki Hiraga
Tomohisa Noda
Satoshi Komatsu
Original Assignee
Daikin Industries, Ltd.
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 Daikin Industries, Ltd. filed Critical Daikin Industries, Ltd.
Publication of WO2001019582A1 publication Critical patent/WO2001019582A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B13/00—Conditioning or physical treatment of the material to be shaped
    • B29B13/02—Conditioning or physical treatment of the material to be shaped by heating
    • B29B13/022—Melting the material to be shaped
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
    • B29K2027/12—Use of polyvinylhalogenides or derivatives thereof as moulding material 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
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages

Definitions

  • the present invention relates to a method for stabilizing a fluorine-containing copolymer, and particularly to stabilizing a fluorine-containing copolymer except for an unstable bond contained in the main chain of a fluorine-containing copolymer that can be melt-processed. About the method.
  • Related technology relates to a method for stabilizing a fluorine-containing copolymer, and particularly to stabilizing a fluorine-containing copolymer except for an unstable bond contained in the main chain of a fluorine-containing copolymer that can be melt-processed.
  • melt processing of an emulsion copolymer of tetrafluoroethylene and hexafluoropropylene to produce a final product may result in the formation of bubbles or voids due to volatile substances in the final product.
  • This volatile material is generated due to the unstable polymer-terminal groups and unstable bonds in the polymer backbone that are unstable to heat and shear.
  • Japanese Patent Publication No. 5-10204 U.S. Pat. No. 4,626,587
  • the fluorocopolymer is removed by removing the unstable bond contained in the main chain of the fluorocopolymer. It states that in the case of stabilization, it is necessary to apply a high shearing force by a twin-screw extruder and mechanically cut the main chain. After that, the pellets obtained were fluorinated for the purpose of improving color tone and stabilizing unstable terminal groups.
  • the melt viscosity of the fluorine-containing copolymer subjected to strong shearing by the extruder changes, it was necessary to control the melt viscosity by using an additive such as alkali metal for adjusting the treatment temperature.
  • twin-screw extruders that process fluorinated copolymers must use expensive materials and require a certain amount of time to stabilize the terminals and to treat unstable main chain sites. In the end, the processing cost as a whole becomes very high.
  • the problem to be solved by the present invention is to provide a method capable of economically improving the stability of a melt-processable fluorine-containing copolymer, and in particular, to include in the main chain of the fluorine-containing copolymer
  • An object of the present invention is to provide a method capable of stably and economically stabilizing a fluorinated copolymer by effectively removing an unstable bond part.
  • the object of the present invention is to stabilize a fluorine-containing copolymer, which is characterized in that a melt-processable fluorine-containing copolymer is heated and melted at a temperature of 360 to 410 ° C in the substantial absence of shearing force. Solved by the method.
  • the fluorine-containing copolymer treated by the method of the present invention is usually tetrafluoroethylene (TFE), hexafluoropropylene (HFP), perfluoroalkyl vinyl ether, ethylene, vinylidene fluoride and Copolymers consisting of at least two monomers selected from the group consisting of trifluoroethylene, preferably from at least two monomers selected from the group consisting of TFE, HFP and perfluoroalkyl vinyl ether Copolymer, especially 5 to 25 weight by weight. /.
  • These copolymers may contain small amounts of other copolymerizable monomers in addition to the above-mentioned monomers.
  • the perfluoroalkyl biel ether is preferably of the formula:
  • n is an integer of 1 to 6.
  • n is an integer from :! to 4.
  • the melt-processable fluorine-containing copolymer is preferably produced by emulsion polymerization or suspension polymerization.
  • the fluorinated copolymer is a TF E-HF P-based copolymer (FE P) such as a TF E-HF P copolymer or a T FE-HF P perfluoroalkylbutyl ether copolymer
  • FE P TF E-HF P-based copolymer
  • the fluorine-containing copolymer is heated at 360 to 40 ° C., preferably at
  • Substantially in the absence of shearing force '' means that the molten fluorinated copolymer is added when stirring or flowing to promote the diffusion of volatiles from the fluorinated copolymer.
  • a small shear force may be applied, but means that the conditions are not such as to provide a high shear rate, such as a twin screw extruder, for example, 100 seconds to 1 or more.
  • Heating is a method in which the fluorinated copolymer is left standing on a plate in an electric furnace to heat it.However, the smooth metal surface is used as a heating source, and the fluorinated copolymer flows down the wall surface according to gravity. It may be a method. Considering the diffusion of the decomposition volatiles in the molten fluorinated copolymer, the thickness of the fluorinated copolymer is preferably about 20 to 25 mm or less.
  • Heating may be performed in a closed container under reduced pressure conditions, or may be performed while forcibly charging air to prevent foreign matter from entering from outside.
  • heating is performed while supplying humidified air, that is, a gas containing water and oxygen, in order to decompose one COF group, which is an unstable terminal group generated during heating and melting, to stabilize the molecular terminal. Is preferred.
  • the time for heating and melting the fluorine-containing copolymer depends on the heating temperature. Generally, the heating time is
  • the amount of the unstable bond in the main chain of the fluorinated copolymer is measured by measuring the main chain volatile substance index (BV I) described in Japanese Patent Publication No. 5-10204 (US Pat. No. 4,626,587). Can be evaluated by The method of measuring the main chain volatile matter index will be described below.
  • BV I main chain volatile substance index
  • the glass container is kept under vacuum (2. OmmHg or less) at 150 ° C for 3 hours.
  • the glass container is then placed in a high temperature block maintained at 380 ° C to achieve thermal equilibrium.
  • V is the volume of the glass container (m 1)
  • W is the mass of the sample.
  • the BVI is preferably 15 or less, more preferably 10 or less, to produce a final product without foaming. Preferred embodiments of the invention
  • BVI was measured by the above method.
  • indexes are known in the field of resin as indexes relating to coloring, but in the following examples, a yellowness index (YI; ASTM D 1 925-70) is adopted and a spectral color sensor CF— It was measured using 1440 (manufactured by Minonoreta Co., Ltd.).
  • YI yellowness index
  • CF spectral color sensor
  • Example 1 Prepared by emulsion polymerization using ammonium persulfate (APS), has a melt viscosity of 3.2 kPa's (372 ° C) and a melting point of 263 ° C, and weighs 11.8. /.
  • the HEP-containing FEP powder was placed on a platinum dish that was allowed to stand in an electric furnace set to each processing temperature shown in Table 1, and was heated and melted for the time shown in Table 1.
  • the main chain volatile matter index of the obtained FEP BVI and YI were measured. Table 1 shows the results.
  • the resin after the treatment is milky white, and YI shows a good value.
  • the melt viscosity slightly changed depending on the processing conditions.
  • a melt viscosity of 2.5 kPa's (37%) was prepared by suspension polymerization using bis ⁇ -hydroxy-hexanyl peroxide (DH () as the initiator.
  • the FEP powder having a melting point of 2 ° C) and 259 ° C and containing 12.0% by weight of HFP was heat-treated in the same manner as in Example 1, and BVI and YI were measured. Table 2 shows the results.
  • the BVI measured in the state of the powder before the heat treatment was 22.6.
  • Example 2 Since the initial value of BVI is larger than that in Example 1, the value of BVI after the heat treatment is larger than that of the corresponding heating conditions in Example 1, but the decrease is smaller than that in Example 1. Greater than 1. On the other hand, YI showed better results than Example 1 under any heating conditions. In each case of Example 2, no unstable terminal groups were found in the copolymer after the heat treatment.
  • the BVI was not less than 15 and did not reach the foaming level usable as a product.

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

Abstract

Cette invention, qui a trait à une technique permettant d'améliorer et ce, de façon économique, la stabilité d'un copolymère fluoré pouvant être traité par fusion, concerne, plus précisément, une technique dans le cadre de laquelle on retire, de manière satisfaisante, des motifs instables contenus dans la chaîne principale d'un copolymère fluoré et ce, afin de stabiliser, facilement ainsi qu'aux meilleurs coûts, le dit copolymère. Ce copolymère fluoré pouvant être traité par fusion est soumis à un traitement thermique à des températures comprises entre 360 et 410 °C sans quasiment subir de forces de cisaillement.
PCT/JP2000/006080 1999-09-10 2000-09-07 Technique de stabilisation de copolymere fluore WO2001019582A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP25711099 1999-09-10
JP11/257110 1999-09-10

Publications (1)

Publication Number Publication Date
WO2001019582A1 true WO2001019582A1 (fr) 2001-03-22

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PCT/JP2000/006080 WO2001019582A1 (fr) 1999-09-10 2000-09-07 Technique de stabilisation de copolymere fluore

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6703464B2 (en) 2002-01-17 2004-03-09 Daikin America, Inc. Flourine-containing copolymer
US6743508B2 (en) 2002-01-17 2004-06-01 Daikin America, Inc. Fep pellet

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3969435A (en) * 1975-04-03 1976-07-13 E. I. Du Pont De Nemours And Company Process for finishing tetrafluoroethylene-hexafluoropropylene copolymers
JPS51116860A (en) * 1975-04-07 1976-10-14 Daikin Ind Ltd Method of heat treatment of ethylene tetrafluorethylene copolymers
US4626587A (en) * 1984-01-16 1986-12-02 E. I. Du Pont De Nemours And Company Extrusion finishing of perfluorinated copolymers
EP0928673A1 (fr) * 1996-09-09 1999-07-14 Daikin Industries, Limited Procede pour stabiliser un fluoropolymere

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3969435A (en) * 1975-04-03 1976-07-13 E. I. Du Pont De Nemours And Company Process for finishing tetrafluoroethylene-hexafluoropropylene copolymers
JPS51116860A (en) * 1975-04-07 1976-10-14 Daikin Ind Ltd Method of heat treatment of ethylene tetrafluorethylene copolymers
US4626587A (en) * 1984-01-16 1986-12-02 E. I. Du Pont De Nemours And Company Extrusion finishing of perfluorinated copolymers
EP0928673A1 (fr) * 1996-09-09 1999-07-14 Daikin Industries, Limited Procede pour stabiliser un fluoropolymere

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6703464B2 (en) 2002-01-17 2004-03-09 Daikin America, Inc. Flourine-containing copolymer
US6743508B2 (en) 2002-01-17 2004-06-01 Daikin America, Inc. Fep pellet
US7105619B2 (en) 2002-01-17 2006-09-12 Daikin Industries, Ltd. Fluorine-containing copolymer
US7923519B2 (en) 2002-01-17 2011-04-12 Daikin Industries, Ltd. FEP pellet
US8334351B2 (en) 2002-01-17 2012-12-18 Daikin Industries, Ltd. FEP pellet

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