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WO2000018811A1 - Procede de production d'un caoutchouc fluore a reticulation rapide - Google Patents

Procede de production d'un caoutchouc fluore a reticulation rapide Download PDF

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Publication number
WO2000018811A1
WO2000018811A1 PCT/EP1999/006836 EP9906836W WO0018811A1 WO 2000018811 A1 WO2000018811 A1 WO 2000018811A1 EP 9906836 W EP9906836 W EP 9906836W WO 0018811 A1 WO0018811 A1 WO 0018811A1
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WO
WIPO (PCT)
Prior art keywords
end groups
polymerization
alkyl
vinylidene fluoride
mol
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/EP1999/006836
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German (de)
English (en)
Inventor
Ralf KRÜGER
David Bryan Harrison
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.)
Bayer AG
Original Assignee
Bayer AG
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 Bayer AG filed Critical Bayer AG
Priority to JP2000572269A priority Critical patent/JP5031943B2/ja
Priority to EP99947359A priority patent/EP1129114A1/fr
Priority to AU60836/99A priority patent/AU6083699A/en
Priority to CA002345461A priority patent/CA2345461A1/fr
Publication of WO2000018811A1 publication Critical patent/WO2000018811A1/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
    • 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

Definitions

  • the present invention relates to a process for producing a fluororubber which, in addition to vinyl end groups, is exclusively hydrogen
  • fluoroelastomers are preferably produced by aqueous emulsion or suspension polymerization (UUmann's Encyclopedia of Industrial Chemistry, Vol. A-11, VCH Verlagsgesellschaft, Weinheim 1988, p.
  • inorganic water-soluble peroxides such as Persulfates, used as initiators and emulsifiers or suspension stabilizers.
  • chain transfer agents such as carbon tetrachloride, acetone, diethyl malonate and methanol, is customary for setting the desired molecular weights.
  • ionic or polar end groups are introduced into the polymer chain, e.g. -COF, -COOH, -COOR or OH groups.
  • EP-A-796 877 describes a 2-stage aqueous process, according to which in the
  • All fluoropolymers produced by known processes contain at least partially ionic end groups which originate from the initiator.
  • certain molecular weight regulators such as Diethyl malonate also has the risk that the ester end groups formed saponify during production (including workup) and thus supply an additional proportion of ionic end groups.
  • EP-A-739 911 describes fluoroelastomers which are “essentially free” of ionic end groups. These fluoroelastomers are produced in an emulsion polymerization in water with the aid of UV radiation. A homogeneous product is not available here because the homogeneous UV Irradiation in large polymerization containers is technically difficult to implement, furthermore the peroxides used are only sparingly soluble in the aqueous medium and there is always the risk of introducing ionic end groups into the polymer through the protic solvent. In addition, the fluoroelastomers described here have no vinyl End group.
  • liquid fluororubbers are produced in inert solvents of the type RF-SO2F or perfluoroalkyl sulfone in the presence of a molecular weight regulator.
  • the fluororubbers described here also have iodine or bromine end groups.
  • fluororubbers can be produced which, in addition to vinyl end groups, carry only hydrogen, alkyl and / or alkoxy end groups by polymerizing at least one fluoromonomer by means of organic peroxides as initiators in inert fluorine-containing solvents in the absence of water and molecular weight regulators, where the solvent is chosen so that the monomers are dissolved by it, but the polymers are no longer soluble above 25 to 30 kg / mol.
  • the present invention therefore relates to a process for the preparation of a fluororubber which, in addition to vinyl end groups, has exclusively hydrogen, alkyl and / or alkoxy end groups, characterized in that at least one fluoromonomer is polymerized using organic peroxides as initiators in at least one inert fluorine-containing solvent in the absence of water and molecular weight regulators, the solvent being chosen so that the monomers are soluble but the polymers having molecular weights above 25 kg / mol are no longer dissolved .
  • fluorinated, optionally substituted ethylenes which may contain hydrogen and / or chlorine in addition to fluorine, such as e.g. Vinylidene fluoride, tetrafluoroethylene and chlorotrifluoroethylene, fluorinated 1-alkenes with 2 to 8 carbon atoms, e.g. Hexafluoropropene, 3,3,3-
  • composition is particularly preferred:
  • end groups are exclusively hydrogen, alkyl or alkoxy groups, preferably methyl groups in addition to other alkyl groups, depending on the organic peroxide used, for example 2-ethyl-pentyl or isobutyl radicals and the t-butoxy radical.
  • the number average molecular weights are in the range from 25 to 100 kg / mol, preferably from 40 to 80 kg / mol with molecular weight distributions, defined as M w / M n in the range from 1.5 to 3.5.
  • the Mooney viscosities ML ⁇ + ⁇ 0 are at 120 ° C in the range of 1 to 40, preferably 4 to 20.
  • the Mooney viscosity is determined according to DLN 53 523.
  • the radical polymerization takes place in the presence of at least one peroxide compound as an initiator.
  • Organic or fluoroorganic dialkylperoxides, diacylperoxides, dialkylperoxydicarbonates, alkylperesters and / or perketals are used as initiators, for example tert-butylperoxipivalate, tert-butylperoxi-2-ethylhexanoate, dicyclohexylperoxidic carbonate, bis (trifluoroacetylperoximide) peroxydimidene peroxydimidene peroxydimidoximide CF 3 CF 2 CF 2 OCF (CF 3 ) COO ⁇ 2 .
  • the type and amount to be used depend on the particular reaction temperature.
  • the half-lives of the peroxide to be selected are preferably between 30 and 500 min.
  • amounts between 0.05 and 1.0 parts by weight of peroxide per 100 parts by weight are preferred. monomers to be converted.
  • the molecular weights and thus viscosities of the target products are determined exclusively by the amount of initiator and the solubility of the polymer chains in the solvent.
  • the desired molecular weight is set in the first approximation by the ratio of monomer to peroxide conversion. Quantities become accordingly implemented in the range of 1 to 10 mmol peroxide per 100 mol of monomers. The use of regulators is completely dispensed with.
  • the inert, fluorinated solvent used is characterized in that it does not undergo any significant transfer reactions under the reaction conditions and that the resulting rubber no longer dissolves homogeneously above molecular weights of 25 kg / mol and has no ozone damage potential.
  • fluorocarbon or fluorocarbon compounds containing fluorocarbon or heteroatoms are suitable, such as 1,1,1,3,3-pentafluoropropane, 1,1,1,2,3,3-hexafluoropropane, 1,1,2,2 , 3,3-hexafluorocyclopentane, 1,1,2,2-tetrafluorocyclobutane, 1-trifluoromethyl-1, 2,2-trifluorocyclobutane, 2,3-dihydrodecafluoropentane, 2,2-bis (trifluoromethyl) -l, 3- dioxolane, perfiuor (tripropylamine), methoxy-2-hydrohexafluoropropane, methoxynonafluorobutane, perfluorobutanesulfofluoride, perfluorosulfolane or also the compounds of the formula (I) or (II) mentioned in the earlier application DE-197 40 633.5
  • R j is a fluorine atom or a perfluoroalkyl radical with 1 -4 C atoms and
  • R 2 represents a perfluoroalkyl radical with 1-4 C atoms
  • n 4 or 5, in particular perfluorobutanesulfofluoride and perfluorosulfolane. 1,1,1,3,3-pentafluoropropane, perfluorobutanesulfofluoride and perfluorosulfolane are preferred individually or in a mixture.
  • the ratio of fluoromonomer (monomer) to solvent and the degree of reactor filling is preferably chosen so that the proportion of the monomer in the liquid phase is at least 20% by weight at the reaction temperature.
  • the amount of monomer dissolved in the liquid phase can e.g. can be determined from the mass balance on the basis of the partial pressures of the monomer in the gas phase.
  • reaction temperatures are in the range from -20 to 130 ° C, preferably from 0 to 80 ° C. Lower temperatures lead to an increase in the running time and a sharp increase in the viscosity of the polymer. The space-time yields can no longer be significantly increased with even higher temperatures.
  • the pressure depends on the aforementioned conditions and on the composition of the monomer mixture and is preferably in the range from 10 to 100 bar, particularly preferably in the range from 15 to 50 bar.
  • the polymerization can be carried out in a batch, continuous or batch / feed process in stirred tank reactors, the batch / feed process being preferred.
  • reaction mixture can easily be passed through a
  • the fluoroelastomers according to the invention are excellently suitable for the preparation of fast crosslinkable fluorine rubber mixtures, in particular with ionic Ver "netzersystemen consisting of a polyhydroxy compound and an onium salt and an acid acceptor.
  • the polymerisation started after a few minutes.
  • copolymer composition was determined by 19 F-NMR analyzes (solvent: acetone; standard: CFC1 3 ): 20.5 mol% of hexafluoropropene,
  • the polymerization was carried out in an analogous manner to that in Example 1, using 1,1,1,3,3-pentafluoropropane instead of PFBSF and 2.5 g of tert-butyl-per-2- instead of TBPPI-75-AL. ethylhexanoate have been used as an initiator, the polymerization temperature has been increased to 78 ° C. and an initial pressure of 33.6 bar has been established accordingly.
  • the polymerization was carried out in a manner analogous to that in Example 1, with 620 ml of 1,1,1,3,3-pentafluoropropane being used as the polymerization medium instead of the PFBSF and the amount of HFP introduced being increased to 1,026 g and an initial pressure correspondingly increasing set from 29 bar.
  • the polymerization was initiated by adding 53 ml of an aqueous solution containing 20 g / l of potassium permanganate. Immediately after the single addition, said solution became continuous at a rate of 39 ml / h, indicated by the beginning of the decrease in pressure, the polymerization started after 20 min During the polymerization, a monomer mixture of 60% by weight vinylidene fluoride and 40% by weight hexafluoropropene was replenished in such a way that the internal pressure in the autoclave was constant at 10 , 3 + 0.2 bar .. After 250 g of monomer conversion, a total of 80 ml of diethyl malonate was added at a metering rate of 20 ml / h.
  • a total of 4,641 g of vinylidene fluoride and 3,078 g of hexafluoropropene were metered in in this way within a reaction time of 7.9 h.
  • the permanganate metering was stopped, the unreacted monomer mixture was removed from the reactor by expansion and evacuation, and the remaining contents of the autoclave were cooled.
  • the resulting latex was precipitated by dropping it into a well-stirred template consisting of 8,000 ml of a 2% CaCl solution, then washed with deionized water and dried in a vacuum drying cabinet at 60 ° C. for 24 h. In this way, 7.5 kg of a rubbery copolymer was isolated.
  • copolymer composition was determined by 19 F-NMR analyzes: 21.4 mol% hexafluoropropene, 78.6 mol% vinylidene fluoride.
  • the number average molecular weight was 79,800 g / mol.
  • the M NV / M n determined by GPC investigations was 1.97.
  • a value of 34 was determined at 120 ° C. for the Mooney viscosity ML ⁇ +10 (Table 1).
  • the examples according to the invention show lower viscosities than the corresponding product produced by aqueous emulsion polymerization.

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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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
  • Polymerization Catalysts (AREA)

Abstract

L'invention concerne un procédé de production d'un caoutchouc fluoré contenant, en plus de groupes terminaux vinyliques, exclusivement des groupes terminaux hydrogène, alkyle et/ou alcoxy. L'invention concerne des mélanges obtenus à partir de ces caoutchoucs fluorés ainsi que leur utilisation dans la production de pièces moulées de toutes sortes.
PCT/EP1999/006836 1998-09-28 1999-09-15 Procede de production d'un caoutchouc fluore a reticulation rapide Ceased WO2000018811A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2000572269A JP5031943B2 (ja) 1998-09-28 1999-09-15 迅速に架橋可能なフッ素ゴムの製造方法
EP99947359A EP1129114A1 (fr) 1998-09-28 1999-09-15 Procede de production d'un caoutchouc fluore a reticulation rapide
AU60836/99A AU6083699A (en) 1998-09-28 1999-09-15 Method for producing a fast crosslinkable fluororubber
CA002345461A CA2345461A1 (fr) 1998-09-28 1999-09-15 Procede de production d'un caoutchouc fluore a reticulation rapide

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1998144188 DE19844188A1 (de) 1998-09-28 1998-09-28 Verfahren zur Herstellung eines schnellvernetzbaren Fluorkautschukes
DE19844188.6 1998-09-28

Publications (1)

Publication Number Publication Date
WO2000018811A1 true WO2000018811A1 (fr) 2000-04-06

Family

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PCT/EP1999/006836 Ceased WO2000018811A1 (fr) 1998-09-28 1999-09-15 Procede de production d'un caoutchouc fluore a reticulation rapide

Country Status (6)

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EP (1) EP1129114A1 (fr)
JP (1) JP5031943B2 (fr)
AU (1) AU6083699A (fr)
CA (1) CA2345461A1 (fr)
DE (1) DE19844188A1 (fr)
WO (1) WO2000018811A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11739243B2 (en) 2018-12-21 2023-08-29 Honeywell International Inc. Azeotrope or azeotrope-like compositions of 1,2,2-trifluoro-1-trifluoromethylcyclobutane (TFMCB) and applications thereof

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4797235B2 (ja) * 2000-10-04 2011-10-19 ダイキン工業株式会社 含フッ素エラストマー
JP2002194008A (ja) 2000-12-22 2002-07-10 Daikin Ind Ltd 含フッ素重合体の製造方法
US6596829B1 (en) * 2002-01-29 2003-07-22 E. I. Du Pont De Nemours And Company Fluoropolymers and processes therefor and therewith
ITMI20020598A1 (it) * 2002-03-22 2003-09-22 Ausimont Spa Fluoroelastomeri vulcanizzabili
US8420739B2 (en) 2008-03-27 2013-04-16 Daikin Industries, Ltd. Fluorine-containing elastomer composition

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994018248A1 (fr) * 1993-02-03 1994-08-18 E.I. Du Pont De Nemours And Company Solvants polymeres a base de sulfure de perfluoroalkyle utilises pour la polymerisation de fluoromonomeres
DE19740633A1 (de) * 1997-09-16 1999-03-18 Bayer Ag Verfahren zur Herstellung von niedrigviskosen Fluorkautschuken
WO1999048937A1 (fr) * 1998-03-23 1999-09-30 Bayer Aktiengesellschaft Procede de production de polymeres fluoro-carbones partiellement fluores

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5125276B2 (fr) * 1973-03-19 1976-07-29
JPH0826098B2 (ja) * 1989-06-14 1996-03-13 イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー 含フッ素重合体の製造方法
US5182342A (en) * 1992-02-28 1993-01-26 E. I. Du Pont De Nemours And Company Hydrofluorocarbon solvents for fluoromonomer polymerization

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994018248A1 (fr) * 1993-02-03 1994-08-18 E.I. Du Pont De Nemours And Company Solvants polymeres a base de sulfure de perfluoroalkyle utilises pour la polymerisation de fluoromonomeres
DE19740633A1 (de) * 1997-09-16 1999-03-18 Bayer Ag Verfahren zur Herstellung von niedrigviskosen Fluorkautschuken
WO1999048937A1 (fr) * 1998-03-23 1999-09-30 Bayer Aktiengesellschaft Procede de production de polymeres fluoro-carbones partiellement fluores

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11739243B2 (en) 2018-12-21 2023-08-29 Honeywell International Inc. Azeotrope or azeotrope-like compositions of 1,2,2-trifluoro-1-trifluoromethylcyclobutane (TFMCB) and applications thereof

Also Published As

Publication number Publication date
AU6083699A (en) 2000-04-17
JP5031943B2 (ja) 2012-09-26
CA2345461A1 (fr) 2000-04-06
EP1129114A1 (fr) 2001-09-05
JP2002525401A (ja) 2002-08-13
DE19844188A1 (de) 2000-03-30

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