JPWO2018177940A5

JPWO2018177940A5 -

Info

Publication number: JPWO2018177940A5
Application number: JP2019553320A
Authority: JP
Publication date: 2022-07-14

Description

試剤（Ａ）が、上で記載されたような、モノマー（ＣＳ－Ｎ）のニトリル基の活性化に向けて触媒活性を保有する化合物の中から選択される場合、試剤（Ａ）は、試剤（Ａ_ｃａｔ）と称され、とりわけ、
－芳香族アンモニア発生化合物、すなわち、加熱すると（例えば、硬化／後硬化中に遭遇するものなどの条件において）アンモニアを発生することができる化合物；
－とりわけアリル－プロパルギル－、トリフェニル－、及びアレニル－スズ硬化剤などの、有機スズ化合物（テトラアルキル又はテトラアリールスズ化合物が好ましい）
からなる群から選択することができる。 If the reagent (A) is selected from among the compounds that have catalytic activity towards activation of the nitrile group of the monomer (CS-N) as described above, the reagent (A) is the reagent. It is called (A _cat ), and above all,
-Aromatic ammonia-generating compounds, ie compounds that can generate ammonia when heated (eg, under conditions such as those encountered during curing / post-curing);
-In particular, organotin compounds such as allyl-propargyl-, triphenyl-, and allenyl-tin hardeners (preferably tetraalkyl or tetraaryltin compounds).
You can choose from the group consisting of.

Claims

A method for manufacturing a cured model [article (P)], wherein the method is
(I)
-Derived from at least one curing site-containing monomer [monomer (CS-N)] having at least a nitrile group of 0.1 to 10.0 mol% with respect to the total mole of the repeating unit of the fluoroelastomer (A). At least one fluoroelastomer containing repeating units [fluoroelastomer (A)];
-At least one curing agent [Reagent (A)];
-The following formula (B-1):

(In the formula, Ar ^B1 is an aromatic group that may contain a fluorine atom; n is zero or an integer of 1 to 4).
At least one bromine-containing marker according to [Marker (B)]
And the step of providing at least one fluoroelastomer composition [composition (C)] comprising;
(Ii) A method comprising a step of molding the composition (C) under heating at a temperature of at most 200 ° C. for at least 30 minutes.

The reagent (A) is selected from compounds having catalytic activity for activation of the nitrile group of the monomer (CS-N), and the reagent (A) is referred to as a reagent (A _cat ).
-Ammonia- generating organic compounds, ie compounds that can generate ammonia when heated;
-In particular, organotin compounds such as allyl-propargyl-, triphenyl-, and allenyl-tin hardeners (preferably tetraalkyl or tetraaryltin compounds).
The method according to claim 1, which is selected from the group consisting of.

The reagent (A _cat )
(A _cat -1): Equation (U):

[In the formula, E is O or S, preferably E is O, and each of the _Rus equal to or different from each other is independent of the group consisting of hydrogen and C ₁ to C ₆ hydrocarbon groups . And be selected]
(Thio) urea compounds and salts thereof;
(A _cat -2): Cycloaddition product of ammonia or primary amine and aldecht;
(A _cat -3): Equation (C):

(In the formula, E is oxygen or sulfur; R _b is a C ₁ to C ₃₆ hydrocarbon group and R c is an H or C ₁ to C ₆ alkyl group).
(Chio) carbamate;
(A _cat -4): In particular, (j) ammonium carboxylate ; (jj) ammonium sulfonate ; (jjj) ammonium phosphate , phosphonate or sulfonate; (jv) consisting of ammonium salts of sulfuric acid, carbonic acid, nitrate and phosphoric acid. The method according to claim 2, wherein the method is selected from the group consisting of ammonium salts of organic and inorganic acids selected from the group.

A reagent (A _cat ) is selected from the group consisting of the following:
(A _cat -1): A (thio) urea compound as detailed above is preferably of formula (U-2) :.

(In the formula, E'is O or S)
Selected from the group consisting of (A _cat -1-A) (thio) urea;
(A _cat -2) : A cycloaddition product of ammonia or a primary amine and an aldehyde is preferable, and the formula (T): (A _cat -2-A):

[In the formula, each of _Ra equal to or different from each other is selected from the group consisting of hydrogen and C ₁ to C ₆ hydrocarbon groups (particularly C ₁ to C ₆ alkyl groups)].
Cyclic aldehyde adduct trimer;
Equation (A _cat -2-B):

Hexamethylenetetramine
Selected from the group consisting of;
(A _cat -3): The (thio) carbamate as detailed above is preferably the formula (C-1) :.

(In the formula, _R'd is _a C1 to _C36 hydrocarbon group, preferably an optionally substituted benzyl group).
Selected from the group consisting of (A _cat -3-A) carbamate,
The method according to claim 3.

The reagent (A) is selected from compounds having a plurality of groups reactive toward activation of the nitrile group of the monomer (CS-N), and the reagent (A) is a reagent (A _func ). )
(A _func -1) Equation:

[During the ceremony:
-A is a bond, -SO _2- , -O-, -C (O)-, or (fluoro) alkyl of 1 to 10 carbon atoms , preferably perfluoroalkyl of 1 to 10 carbon atoms. , More preferably -C (CF ₃ ) _2- ;
-Equal or different for each appearance, each of E is oxygen or sulfur, preferably oxygen, and where the amino and -EH groups are compatible at the ortho, meta or para position with respect to group A. Is)
Bis-amino (thio) phenol compound [aminophenol (AP)];
(A _func -2) Equation:

-A'is a bond, -SO _2- , -O-, -C (O)-, a (fluoro) alkyl of 1 to 10 carbon atoms , preferably a perfluoroalkyl of 1 to 10 carbon atoms. , More preferably -C (CF ₃ ) _2- ;
_-Each of the _RNs _equal to or different from each other is a hydrogen atom or a C1 to C12 hydrocarbon group, preferably an aryl group;
-Amino groups are compatible at the ortho-, meta-position or para-position with respect to group A')
Aromatic tetraamine compound [amine (TA)];
-(A _func -3) formula:

(In the formula, R _a1 is -OH or -H, R _a2 is H or NH ₂ , and E is a C ₁ to C ₁₈ divalent group optionally containing a fluorine atom.)
Bis-amidexim / amidine / amidorazone compound;
-(A _func -4) equation:

(In the formula, E ^b is a C ₁ to C ₁₈ divalent group optionally containing a fluorine atom, and R ^b is an optional fluorinated C ₁ to C ₁₂ group).
The method according to claim 1, which is selected from the group consisting of the bis-imidoylamidine compound of the above.

The reagent (A _func ) has the formula:

The method according to claim 5 , wherein the product is 4,4'-[2,2,2-trifluoro-1- (trifluoromethyl) -ethylidene] bis (2-aminophenol).

Marker (B) is the formula:

4,4'-Dibromooctafluorobiphenyl and formula:

The method according to any one of claims 1 to 6, which is selected from the group consisting of 4-bromobiphenyl.

The composition (C) is
-For the fluoroelastomer (A), generally in the range of 0.10 to 10 phr, preferably in an amount of 0.25 to 6 phr, the marker (B); and / or-0 for the fluoroelastomer (A). The reagent (A) is in the range of 10 to 10 phr, preferably in an amount of 0.25 to 5 phr.
The method according to any one of claims 1 to 7, comprising the method according to any one of claims 1 to 7.

The type (CS-N) of the cured site-containing monomer is
(CS-N1) X ^CN is F or CF ₃ , m is 0, 1, 2, 3 or 4; n is an integer of 1-12, equation CF ₂ = CF- (OCF ₂ CFX ^CN ). ) _M -O- (CF ₂ ) _n -CN perfluorovinyl ether containing a nitrile group;
(CS-N2) X ^CN is F or CF ₃ , m'is 0, 1, 2, 3 or 4, formula CF ₂ = CF- (OCF ₂ CFX ^CN ) _m' -O-CF _2- The method according to any one of claims 1 to 8, which is selected from the group consisting of perfluorovinyl ether containing a nitrile group of CF (CF ₃ ) -CN.

The first step of molding comprises at least one of injection molding, compression molding, extrusion molding, coating, screen printing, pouring, and calendar processing of the composition (C) into a desired molded product. The method described in any one of the above.

Molding is at a temperature of at most 195 ° C., more preferably at a temperature of 190 ° C., even more preferably at a temperature of 185 ° C. and / or at least 160 ° C., preferably at least 165 ° C., more preferably at least 170 ° C. The method according to any one of claims 1 to 10, which is carried out under heating at a temperature.

Claim 1 that the heating is continued for a duration of at least 45 minutes, more preferably at least 1 hour and / or less than 16 hours, preferably less than 14 hours, preferably less than 12 hours. The method according to any one of 11 to 11 .

The cured model consists of a group of sealing articles such as O (corner) -rings, packings, gaskets, diaphragms, shaft seals, valve shaft seals, piston rings, crank shaft seals, cam shaft seals, and oil seals. The method of any one of claims 1-12, which is a flexible hose or other item of choice, such as piping and tubing materials, in particular conduits for delivery of hydrocarbon fluids and fuels.

A method for detecting wear / damage in a cured molded product (P) obtained from the composition (C) using the method according to any one of claims 1 to 13, wherein the method is a method thereof. A method comprising monitoring the release of a bromine-containing compound.