WO2000043349A1 - Nouveaux composes triphenyle - Google Patents

Nouveaux composes triphenyle Download PDF

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Publication number
WO2000043349A1
WO2000043349A1 PCT/JP2000/000191 JP0000191W WO0043349A1 WO 2000043349 A1 WO2000043349 A1 WO 2000043349A1 JP 0000191 W JP0000191 W JP 0000191W WO 0043349 A1 WO0043349 A1 WO 0043349A1
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WO
WIPO (PCT)
Prior art keywords
group
elastomer
cross
amino
compound
Prior art date
Application number
PCT/JP2000/000191
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English (en)
Japanese (ja)
Inventor
Katsuhiko Iseki
Tsuyoshi Itagaki
Mitsuru Kishine
Masaki Irie
Tsuyoshi Noguchi
Kazuyoshi Kawasaki
Original Assignee
Daikin Industries, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Daikin Industries, Ltd. filed Critical Daikin Industries, Ltd.
Publication of WO2000043349A1 publication Critical patent/WO2000043349A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines

Definitions

  • the present invention relates to a novel triphenyl compound useful as a cross-linking agent, especially as a cross-linking agent for elastomers, a cross-linking agent and a cross-linkable cross-linking agent.
  • the present invention relates to a composition comprising an elastomer, and a bridge obtained by forming the composition into a bridge. Background technology
  • cross-linking agents for elastomers for example, Japanese Patent Publication No. 59-11056, Japanese Patent Publication No. 6-263952, and Japanese Patent Publication No. Japanese Unexamined Patent Publication No. Hei 8 (1996) No. 1
  • the present invention is useful as a cross-linking agent, and when used as a cross-linking agent, reduces the amount of cure site monomer in cross-linkable polymers.
  • a composition comprising a novel triphenyl compound or a salt thereof, a crosslinkable agent and a crosslinkable elastomer, and a mixture thereof.
  • An object of the present invention is to provide a crosslinked product obtained by forming a bridge composition from a rubber composition. Disclosure of the invention
  • the present invention is based on the formula (I a)
  • X 1 , X 2 and X 3 are the same or different, and all are hydroxyl, mercapto or amino; ⁇ is an amino; R Is a trivalent hydrocarbon group having 1 to 12 carbon atoms, which may be substituted by a fluorine atom, and may contain an oxygen atom having a ether bond; X 1 , X 2 , X 3 and ⁇ are one in the meta position and the other in the para position) or the formula (I b):
  • X 1 , X 2 and X 3 are all hydroxyl groups, and R may have 1 to 3 carbon atoms which may be substituted with a fluorine atom.
  • trivalent Oh Ru Application Benefits full et two Le compounds with a hydrocarbon group the is et to have you to formula (la)
  • XX 2 X and X 3 are both hydroxyl groups, and
  • R 1 is a methyl group or a trifluoromethyl group
  • a triphenyl compound or a salt thereof is preferred.
  • Examples of the salt of the triphenyl compound of the present invention include sodium salt, potassium salt, hydrochloride, and the like.
  • the present invention also relates to a bridging agent comprising these triphenyl compounds or salts thereof.
  • the present invention relates to an elastomer composition comprising the novel cross-linking agent and a crosslinkable elastomer, and an elastomer comprising the same.
  • the present invention also relates to a bridge obtained by forming the composition into a bridge.
  • X 1 , X 2 or X 3 hereinafter unless otherwise specified
  • the combination of "X", (U) and Y (Amino group) is, for example, as shown below.
  • X is a hydroxyl group and Y is an amino group
  • a nitrile group, a carboxyl group, or an alkoxycarbonyl group is preferable as a bridge point on one side of the elastomer.
  • the cross-linking reaction looks like this:
  • R 2 is a hydrogen atom or an alkyl group.
  • a cross-linking point on one side of the elastomer a nitrile group, a carboxyl group, or an alkoxyl-ponyl group is preferable.
  • the cross-linking reaction looks like this:
  • a nitrile group is preferred as a crosslinking point on one side of the elastomer.
  • the cross-linking reaction is as follows.
  • R may be substituted with a fluorine atom or may have an ether-bonding oxygen atom, and may have 1 to 1 carbon atoms. It is a bivalent trivalent hydrocarbon group.
  • a trivalent hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a fluorine atom is, for example,
  • Aliphatic hydrocarbon groups having 1 to 3 carbon atoms such as
  • a perfluoroaliphatic hydrocarbon group having 1 to 3 carbon atoms is preferred.
  • R is a trivalent hydrocarbon group having 1 to 12 carbon atoms containing an oxygen atom having an ether bond, for example,
  • OCF 3 CF 3 CF 3 etc. are exempted from the viewpoint of ease of synthesis and availability of raw materials.
  • the compound having a triazine represented by the formula (Ib) can be expected to have thermal stability and chemical resistance.
  • triphenyl compound represented by the formula (Ia) of the present invention can be produced by the following reaction.
  • the reduction reaction of the tris (nitrophenol) of the formula (III) is carried out by supplying hydrogen gas in the presence of a catalyst such as palladium carbon. (See Japanese Patent Laid-Open Publication No. Hei 6—2 1).
  • thiophenate is added to the aromatic ring of a tris (4-aminophenol) compound by using bromine as an oxidizing agent, thereby forming a nucleophile.
  • a tris (5—amino—4, 6—benzothiazolyl) compound is obtained by a reactive ring closure reaction. This is heated in an aqueous solution of a hydroxylated alkali metal such as lithium hydroxide to form a tris (4-amino-3 -medium).
  • Lecaptophenyl is added to the aromatic ring of a tris (4-aminophenol) compound by using bromine as an oxidizing agent, thereby forming a nucleophile.
  • a tris (5—amino—4, 6—benzothiazolyl) compound is obtained by a reactive ring closure reaction. This is heated in an aqueous solution of a hydroxylated alkali metal such as lithium hydroxide to form a tris (4-amino-3 -medium).
  • a compound in which X is an amino group can be produced by the following method (see Japanese Patent Publication No. Sho 64-129343).
  • a tris (3-aminophenyl) compound is converted into an acyl under a normal acylation condition to form a tris (3-asial). Midfer) The compound is obtained. This is converted to a tris (3—acyl amide 412 trofenyl) compound, and then converted to an acid or alkaline compound. Detrisylation is performed under the conditions to obtain a tris (3-amino-4-nitrophenyl) compound. Then, tris (3,4-diaminophenyl) is formed by direct catalytic reduction with hydrogen gas using Pd / C as a catalyst. To obtain the compound.
  • the compound containing a triadine represented by the formula (lb) can be produced, for example, by the following method.
  • the triphenyl compound may be in the form of a salt.
  • the salt include alkali metal salts such as sodium salt and calcium salt, as well as hydrochloride, nitrate, sulfate, and carbonate. Etc. are exterminated.
  • the salt can be produced by a conventional method, for example, by adding a sodium hydroxide aqueous solution or hydrochloric acid and drying.
  • the triphenyl compound or salt of the present invention is composed of a nitrile group, a sulfoxyl group and an oxazole. It forms a ring, a thiazole ring, or an imidazole ring, so that it has a tri- or tri-oxyl group as a cross-linking point.
  • it is useful as a bridge for elastomers, especially for fluoroelastomer.
  • the triphenyl compound of the present invention has three bridging points, if it is used as a cross-linking agent, it will only have a cross-linking point at the end of the polymer. Even if the elastomer or the bridge point is a small amount of elastomer, it can form a three-dimensional network structure. I will. Further, when R is a perfluorinated hydrocarbon group, the heat resistance and chemical resistance are further improved by the influence of the fluorine atom.
  • the cross-linking agent of the present invention is suitable for cross-linking (vulcanization) of a cross-linkable elastomer, and the cross-linking agent of the present invention is cross-linkable with the cross-linking agent.
  • the present invention also relates to an elastomer composition which is made up of an elastomer.
  • Elastomers that can be cross-linked by the crosslinking agent of the present invention include, as cross-linkable groups (cross-linking points), hydroxyl groups and alkoxy groups. Fluorine-containing elastomers or non-fluorine-based compounds containing a poly group, an iodine atom, a bromine atom, a sulphonic acid group, a nitrile group, etc. The elastoma is exposed.
  • fluorine-containing elastomer tetrafluoroethylene ( ⁇ FE) / perfluoro mouth (alkyl vinyl ether) (PAVE) copolymer, TFE / hexafluoropropylene (HFP) / PAVE copolymer, etc .; perfluoroelastomer; Fluoride (VdF) ZHFP copolymer, VdFZTFE / HFP copolymer, VdF / c ⁇ D Trifluoroethylene (CTFE) copolymer, VdF / TFEZPAVE copolymer, TFEZ ethylene (Et) / PAVE copolymer, TFEZ propylene (Pr) copolymer, Et / HFP copolymer, Et ZTFE / Non-perfluoroelastomer such as PAVE copolymer; and furthermore, these fluoroelastomer can be converted into an elastomeric polymer.
  • VdF
  • Non-elastomer as a chain segment Fluorine-containing multi-segment obtained by block copolymerization of resinous fluorine-containing polymer segment as a polymer chain segment Utilization Rustoma Japanese Patent Publication No. (See Japanese Patent Publication No. 6-222001).
  • non-fluoroelastomer natural or synthetic rubber, which has been widely used in the past, is exposed. For example, acrylic rubber is used.
  • Natural rubber Isoprene rubber, Ethylene Z propylene rubber, Ethylene / Propylene rubber, Butagen / Styrene rubber , Polybutadiene rubber, Butyri rubber, Halogenidani butyl rubber, Chloroprene rubber, Isobutylene ⁇ Isoprene rubber, Butadiene Z acrylonitrile rubber, chlorosulfone rubber, lipstick rubber, lipstick lipstick, epiplor hydrin ⁇ Ethyrenoxyside rubber etc. are exfoliated.
  • these elastomers may have a bridging group, a carboxyl group, or an alkoxycarbonyl group, which is a bridging group as described above. In order to introduce them, for example, it is only necessary to co-polymerize the monomers.
  • CF 2 CF (OCF 2 CF3 ⁇ 4-0- (CF 3 ⁇ 4-X 4 (where m is 0 5 n is 18)
  • CF 2 CFO (CF 2 ⁇ OCF (CF 3 ) X 4 (n is 25)
  • CF 2 CF [OCF 2 CF (CF 3 )] n OCF 2 CF (CF 3 ) X 4 (where n is 1 to 2), or
  • These elastomers may have an iodine atom or a bromine atom, which is a crosslinkable group, introduced therein.
  • the crosslinking agent of the present invention is usually added to these crosslinkable elastomers in an amount of up to 10% by weight, preferably 0.5 to 5% by weight of the elastomer.
  • a crosslinkable elastomer composition can be prepared.
  • Additives which can usually be added to the elastomer composition such as fillers such as carbon black and silica, vulcanization aids, vulcanizing agents, and the like. Sulfur accelerators, plasticizers, coloring agents, etc. can be added.
  • Crosslinking (vulcanization) of a crosslinkable elastomer composition is usually carried out.
  • Vulcanization methods for example, open vulcanization, press vulcanization, etc.
  • the bridge thus obtained is excellent in heat resistance, compression set resistance and the like.
  • the crosslinked product of the present invention is useful as various molded products in the fields shown in Tables 1, 2 and 3 below.
  • Kameki Semiconductor-related semiconductor manufacturing equipment CVD equipment 0 square
  • packing packing
  • sealing material tube, roll
  • Liquid crystal panel manufacturing equipment Dry etching equipment Coating, lining, gasket, diaphragm, hose Plasma panel manufacturing equipment Pet etching equipment.
  • Fuel properties, fuel permeability, shochu heat properties Material properties, fuel permeability, shochu heat properties
  • Attachment O-ring of quartz window of applicable product equipment sealing material O-ring of chamber of applicable product equipment, seal material O-ring of sealing of applicable product equipment, sealing material
  • O-ring and sealing material for the power supply of the applicable product equipment O-ring and seal material for the pump of the applicable product equipment
  • seal material O-ring for resist developer and stripper seal material O-ring for wafer-cleaning solution
  • the above-mentioned 300 is suitable as a seal material used in the above operating environment.
  • the crystals were dissolved in a 300-m1 black hole holm, and 30 ml of saturated saline was added thereto to extract the black hole holm.
  • the organic layer was dried over magnesium sulfate and dried.
  • the solvent was removed by distillation to remove the yellow crystalline 1,1,1,1-tris (3-nitro- 4 — 10.8 g (yield: 75%) of hydroxyfenyl) was obtained.
  • 1,1,1—trifluoro-1,2,2,2—tris (3—nitro14—hydroxy 1,2,2,3-Tris (3—Amino 1-4—Hydroxy) (Encapsulated) (yield: 90%) in gray solid Obtained .
  • CF 2 CFOCF 2 CF (CF 3) OCF 2 CF 2 CN (CNVE) 3 g is converted to nitrogen. Pressed in with pressure. Then, 4.7 g of TFE and 5.3 g of PMVE were press-fitted under their own pressure so that the pressure would be 0.78 MPa a * G. After that, the TFE, PMVE is press-fitted and the pressure rises and falls repeatedly at 0.69 to 0.78 MPa ⁇ G, and the combined weight of TFE and PMVE weighs 70 g and 130 g. , 19 Og and 250 g, respectively, 3 g of CNVE were injected under nitrogen pressure.
  • Example 1 It was synthesized in Example 1 with a fluorine-containing elastomer containing a nitrile (CN) group having a carboxyl group at the terminal of the polymer obtained in Production Example 1.
  • 1,1,1,1 Tris (3-amino 14-hydroxyphenyl) ethane as a cross-linking agent and MT bonbonbura as a filler Weight (T hermax N-990 from Canearb) and a weight ratio of 100 / 1.2.28 /
  • the mixture was mixed at 20 ° C and kneaded in an open roll to prepare a fluorine-containing elastomer composition capable of being bridged.
  • This fluorine-containing elastomer composition was press-crosslinked (primary crosslinking) at 180 for 20 minutes to obtain a 2 mm-thick sheet and O-lin. (P — 24). This sheet and the O-ring are oven-processed in an electric furnace for 18 hours at 204 and then 18 hours at 288. The test sample was made by cross-linking (secondary bridge).
  • a vulcanization curve was obtained at 180 by using a JSR-type elastomer-II type.
  • most low viscosity (vmin) the most high-viscosity (vma X)
  • induction time between (T E Q) your good beauty between the optimum vulcanization time (T 9.)
  • test sample 100% modulus, tensile strength and tensile elongation of the test sample (cross-linked sheet with a thickness of 2 mm) in the normal state (25 :) according to JISK6301 Measure bio and hardness (JISA hardness).
  • each of the test samples (O-ring (P-24)) at 200, 230 and 275, respectively.
  • Example 4 In Example 3, the weight ratio of the combination ratio of the fluorine-containing CN-containing elastomer, the crosslinking agent, and the MT-carbon black was determined.
  • Example 3 the compound synthesized in Example 2 was used as a crosslinking agent.
  • Example 3 was the same as Example 3 except that the mixing ratio of the fluorine elastomer, the cross-linking agent, and the MT carbon black was set to 100 Z1.48 / 20 by weight.
  • a crosslinkable fluorine-containing elastomer composition was prepared in the same manner as described above, and various physical properties were measured in the same manner as in Example 3. The results are shown in Table 4.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne des composés triphényle représentés par la formule (I) ou des sels de ceux-ci. Dans cette formule, X?1, X2 et X3¿ représentent chacun indépendamment hydroxyle, mercapto ou amino; Y représente amino; et R4 représente un groupe hydrocarbone trivalent en C¿1?-C12 qui peut être fluoriné ou contenir un atome d'oxygène éthérique, ou un résidu triazine, à condition que soit chacun de X?1, X2 et X3¿ soit Y soit lié au niveau de la position méta, l'autre étant lié à la position para. Ces composés sont utiles comme agents de réticulation pour les élastomères, et fournissent des produits réticulés présentant une excellente résistance à la chaleur.
PCT/JP2000/000191 1999-01-21 2000-01-18 Nouveaux composes triphenyle WO2000043349A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP1353099 1999-01-21
JP11/13530 1999-01-21

Publications (1)

Publication Number Publication Date
WO2000043349A1 true WO2000043349A1 (fr) 2000-07-27

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004500459A (ja) * 2000-02-08 2004-01-08 デュポン　ダウ　エラストマーズ　エルエルシー 硬化性パーフルオロエラストマー組成物
KR20190125765A (ko) * 2018-04-30 2019-11-07 삼성에스디아이 주식회사 유기막 조성물 및 패턴 형성 방법
WO2022220018A1 (fr) 2021-04-15 2022-10-20 ダイキン工業株式会社 Composition de réticulation de caoutchouc fluoré, produit moulé et élément d'étanchéité

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4892812A (en) * 1983-02-04 1990-01-09 Mitsubishi Paper Mills, Ltd. Silver halide photosensitive materials
US4897436A (en) * 1987-01-22 1990-01-30 Bayer Aktiengesellschaft New Stabilizers and their use for the production of stabilized polyamides and rubber materials
US5700879A (en) * 1994-10-21 1997-12-23 The Central Synthetic Rubbers Research Institute Fluorine-containing elastomer composition

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4892812A (en) * 1983-02-04 1990-01-09 Mitsubishi Paper Mills, Ltd. Silver halide photosensitive materials
US4897436A (en) * 1987-01-22 1990-01-30 Bayer Aktiengesellschaft New Stabilizers and their use for the production of stabilized polyamides and rubber materials
US5700879A (en) * 1994-10-21 1997-12-23 The Central Synthetic Rubbers Research Institute Fluorine-containing elastomer composition

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004500459A (ja) * 2000-02-08 2004-01-08 デュポン　ダウ　エラストマーズ　エルエルシー 硬化性パーフルオロエラストマー組成物
KR20190125765A (ko) * 2018-04-30 2019-11-07 삼성에스디아이 주식회사 유기막 조성물 및 패턴 형성 방법
KR102222780B1 (ko) 2018-04-30 2021-03-03 삼성에스디아이 주식회사 유기막 조성물 및 패턴 형성 방법
WO2022220018A1 (fr) 2021-04-15 2022-10-20 ダイキン工業株式会社 Composition de réticulation de caoutchouc fluoré, produit moulé et élément d'étanchéité

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