WO2010053056A1 - 含フッ素弾性共重合体、その製造方法および架橋ゴム - Google Patents
含フッ素弾性共重合体、その製造方法および架橋ゴム Download PDFInfo
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- WO2010053056A1 WO2010053056A1 PCT/JP2009/068692 JP2009068692W WO2010053056A1 WO 2010053056 A1 WO2010053056 A1 WO 2010053056A1 JP 2009068692 W JP2009068692 W JP 2009068692W WO 2010053056 A1 WO2010053056 A1 WO 2010053056A1
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- 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
- C08F214/186—Monomers containing fluorine with non-fluorinated comonomers
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- 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
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- 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
- C08F214/26—Tetrafluoroethene
- C08F214/265—Tetrafluoroethene with non-fluorinated comonomers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
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- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use 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; Derivatives of such polymers
Definitions
- the present invention relates to a fluorinated elastic copolymer having excellent crosslinking reactivity, a method for producing the same, and a crosslinked rubber.
- Fluorine-containing elastic copolymers are excellent in heat resistance, chemical resistance, oil resistance, weather resistance, etc., and are therefore harsh that ordinary hydrocarbon materials cannot withstand. Applied in the environment.
- fluorine-containing elastic copolymers include vinylidene fluoride / hexafluoropropylene copolymers, tetrafluoroethylene / propylene copolymers, tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymers, and the like. Yes.
- the tetrafluoroethylene / propylene copolymer is excellent in amine resistance and high temperature steam resistance as compared with the fluorinated elastic copolymer containing a vinylidene fluoride repeating unit.
- a fluorine-containing elastic copolymer obtained by copolymerizing tetrafluoroethylene / propylene in the presence of a fluorine-containing chain transfer agent having an iodine atom has also been proposed (see Patent Document 2).
- Patent Document 2 the polymerization rate was slow, and the productivity of the fluorinated elastic copolymer was very low.
- the obtained fluorinated elastic copolymer has insufficient crosslinking reactivity, and various physical properties of the crosslinked rubber including compression set were not satisfactory.
- the copolymerization ratio of the necessary crosslinkable monomer when the copolymerization ratio of the necessary crosslinkable monomer is increased in order to obtain a crosslinked rubber having a desired strength and compression set, the strength at a high temperature may be remarkably lowered. Furthermore, if the copolymerization ratio of the crosslinkable monomer is reduced, there is a problem that the crosslinking reactivity is lowered, and it is possible to obtain a crosslinked rubber having an excellent balance between crosslinking reactivity and strength, compression set, elongation, and strength at high temperature. It was difficult.
- An object of the present invention is to provide a fluorinated elastic copolymer having excellent crosslinking reactivity, excellent balance of heat resistance, chemical resistance, compression set resistance, and excellent mechanical properties at high temperature, a method for producing the same, and crosslinking. Is to provide rubber.
- the present invention provides a fluorinated elastic copolymer having the following constitution, a method for producing the same, and a crosslinked rubber.
- Monomer (b) selected from the group consisting of the monomer represented by the following formula (I), the monomer represented by the formula (II) and the monomer represented by the formula (III) One or more.
- R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 12 , R 13 , R 14 , and R 17 are each independently hydrogen atom, a fluorine atom or a methyl group
- R 4 and R 11 each independently represents an alkylene group having an etheric oxygen atom may contain an carbon atoms 1 ⁇ 10, R 15, and R 16, Each independently represents a hydrogen atom or
- the molar ratio [(B) / ⁇ (A) + (C) ⁇ ] of the repeating unit (B) to the total of the repeating unit (A) and the repeating unit (C) is 0.01 /
- the content according to any one of [1] to [3] above, which contains the repeating unit (C), and (C) / (A) 1/99 to 70/30 (molar ratio).
- Fluoroelastic copolymer [5] The fluorine-containing elastic material according to any one of the above [1] to [4], wherein in the formula (I), R 1 , R 2 , R 3 , R 5 , R 6 , and R 7 are hydrogen atoms. Copolymer.
- R is a carbon number of 3
- the fluorinated elastic copolymer of the present invention is excellent in cross-linking reactivity, excellent in balance of heat resistance, chemical resistance and compression set resistance, and excellent in mechanical properties at high temperatures.
- the crosslinked rubber of the present invention is relatively inexpensive and is excellent in crosslinked rubber physical properties, heat resistance, chemical resistance, oil resistance, and weather resistance.
- Tetrafluoroethylene is TFE
- hexafluoropropylene is HFP
- vinylidene fluoride is VdF
- chlorotrifluoroethylene is CTFE
- perfluoro (alkyl vinyl ether) is PAVE
- perfluoro (methyl vinyl ether) is PMVE
- PPVE ethylene as E
- propylene as P.
- the fluorinated elastic copolymer of the present invention comprises a repeating unit (A) based on the monomer (a), a repeating unit (B) based on the monomer (b) and, if necessary, a monomer (c). Based on repeating units (C).
- the monomer (a) is at least one selected from the group consisting of TFE, HFP, VdF, CTFE and PAVE.
- PAVE is preferably a monomer represented by the following formula (IV).
- CF 2 CF—O—R f (IV)
- R f represents a perfluoroalkyl group having 1 to 8 carbon atoms or a perfluoroalkyl group having an etheric oxygen atom having 1 to 8 carbon atoms.
- R f preferably has 1 to 6 carbon atoms, and more preferably 1 to 5 carbon atoms.
- PAVE examples include PMVE, perfluoro (ethyl vinyl ether), PPVE, perfluoro (3,6-dioxa-1-heptene), perfluoro (3,6-dioxa-1-octene), perfluoro (5 -Methyl-3,6-dioxa-1-nonene) and the like.
- the monomer (a) one or more selected from the group consisting of TFE, HFP, VdF and PAVE are more preferable, and TFE is most preferable.
- the monomer (b) is selected from the group consisting of a monomer represented by the following formula (I), a monomer represented by the formula (II), and a monomer represented by the formula (III) One or more types.
- R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 12 , R 13 , R 14 , and R 17 are each independently hydrogen atom, a fluorine atom or a methyl group
- R 4 and R 11 each independently represents an alkylene group having an etheric oxygen atom may contain an carbon atoms 1 ⁇ 10, R 15, and R 16, Each independently represents
- Examples of the formula (I) include divinyl ether, allyl vinyl ether, butenyl vinyl ether and the like. A compound in which a part or all of these compounds are fluorinated can be used, but R 1 , R 2 , R 3 , R 5 , R 6 , and R 7 are preferably hydrogen atoms, and particularly preferred formula ( Specific examples of I) include 1,4-butanediol divinyl ether.
- Examples of the formula (II) include divinyl ester, allyl vinyl ester, butenyl vinyl ester and the like. A compound in which some or all of these compounds are fluorinated may be used, but R 8 , R 9 , R 10 , R 12 , R 13 , and R 14 are preferably hydrogen atoms, and particularly preferred formula ( Specific examples of I) include divinyl adipate.
- R 16 and R 17 are preferably hydrogen atoms.
- Specific examples of the formula (III) include vinyl crotonate and vinyl methacrylate, and vinyl crotonate is particularly preferable.
- the monomer represented by the formula (I), the formula (II) or the formula (III) is copolymerized, a double bond of a side chain partially reacts during the polymerization, and a fluorine-containing elastic copolymer having a branched chain Coalescence is obtained. Moreover, the double bond of the remaining side chain can be utilized as a crosslinking group.
- the monomer (c) is at least one selected from the group consisting of E and P. As the monomer (c), P is preferable.
- the molar ratio [(B) / ⁇ (A) + (C) ⁇ ] of the repeating unit (B) to the total of the repeating unit (A) and the repeating unit (C) is 0.01 / 100 to 1.5 / 100 is preferable, 0.01 / 100 to 0.5 / 100 is more preferable, 0.02 / 100 to 0.3 / 100 is further preferable, and 0.05 / 100 Particularly preferred is .about.0.2 / 100.
- the resulting fluorinated elastic copolymer is excellent in crosslinking reactivity, and the resulting crosslinked rubber is excellent in crosslinked rubber properties.
- the molar ratio [(C) / (A)] of the repeating unit (C) to the repeating unit (A) is preferably 1/99 to 70/30, more preferably 30/70 to 70/30, and 40/60 to 60/40 is most preferred. Within this range, the resulting crosslinked rubber is excellent in the properties of the crosslinked rubber and excellent in heat resistance, chemical resistance, oil resistance, and weather resistance.
- specific examples of the combination of the repeating unit (A) and the repeating unit (C) include the following (X1) to (X4). Since the fluorinated elastic copolymer is excellent in productivity and the obtained crosslinked rubber is excellent in mechanical properties, heat resistance, chemical resistance, oil resistance, and weather resistance, (X1), (X2), (X4 ) Is more preferable, and (X1) is most preferable.
- (X1) A combination of a repeating unit based on TFE and a repeating unit based on P
- (X2) A combination of a repeating unit based on TFE, a repeating unit based on P, and a repeating unit based on VdF
- (X3) A combination of a repeating unit based on TFE, a repeating unit based on P, and a repeating unit based on PPVE
- (X4) A combination of a repeating unit based on TFE, a repeating unit based on P, and a repeating unit based on PMVE.
- the obtained cross-linked rubber is excellent in cross-linked rubber properties, heat resistance, chemical resistance, oil resistance, and weather resistance.
- (X1): repeating unit based on TFE / repeating unit based on P 40/60 to 60/40 (molar ratio)
- (X2): repeating unit based on TFE / repeating unit based on P / repeating unit based on VdF 40 to 60/60 to 40/1 to 10 (molar ratio)
- (X3): repeating unit based on TFE / repeating unit based on P / repeating unit based on PPVE 30 to 60/10 to 40/10 to 40 (molar ratio)
- (X4): repeating unit based on TFE / repeating unit based on P / repeating unit based on PMVE 30 to 60/10 to 40/10 to 40 (molar ratio).
- the fluorinated elastic copolymer of the present invention is within the range not impairing the effects of the present invention. You may have a repeating unit based on.
- the monomer which has an iodine atom can also be used as another monomer.
- the iodine atom can also be introduced into the side chain of the fluorinated elastic copolymer of the present invention.
- the monomer having an iodine atom include iodoethylene, 4-iodo-3,3,4,4-tetrafluoro-1-butene, 2-iodo-1,1,2,2-tetrafluoro-1-vinyloxyethane.
- 2-iodoethyl vinyl ether allyl iodide, 1,1,2,3,3,3-hexafluoro-2-iodo-1- (perfluorovinyloxy) propane, 3,3,4,5,5,5- Hexafluoro-4-iodopentene, iodotrifluoroethylene, 2-iodoperfluoro (ethyl vinyl ether) and the like can be mentioned.
- the content of repeating units based on other monomers is preferably 0.001 to 2.0 mol%, more preferably 0.01 to 1.0 mol% in the fluorinated elastic copolymer, ⁇ 0.5 mol% is particularly preferred.
- the Mooney viscosity of the fluorinated elastic copolymer of the present invention is preferably 10 to 200, more preferably 20 to 180, and further preferably 30 to 170.
- Mooney viscosity is a measure of molecular weight, and a large molecular weight indicates a large molecular weight, and a small molecular weight indicates a small molecular weight. When the Mooney viscosity is within this range, the processability of the fluorinated elastic copolymer and the crosslinked rubber properties of the crosslinked rubber are improved.
- the Mooney viscosity is a value measured according to JIS K6300 described in Examples.
- the method for producing the fluorinated elastic copolymer of the present invention is represented by a radical polymerization initiator and a general formula RI 2 (wherein R is an alkylene group having 3 or more carbon atoms or a perfluoroalkylene group).
- R is an alkylene group having 3 or more carbon atoms or a perfluoroalkylene group.
- a method of copolymerizing the monomer (a), the monomer (b), and, if necessary, the monomer (c) in the presence of the iodine compound to be formed is preferable.
- the iodo compound represented by the general formula RI 2 is a compound in which iodine atoms are bonded to both ends of an alkylene group having 3 or more carbon atoms or a perfluoroalkylene group.
- Examples include 1,3-diiodopropane, 1,4-diiodobutane, 1,6-diiodohexane, 1,8-diiodooctane, 1,3-diiodoperfluoropropane, 1,4-diiodopropane.
- Examples include iodoperfluorobutane, 1,6-diiodoperfluorohexane, 1,8-diiodoperfluorooctane, and the like.
- the carbon number of the iodo compound represented by the general formula RI 2 is preferably 3 to 8.
- the iodo compound represented by the general formula RI 2 is more preferably an iodo compound having a perfluoroalkylene group, and most preferably 1,4-diiodoperfluorobutane.
- these iodo compounds function as chain transfer agents, when the monomer is polymerized in the presence of these iodo compounds, an iodine atom is bonded to the main chain terminal of the polymer of the fluorinated elastic copolymer. be able to.
- a fluorinated elastic copolymer having a branched chain may be obtained, and iodine atoms can be similarly bonded to this branched chain end. Therefore, in the present invention, the polymer chain end may be a main chain end or a branched chain end.
- the iodine atom content in the fluorinated elastic copolymer is preferably from 0.01 to 5.0 mass%, more preferably from 0.05 to 2.0 mass%.
- the fluorinated elastic copolymer is excellent in cross-linking reactivity, and the cross-linked rubber is excellent in mechanical properties.
- the monomer is polymerized in the presence of an iodo compound, and the monomer is copolymerized in the presence of a radical polymerization initiator and the iodo compound. Is preferred.
- the abundance of the iodo compound depends on the desired amount of the fluorinated elastic copolymer, but is preferably 0.005 to 10 parts by mass, particularly preferably 0.02 to 5 parts by mass with respect to 100 parts by mass of the aqueous medium. .
- Examples of the polymerization method of the fluorinated elastic copolymer of the present invention include an emulsion polymerization method, a solution polymerization method, a suspension polymerization method, a bulk polymerization method and the like.
- An emulsion polymerization method in which a monomer is copolymerized in an aqueous medium in the presence of an emulsifier is preferable because the molecular weight and copolymer composition of the fluorinated elastic copolymer can be easily adjusted and the productivity is excellent.
- the aqueous medium water or water containing a water-soluble organic solvent is preferable.
- the water-soluble organic solvent include tert-butanol, propylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether, and tripropylene glycol, and tert-butanol, propylene glycol, and dipropylene glycol monomethyl ether are preferable.
- the content of the water-soluble organic solvent is preferably 1 to 50 parts by mass and more preferably 3 to 20 parts by mass with respect to 100 parts by mass of water.
- the pH of the aqueous medium is preferably 7 to 14, more preferably 7 to 11, further preferably 7.5 to 11, and most preferably 8 to 10.5. If the pH is less than 7, the stability of the iodo compound may decrease, and the crosslinking reactivity of the resulting fluorinated elastic copolymer may decrease.
- the period during which the pH of the aqueous medium is maintained within the above range is desirably the entire polymerization period from the start of polymerization to the end of the polymerization, but may not be the total polymerization period.
- the period during which the pH is maintained in the above range is preferably 80% or more of the total polymerization period, more preferably 90% or more, and still more preferably 95% or more.
- pH buffering agents include inorganic salts.
- inorganic salts include phosphates such as disodium hydrogen phosphate and sodium dihydrogen phosphate, and carbonates such as sodium bicarbonate and sodium carbonate. More preferable specific examples of the phosphate include disodium hydrogen phosphate dihydrate and disodium hydrogen phosphate dodecahydrate.
- an ionic emulsifier is preferable and an anionic emulsifier is more preferable because the resulting fluorinated elastic copolymer latex is excellent in mechanical and chemical stability.
- X represents a fluorine atom or a perfluoroalkyl group having 1 to 3 carbon atoms
- A represents a hydrogen atom, an alkali metal, or NH 4
- p represents an integer of 1 to 10
- q represents an integer of 0 to 3.
- p is preferably an integer of 1 to 4, more preferably an integer of 1 to 3.
- q is preferably an integer of 0 to 2, more preferably an integer of 1 to 2.
- A a hydrogen atom, Na and NH 4 are preferable, and NH 4 is more preferable.
- emulsifier (V) when A is NH 4 include the following emulsifiers.
- the content of the emulsifier is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and most preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the aqueous medium.
- a water-soluble polymerization initiator and a redox polymerization initiator are preferable.
- the water-soluble polymerization initiator include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate, organic polymerization initiators such as disuccinic acid peroxide, azobisisobutylamidine dihydrochloride, and the like. Persulfates are more preferred, and ammonium persulfate is most preferred.
- the content of the water-soluble polymerization initiator is preferably 0.0001 to 3% by mass and more preferably 0.001 to 1% by mass with respect to the total mass of the monomers.
- the redox polymerization initiator includes a combination of persulfuric acid and a reducing agent, and is a polymerization initiator that can polymerize monomers such as TFE and P within a polymerization temperature range of 0 ° C to 60 ° C.
- the persulfate include persulfuric acid alkali metal salts such as ammonium persulfate, sodium persulfate, and potassium persulfate, and ammonium persulfate is more preferable.
- examples of the reducing agent include thiosulfate, sulfite, bisulfite, pyrosulfite, hydroxymethanesulfinate, etc., hydroxymethanesulfinate is preferred, and sodium hydroxymethanesulfinate is most preferred.
- the redox polymerization initiator preferably contains a small amount of iron, iron salt such as ferrous salt, silver sulfate or the like as the third component, and more preferably water-soluble iron salt coexists.
- water-soluble iron salts include ferrous sulfate, ferric sulfate, ferrous nitrate, ferric nitrate, ferrous chloride, ferric chloride, ferrous ammonium sulfate, ferric sulfate Ammonium etc. are mentioned.
- a chelating agent ethylenediaminetetraacetic acid disodium salt is most preferred.
- the amount of persulfate used is preferably 0.001 to 3% by mass in the aqueous medium, more preferably 0.01 to 1% by mass, and particularly preferably 0.05 to 0.5% by mass. preferable.
- the amount of the reducing agent used in the aqueous medium is preferably 0.001 to 3% by mass, more preferably 0.01 to 1% by mass, and particularly preferably 0.05 to 0.5% by mass.
- the amount of iron salt such as iron and ferrous salt, and the third component such as silver sulfate is preferably 0.0001 to 0.3% by mass, 0.001 to 0.1% by mass in the aqueous medium. Is more preferable, and 0.01 to 0.1% by mass is particularly preferable.
- the amount of the chelating agent used is preferably 0.0001 to 0.3% by mass in the aqueous medium, more preferably 0.001 to 0.1% by mass, and particularly preferably 0.01 to 0.1% by mass.
- the polymerization conditions such as polymerization pressure and polymerization temperature in the method for producing a fluorinated elastic copolymer of the present invention are appropriately selected depending on the composition of the monomer, the decomposition temperature of the radical polymerization initiator, and the like.
- the polymerization pressure is preferably 1.0 to 10 MPaG, more preferably 1.5 to 5.0 MPaG, and most preferably 2.0 to 4.0 MPaG.
- the polymerization pressure is less than 1.0 MPaG, the polymerization rate is extremely low, which is not preferable. Within this range, the polymerization rate is appropriate and easy to control, and the productivity is excellent. If it exceeds 10 MPaG, the polymerization equipment becomes expensive in order to increase pressure resistance.
- the polymerization temperature is preferably 0 to 60 ° C, more preferably 10 to 50 ° C, and particularly preferably 20 to 40 ° C. If the polymerization temperature exceeds 60 ° C., the crosslinking reactivity of the resulting fluorinated elastic copolymer may be significantly reduced. When the polymerization temperature and the polymerization pressure are within these ranges, the obtained fluorinated elastic copolymer is excellent in crosslinking reactivity, and the crosslinked rubber is excellent in mechanical properties.
- the polymerization rate is preferably 10 to 100 g / L ⁇ hour, more preferably 5 to 70 g / L ⁇ hour, and most preferably 30 to 50 g / L ⁇ hour.
- productivity is low, which is not preferable in practice.
- the resulting fluorinated elastic copolymer has a low molecular weight and insufficient crosslinking reactivity. Within this range, productivity is excellent, and the resulting fluorinated elastic copolymer has an appropriate molecular weight and excellent crosslinking reactivity.
- the fluorine-containing elastic copolymer latex obtained by the emulsion polymerization method is aggregated by a known method to isolate the fluorine-containing elastic copolymer.
- the aggregation method include a method of adding a metal salt (salting out), a method of adding an inorganic acid (hydrochloric acid, etc.), a method by mechanical shearing, a method by freezing and thawing, and the like.
- the obtained fluorinated elastic copolymer is preferably dried using a drying device such as an oven.
- the drying temperature is preferably 60 to 150 ° C, more preferably 80 to 120 ° C. Within this range, the dried fluorinated elastic copolymer is excellent in cross-linking reactivity, and the cross-linked rubber is excellent in mechanical properties.
- the fluorinated elastic copolymer of the present invention is preferably crosslinked using an organic peroxide.
- organic peroxides include dialkyl peroxides (di-tert-butyl peroxide, tert-butyl cumyl peroxide, dicumyl peroxide, ⁇ , ⁇ -bis (tert-butylperoxy) -p-diisopropylbenzene, 2 , 5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane-3, etc.), 1,1-di ( tert-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroxyperoxide, benzoyl peroxide, tert-butylperoxybenzene, 2,5-dimethyl-2, 5-di
- the amount of the organic peroxide used is preferably 0.3 to 10 parts by weight, more preferably 0.3 to 5 parts by weight, and 0.5 to 3 parts by weight with respect to 100 parts by weight of the fluorinated elastic copolymer. Part is more preferable.
- the amount of the organic peroxide used is within this range, the crosslinking rate is appropriate, and the resulting crosslinked rubber is excellent in the balance between tensile strength and elongation.
- crosslinking aids include triallyl cyanurate, triallyl isocyanurate, trimethallyl isocyanurate, 1,3,5-triacryloylhexahydro-1,3,5-triazine, triallyl trimellitate, m-phenylenediamine Bismaleimide, p-quinone dioxime, p, p'-dibenzoylquinone dioxime, dipropargyl terephthalate, diallyl phthalate, N, N ', N' ', N' '-tetraallyl terephthalamide, containing vinyl group
- siloxane oligomers polymethylvinylsiloxane, polymethylphenylvinylsiloxane, etc.
- triallyl cyanurate triallyl cyanurate
- the blending amount of the crosslinking aid is preferably 0.1 to 20 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the fluorinated elastic copolymer.
- the crosslinking speed is appropriate, and the obtained crosslinked rubber is excellent in the balance between strength and elongation.
- the metal oxide is preferably a divalent metal oxide. Preferred examples of the divalent metal oxide include magnesium oxide, calcium oxide, zinc oxide, lead oxide and the like.
- the compounding amount of the metal oxide is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the fluorinated elastic copolymer.
- pigments, fillers, reinforcing agents, etc. for coloring may be used.
- Fillers or reinforcing agents include carbon black, titanium oxide, silicon dioxide, clay, talc, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, polychlorotrifluoroethylene, ethylene tetrafluoride / ethylene copolymer And ethylene tetrafluoride / vinylidene fluoride copolymer.
- a rubber mixing device such as a roll, a kneader, a Banbury mixer, or an extruder is usually used. Used. With the rubber mixing device, a fluorinated elastic copolymer composition having excellent crosslinking reactivity can be easily obtained.
- the fluorinated elastic copolymer composition is usually crosslinked simultaneously with molding by a method such as hot pressing, but may be crosslinked after being previously molded.
- a method such as hot pressing
- the molding method compression molding, injection molding, extrusion molding, calendar molding, or dipping or coating by dissolving in a solvent is employed.
- crosslinking conditions various conditions such as hot press crosslinking, steam crosslinking, hot air crosslinking and the like are adopted in consideration of the molding method and the shape of the crosslinked product.
- the cross-linking temperature is preferably 100 to 400 ° C. and several seconds to 24 hours.
- secondary crosslinking is preferably employed for the purpose of improving mechanical properties and compression set of the crosslinked product and stabilizing other properties.
- the secondary crosslinking conditions are preferably 100 to 300 ° C. for 30 minutes to 48 hours.
- the fluorinated elastic copolymer composition may be crosslink by irradiation.
- radiation to be irradiated include electron beams and ultraviolet rays.
- the irradiation amount in electron beam irradiation is preferably 0.1 to 30 Mrad, and more preferably 1 to 20 Mrad.
- the fluorinated elastic copolymer composition may be a composition not containing an organic peroxide.
- the iodine content in the fluorinated elastic copolymer was quantified with an apparatus combining a pretreatment device AQF-100 for automatic sample combustion device ion chromatography manufactured by Dia Instruments and an ion chromatograph.
- the Mooney viscosity of the fluorinated elastic copolymer is an L-shaped rotor having a diameter of 38.1 mm and a thickness of 5.54 mm in accordance with JIS K6300. The time was set at 4 minutes and measured. (Specific gravity) The specific gravity of the fluorinated elastic copolymer was measured by a method according to JIS K6220-1 using a specific gravity meter manufactured by Shinko Denshi.
- the obtained fluorinated elastic copolymer composition was measured for cross-linking characteristics using a cross-linking characteristic measuring machine (manufactured by Alpha Technologies, trade name “RPA2000”) at 177 ° C. for 12 minutes under conditions of an amplitude of 3 degrees.
- a cross-linking characteristic measuring machine manufactured by Alpha Technologies, trade name “RPA2000”
- M H represents the maximum torque
- M L represents the minimum value of the torque
- M H -M L indicates the degree of crosslinking.
- the cross-linking characteristics serve as an index of cross-linking reactivity of the fluorinated elastic copolymer, and the larger the value of (M H ⁇ M L ), the better the cross-linking reactivity.
- the fluorine-containing elastic copolymer composition was hot-pressed at 170 ° C. for 20 minutes, and then subjected to secondary crosslinking in an oven at 200 ° C. for 4 hours to obtain a thickness of the fluorine-containing elastic copolymer composition.
- a 2 mm cross-linked rubber sheet was obtained.
- the obtained crosslinked rubber sheet was punched out with a No. 3 dumbbell, and 100% tensile stress, tensile strength and elongation at break were measured at 25 ° C. according to JISK6251.
- the hardness was measured according to JISK6253.
- Example 1 (Production of fluorinated elastic copolymer A (TFE / P / vinyl crotonate copolymer)) After degassing the inside of a 3200 mL stainless steel pressure-resistant reactor equipped with an anchor blade for stirring, 1500 g of ion-exchanged water, 60 g of disodium hydrogenphosphate dodecahydrate, water 0.9 g of sodium oxide, 198 g of tert-butanol, 9 g of C 2 F 5 OCF 2 CF 2 OCF 2 COONH 4 as a fluorine-containing emulsifier, and 3.8 g of ammonium persulfate were added.
- ion-exchanged water 60 g of disodium hydrogenphosphate dodecahydrate, water 0.9 g of sodium oxide, 198 g of tert-butanol, 9 g of C 2 F 5 OCF 2 CF 2 OCF 2 COONH 4 as a fluorine-containing emulsifier, and 3.8
- EDTA ethylenediaminetetraacetic acid disodium salt dihydrate
- ferrous sulfate heptahydrate aqueous solution in which 0.4 g of ethylenediaminetetraacetic acid disodium salt dihydrate (hereinafter referred to as EDTA) and 0.3 g of ferrous sulfate heptahydrate were dissolved in 200 g of ion-exchanged water, Added to the reactor. At this time, the pH of the aqueous medium in the reactor was 9.5.
- EDTA ethylenediaminetetraacetic acid disodium salt dihydrate
- the anchor blade was rotated at 300 rpm and 6.4 g of 1,4-diiodoperfluorobutane was added.
- a 2.5% by mass aqueous solution of sodium hydroxymethanesulfinate dihydrate (hereinafter referred to as Rongalite) adjusted to pH 10.0 with sodium hydroxide (hereinafter referred to as Rongalit 2.5% by mass aqueous solution). .) was added to the reactor to initiate the polymerization reaction.
- Rongalite 2.5 mass% aqueous solution was continuously added to the reactor using a high-pressure pump.
- the iodine content in the fluorinated elastic copolymer A was 0.5% by mass.
- the fluorinated elastic copolymer A had a Mooney viscosity of 90 and a specific gravity of 1.55. Table 1 shows the crosslinking properties and the physical properties of the crosslinked rubber of the fluorinated elastic copolymer A.
- Example 2 (Production of fluorinated elastic copolymer B (TFE / P / vinyl crotonate copolymer))
- An elastic copolymer B latex was obtained.
- the amount of Rongalite 2.5 mass% aqueous solution added was 66 g.
- the polymerization time was 6 hours.
- the fluorinated elastic copolymer B was recovered from the latex of the fluorinated elastic copolymer B, then washed and dried to obtain 695 g of a white fluorinated elastic copolymer B. .
- the iodine content in the fluorinated elastic copolymer B was 0.5% by mass.
- the fluorinated elastic copolymer B had a Mooney viscosity of 105 and a specific gravity of 1.54. Table 1 shows the crosslinking properties and crosslinked rubber properties of the fluorinated elastic copolymer B.
- Example 3 (Production of fluorinated elastic copolymer C (TFE / P / vinyl crotonate copolymer)) A latex of fluorinated elastic copolymer C was obtained in the same manner as in Example 1, except that the amount of 1,4-diiodoperfluorobutane added was 3.2 g. The amount of Rongalite 2.5 mass% aqueous solution added was 61 g. The polymerization time was about 6 hours. In the same manner as in Example 1, 690 g of fluorinated elastic copolymer C was obtained from the latex of fluorinated elastic copolymer C.
- the iodine content in the fluorinated elastic copolymer C was 0.25% by mass.
- the Mooney viscosity of the fluorinated elastic copolymer C was 160, and the specific gravity was 1.55.
- Table 1 shows the crosslinking properties and crosslinked rubber physical properties of the fluorinated elastic copolymer C.
- Example 4 (Production of fluorinated elastic copolymer D (TFE / P / vinyl crotonate copolymer))
- a latex of elastic copolymer D was obtained.
- the addition amount of Rongalite 2.5 mass% aqueous solution was 75 g.
- the polymerization time was about 6 hours.
- the fluorinated elastic copolymer D was recovered from the latex of the fluorinated elastic copolymer D, then washed and dried to obtain 670 g of a white fluorinated elastic copolymer D. .
- the iodine content in the fluorinated elastic copolymer D was 0.5% by mass.
- the Mooney viscosity of the fluorinated elastic copolymer D was 170, and the specific gravity was 1.55.
- Table 1 shows the crosslinking properties and crosslinked rubber physical properties of the fluorinated elastic copolymer D.
- the fluorinated elastic copolymer F was recovered from the latex of the fluorinated elastic copolymer F, then washed and dried to obtain 690 g of a white fluorinated elastic copolymer F. .
- the Mooney viscosity of the fluorinated elastic copolymer F was 140, and the specific gravity was 1.55.
- Table 1 shows the cross-linking properties and physical properties of the cross-linked rubber of the fluorinated elastic copolymer F.
- Example 3 (Production of fluorinated elastic copolymer G (TFE / P / vinyl crotonate copolymer))
- the monomer was polymerized in the same manner as above to obtain a latex of the fluorinated elastic copolymer G.
- the addition amount of Rongalite 2.5% by mass aqueous solution was 70 g.
- the polymerization time was about 6 hours.
- the fluorinated elastic copolymer G was recovered from the latex of the fluorinated elastic copolymer G, then washed and dried to obtain 690 g of a white fluorinated elastic copolymer G. .
- the iodine content in the fluorinated elastic copolymer G was 0.5% by mass.
- the Mooney viscosity of the fluorinated elastic copolymer G was 155, and the specific gravity was 1.55.
- Table 1 shows the cross-linking characteristics and physical properties of the cross-linked rubber of the fluorinated elastic copolymer G.
- Example 3 The crosslinked rubber obtained in Example 3, Example 4, and Comparative Example 3 was subjected to a hot tensile test. The results are shown in Table 2.
- a latex of fluorinated elastic copolymer H was obtained.
- the addition amount of Rongalite 2.5% by mass aqueous solution was 70 g.
- the polymerization time was 6 hours. Since divinyl adipate remaining in the latex was not detected by gas chromatography, it was suggested that all of the added divinyl adipate reacted and copolymerized.
- the iodine content in the fluorinated elastic copolymer H was 0.5% by mass.
- the Mooney viscosity of the fluorinated elastic copolymer H was 90, and the specific gravity was 1.55.
- Table 3 shows the cross-linking properties and physical properties of the cross-linked rubber of the fluorinated elastic copolymer H.
- Example 6 (Production of fluorinated elastic copolymer J (TFE / P / divinyl adipate copolymer))
- An elastic copolymer J latex was obtained.
- the amount of Rongalite 2.5 mass% aqueous solution added was 76 g.
- the polymerization time was 6 hours.
- the fluorinated elastic copolymer J was recovered from the latex of the fluorinated elastic copolymer J, then washed and dried to obtain 695 g of a white fluorinated elastic copolymer J. . Since divinyl adipate remaining in the latex was not detected by gas chromatography, it was suggested that all of the added divinyl adipate reacted and copolymerized.
- the iodine content in the fluorinated elastic copolymer J was 0.5% by mass.
- the Mooney viscosity of the fluorinated elastic copolymer J was 105, and the specific gravity was 1.56.
- Table 3 shows the cross-linking properties and physical properties of the cross-linked rubber of the fluorinated elastic copolymer J.
- the amount of Rongalite 2.5 mass% aqueous solution added was 71 g.
- the polymerization time was about 6 hours.
- 690 g of the fluorinated elastic copolymer K was obtained from the latex of the fluorinated elastic copolymer K.
- the 1,4-butanediol divinyl ether remaining in the latex was not detected by gas chromatography, suggesting that all of the added 1,4-butanediol divinyl ether had reacted and copolymerized. It was.
- the iodine content in the fluorinated elastic copolymer K was 0.5% by mass.
- the Mooney viscosity of the fluorinated elastic copolymer K was 85, and the specific gravity was 1.55.
- Table 3 shows the cross-linking properties and physical properties of the cross-linked rubber of the fluorinated elastic copolymer K.
- Example 8 (Production of fluorinated elastic copolymer L (TFE / P / divinyl adipate copolymer))
- An elastic copolymer L latex was obtained.
- the addition amount of Rongalite 2.5 mass% aqueous solution was 75 g.
- the polymerization time was about 6 hours.
- the fluorinated elastic copolymer L was recovered from the latex of the fluorinated elastic copolymer L, then washed and dried to obtain 670 g of a white fluorinated elastic copolymer L. .
- the fluorinated elastic copolymer M was recovered from the latex of the fluorinated elastic copolymer M, then washed and dried to obtain 690 g of a white fluorinated elastic copolymer M. . Since divinyl adipate remaining in the latex was not detected by gas chromatography, it was suggested that all of the added divinyl adipate reacted and copolymerized.
- the Mooney viscosity of the fluorinated elastic copolymer M was 160, and the specific gravity was 1.55.
- Table 3 shows the cross-linking characteristics and physical properties of the cross-linked rubber of the fluorinated elastic copolymer M.
- the fluorinated elastic copolymers of Examples 1 to 8 obtained by copolymerizing the monomer represented by monomer (b) in the presence of an iodo compound at a specific addition amount are as follows. In both cases, the value of (M H ⁇ M L ) was large, the crosslinking reactivity was excellent, the properties of the crosslinked rubber were excellent, and the tensile properties at high temperatures were excellent. In particular, the fluorinated elastic copolymers of Examples 1 to 3 and Examples 5 to 7 obtained by copolymerizing monomers at a predetermined ratio showed more excellent cross-linking reactivity and cross-linked rubber physical properties. .
- the fluoroelastic copolymers of Example 4 and Example 8 having a slightly higher content of repeating units based on the monomer (b) exhibited crosslinked rubber properties that were slightly brittle.
- the fluorinated elastic copolymer of the present invention can provide a crosslinked rubber having excellent crosslinking reactivity and excellent mechanical properties, heat resistance, chemical resistance, oil resistance, and weather resistance.
- the obtained crosslinked rubber is suitable for materials such as O-rings, sheets, gaskets, oil seals, diaphragms and V-rings. It can also be applied to uses such as heat-resistant chemical-resistant sealing materials, heat-resistant oil-resistant sealing materials, wire coating materials, semiconductor device sealing materials, corrosion-resistant rubber paints, and urea-based grease sealing materials.
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Abstract
Description
しかし、該特許文献2に記載された方法では、重合速度が遅く、含フッ素弾性共重合体の生産性が非常に低くかった。また、得られる含フッ素弾性共重合体は架橋反応性が不十分であり、圧縮永久歪をはじめとする架橋ゴムの諸物性も満足のいくものではなかった。
しかし、該含フッ素弾性共重合体(テトラフルオロエチレン/プロピレン共重合体)では、架橋性単量体の共重合割合が多くなると、生成した共重合体の側鎖の二重結合が重合中に一部反応し、該含フッ素弾性共重合体の粘度が増大するなどの問題がある。また所望の強度、圧縮永久歪を有する架橋ゴムを得るために、必要な架橋性単量体の共重合割合を増加すると、高温下での強度が著しく低下する場合がある。さらに、架橋性単量体の共重合割合を減らすと、架橋反応性が低下する問題があり、架橋反応性と強度、圧縮永久歪、伸び、高温下強度のバランスに優れる架橋ゴムを得ることは困難であった。
単量体(a):テトラフルオロエチレン、ヘキサフルオロプロピレン、フッ化ビニリデン、クロロトリフルオロエチレンおよびパーフルオロ(アルキルビニルエーテル)からなる群より選ばれる1種以上。
CR1R2=CR3-O-R4-O-CR5=CR6R7 ・・・(I)
CR8R9=CR10-OCO-R11-COO-CR12=CR13R14・・・(II)
CR15R16=CR17COOCH=CH2 ・・・(III)
(式中、R1、R2、R3、R5、R6、R7、R8、R9、R10、R12、R13、R14、およびR17は、それぞれ独立に、水素原子、フッ素原子またはメチル基を示し、R4、およびR11は、それぞれ独立に、エーテル性酸素原子を含んでもよい炭素原子数1~10のアルキレン基を示し、R15、およびR16は、それぞれ独立に、水素原子、またはエーテル性酸素原子を含んでもよい炭素原子数1~10のアルキル基を示す。)
単量体(c):エチレンおよびプロピレンからなる群から選ばれる1種以上。
[3]前記含フッ素弾性共重合体が、高分子鎖末端にヨウ素原子を有する上記[1]または[2]に記載の含フッ素弾性共重合体。
[4]前記繰り返し単位(C)を含有し、(C)/(A)=1/99~70/30(モル比)である、上記[1]~[3]のいずれかに記載の含フッ素弾性共重合体。
[5]前記式(I)において、R1、R2、R3、R5、R6、およびR7が水素原子である上記[1]~[4]のいずれかに記載の含フッ素弾性共重合体。
[7]前記式(II)において、R8、R9、R10、R12、R13、およびR14が水素原子である上記[1]~[4]のいずれかに記載の含フッ素弾性共重合体。
[8]前記単量体(b)がアジピン酸ジビニルである上記[1]~[4]のいずれかに記載の含フッ素弾性共重合体。
[9]前記式(III)において、R16およびR17が水素原子である上記[1]~[4]のいずれかに記載の含フッ素弾性共重合体。
[11]前記含フッ素弾性共重合体に含まれるヨウ素原子の含有量が0.01~5質量%である上記[1]~[10]のいずれかに記載の含フッ素弾性共重合体。
[12]前記単量体(a)がテトラフルオロエチレンであり、前記単量体(c)がプロピレンであり、繰返し単位の比率が(C)/(A)=40/60~60/40(モル比)である上記[1]~[11]のいずれかに記載の含フッ素弾性共重合体。
[14]重合温度が、0℃~60℃の範囲である上記[13]に記載の含フッ素弾性共重合体の製造方法。
[15]上記[1]~[12]のいずれかに記載の含フッ素弾性共重合体を有機過酸化物で架橋してなることを特徴とする架橋ゴム。
本発明の架橋ゴムは、比較的安価であり、架橋ゴム物性、耐熱性、耐薬品性、耐油性、耐候性に優れる。
本発明の含フッ素弾性共重合体は、単量体(a)に基づく繰り返し単位(A)、単量体(b)に基づく繰り返し単位(B)および必要に応じて単量体(c)に基づく繰り返し単位(C)を有する。
PAVEとしては、下記式(IV)で表される単量体が好ましい。
CF2=CF-O-Rf ・・・(IV)
(式中、Rfは、炭素原子数1~8のパーフルオロアルキル基または炭素原子数1~8のエーテル性酸素原子を有するパーフルオロアルキル基を示す。)
Rfとしては、炭素原子数1~6が好ましく、1~5がより好ましい。
単量体(a)としては、TFE、HFP、VdFおよびPAVEからなる群より選ばれる1種以上がより好ましく、TFEが最も好ましい。
CR1R2=CR3-O-R4-O-CR5=CR6R7 ・・・(I)
CR8R9=CR10-OCO-R11-COO-CR12=CR13R14・・・(II)
CR15R16=CR17COOCH=CH2 ・・・(III)
(式中、R1、R2、R3、R5、R6、R7、R8、R9、R10、R12、R13、R14、およびR17は、それぞれ独立に、水素原子、フッ素原子またはメチル基を示し、R4、およびR11は、それぞれ独立に、エーテル性酸素原子を含んでもよい炭素原子数1~10のアルキレン基を示し、R15、およびR16は、それぞれ独立に、水素原子、またはエーテル性酸素原子を含んでもよい炭素原子数1~10のアルキル基を示す。)
単量体(c)は、EおよびPからなる群から選ばれる1種以上である。単量体(c)としては、Pが好ましい。
(X2)TFEに基づく繰り返し単位と、Pに基づく繰り返し単位と、VdFに基づく繰り返し単位との組み合わせ、
(X3)TFEに基づく繰り返し単位と、Pに基づく繰り返し単位と、PPVEに基づく繰り返し単位との組み合わせ、
(X4)TFEに基づく繰り返し単位と、Pに基づく繰り返し単位と、PMVEに基づく繰り返し単位との組み合わせ。
(X1):TFEに基づく繰り返し単位/Pに基づく繰り返し単位=40/60~60/40(モル比)、
(X2):TFEに基づく繰り返し単位/Pに基づく繰り返し単位/VdFに基づく繰り返し単位=40~60/60~40/1~10(モル比)、
(X3):TFEに基づく繰り返し単位/Pに基づく繰り返し単位/PPVEに基づく繰り返し単位=30~60/10~40/10~40(モル比)、
(X4):TFEに基づく繰り返し単位/Pに基づく繰り返し単位/PMVEに基づく繰り返し単位=30~60/10~40/10~40(モル比)。
その他の単量体としては、フッ化ビニル、ペンタフルオロプロピレン、パーフルオロシクロブテン、CH2=CHCF3、CH2=CHCF2CF3、CH2=CHCF2CF2CF3、CH2=CHCF2CF2CF2CF3、CH2=CHCF2CF2CF2CF2CF3等の(パーフルオロアルキル)エチレン類等の含フッ素系単量体;イソブチレン、ペンテンなどのα-オレフィン類、メチルビニルエーテル、エチルビニルエーテル、プロピルビニルエーテル、ブチルビニルエーテル等のビニルエーテル類、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、カプロン酸ビニル、カプリル酸ビニル等のビニルエステル類等の非フッ素系単量体;等が挙げられる。
ヨウ素原子を有する単量体としては、ヨードエチレン、4-ヨード-3,3,4,4-テトラフルオロ-1-ブテン、2-ヨード-1,1,2,2-テトラフルオロ-1-ビニロキシエタン、2-ヨードエチルビニルエーテル、アリルヨージド、1,1,2,3,3,3-ヘキサフルオロ-2-ヨード-1-(パーフルオロビニロキシ)プロパン、3,3,4,5,5,5-ヘキサフルオロ-4-ヨードペンテン、ヨードトリフルオロエチレン、2-ヨードパーフルオロ(エチルビニルエーテル)などが挙げられる。
その他の単量体に基づく繰り返し単位の含有量は、含フッ素弾性共重合体中、0.001~2.0モル%が好ましく、0.01~1.0モル%がより好ましく、0.01~0.5モル%が特に好ましい。
該ムーニー粘度は、実施例に記載のJIS K6300に準じて測定される値である。
本発明における、一般式RI2で表されるヨード化合物は、炭素数3以上のアルキレン基またはパーフルオロアルキレン基の両末端にヨウ素原子が結合した化合物である。
具体例としては、1,3-ジヨードプロパン、1,4-ジヨードブタン、1,6-ジヨードヘキサン、1,8-ジヨードオクタン、1,3-ジヨードパーフルオロプロパン、1,4-ジヨードパーフルオロブタン、1,6-ジヨードパーフルオロヘキサン、1,8-ジヨードパーフルオロオクタン等が挙げられる。一般式RI2で表されるヨード化合物の炭素数は、好ましくは3~8である。一般式RI2で表されるヨード化合物としては、パーフルオロアルキレン基を有するヨード化合物がより好ましく、特に1,4-ジヨードパーフルオロブタンが最も好ましい。
本発明の含フッ素弾性共重合体の製造方法は、ヨード化合物の存在下に前記単量体を重合させるが、ラジカル重合開始剤、および前記ヨード化合物の存在下に、前記単量体を共重合する方法が好ましい。
ヨード化合物の存在量は、所望の含フッ素弾性共重合体量によって左右されるが、水性媒体100質量に対して、0.005~10質量部が好ましく、0.02~5質量部が特に好ましい。
水溶性有機溶媒としては、tert-ブタノール、プロピレングリコール、ジプロピレングリコール、ジプロピレングリコールモノメチルエーテル、トリプロピレングリコール等が挙げられ、tert-ブタノール、プロピレングリコール、ジプロピレングリコールモノメチルエーテルが好ましい。
水性媒体が水溶性有機溶媒を含む場合、水溶性有機溶媒の含有量は、水の100質量部に対して、1~50質量部が好ましく、3~20質量部がより好ましい。
水性媒体のpHを上記範囲に保持する期間は、乳化重合の重合開始から重合終了の間の全重合期間であることが望ましいが、全重合期間でなくてもよい。pHを上記範囲に保持する期間は、好ましくは全重合期間の80%以上であり、より好ましくは90%以上であり、さらに好ましくは95%以上である。
ここで、Xは、フッ素原子または炭素原子数1~3のパーフルオロアルキル基を表し、Aは、水素原子、アルカリ金属、またはNH4を表し、pは、1~10の整数を表し、qは、0~3の整数を表す。
式(V)において、pとしては、1~4の整数が好ましく、1~3の整数がより好ましい。qとしては、0~2の整数が好ましく、1~2の整数がより好ましい。Aとしては、水素原子、NaおよびNH4が好ましく、NH4がより好ましい。
CF3OCF2CF2OCF2COONH4、
CF3O(CF2CF2O)2CF2COONH4、
F(CF2)2OCF2CF2OCF2COONH4、
F(CF2)2O(CF2CF2O)2CF2COONH4、
CF3O(CF(CF3)CF2O)2CF(CF3)COONH4、
F(CF2)2O(CF(CF3)CF2O)2CF(CF3)COONH4、
F(CF2)3O(CF(CF3)CF2O)2CF(CF3)COONH4、
F(CF2)3OCF2CF2OCF2COONH4、
F(CF2)3O(CF2CF2O)2CF2COONH4、
F(CF2)4OCF2CF2OCF2COONH4、
F(CF2)4O(CF2CF2O)2CF2COONH4、
CF3OCF(CF3)CF2OCF(CF3)COONH4、
F(CF2)2OCF(CF3)CF2OCF(CF3)COONH4、
F(CF2)3OCF(CF3)CF2OCF(CF3)COONH4等。
水溶性重合開始剤としては、過硫酸アンモニウム、過硫酸ナトリウム、過硫酸カリウム等の過硫酸類、ジコハク酸過酸化物、アゾビスイソブチルアミジン二塩酸塩等の有機系重合開始剤類等が挙げられ、過硫酸類がより好ましく、過硫酸アンモニウムが最も好ましい。
水溶性重合開始剤の含有量は、単量体の合計の質量に対して、0.0001~3質量%が好ましく、0.001~1質量%がより好ましい。
水溶性鉄塩の具体例としては、硫酸第一鉄、硫酸第二鉄、硝酸第一鉄、硝酸第二鉄、塩化第一鉄、塩化第二鉄、硫酸第一鉄アンモニウム、硫酸第二鉄アンモニウム等が挙げられる。
レドックス重合開始剤には、キレート剤を加えることが最も好ましい。キレート剤としては、エチレンジアミン四酢酸二ナトリウム塩が最も好ましい。
重合圧力としては、1.0~10MPaGが好ましく、1.5~5.0MPaGがより好ましく、2.0~4.0MPaGが最も好ましい。重合圧力が1.0MPaG未満であると、重合速度が極めて低くなり、好ましくない。この範囲にあると重合速度が適切で制御しやすく、また、生産性に優れる。10MPaGを超えると、耐圧性を高くするために、重合設備が高価となる。
重合温度、および重合圧力がこの範囲にあると、得られた含フッ素弾性共重合体は、架橋反応性に優れ、架橋ゴムが機械特性に優れる。
また、得られた含フッ素弾性共重合体は、オーブン等の乾燥装置を用いて乾燥することが好ましい。乾燥温度は、60~150℃が好ましく、80~120℃がより好ましい。この範囲にあると、乾燥された含フッ素弾性共重合体は、架橋反応性に優れ、架橋ゴムは機械的特性に優れる。
有機過酸化物としては、ジアルキルパーオキシド類(ジtert-ブチルパーオキシド、tert-ブチルクミルパーオキシド、ジクミルパーオキシド、α,α-ビス(tert-ブチルパーオキシ)-p-ジイソプロピルベンゼン、2,5-ジメチル-2,5-ジ(tert-ブチルパーオキシ)ヘキサン、2,5-ジメチル-2,5-ジ(tert-ブチルパーオキシ)ヘキサン-3等。)、1,1-ジ(tert-ブチルパーオキシ)-3,3,5-トリメチルシクロヘキサン、2,5-ジメチルヘキサン-2,5-ジヒドロキシパーオキシド、ベンゾイルパーオキシド、tert-ブチルパーオキシベンゼン、2,5-ジメチル-2,5-ジ(ベンゾイルパーオキシ)ヘキサン、tert-ブチルパーオキシマレイン酸、tert-ブチルパーオキシソプロピルカーボネート等が挙げられ、ジアルキルパーオキシド類が好ましい。
また、必要に応じて含フッ素弾性共重合体に金属酸化物を配合してもよい。金属酸化物としては、2価金属の酸化物が好ましい。2価金属の酸化物としては、酸化マグネシウム、酸化カルシウム、酸化亜鉛、酸化鉛等が好ましく挙げられる。金属酸化物の配合量は、含フッ素弾性共重合体の100質量部に対して、0.1~10質量部が好ましく、0.5~5質量部がより好ましい。
成形方法としては、圧縮成形、射出成形、押し出し成形、カレンダー成形または溶剤に溶かしてディッピング、コーティングなどが採用される。
各物性の測定は、下記の方法を用いた。
(共重合組成)含フッ素弾性共重合体中のTFEに基づく単量体単位の含有量をフッ素含有量分析により、また、赤外吸収スペクトルによりビニルエステルおよびビニルエーテルに基づく単量体単位の含有量を算出し、共重合組成を分析した。
(比重)含フッ素弾性共重合体の比重は、新光電子社製の比重計を用い、JIS K6220-1に準ずる方法にて測定した。
(圧縮永久歪)前記含フッ素弾性共重合体組成物につき、JIS K6262に準じて200℃で72時間の圧縮永久歪試験を行い、永久歪を測定した。
撹拌用アンカー翼を備えた内容積3200mLのステンレス鋼製の耐圧反応器の内部を脱気した後、該反応器に、イオン交換水の1500g、リン酸水素二ナトリウム12水和物の60g、水酸化ナトリウムの0.9g、tert-ブタノールの198g、含フッ素乳化剤としてC2F5OCF2CF2OCF2COONH4の9g、および過硫酸アンモニウムの3.8gを加えた。さらに、200gのイオン交換水に0.4gのエチレンジアミン四酢酸二ナトリウム塩二水和物(以下、EDTAと記す。)および0.3gの硫酸第一鉄7水和物を溶解させた水溶液を、反応器に加えた。このときの反応器内の水性媒体のpHは9.5であった。
含フッ素弾性共重合体Aの架橋特性および架橋ゴム物性を表1に示す。
圧入するクロトン酸ビニル/tert-ブタノール溶液の濃度を、クロトン酸ビニル/tert-ブタノール=98/2(質量比)とした以外は実施例1と同様にして単量体の重合を行い、含フッ素弾性共重合体Bのラテックスを得た。ロンガリット2.5質量%水溶液の添加量は66gであった。重合時間は6時間であった。
実施例1と同様にして、含フッ素弾性共重合体Bのラテックスから含フッ素弾性共重合体Bを回収し、ついで洗浄、乾燥して、白色の含フッ素弾性共重合体Bの695gを得た。
含フッ素弾性共重合体Bの架橋特性および架橋ゴム物性を表1に示す。
1,4-ジヨードパーフルオロブタンの添加量を3.2gとした以外は、実施例1と同様にして、含フッ素弾性共重合体Cのラテックスを得た。ロンガリット2.5質量%水溶液の添加量は61gであった。重合時間は約6時間であった。
実施例1と同様にして、含フッ素弾性共重合体Cのラテックスから含フッ素弾性共重合体Cの690gを得た。
含フッ素弾性共重合体Cの架橋特性および架橋ゴム物性を表1に示す。
圧入するクロトン酸ビニル/tert-ブタノール溶液の濃度を、クロトン酸ビニル/tert-ブタノール=80/20(質量比)とした以外は実施例1と同様にして単量体の重合を行い、含フッ素弾性共重合体Dのラテックスを得た。ロンガリット2.5質量%水溶液の添加量は75gであった。重合時間は約6時間であった。
実施例1と同様にして、含フッ素弾性共重合体Dのラテックスから含フッ素弾性共重合体Dを回収し、ついで洗浄、乾燥して、白色の含フッ素弾性共重合体Dの670gを得た。
含フッ素弾性共重合体Dの架橋特性および架橋ゴム物性を表1に示す。
クロトン酸ビニルを添加しない以外は、実施例1と同様にして製造し、含フッ素弾性共重合体Eのラテックスを得た。ロンガリット2.5質量%水溶液の添加量は70gであった。重合時間は約6時間であった。
実施例1と同様にして、含フッ素弾性共重合体Eのラテックスから含フッ素弾性共重合体Eを回収し、ついで洗浄、乾燥して、白色の含フッ素弾性共重合体Eの690gを得た。
含フッ素弾性共重合体Eの架橋特性および架橋ゴム物性を表1に示す。
1,4-ジヨードパーフルオロブタンを添加しない以外は実施例1と同様にして単量体の重合を行い、含フッ素弾性共重合体Fのラテックスを得た。ロンガリット2.5質量%水溶液の添加量は65gであった。重合時間は約6時間であった。
実施例1と同様にして、含フッ素弾性共重合体Fのラテックスから含フッ素弾性共重合体Fを回収し、ついで洗浄、乾燥して、白色の含フッ素弾性共重合体Fの690gを得た。
含フッ素弾性共重合体Fの架橋特性および架橋ゴム物性を表1に示す。
1,4-ジヨードパーフルオロブタンを添加せず、圧入するクロトン酸ビニル/tert-ブタノール溶液の濃度を、クロトン酸ビニル/tert-ブタノール=96/4(質量比)とした以外は実施例1と同様にして単量体の重合を行い、含フッ素弾性共重合体Gのラテックスを得た。ロンガリット2.5質量%水溶液の添加量は70gであった。重合時間は約6時間であった。
実施例1と同様にして、含フッ素弾性共重合体Gのラテックスから含フッ素弾性共重合体Gを回収し、ついで洗浄、乾燥して、白色の含フッ素弾性共重合体Gの690gを得た。
含フッ素弾性共重合体Gの架橋特性および架橋ゴム物性を表1に示す。
クロトン酸ビニルの代わりにアジピン酸ジビニルを使用し、圧入するアジピン酸ジビニル/tert-ブタノール溶液の濃度を、アジピン酸ジビニル/tert-ブタノール=1.7/98.3(質量比)とした以外は、実施例1と同様にして、含フッ素弾性共重合体Hのラテックスを得た。ロンガリット2.5質量%水溶液の添加量は70gであった。重合時間は6時間であった。該ラテックス中に残存するアジピン酸ジビニルは、ガスクロマトグラフでは検出されなかったことから、添加したアジピン酸ジビニルは全て反応し、共重合していることが示唆された。
含フッ素弾性共重合体Hの架橋特性および架橋ゴム物性を表3に示す。
圧入するアジピン酸ジビニル/tert-ブタノール溶液の濃度を、アジピン酸ジビニル/tert-ブタノール=5/95(質量比)とした以外は実施例5と同様にして単量体の重合を行い、含フッ素弾性共重合体Jのラテックスを得た。ロンガリット2.5質量%水溶液の添加量は76gであった。重合時間は6時間であった。
実施例5と同様にして、含フッ素弾性共重合体Jのラテックスから含フッ素弾性共重合体Jを回収し、ついで洗浄、乾燥して、白色の含フッ素弾性共重合体Jの695gを得た。
該ラテックス中に残存するアジピン酸ジビニルは、ガスクロマトグラフでは検出されなかったことから、添加したアジピン酸ジビニルは全て反応し、共重合していることが示唆された。
含フッ素弾性共重合体Jの架橋特性および架橋ゴム物性を表3に示す。
アジピン酸ジビニルの代わりに1,4-ブタンジオールジビニルエーテルを使用し、圧入する1,4-ブタンジオールジビニルエーテル/tert-ブタノール溶液の濃度を、1,4-ブタンジオールジビニルエーテル/tert-ブタノール=4/96(質量比)とした以外は、実施例5と同様にして、含フッ素弾性共重合体Kのラテックスを得た。ロンガリット2.5質量%水溶液の添加量は71gであった。重合時間は約6時間であった。実施例1と同様にして、含フッ素弾性共重合体Kのラテックスから含フッ素弾性共重合体Kの690gを得た。該ラテックス中に残存する1,4-ブタンジオールジビニルエーテルは、ガスクロマトグラフでは検出されなかったことから、添加した1,4-ブタンジオールジビニルエーテルは全て反応し、共重合していることが示唆された。
含フッ素弾性共重合体Kの架橋特性および架橋ゴム物性を表3に示す。
圧入するアジピン酸ジビニル/tert-ブタノール溶液の濃度を、アジピン酸ジビニル/tert-ブタノール=40/60(質量比)とした以外は実施例5と同様にして単量体の重合を行い、含フッ素弾性共重合体Lのラテックスを得た。ロンガリット2.5質量%水溶液の添加量は75gであった。重合時間は約6時間であった。
実施例1と同様にして、含フッ素弾性共重合体Lのラテックスから含フッ素弾性共重合体Lを回収し、ついで洗浄、乾燥して、白色の含フッ素弾性共重合体Lの670gを得た。
含フッ素弾性共重合体Lの架橋特性および架橋ゴム物性を表3に示す。
1,4-ジヨードパーフルオロブタンを添加しない以外は実施例5と同様にして単量体の重合を行い、含フッ素弾性共重合体Mのラテックスを得た。ロンガリット2.5質量%水溶液の添加量は65gであった。重合時間は約6時間であった。
実施例1と同様にして、含フッ素弾性共重合体Mのラテックスから含フッ素弾性共重合体Mを回収し、ついで洗浄、乾燥して、白色の含フッ素弾性共重合体Mの690gを得た。
該ラテックス中に残存するアジピン酸ジビニルは、ガスクロマトグラフでは検出されなかったことから、添加したアジピン酸ジビニルは全て反応し、共重合していることが示唆された。
含フッ素弾性共重合体Mの架橋特性および架橋ゴム物性を表3に示す。
一方、単量体(b)に基づく繰り返し単位を有しない比較例1の含フッ素弾性共重合体、ヨウ素原子を含まない比較例2、比較例3、および比較例4の含フッ素弾性共重合体はいずれも、架橋反応性に乏しく、架橋ゴム物性が不充分であった。
また、単量体(b)に基づく繰り返し単位の含有量がやや多い実施例4、および実施例8のフッ素弾性共重合体は、やや脆性が高い架橋ゴム物性を示した。
なお、2008年11月5日に出願された日本特許出願2008-283984号の明細書、特許請求の範囲、および要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
Claims (15)
- 下記単量体(a)に基づく繰り返し単位(A)、下記単量体(b)に基づく繰り返し単位(B)および必要に応じて下記単量体(c)に基づく繰り返し単位(C)を含有する含フッ素弾性共重合体であって、
該含フッ素弾性共重合体がヨウ素原子を有することを特徴とする含フッ素弾性共重合体。
単量体(a):テトラフルオロエチレン、ヘキサフルオロプロピレン、フッ化ビニリデン、クロロトリフルオロエチレンおよびパーフルオロ(アルキルビニルエーテル)からなる群より選ばれる1種以上。
単量体(b):下記の式(I)で表される単量体、式(II)で表される単量体および式(III)で表される単量体からなる群から選ばれる1種以上。
CR1R2=CR3-O-R4-O-CR5=CR6R7 ・・・(I)
CR8R9=CR10-OCO-R11-COO-CR12=CR13R14・・・(II)
CR15R16=CR17COOCH=CH2 ・・・(III)
(式中、R1、R2、R3、R5、R6、R7、R8、R9、R10、R12、R13、R14、およびR17は、それぞれ独立に、水素原子、フッ素原子またはメチル基を示し、R4、およびR11は、それぞれ独立に、エーテル性酸素原子を含んでもよい炭素原子数1~10のアルキレン基を示し、R15、およびR16は、それぞれ独立に、水素原子、またはエーテル性酸素原子を含んでもよい炭素原子数1~10のアルキル基を示す。)
単量体(c):エチレンおよびプロピレンからなる群から選ばれる1種以上。 - 前記繰り返し単位(A)と前記繰り返し単位(C)との合計に対する前記繰り返し単位(B)のモル比[(B)/{(A)+(C)}]が、0.01/100~1.5/100である、請求項1に記載の含フッ素弾性共重合体。
- 前記含フッ素弾性共重合体が、高分子鎖末端にヨウ素原子を有する請求項1または2に記載の含フッ素弾性共重合体。
- 前記繰り返し単位(C)を含有し、(C)/(A)=1/99~70/30(モル比)である請求項1~3のいずれかに記載の含フッ素弾性共重合体。
- 前記式(I)において、R1、R2、R3、R5、R6、およびR7が水素原子である請求項1~4のいずれかに記載の含フッ素弾性共重合体。
- 前記単量体(b)が1,4-ブタンジオールジビニルエーテルである請求項1~4のいずれかに記載の含フッ素弾性共重合体。
- 前記式(II)において、R8、R9、R10、R12、R13、およびR14が水素原子である請求項1~4のいずれかに記載の含フッ素弾性共重合体。
- 前記単量体(b)がアジピン酸ジビニルである請求項1~4のいずれかに記載の含フッ素弾性共重合体。
- 前記式(III)において、R16およびR17が水素原子である請求項1~4のいずれかに記載の含フッ素弾性共重合体。
- 前記単量体(b)がクロトン酸ビニルである請求項1~4のいずれかに記載の含フッ素弾性共重合体。
- 前記含フッ素弾性共重合体に含まれるヨウ素原子の含有量が0.01~5質量%である請求項1~10のいずれかに記載の含フッ素弾性共重合体。
- 前記単量体(a)がテトラフルオロエチレンであり、前記単量体(c)がプロピレンであり、繰返し単位の比率が(C)/(A)=40/60~60/40(モル比)である請求項1~11のいずれかに記載の含フッ素弾性共重合体。
- 請求項1~12のいずれかに記載の含フッ素弾性共重合体の製造方法であって、
ラジカル重合開始剤、および、一般式RI2(式中、Rは炭素数3以上のアルキレン基またはパーフルオロアルキレン基である。)で表されるヨード化合物の存在下、前記単量体(a)と、前記単量体(b)と、必要に応じて前記単量体(c)を共重合することを特徴とする含フッ素弾性共重合体の製造方法。 - 重合温度が、0℃~60℃の範囲である請求項13に記載の含フッ素弾性共重合体の製造方法。
- 請求項1~12のいずれかに記載の含フッ素弾性共重合体を有機過酸化物で架橋してなることを特徴とする架橋ゴム。
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EP2530096A1 (en) * | 2010-01-29 | 2012-12-05 | Asahi Glass Company, Limited | Fluorinated elastic copolymer and process for production thereof |
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WO2014062469A1 (en) * | 2012-10-18 | 2014-04-24 | 3M Innovative Properties Company | Fluoroiodo compounds for fluoropolymers |
KR20150076155A (ko) | 2012-10-19 | 2015-07-06 | 아사히 가라스 가부시키가이샤 | 축전 디바이스용 바인더 조성물의 제조 방법 |
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Also Published As
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US20110207889A1 (en) | 2011-08-25 |
CN102203147A (zh) | 2011-09-28 |
EP2343325A4 (en) | 2012-04-11 |
EP2343325A1 (en) | 2011-07-13 |
JPWO2010053056A1 (ja) | 2012-04-05 |
JP5644502B2 (ja) | 2014-12-24 |
RU2011122653A (ru) | 2012-12-20 |
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