JP2010018571A - Fluorinated polytriazine compound and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a fluorinated polytriazine containing two or more triazine rings in one molecule, useful for synthesizing a fluorine-containing elastomer having high heat resistance. <P>SOLUTION: In the method for producing a fluorinated polytriazine compound, the fluorinated polytriazine compound essentially comprising two or more triazine rings and a fluorine atom is obtained by reacting a compound (A) containing n groups represented by the formula: -COX with a compound represented by formula (b) (wherein n is an integer of ≥1; m is an integer of ≥0; (n+m) is an integer of ≥2; R<SP>2</SP>is a fluorinated monofunctional hydrocarbon group or a fluorinated monofunctional hydrocarbon group having an etherial oxygen atom; and R<SP>3</SP>is a fluorinated bifunctional hydrocarbon group or a fluorinated bifunctional hydrocarbon group having an etherial oxygen atom). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a novel fluorinated polytriazine compound essentially comprising two or more triazine rings and a fluorine atom, and a method for producing the same.

Fluorine-containing elastomers have excellent heat resistance, chemical resistance, plasma resistance, etc., and molding materials such as sealing materials, O-rings, gaskets, packings, hoses, etc. in various fields such as electricity, chemistry, and machinery. As widely used. In particular, materials used in the semiconductor manufacturing field are required to further improve heat resistance. In order to improve heat resistance, it is effective to crosslink between polymer molecules. However, triallyl isocyanurate (trade name: TAIC), which is currently used in the mainstream, has a heat resistance at the crosslinking site. Was insufficient.
In order to improve the heat resistance of the cross-linked site, studies have been made to make the entire polymer including the cross-linked site a perfluoro structure. In particular, examples have been proposed in which perfluorovinyl ether having a cyano group is copolymerized and the cyano group is triazine-crosslinked by a heating reaction in the presence of a catalyst (Non-patent Document 1 and Patent Document 1).
However, it is difficult for all nitrile groups to react to form a triazine ring, and there is a problem that an intermediate before forming the triazine ring may remain. Further, the content of perfluorovinyl ether having a cyano group in the polymer is as low as about 1 mol%, and even when all nitrile groups form a triazine ring, the density of the triazine ring in the polymer is extremely low, It was difficult to improve heat resistance.
In order to introduce triazine crosslinking at a high density in a polymer, examples in which a triazine compound having two or more polymerizable unsaturated groups is once synthesized and copolymerized are reported (Patent Documents 2 and 3). ). As the triazine compound having two perfluorovinyl ether groups, a compound represented by the following formula (x) is shown, and as the triazine compound having three perfluorovinyl ether groups, a compound represented by the following formula (y): It is shown.

However, a perfluorotriazine compound in which a plurality of triazine rings are linked in a molecule and a crosslinking site can be introduced into a polymer at a higher density is not known.
US Pat. No. 4,281,092 JP-A-6-340640 Japanese Patent No. 3463318 Journal of Fluorine Chemistry, 2003, Vol. 122, p. 113-119

  The present invention provides a method for producing a fluorinated polytriazine compound, which is a compound useful for the synthesis of a fluorine-containing elastomer having high heat resistance, and which contains two or more triazine rings and a fluorine atom, and a novel fluorinated polytriazine. provide.

The present invention is as follows.
1) Fluorination in which two or more triazine rings and a fluorine atom are essential by reacting a compound (A) having n groups represented by the formula —COX with a compound represented by the following formula (b) A method for producing a fluorinated polytriazine compound, comprising obtaining a polytriazine compound.

(Where X represents a halogen atom, n represents an integer of 1 or more, m represents an integer of 0 or more, (n + m) represents an integer of 2 or more, and R ² represents a fluorinated monovalent hydrocarbon group, or It indicates fluorinated monovalent hydrocarbon group having an etheric oxygen atom, R ³ represents a fluorinated divalent hydrocarbon group having a fluorinated divalent hydrocarbon group or ether oxygen atoms.)
2) The production method according to 1) above, wherein the compound (A) is a compound represented by the following formula (a).

(However, n and X have the same meaning as described above, and R ¹ represents a fluorinated n-valent hydrocarbon group or a fluorinated n-valent hydrocarbon group having an etheric oxygen atom.)
3) The fluorination according to 2) above, wherein a compound represented by the formula (a) wherein n is an integer of 1 or more is reacted with a compound represented by the formula (b) wherein m is an integer of 1 or more. A method for producing a polytriazine compound.
4) Production of a compound represented by the following formula (c-1), which comprises reacting a compound represented by the following formula (a-1) with a compound represented by the following formula (b-1): Method.

(Wherein R ¹¹ represents a fluorinated monovalent hydrocarbon group or a fluorinated monovalent hydrocarbon group having an etheric oxygen atom, X ¹ represents a halogen atom, —OR ^a (where R ^a is a hydrogen atom, Or represents an alkyl group.), —SCOR ²⁰ , —OC (O) R ²⁰ , —OSO ₂ R ²⁰ , —NR ⁴⁰ (COR ²⁰ ), or —NH (SO ₂ R ³⁰ ) (provided that R ²⁰ , R ³⁰ and R ⁴⁰ each independently represents a monovalent hydrocarbon group or a halogenated monovalent hydrocarbon group, and R ⁴⁰ may be a hydrogen atom), and R ² represents fluorine. Represents a fluorinated monovalent hydrocarbon group or a fluorinated monovalent hydrocarbon group having an etheric oxygen atom, and R ³¹ represents a fluorinated divalent hydrocarbon group or a fluorinated divalent hydrocarbon group having an etheric oxygen atom. .)
5) The fluorination according to 2) above, wherein a compound represented by the formula (a) in which n is an integer of 2 or more and a compound represented by the formula (b) in which m is an integer of 0 or more are reacted. A method for producing a polytriazine compound.
6) A compound represented by the following formula (c-2), wherein the compound represented by the following formula (a-2) is reacted with a compound represented by the following formula (b-2): Production method.

(Wherein R ¹² represents a fluorinated divalent hydrocarbon group or a fluorinated divalent hydrocarbon group having an etheric oxygen atom, X represents a halogen atom, R ² represents a fluorinated monovalent hydrocarbon group, or A fluorinated monovalent hydrocarbon group having an etheric oxygen atom is shown.)
7) The total amount of —COX groups in the compound represented by the formula (a) is 0.8 to 1 with respect to the total amount of the structure represented by the following formula (B ′) in the compound represented by the formula (b). The manufacturing method in any one of said 1) -6) which reacts in the quantity used as 2 times mole.

  8) A compound represented by the following formula (c-1).

(Wherein R ¹¹ represents a fluorinated monovalent hydrocarbon group or a fluorinated monovalent hydrocarbon group having an etheric oxygen atom, and R ² represents a fluorinated group having a fluorinated monovalent hydrocarbon group or an etheric oxygen atom. A monovalent hydrocarbon group, R ³¹ represents a fluorinated divalent hydrocarbon group or a fluorinated divalent hydrocarbon group having an etheric oxygen atom.)
9) R ² and R ¹¹ may be the same or different and each independently represent a fluorinated monovalent hydrocarbon group having 1 to 10 carbon atoms or an etheric oxygen atom having 1 to 10 carbon atoms. A fluorinated monovalent hydrocarbon group, two or more groups selected from R ² and R ¹¹ represent a group containing a polymerizable unsaturated group, R ³¹ represents a fluoroalkylene group having 1 to 10 carbon atoms, Or the compound as described in said 8) which shows the fluoroalkylene group which has a C1-C10 ether oxygen atom.
10) A compound represented by the following formula (c-1-1).

(However, R ³¹ represents a perfluoroalkylene group having 1 to 10 carbon atoms or a perfluoroalkylene group having an etheric oxygen atom having 1 to 10 carbon atoms.)

In the present invention, the compound represented by formula (a) is referred to as compound (a). The same applies to compounds represented by other formulas.
In the notation of the compound of the present invention, the double bond in the partial structure represented by the formula (B ′) is conjugated, and the structure represented by the following formula (B′-1) and the following formula (B′-2) ) Means that both structures of the structure represented by are present in an equilibrium state. In this specification, without distinguishing both structures, it describes as a structure represented by Formula (B'-1), or a structure represented by Formula (B'-2). Similarly, the position of the double bond is not specified in the notation of the triazine ring in the present specification.

  The hydrocarbon group in the present invention refers to a group consisting of a carbon atom and a hydrogen atom, and may be either a saturated group or an unsaturated group. Further, the hydrocarbon group may be either an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and an aliphatic hydrocarbon group is preferable. The structure of the aliphatic hydrocarbon group may be linear, branched, cyclic, or partially having a cyclic structure. The carbon number of the hydrocarbon group is preferably 1 to 10 and particularly preferably 3 to 10 unless otherwise specified. Examples of the case where the aliphatic hydrocarbon group is a monovalent group include an alkyl group, an alkenyl group, and an alkynyl group. Examples of the case where the aliphatic hydrocarbon group is a divalent group include an alkylene group, an alkenylene group, and an alkynylene group.

  In the present invention, the hydrocarbon group having an etheric oxygen atom is a group in which an etheric oxygen atom is inserted between carbon atoms of the hydrocarbon group, or an etheric oxygen atom is bonded to the end of the hydrocarbon group. Group. The number of etheric oxygen atoms is not particularly limited.

  In the present invention, the fluorinated n-valent hydrocarbon group means a group in which one or more hydrogen atoms in the n-valent hydrocarbon group are substituted with fluorine atoms. A group in which all of the hydrogen atoms in the n-valent hydrocarbon group are substituted with fluorine atoms (also referred to as perfluorination) is referred to as a perfluoro n-valent hydrocarbon group. A group in which an alkyl group is perfluorinated is referred to as a perfluoroalkyl group, and a group in which a divalent hydrocarbon group is perfluorinated is referred to as a perfluorodivalent hydrocarbon group. The same applies to a group in which an n-valent hydrocarbon group having an etheric oxygen atom is fluorinated, like a fluorinated n-valent hydrocarbon group having an etheric oxygen atom.

In the present invention, the halogen atom means a fluorine atom, a chlorine atom, an iodine atom, or a bromine atom. Unless otherwise specified, a fluorine atom or a chlorine atom is preferable, and a fluorine atom is particularly preferable.
The halogenated monovalent hydrocarbon group refers to a group in which one or more hydrogen atoms of the monovalent hydrocarbon group are substituted with halogen atoms. When the halogen atom is a fluorine atom, it becomes a fluorinated monovalent hydrocarbon group.

The present invention essentially comprises two or more triazine rings and a fluorine atom by reacting a compound (A) having n groups represented by the formula -COX with a compound represented by the following formula (b). A method for producing a fluorinated polytriazine compound is provided.
Examples of the compound (A) having n groups represented by the formula -COX include a polymer containing a monomer unit of a polymerizable compound having a group represented by the formula -COX in addition to the compound (a) described later.
As the polymerizable compound having a group represented by the formula _{-COX, CF 2 = CFO (CF} 2) t COF (t is an integer of from 1 to 5), and the like.

As the compound (A), a compound (a) represented by the formula R ¹ (COX) _n is preferable. N in the compound (a) refers to the number of groups bonded to ^{R 1} (-COX), n is an integer of 1 or more, preferably an integer of from 1 to 10, particularly preferably an integer of 1 to 4, 1 Or 2 is particularly preferred.
When n is 1, R ¹ is preferably a group selected from a fluoroalkyl group, a fluoroalkenyl group and a fluoroalkynyl group, or the selected group having an etheric oxygen atom. When it is desired to obtain a polymerizable compound as a product, R ¹ is particularly preferably a fluoroalkenyl group or a fluoroalkenyl group having an etheric oxygen atom, particularly preferably those groups having 1 to 20 carbon atoms, 1 to 10 of these groups are preferred.
When R ¹ is a group having a polymerizable group or polymerizable group as a partial _{^{structure, CF 2 = CFR f -,}} CF 2 = CFOR f -, or ^{_{CF 2 = CFCF 2 OR f -}} ( provided that, ^{R f} Represents a perfluoro divalent hydrocarbon group). The perfluoro divalent hydrocarbon group is a group in which all of the hydrogen atoms bonded to the carbon atoms in the divalent hydrocarbon group are substituted with fluorine atoms, or an etheric oxygen atom is inserted between the carbon-carbon bonds of the group. Group. R ^f is particularly preferably a C 1-10 perfluoroalkylene group or a C 1-10 perfluoroalkylene group having an etheric oxygen atom. When n is 2, R ¹ is preferably a fluoroalkylene group, a fluoroalkenylene group, a fluoroalkylene group containing an etheric oxygen atom, or a fluoroalkenylene group containing an etheric oxygen atom. n is the number of carbon atoms in ^{R 1} is 2, preferably from 1 to 20, 1 to 8 is particularly preferred.

  Regarding X in the -COX part of the compound (A), when X is a halogen atom, a chlorine atom or a fluorine atom is preferable, and a fluorine atom is particularly preferable. Specific examples of the compound (a) will be described later.

In the compound (b), m represents the number of structural units in (), and m represents an integer of 0 or more. When m is 0, it indicates that there is no structural unit in (), and when m is 1 or more, it means that one or more structural units in () are connected. m is preferably 0 to 7, particularly preferably 0 to 3, and particularly preferably 0 or 1.
The aspect in which R ³ is a fluorinated divalent hydrocarbon group or a fluorinated divalent hydrocarbon group having an etheric oxygen atom is the same as the aspect of R ¹ in the case where n is 2. R ³ is preferably a C 1-10 fluoroalkylene group or a C 1-10 fluoroalkylene group containing an etheric oxygen atom, a C 1-10 perfluoroalkylene group, or an etheric oxygen. A C1-C10 perfluoroalkylene group containing an atom is particularly preferred.
A preferred embodiment in the case where R ² is a fluorinated monovalent hydrocarbon group or a fluorinated monovalent hydrocarbon group having an etheric oxygen atom is the same as the embodiment described in R ¹ . Furthermore, ^{R 2 _{may, CF 2 = CFR f -,}} CF 2 = CFOR f -, or _{CF 2} = CFCF 2 OR ^f -, and the like are preferable ^{(R f} are as defined above.).
Examples of the compound (b) will be described later.

In the present invention, the compound (A) having n groups represented by the formula —COX and the compound (b) are reacted to produce a fluorinated polytriazine compound. The fluorinated polytriazine compound refers to a compound having two or more triazine rings in the structure, and one or more groups bonded to the triazine ring are groups in which a fluorine atom is essential. In the fluorinated polytriazine compound obtained by the production method of the present invention, R ² is essential as a group bonded to the triazine ring, and R ² is a fluorine-containing group. In addition, when there is another group bonded to the triazine ring, the other group may or may not contain a fluorine atom, but from the viewpoint of the usefulness of the product. Is a fluorine-containing group, and therefore all the groups bonded to the triazine ring are preferably fluorine-containing groups, particularly preferably perfluorinated groups.
The reaction of the present invention will be described first in a method for producing a ditriazine compound having two triazine rings in the structure and having one or more fluorine atoms.

  The following method 1 and method 2 are mentioned as a manufacturing method of a ditriazine compound. Method 1 is a method in which the following compound (a-1) where n is 1 and the following compound (b-1) where m is 1 are reacted to obtain the following compound (c-1).

^{R 11} in compound (a-1), perfluoroalkyl group having 1 to 10 carbon atoms or perfluoroalkyl group having an etheric oxygen atom having 1 to 10 carbon _{^{atoms,, CF 2 = CFR f -}} , CF 2 = CFOR f -, or ^{_{CF 2 = CFCF 2 oR f -}} (. However, ^{R f} is as defined above) ^{is, R 31} is the same group as ^{R 11,} perfluoroalkylene group having 1 to 10 carbon atoms or carbon, A perfluoroalkylene group having an etheric oxygen atom of 1 to 10 is particularly preferable. Specific examples of R ¹¹ are shown in specific examples of the compounds described below.
Examples of when X ¹ in the compound (a-1) is a halogen atom is the same as X.
As an embodiment when X ¹ is other than a halogen atom, when X ¹ is —OR ^a (wherein R ^a represents a hydrogen atom or an alkyl group), a methoxy group, an ethoxy group, or a propoxy group When the group is -SCOR ²⁰ , -SCOCF ₃ is preferable, -OC (O) R ²⁰ is preferable -OC (O) CF ₂ CF ₃ and -OSO ₂ R ²⁰ preferably -OSO ₂ CF ₃ in ^preferably _{-N (CF 3) COCF 2 CF} 3 in the case of -NR 40 ^{(COR 20),} in the case of -NH _(SO 2 ^{R 3)} is -NH (SO ₂ CF ₂ CF ₃ ) is preferred. X ¹ is preferably a halogen atom or —OC (O) R ²⁰ .
Example in which X ^{1 of} compound (a-1) is a halogen atom: CF ₃ COF, CF ₃ COCl, CF ₃ COBr, CF ₃ COI, CF ₃ CF ₂ COF, CF ₃ CF ₂ CF ₂ COF, (CF ₃ ) ₂ CCFOF, Cy ^F CCFOF (Cy ^F represents a perfluorocyclohexyl group), CF ₃ CF ₂ OCF ₂ COF, CF ₃ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ COF, CF ₂ = CFOCF ₂ CF _{2 CF 2 COF, CF 2 = CFOCF} 2 CF (CF 3) OCF 2 CF 2 CF 2 COF, CF 2 = CFCF 2 COF, CF 2 = CFCF 2 OCF 2 CF 2 COF.
Example ^{X 1} of the compound (a-1) is a _{^{-OR a: CF 3 COOCH 3,}} CF 3 COOCF 3, CF 3 CF 2 COOCF compounds such ₂ CF _3.
An example in which X ^{1 of the} compound (a-1) is —SCOR ²⁰ : CF ₃ C (O) SCOCF ₃ .
Example in which X ^{1 of} compound (a-1) is —OC (O) R ²⁰ : (CF ₃ CO) ₂ O, (CF ₃ CF ₂ CO) ₂ O, CF ₃ C (O) OC (O) CF ₂ CF _3.
Example in which X ^{1 of} compound (a-1) is —OSO ₂ R ²⁰ : Compound such as CF ₃ C (O) OSO ₂ CF ₃ X ^{1 in} compound (a-1) is —NR ⁴⁰ (COR ²⁰ ) some _{examples: CF 3 C (O) N} (CF 3) COCF 2 CF 3, (CF 3 CO) 2 NCH 3, (CF 3 CO) 2 NH.
An example in which X ^{1 of the} compound (a-1) is —NH (SO ₂ R ³ ): CF ₃ C (O) NHSO ₂ CF ₂ CF ₃ .

^Furthermore, at least one of groups ^{R 11} and ^{R _{2, CF 2 = CFR f -,}} CF 2 = CFOR f -, and _{CF 2} = CFCF 2 OR ^f - polymerizable unsaturated group selected from (wherein, ^{R f} And the other group is a polymerizable unsaturated, a perfluoroalkyl group having a prime number of 1 to 10, or a perfluoroalkyl group having an etheric oxygen atom having 1 to 10 carbon atoms. More preferably it is.
R ³¹ is preferably a perfluoro divalent hydrocarbon group or a perfluoro divalent hydrocarbon group containing an etheric oxygen atom, and a perfluoro divalent saturated hydrocarbon group or a perfluoro divalent saturated hydrocarbon group containing an etheric oxygen atom. Particularly preferred. The number of carbon atoms in R ³¹ is preferably 1 to 20, 1 to 8 is particularly preferred.

  Specific examples of the compound (b-1) include the following compounds.

化合物（ｃ−１）としては、下記化合物（ｃ−１−１）が有用性の観点から好ましい（ただし、Ｒ^３１は、炭素数１〜１０のペルフルオロアルキレン基、または炭素数１〜１０のエーテル性酸素原子を有するペルフルロアルキレン基を示し、−ＣＦ_２Ｏ（ＣＦ_２）_２ＯＣＦ_２−が好ましい。）。化合物（ｃ−１−１）は文献未記載の新規化合物である。

As the compound (c-1), the following compound (c-1-1) is preferable from the viewpoint of usefulness (wherein R ³¹ is a C 1-10 perfluoroalkylene group or a C 1-10 ether). A perfluoroalkylene group having a reactive oxygen atom, and —CF ₂ O (CF ₂ ) ₂ OCF ₂ — is preferred). Compound (c-1-1) is a novel compound not described in any literature.

  Another method for producing a ditriazine compound (Method 2) is a method in which a compound (a-2) in which n is 2 and a compound (b-2) in which m is 0 are reacted (provided that the formula The symbol inside shows the same meaning as above.)

R ¹² of the compound (a-2) is preferably the same group as R ³¹ . X is a halogen atom, and is the same as in formula (A). A preferred embodiment of R ² in compound (c-2) is the same as R ¹¹ and R ² in compound (c-1).

When a ditriazine compound is produced by Method 1, a compound (c-1) in which two groups (R ² and R ¹¹ ) bonded to the ditriazine ring may be the same or different can be produced. When the ditriazine compound (c-2) is produced by Method 2, the two groups (R ² ) bonded to the ditriazine ring are the same group.
The production method of the present invention can be used not only as a method for producing a ditriazine compound but also as a method for producing a compound having three or more triazine rings. A product having three or more triazine ring compounds can be produced.
For example, when the compound (a) where n is 1 and the compound (b) where m is 2 are reacted, the following compound (c-30) is produced.

When the compound (a) where n is 3 and the compound (b) where m is 0 are reacted, the following compound (c-31) is produced. R ¹ represents a fluorinated trivalent hydrocarbon group or a trivalent hydrocarbon group having an etheric oxygen atom.

Although it is difficult to represent the compound (c) in the case where n is an integer of 2 or more and m is an integer of 1 or more in chemical formula, the compound (c) that can be produced is schematically represented and described. To do.
For example, when the compound (a-2) in which n is an integer of 2 and the compound (b-1) in which m is an integer of 1 are reacted, a mixture of the following compounds having two or more triazine rings Can be generated. However, the portion indicated by a triangular symbol in the following formula represents a triazine-triyl group, and COX bonded to R ¹ represents an unreacted group (—COX).

As another example, when a compound (a) where n is 3 and a compound (b) where m is 1 are reacted, a polytriazine compound represented by the following formula can be produced. However, the portion indicated by a triangular symbol in the following formula indicates a triazine-triyl group, and the wavy bond extending from R ³ indicates that the structure of the group bonded to the bond is not limited; A group surrounded by [] or a group described as a group bonded to R ³ in the structure represented by the following formula is bonded. COX bonded to R ¹ represents an unreacted group (—COX).

In the production method of the present invention, the number of triazine rings present in the reaction product is 2 or more. For example, a compound (A) having n —COX groups (where n represents an integer of 1 or more) and a compound (b) having two or more structures represented by the formula (B ′) (that is, M + 1 is an integer of 2 or more.) In the reaction with the compound (A), the COX group in the compound (A) and the structure represented by the formula (B ′) in the compound (B) all react between the same molecules. When triazine rings are generated, the number of triazine rings in the product can be n when n> m + 1 and m + 1 when n <m + 1. For example, when the compound (a) where n is 10 and the compound (b) where m + 1 is 5, the product can be a compound having 10 triazine rings. In fact, since all may not react, the maximum number of triazine rings in the product is considered to be 10.
In addition, the COX group in the compound (A) and the structure represented by the formula (B ′) in the compound (B) may react between different molecules. In that case, the number of triazine rings in the product is infinite. However, the theoretical maximum number of triazine rings is a large number among the number of COX groups in the compound (A) present in the reaction system and the number of structures represented by the formula (B ′).

In the case where n is an integer of 2 or more and m + 1 is an integer of 2 or more, the structure of the compound (b) is not limited to one type, and can usually be two or more types. Therefore, the structure of the compound (c) includes the number of COX groups in the compound (A) (the structure of R ¹ when the compound (a) is used) and the number of the structures (B ′) of the compound (b). , R ³ , and the ratio of compound (a) to compound (b) and the reaction conditions can be changed.

  Examples of the case where the compound (c) is a fluorinated ditriazine having two triazine rings include the following.

Examples of the case where the compound (c) is a fluorinated tritriazine having three triazine rings include the following.
In the case where the compound (a) is CF [(CF ₂ CF ₂ O) _a1 CF ₂ COF] ₃ , the compound (b) is m and R ² is CF ₂ ═CFO (CF ₂ ) ₃ — Production example of compound (c-30).

Compound (a) is CF [(CF ₂ CF ₂ O) _a1 CF ₂ COF] ₃ , Compound (b) is an integer of 1 or more, R ² is CF ₂ ═CFO (CF ₂ ) ₃ —, R Production Example of Compound (c-31) when ³ is —CF ₂ O (CF ₂ ) ₂ OCF ₂ —.

Examples of the case where the compound (c) is a triazine ring is three or more, the compound (a) is obtained by polymerizing _{CF 2 = CFO (CF 2)} 3 COF - (CF 2 -CF (O (CF 2) 3 COF))-a polymer having two or more units, and the following repeating unit is essential when the compound (b) is m = 0 and R ² is CF ₂ ═CFO (CF ₂ ) ₃ — Production example of compound (c-32a).

Compound (a) is obtained by polymerizing _{CF 2 = CFO (CF 2)} 3 COF - (CF 2 -CF (O (CF 2) 3 COF)) - is a polymer having two or more units, the compound (b) Of m is 0 and R ² is CF ₃ (CF ₂ ) _b4 —, a production example of the following compound (c-32b), which essentially comprises the following repeating unit.

Compound (a) is _{CF 2 = CFO (CF 2)} 3 COF, compound (b) is m is an integer of 1 or more, ^{R 2} is _{F (CF 2) b1 -,} R 3 is - _{(CF 2) b2} -The manufacture example of the following compound (c-33a) which is-.

Compound (a) is CF ₃ (CF ₂ ) _b4 COF, Compound (b) is an integer greater than or equal to 1, R ² is F (CF ₂ ) _b1- , R ³ _is- (CF ₂ ) _b2- A production example of a certain compound (c-33b) below.

  The reaction conditions for the compound (A) and the compound (b) can be appropriately changed depending on the structure of the compound, but in general, the reaction temperature is preferably -60 ° C to 100 ° C, preferably 0 ° C to 40 ° C. Is more preferable. The reaction may be performed without a solvent, but when the raw material is a solid, it may be performed in the presence of a solvent, and the selected solvent is not particularly limited as long as it does not react with the raw material compound, Benzene, toluene, diethyl ether, tetrahydrofuran, 1,4-dioxane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tertiary butyl methyl ether, chloroform, dichloromethane, 1,2-dichloroethane, chlorofluorocarbon, hydrochlorofluorocarbon, carbon tetrachloride, Acetone, acetonitrile, ethyl acetate, and the like are preferred. The shorter the reaction time, the higher the productivity, but it is usually preferable to carry out in about 10 minutes to 48 hours.

  The reaction of the present invention proceeds only with a compound serving as a reaction substrate, but other components that promote the reaction may be present in the reaction system as necessary. Examples of other components include alkali metal salts such as NaF and KF and basic organic compounds such as triethylamine, which are used for the purpose of removing the generated acid. Examples of the catalyst include acidic compounds such as hydrogen chloride and sulfuric acid, and Lewis acid compounds such as aluminum trichloride and titanium tetrachloride.

The amount ratio of the compound (A) to the compound (b) is the total amount of the structure A of the compound (b) with respect to the total amount of COX groups (n × k1) mol when the compound (A) is used in k1 mol [(m + 1) × k2] mole [ie (n × k1) / [(m + 1) × k2] is preferably 0.8 to 1.2 times mole, particularly preferably 0.9 to 1.1 times mole, It is especially preferable to set it as 95-1.05 times mole.
In the case of using the compound (a-1) as the compound (A) and the compound (b-1) as the compound (b), the amount ratio is preferably such that k1 / k2 is 0.8 to 1.2 times mol. 0.9 to 1.1 times mole is particularly preferred, and 0.95 to 1.05 times mole is particularly preferred.

  The following groups are mentioned as an example of the group in the manufacturing method of this invention demonstrated above, and the compound of this invention.

Among fluorinated monovalent hydrocarbon groups, examples of saturated groups: F (CF ₂ ) _p — (p is preferably 2 to 8), F (CF (C _x F _{2x + 1} )) _p — (x is 1 to 2, p is 1 are preferred), and _{F (C (C x F 2x} + 1) (C y F 2y + 1)) p -. (x and y are groups independently 1-2 selected from preferred) or, A group formed by linking these groups. A perfluoro (1-adamantyl) group or a group in which one or more fluorine atoms in the group are substituted with a C 1-6 perfluoroalkyl group or perfluoroalkoxy group.

Among fluorinated monovalent hydrocarbon group, examples of the polymerizable ^{_{group: CF 2 = CFR f -,}} CF 2 = CFOR f -, CF 2 = CFCF 2 OR f -, BrCF 2 R f -, ICF 2 R f -(Wherein R ^f has the same meaning as described above).
Examples of perfluoroalkylene groups (where x, y and p are integers of 1 or more, and the same shall apply hereinafter): — (CF ₂ ) _p — (p is preferably 2 to 8), — (CF (C _{x F 2x + 1)) p} - (x is 1 to 2, p is 1 are preferred), and _{-. (C (C x F} 2x + 1) (C y F 2y + 1)) p - (x and y are each independently Or a group formed by linking these groups.

  A group selected from a perfluorocyclopentylene group represented by the following formula and a perfluorocyclohexylene group represented by the following formula, or a perfluoroalkyl group having 1 to 5 carbon atoms as a fluorine atom in the selected group: A group substituted with.

Examples of perfluoroalkylene groups containing an etheric oxygen atom (where q represents an integer of 0 or more): — (CF ₂ ) _p O (CF ₂ ) _q — (p is 1 to 7, p is 1 to 3) _{preferably), - (CF 2) p} (OCF 2 CF 2) q OCF 2 - are (p 1, p is preferably _{1~2), - (CF 2)} p O (CF (C x F 2x + 1) CF _{2 O) q CF (C x} F 2x + 1) - (p is 1, x is 1 to 2, q is preferably 0 to 1 _{is), - (CF 2) p} O (CF 2) q O (CF (C x _{F 2x + 1) CF 2 O} ) r CF (C x F 2x + 1) - (p is 1, x is 1 to 2, q is preferably 0 to 1 _{is), - CF (C x F} 2x + 1) (OCF 2 CF (C _{x F 2x + 1)) r} O (CF 2) p O (CF (C x F 2x + 1) CF 2 O) q CF ( _{x F 2x + 1) - (} p is 1 to 7, x is 1 to 2, q is preferably 0 to 1 is), or _{-CF (C x F 2x + 1} ) (OCF 2 CF (C x F 2x + 1)) s O ( _{CF 2) p O (CF 2} ) q O (CF (C x F 2x + 1) CF 2 O) r CF (C x F 2x + 1) - (s, p is 1 to 7, q is 0 to 1, r is 0 -1 and x are preferably 1-2).

  A group represented by the following formula, or a group in which one or more fluorine atoms bonded to the ring of the group are substituted with a C 1-5 perfluoroalkyl group or a C 1-5 perfluoroalkoxy group.

The compound (A) used in the production method of the present invention can be produced using a known production method.
On the other hand, for obtaining the compound (b), for example, the compound (b) in which m is 1 can be synthesized according to the following scheme. The meaning of the symbol of the substituent is the same as described above. Other compounds of the present invention can also be synthesized according to the following.

  Examples of the compound (h) include commercially available compounds or derivatives derived from perfluoroesters synthesized according to the method described in International Publication No. 00/56694 pamphlet and the like.

  As a method for converting the compound (h) through the compound (g) into the compound (f), for example, Journal of Organic Chemistry, 1969, Vol. 34, p. The method of 1841-1844 is mentioned.

As a method for synthesizing the compound (e) by the reaction of the compound (f) with ammonia, for example, Journal of Fluorine Chemistry, 1980, Vol. 15, p. And the method described in 327-331.
Compound (d) can be synthesized by the method described in JP-A-9-3027.
Compound (b-1) can be synthesized by reacting compound (e) with compound (d).
The reaction between the compound (e) and the compound (d) is preferably performed by adding the compound (e) to the compound (d). It is added the compound (e) Compound (d), since the above than the ratio is always the compound of Compound (d) (e), when R ² of the compound (d) is a polymerizable unsaturated group, the polymerizable It becomes difficult for the unsaturated group and the amidine group of the compound (e) to react with each other, and a decrease in yield is suppressed.
From this viewpoint, the amount of the compound (d) is preferably 2 to 5 equivalents, more preferably 2 to 2.2 equivalents with respect to the compound (e). The compound (d) used in excess can be recovered by distillation or the like after completion of the reaction.

The reaction of the compound (e) and the compound (d) may be performed without a solvent, or may be performed using a solvent inert to the compound (d) and the compound (e). Since the compound (e) is often a solid, it is preferable that the compound (e) is dissolved in a solvent and dropped from the viewpoint of the reaction process.
Examples of the solvent include ether, tert-butyl methyl ether, dioxane, tetrahydrofuran, monoglyme, diglyme, triglyme, tetraglyme, diethylene glycol diethyl ether, chloroform, dichloromethane, carbon tetrachloride, C ₃ F ₅ Cl ₂ H and the like. It is done.
The temperature in the reaction between the compound (e) and the compound (d) is usually −60 ° C. to room temperature, preferably 0 ° C. to 20 ° C. You may heat.

The fluorinated polytriazine compound of the present invention can be produced by reacting compound (b) with compound (A). Examples of the compound (A) include commercially available compounds or derivatives derived from perfluoroester compounds synthesized according to the method described in International Publication No. 00/56694 pamphlet and the like.
Moreover, as a manufacturing method of a compound (b) in case m is 2 or more, the method of changing the said starting material (h) into a corresponding structure and manufacturing similarly is mentioned. Examples of the production of the compound (b) in which m is 3 or more include an example in which the following reaction is performed using the compound (d ′) in which the cyano group of the compound (d) is 2 or more. That is, the compound (e) is reacted with the compound (d ′) and then reacted with the compound (d) represented by the formula R ² —CN to obtain the compound (b-2). .

  The compound produced by the production method of the present invention is a novel compound having a plurality of triazine rings. In particular, a compound having a polymerizable unsaturated group in the triazine ring compound can introduce triazine ring crosslinking points at high density into the elastomer by a crosslinking reaction, and can improve heat resistance. In addition, since it is a perfluoro product, a higher heat-resistant fluorine-containing elastomer can be obtained.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.
GC for gas chromatography analysis, MS for mass spectral analysis, IR for infrared absorption spectroscopy, R-113 for CCl ₂ FCClF ₂ , CF ₂ ClCF ₂ CHClF and CHCl ₂ CF ₂ CF ₃ The mixed solution is described as R-225, and tetrahydrofuran as THF.

[Example 1]
Compound (c-1-1) was synthesized according to the following synthesis scheme.

Synthesis of compound (j-1-1):
A round bottom flask equipped with a thermometer and a dropping funnel was charged with 50 g of triethylene glycol, 84 g of sodium fluoride powder, and 100 g of R-225 and stirred vigorously while cooling with ice. Into the flask, 245 g of C ₃ F ₇ OCF (CF ₃ ) COF was slowly added dropwise so that the internal temperature did not exceed 10 ° C. After dropwise addition of the entire amount of C ₃ F ₇ OCF (CF ₃ ) COF, stirring was continued for 1.5 hours at room temperature. The disappearance of triethylene glycol was confirmed by GC, and the reaction was stopped. Sodium fluoride powder was removed from the resulting solution by pressure filtration, and concentrated with an evaporator to remove R-225 and excess C ₃ F ₇ OCF (CF ₃ ) COF to obtain a concentrated solution. The concentrate was distilled under reduced pressure to obtain a fraction (251 g) having a GC purity of 99%. As a result of analyzing the fraction, production of the compound (j-1-1) was confirmed.

Synthesis of compound (i-1-1):
An autoclave (made of nickel, internal volume 500 mL) was prepared, and a cooler maintained at 20 ° C., a NaF pellet packed bed, and a cooler maintained at −10 ° C. were installed in series at the gas outlet of the autoclave. Moreover, the liquid return line which returns the liquid aggregated from the cooler hold | maintained at -10 degreeC to an autoclave was installed.
The autoclave was charged with 312 g of R-113 and stirred while maintaining at 20 ° C. After blowing nitrogen gas into the autoclave at 20 ° C. for 1 hour, fluorine gas diluted to 20% by volume with nitrogen gas (hereinafter referred to as 20% fluorine gas) was added at 20 ° C. and a flow rate of 17.0 L / h for 1 hour. Infused. Next, a solution of 124 g of compound (j-1-1) dissolved in 497 g of R-113 was injected into the autoclave over 24 hours while blowing 20% fluorine gas at the same flow rate.

Next, the internal pressure of the autoclave was increased to 0.15 MPa (gauge pressure) while blowing 20% fluorine gas at the same flow rate. 9 mL of a benzene solution containing 0.01 g / mL benzene in R-113 was injected into the autoclave while heating from 25 ° C. to 40 ° C., and the benzene solution inlet of the autoclave was closed. The total amount of benzene injected was 0.09 g.
Further, stirring was continued for 1 hour while blowing 20% fluorine gas at the same flow rate. Subsequently, the pressure in the autoclave was set to atmospheric pressure, and nitrogen gas was blown in for 1 hour. As a result of analyzing the contents of the autoclave by NMR, it was confirmed that the compound (i-1-1) (NMR yield 98%) was produced.

Synthesis of compound (h-1-1):
A round bottom flask equipped with a thermometer and a dropping funnel was charged with 150 g of compound (i-1-1), 39 g of sodium fluoride powder, and 150 g of R-225, and stirred vigorously while the flask was immersed in an ice bath. . 22 g of methanol was dropped into the flask so that the internal temperature did not exceed 10 ° C. After dropwise addition of the entire amount of methanol, the ice bath was removed and the mixture was further stirred at room temperature for 2 hours. The disappearance of compound (i-1-1) was confirmed by GC. From the resulting solution, sodium fluoride powder was removed by pressure filtration, and concentrated with an evaporator to remove R-225 and excess methanol, thereby obtaining a concentrated solution. The concentrated liquid was subjected to simple distillation, and C ₃ F ₇ OCF (CF ₃ ) COOCH ₃ produced as a by-product was separated to obtain 54 g of a colorless liquid. As a result of analyzing by NMR and GC-MS, the production | generation of the compound (h-1-1) (GC purity 98%, yield 98%) was confirmed.

Synthesis of compound (g-1-1):
A round bottom flask equipped with a thermometer, a dropping funnel, a cold trap, and a gas introduction tube was charged with 210 g of R-225, and ammonia gas was blown into the flask while the flask was immersed in an ice bath. After stirring for a while, 54 g of the compound (h-1-1) was slowly added dropwise to the flask so that the internal temperature did not exceed 10 ° C. After the total amount of compound (h-1-1) was added dropwise, stirring was continued for another hour, and when the disappearance of compound (h-1-1) was confirmed by GC, the reaction was terminated. Nitrogen gas was blown into the flask for 2 hours to remove excess ammonia, and then the solvent was removed, followed by vacuum drying with a vacuum pump to obtain 49 g of white powder. As a result of analysis by NMR and IR, it was confirmed that the compound (g-1-1) was quantitatively produced.

Synthesis of compound (f-1-1):
In a round bottom flask, 49 g of the compound (g-1-1) and 65 g of P ₂ O ₅ powder were added, and vigorously shaken and mixed well. In order from the top of the flask, a distiller, a trap tube, and a vacuum pump were attached, and the flask was placed in a mantle heater. While reducing the pressure in the flask to 66 kPa with a vacuum pump, the flask was heated to 270 ° C. and heated for 30 minutes. When the pressure was further reduced to 50 kPa, liquid distillation started. The liquid was distilled while reducing the pressure to 13 to 50 kPa to obtain 24 g of a colorless liquid. Also, 7 g of colorless liquid was recovered from the trap tube. As a result of analysis by GC and GC-MS, it was confirmed that the compound (f-1-1) was produced with GC purity of 97% and 95%, respectively.

Showing the ¹⁹ F-NMR spectral data of the compound (f-1-1).
¹⁹ F-NMR (282.6 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ), δ (ppm): −58.4 (4F), −88.4 (4F).

Synthesis of compound (e-1-1):
10 g of tert-butyl methyl ether was put into a round bottom flask equipped with a thermometer, a dropping funnel, a cold trap, and a gas introduction tube, and ammonia gas was blown into the flask while cooling to −50 ° C. After stirring for a while, a solution obtained by diluting 15 g of the compound (f-1-1) with 17 g of tert-butyl methyl ether was slowly dropped into the flask. The inside of the flask gradually became cloudy, and precipitation of solid matter was confirmed. After the whole amount of the compound (f-1-1) was added dropwise, 10 g of tert-butyl methyl ether was added, the supply of ammonia gas was stopped, and stirring was continued for 6 hours while gradually warming to room temperature. When the disappearance of compound (f-1-1) was confirmed by GC, the reaction was stopped, and the solvent was removed to obtain 16 g of a white solid. As a result of analysis by NMR and IR, it was confirmed that the compound (e-1-1) was produced almost quantitatively. In IR, the absorption attributed to the amidine group was observed at 1668 cm ⁻¹ .

The ¹⁹ F-NMR spectral data of a compound (e-1-1) are shown.
¹⁹ F-NMR (282.6 MHz, solvent: THF, external standard: acetone-d6 / CFCl ₃ ), δ (ppm): −78.6 (4F), −91.3 (4F).

Synthesis of compound (b-1-1):
A round bottom flask equipped with a thermometer and a dropping funnel was charged with 25.5 g of compound (d-1) and 50 g of THF, and the flask was immersed in an ice bath and stirred. A solution obtained by diluting 13.5 g of) with 20 g of THF was slowly added dropwise. After the whole amount of the compound (e-1-1) was added dropwise, stirring was further continued at room temperature for 1 hour. The progress of the reaction was confirmed by GC and NMR, and the solvent was removed to obtain a colorless viscous solution of compound (b-1-1).

Synthesis of compound (c-1-1):
To the solution containing the compound (b-1-1), 100 g of R-225 and 11 g of sodium fluoride powder were added, and the flask was immersed in an ice bath and stirred. -2) 27.3g was dripped slowly. The ice bath was removed, stirring was continued overnight, and the reaction was terminated when the progress of the reaction was confirmed by NMR and IR. From the resulting solution, sodium fluoride is removed by pressure filtration, and concentrated by an evaporator to remove R-225 and excess compound (a-1-2), and a colorless liquid compound (c-1-1) ) Purification by a silica gel column (developing solvent: hexane / ethyl acetate = 95/5) yielded 19.2 g (NMR purity 96%, yield 27%) of a colorless liquid compound (c-1-1). In IR, absorption by triazine ring to 1558cm ^-1, absorption by unsaturated bonds in 1839cm ^-1, it was observed respectively.

The ¹⁹ F-NMR spectral data of a compound (c-1-1) are shown.
¹⁹ F-NMR (282.6 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ), δ (ppm): −75.4 (4F), −85.4 (8F), −88.6 (4F), − 115.2 (4F), -117.3 (8F), -122.9 (4F), -126.1 (8F), -136.2 (4F).

  According to the present invention, a fluorinated polytriazine compound having a triazine ring of two or more triazines can be efficiently produced. The present invention also provides a novel compound having a polymerizable unsaturated group as the polytriazine compound. The novel compound is useful as a crosslinking agent for fluorine-containing elastomers having high heat resistance.

Claims (10)

A fluorinated polytriazine having two or more triazine rings and a fluorine atom as essential by reacting the compound (A) having n groups represented by the formula -COX with the compound represented by the following formula (b) A method for producing a fluorinated polytriazine compound, which comprises obtaining a compound.

(Wherein, X represents a halogen atom, n represents an integer of 1 or more, m represents an integer of 0 or more, (n + m) is an integer of 2 or more, R ² is fluorinated monovalent hydrocarbon radical or an ether, A fluorinated monovalent hydrocarbon group having an ionic oxygen atom, and R ³ represents a fluorinated divalent hydrocarbon group or a fluorinated divalent hydrocarbon group having an etheric oxygen atom.) The production method according to claim 1, wherein the compound (A) is a compound represented by the following formula (a).

(However, n and X have the same meaning as described above, and R ¹ represents a fluorinated n-valent hydrocarbon group or a fluorinated n-valent hydrocarbon group having an etheric oxygen atom.)   The fluorinated polytriazine according to claim 2, wherein a compound represented by the formula (a) wherein n is an integer of 1 or more is reacted with a compound represented by the formula (b) wherein m is an integer of 1 or more. Compound production method. A method for producing a compound represented by the following formula (c-1), comprising reacting a compound represented by the following formula (a-1) with a compound represented by the following formula (b-1).

(Wherein R ¹¹ represents a fluorinated monovalent hydrocarbon group or a fluorinated monovalent hydrocarbon group having an etheric oxygen atom, X ¹ represents a halogen atom, —OR ^a (where R ^a is a hydrogen atom, Or represents an alkyl group.), —SCOR ²⁰ , —OC (O) R ²⁰ , —OSO ₂ R ²⁰ , —NR ⁴⁰ (COR ²⁰ ), or —NH (SO ₂ R ³⁰ ) (provided that R ²⁰ , R ³⁰ and R ⁴⁰ each independently represents a monovalent hydrocarbon group or a halogenated monovalent hydrocarbon group, and R ⁴⁰ may be a hydrogen atom), and R ² represents fluorine. Represents a fluorinated monovalent hydrocarbon group or a fluorinated monovalent hydrocarbon group having an etheric oxygen atom, and R ³¹ represents a fluorinated divalent hydrocarbon group or a fluorinated divalent hydrocarbon group having an etheric oxygen atom. .)   The fluorinated polytriazine according to claim 2, wherein a compound represented by the formula (a) wherein n is an integer of 2 or more is reacted with a compound represented by the formula (b) wherein m is an integer of 0 or more. Compound production method. A method for producing a compound represented by the following formula (c-2), comprising reacting a compound represented by the following formula (a-2) with a compound represented by the following formula (b-2): .

(Wherein R ¹² represents a fluorinated divalent hydrocarbon group or a fluorinated divalent hydrocarbon group having an etheric oxygen atom, X represents a halogen atom, R ² represents a fluorinated monovalent hydrocarbon group, or A fluorinated monovalent hydrocarbon group having an etheric oxygen atom is shown.) The total amount of —COX groups in the compound represented by formula (a) is 0.8 to 1.2 with respect to the total amount of the structure represented by the following formula (B ′) in the compound represented by formula (b). The production method according to any one of claims 1 to 6, wherein the reaction is carried out in an amount of a double mole.

A compound represented by the following formula (c-1).

(Wherein R ¹¹ represents a fluorinated monovalent hydrocarbon group or a fluorinated monovalent hydrocarbon group having an etheric oxygen atom, and R ² represents a fluorinated group having a fluorinated monovalent hydrocarbon group or an etheric oxygen atom. A monovalent hydrocarbon group, R ³¹ represents a fluorinated divalent hydrocarbon group or a fluorinated divalent hydrocarbon group having an etheric oxygen atom.) R ² and R ¹¹ may be the same or different and are each independently a fluorine having a fluorinated monovalent hydrocarbon group having 1 to 10 carbon atoms or an etheric oxygen atom having 1 to 10 carbon atoms. 2 or more groups selected from R ² and R ¹¹ represent a group containing a polymerizable unsaturated group, R ³¹ represents a fluoroalkylene group having 1 to 10 carbon atoms, or carbon The compound according to claim 8, which represents a fluoroalkylene group having an etheric oxygen atom of 1 to 10. A compound represented by the following formula (c-1-1).

(However, R ³¹ represents a perfluoroalkylene group having 1 to 10 carbon atoms or a perfluoroalkylene group having an etheric oxygen atom having 1 to 10 carbon atoms.)