WO2000043349A1

WO2000043349A1 - Novel triphenyl compounds

Info

Publication number: WO2000043349A1
Application number: PCT/JP2000/000191
Authority: WO
Inventors: Katsuhiko Iseki; Tsuyoshi Itagaki; Mitsuru Kishine; Masaki Irie; Tsuyoshi Noguchi; Kazuyoshi Kawasaki
Original assignee: Daikin Industries, Ltd.
Priority date: 1999-01-21
Filing date: 2000-01-18
Publication date: 2000-07-27

Abstract

Triphenyl compounds represented by general formula (I) or salts thereof, wherein X?1, X2 and X3¿ are each independently hydroxyl, mercapto, or amino; Y is amino; and R4 is a C¿1?-C12 trivalent hydrocarbon group which may be fluorinated or contain an etheric oxygen atom, or a triazine residue, with the proviso that either each of X?1, X2 and X3¿ or Y is bonded at the meta position and the other at the para position. The compounds are useful as crosslinking agents for elastomers and give crosslinked products excellent in heat resistance.

Description

Akira Itoda New triphenyl compound technical field

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

As 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

In the publication of No. 6, etc., a compound having two aminophenol groups (a bisaminophenol compound) is described. Bridges made of aluminum phenolic compounds are very expensive, and they are very expensive, such as those having a cure site monomer (CN or COOH group). It is possible for a polymer to be obtained by co-polymerization of a dimer compound), but it does not have a cure site (cross-linking point) at only one end of the polymer. Elastomers were not able to form a three-dimensional network structure.

INDUSTRIAL APPLICABILITY 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)

(Wherein, X ¹ , X ² and X ³ are the same or different, and all are hydroxyl, mercapto or amino; Υ 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 Υ are one in the meta position and the other in the para position) or the formula (I b):

(Wherein X ¹ , X ² , X ³ and Y are the same as defined above) or a salt thereof.

In particular, in the formula (Ia), 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

-C-R ¹

(Wherein R ¹ is a methyl group or a trifluoromethyl group), and 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.

Further, 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. In the best formula (la) and formula (lb) for carrying out the invention, 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.

(1) X is a hydroxyl group and Y is an amino group

In this case, as a bridge point on one side of the elastomer, a nitrile group, a carboxyl group, or an alkoxycarbonyl group is preferable. . The cross-linking reaction looks like this:

+ HO + R ² 0H

OH (In the formula, R ² is a hydrogen atom or an alkyl group).

(2) X is a merilecapto group and Y is an amino group

In this case, as 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:

(3) X is an amino group and Y is also an amino group

In this case, a nitrile group is preferred as a crosslinking point on one side of the elastomer. The cross-linking reaction is as follows.

As described above, 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.

For example, a trivalent hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a fluorine atom is, for example,

≡ C— CH ₃ , ≡ C-1 C ₂ H ₅ , ≡ C-CH ₂ CH ₂ CHo C-nC ₄ 4H ^Π 9 C C CH (CH ₃ ) ₂ , C C C (CH ₃ ) ₃ etc. Aliphatic hydrocarbon group;

C-CF ₃ , _{≡ C} -C ₂ F ₅ , ≡ C-CF ₂ CF ₂ CF ₃ , ≡ C-nC ₄ F _g , C-CF (CF ₃ ) ₂ , C-C (CF ₃ ) ₃ Fluoroaliphatic hydrocarbon groups such as trivalent benzene radicals; Aromatic hydrocarbon radicals such as trivalent benzene radicals; trivalent trifluorobenzene radicals Such as fluorinated aromatic hydrocarbon groups. Of these, the ease of synthesis, the availability of raw materials, etc.

C-C H

Aliphatic hydrocarbon groups having 1 to 3 carbon atoms, such as

≡ C-CF ₃

For example, a perfluoroaliphatic hydrocarbon group having 1 to 3 carbon atoms is preferred.

For example, when R is a trivalent hydrocarbon group having 1 to 12 carbon atoms containing an oxygen atom having an ether bond, for example,

一 C-CF ₂ OCF _? CF ₃ , ≡ C-CF ₂ CF and OCF ₂ CF ₃ ,

一 C-CFCF ₂ CF ₃ , ≡ C-CFCF ₂ OCF ₂ CFOCF CF ₂ CF ₃

OCF ₃ CF ₃ CF ₃ etc. are exempted from the viewpoint of ease of synthesis and availability of raw materials.

≡ C-CFCF OCF ₂ CFOCF ₂ CF ₂ CF ₃

CF ₃ CF ₃

Is preferred.

The compound having a triazine represented by the formula (Ib) can be expected to have thermal stability and chemical resistance.

The triphenyl compound represented by the formula (Ia) of the present invention can be produced by the following reaction.

When X is a hydroxyl group and R is a hydrocarbon group, the following production method is preferred.

(ID (III)

(Ial) The nitrification reaction of trisphenol of the formula (II) proceeds in the presence of nitric acid in a lower fatty acid solvent under conditions of stirring at room temperature ( The conditions described in the official gazette of Japanese Patent Publication No. 2001-16353).

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).

See No. 1,752).

The tris (phenol) of formula (II), which is the starting substance, is that R is

The compound which is H 3 is described in German Patent No. 1933033 and has a length of

≡ ^C -CF ₃

0 (1982)

(Ila) (ID

Can be obtained by deprotecting the tris (methoxyphenyl) compound represented by the formula (B) with boron bromide. Synth., Collect. Vol. V, 412-413 (1973)). In addition, a compound in which X is a mercapto group can be manufactured by the following method (see Japanese Patent Publication No. 8-1444353). .

That is, 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) compound.

Further, a compound in which X is an amino group can be produced by the following method (see Japanese Patent Publication No. Sho 64-129343).

That is, 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.

By heating the 4-cyano-metal sulfide using the catalyst as a catalyst, the tris (4-methane sulfide) is heated. Nil) to obtain triazine. This is a to have use the etc. BB r ₃ deprotected, door re-scan - Ru obtained (4 human mud key shea off d two relay) Application Benefits A di down. This is subjected to nitration under normal nitration conditions to obtain a tris (4—hydroxy-13_nitrophenyl) triazine. Then, by direct catalytic reduction with hydrogen gas using Pd / C etc. as a catalyst, tris (3—amino-4—hydroxifene) is obtained. Nil) to obtain triazine.

In these reactions, at least the compound (II) and the compound (III) are new compounds.

The triphenyl compound may be in the form of a salt. Examples of 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.

As described above, the triphenyl compound or salt of the present invention, particularly the triphenyl compound, 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. For example, it is useful as a bridge for elastomers, especially for fluoroelastomer.

Since 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.

As described above, 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.

As a fluorine-containing elastomer, tetrafluoroethylene (τFE) / 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. 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). As 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 ΖEthyrenoxyside rubber etc. are exfoliated.

If necessary, 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 ₃

CF ₂ = CF (OCF ₂ CF¾-0- (CF ¾-X ⁴ (where m is 0 5 n is 18)

CF _3- CF- (CF ₂ OCF CF ゥ OCF = CF ₂

X ⁴ CF ₃

(n is 1 4)

CF ₂ = CFO (CF ₂ ^ OCF (CF ₃ ) X ⁴ (n is 25)

CF ₂ =

(n is 1 6) CF ₂ = CF [OCF ₂ CF (CF ₃ )] _n OCF ₂ CF (CF ₃ ) X ⁴ (where n is 1 to 2), or

CH ₂ = CFCF ₂ 0- CFCF ₂ O ^ CF-X ⁴

CF ₃ CF ₃

[X ⁴ is CN, COOH or is COOR ^² (R ² is A Le kill based on but it may also be had with you including a full Tsu atom of 1 to 1 0 carbon atoms) Ru Oh in]

These elastomers may have an iodine atom or a bromine atom, which is a crosslinkable group, introduced therein. The introduce iodine atoms was example, if ^{_{^{CX 5 2 = CX 5 - R}}} f - CHR 3 - I (X 5 is was H or F, R ³ is methylation group was H or) , CF ₂ = CFO-(CF ₂ -CF (CF ₃ ) 0)-CF ₂ CF ₂ CH ₂ -I and other iodine-containing monomers can be copolymerized, and bromine atoms are introduced. the order was you, was example, if ^{_{^{CX 5 2 = CX 5 - R}}} f - CHR 3 - B r (X 5 is was H or F, R ³ is main Chi Le group was H or), CF ₂ = CFO — (CF ₂ — CF (CF ₃ ) 0)-CF ₂ CF ₂ CH _2- Br.

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. As a result, 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.

Industry Fields Final products Final products Parts

Kameki Semiconductor-related semiconductor manufacturing equipment CVD equipment 0 (square) ring, 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.

Oxidation diffusion device

Sputtering equipment

Atthing device

Ion injection device

Conveyor automatic closing automatic engine and peripheral equipment gasket '"auto-shaft seal, lube stem seal, sealing material,

Hose

Place; ―sushi; fct "

Swords; swords 0 (square) ring, tube, packing, valve core, hose-seal material, diaphragm Aircraft Aircraft Fuel system Diaphragm, 0 (square) ring, valve, tube, * kin, hose , Wood

Location '' Location '' Fuel Fuel IHI

Ship ^ White Ship Fuel | Hl

Chemicals Chemicals Plants Iran, pesticides, paints, resins, linings, revs, packings, rolls, hoses, diaphragms,

Chemical product manufacturing culm 0 (square) ring-tube, seal material

(Oil)

Medicine medicine medicine stopper

Yoko Photo Developing machine Film developing machine

X-ray film developing machine roll

Printing printing machine printing roll

Painting Painting equipment

Analytical physicochemical tube

Άαα Brand Food manufacturing process Lining, valve, backing, roll, hose, diaphragm,

0 (square) ring, tube, sealing material

Metal 妷 Steel Failwork processing equipment Ironwork processing roll

Industry basic needs

Plasma resistance, acid resistance, alkali resistance, shochu amine, ozone resistance, gas resistance, chemical resistance, cleanliness, heat resistance

Heat transfer, heat resistance

Fuel properties, fuel permeability, shochu heat properties Material properties, fuel permeability, shochu heat properties

ίίFuel properties, fuel permeability, heat resistance

Material, fuel permeability, alertness

Chemical resistance, solvent resistance, heat resistance

Chemical properties, solvent resistance, heat resistance

Cleanliness

Mechanical properties

Alertness

Elbow solvent

Sometimes solvent-based food. Elbow chemical properties, solvent properties, heat resistance

Metallic heat, Shochu acid Three

Body name

Gold eclipse 0 ring and seal material of gate valve of applicable product equipment

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 of bell jar of applicable product equipment, seal 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

O-ring of semiconductor gas control device of applicable product, seal material O-ring for resist developer and stripper, seal material O-ring for wafer-cleaning solution, seal

Diaphragm of the pump of this production equipment

Hose for resist developer and stripper

Hose and tube for wafer cleaning solution

ゥヱ σ-roll for single transfer

Lining and coating of resist developer bath and stripper bath Lining and coating of wafer-cleaning bath

Lining and coating of wet etching tank へ Head gasket for transport engine

Metal gasket

Crankshaft

Camshaft seal

Noreb Stem

Maniho Noredono Cooking

| Oil Horse

IATF hose

Injector 1 ring

Injector packing

Fuel bomb 0 ring, diaphragm

Fuel hose

Machine ¾¾¾ difficult roll

Circular statue roll

Gravure roll

Guide roll

Gravure roll for tape production coating line

Guide roll for tape production coating line

| §Seed Coatings In particular, it can be used by incorporating it into the following semiconductor manufacturing equipment.

(1) Etching device

Dry-etching device

Plasma etching equipment

Reactive ion etching equipment

Reactive ion beam etching device

Sputter etching device

Ion beam etching device

ゥ Etching device

Atsushiching equipment

(2) Cleaning device

Dry etching cleaning equipment

uvzo ₃ cleaning equipment

Ion beam cleaning equipment

Laser beam cleaning equipment

Plasma cleaning equipment

Gas etching cleaning equipment

Extraction cleaning device

Sock slide extraction Cleaning device

High-temperature high-pressure extraction cleaning device

Microwave extraction Cleaning device

Ultra-critical extraction cleaning device

(3) Exposure equipment

State of the art

Co-developed. One

(4) Polishing device

CMP equipment (5) Deposition equipment

C V D device

Spanning ring device

, H

(6) Diffusion unit 1-ion injection device

Chemical diffusion equipment

Ion injection device

Especially in automobiles for error down di emissions of O ₂ cell down support over for sheet Lumpur material, aerospace for E down-di-down of the city Lumpur material, etc. death Lumpur material of oil field drilling equipment theft The above-mentioned 300 is suitable as a seal material used in the above operating environment.

Next, the present invention will be described by way of examples with reference to the triphenyl compound. However, the present invention is limited to only such examples. Rather, those skilled in the art will be aware of the compounds described in formulas (Ia) and (Ib) based on the specific description above and the description of the examples below. Can be easily manufactured. Example

(1, tris (3 amino 4 production of hydroxyphenyl)

(1) Synthesis of 1, 1, 1-tris (3-nitro-4-hydroxyphenyl) ethane

Dissolve 10 g (32.4 mmol) of 1,1,1-tris (4-hydroxyphenyl) ethane in 90 ml of acetic acid. After stirring for 1 hour, in a water bath, dissolve 12.32 g (117 mmo1) of 60% nitric acid in 90 ml of acetic acid for 1 hour. Dropped. After the completion of the dropwise addition, the water bath was removed, and the mixture was stirred at room temperature for 12 hours. After confirming the disappearance of the raw materials by TLC, 500 ml of water was added, and the precipitated yellow crystals were separated by suction filtration and washed with 50 ml of water. Was

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 H-NMR in CDC 1 3}} : δ (ppm) = 2.19 (3 H, s), 7.16 (3 H, d,

J = 8.89Hz), 7.35 (3H, dd, J = 8.89, 2.48Hz), 7.82 (3H, d, J = 2.48Hz), 10.57 (3H, s)

IR (KBr): cnT '= 3270, 1628, 1580, 1536, 1488, 1420

MS m / z = 441 (m ⁺ ), 426

(2) Synthesis of 1, 1, 1-tris (3-amino-4-hydroxyphenyl) ethane

7 g (15.9 mmo 1) of the obtained 1, 1, 1-tris (3-nitro-4-hydroxyphenyl) ethane was added to the medium. Dissolve in 25 ml, and use 10% Pd / C as catalyst as catalyst, hydrogen pressure is 10 kcm ² , reaction temperature is 10

0: The reduction reaction was carried out directly for 18 hours. After filtration through celite, the solvent is distilled off, and 1,1 is added by short-cut column (ethyl acetate) and recrystallized (ethyl acetate: hexane). 5 g (yield: 89%) of 1,1-tris (3-amino-4-hydroxyphenyl) ethane were obtained as gray crystals. NMR-NMR in THFd ₈ : δ (ppm) = 1.90 (3H, s), 3.91 (6H, s), 6.16 to 6.21 (3H, m), 6.36 to 6.42 (6H, m), 7.69 (3H, s)

IR (KBr): cm " ¹ = 3330 2976, 1698, 1612, 1519, 1438

MS m / z = 351 (m ⁺ ), 336

Example 2

(1, 1, 1-Trifluoro2, 2, 2-Manufacture of tris (3-amino-4-hydroxyphenyl) ethane)

(-78 ° C → r.t.l8hr)

BBrj (2.2eq)

(1) CF ₃ C -KQV-OCH, CH ₂ C1 CF ₃ C ~ 〇>" ^0H

(1) Synthesis of 1, 1, 1-Trifluoro2, 2, 2—Tris (4—Hydroxysifenil) Ethane

1, 1, 1 1 Tri-Follow 2, 2, 2-Tris (4-Methoxyfenyl) ethane 7.3 1 g (18.18 mmo 1 ) Was dissolved in 40 ml of dichloromethane, and the solution was dissolved in _78 with 1 M-3 boron bromide / dichloromethane solution 40 m 1 (40 mm 0. 1) was dropped. After 15 minutes, the temperature was brought to room temperature, and stirring was continued for 18 hours. 100 ml of water was added to the reaction solution, and ether extraction was performed twice with 200 ml of ether. After drying over anhydrous magnesium sulfate, the solvent is distilled off under reduced pressure and recrystallized (ethyl acetate: hexan) to give 1,1,1—trifurel. Ori 2, 2, 2 — Tris (4-Hydroxy 5.4 g (yield: 83%) of nil) ethane were obtained as colorless needle crystals.

Ή-NMR in Acetone-d ₆ : δ (ppm) = 6.79 (6H, d, J = 8.96Hz), 6

96 (6H, d, J = 8.96Hz), 8.43 (3H, s)

^{1 9 F-NMR in A cetone} - d 6 (CFC 1 3 reference): δ (ppm) = - 59.00 (s) IR (KBr): cm- '= 3374, 1612, 1514, 1223, 1185, 1150

MS m / z = 360 (m +), 291

(2) Synthesis of 1,1,1—tri-fluoro 2,2,2—tris (32-tro-4—hydroxy phenyl) ethane

According to the same method as (1) in Example 1, 1, 1, 1-trifluoro-mouth 1, 2, 2, 2-tris (4-hydroxyphenyl) Do not perform nitronation on the pattern, and use 1,1,1 and 1-trifluoro —2,2,2—tris (3—nitro1-4—hydroxif) Enil) (yield: 77%) was obtained as yellow crystals.

Ή-NMR in CDC1 ₃ : δ (ppm) = 7.24 (3H, d, J = 9.00Hz)

7.46 (3H, dd ₎ J = 9.00,2.56Hz) 7.82 (3H, d, J = 2.56Hz), 10.67 (3H, s)

^{_{19 FN R in CDC 1 3 (}} CFC 1 3 reference): δ (ppm) = - 60.52 (s) IR (KBr): cnT '= 3253, 1632, 1582, 1536, 1485, 1310, 1186, 1084

MS m / z = 495 (m +), 426

(3) 1, 1, 1 — Tri-reflex mouth 1, 2, 2, 2 — Tris (3 — Amino 4-hydroxyphenyl)

In accordance with the same method as in (2) of the first embodiment, 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 .

NMR-NMR in THF- d ₈ : δ (ppm) = 4.08 (6H, s), 6.21 to 6.26 (3H, m), 6.42 to 6.46 (6H, m), 8.00 (3H, s)

^{_{19 FN R in THF - d 8}} (CFC 1 3 reference): δ (ppm) = - 58.24 (s)

IR (KBr): cnT '= 3319, 2968, 1618, 1522, 1284, 1228, 1134

MS m / z = 405 (m +), 336

Production Example 1 (Synthesis of Fluorine Elastomer Containing CN Group) Autoclave made of stainless steel with 3 liters of internal volume without ignition source 1 liter of pure water and emulsifier

C F 3 C F 3

C ₃ F ₇ OCFCF, OCFCOONH ₄

Charge 10 g of hydrogen phosphate, sodium sodium phosphate and 0.09 g of pH 1.2 as a pH adjuster, and sufficiently replace the inside of the system with nitrogen gas. After degassing, while stirring at 600 rpm, the temperature was raised to 50 X :, and tetrafluoroethylene (TFE) and perfluoro (medium) were added. The mixed gas (chilled vinyl ether) (PMVE) (PMFE = PM £ = 2575 mol ratio) is charged so that the internal pressure becomes 0.78 MPa a-G. It is. Then, a reaction was started by injecting 10 ml of an aqueous solution of ammonium persulfate (APS) having a concentration of 527 mg Zml with a nitrogen pressure.

When the internal pressure drops to 0.69 MPa a * G due to the progress of polymerization, 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.

After 19 hours from the start of the polymerization reaction, when the total charged amount of TFE and PMVE reached 300 g, the autoclave was cooled. The reaction monomer was discharged to obtain 1330 g of an aqueous dispersion having a solid concentration of 21.2% by weight.

Of this aqueous dispersion, 1196 g was diluted with 3.588 g of water, and stirred while stirring in 2800 g of a 3.5 wt% hydrochloric acid aqueous solution. It was added in a small amount. After stirring for 5 minutes after the addition, the coagulated product was separated by filtration, and the obtained polymer was further poured into 2 kg of HCFC-141b and stirred for 5 minutes. I separated again. After that, washing with HCFC-141b and another operation were repeated four more times, followed by drying in vacuum at 60 X: for 72 hours. As a result, 40 g of a polymer (a nitrile group-containing elastomer) was obtained.

As a result of ¹⁹ F-NMR analysis, the monomer composition of this polymer was found to be TFE / PMVEZCNVE = 56.6 / 42.3 / 1.1 mol%.

Example 3

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).

The crosslinkability, normal physical properties, and compression set of this test sample were measured by the following methods. Table 4 shows the results.

(Vulcanizable)

For a crosslinkable fluorine-containing elastomer composition, 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.) Ru and asked Me,

(Normal physical properties)

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).

(Compression set)

In accordance with JISK6301, each of the test samples (O-ring (P-24)) at 200, 230 and 275, respectively. Measure the permanent compression set (CS) after 72 hours, 168 hours and 360 hours.

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.

In the same manner as in Example 3, except that the composition was changed to 100 / 1.92 / 20, a fluorine-containing elastomer composition capable of being bridged was prepared. Various physical properties were measured in the same manner as described above. The results are shown in Table 4.

Example 5

In Example 3, the compound synthesized in Example 2 was used as a crosslinking agent.

1 Trifluoride port — 2, 2, 2 — Tris (3 — Amino 4-hydro □ Kishifueniriren) 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.

Four

Industrial availability

By using the novel compound of the present invention as a cross-linking agent, an elastomer cross-linked product having excellent heat resistance can be obtained.

Claims

Scope of demand

1. Equation (Ia)

(Wherein, X ¹ , X ² and X ³ are the same or different and all are hydroxyl, mercapto or amino; Υ is an amino; R is A trivalent hydrocarbon group having 1 to 12 carbon atoms, which may be substituted with a fluorine atom or may contain an etheric oxygen atom; however, X ¹ , X ² and X ³ and Υ are one in the meta position and the other in the para position) or the formula (I b):

(Wherein XX ² , X ³ and Y are the same as defined above) or a salt thereof.

2. In the formula (la), X ¹ , X ² , and X ³ are all hydroxyl groups, and R is a carbon atom of 1 to 3 which may be substituted with a fluorine atom. The triphenyl compound or a salt thereof according to claim 1, which is a monovalent hydrocarbon group.

Four

3. came out and had off ί formula ^{(I a), X 1,} X 2 your good beauty X ³ stomach shift also請式Ea is Ri Oh with a hydroxyl group, is long

- C - R ^1, R ¹ was or main Chi le groups Application Benefits full O b menu Chi le group) Ru claimed range Application Benefits full et two Le of compounds or their salts of claim 1 wherein the .

A cross-linking agent comprising the trilinyl compound or a salt thereof according to any one of the above-mentioned items 1 to 3.

5. Scope of Claim A crosslinkable elastomer composition comprising the crosslinking agent according to paragraph 4 and an elastomer having a crosslinkable group.

6. The elastomer composition according to claim 5, wherein the elastomer is a fluorine-containing elastomer.

7. A bridge obtained by cross-linking the crosslinkable elastomer composition according to claim 5 or 6.