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WO1996032428A1 - Fuoroelastomere - Google Patents

Fuoroelastomere Download PDF

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Publication number
WO1996032428A1
WO1996032428A1 PCT/JP1995/000712 JP9500712W WO9632428A1 WO 1996032428 A1 WO1996032428 A1 WO 1996032428A1 JP 9500712 W JP9500712 W JP 9500712W WO 9632428 A1 WO9632428 A1 WO 9632428A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
molecular weight
parts
fluorine
elastomer
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/JP1995/000712
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English (en)
Japanese (ja)
Inventor
Michio Kasahara
Hiroshi Saitoh
Kenichi Hayashi
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.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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 to JP5257929A priority Critical patent/JPH07118349A/ja
Priority claimed from JP5257929A external-priority patent/JPH07118349A/ja
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to PCT/JP1995/000712 priority patent/WO1996032428A1/fr
Publication of WO1996032428A1 publication Critical patent/WO1996032428A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08F214/00—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
    • C08F214/18—Monomers containing fluorine

Definitions

  • the present invention relates to a novel fluorine-containing elastomer. More specifically, it has excellent heat resistance, solvent resistance, and chemical resistance equivalent to those of conventionally known fluorine-containing elastomers, but also has high tensile strength, excellent compression set resistance, and gasoline permeability.
  • the present invention relates to a fluorine-containing elastomer which is small, does not easily extract low molecular weight components in a solvent, and has excellent extrudability. Therefore, the fluorinated elastomer of the present invention is suitable as a material for a fuel hose, a filler hose, an in-tank hose, and the like of an automobile, for example.
  • fluorinated elastomers are extremely superior in heat resistance, solvent resistance, and chemical resistance compared to other general-purpose elastomers, they can be used in various industrial fields, such as general machinery, pollution-related sectors, automobiles, ships, aircraft, Used in hydraulic equipment, such as O-rings, gaskets, oil seals, diaphragms, valves, hoses, rolls, and sheet materials.
  • fluorine-containing elastomers generally have a drawback that they are difficult to process, and various proposals have been made to solve this problem.
  • a method of producing a vinylidene fluoride copolymer having a wide molecular weight distribution containing a low molecular weight polymer and a high molecular weight polymer by a continuous emulsion polymerization method in which a chain transfer agent is periodically added Japanese Patent Publication No. No.
  • fluorine-containing elastomers having a specific multi-peak molecular weight distribution have been proposed (Japanese Patent Application Laid-Open Nos. Hei 4-210, 1988 and Hei 4-125). No. 8614).
  • a fluorine-containing elastomer having a specific multi-peak molecular weight distribution and containing bound iodine is vulcanized using a combination of polyol vulcanization and Z or polyamine vulcanization with peroxide vulcanization to achieve mechanical strength and compression set.
  • Studies have been made to improve the solvent and to reduce the solvent extractability (Japanese Patent Application Laid-Open No. 2-160810).
  • the present inventors have previously proposed a fluorinated elastomer (Japanese Patent Application Laid-Open No. 2-160810). Based on the present invention, the processability, especially the extrudability, has been improved.
  • An object of the present invention is to provide excellent heat resistance, solvent resistance, and chemical resistance equivalent to those of conventionally known fluorine-containing elastomers, high tensile strength, excellent compression set resistance, and gasoline permeability.
  • the present invention relates to a fluorinated elastomer which is small in size, hardly extracts low molecular weight components into a solvent, and has excellent extrudability.
  • the present invention relates to (a) (a) vinylidene fluoride unit (hereinafter referred to as Below, abbreviated as VdF unit) and the weight ratio of (b) hexafluoropropylene unit (hereinafter abbreviated as HFP unit) is 40:60 to 80:20.
  • VdF unit vinylidene fluoride unit
  • HFP unit hexafluoropropylene unit
  • HFP unit hexafluoropropylene unit
  • (E) 0.6 to 2.0% by weight of iodine per 100% by weight of the fluorinated elastomer is the polymer chain terminal of the polymer derived from the low molecular weight side peak of the molecular weight distribution.
  • the fluorine-containing elastomer of the present invention needs to have a weight ratio of (a) VdF unit to (b) HFP unit of 40:60 to 80:20.
  • TFE unit tetrafluoroethylene unit
  • the intrinsic viscosity number [] which is an index of the molecular weight, is 60 to 100 ml Zg. If this [] is less than 60 m 1 / g, the tackiness during roll kneading becomes large, If it exceeds 0 O m 1, the fluidity decreases, and it is difficult to obtain good extrusion.
  • a particularly preferred intrinsic viscosity number is 70 to 9 Om1Zg.
  • the molecular weight distribution is a multi-peak type formed from two or more peaks.
  • the molecular weight distribution of the fluorine-containing elastomer of the present invention is composed of a low molecular weight peak having a molecular weight of 50,000 or less and a high molecular weight peak having a molecular weight of 50,000 or more.
  • Low molecular weight side polymers are required to improve flowability, and high molecular weight side polymers are required to maintain the green strength of the fluorinated elastomer formulation.
  • iodine in order to carry out combined vulcanization, it is necessary that 0.6 to 2.0% by weight of iodine is bound to the terminal of the polymer chain of the low molecular weight side polymer.
  • the bound iodine is easily liberated during peroxide vulcanization to form a radical at the polymer chain end, and this radical becomes a bridge point.
  • a polymer having a high molecular weight is crosslinked by polyol vulcanization and Z or polyamine vulcanization, and a polymer having a low molecular weight is simultaneously crosslinked by peroxide vulcanization.
  • the reaction proceeds, resulting in a molded product with high tensile strength, excellent compression set resistance, low gasoline permeability, and low extraction of low molecular weight components into the solvent.
  • a method for introducing iodine which can be a bridging point to the polymer chain terminal a method using an iodine compound as a chain transfer agent (JP-B-63-41928, JP-A-60-221409, etc.) is effective.
  • the iodine bound to the polymer chain end of the low molecular weight side polymer is in the range of 0.6 to 2.0% by weight based on 100% by weight of the fluorine-containing elastomer. Is insufficient, and even if it exceeds 2.0% by weight, there is no substantial effect of increasing iodine.
  • a particularly preferred iodine range is 0.8 to: L.6% by weight.
  • the ratio MwZMn of the weight average molecular weight (Mw) to the number average molecular weight (Mn) needs to be 20 to 25. If the MwZMn is less than 20, the molecular weight distribution is not widened, and the extrudability, such as extrusion speed and extruded skin, is poor.If it exceeds 25, ultra-high molecular weight polymers and ultra-low molecular weight polymers increase. The time dice is worse. Particularly preferred MwZMn is in the range of 21-23.
  • the fluorine-containing elastomer of the present invention can be produced, for example, by blending a high-molecular weight polymer and a low-molecular weight polymer, which are produced separately, respectively, or can be produced by an emulsion polymerization method, a suspension polymerization method, It can also be produced by adding an iodine compound such as a chain transfer agent such as iodomethane or 1,4-jodoperfluorobutane during polymerization by a solution polymerization method.
  • an iodine compound such as a chain transfer agent such as iodomethane or 1,4-jodoperfluorobutane
  • a method for producing the fluorine-containing elastomer of the present invention will be described by taking a suspension polymerization method as an example.
  • a predetermined mixed monomer (prepared monomer) is dispersed in an aqueous medium, the pressure is preferably set in the range of SSO kgZcm 2 'G, and a suspension stabilizer and an oil-soluble catalyst dissolved in an inert organic solvent.
  • the temperature is preferably maintained at 50 to 80 ° C while mechanically stirring to initiate polymerization. Start.
  • a new mixed monomer (additional monomer) is added so as to keep the pressure preferably within a range of 5 to 30 kgZcm 2 ⁇ G, and the polymerization is advanced.
  • the composition of the monomer units in the generated fluorinated elastomer is determined by the relationship between the charged monomer composition and the additional monomer composition.
  • the composition of the charged monomer and the composition of the additional monomer are measured by gas chromatography, and the composition of the monomer unit in the fluorinated elastomer is measured by 19 F-NMR after dissolving the elastomer in acetone. Further, during the polymerization, the molecular weight distribution is adjusted and the bound iodine is introduced into the polymer chain terminal by adding the iodine compound agent.
  • the turbidity stabilizer used in this suspension polymerization method is preferably methylcellulose.
  • dialkyl peroxydicarbonate such as diisopropyl peroxydicarbonate (hereinafter abbreviated as IPP) is preferable because it has a high decomposition temperature.
  • the inert organic solvent include 1,1,2-trichloro-1,2,2-trifluoroethane, 1,1-dichlorobenzene, 11-fluoroethane (hereinafter abbreviated as R-141b), 1.3-dichloro- 1, 1, 2, 2, 3-pentafluoropropane (hereinafter abbreviated as R-225 cb), and R-141 b.
  • R-225 cb having a small ozone depletion potential is more preferable.
  • the fluorine-containing elastomer of the present invention can be vulcanized with a polyol, a polyamine or a peroxide, vulcanization in combination is desirable to achieve the object of the present invention.
  • component (d) boroxyhydroxy aromatic compound examples include bisphenol AF, bisphenol A, bisphenol S, dihydroxybenzozophenone, hydroquinone, 4,4'-thiodiphenol, and their gold salts. Particularly preferred is bisphenol AF.
  • the mixing ratio is usually 0.1 to 10 parts by weight, preferably 0.6 to 5 parts by weight, per 100 parts by weight of the fluorine-containing elastomer. The reason that the component (d) is in this range is that if less than 0.1 part by weight, a vulcanized molded article cannot be obtained, and if it exceeds 10 parts by weight, elastomeric elasticity is lost.
  • one kind of these polyhydroxy aromatic compounds may be used, or two or more kinds may be used in combination.
  • phosphonium salts As the vulcanization accelerator of the component (e), phosphonium salts, ammonium salts, iminium salts, sulfonium salts, aminophosphine derivatives and the like are used.
  • benzyltriphenylphosphonium chloride hereinafter referred to as BT PPC and Abbreviated
  • methyltriphenylphosphoniummethylmethanephosphonate tetrabutylammonium fluoride
  • tetrabutylammonium amide 8-benzyl-1,8-diazabicyclo (5,4,0)- ⁇
  • Examples include butadiene dimethyl chloride, bis (benzyldiphenylphosphine) imidium chloride, and the like, especially BTP PC, 8-benziru-1,8-diazabicyclo (5,4,0) — ⁇ Preferred are ndecenonium chloride and bis (benzyldiphenylphosphine) imid
  • the mixing ratio is usually from 0.05 to 2 parts by weight, preferably from 0.1 to 1 part by weight, per 100 parts by weight of the fluorine-containing elastomer.
  • the component is within the range, if the amount is less than 0.05 parts by weight, the vulcanization rate becomes extremely slow,
  • vulcanization accelerators may be used alone or in combination of two or more.
  • the divalent gold hydroxide and / or divalent metal oxide of the component (f) for example, oxides and hydroxides of magnesium, calcium, zinc, lead and the like are used, and in particular, oxidation of magnesium and calcium Objects and hydroxides are preferred.
  • the mixing ratio is usually 1 to 30 parts by weight, preferably 2 to 20 parts by weight, per 100 parts by weight of the fluorine-containing elastomer.
  • the reason why the component (f) is in this range is that if the amount is less than 1 part by weight, the vulcanization does not sufficiently proceed, and if it exceeds 30 parts by weight, the compression set resistance deteriorates. These may be used alone or in combination of two or more.
  • an organic peroxide that generates peroxyradical under vulcanization conditions is used.
  • Isopropyl) benzene and particularly preferred are 2,5-dimethyl-2,5-di (tert-butylbaroxy) hexane, dicumylperoxide, ⁇ , ⁇ '-bis (tert-butylperoxy-m-).
  • Isop pill) It is benzene.
  • the mixing ratio is usually 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight, per 100 parts by weight of the fluorine-containing elastomer. If the component (g) is in this range, if it is less than 0.05, a sufficient vulcanization rate cannot be obtained, and the mold releasability will be poor. If it exceeds 5 parts by weight, the compression set resistance will be large. This is because it gets worse. Further, one kind of the organic peroxide may be used, or two or more kinds may be used in combination.
  • Examples of the polyfunctional unsaturated compound as the component (h) include triallyl cyanurate, trimethallyl isocyanurate, triallyl isocyanurate, triacryl formal, triallyl trimellitate, N, N'—m— Phenylene bismaleimide, diaryl phthalate, tetraaryl terephthalamide, tris (diarylamine) -s-triazine, triaryl phosphite, ⁇ , ⁇ -diarylacrylamide, etc. Preferred is triallyl isocyanurate.
  • the mixing ratio is usually 0.1 to 10 parts by weight with respect to 100 parts by weight of the fluorinated elastomer.
  • component (h) is within this range, a sufficient crosslinking density cannot be obtained if the content is less than 0.1 part by weight. If the amount exceeds 10 parts by weight, the component (h) bleeds on the surface of the elastomer at the time of molding to cause molding failure.
  • a particularly preferred range for component (h) is from 0.2 to 6 parts by weight.
  • the polyfunctional unsaturated compound may be used alone or in combination of two or more.
  • fluorinated elastomeric vulcanizing composition of the present invention if necessary, other components such as carbon black, austin black, graphite, silica, clay, diatomaceous earth, talc, wollastonite, and calcium carbonate may be used.
  • the mixing ratio of the filler is preferably in the range of 0.1 to 100 parts by weight based on 100 parts by weight of the fluorine-containing elastomer, and particularly preferably in the range of 1 to 60 parts by weight.
  • the reason why the content of the filler is within this range is that if the content is less than 0.1 part by weight, there is no effect of blending, and if the content exceeds 100 parts by weight, elastomeric elasticity is lost.
  • the mixing ratio of the processing aid is usually preferably 10 parts or less, more preferably 5 parts or less, per 100 parts by weight of the fluorine-containing elastomer. When the mixing ratio of the processing aid exceeds this range, heat resistance is adversely affected.
  • the mixing ratio of the coloring agent is preferably not more than 50 parts by weight, more preferably not more than 30 parts by weight, based on 100 parts by weight of the fluorine-containing elastomer. The mixing ratio of the coloring agent is within this range because if it exceeds 50 parts by weight, the compression resistance becomes permanent. This is because the strainability deteriorates.
  • a polyamine compound for example, Hexamethylene diamine, hexamethylene diamine rubamate, ethylene diamine rubamate, N, N-dicinnamilidene 1,6-hexamethylene diamine, 4,4'-bis (aminocyclocyclo Xyl) Methane carbamate is preferably used.
  • the mixing ratio is usually 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the fluorine-containing elastomer.
  • component (h) is in this range is that if it is less than 0.1 part by weight, a vulcanized molded article cannot be obtained, and if it exceeds 10 parts by weight, elastomeric elasticity is lost. Further, these polyamine compounds may be used alone or in combination of two or more.
  • the fluorine-containing elastomer of the present invention for example, after kneading with an open kneading roll or a closed kneading roll (Banbury mixer, pressurized kneader 1 or the like), a long strip is cut out and applied to an extruder. Thereby, a tube-shaped rod-shaped object can be obtained. It is also possible to carry out molding by injection molding, press molding, calendar molding, or the like. Next Ide, by performing secondary vulcanization necessary, the desired characteristics of the vulcanizates obtained £ fluorinated elastomer scratch, was determined by the following methods.
  • Intrinsic viscosity [] is measured at 35 ° C using a capillary viscometer with a 0.1100 ml concentration solution of methyl ethyl ketone.
  • MwZMn to 1.2 (max) monodisperse polystyrene
  • Mn and Mw are measured under the above conditions for measuring the molecular weight distribution.
  • the fluorine-containing elastomer had [7?] Of 89 m 1 Zg, 43.5% by weight of VdF unit, 27.8% by weight of HFP unit and 27.3% by weight of TFE unit, and contained 1.4% by weight of iodine.
  • the molecular weight distribution is formed from two peaks, with an MwZMn of 23.0.
  • Perhexa 25B-40 (containing 40% by weight of 2,5-dimethyl-2,5-di (tert-butylbaroxy) hexane") 0.7 part by weight Knead 0.6 parts by weight of triaryl isocyanurate “TA IC” manufactured by Nippon Kasei Co., Ltd., and leave it overnight to ripen it. Then, after re-kneading, put it into an extrusion test, put it in a mold, press vulcanize it at a temperature of 160 for 45 minutes to form a 2 mm thick sheet and a test piece for measuring compression set, and perform various tests .
  • TA IC triaryl isocyanurate
  • Table 1 shows the extrusion characteristics of the compound thus obtained and the physical properties of the vulcanized molded product.
  • Example 1 The same procedure as in Example 1 was repeated except that “Perhexa 25B-40” was replaced by an organic peroxide manufactured by NOF Corporation “Park Mill D-40 (containing 40% by weight of dicumyl peroxide)”. Perform the test. Table 1 shows the results.
  • Example 1 instead of the fluorine-containing elastomer of Example 1, 43.7% by weight of VdF unit, 29.2% by weight of HFP unit and 26.6% by weight of TFE unit were used, the iodine content was 0.5% by weight, and [77] was 8 lm 1 / g.
  • Various tests are carried out in the same manner as in Example 1 except that a fluorine-containing elastomer having a molecular weight distribution formed from two peaks and having Mw / Mn of 22.7 is used. Table 1 shows the results. ⁇ Example 1 ⁇ Example 'J 9 £ d Comparative Example 1 Comparative Grain Example 2 Vulcanized wit tj tyj
  • the fluorinated elastomer of the present invention has a high tensile strength, excellent compression permanent distortion resistance, and extrudability (even if the extrusion speed is increased, the fluorinated elastomer comprises the fluorinated elastomer of the present invention). It has excellent extruded skin), and is suitable as a material for automotive fuel hoses, filler hoses, in-tank hoses, etc., and has an extremely large industrial value.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Fluoroélastomère composé d'unités de fluorure de vinylidène et d'unités d'exafluoropropilène sous un rapport de poids allant de 40/60 à 80/20. Ce fluoroélastomère présente un indice à limite de viscosité [θ] de 60-100 ml/g, du type à plusieurs pics, selon lequel la courbe de répartition du poids moléculaire présente deux ou plus de deux pics. Ce fluoroélastomère présente un rapport du poids moléculaire moyen au poids (Mw) au poids moléculaire moyen au nombre (Mn) de 20 à 25. Dans ce fluoroélastomère, de 0,6 à 2,0 % en poids d'iode pour 100 % en poids d'élastomère est lié à la terminaison de chaîne moléculaire du polymère correspondant au pic du côté à faible poids moléculaire de la courbe de répartition de poids moléculaire. Comparé aux fluoroélastomères classiques, l'élastomère visé ici présente d'excellentes caractéristiques physiques et une excellente aptitude à l'extrusion, ce qui le rend particulièrement approprié pour la réalisation de tuyaux souples pour carburants automobiles, de tuyaux de remplissage ou de tuyaux immergés.
PCT/JP1995/000712 1993-10-15 1995-04-12 Fuoroelastomere Ceased WO1996032428A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP5257929A JPH07118349A (ja) 1993-10-15 1993-10-15 含フッ素エラストマー
PCT/JP1995/000712 WO1996032428A1 (fr) 1993-10-15 1995-04-12 Fuoroelastomere

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP5257929A JPH07118349A (ja) 1993-10-15 1993-10-15 含フッ素エラストマー
PCT/JP1995/000712 WO1996032428A1 (fr) 1993-10-15 1995-04-12 Fuoroelastomere

Publications (1)

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WO1996032428A1 true WO1996032428A1 (fr) 1996-10-17

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PCT/JP1995/000712 Ceased WO1996032428A1 (fr) 1993-10-15 1995-04-12 Fuoroelastomere

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002055567A3 (fr) * 2001-01-10 2003-10-16 Solvay Procede de preparation de polymeres halogenes en deux etapes et polymeres halogenes plurimodales
US8555931B2 (en) 2010-03-18 2013-10-15 Tokai Rubber Industries, Ltd. In-tank tube for automotive fuel and method of producing the tube

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62156111A (ja) * 1984-12-26 1987-07-11 Asahi Chem Ind Co Ltd 高性能含フツ素エラストマ−
JPH02160810A (ja) * 1988-12-15 1990-06-20 Asahi Chem Ind Co Ltd 含フッ素エラストマー
JPH0370759A (ja) * 1989-08-11 1991-03-26 Asahi Chem Ind Co Ltd 加硫性含フッ素エラストマー組成物
JPH04209623A (ja) * 1990-12-10 1992-07-31 Nippon Kayaku Co Ltd エポキシ樹脂組成物及びその硬化物
JPH04258614A (ja) * 1991-02-14 1992-09-14 Asahi Chem Ind Co Ltd 含フッ素エラストマー
JPH06279547A (ja) * 1989-12-20 1994-10-04 Asahi Chem Ind Co Ltd 含フッ素エラストマー
JPH06279548A (ja) * 1989-12-20 1994-10-04 Asahi Chem Ind Co Ltd 含フッ素エラストマー

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62156111A (ja) * 1984-12-26 1987-07-11 Asahi Chem Ind Co Ltd 高性能含フツ素エラストマ−
JPH02160810A (ja) * 1988-12-15 1990-06-20 Asahi Chem Ind Co Ltd 含フッ素エラストマー
JPH0370759A (ja) * 1989-08-11 1991-03-26 Asahi Chem Ind Co Ltd 加硫性含フッ素エラストマー組成物
JPH06279547A (ja) * 1989-12-20 1994-10-04 Asahi Chem Ind Co Ltd 含フッ素エラストマー
JPH06279548A (ja) * 1989-12-20 1994-10-04 Asahi Chem Ind Co Ltd 含フッ素エラストマー
JPH04209623A (ja) * 1990-12-10 1992-07-31 Nippon Kayaku Co Ltd エポキシ樹脂組成物及びその硬化物
JPH04258614A (ja) * 1991-02-14 1992-09-14 Asahi Chem Ind Co Ltd 含フッ素エラストマー

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002055567A3 (fr) * 2001-01-10 2003-10-16 Solvay Procede de preparation de polymeres halogenes en deux etapes et polymeres halogenes plurimodales
US8555931B2 (en) 2010-03-18 2013-10-15 Tokai Rubber Industries, Ltd. In-tank tube for automotive fuel and method of producing the tube

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