WO1996034051A2 - Compositions de resine fluoree thermoplastique et articles moules et/ou extrudes produits a partir de celles-ci - Google Patents

Compositions de resine fluoree thermoplastique et articles moules et/ou extrudes produits a partir de celles-ci Download PDF

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Publication number
WO1996034051A2
WO1996034051A2 PCT/EP1996/001741 EP9601741W WO9634051A2 WO 1996034051 A2 WO1996034051 A2 WO 1996034051A2 EP 9601741 W EP9601741 W EP 9601741W WO 9634051 A2 WO9634051 A2 WO 9634051A2
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WO
WIPO (PCT)
Prior art keywords
fluoro resin
moulded
polyoxyalkylene
thermoplastic fluoro
weight
Prior art date
Application number
PCT/EP1996/001741
Other languages
English (en)
Other versions
WO1996034051A3 (fr
Inventor
Takatoshi Kuratsuji
Yoshiyuki Miyaki
Kazuyoshi Ohashi
Jérôme MAILLET
Original Assignee
Elf Atochem S.A.
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 JP10606295A external-priority patent/JPH08302135A/ja
Priority claimed from JP19721795A external-priority patent/JPH0940833A/ja
Application filed by Elf Atochem S.A. filed Critical Elf Atochem S.A.
Priority to AU56926/96A priority Critical patent/AU5692696A/en
Publication of WO1996034051A2 publication Critical patent/WO1996034051A2/fr
Publication of WO1996034051A3 publication Critical patent/WO1996034051A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or 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; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/16—Homopolymers or copolymers or vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides

Definitions

  • thermoplastic fluoro resin compositions and moulded articles produced therefrom.
  • the thermoplastic fluoro resin compositions of the present invention have improved mouldability, flexibility, adhesive and antistatic properties and can be used to produce moulded articles, films and fibres.
  • Thermoplastic fluoro resins possessing high weather- and chemical resistance are utilized in many fields such as paint, electrical or electronics components, steel pipe liner, materials for chemical plant and stain- and weather-resistant film. These resins, however, are difficult to combine with other materials owing to their poor adhesiveness. Fluoro resins are resistant to staining but show rather poor antistatic properties. Fibres and films based on fluoro resin are difficult to stretch owing to their high viscosity and crystallinity.
  • JP-A-54-106622 isobutylene copolymer
  • acrylate resin JP-B-56-
  • An objective of the present invention is to improve the flexibility, adhesive properties and antistatic properties of thermoplastic fluoro resin compositions.
  • thermoplastic fluoro resin composition comprising (A) 99.5 to 55 % by weight of thermoplastic fluoro resin(s) containing at least 50 % by weight of vinylidene fluoride and (B) 0.5 to 45 parts by weight of polyoxyalkylene(s) and/or polyether ester resin(s).
  • the thermoplastic fluoro resin (A) contains at least 50 % by weight of vinylidene fluoride (VF2), and may contain less than 50 % by weight of other components.
  • the comonomers may be tetrafluoroethylene (TFE), trifluoroethylene, chlorotrifluoroethylene (CTFE), vinyl fluoride (VF), hexafluoropropylene (HFP), ethylene and/or perfluoroalkyl vinyl ethers.
  • the content of VF2 in resin (A) is at least 50 % by weight, preferably above 70 % by weight, more preferably above 90 % by weight.
  • Resin (A) according to the present invention can be obtained by any usual polymerization method including emulsion polymerization and dispersion polymerization and preferably has a melt flow index (MFI) measured at 230 °C under a load of 2.16 kg according to ISO 1133 in the range of 0.1 to 500 g/10 min.
  • MFI melt flow index
  • the polyoxyalkylene (B) is a polymer of oxyalkylene.
  • a polyoxyalkylene can be prepared by ring-opening polycondensation of an alkylene glycol with an alkylene oxide of relatively low molecular mass and by ring-opening polymerization of an alkylene oxide of relatively high molecular mass.
  • the polyoxyalkylene (B) may be poly(oxyethylene), poly(1 ,2- or 1 ,3- propylene)oxide, polytetramethylene oxide, polyhexamethylene oxide, a block, random or graft copolymer of ethylene oxide and propylene oxide and a block or random copolymer of ethylene oxide and tetrahydrofuran. Polyoxyethylene is preferred.
  • the number-average molecular weight Mn of the polyoxyalkylene is preferred.
  • 1 ,000 to 5,000,000 preferably 10,000 to 1 ,000,000, and more preferably 20,000 to 600,000 and depends on applications.
  • a relatively low molecular mass 10,000 to 50,000
  • relatively a high molecular mass 100,000 to 1 ,000,000
  • Too high molecular masses are not preferred because of too high viscosity and low thermal stability.
  • the polyether ester resin (B)" according to the present invention is a resin in which polyoxyalkylene units of relatively low molecular mass such as defined above are bonded to each other by ester bonds through a compound of relatively low molecular mass, called a “bonding compound”. Consequently, the polyether ester resin (B) according to the present invention is different from a polyetherpolyester block copolymer (so-called thermoplastic polyester elastomer, TPEE).
  • the number-average molecular weight Mn of the polyoxyalkylene units is generally lower than 20,000, preferably lower than 10,000, more preferably lower than 5,000.
  • the polyoxyalkylene units are bonded to each other through a compound of relatively low molecular mass to produce a polyether ester having a molecular mass higher than 40,000, preferably being 100,000 to 1,000,000.
  • a polyoxyalkylene of high molecular mass is difficult to mix with thermoplastic fluoro resin owing to high crystallinity, so that the resulting product shows poor uniformity and antistatic properties when compared with a polyether ester obtained by bonding polyoxyalkylene units through relatively low molecular mass compounds.
  • the relatively low molecular mass bonding compounds have generally a molecular mass of less than 500 and may be chosen from carboxylic acids, hydroxyl compounds, epoxy compounds and oxazoline compounds (in this case, there are some amide bonds but the polyoxyalkylene units must be bonded by ester bond).
  • the choice of preferred bonding compounds depends on the terminal groups of the polyoxyalkylene units. For example, if the polyoxyalkylene units have hydroxyl end groups, dicarboxylic acids, bisoxazoline compounds or the like are preferably used. If the polyoxyalkylene units have carboxyl end groups, dihydroxyl compounds, diepoxy compounds, bisoxazoline compounds or the like are preferably used.
  • the carboxylic acids may be oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid and pyromellitic acid.
  • the hydroxy acids may be glycolic acid and hydroxybenzoic acid.
  • the hydroxyl compounds may be ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, neopentyl glycol, hexamethylene glycol, glycerol and trimethylolpropane.
  • the oxazoline compounds may be ethylene bisoxazoline and phenylene bisoxazoline.
  • the epoxy compounds may be bisglycidyl terephthalate or the like.
  • the polyether ester obtained from polyoxyalkylene units with hydroxyl end groups and a dicarboxylic acid or its derivative is easy to produce and hence is advantageous.
  • Derivatives of dicarboxylic acids may be used such as anhydrides and C1-C3 alkyl esters.
  • thermoplastic fluoro resin(s) (A) to polyoxyalkylene(s) and/or polyether ester(s) (B) is 95.5/0.5 to 55/45, preferably 95/1 to 70/30, and depends on the application.
  • the composition according to the present invention can be used directly from a dry blend of components (A) and (B) but is preferably melt-kneaded before moulding.
  • the kneading can be done by any known technique without using any compatibility-improving agent in any known kneader such as a Banbury mixer, rubber rolls and a single- or a twin-screw extruder.
  • the resin composition is melt-kneaded usually at 100 to 300 °C, preferably 150 to 270 C, to prepare a moulding compound.
  • the mouldability of the composition according to the present invention in injection and extrusion moulding is excellent because no rise in pressure caused by viscosity is observed even in high-speed moulding.
  • the composition according to the present invention can be spun by the usual melt-spinning drawing techniques to produce fibres and can be extruded to produce films, sheets and plates.
  • the fibre can be multifilament, monofilament, staple, or be made into a textile or knitted article or nonwoven web and can have a solid, hollow or profiled cross section.
  • the fibre can be mixed advantageously with other materials to produce a mixed nonwoven web because of its improved adhesive properties.
  • composition according to the present invention may contain known additives such as antioxidants, antipyrolysis agents, UV absorbers, antihydrolysis agents, colorants (dyes, pigments), antistatic agents, electrically conductive agents, crystal nucleating agents, plasticizers, slip agents, lubricants, mould release agents, flame retardants, reinforcements, fillers, adhesives and tackifiers.
  • additives such as antioxidants, antipyrolysis agents, UV absorbers, antihydrolysis agents, colorants (dyes, pigments), antistatic agents, electrically conductive agents, crystal nucleating agents, plasticizers, slip agents, lubricants, mould release agents, flame retardants, reinforcements, fillers, adhesives and tackifiers.
  • compositions according to the present invention possess useful properties such as mouldability, flexibility and antistatic and adhesive properties and are useful as materials for moulded materials, fibre and film.
  • composition according to the present invention shows a reduced pressure increase in high-speed moulding and the moulded articles obtained therefrom show improved flexibility, antistatic properties and adhesion to other materials and possess improved properties for moulded articles, fibres and films.
  • the pressure is not greatly increased, even in high-speed moulding operation.
  • MFI Melt Flow Index
  • Viscosity-average molecular mass of polyoxyalkylene (POA) and polyether ester (PEE) calculated by Bailey's experimental equation from the solution viscosity of an aqueous solution containing 0.1 % by weight of polymer at 35 °C
  • compositions a) Pellets of fluoro resin and of POA are mixed in a blender and extruded using a single-screw extruder (20 mm ⁇ ) equipped with a die of 3 mm ⁇ to prepare pellets for fibre and film at barrel temperatures of 160 to 260 °C and at a screw speed of 10 rev/min. b) Predetermined amounts of pellets of fluoro resin and of PEE are blended in a blender. The resulting mixture is extruded using a single- screw extruder having a barrel temperature of 160 to 260 °C at a screw speed of 20 rev/min through a die having a hole of 3 mm ⁇ to prepare pellets from which samples of fibre, film and moulded articles are prepared.
  • a film of 1 mm thickness was prepared from the pellets prepared in 3a) or in 3b) and its surface resistivity was measured at 23 °C in 50 % relative humidity according to JIS K -6911.
  • the following polymers were used in the Examples :
  • PVDF-1 100 % PVDF homopolymer
  • MFI 20 PVDF-2: copolymer of VF2 and HFP (15%)
  • MFI 10 PVDF-3: copolymer of VF2 and HFP (5%)
  • MFI 8
  • POA-1 polyoxyethylene (viscosity-average molecular mass of 150,000) POA-2 polyoxyethylene (viscosity-average molecular mass of 280,000) POA-3 polyoxyethylene (viscosity-average molecular mass of viscosity- average molecular mass of 20,000) POA-4: polyoxyethylene (viscosity-average molecular mass of 10,000) PEE-1 polyether ester (viscosity-average molecular mass of 150,000) prepared by polycondensation of polyoxyethylene possessing a viscosity-average molecular mass of 2,500 and dimethyl terephthalate.
  • PEE-2 polyether ester (viscosity-average molecular weight of 130,000) prepared by polycondensation of polyoxyethylene of viscosity- average molecular mass of 5,000 and adipic acid.
  • Example 1 Pellets of PVDF-1 and pellets of POA-1 were blended in a weight ratio of
  • a test sample prepared by an injection moulding machine from the pellets at a mould clamping pressure of 80 tons showed a fiexural modulus of 1 ,100 MPa, an impact strength of 11 kJ/m 2 and a surface resistivity of 10 10 ⁇ /L 2 .
  • Example 1 was repeated but the pellets of PVDF-1 and pellets of POA-1 were blended in a weight ratio of 95/5 at a head pressure of 5 MPa. The head pressure was increased 1.5-fold, the fiexural modulus was 1 ,150 MPa, the impact strength 10 kJ/m 2 and the surface resistivity 10 11 ⁇ /L 2 . Comparative Example 1
  • Example 1 was repeated but only PVDF-1 was used.
  • the head pressure was 8 MPa
  • the increase in head pressure was 1.8-fold
  • the fiexural modulus was 1,800 MPa
  • the impact strength was 5 kJ/m 2
  • the surface resistivity was lO ⁇ /L 2 .
  • Example 6 The POA-1 of Example 1 was replaced by POA-2 (Example 3), POA-3 (Example 4) and POA-4 (Example 5) and the PVDF-1 of Example 1 was replaced by PVDF-2 (Example 6, in this case the barrel temperature was set at 240 °C).
  • Example 8 A filament was spun at 270 °C through a die having a hole of 0.3 mm ⁇ using the pellets of Example 1. The observation of the resulting fibre by microscope showed a structure of a fine dispersion although not perfectly compatible. The fibre has good adhesion to polypropylene fibre. The fibre made of PVDF-1 alone (Comparative Example 1) has no adhesion to polypropylene. Example 8
  • the resulting mixture was extruded using a single-screw extruder (barrel temperature - 250 °C) to obtain strands from which pellets were prepared.
  • the head pressure at extrusion was 4.5 MPa. This extrusion head pressure increased to 1.3-fold when the number of revolutions of the screw was doubled.
  • Example 8 was repeated but POA-1 was used instead of PEE-1.
  • the extrusion head pressure was 5 MPa, which is 10 % higher than in the case of PEE-1.
  • a sheet of 1 mm thickness prepared from this composition showed a surface resistivity of ⁇ .lO ⁇ . ⁇ /L 2 so that this film was a little less antistatic than the one of PEE-1.
  • Example 10
  • Example 8 was repeated but the A/B ratio was changed to 95/5.
  • the extrusion head pressure was 5 MPa.
  • the increase in pressure was 1 , 4-fold, the fiexural modulus was 1 ,150 MPa, the impact strength was 9.5 kJ/m 2 and the surface resistivity 8.10 10 ⁇ /L 2 .
  • Example 8 was repeated but PVDF alone was used.
  • the extrusion head pressure was 8 MPa.
  • the increase in pressure was 1.8-fold
  • the fiexural modulus was 1 ,800 MPa
  • the impact strength was 5 kg J/m 2
  • the surface resistivity 10 ⁇ /L 2 was 5 .
  • Example 11 Example 8 was repeated but the PVDF-1 was replaced by PVDF-3 and
  • PEE-1 was replaced by PEE-2.

Abstract

La présente invention concerne une composition de résine fluorée, thermoplastique, améliorée quant à sa possibilité d'être moulée très rapidement et quant à ses propriétés adhésives et antistatiques, et permettant ainsi une production d'articles moulés et/ou extrudés. Cette composition comprend (A) une (des) résine(s) fluorée(s) thermoplastique(s) contenant au moins 50 % en poids de fluorure de vinylidène et (B) un ester de polyoxyalkylène et/ou de polyéther, le rapport pondéral (A)/(B) se situant entre 99,5/0,5 et 55/45. Les articles moulés et/ou extrudés, obtenus à partir de cette composition, présentent les mêmes propriétés améliorées que celles indiquées ci-dessus.
PCT/EP1996/001741 1995-04-28 1996-04-25 Compositions de resine fluoree thermoplastique et articles moules et/ou extrudes produits a partir de celles-ci WO1996034051A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU56926/96A AU5692696A (en) 1995-04-28 1996-04-25 Thermoplastic fluoro resin compositions and moulded and/or e xtruded articles produced therefrom

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP10606295A JPH08302135A (ja) 1995-04-28 1995-04-28 熱可塑性フッ素系樹脂組成物及びそれから製造された成形品
JP7/106062 1995-04-28
JP19721795A JPH0940833A (ja) 1995-08-02 1995-08-02 熱可塑性フッ素系樹脂組成物及びその成形品
JP7/197217 1995-08-02

Publications (2)

Publication Number Publication Date
WO1996034051A2 true WO1996034051A2 (fr) 1996-10-31
WO1996034051A3 WO1996034051A3 (fr) 1996-12-05

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WO (1) WO1996034051A2 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7212273B2 (en) * 2003-03-04 2007-05-01 Canon Kabushiki Kaisha Exposure apparatus and method of producing device
US7236228B2 (en) * 2003-07-08 2007-06-26 Canon Kabushiki Kaisha Exposure apparatus
CN105073839A (zh) * 2012-12-21 2015-11-18 索尔维特殊聚合物意大利有限公司 致密氟聚合物薄膜
US10745555B2 (en) 2011-06-23 2020-08-18 Solvay Specialty Polymer Italy S.P.A. Process for manufacturing porous membranes

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4855360A (en) * 1988-04-15 1989-08-08 Minnesota Mining And Manufacturing Company Extrudable thermoplastic hydrocarbon polymer composition
WO1996007700A1 (fr) * 1994-09-02 1996-03-14 Minnesota Mining And Manufacturing Company Plastique fluore a aptitude de mise en ×uvre en fusion

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0712419B2 (ja) * 1986-05-30 1995-02-15 エヌオーケー株式会社 ポリフツ化ビニリデン多孔質中空糸膜の製造法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4855360A (en) * 1988-04-15 1989-08-08 Minnesota Mining And Manufacturing Company Extrudable thermoplastic hydrocarbon polymer composition
WO1996007700A1 (fr) * 1994-09-02 1996-03-14 Minnesota Mining And Manufacturing Company Plastique fluore a aptitude de mise en ×uvre en fusion

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 106, no. 2, 12 January 1987, Columbus, Ohio, US; abstract no. 5682, LIPATOV, YU. S. ET AL 'Microstructure of polyethylene glycol-poly(vinylidene fluoride) blend' & DOPOV. AKAD. NAUK UKR. RSR, SER. B: GEOL., KHIM. BIOL. NAUKI (1986), (9), 42-4 CODEN: DANND6;ISSN: 0377-9785, 1986 *
DATABASE WPI Section Ch, Week 8803, Derwent Publications Ltd., London, GB; Class A32, AN 88-019079 & JP,A,62 282 606 (NIPPON OIL SEAL IND) 8 December 1987 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7212273B2 (en) * 2003-03-04 2007-05-01 Canon Kabushiki Kaisha Exposure apparatus and method of producing device
US7236228B2 (en) * 2003-07-08 2007-06-26 Canon Kabushiki Kaisha Exposure apparatus
US10745555B2 (en) 2011-06-23 2020-08-18 Solvay Specialty Polymer Italy S.P.A. Process for manufacturing porous membranes
CN105073839A (zh) * 2012-12-21 2015-11-18 索尔维特殊聚合物意大利有限公司 致密氟聚合物薄膜

Also Published As

Publication number Publication date
WO1996034051A3 (fr) 1996-12-05
AU5692696A (en) 1996-11-18

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