JP5776554B2 - Fluorene compound, synthetic polymer stabilizer containing the fluorene compound, and composition containing the fluorene compound - Google Patents

Description

  The present invention is a novel fluorene compound capable of imparting high processing stability, heat resistance, and long life to an organic material such as a polymer without using a phosphorus-based anti-aging agent that is a secondary anti-aging agent, The present invention relates to a stabilizer containing a fluorene compound, and an organic material and a composition containing the fluorene compound.

Organic materials such as polymers are susceptible to degradation due to heat, oxygen, shearing forces during processing, or the like as they are. Therefore, in order to improve the processing stability and heat resistance and extend the life, it is common to add various anti-aging agents.
As anti-aging agents, phenol-based anti-aging agents, amine-based anti-aging agents and the like are known as primary anti-aging agents (see Non-Patent Document 1, etc.).
Representative examples of the primary antiaging agent include the following compounds as commercially available products.

Moreover, a high synergistic effect is acquired by using together with these anti-aging agents, and the secondary anti-aging agent which provides high process stability, heat resistance, and long lifetime to organic materials, such as a polymer, is also used widely.
Typical examples of the secondary anti-aging agent include the phosphorus-based anti-aging agents shown below as commercially available products.

  However, many of these phosphorus-based anti-aging agents are highly toxic. When a thermoplastic resin containing a phosphorus-based anti-aging agent is used in a food storage container or the like, the anti-aging agent is transferred to food in a small amount. There is a risk of ingestion. Therefore, when using phosphorus-based anti-aging agents, the usable chemical structure and addition amount are finely regulated by industry organizations such as the Sanitation Council for Polyolefins, etc., and it was necessary to pay close attention when using them. .

In addition, due to the recent increase in safety awareness, only the above-mentioned approved materials are being used even in applications where the risk of direct ingestion by humans is low, such as automobile bumpers. There are many constraints on.
Furthermore, due to the recent increase in awareness of nature protection and environmental protection, the release of phosphorus-based antioxidants into the environment is becoming a problem.

On the other hand, in terms of characteristics, phosphorus-based anti-aging agents have poor compatibility with thermoplastic resins such as polyolefins, and there are many cases where bleeding occurs, and there is a problem that the use and addition amount are limited. .
Because of these many problems, there is a strong demand for stabilizers having an antiaging effect equal to or higher than that without using secondary antiaging agents such as phosphorus-based antiaging agents.

"Encyclopedia of polymer materials", published by Nikkan Kogyo Shimbun, July 30, 1999

  The present invention has been made in view of the above-described prior art, and its purpose is to provide high processing stability and heat resistance to organic materials such as polymers without using secondary anti-aging agents such as phosphorus-based anti-aging agents. It is to provide a novel fluorene compound capable of imparting properties and long life, a stabilizer containing the fluorene compound, and an organic material and a composition containing the fluorene compound.

  As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that high processing stability and organic materials such as polymers can be obtained without using a phosphorus-based anti-aging agent that is a secondary anti-aging agent. The inventors have found a stabilizer having a novel chemical structure capable of imparting heat resistance and long life, and have completed the present invention.

Thus, according to the present invention, the following fluorene compounds (1) to (4), a stabilizer (5) and compositions (6) to (9) are provided.
(1) A fluorene compound represented by the following formula (I).

{In the above formula (I), Y ₁ represents a chemical single bond, —O—, —S—, —C (═O) —O—, —C (═O) —NR ¹ —, —C ( ═O) —, —S (═O) —, —O—C (═O) —, —NR ¹ —C (═O) —, —SO ₂ —, —O—C (═O) —O—. or, - _{(CH 2)} represents an n -O-. Here, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n represents any integer of 1 to 6.
X _{1 to} X ₈ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or an optionally substituted group having 2 to 12 carbon atoms. An alkenyl group, a cyano group, a nitro group, —OR ² , —O—C (═O) —R ² , —C (═O) —OR ² , —O—C (═O) —OR ² , —N ( R ³ ) R ⁴ , —NR ³ —C (═O) —R ² , —C (═O) —N (R ³ ) R ⁴ , or —O—C (═O) —N (R ³ ) R ⁴ is represented. Here, R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent,
a is 0 or 1; However, when b or d below is 0, a is also 0.
A is the following formula (A1)

[In the formula (A1), _{G 1} represents a (c + 1) -valent organic group having 1 to 20 carbon atoms that may have a substituent,
b is 0 or 1,
c is an integer of 1 to 3.
Y ₂ represents a chemical single bond, —O—, —S—, —O—C (═O) —, —C (═O) —O—, —O—C (═O) —O—, —NR ⁵ —C (═O) —, —C (═O) —NR ⁵ —, —O—C (═O) —NR ⁵ —, —NR ⁵ —C (═O) —O—, —NR ^{5 -C (= O) -NR 6} -, - O-NR 5 -, or represents a ^-NR 5 -O-. Here, R ⁵ and R ⁶ each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent.
X _{9 to} X ₁₂ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or an optionally substituted substituent having 2 to 12 carbon atoms. Alkenyl group, cyano group, nitro group, —OR ⁷ , —O—C (═O) —R ⁷ , —C (═O) —OR ⁷ , —O—C (═O) —OR ⁷ , —N ( ^{R 8) R 9, -NR 8} -C (= O) -R 7, -C (= O) -N (R 8) R 9, or, -O-C (= O) -N (R 8) R ⁹ is represented. Here, R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent. Or the formula (A2)

[In the formula (A2), _{G 2} represents a divalent organic group having 1 to 20 carbon atoms,
Y ₃ represents the same meaning as Y ₂ ,
d is 0 or 1.
X _{13 to} X ₂₁ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or an optionally substituted substituent having 2 to 12 carbon atoms. An alkenyl group, a cyano group, a nitro group, —CF ₃ , —OR ¹⁰ , —O—C (═O) —R ¹⁰ , —C (═O) —OR ¹⁰ , —O—C (═O) —OR ^10. , —N (R ¹¹ ) R ¹² , —NR ¹¹ —C (═O) —R ¹⁰ , —C (═O) —N (R ¹¹ ) R ¹² , or —O—C (═O) —N (R ¹¹ ) R ¹² is represented.
Here, R < ¹⁰ >, R < ¹¹ > and R < ¹² > represent the C1-C20 organic group which may have a hydrogen atom or a substituent. Represents a group represented by the formula: }

(2) Y ₁ , Y ₂ and Y ₃ are each independently a chemical single bond, —C (═O) —O—, —C (═O) —NR ¹³ — (where R ¹³ is Represents a hydrogen atom or an optionally substituted organic group having 1 to 20 carbon atoms.), Or —C (═O) —, wherein X _{1 to} X ₂₁ are each independently hydrogen. The fluorene compound according to (1), which is an alkyl group having 1 to 12 carbon atoms which may have an atom or a substituent.

(3) The formula (A) is converted to the formula (A11).

(In the above formula (A11), X _{9 to} X ₁₂ represent the same meaning as described above), or a group represented by formula (A21)

(In the formula _{(A21), X} 13 ~X ₂₁ are as defined above.) Represented by the group represented by (1) or a fluorene compound according to (2).
(4) In (1) or (2), Y ₁ is —C (═O) —O— or —C (═O) —NR ¹ — (R ¹ represents the same meaning as described above). The fluorene compound described.
(5) The stabilizer containing the fluorene compound in any one of said (1)-(4).
(6) A composition containing the component (a): an organic material and the component (b): the fluorene compound according to any one of (1) to (4).
(7) The composition according to (6), wherein the component (a) is a synthetic organic material.
(8) The composition according to (6) or (7), wherein the component (a) is a synthetic rubber.
(9) The composition according to (6) or (7), wherein the component (a) is a polyolefin.
(10) The composition according to any one of (6) to (9), further containing other additives in addition to the component (a) and the component (b).

  According to the present invention, a novel fluorene capable of imparting high processing stability, heat resistance and long life to an organic material such as a polymer without using a phosphorus-based anti-aging agent which is a secondary anti-aging agent. A compound, a stabilizer containing the fluorene compound, and an organic material and a composition containing the fluorene compound are provided.

  Hereinafter, the present invention will be described in detail by dividing into 1) a fluorene compound, 2) a stabilizer containing a fluorene compound, and 3) a composition.

1) Fluorene Compound The fluorene compound of the present invention is a compound represented by the following formula (I).

In formula (I), Y ₁ represents a chemical single bond, —O—, —S—, —C (═O) —O—, —C (═O) —NR ¹ —, —C (═O ) —, —S (═O) —, —O—C (═O) —, —NR ¹ —C (═O) —, —SO ₂ —, —O—C (═O) —O—, or , - _{(CH 2)} represents an n -O-.

Here, R ¹ is a hydrogen atom; or methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, n -An alkyl group having 1 to 6 carbon atoms such as a hexyl group.
n represents an integer of 1 to 6.

  Further, a is 0 or 1, but when b or d described later is 0, a is also 0.

X _{1 to} X ₈ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or an optionally substituted group having 2 to 12 carbon atoms. An alkenyl group, a cyano group, a nitro group, —OR ² , —O—C (═O) —R ² , —C (═O) —OR ² , —O—C (═O) —OR ² , —N ( R ³ ) R ⁴ , —NR ³ —C (═O) —R ² , —C (═O) —N (R ³ ) R ⁴ , or —O—C (═O) —N (R ³ ) R ⁴ is represented.

Examples of the halogen atom for X _{1 to} X ₈ include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the alkyl group having 1 to 12 carbon atoms which may have a substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, t -Butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like can be mentioned.

Examples of the substituent for the alkyl group having 1 to 12 carbon atoms include halogen atoms such as fluorine atom, chlorine atom and bromine atom; methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, t-butoxy An alkoxy group such as a group; a nitro group; a cyano group and the like.
Examples of the alkenyl group having 2 to 12 carbon atoms include a vinyl group, a propenyl group, and an isopropenyl group.

R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent.

Examples of the organic group having 1 to 20 carbon atoms of R ² , R ³ and R ⁴ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n- An alkyl group having 1 to 20 carbon atoms such as a pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group;
A cycloalkyl group having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group;
Aryl groups having 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, and an anthranyl group;
1 to C carbon atoms such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, n-pentyloxy group, n-hexyloxy group, etc. 20 alkoxy groups; and the like.

  Examples of the substituent of the organic group include a halogen atom, an alkoxy group, a nitro group, and a cyano group when the organic group is an alkyl group, and a halogen atom when the organic group is a cycloalkyl group and an aryl group. Atoms, alkoxy groups, nitro groups, cyano groups, alkyl groups; and the like, and in the case of alkoxy groups, halogen atoms, nitro groups, cyano groups, and the like.

Among these, X _{1 to} X ₈ are each independently preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms which may have a substituent, from the viewpoint of availability.

  A represents a group represented by the following formula (A1) or (A2).

In formula (A1), G ₁ represents a (b + 1) -valent organic group having 1 to 20 carbon atoms which may have a substituent. Here, b is 0 or 1, and c is any integer of 1 to 3.

That is, when b is 1 and c is 1, G ₁ is an optionally substituted divalent organic group having 1 to 20 carbon atoms, and when b is 1 and c is 2, G ₁ is an optionally substituted trivalent organic group having 1 to 20 carbon atoms, and when b is 1 and c is 3, G ₁ is an optionally substituted carbon. It is a tetravalent organic group of number 1-20.
Specific examples of the divalent organic group having 1 to 20 carbon atoms of G ₁ include the following, but are not limited thereto.

(In the above formula, p represents an integer of 1 to 20, and q represents an integer of 1 to 6.)
Specific examples of the trivalent organic group having 1 to 20 carbon atoms of G ₁ include the following, but are not limited thereto.

(In the above formula, r represents an integer of 0 to 19.)
Specific examples of the tetravalent organic group having 1 to 20 carbon atoms of G ₁ include, but are not limited to, the following.

(In the above formula, s represents an integer of 0 to 14.)
Examples of the substituent for the organic group having 1 to 20 carbon atoms of G ₁ include halogen atoms such as fluorine atom and chlorine atom; alkyl groups such as methyl group and ethyl group; alkoxy groups such as methoxy group and ethoxy group; Can be mentioned.

Y ₂ represents a chemical single bond, —O—, —S—, —O—C (═O) —, —C (═O) —O—, —O—C (═O) —O—, —NR ⁵ —C (═O) —, —C (═O) —NR ⁵ —, —O—C (═O) —NR ⁵ —, —NR ⁵ —C (═O) —O—, —NR ^{5 -C (= O) -NR 6} -, - O-NR 5 -, or represents a ^-NR 5 -O-.

Here, R ⁵ and R ⁶ are each independently the same as the hydrogen atom or the organic group having 1 to 20 carbon atoms which may have a substituent of R ² , R ³ and R ⁴ . The C1-C20 organic group which may have a substituent is represented.

X _{9 to} X ₁₂ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or an optionally substituted substituent having 2 to 12 carbon atoms. Alkenyl group, cyano group, nitro group, —OR ⁷ , —O—C (═O) —R ⁷ , —C (═O) —OR ⁷ , —O—C (═O) —OR ⁷ , —N ( ^{R 8) R 9, -NR 8} -C (= O) -R 7, -C (= O) -N (R 8) R 9, or, -O-C (= O) -N (R 8) R ⁹ is represented.
Here, R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent.

Specific examples of X _{9 to} X ₁₂ include a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, and an optionally substituted alkenyl group having 2 to 12 carbon atoms. Specific examples of X _{1 to} X ₈ , a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, and an optionally substituted alkenyl group having 2 to 12 carbon atoms Are similar to those listed.

Moreover, as a specific example of the C1-C20 organic group which may have a substituent of R < ⁷ >, R < ⁸ > and R < ⁹ >, it has a substituent of said R < ² >, R < ³ > and R < ⁴ >. Specific examples of the organic group having 1 to 20 carbon atoms may be the same as those listed.
Preferable specific examples of the group represented by the formula (A) include a group represented by the following formula (A11).

(In the formula (A11), X _{9 to} X ₁₂ represent the same meaning as described above.)

Wherein (A2), _{G 2} represents a divalent organic group having 1 to 20 carbon atoms.
Specific examples of the divalent organic group having 1 to 20 carbon atoms of G ₂ include the same ones listed as specific examples of the divalent organic group having 1 to 20 carbon atoms of G ₁ .

Y ₃ represents the same meaning as Y _2, and d is 0 or 1.
X _{13 to} X ₂₁ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or an optionally substituted substituent having 2 to 12 carbon atoms. An alkenyl group, a cyano group, a nitro group, —CF ₃ , —OR ¹⁰ , —O—C (═O) —R ¹⁰ , —C (═O) —OR ¹⁰ , —O—C (═O) —OR ^10. , —N (R ¹¹ ) R ¹² , —NR ¹¹ —C (═O) —R ¹⁰ , —C (═O) —N (R ¹¹ ) R ¹² , or —O—C (═O) —N (R ¹¹ ) R ¹² is represented.
Here, R < ¹⁰ >, R < ¹¹ > and R < ¹² > represent the C1-C20 organic group which may have a hydrogen atom or a substituent.

Specific examples of X _{13 to} X ₂₁ include a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, and an optionally substituted alkenyl group having 2 to 12 carbon atoms. Specific examples of X _{1 to} X ₈ , a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, and an optionally substituted alkenyl group having 2 to 12 carbon atoms Are similar to those listed.

^Specific examples of the organic groups R ^{10, R 11} and carbon atoms which may have a substituent ^{R 12} 1 to 20 is substituted for the ^R 2, ^{R 3} and ^{R 4} Specific examples of the organic group having 1 to 20 carbon atoms may be the same as those listed.

  Preferable specific examples of the group represented by the formula (A) include a group represented by the following formula (A21).

(In the formula (A21), X _{13 to} X ₂₁ represent the same meaning as described above.)

In the present invention, among the compounds represented by the formula (I), in the formula (I), Y ₁ , Y ₂ and Y ₃ are each independently a chemical single bond, —C (═O ) —O—, —C (═O) —NR ¹³ —, or —C (═O) — (wherein R ¹³ has 1 to 20 carbon atoms which may have a hydrogen atom or a substituent) In which X _{1 to} X ₂₁ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms that may have a substituent,
A compound in which Y ₁ is —C (═O) —O— or —C (═O) —NR ¹ — (R ¹ represents the same meaning as described above) is more preferred, and the following formula (I-1) And (I-2)

(In the above formulas (I-1) and (I-2), A ₁₁ and A ₂₁ represent the same meaning as described above.) Are particularly preferable.

  Particularly preferred specific examples of the formula (A11) are as follows.

  Particularly preferred specific examples of the formula (A21) are as follows.

(Method for producing fluorene compound)
The fluorolene compound represented by the formula (I) has the following formula (II)

(Hereinafter, abbreviated as “compound represented by formula Q-L ₁ ”) and a compound represented by formula A-L ₂ can be obtained.

Here, X _{1 to} X ₈ represent the same meaning as described above, and each independently has a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 12 carbon atoms or a substituent. An alkenyl group having 2 to 12 carbon atoms, a cyano group, a nitro group, —OR ² , —O—C (═O) —R ² , —C (═O) —OR ² , —O—C ( ^{= O) -OR 2, -N (} R 3) R 4, -NR 3 -C (= O) -R 2, -C (= O) -N (R 3) R 4, or, -O-C (═O) —N (R ³ ) R ⁴ is represented. L ₁ and L ₂ react with a compound represented by the formula: Q-L ₁ and a compound represented by the formula: A-L ₂ to produce a compound represented by the formula: Q-Y ₁ -A. Represents a group.
Examples of combinations of Y ₁ , L ₁ and L ₂ are shown below.

As a method of reacting the compound represented by the formula: Q-L ₁ and the compound represented by the formula: A-L ₂ , —O—, —S—, —NR ¹ —C (═O) — , —C (═O) NR ¹ —, —NR ¹ C (═O) NR ¹ —, —O—C (═O) —, —C (═O) —O— and the like are formed. (For example, the organic compound synthesis method according to Sandler Caro functional group [I], [II] Yodogawa Shoten, published in 1976) can be employed.

The fluorene compound of the present invention typically has an ether bond (—O—), an ester bond (—C (═O) —O—), an amide bond (—C (═O) —NR ¹ —), and It can be produced by appropriately combining and modifying a known compound having a desired structure by arbitrarily combining acid chloride (—COCl) formation reactions.

Formation of an ether bond (—O—) can be performed, for example, by the following methods 1) to 5).
1) A compound represented by the formula: Q-OM (Q represents the same meaning as described above, M represents an alkali metal, and the same shall apply hereinafter) and a formula: AX (A represents the same meaning as described above; X represents a halogen atom. The same shall apply hereinafter.) And is condensed. This reaction is generally called Williamson synthesis.
2) A compound represented by the formula: Q-OH and a compound represented by the formula: AX are mixed and condensed in the presence of a base such as sodium hydroxide or potassium hydroxide.
3) A compound represented by the formula: QE (E represents an epoxy group) and a compound represented by the formula: A-OH were mixed in the presence of a base such as sodium hydroxide or potassium hydroxide. To condense.
4) A compound represented by the formula: Q-OFN (OFN represents a group having an unsaturated bond) and a compound represented by the formula: A-OM in the presence of a base such as sodium hydroxide or potassium hydroxide. , Mixed to cause addition reaction.
5) A compound represented by the formula: Q-X and a compound represented by the formula: A-OM are mixed and condensed in the presence of copper or cuprous chloride. This reaction is generally called Ullmann condensation.

Formation of an ester bond and an amide bond can be performed as follows, for example.
1) A compound represented by the formula: Q—COOH and a compound represented by the formula: A—OH or A—NH ₂ are subjected to dehydration condensation in the presence of a dehydration condensing agent described later.

Examples of the dehydrating condensing agent used here include N, N-dicyclohexylcarbodiimide (DCC), 1- [3- (dimethylamino) propyl] -3-ethylcarbodiimide (WSC), 1,1-carbonyldiimidazole (CDI), N, N-disuccinimidyl carbonate (DSC), Bop reagent (Aldrich, USA), 2- (1H-benzotriazol-1-yl) -1,1,3,3-tetramethyluronium hexafluorophos Fert (HBTU), 2- (1H-benzotriazol-1-yl) -1,1,3,3-tetramethyluronium tetrafluoroborate (TBTU), bromotrispyrrolidinophosphonium hexafluorophosphate (PyBroP ( Registered trademark): Novabiochem, Germany), diphenyllin Azide (DPPA), phosphorus oxychloride, phosphorus trichloride, triphenylphosphine / N- bromosuccinimide, and the like.
The amount of the dehydrating condensing agent to be used is usually 1 to 3 mol per 1 mol of the compound represented by the formula: Q-COOH.

In this case, it is preferable that a base such as pyridine, 4- (dimethylamino) pyridine, triethylamine, diisopropylethylamine, diazabicyclo [5.4.0] undec-7-ene (DBU) coexists in the reaction system. These bases can be used alone or in combination of two or more.
The usage-amount of a base is 0.0001-1 mol normally with respect to 1 mol of compounds represented by a formula: Q-COOH.

2) An acid halide represented by the formula: Q-COX is obtained by allowing a halogenating agent to act on the compound represented by the formula: Q-COOH, and the acid halide and the formula: A-OH or A-NH ₂ are obtained. Is reacted in the presence of a base.

The acid halide can be formed, for example, as follows.
(I) A phosphorus trihalide or phosphorus pentahalide is allowed to act on the compound represented by the formula: Q-COOH.
(Ii) A thionyl halide is allowed to act on a compound represented by the formula: Q—COOH.
(Iii) Oxalyl halide is allowed to act on the compound represented by the formula: Q—COOH.
(Iv) Chlorine or bromine is allowed to act on the compound represented by the formula: Q-COOAg.
(V) A carbon tetrahalide solution of red mercuric oxide is allowed to act on the compound represented by the formula: Q-COOH.

Examples of the base used herein include organic bases such as triethylamine, diisopropylethylamine, pyridine, 4- (dimethylamino) pyridine, diazabicyclo [5.4.0] undec-7-ene (DBU); sodium hydroxide, potassium hydroxide Inorganic bases such as magnesium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, sodium ethoxide, potassium t-butoxide, and the like. These bases can be used alone or in combination of two or more.
The usage-amount of a base is 1-3 mol normally with respect to 1 mol of compounds represented by a formula: Q-COX.

3): a compound represented by Q-COOH, by the action of an acid anhydride, after obtaining a mixed acid anhydride, on the mixed acid anhydride of the formula: with A-OH or A-NH ₂ The compound represented is reacted.
The acid anhydride to be used is not particularly limited. Examples thereof include acetic anhydride, trifluoroacetic anhydride, monochloroacetic anhydride and the like.
The usage-amount of an acid anhydride is 1-10 mol normally with respect to 1 mol of compounds represented by a formula: Q-COOH.

4) A compound represented by the formula: Q—COOH and a compound represented by the formula: A—OH or A—NH ₂ are subjected to dehydration condensation in the presence of an acid catalyst or a base catalyst.

  Moreover, in the synthesis | combination of the fluorene compound of this invention, a yield can be improved by protecting the hydroxyl group which exists in an intermediate body. As a method for protecting a hydroxyl group, it can be produced by using a known method (for example, see Green's Protective Groups in Organic Synthesis 3rd edition published by Wiley-Interscience, 1999).

  The deprotection of the protecting group for the hydroxyl group can be deprotected by utilizing a known method depending on the structure and type of the protecting group.

Any reaction can be performed in a suitable solvent.
The solvent to be used is not particularly limited as long as it is an inert solvent for the reaction. For example, ether solvents such as tetrahydrofuran, diethyl ether, diisopropyl ether, 1,3-dimethoxyethane, 1,4-dioxane; N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethylimidazolinone, Amide solvents such as N-methylpyrrolidone; Halogenated hydrocarbon solvents such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene; Aromatic hydrocarbon solvents such as benzene, toluene and xylene; Pentane Aliphatic hydrocarbon solvents such as hexane, heptane, etc .; alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane, etc .; acetonitrile; dimethyl sulfoxide; and a mixed solvent composed of two or more of these solvents; .
The amount of the solvent to be used, the formula: with respect to the compound represented by 1g in _{Q-L 1,} usually 0.1～1000G.

The reaction proceeds smoothly in the temperature range from −20 ° C. to the boiling point of the solvent used.
Although the reaction time depends on the reaction scale, it is usually from several minutes to several hours.

In any reaction, after the completion of the reaction, the usual post-treatment operation in organic synthetic chemistry is performed, and if desired, by applying known separation / purification means such as column chromatography, recrystallization method, distillation method, etc. Product can be isolated.
The structure of the target product can be identified by measurement of NMR spectrum, IR spectrum, mass spectrum, etc., elemental analysis or the like.

  The fluorene compound obtained as described above can impart high processing stability, heat resistance, and long life to an organic material such as a polymer.

The fact that the fluorene compound of the present invention is excellent in anti-aging performance can be confirmed, for example, as follows.
That is, a predetermined amount of a fluorene compound is added to a predetermined amount of polyolefin (polyethylene, etc.) powder, and the resulting mixture is kneaded. During this time, kneading resistance is continuously recorded as torque. In the middle of the kneading time, when the stabilizer (anti-aging agent) is consumed and the effect becomes weak, the polymer starts to crosslink, and its deterioration is measured as an increase in torque. The time taken for the torque to start increasing can be used as a measure of the stabilizing action (anti-aging performance).
In the fluorene compound of the present invention, the time required for the torque to start increasing is much longer than that of conventional anti-aging agents, and is excellent in stabilizing action (anti-aging performance).

  Moreover, the heat resistance of the rubber composition containing the fluorene compound of the present invention is remarkably improved. For example, when the elongation was measured according to JIS K6301 before and after leaving the rubber composition containing the fluorene compound of the present invention in an environment of 190 ° C. for 504 hours, the rate of change was determined by adding a conventional anti-aging agent. It is smaller than the rubber composition, and it can be seen that the rubber composition containing the fluorene compound of the present invention is excellent in heat resistance.

2) Stabilizer containing fluorene compound The second of the present invention is a stabilizer containing the fluorene compound.
The fluorene compound of the present invention has a function of stabilizing an organic material against oxidative, thermal or light-induced decay. In particular, the fluorene compound of the present invention can suppress natural oxidation of organic materials used at high temperatures and deterioration due to heat, improve the heat resistance and processing stability of the organic materials, and can extend the life. .

  The applicable organic material is not particularly limited, and may be a natural organic material or a synthetic organic material. Of these, synthetic organic materials, particularly polyolefins, rubbers, polystyrene resins, polyesters, polycarbonates, polyamides, and the like, which are used for applications requiring heat resistance, are preferred, and in recent years, higher heat resistance than conventional ones is preferable. Polyolefins and rubbers that have come to be required are more preferable.

  Examples of polyolefins include polyolefins used in fields requiring heat resistance among polyethylene, polypropylene, polybutene, cycloolefin polymers, etc., and particularly known as heat resistant materials, such as mounting parts such as semiconductors, vehicle parts and civil engineering. By applying to a cycloolefin polymer used in the field of building members and the like, it can be used in a higher temperature environment than before.

  The cycloolefin polymer is obtained by polymerizing a cycloolefin monomer having a ring structure formed of carbon atoms in the molecule and having a carbon-carbon double bond in the ring.

  Examples of the cycloolefin monomer include a monocyclic cycloolefin monomer and a norbornene monomer, and a norbornene monomer is preferable. The norbornene-based monomer is a cycloolefin monomer having a norbornene ring structure in the molecule. These may be substituted with a hydrocarbon group such as an alkyl group, an alkenyl group, an alkylidene group or an aryl group, or a polar group. Further, the norbornene-based monomer may have a double bond in addition to the double bond of the norbornene ring.

  Examples of the monocyclic cycloolefin monomer include cyclobutene, cyclopentene, cyclooctene, cyclododecene, 1,5-cyclooctadiene, and the like.

Specific examples of the norbornene-based monomer include dicyclopentadiene such as dicyclopentadiene and methyldicyclopentadiene; tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-phenyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylic acid, tetracyclo [6.2.1.1 ^3,6 . ^{Tetracyclododecenes} such as 0 ^2,7 ] dodec-9-ene-4,5-dicarboxylic anhydride; 2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-phenyl 2-norbornene, 5-norbornen-2-yl acrylate, 5-norbornen-2-yl methacrylate, 5-norbornene-2-carboxylic acid, 5-norbornene-2,3-dicarboxylic acid, 5-norbornene-2 , norbornenes such as 3-dicarboxylic anhydride; 7-oxa-2-norbornene, 5-ethylidene-7-oxa norbornenes oxa-2-norbornene and the like; tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8] tetradec -3,5,7,12- tetraene (1,4-methano -1,4,4a, also referred to as a 9a- tetrahydro -9H- fluorene), pentacyclo [6.5.1.1 ^{3 , 6} . 0 ^2,7 . 0 ^9,13] pentadeca-4,10-diene, pentacyclo ^{[9.2.1.0 2,10.} 0 ^3,8] pentadeca-5,12 tetracyclic or more cyclic olefins such as dienes; and the like.

  The polymerization method may be bulk polymerization or solution polymerization, but it is preferable that the cycloolefin monomer is subjected to bulk ring-opening polymerization using a metathesis catalyst.

  Although it does not specifically limit as rubber, For example, natural rubber, isoprene rubber, butadiene rubber, butyl rubber, chloroprene rubber, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber (nitrile rubber), styrene-butadiene-isoprene copolymer Examples thereof include rubbers containing conjugated diene units such as rubber, butadiene-isoprene copolymer rubber, acrylonitrile-styrene-butadiene copolymer rubber; acrylic rubber; hydrin rubber, ethylene propylene rubber; These rubbers may have a hydroxyl group, a carboxyl group, an alkoxysilyl group, an amino group, an epoxy group, and the like. These rubbers may be hydrogenated, and examples thereof include acrylonitrile-butadiene copolymer rubber hydrogenated products (hydrogenated nitrile rubber). These rubbers may be used alone or in combination of two or more. Among these, it is particularly preferable to apply to acrylic rubber or hydrogenated nitrile rubber, which requires high heat resistance, from the viewpoint of improving heat resistance.

  When using the fluorene compound of this invention as a stabilizer of an organic material, the compounding quantity of the fluoreon compound of this invention is 0.01-10 mass parts of fluorene compounds of this invention with respect to 100 mass parts of organic materials. , Preferably 0.03 to 5 parts by mass, particularly preferably 0.05 to 3 parts by mass. When the blending amount of the fluorene compound of the present invention is less than 0.01 parts by mass, the effect as a stabilizer is not achieved. On the other hand, when it is more than 10 parts by mass, the effect as a stabilizer is not improved. In addition, bleed out and discoloration of the molded product may occur, which is not preferable.

  The fluorene compound of the present invention may be used alone or in combination of two or more. Moreover, it can use in combination with the other anti-aging agent etc. which are conventionally used in the range which does not impair the effect of invention.

3) Composition The third of the present invention is a composition containing component (a): an organic material and component (b): the fluorene compound of the present invention.

  The organic material of component (a) is not particularly limited, and may be a natural organic material or a synthetic organic material. Of these, synthetic organic materials, particularly polyolefins, rubbers, polystyrene resins, polyesters, polycarbonates, polyamides, and the like, which are used for applications requiring heat resistance, are preferred, and in recent years, higher heat resistance than conventional ones is preferable. Polyolefins and rubbers that have come to be required are more preferred, and polyolefins are particularly preferred. These specific examples are the same as those described above.

  The fluorene compound of component (b) is the fluorene compound of the present invention. The fluorene compound of this invention can be used individually by 1 type or in combination of 2 or more types.

The composition of the present invention may further contain other additives in addition to the component (a) and the component (b).
Examples of other additives include additives usually used in the field of using synthetic polymer materials. For example, reinforcing fillers such as carbon black and silica; non-reinforcing fillers such as calcium carbonate and clay; light stabilizers; scorch inhibitors; plasticizers; processing aids; lubricants; An antifungal agent, an antistatic agent, a coloring agent, a silane coupling agent, a crosslinking agent (vulcanizing agent), a crosslinking accelerator, a crosslinking retarder, and the like. The compounding amount of these additives is not particularly limited as long as it does not impair the object and effect of the present invention, and an amount corresponding to the compounding purpose can be appropriately compounded.

(Method for preparing composition)
The composition of the present invention is mixed and kneaded with a component (a), component (b) and, if desired, other additives with a Banbury mixer or kneader, and then further kneaded using a kneading roll. Can be prepared.
The blending order of each component is not particularly limited, but after thoroughly mixing components that are difficult to react or decompose with heat, a crosslinking agent that is susceptible to reaction or decomposition with heat can be shortened at a temperature at which reaction or decomposition does not occur. Mixing on time is preferred.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Production Examples and Examples.
Example 1 Synthesis of Compound 1

In a four-necked reactor equipped with a condenser and a thermometer, in a nitrogen stream, 15 g (71.35 mmol) of fluorenecarboxylic acid, 16.86 g (71.35 mmol) of 2,6-ditertiarybutyl-4-hydroxymethylphenol, 4- (Dimethylamino) pyridine (1.53 g, 8.56 mmol) was dissolved in N-methylpyrrolidone (NMP) (500 mL). To this solution, 16.41 g (85.62 mmol) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (WSC) was added, and the whole volume was stirred at room temperature for 14 hours.
After completion of the reaction, the reaction solution was poured into 5 liters of water and extracted twice with 800 mL of ethyl acetate. The obtained ethyl acetate layer was washed with 500 mL of saturated brine. The ethyl acetate layer was dried over anhydrous magnesium sulfate and filtered with suction. The filtrate was concentrated with a rotary evaporator to obtain 30 g of a yellow oil. The obtained oil was purified by silica gel column chromatography (n-hexane: toluene = 2: 1 (volume ratio)) to obtain 20.3 g (yield 66.4%) of Compound 1 as a pale yellow solid.

The structure was identified by ¹ H-NMR.
¹ H-NMR (500 MHz, CDCl ₃ , TMS, δ ppm): 7.70 (d, 2H, J = 4.0 Hz), 7.34-7.29 (m, 2H), 7.22 (d, 4H , J = 4.0 Hz), 6.85 (s, 2H), 5.03 (s, 1H), 4.15 (t, 1H, J = 7.0 Hz), 3.06 (d, 2H, J = 7.0 Hz), 1.36 (s, 18 H)

Example 2 Synthesis of Compound 2

In a four-necked reactor equipped with a condenser and a thermometer, in a nitrogen stream, 10 g (47.57 mmol) of fluorenecarboxylic acid, 7.89 g (42.81 mmol) of 4-aminodiphenylamine, 4- (dimethylamino) pyridine 0 0.7 g (5.7 mmol) was dissolved in 300 mL of N-methylpyrrolidone (NMP). To this solution was added 10.94 g (57.1 mmol) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (WSC), and the whole volume was stirred at room temperature for 12 hours.
After completion of the reaction, the reaction solution was poured into 3 liters of water and extracted twice with 500 mL of ethyl acetate. The obtained ethyl acetate layer was washed with 300 mL of saturated brine. The ethyl acetate layer was dried over anhydrous magnesium sulfate and filtered with suction. The filtrate was concentrated with a rotary evaporator to obtain 15 g of yellow oil. The obtained oil was purified by silica gel column chromatography (toluene: ethyl acetate = 9: 1 (volume ratio)) to obtain 12.1 g of Compound 2 as a light gray solid. (Yield 67.6%)

The structure was identified by ¹ H-NMR.
¹ H-NMR (500 MHz, CDCl ₃ , TMS, δ ppm): 7.83 (d, 2H, J = 7.5 Hz), 7.77 (d, 2H, J = 7.5 Hz), 7.48 (t 2H, J = 7.5 Hz), 7.40 (t, 2H, J = 7.5 Hz), 7.23-7.20 (m, 4H), 6.97-6.94 (m, 4H) 6.89 (t, 1H, J = 7.5 Hz), 6.78 (s, 1H), 5.60 (s, 1H), 4.91 (s, 1H)

(Evaluation of anti-aging performance)
The anti-aging performance of compounds 1 and 2 synthesized in Examples 1 and 2 was evaluated as follows.
In addition, the anti-aging agent AJ shown below was used as a comparative example.
Compounds (a) to (g) are the compounds shown below.

Anti-aging agent A: Composition containing compounds (a), (b) and (c) in a mass ratio of compound (a): compound (b): compound (c) = 15: 28.3: 56.7 (IRGANOX HP2251, manufactured by Ciba Specials Chemicals)
Anti-aging agent B; a composition containing compounds (b) and (d) at a mass ratio of compound (b): compound (d) = 66.7: 33.3 (IRGANOX B921, manufactured by Ciba Specials Chemicals) )
Anti-aging agent C; Compound (e) (Sumilyzer GS, manufactured by Sumitomo Chemical Co., Ltd.)
Anti-aging agent D; Compound (c) (IRGANOX 1010, manufactured by Ciba Specials Chemicals)
Anti-aging agent E; Composition containing compounds (f) and (b) (IRGASTAB FS 301, manufactured by Ciba Specials Chemicals)
Anti-aging agent F; composition containing compounds (e) and (b) in a mass ratio of compound (e): compound (b) = 50: 50; anti-aging agent G; compound (g)
Anti-aging agent H; a composition containing compounds (g) and (b) in a mass ratio of compound (g): compound (b) = 70: 30

(I) Evaluation test I
100 parts by mass of polyethylene powder (Sunfine UH900D, manufactured by Asahi Kasei Co., Ltd.) was mixed with 0.1 part by mass of each of Compound 1 and anti-aging agents A to F, and the resulting mixture was subjected to Laboplast mill (20C200 type, Toyo). Kneading at 220 ° C. and 50 rpm.
During this time, kneading resistance is continuously recorded as torque. In the middle of the kneading time, when the anti-aging agent (compound 1) is consumed and the effect becomes weak, the polymer starts to crosslink, and its deterioration is measured as an increase in torque. The time taken for the torque to start increasing was measured as a measure of stabilization. The results are shown in Table 1.

  From Table 1, in the resin composition (Example 3) to which the fluorene compound of Example 1 was added, the time taken for the torque to start increasing was the anti-aging agent A to A containing a conventional phosphorus-based anti-aging agent. It is longer than when F is used (Comparative Examples 1 to 6), and it can be seen that the fluorene compound of Example 1 is excellent in the stabilizing action (anti-aging performance) of polyethylene.

(II) Evaluation test II
(II-1) Preparation of Rubber Composition 100 parts by mass of acrylic elastomer (Nipol AR22, manufactured by Nippon Zeon Co., Ltd.), 60 parts by mass of carbon black (Shiest SO, manufactured by Tokai Carbon Co., Ltd.), 2 parts by mass of stearic acid, and Compound 2 3 parts by weight of each of antioxidants G and H were added and the whole volume was kneaded at 50 ° C. using a 0.8 liter Banbury, and then hexamethylenediamine carbamate (Diak No. 1, DuPont Dow Elastomer Japan) as a crosslinking agent. 0.5 parts by mass) and 2 parts by mass of di-o-tolylguanidine (Noxeller DT, manufactured by Ouchi Shinsei Chemical Co., Ltd.) as a crosslinking accelerator were kneaded with an open roll to prepare a rubber composition.

(II-2) Preparation of test piece The rubber composition prepared in (II-1) was molded and crosslinked by pressing at 170 ° C. for 20 minutes, and then a sheet of 15 cm × 15 cm × 2 mm (thickness) was prepared. Further, this sheet was heated at 170 ° C. for 4 hours for secondary crosslinking. The obtained sheet was used as a test piece.

(II-3) Evaluation of heat resistance Before and after leaving the test piece prepared in (II-2) in an environment of 190 ° C. for 504 hours, the elongation was measured according to JIS K6301 and the change was observed according to the following calculation formula: The rate was calculated. It is judged that the heat resistance is higher as the change rate is closer to zero, and a preferable result is obtained. The results of heat resistance evaluation are summarized in Table 2.

  From Table 2, in the case of the rubber composition containing the fluorene compound of Example 2 (Example 4), the rate of change is compared with the rubber compositions (Comparative Examples 7 to 9) to which a conventional anti-aging agent was added. It can be seen that the rubber composition containing the fluorene compound of Example 2 is excellent in heat resistance.

Claims (6)

A fluorene compound represented by the following formula (I):

{In the above formula (I), Y ₁ represents —C (═O) —O— or —C (═O) —NR ¹ — .
Here, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n represents any integer of 1 to 6.
X _{1 to} X ₈ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or an optionally substituted group having 2 to 12 carbon atoms. An alkenyl group, a cyano group, a nitro group, —OR ² , —O—C (═O) —R ² , —C (═O) —OR ² , —O—C (═O) —OR ² , —N ( R ³ ) R ⁴ , —NR ³ —C (═O) —R ² , —C (═O) —N (R ³ ) R ⁴ , or —O—C (═O) —N (R ³ ) R ⁴ is represented. Here, R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent,
a is 1.
A is the following formula (A11)

[In said formula (A11) , X < ₉ > -X < ₁₂ > has a C1-C12 alkyl group and substituent which may have a hydrogen atom, a halogen atom, and a substituent each independently. also an alkenyl group having 2 to 12 carbon atoms, a cyano group, a nitro ^{group, -OR 7, -O-C (} = O) -R 7, -C (= O) -OR 7, -O-C (= O ^{) -OR 7, -N (R 8} ) R 9, -NR 8 -C (= O) -R 7, -C (= O) -N (R 8) R 9, or, -O-C (= O) —N (R ⁸ ) R ⁹ is represented. Here, R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent. ]
Or a group represented by formula (A21)

[In the above formula (A21) , X _{13 to} X ₂₁ each independently have a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a substituent. also an alkenyl group having 2 to 12 carbon atoms, a cyano group, a nitro ^{_{group, -CF 3, -OR 10, -O}} -C (= O) -R 10, -C (= O) -OR 10, -O- ^{C (= O) -OR 10,} -N (R 11) R 12, -NR 11 -C (= O) -R 10, -C (= O) -N (R 11) R 12, or, -O —C (═O) —N (R ¹¹ ) R ¹² is represented. Here, R < ¹⁰ >, R < ¹¹ > and R < ¹² > represent the C1-C20 organic group which may have a hydrogen atom or a substituent. ]
Represents a group represented by } A stabilizer for a synthetic polymer comprising the fluorene compound according to claim 1 . A composition containing the component (a): a synthetic polymer material and the component (b): the fluorene compound according to claim 1 . The composition according to claim 3 , wherein the component (a) is a synthetic rubber. The composition according to claim 3 , wherein the component (a) is a polyolefin. The composition according to any one of claims 3 to 5 , further comprising another additive in addition to the component (a) and the component (b).