WO2022114109A1 - Composition de fluoroélastomère, corps moulé de caoutchouc fluoré, agent de réticulation pour fabriquer un corps moulé de caoutchouc fluoré, promoteur de réticulation pour fabriquer un corps moulé de caoutchouc fluoré, mélange de sel et sel d'onium - Google Patents

Composition de fluoroélastomère, corps moulé de caoutchouc fluoré, agent de réticulation pour fabriquer un corps moulé de caoutchouc fluoré, promoteur de réticulation pour fabriquer un corps moulé de caoutchouc fluoré, mélange de sel et sel d'onium Download PDF

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WO2022114109A1
WO2022114109A1 PCT/JP2021/043340 JP2021043340W WO2022114109A1 WO 2022114109 A1 WO2022114109 A1 WO 2022114109A1 JP 2021043340 W JP2021043340 W JP 2021043340W WO 2022114109 A1 WO2022114109 A1 WO 2022114109A1
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polyhydroxy compound
salt
compound
cross
group
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PCT/JP2021/043340
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English (en)
Japanese (ja)
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裕力 名倉
謙亮 廣瀧
健史 細井
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セントラル硝子株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C22/00—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom
    • C07C22/02—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings
    • C07C22/04—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings containing six-membered aromatic rings
    • C07C22/08—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings containing six-membered aromatic rings containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms

Definitions

  • the present invention relates to a fluoropolymer composition, a fluororubber molded product, a cross-linking agent for producing a fluororubber molded product, a cross-linking accelerator for producing a fluororubber molded product, a mixed salt and an onium salt.
  • Fluorororubber is usually used by cross-linking.
  • a fluorororubber fluororesin
  • the cross-linking agent include a polyamine cross-linking agent, a polyhydroxy compound cross-linking agent, and a peroxide cross-linking agent.
  • 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane commonly known as bisphenol
  • a cross-linking agent having a phenolic hydroxy group, such as AF) is often used (Patent Document 1).
  • Indexes for evaluating the performance of the fluororubber molded product include processability (crosslinking characteristics in the fluoroelastomer composition), flexibility (elongability), resistance to breakage, compression set, and thermal stability.
  • processability crosslinking characteristics in the fluoroelastomer composition
  • flexibility elongability
  • resistance to breakage compression set
  • thermal stability e.g., thermal stability
  • the performance that is emphasized differs depending on the application of the fluororubber molded product.
  • the present inventor has repeated studies in order to achieve the above object.
  • a fluororubber molded product is produced using a polyhydroxy compound having a structure in which two aromatic rings are linked by -CH (CF 3 )-as a cross-linking agent for fluororubber
  • the fluoroelastomer composition is conventionally used.
  • the resulting molded product showed the same cross-linking characteristics as the conventional bisphenol AF, and showed the same thermal stability as the case of using the conventional bisphenol AF as the cross-linking agent, while using the conventional bisphenol AF as the cross-linking agent. We have found that it exhibits greater flexibility than the case.
  • the present invention is as follows.
  • the present invention Fluorororubber (a) that can be crosslinked with a polyhydroxy compound, A polyhydroxy compound (b) having a structure in which two aromatic rings are linked by -CH (CF 3 )-and It is a fluoroelastomer composition containing.
  • the present invention It is a fluororubber molded product obtained by heating the above fluoroelastomer composition.
  • the present invention It is a cross-linking agent for producing a fluororubber molded product, which has a structure in which two aromatic rings are linked by -CH (CF 3 )-and contains a compound that can be crosslinked with fluororubber.
  • a cross-linking accelerator for producing a fluororubber molded product which comprises one or both of the following (i) and (ii).
  • the present invention is a mixed salt with an onium salt of a polyhydroxy compound having a structure in which two aromatic rings are linked by -CH (CF 3 )-.
  • the present invention It is an onium salt of a polyhydroxy compound having a structure in which two aromatic rings are linked by -CH (CF 3 )-.
  • the fluoroelastomer composition of the present invention exhibits processability (crosslinking characteristics) equivalent to that of the fluoroelastomer composition containing bisphenol AF as a crosslinking agent. Further, the flexibility of the fluororubber molded product obtained by curing the fluoroelastomer composition of the present invention is excellent, and other properties including thermal stability are inferior to those of the fluororubber molded product using bisphenol AF as a cross-linking agent. There is no.
  • the notation "XY” in the description of the numerical range indicates X or more and Y or less unless otherwise specified.
  • “1 to 5% by mass” means “1% by mass or more and 5% by mass or less”.
  • the notation that does not indicate whether it is substituted or unsubstituted includes both those having no substituent and those having a substituent.
  • the "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • organic group as used herein means an atomic group obtained by removing one or more hydrogen atoms from an organic compound.
  • the "monovalent organic group” represents an atomic group obtained by removing one hydrogen atom from an arbitrary organic compound.
  • the fluoroelastomer composition of the present embodiment has at least a polyhydroxy compound (b) having a structure in which a fluororubber (a) crosslinkable with the polyhydroxy compound and two aromatic rings are linked by ⁇ CH (CF 3 ) ⁇ . ) And, including. Further, the fluoroelastomer composition of the present embodiment may be used as a combination cross-linking agent (b'), a cross-linking accelerator (c), an acid receiving agent (d), a filler (e), a processing aid and the like, if necessary. It can also contain ingredients.
  • the fluororubber molded product obtained by heating the fluoroelastomer composition of the present embodiment has good flexibility. It is presumed that this is mainly due to the chemical structure "-CH (CF 3 )-" in the polyhydroxy compound (b) that acts as a cross-linking agent in the composition. Specifically, the -CH (CF 3 ) -linkage structure contained in the polyhydroxy compound (b) is higher than the -C (CF 3 ) 2 -linkage structure contained in the bisphenol AF conventionally used as a cross-linking agent. It is presumed that the flexibility of the fluororubber molded product is improved due to the low symmetry.
  • the hardness of the molded product produced by heating the fluoroelastomer composition of the present embodiment is about the same as that of the conventional molded product of the fluoroelastomer composition using bisphenol AF as a cross-linking agent.
  • the polyhydroxy compound (b) has a structure in which two aromatic rings are linked by a group having only one trifluoromethyl group called -CH (CF 3 ) -, so that the flexibility and hardness in the molded product are obtained. It is presumed that this is because the balance between the two is compatible.
  • the fluoroelastomer composition of the present embodiment exhibits cross-linking characteristics similar to those of the fluoroelastomer composition using bisphenol AF as a cross-linking agent. It is presumed that this is due to the similarity in chemical structure between bisphenol AF and the polyhydroxy compound (b) in the present embodiment. That is, since both bisphenol AF and polyhydroxy compound (b) are similar in that they have a structure in which two aromatic rings are linked by a fluorine-containing linking group, the behavior during curing (crosslinking reaction) is similar. It is presumed to do.
  • the molded body of the fluoroelastomer composition of the present embodiment has the same thermal stability as the conventional molded body of the fluoroelastomer composition containing bisphenol AF as a cross-linking agent. It is presumed that one of the factors is that the polyhydroxy compound (b) acting as a cross-linking agent appropriately contains a fluorine atom.
  • the fluororubber (a) is not particularly limited as long as it can be crosslinked with the polyhydroxy compound.
  • Specific examples of the fluororubber (a) include fluororubbers that have fluorine in their molecules, have crosslinkability, and can exhibit rubber elasticity by crosslinking, and can be crosslinked by a polyhydroxy compound. .. More specifically, as the fluororubber (a), for example, polyfluorinated vinylidene (PVDF), fluorovinylidene-tetrafluoroethylene binary copolymer (poly (VDF / CTFE)), fluorovinylidene-hexafluoro.
  • PVDF polyfluorinated vinylidene
  • poly (VDF / CTFE) fluorovinylidene-hexafluoro.
  • Propropylene binary copolymer poly (VDF / HFP)
  • vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene ternary copolymer poly (VDF / HFP / TFE)
  • vinylidene fluoride-tetrafluoroethylene- Vinylidene fluoride rubber FKM
  • perfluorovinyl ether ternary copolymer poly (VDF / TFE / PFVE)
  • FEPM tetrafluoroethylene-propylene rubber
  • FEPM tetrafluoroethylene-perfluorovinyl ether rubber
  • FEPM tetrafluoroethylene-perfluorovinyl ether rubber
  • the fluororubber (a) may be used alone, or two or more fluororubbers (a) may be used in any combination.
  • vinylidene fluoride rubber is preferably used. This is because it is easy to obtain a fluororubber molded product having excellent rubber elasticity, wear resistance, tensile strength, etc., in addition to being excellent in versatility and handleability.
  • fluororubber there are two types of fluorororubber: a pre-compound type that is supplied with a polyhydroxy compound cross-linking agent added in advance, and a raw rubber type that is supplied in the state of raw rubber to which a polyhydroxy compound cross-linking agent is not added.
  • a pre-compound type that is supplied with a polyhydroxy compound cross-linking agent added in advance
  • a raw rubber type that is supplied in the state of raw rubber to which a polyhydroxy compound cross-linking agent is not added.
  • any type of fluororubber may be used as the fluororubber (a) in the present embodiment.
  • vinylidene fluoride rubber As a specific example of vinylidene fluoride rubber, among “Baiton (registered trademark)” manufactured by DuPont Elastomer Co., Ltd., “Daiel (registered trademark)” manufactured by Daikin Industries, Ltd. such as A, B, F, AL type, etc. Among them, G-700, G-800, G-550 series and the like can be mentioned. Among the vinylidene fluoride-based rubbers, the vinylidene fluoride-hexafluoropropylene binary copolymer is preferable.
  • the polyhydroxy compound (b) usually functions as a cross-linking agent for the fluororubber (a).
  • the polyhydroxy compound (b) has a "partial structure in which two aromatic rings are linked by -CH (CF 3 )-and can be crosslinked with fluororubber, which is a cross-linking agent for producing a fluororubber molded product. It can also be expressed as.
  • the polyhydroxy compound (b) is not particularly limited as long as it has a partial structure in which two aromatic rings are linked by ⁇ CH (CF 3 ) ⁇ and has two or more hydroxy groups.
  • the hydroxy group contained in the polyhydroxy compound (b) may be an alcoholic hydroxy group or a phenolic hydroxy group.
  • the polyhydroxy compound (b) preferably contains a compound represented by the following general formula (1). Further, it may be substantially composed of a compound represented by the following general formula.
  • R represents a monovalent organic group, a nitro group or a halogeno group, and when there are multiple Rs, they may be the same or different.
  • Each of the two m independently represents an integer of 0 to 4.
  • Examples of the monovalent organic group of R include an alkyl group, an alkoxy group, an alkenyl group, an alkynyl group, an aryl group, an aryloxy group, an amino group, a cyano group, a silyl group and the like.
  • the alkyl group is not limited, but is preferably a linear or branched alkyl group having 1 to 6 carbon atoms.
  • n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-propyl group, i-propyl group, ethyl group, and methyl group are preferable, and ethyl group and methyl group are particularly preferable.
  • the alkoxy group is not limited, but is preferably a linear or branched alkoxy group having 1 to 6 carbon atoms. Among them, n-butoxy group, s-butoxy group, isobutoxy group, t-butoxy group, n-propoxy group, i-propoxy group, ethoxy group, and methoxy group are preferable, and ethoxy group and methoxy group are particularly preferable.
  • the alkenyl group is not limited, but is preferably a linear or branched alkenyl group having 2 to 6 carbon atoms.
  • a vinyl group, an allyl group, and a 1-butenyl group are preferable, and a vinyl group is particularly preferable.
  • the alkynyl group is not limited, but is preferably a linear or branched alkynyl group having 2 to 6 carbon atoms. Of these, an ethynyl group and a propargyl group are preferable, and an ethynyl group is particularly preferable.
  • the aryl group is not limited, but preferably has 6 to 12 carbon atoms. Of these, a phenyl group and a naphthyl group are preferable, and a phenyl group is particularly preferable.
  • the aryloxy group is not limited, but preferably has 6 to 12 carbon atoms. Of these, a phenoxy group and a naphthoxy group are preferable, and a phenoxy group is particularly preferable.
  • the silyl group is not limited, but a trimethylsilyl group, a triethylsilyl group, a trimethoxysilyl group, or a triethoxysilyl group is preferable, and a trimethylsilyl group is particularly preferable.
  • halogeno group examples include a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br) and an iodine atom (I). F is particularly preferable.
  • alkyl group, alkoxy group, alkenyl group, alkynyl group, aryl group, and aryloxy group may have a substituent. That is, on any carbon of these groups, for example, a halogen atom, an alkoxy group, an alkoxycarbonyl group, a protector of a carboxyl group, a protector of an amino group, a protector of a hydroxyl group, etc. are any number and any combination. It may be replaced with.
  • Protecting groups for carboxyl, amino and hydroxyl groups are described in Protective Groups in Organic Synthesis, Third Edition, 1999, John Wiley & Sons, Inc. Etc. are the protecting groups described in. Further, when the number of Rs in the general formula (1) is 2 or more, two or more Rs are linked to form a saturated or unsaturated, monocyclic or polycyclic ring having 3 to 10 carbon atoms. A group may be formed.
  • the two m are preferably 0 to 2, more preferably 0 to 1, and even more preferably 0, respectively.
  • Specific examples of the compound represented by the general formula (1) include the following compounds.
  • 1,1-bis (4-hydroxyphenyl) -2,2,2-trifluoroethane can be mentioned as a particularly preferable compound.
  • the polyhydroxy compound (b) may be a compound in which the compound represented by the general formula (1) and the fluororubber are condensed.
  • a phenol compound containing two aromatic rings linked by [-CH (CF 3 )-] as a partial structure can also be mentioned. ..
  • a phenol compound condensed with fluororubber and the like can also be mentioned.
  • the compound represented by the following general formula (2) can be mentioned.
  • R represents a monovalent organic group, a nitro group or a halogeno group, and when there are multiple Rs, they may be the same or different.
  • n represents an integer from 0 to 40 and represents m independently represents an integer of 0 to 4.
  • R in the general formula (2) is the same as those in the general formula (1).
  • the m in the general formula (2) is preferably 0 to 2, more preferably 0 to 1, and even more preferably 0, respectively.
  • the compound represented by the general formula (1) is typically produced by reacting a fluor (2,2,2-trifluoroacetaldehyde) or a fluoral equivalent with a phenol compound in the presence of an acid catalyst.
  • the fluoroelastomer composition of the present embodiment can crosslink a fluororubber (a), which is different from the polyhydroxy compound (b) having a partial structure in which two aromatic rings are linked by ⁇ CH (CF 3 ) ⁇ .
  • a cross-linking agent (combined cross-linking agent) may be further contained.
  • the combined cross-linking agent include known polyhydroxy compounds.
  • a polyhydroxyaromatic compound can be preferably used from the viewpoint of excellent thermal stability.
  • polyhydroxyaromatic compound examples include 4,4'-dihydroxydiphenylmethane, 2,2-bis (4-hydroxyphenyl) propane, bisphenolAF, 1,3-dihydroxybenzene, 1,7-dihydroxynaphthalene, 2 , 7-Dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxystylben, 2,6-dihydroxyanthracene, hydroquinone, catechol, 2,2-bis (4-hydroxyphenyl) ) Butane, 2,2-bis (4-hydroxyphenyl) valeric acid, 2,2-bis (4-hydroxyphenyl) tetrafluorodichloropropane, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylketone , Tri (4-hydroxyphenyl) methane, 3,3', 5,5'-tetrachlorobisphenol A, 3,3'
  • the total amount of the polyhydroxy compound (b) and the combined cross-linking agent (b') in the fluoroelastomer composition of the present embodiment is from the viewpoint of the balance between steam resistance and thermal stability and the hardness of the rubber molded product.
  • the fluororubber (a) is preferably 0.5 to 15 parts by mass, more preferably 0.5 to 10 parts by mass, and further preferably 0.5 to 5 parts by mass with respect to 100 parts by mass.
  • the amount used is, for example, 1 to 100 parts by mass, preferably 1 to 100 parts by mass with respect to 100 parts by mass of the polyhydroxy compound (b), from the viewpoint of reliable performance improvement. It is 1 to 50 parts by mass.
  • the fluoroelastomer composition of the present embodiment may not contain the combined cross-linking agent (b') as long as the desired effect can be obtained.
  • Cross-linking accelerator examples include onium compounds. Specific examples thereof include ammonium compounds such as quaternary ammonium salts, phosphonium compounds such as quaternary phosphonium salts, oxonium compounds, and sulfonium compounds. In addition, amine compounds and the like can also be mentioned. As the cross-linking accelerator, a quaternary ammonium salt or a quaternary phosphonium salt is particularly preferable. From another viewpoint, onium halide is preferable as the cross-linking accelerator. These may be used alone or in combination of two or more.
  • the quaternary ammonium salt is not particularly limited, and is, for example, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide, 8-methyl-1,8-diazabicyclo [5,4.
  • the quaternary phosphonium salt is not particularly limited, and for example, tetrabutylphosphonium chloride, tetraoctylphosphonium chloride, tetraphenylphosphonium chloride, benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, trioctylmethylphosphonium chloride, trioctylbenzylphosphonium chloride. , Tetravinyl phosphonium chloride, tetraallyl phosphonium chloride and other quaternary phosphonium halides. In particular, benzyltriphenylphosphonium chloride is preferred.
  • a mixture of the polyhydroxy compound (b) and the above-mentioned cross-linking accelerator can also be used as the cross-linking accelerator (c).
  • the mixture of the polyhydroxy compound (b) and the cross-linking accelerator include a mixed salt of an onium salt such as the above-mentioned quaternary ammonium salt or quaternary phosphonium salt and a bisphenol compound.
  • the "mixed salt” here represents a mixture of the following components (X) and (Y).
  • the number of moles of (X) (molar ratio (X) / (Y)) with respect to the number of moles of (Y) is preferably 0.05 to 5, more preferably 0.06 to 4, and even more preferably.
  • polyhydroxy compound (b) in which the hydroxy group is not anionic and is uncharged, may provide favorable effects such as a lower melting point of the mixture.
  • X A polyhydroxy compound (b) in which the hydroxy group is not anionized and is uncharged.
  • Y A salt of a polyhydroxy compound (b) in which at least a part of a hydroxy group is anionized and an onium cation.
  • a compound in which the hydrogen of the hydroxy group of the polyhydroxy compound (b) is replaced with the cation of the onium compound shown in the above-mentioned cross-linking accelerator that is, the onium salt of the polyhydroxy compound (b) is also a cross-linking accelerator ( It can be used as c).
  • the onium salt of the polyhydroxy compound (b) is also a cross-linking accelerator ( It can be used as c).
  • a mixed salt of bisphenols represented by the general formula (1) and benzyltriphenylphosphonium chloride, or a benzyltriphenylphosphonium salt of bisphenols represented by the general formula (1) is preferable. That is, at least a part of the cross-linking accelerator (c) may be a mixed salt of the polyhydroxy compound (b) and the onium salt, or the onium salt of the polyhydroxy compound (b).
  • the onium salt here is preferably a phosphonium salt, more preferably a benzyltriphenylphosphonium salt.
  • a mixed salt of the polyhydroxy compound (b) and the benzyltriphenylphosphonium chloride, or the benzyltriphenylphosphonium salt of the polyhydroxy compound (b) is preferably used as a cross-linking accelerator for producing a fluororubber molded product. Be done.
  • the cross-linking agent and the cross-linking accelerator can be easily dispersed in a uniform ratio. Then, it is considered that it becomes easy to suppress the variation in the cross-linking characteristics in the fluoroelastomer composition. Further, when a salt is formed, depending on the compound, the melting point may be lowered as compared with the case where each compound is used alone, and the reactivity at the time of heating (crosslinking property) may be improved.
  • the melting point of the mixed salt of the polyhydroxy compound (b) and the onium salt and the onium salt of the polyhydroxy compound (b) is preferably 200 ° C. or lower, more preferably 50 to 200 ° C. More preferably, it is 75 to 180 ° C.
  • the melting point is preferably 200 ° C. or lower, more preferably 50 to 200 ° C. More preferably, it is 75 to 180 ° C.
  • (T2 + T1) / 2 is set when the temperature at the start of melting is T1 and the temperature at the end of melting is T2 under the measurement conditions of the examples.
  • the melting point is preferably within the above numerical range.
  • the fluoroelastomer of the present embodiment contains the crosslinking accelerator (c), the crosslinking efficiency can be improved, and the thermal stability of the obtained rubber molded product can be improved.
  • the cross-linking accelerator (c) is used, the amount thereof is usually 0.1 to 10 parts by mass, preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the fluororubber (a).
  • acid receiving agent metal oxides such as magnesium oxide and calcium oxide, and metal hydroxides such as calcium hydroxide can be used. In particular, magnesium oxide and calcium hydroxide are preferred. These may be used alone or in combination of two or more.
  • the amount thereof is usually 1 to 30 parts by mass, preferably 1 to 15 parts by mass with respect to 100 parts by mass of the fluororubber (a).
  • filler (e) As the filler (e), known fillers such as carbon black, talc, clay, silica, potassium carbonate, and barium sulfate, which are blended with conventional fluororubber, can be used. When the filler (e) is used, the amount thereof is preferably 0 to 150 parts by mass, more preferably 1 to 100 parts by mass with respect to 100 parts by mass of the fluororubber (a).
  • the fluoroelastomer composition of the present embodiment may contain an additive known to be blended with fluororubber, if necessary.
  • the additive include processing aids (wax, etc.), plasticizers, colorants, stabilizers, tackifiers, mold release agents, conductivity-imparting agents, thermal conductivity-imparting agents, surface non-adhesives, and softness.
  • processing aids wax, etc.
  • plasticizers plasticizers
  • colorants colorants
  • stabilizers stabilizers
  • tackifiers tackifiers
  • mold release agents include conductivity-imparting agents, thermal conductivity-imparting agents, surface non-adhesives, and softness.
  • conductivity-imparting agents include a sex-imparting agent, a heat stability improving agent, and a flame-retardant agent.
  • the fluoroelastomer composition of the present embodiment can be obtained, for example, by kneading each of the above components using a commonly used rubber kneading device.
  • a rubber kneading device a roll, a kneader, a Banbury mixer, an internal mixer, a twin-screw extruder, or the like can be used.
  • the following two-step kneading may be adopted.
  • the fluorororubber (a), the polyhydroxy compound (b) and the crosslinking accelerator (c) are kneaded while being melted at a high temperature of 100 to 200 ° C. using a closed kneader such as a kneader.
  • other components such as the acid receiving agent (d), the filler (e), and the processing aid are kneaded at a low temperature equal to or lower than the temperature at which the kneading of (i) is carried out.
  • a fluororubber molded body By heating the above fluoroelastomer composition to proceed with the crosslinking reaction, a fluorororubber molded product can be obtained.
  • the method and conditions for molding and heating (crosslinking) known methods and conditions may be appropriately adopted according to the form of the molded product to be obtained.
  • the order of molding and heating (crosslinking) is not particularly limited. It may be molded after heating (crosslinking), may be heated (crosslinked) after molding, or may be molded and heated (crosslinked) at the same time.
  • the molding method various molding methods such as a press molding method, an extrusion molding method, a transfer molding method, and an injection molding method can be adopted.
  • the heating (crosslinking) method for example, a conventional method in the field of fluororubber, which is heated by using a press machine, a vulcanizing can, or the like, can be adopted.
  • the heating (crosslinking) conditions are usually at a temperature of 140 to 250 ° C. for 1 minute to 24 hours. The conditions may be appropriately set depending on the type of the polyhydroxy compound (b), the crosslinking accelerator (c) and the like.
  • heating may be performed in two stages of primary crosslinking and secondary crosslinking.
  • it may be subjected to primary cross-linking at the same time as molding by a press molding method or a transfer molding method, then demolded, and secondarily cross-linked using a vulcanizing can or the like.
  • hoses such as oil tubes, turbocharger hoses, EGR hoses, large computer cooling hoses, fuel hoses, air hoses, PCV hoses, inlet hoses; O-rings for chemical pumps, O-rings for semiconductor manufacturing equipment, in-mani gaskets, gaskets for computers, gaskets for hydraulic equipment, head gaskets, packing for high temperature vacuum dryers, sanitary pipe packing, jar pot packing, pressure pan packing, hard disk packing, oil seals, bearings.
  • valve stem seals valve stem seals, fuel sender seals, liquid seal type transformer ventilation seals, chemical pumps / flow meters / pipe seals, heat exchanger seals, gas pipe seals, hydraulic / lubrication machine seals, dry cleaning equipment Seals, automatic packaging machine seals, plate heat exchanger seals, vending machine electromagnetic valve seals, water heater seals, stern tube seals, rotating shaft seals, fireproof wall seals, etc.
  • Rolls such as dyeing rolls, solvent rolls, squeezing rolls for pickling; crank shafts, fuel pump diaphragms, needle tips, fluororubber wires, cleaning blades, Shinkansen insulation oil caps, oil well cable jackets, robot cables, plating It is possible to obtain a molded body suitable for coating of jigs, valve seats of butterfly valves, O 2 sensor bushes, pump linings, telescopic joints, rubber plates, rods, paints, coking, binders and the like.
  • the fluororubber molded product obtained by heating the fluoroelastomer composition of the present embodiment has good flexibility. Therefore, the fluoroelastomer composition of the present embodiment is preferably applied to the production of hoses, sealing materials or rolls.
  • Crosslinking properties of fluoroelastomer composition Crosslinking properties of the uncured fluoroelastomer composition were measured using JSR Trading's Curastometer 7 Type P. Specifically, in accordance with the JIS K 6300-2A method, the minimum torque (ML) obtained after a certain period of time at 177 ° C. and the maximum torque (MH) when a flat portion or the maximum torque cannot be obtained. And both were measured. Then, the time until the torque reaches a value equal to each of ML + 0.1 (MH-ML) and ML + 0.9 (MH-ML) (“t 10 ” and “t 90 ”, respectively) was defined as the cross-linking characteristic. ..
  • Measurements were made in accordance with JIS K 6253-3: 2012 by GS-620R-G manufactured by Teclock Co., Ltd. using a stack of three disk-shaped molded bodies having a thickness of 2 mm and a diameter of 50 mm.
  • Thermal stability Using STA7200 manufactured by Hitachi High-Tech Science Corporation, the 5% weight loss temperature of the molded product was measured. The measurement conditions were an air atmosphere and a heating rate of 10 ° C./min.
  • the volume swelling rate ( ⁇ V) is the rate of change in volume after the test piece is immersed under predetermined conditions.
  • ⁇ V ⁇ (V). -V0) / V0 ⁇ x 100.
  • Example 1 [Preparation of fluoroelastomer composition and preparation of fluororubber molded product] (Example 1) 100 parts by mass of a raw rubber type fluororubber which is a vinylidene fluoride type and can be crosslinked with a polyhydroxy compound was put into a mixing roll at room temperature. 30 parts by mass of carbon black was added thereto and kneaded until uniform. Then, 6 parts by mass of calcium hydroxide and 3 parts by mass of magnesium oxide were added in this order and kneaded until uniform.
  • a raw rubber type fluororubber which is a vinylidene fluoride type and can be crosslinked with a polyhydroxy compound was put into a mixing roll at room temperature. 30 parts by mass of carbon black was added thereto and kneaded until uniform. Then, 6 parts by mass of calcium hydroxide and 3 parts by mass of magnesium oxide were added in this order and kneaded until uniform.
  • the cross-linking accelerator benzyltriphenylphosphonium chloride
  • the cross-linking accelerator in the composition is a mixed salt of 1,1-bis (4-hydroxyphenyl) -2,2,2-trifluoroethane and benzyltriphenylphosphonium chloride. It was put into a mixing roll. Then, it was kneaded until it became uniform. In this way, the fluoroelastomer composition was prepared.
  • Fluoro rubber Product name "Daiel G-801", Daikin Kogyo Co., Ltd. Carbon black: Product name "Dia Black H”, Mitsubishi Chemical Co., Ltd. Benzyltriphenylphosphonium chloride: Tokyo Kasei Co., Ltd. Calcium hydroxide: Kanto Chemical Co., Ltd. Oxidation Magnesium: Product name "Kyowa Mug 150", manufactured by Kyowa Chemical Co., Ltd.
  • polyhydroxy compound (1,1-bis (4-hydroxyphenyl) -2,2,2-trifluoroethane) was synthesized with reference to the description of Example 5 of International Publication No. 2020/162408.
  • the obtained fluoroelastomer composition was put into a mold and pressed at a temperature of 177 ° C. and a pressure of 10 MPa for 15 minutes to allow the crosslinking reaction to proceed. Then, a sheet-shaped molded product (length: 150 mm, width: 150 mm, thickness: 2 mm, or length: 100 mm, width: 100 mm, thickness: 4 mm) was obtained. The resulting compact was then transferred to an oven and secondarily crosslinked at 232 ° C. for 24 hours. Various characteristics were evaluated using the test pieces obtained by punching out the obtained sheet-shaped molded product.
  • Example 2 As a cross-linking accelerator, 1,1-bis (4-hydroxyphenyl) -2,2,2-trifluoroethane-benzyltriphenylphosphonium (a salt having a molar ratio of 1: 1) was used instead of benzyltriphenylphosphonium chloride.
  • a fluoropolymer composition was prepared in the same manner as in Example 1 except that the ratio of each component used was as shown in Table 1 below.
  • the obtained fluoroelastomer composition was put into a mold and subjected to press-crosslinking (primary cross-linking) at a temperature of 177 ° C. and a pressure of 10 MPa for 15 minutes to form a sheet-shaped molded product (length: 150 mm, width: 150 mm, thickness: 2 mm). , Length: 100 mm, Width: 100 mm, Thickness: 4 mm).
  • the resulting compact was then transferred to an oven and secondarily crosslinked at 232 ° C. for 24 hours.
  • Various characteristics were evaluated using the test pieces obtained by punching out the sheet-shaped molded product thus obtained.
  • the obtained fluoroelastomer composition was put into a mold and subjected to press-crosslinking (primary cross-linking) at a temperature of 177 ° C. and a pressure of 10 MPa for 15 minutes to form a sheet-shaped molded product (length: 150 mm, width: 150 mm, thickness: 2 mm). , Length: 100 mm, Width: 100 mm, Thickness: 4 mm).
  • the resulting compact was then transferred to an oven and secondarily crosslinked at 232 ° C. for 24 hours.
  • Various physical characteristics were evaluated using the test pieces obtained by punching out the sheet-shaped molded product thus obtained.
  • Table 1 summarizes various information. "-" In Table 1 indicates that the composition does not contain the corresponding component.
  • the fluoroelastomer composition using 1,1-bis (4-hydroxyphenyl) -2,2,2-trifluoroethane as a cross-linking agent is equivalent to the fluoroelastomer composition using bisphenol AF as a cross-linking agent. It is understood that it has the cross-linking property of.
  • the obtained molded product as shown in Examples 1 and 2, when 1,1-bis (4-hydroxyphenyl) -2,2,2-trifluoroethane was used as a cross-linking agent, bisphenol AF was used. Compared with the case of using a cross-linking agent, the elongation at the time of tearing was large and the flexibility was improved.
  • the cross-linking accelerator As the cross-linking accelerator, the case of using 1,1-bis (4-hydroxyphenyl) -2,2,2-trifluoroethane-benzyltriphenylphosphonium and the case of using benzyltriphenylphosphonium chloride are equivalent. there were. In addition, other characteristics were almost the same in Examples 1 and 2 and Comparative Example. That is, it is understood that the molded bodies obtained in Examples 1 and 2 have physical properties suitable for application to hoses, sealing materials, and the like.
  • the melting point of benzyltriphenylphosphonium chloride was 300 ° C or higher.
  • the compounds obtained in Synthesis Examples 1 to 3 showed a lower melting point, and 1,1-bis (4-hydroxyphenyl) -2,2,2-trifluoroethane-benzyltriphenylphosphonium. It is understood that the melting point is lowered by using the salt of. Further, when compared with the compounds of Synthesis Examples 1 to 3, the higher the ratio of 1,1-bis (4-hydroxyphenyl) -2,2,2-trifluoroethane, the lower the melting point. From this, it is presumed that the higher the ratio of the structure derived from the polyhydroxy compound (b) contained in the onium salt, the lower the melting point.

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

Abstract

L'invention concerne une composition de fluoroélastomère comprenant : un caoutchouc fluoré (a) qui peut se réticuler avec un composé polyhydroxy ; et un composé polyhydroxy (b) ayant une structure dans laquelle deux cycles aromatiques sont liés par -CH(CF3)-.
PCT/JP2021/043340 2020-11-30 2021-11-26 Composition de fluoroélastomère, corps moulé de caoutchouc fluoré, agent de réticulation pour fabriquer un corps moulé de caoutchouc fluoré, promoteur de réticulation pour fabriquer un corps moulé de caoutchouc fluoré, mélange de sel et sel d'onium WO2022114109A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001508105A (ja) * 1997-01-06 2001-06-19 ダイネオン エルエルシー 良好な低温特性を有するパーフルオロエーテル含有フルオロエラストマー
JP2005524748A (ja) * 2002-05-09 2005-08-18 デュポン　ダウ　エラストマーズ　エルエルシー 金属、セラミックまたはガラス基材に対する耐塩基性フルオロエラストマーの接着性を改良するための組成物
JP2006514125A (ja) * 2003-07-25 2006-04-27 スリーエム イノベイティブ プロパティズ カンパニー テトラフルオロエチレン、クロロトリフルオロエチレン、ヘキサフルオロプロピレン及びフッ化ビニリデンに基づくフルオロエラストマーコポリマー
WO2010029899A1 (fr) * 2008-09-09 2010-03-18 ダイキン工業株式会社 Procédé de production de corps moulé réticulé en caoutchouc fluoré
WO2020162408A1 (fr) * 2019-02-06 2020-08-13 セントラル硝子株式会社 １，１，１－trifluoro－２，２－bisaryléthane, et procédé de fabrication de celui-ci

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001508105A (ja) * 1997-01-06 2001-06-19 ダイネオン エルエルシー 良好な低温特性を有するパーフルオロエーテル含有フルオロエラストマー
JP2005524748A (ja) * 2002-05-09 2005-08-18 デュポン　ダウ　エラストマーズ　エルエルシー 金属、セラミックまたはガラス基材に対する耐塩基性フルオロエラストマーの接着性を改良するための組成物
JP2006514125A (ja) * 2003-07-25 2006-04-27 スリーエム イノベイティブ プロパティズ カンパニー テトラフルオロエチレン、クロロトリフルオロエチレン、ヘキサフルオロプロピレン及びフッ化ビニリデンに基づくフルオロエラストマーコポリマー
WO2010029899A1 (fr) * 2008-09-09 2010-03-18 ダイキン工業株式会社 Procédé de production de corps moulé réticulé en caoutchouc fluoré
WO2020162408A1 (fr) * 2019-02-06 2020-08-13 セントラル硝子株式会社 １，１，１－trifluoro－２，２－bisaryléthane, et procédé de fabrication de celui-ci

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