U.S. patent application number 14/560911 was filed with the patent office on 2015-03-26 for condensed heterocyclic compound and composition.
This patent application is currently assigned to ZEON CORPORATION. The applicant listed for this patent is ZEON CORPORATION. Invention is credited to Satoshi KIRIKI, Tomonori OGAWA, Kei SAKAMOTO, Masanobu SHINOHARA.
Application Number | 20150087754 14/560911 |
Document ID | / |
Family ID | 44319424 |
Filed Date | 2015-03-26 |
United States Patent
Application |
20150087754 |
Kind Code |
A1 |
SAKAMOTO; Kei ; et
al. |
March 26, 2015 |
CONDENSED HETEROCYCLIC COMPOUND AND COMPOSITION
Abstract
A condensed heterocyclic compound which is shown by the
following formula (I) and a composition containing an (a) organic
material and (b) at least one type of the condensed heterocyclic
compound are provided. ##STR00001## (Y indicates a chemical single
bond, --S(.dbd.O)--, or --SO.sub.2--. R.sup.a and R.sup.b indicate
substitutable C.sub.1 to C.sub.30 organic groups. Z.sup.a and
Z.sup.b indicate chemical single bonds or --SO.sub.2--. X.sup.1 and
X.sup.2 indicate hydrogen atoms etc. n and m respectively
independently indicate integers of 0 to 2, where one of n and m is
not 0).
Inventors: |
SAKAMOTO; Kei; (Tokyo,
JP) ; KIRIKI; Satoshi; (Tokyo, JP) ; OGAWA;
Tomonori; (Tokyo, JP) ; SHINOHARA; Masanobu;
(Tokyo, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ZEON CORPORATION |
Tokyo |
|
JP |
|
|
Assignee: |
ZEON CORPORATION
Tokyo
JP
|
Family ID: |
44319424 |
Appl. No.: |
14/560911 |
Filed: |
December 4, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
13575853 |
Jul 27, 2012 |
8937121 |
|
|
PCT/JP2011/051740 |
Jan 28, 2011 |
|
|
|
14560911 |
|
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Current U.S.
Class: |
524/83 ; 524/89;
544/35; 548/444 |
Current CPC
Class: |
C08K 5/3417 20130101;
C07D 209/88 20130101; C08K 5/46 20130101; C07D 279/34 20130101 |
Class at
Publication: |
524/83 ; 544/35;
548/444; 524/89 |
International
Class: |
C08K 5/46 20060101
C08K005/46; C07D 209/88 20060101 C07D209/88; C08K 5/3417 20060101
C08K005/3417; C07D 279/34 20060101 C07D279/34 |
Foreign Application Data
Date |
Code |
Application Number |
Jan 29, 2010 |
JP |
2010-019346 |
Claims
1. An antiaging agent comprising a condensed heterocyclic compound
which is shown in the following formula (I), ##STR00014## where, in
the formula, Y indicates a chemical single bond, --S(.dbd.O)--, or
--SO.sub.2--, R.sup.a and R.sup.b respectively independently
indicate substitutable C.sub.1 to C.sub.30 organic groups, Z.sup.a
and Z.sup.b respectively independently indicate chemical single
bonds or --SO.sub.2--, X.sup.1 and X.sup.2 respectively
independently indicate hydrogen atoms, halogen atoms, substitutable
C.sub.1 to C.sub.10 alkyl groups, cyano groups, nitro groups,
--OR.sup.1, --O--C(.dbd.O)--R.sup.1, --C(.dbd.O)--OR.sup.1,
--O--C(.dbd.O)--OR.sup.1, --NR.sup.2(R.sup.3),
--NR.sup.2--C(.dbd.O)--OR.sup.1, --C(.dbd.O)--NR.sup.2(R.sup.3), or
--O--C(.dbd.O)--NR.sup.2(R.sup.3), here, R.sup.1, R.sup.2, and
R.sup.3 respectively independently indicate hydrogen atoms or
substitutable to C.sub.20 organic groups, n and m respectively
independently indicate integers of 0 to 2, where either of n and m
is not 0, and when n and/or m is 2, two of R.sup.a and two of
R.sup.b may be the same as each other or may be different.
2. The antiaging agent as set forth in claim 1, wherein in said
formula (I), R.sup.a and R.sup.b respectively independently
indicate substitutable linear or branched C.sub.1 to C.sub.20 alkyl
groups or substitutable phenyl groups.
3. The antiaging agent set forth in claim 2, wherein in said
formula (I), R.sup.a and R.sup.b respectively independently
indicate .alpha.-methylbenzyl groups,
.alpha.,.alpha.-dimethylbenzyl groups, t-butyl groups, phenyl
groups, or 4-methylphenyl groups.
4. A composition which contains (a) an organic material and (b) the
antiaging agent as set forth in claim 1.
5. A composition which contains (a) an organic material and (b) the
antiaging agent as set forth in claim 2.
6. A composition which contains (a) an organic material and (b) the
antiaging agent as set forth in claim 3.
7. The composition as set forth in claim 4, wherein said ingredient
(a) is a synthetic polymer.
8. The composition as set forth in claim 4, wherein said ingredient
(a) is a synthetic rubber.
9. The composition as set forth in claim 4, wherein said ingredient
(a) is acrylic rubber or hydrogenated nitrile rubber.
10. The composition as set forth in claim 4, wherein said
ingredient (a) is acrylic rubber.
Description
CROSS-REFERENCE PARAGRAPH
[0001] This application is a Divisional of application Ser. No.
13/575,853 filed on Jul. 27, 2012, which is the national phase of
PCT International Application No. PCT/JP2011/051740 filed on Jan.
28, 2011, and which claims priority to Application No. 2010-019346
filed in Japan on Jan. 29, 2010. The entire contents of all of the
above applications are hereby incorporated by reference.
TECHNICAL FIELD
[0002] The present invention relates to a novel condensed
heterocyclic compound which can impart high processing stability
and heat resistance, and long life to a polymer or other organic
material which is susceptible to oxidation, heat, or light induced
breakdown and to a composition which contains an organic material
and that condensed heterocyclic compound.
BACKGROUND ART
[0003] Polymers and other organic materials are susceptible to
degradation by oxidation due to heat etc. if left as they are, so
to improve their heat resistances, various antiaging agents are
added to obtain heat resistances according to the particular
objectives. As such antiaging agents, for example,
diphenylamine-based antiaging agents which are described in Patent
Documents 1 to 3 are widely known.
[0004] In this regard, in recent years, polymers and other organic
materials have been increasingly used at tougher high temperatures.
For example, for the rubber materials which are used around the
engines of automobiles, the temperatures in the engine compartments
have been rising as a general trend due to the higher outputs of
automobile engines and the appearance of low pollution engines etc.
Therefore, the rubber materials which are used in their
surroundings are required to exhibit better heat resistance.
[0005] Therefore, as one measure for achieving this object,
development of a new antiaging agent which has a better effect than
conventional diphenylamine-based antiaging agents has been
desired.
PRIOR ART DOCUMENTS
Patent Documents
Patent Document 1: Japanese Patent Publication No. 9-53070
Patent Document 2: Japanese Patent Publication No. 10-298551
Patent Document 3: Japanese Patent Publication No. 11-21411
SUMMARY OF THE INVENTION
Problem to be Solved by the Invention
[0006] The present invention was made in consideration of the above
situation and has as its object the provision of a novel condensed
heterocyclic compound which is able to be synthesized easily and
has a superior antiaging action on organic materials which are
susceptible to oxidation, heat, or light induced breakdown and of a
composition which contains an organic material and that condensed
heterocyclic compound.
Means for Solving the Problems
[0007] The inventors engaged in intensive research for achieving
the above object and as a result discovered novel condensed
heterocyclic compounds which can impart extremely superior heat
stability or other property to polymers and other organic
materials.
[0008] Therefore, according to a first aspect of the present
invention, there are provided condensed heterocyclic compounds of
the following (1) to (5).
[0009] (1) The condensed heterocyclic compound which is shown in
the following formula (I).
##STR00002##
[0010] [where, in the formula, Y indicates a chemical single bond,
--S(.dbd.O)--, or --SO.sub.2--.
R.sup.a and R.sup.b respectively independently indicate
substitutable C.sub.1 to C.sub.30 organic groups. Z.sup.a and
Z.sup.b respectively independently indicate chemical single bonds
or --SO.sub.2--. X.sup.1 and X.sup.2 respectively independently
indicate hydrogen atoms, halogen atoms, substitutable C.sub.1 to
C.sub.10 alkyl groups, cyano groups, nitro groups, --OR.sup.1,
--O--C(.dbd.O)--R.sup.1, --C(.dbd.O)--OR.sup.1,
--O--C(.dbd.O)--OR.sup.1, --NR.sup.2(R.sup.3),
--NR.sup.2--C(.dbd.O)--OR.sup.1, --C(.dbd.O)--NR.sup.2(R.sup.3), or
--O--C(.dbd.O)--NR.sup.2(R.sup.3). Here, R.sup.1, R.sup.2, and
R.sup.3 respectively independently indicate hydrogen atoms or
substitutable C.sub.1 to C.sub.20 organic groups. n and m
respectively independently indicate integers of 0 to 2, where
either of n and m is not 0. Further, when n and/or m is 2, two of
R.sup.a and two of R.sup.b may be the same as each other or may be
different.]
[0011] (2) The condensed heterocyclic compound as set forth in (1),
wherein in the formula (I), R.sup.a and R.sup.b respectively
independently indicate substitutable linear or branched C.sub.1 to
C.sub.20 alkyl groups or substitutable phenyl groups.
[0012] (3) The condensed heterocyclic compound as set forth in (2),
wherein in the formula (I), R.sup.a and R.sup.b respectively
independently indicate .alpha.-methylbenzyl groups,
.alpha.,.alpha.-dimethylbenzyl groups, t-butyl groups, phenyl
groups, or 4-methylphenyl groups.
[0013] (4) The condensed heterocyclic compound as set forth in any
one of (1) to (3), which is an antiaging agent.
[0014] According to a second aspect of the present invention, there
are provided the compositions of the following (5) to (9):
[0015] (5) The composition which contains (a) an organic material
and (b) at least one type of condensed heterocyclic compound as set
forth in any one of (1) to (4).
[0016] (6) The composition as set forth in (5), wherein the
ingredient (a) is a synthetic polymer.
[0017] (7) The composition as set forth in (5) or (6), wherein the
ingredient (a) is a synthetic rubber.
[0018] (8) The composition as set forth in any one of (5) to (7),
wherein the ingredient (a) is acrylic rubber or hydrogenated
nitrile rubber.
[0019] (9) The composition as set forth in any one of (5) to (8),
wherein the ingredient (a) is acrylic rubber.
Effects of the Invention
[0020] According to the present invention, there are provided a
novel condensed heterocyclic compound which can impart high
processing stability and heat resistance, and long life to a
polymer or other organic material which is susceptible to
oxidation, heat, or light induced breakdown and a composition which
contains an organic material and that condensed heterocyclic
compound.
DESCRIPTION OF EMBODIMENTS
[0021] Below, the present invention will be explained divided into
1) condensed heterocyclic compounds and 2) compositions which
contain organic materials and the condensed heterocyclic
compounds.
[0022] 1) Condensed Heterocyclic Compounds
[0023] A first aspect of the present invention is a condensed
heterocyclic compound which is shown by the above formula (I).
[0024] Where, in formula (I), Y indicates a chemical single bond,
--S(.dbd.O)--, or --SO.sub.2--. In formula (I), --S(.dbd.O)-- and
--SO.sub.2-- are preferable, and --SO.sub.2-- is more
preferable.
[0025] In formula (I), R.sup.a and R.sup.b respectively
independently indicate substitutable C.sub.1 to C.sub.30 organic
groups.
[0026] As the C.sub.1 to C.sub.30 organic groups which form the
R.sup.a and R.sup.b, C.sub.1 to C.sub.30 alkyl group such as methyl
group, ethyl group, n-propyl group, isopropyl group, n-butyl group,
isobutyl group, sec-butyl group, t-butyl group, n-pentyl group,
n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, and
n-decyl group; C.sub.3 to C.sub.30 cycloalkyl group such as
cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl
group, and cyclooctyl group; C.sub.6 to C.sub.30 aryl group such as
phenyl group, biphenyl group, naphthyl group, and anthranyl group;
C.sub.1 to C.sub.30 alkoxy group 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, and
n-hexyloxy group; etc. may be mentioned.
[0027] Further, the above-mentioned organic groups which form
R.sup.a and R.sup.b may have substituents. The positions of the
substituents may be made any positions.
[0028] As the substituents of the organic groups, when the organic
groups are alkyl groups, a halogen atom such as fluorine atom,
chlorine atom, and bromine atom; C.sub.1 to C.sub.10 alkoxy group
such as methoxy group, ethoxy group, and isopropoxy group; nitro
group; cyano group; substitutable phenyl group such as phenyl
group, 4-methylphenyl group, and 2-chlorophenyl group; etc. may be
mentioned.
[0029] When the organic groups are cycloalkyl groups and aryl
groups, a halogen atom such as fluorine atom, chlorine atom, and
bromine atom; C.sub.1 to C.sub.10 alkoxy group such as methoxy
group, ethoxy group, and isopropoxy group; nitro group; cyano
group; C.sub.1 to C.sub.10 alkyl group such as methyl group, ethyl
group, and t-butyl group; etc. may be mentioned.
[0030] Further, when the organic groups are alkoxy groups, a
halogen atom such as fluorine atom, chlorine atom, and bromine
atom; nitro group; cyano group; etc. may be mentioned.
[0031] Note that, in the present invention, when the organic groups
which form the R.sup.a and R.sup.b have substituents, the numbers
of carbon atoms of organic groups are deemed to not include the
numbers of carbon atoms of the substituents. That is, the organic
groups which form the R.sup.a and R.sup.b should have numbers of
carbon atoms, minus the carbon atoms which are included in the
substituents, of 1 to 30 in range. For example, when the organic
group which form the R.sup.a and R.sup.b is methoxyethyl group, the
numbers of carbon atoms of the organic groups become 2. That is, in
this case, since the methoxy group is substituent, so the numbers
of carbon atoms of the organic groups become the numbers of carbon
atoms minus those of methoxy group as the substituent.
[0032] In the present invention, as R.sup.a and R.sup.b,
respectively independently substitutable linear or branched C.sub.1
to C.sub.20 alkyl groups, substitutable phenyl groups and
substitutable naphthyl groups are preferable, while substitutable
linear or branched C.sub.2 to C.sub.8 alkyl groups and
substitutable phenyl groups are more preferable.
[0033] As preferable specific examples of such organic groups which
form the R.sup.a and R.sup.b, an .alpha.-methylbenzyl group,
.alpha.,.alpha.-dimethylbenzyl group, t-butyl group, phenyl group
or 4-methylphenyl group, etc. may be mentioned, Among these as
well, an .alpha.,.alpha.-dimethylbenzyl group or 4-methylphenyl
group is particularly preferable. Note that, these may be
respectively made independent.
[0034] In the formula (I), Z.sup.a and Z.sup.b respectively
independently indicate chemical single bonds or --SO.sub.2--.
Chemical single bonds are preferable.
[0035] In the formula (I), X.sup.1 and X.sup.2 respectively
independently indicate hydrogen atoms, halogen atoms, substitutable
C.sub.1 to C.sub.10 alkyl groups, cyano groups, nitro groups,
--OR.sup.1, --O--C(.dbd.O)--R.sup.1, --C(.dbd.O)--OR.sup.1,
--O--C(.dbd.O)--OR.sup.1, --NR.sup.2(R.sup.3),
--NR.sup.2--C(.dbd.O)--OR.sup.1, --C(.dbd.O)--NR.sup.2(R.sup.3), or
--O--C(.dbd.O)--NR.sup.2(R.sup.3).
[0036] As the halogen atoms which form the X.sup.1 and X.sup.2, a
fluorine atom, chlorine atom, bromine atom, etc. may be
mentioned.
[0037] As the C.sub.1 to C.sub.10 alkyl groups of the substitutable
C.sub.1 to C.sub.10 alkyl groups, a methyl group, ethyl group,
propyl group, isopropyl group, n-butyl group, isobutyl group,
t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group,
n-octyl group, n-nonyl group, n-decyl group, etc. may be
mentioned.
[0038] As the substituents of the C.sub.1 to C.sub.10 alkyl groups,
halogen atom such as fluorine atom, chlorine atom, and bromine
atom; alkoxy group such as methoxy group, ethoxy group, n-propoxy
group, isopropoxy group, n-butoxy group, and t-butoxy group; nitro
group; cyano group, etc. may be mentioned.
[0039] R.sup.1, R.sup.2, and R.sup.3 respectively independently
express hydrogen atoms or substitutable C.sub.1 to C.sub.20 organic
groups, while all of R.sup.2, and R.sup.3 being hydrogen atoms is
preferable.
[0040] As the C.sub.1 to C.sub.20 organic groups of the
substitutable C.sub.1 to C.sub.20 organic groups which form the
R.sup.1, R.sup.2, and R.sup.3, C.sub.1 to C.sub.20 alkyl group such
as methyl group, ethyl group, n-propyl group, isopropyl group,
n-butyl group, isobutyl group, t-butyl group, n-pentyl group,
n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, and
n-decyl group; C.sub.3 to C.sub.20 cycloalkyl group such as
cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl
group, and cyclooctyl group; C.sub.6 to C.sub.20 aryl group such as
phenyl group, naphthyl group, and anthranyl group; C.sub.1 to
C.sub.20 alkoxy group 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, and n-hexyloxy
group; etc. may be mentioned.
[0041] As the substituents of the organic groups which form the
R.sup.1, R.sup.2, and R.sup.3, ones similar to those listed as
substituents of the organic groups which form the R.sup.a and
R.sup.b explained above may be mentioned.
[0042] Among these as well, as X.sup.1 and X.sup.2, from the
viewpoints of ease of acquisition etc., both being hydrogen atoms
is preferable.
[0043] In the formula (I), n and m respectively independently
indicate integers of 0 to 2, where either of n and m is not 0. n
and m respectively independently being 0 or 1 (where either of n
and m is not 0) is preferable, while n and m being 1 is more
preferable.
[0044] Further, when n and/or m is 2, two of R.sup.a and two of
R.sup.b may be the same or different.
[0045] As the condensed heterocyclic compound of the present
invention, any of the compounds which are expressed by the
following formulae (II) to (IX) is preferable.
##STR00003##
(in the above formulae, R.sup.a, R.sup.b, Z.sup.a, and Z.sup.b
express the same meanings as the formula (I).)
[0046] Among the compounds which are expressed by the formulae (II)
to (IX) as well, compounds which are expressed by the formulae
(II), (VI), and (VII) are more preferable, compounds which are
expressed by the formulae (VI) and (VII) are furthermore
preferable, and compounds which are expressed by the formula (VI)
are particularly preferable.
[0047] Further, among the general formulae (II) to (IX), the
compound in which --Z.sup.a--R.sup.a and --Z.sup.b--R.sup.b
respectively independently are .alpha.-methylbenzyl groups,
.alpha.,.alpha.-dimethylbenzyl groups, t-butyl groups,
phenylsulfonyl groups, or 4-methylphenylsulfonyl groups is more
preferable, the compound in which --Z.sup.a--R.sup.a and
--Z.sup.b--R.sup.b are .alpha.,.alpha.-dimethylbenzyl groups is
particularly preferable.
[0048] (Method of Production of Condensed Heterocyclic Compound
Expressed by Formula (I))
[0049] Among the compounds which are expressed by the formula (I),
compounds where Y is --SO.sub.2-- can be produced by applying the
known method of production of phenothiazine-based compounds to
obtain a compound of the formula (I) where Y is S, then oxidizing
the obtained compound.
[0050] Further, among the compounds which are expressed by the
formula (I), compounds where Y is a single bond can be produced by
applying the known method of production of a carbazole-based
compound.
[0051] Further, compounds which are expressed by the formula (I)
can be obtained by using compounds which are expressed by the
following formula (2) [phenothiazine (Y.sup.1=S) and carbazole
(Y.sup.1=chemical single bond)] as starting materials and using a
known reaction method to introduce substituents (--Z.sup.a--R.sup.a
and --Z.sup.b--R.sup.b) into the 1-position, 3-position,
6-position, and/or 8-position of the aromatic rings of the formula
(2) and, when Y.sup.1=S, making Y.sup.1 into --SO.sub.2-- by
oxidation. Note that, the compounds which are expressed by the
formula (2) are nonsubstituted, but compounds which have the
substituents (X.sup.1a, X.sup.2a) at any positions of the aromatic
rings may also be used as starting materials. Here, X.sup.1a and
X.sup.2a respectively indicate the atoms and substituents other
than hydrogen atoms which form the above-mentioned X.sup.1 and
X.sup.2.
##STR00004##
[0052] (in the formula (2), Y.sup.1 is S or a chemical single
bond)
[0053] As the reaction method which introduces one or more
substituents (--Z.sup.a--R.sup.a, --Z.sup.b--R.sup.b) at the
1-position, 3-position, 6-position, and/or 8-position of the
aromatic rings in the formula (2), for example, a reaction which
causes the formation of a carbon-carbon bond at the carbon atoms of
the 1-position, 3-position, 6-position, and/or 8-position of the
aromatic rings in the formula (2) (this reaction method will be
referred to as the "reaction method .alpha."), a reaction which
causes the formation of a carbon-SO.sub.2 bond at the carbon atoms
of the 1-position, 3-position, 6-position, and/or 8-position of the
aromatic rings in the formula (2) (this reaction method will be
referred to as the "reaction method .beta."), a reaction which
causes the formation of a carbon-sulfur bond at the carbon atoms of
the 1-position, 3-position, 6-position, and/or 8-position of the
aromatic rings in the formula (2) (this reaction method will be
referred to as the "reaction method .gamma."), etc. may be
mentioned.
[0054] Below, the method of production of the compound which is
expressed by the formula (I) will be explained in detail while
using as an example the case of using compounds which are expressed
by the formula (2) as a starting material and using the methods of
the above-mentioned reaction method .alpha., reaction method
.beta., and reaction method .gamma..
[0055] [A. Method of Production (1) Using Reaction Method
.alpha.]
[0056] The reaction formula of the method of production (1) which
uses the reaction method .alpha. is shown below. Note that, in the
following reaction formula, among the compounds which are expressed
by the formula (I), the case where Y is a chemical single bond or
--SO.sub.2--, n or m is 0, and --Z.sup.a--R.sup.a or
--Z.sup.b--R.sup.b is a group which is indicated by the formula:
--C(CH.sub.3)(r)-Ar (wherein, r indicates a hydrogen atom or alkyl
group, and Ar indicates a substitutable phenyl group) is
illustrated.
##STR00005##
[0057] Further, in accordance with the above reaction formula,
among the compounds which are expressed by the formula (I), a
compound where Y is a chemical single bond can be obtained as a
compound which is shown in the formula (3a) and/or (3b) by using a
compound which is expressed by the formula (2) (carbazole where
Y.sup.1=chemical single bond) as a starting material and reacting
the styrene compound which is expressed by the formula (4) in the
presence of an acid catalyst.
[0058] Further, in accordance with the above reaction formula,
among the compounds which are expressed by the formula (I), a
compound where Y is --SO.sub.2-- can be obtained as a compound
which is shown in the formula (Ia) and/or (Ib) by using a compound
which is expressed by the formula (2) (phenothiazine where
Y.sup.1=S) as a starting material, reacting the styrene compound
which is expressed by the formula (4) in the presence of an acid
catalyst, and oxidizing the compound which is obtained by the
reaction (compound which is shown in the formula (3a) and/or
(3b)).
[0059] As a compound which is expressed by the formula (4) which is
used for this reaction, styrene; an alkylated styrene such as
4-methylstyrene, .alpha.-methylstyrene, 4, .alpha.-dimethylstyrene,
2,4-dimethylstyrene, ethylstyrene, and p-t-butylstyrene; a
halogenated styrene such as 2-chlorostyrene, and
2,4-dichlorostyrene; etc. may be mentioned.
[0060] The amount of use of the compound which is expressed by the
formula (4) is 0.5 to 1.5 moles per 1 mole of the compound which is
expressed by the formula (2).
[0061] As an acid catalyst which is used, sulfonic acids such as
methanesulfonic acid, phenylsulfonic acid, and p-toluenesulfonic
acid; inorganic acids such as hydrochloric acid, and sulfuric acid;
etc. may be mentioned. The acid catalyst is usually charged at the
time of start of the reaction, but may also be added in the middle
of the reaction.
[0062] The amount of use of the acid catalyst is usually 0.005 to
0.5 mole per 1 mole of the compound which is expressed by the
formula (2), preferably 0.01 to 0.3 mole, more preferably 0.02 to
0.1 mole.
[0063] This reaction can be performed in a suitable solvent. The
solvent which is used is not particularly limited so long as being
inert to the reaction, but, for example, aromatic hydrocarbon-based
solvent such as benzene, toluene, and xylene; aliphatic
hydrocarbon-based solvent such as n-pentane, n-hexane, n-octane,
cyclopentane, and cyclohexane; halogenated hydrocarbon-based
solvent such as 1,2-dichloroethane, and monochlorobenzene; etc. may
be mentioned. These solvents may be used as single type alone or as
two or more types combined.
The amount of use of the solvent depends on the reaction scale
etc., but is 1 nil to 100 ml per 1 g of the compound which is
expressed by the formula (2).
[0064] Further, in the compound which is expressed by the formula
(2), when the oxidizing agent which is used for oxidation is not
particularly limited. Acetic acid-hydrogen peroxide, organic
peroxide such as m-chloroperbenzoic acid may be mentioned.
[0065] The amount of use of the oxidizing agent is 2 to 5 moles per
1 mole of the compound which is expressed by the formula (3a) or
(3b).
[0066] Note that, when synthesizing a compound where Y is --SO--,
the oxidizing agent should be used in an amount of 0.5 to 1.5 moles
per 1 mole of the compound which is expressed by the formula (3a)
or (3b).
[0067] Such an oxidation reaction can be performed in a suitable
solvent. The solvent which is used is not particularly limited so
long as being inert to the reaction, but, for example, aromatic
hydrocarbon-based solvent such as benzene, toluene, and xylene;
aliphatic hydrocarbon-based solvent such as n-pentane, n-hexane,
n-octane, cyclopentane, and cyclohexane; halogenated
hydrocarbon-based solvent such as dichloromethane, chloroform,
1,2-dichloroethane, and monochlorobenzene; acetic acid; etc. may be
mentioned. These solvents may be used as single type alone or as
two or more types combined.
[0068] The amount of use of the solvent depends in the reaction
scale etc., but is 1 ml to 100 ml per 1 g of the compound which is
expressed by the formula (3a) or (3b).
[0069] Furthermore, this reaction can also be performed
continuously by adding to a reaction solution which includes a
compound which is expressed by the formula (3a) and/or (3b)
predetermined amounts of acetic acid and hydrogen peroxide.
[0070] [B. Method of Production (2) Using Reaction Method
.alpha.]
[0071] The reaction formula of the method of production (2) which
uses the reaction method .alpha. is shown below. Note that, in the
following reaction formula, the case where, in the compound which
is expressed by the formula (I), Y is a chemical single bond or
--SO.sub.2--, n and m are 1, and --Z.sup.a--R.sup.a and
--Z.sup.b--R.sup.b are groups which are shown by the formula:
--C(CH.sub.3)(r)-Ar (wherein, r indicates a hydrogen atom or alkyl
group, and Ar indicates a substitutable phenyl group) is
illustrated.
##STR00006##
[0072] Further, in accordance with the above reaction formula, in
the compound which is expressed by the formula (I), the compound
where Y is a chemical single bond can be obtained as a compound of
the formula (3c) and/or (3d) by using the compound which is
expressed by the formula (2) (carbazole where Y.sup.1=chemical
single bond) as a starting material and reacting the styrene
compound which is expressed by the formula (4) in the presence of
an acid catalyst.
[0073] Further, in accordance with the above reaction formula, in
the compound which is expressed by the formula (I), the compound
where Y is --SO.sub.2--can be obtained as a compound of the formula
(Ic) and/or (Id) by using the compound which is expressed by the
formula (2) (phenothiazine where Y.sup.1=S) as a starting material,
reacting the styrene compound which is expressed by the formula (4)
in the presence of an acid catalyst, and oxidizing the compound
which is obtained by the reaction (the compound which is shown by
the formula (3c) and/or (3d)).
[0074] Note that, in the above reaction, as the compound which is
expressed by the formula (4), acid catalyst, solvent, and oxidizing
agent, ones similar to the above-mentioned method of production (1)
which uses the reaction method .alpha. can be used. Further, for
the amounts of use of these, except for making the amount of use of
the compound which is expressed by the formula (4) 2 to 3 moles per
1 mole of the compound which is expressed by the formula (2) and
making the amount of use of the oxidizing agent 2 to 10 moles per 1
mole of the compound which is expressed by the formula (3c) or
(3d), similar amounts to the above-mentioned method of production
(1) which uses the reaction method .alpha. can be used.
[0075] [C. Method of Production Using Reaction Method .beta.]
[0076] The reaction formula of the method of production which uses
the reaction method .beta. is shown below. Note that, in the
following reaction formula, the case where, in the compound which
is expressed by the formula (I), Y is a chemical single bond or
--SO.sub.2--, n or m are 0, and --Z.sup.a--R.sup.a or
--Z.sup.b--R.sup.b are groups which are shown by the formula:
--SO.sub.2--Ar (wherein, Ar indicates a substitutable phenyl group)
is illustrated.
##STR00007##
[0077] Further, in accordance with the above reaction formula, in
the compound which is expressed by the formula (I), the compound
where Y is a chemical single bond can be obtained as a compound of
the formula (3e) and/or (3f) by using the compound which is
expressed by the general formula (2) (carbazole where
Y.sup.1=chemical single bond) as a starting material and reacting
the sulfinate which is expressed by the formula (5) in the presence
of Lewis acid such as ferric chloride and acetate such as potassium
acetate (M expressed alkali metal such as sodium).
[0078] Further, in accordance with the above reaction formula, in
the compound which is expressed by the formula (I), the compound
where Y is --SO.sub.2-- can be obtained as a compound of the
formula (Ie) and/or (If) by using the compound which is expressed
by the formula (2) (phenothiazine where Y.sup.1=S) as a starting
material, reacting the sulfinate which is expressed by the formula
(5) in the presence of Lewis acid such as ferric chloride and
acetate such as potassium acetate, and oxidizing the compound which
is obtained by the reaction (compound which is shown by the formula
(3e) and/or (3f)).
[0079] As the sulfinate which is expressed by the formula (5) which
is used for the reaction, sodium phenylsulfinate, potassium
phenylsulfinate, sodium p-toluenesulfinate, potassium
p-toluenesulfinate, etc. may be mentioned.
[0080] The amount of use of the sulfinate which is expressed by the
formula (5) is 0.5 to 1.5 moles per 1 mole of the compound which is
expressed by the formula (2).
[0081] The amount of use of the Lewis acid is usually 5 to 10 moles
per 1 mole of the compound which is expressed by the formula (2),
while the amount of use of the acetate is usually 1 to 3 moles per
1 mole of the compound which is expressed by the formula (2).
[0082] The reaction can be performed in a suitable solvent. The
solvent which is used is not particularly limited so long as being
inert to the reaction, but, for example, alcohol-based solvent such
as methyl alcohol, ethyl alcohol, propyl alcohol, and isopropyl
alcohol may be mentioned.
[0083] The solvent which is used can be used as single type alone
or as two or more types combined.
[0084] The amount of use of the solvent depends on the reaction
scale etc., but is 1 ml to 100 ml per 1 g of the compound which is
expressed by the formula (2).
[0085] Note that, in the compound which is expressed by the formula
(2), when Y.sup.1=S, the oxidation reaction can be performed in the
same way as the above-mentioned method of production (1) which uses
the reaction method .alpha..
[0086] [D. Method of Production Using Reaction Method .gamma.]
[0087] The reaction formula of the method of production which uses
the reaction method .gamma. is shown below. Note that, in the
following reaction formula, the case where, in the compound which
is expressed by the formula (I), Y is a chemical single bond, n and
m are 1, and --Z.sup.a--R.sup.a or --Z.sup.b--R.sup.b are groups
which are shown by the formula: --SO.sub.2--R (wherein, R expresses
a C.sub.1 to C.sub.30 organic group) is illustrated.
##STR00008##
[0088] Further, in accordance with the above reaction formula, a
compound which is expressed by the formula (2a) (carbazole) can be
used as a starting material and iodine can be reacted in the
presence of periodate and a catalytic amount of sulfuric acid to
obtain diiodo which is expressed by the formula (6), then the
obtained diiodo can be reacted with mercaptan which is expressed by
the formula: R--SH (wherein, R indicates a C.sub.1 to C.sub.30
organic group) in the presence of a base and a catalytic amount of
palladium (II) complex so as to obtain the compound which is
expressed by the formula (7), then the obtained compound can be
oxidized to obtain a compound which is expressed by the formula
(Ig)
[0089] As the periodate which is used for the reaction for
obtaining the diiodo which is shown in the formula (6), sodium
periodate, potassium periodate, etc. may be mentioned.
[0090] The amount of use of the periodate is 0.1 mole to 1 mole per
1 mole of the compound which is expressed by the formula (2a).
[0091] The amount of use of iodine is 1 mole to 3 moles per 1 mole
of the compound which is expressed by the formula (2a).
[0092] The reaction which obtains the diodo which is expressed by
the formula (6) can be performed in a suitable solvent. The solvent
which is used is not particularly limited so long as being inert to
the reaction, but for example, alcohol-based solvent such as methyl
alcohol, ethyl alcohol, propyl alcohol, and isopropyl alcohol may
be mentioned.
[0093] The solvent which is used can be used as single type alone
or as two or more types combined.
[0094] The amount of use of the solvent depends on the reaction
scale etc., but is 1 ml to 100 ml per 1 g of the compound which is
expressed by the formula (2a).
[0095] As a mercaptan which is used for the reaction for obtaining
the compound which is expressed by the formula (7), thiophenol,
p-toluenethiol, benzylmercaptan, .alpha.-methylbenzylmercaptan,
.alpha.,.alpha.-dimethylmercaptan, t-butylmercaptan, etc. may be
mentioned.
The amount of use of the mercaptan is 1 mole to 3 moles per 1 mole
of the compound which is expressed by the formula (6).
[0096] As the base which is used for the reaction for obtaining the
compound which is expressed by the formula (7), metal alkoxide such
as sodium t-butoxide and potassium t-butoxide; organic base such as
DBU (1,8-diazabicyclo[5.4.0]undeca-7-en), and DABCO
(1,4-diazabicyclo[2.2.2]octane),; etc. may be mentioned.
[0097] The amount of use of the base is usually 1 mole to 10 moles
per 1 mole of compound which is expressed by the formula (6).
[0098] As a palladium (II) complex which is used for the reaction
for obtaining the compound which is expressed by the formula (7),
[1,1'-bis(diphenylphosphino) ferrocene]palladium (II) dichloride
dichloromethane adduct etc. may be mentioned.
[0099] The reaction for obtaining the compound which is expressed
by the formula (7) can be performed in a suitable solvent. The
solvent which is used is not particularly limited so long as being
inert to the reaction, but for example, aromatic hydrocarbon-based
solvent such as benzene, toluene, and xylene; aliphatic
hydrocarbon-based solvent such as n-pentane, n-hexane, n-octane,
cyclopentane, and cyclohexane; halogenated hydrocarbon-based
solvent such as di chloromethane, chloroform, 1,2-dichloroethane,
and monochlorobenzene; etc. may be mentioned. These solvents can be
used as single type alone or as two or more types combined.
[0100] The amount of use of the solvent depends on the reaction
scale etc., but is 1 ml to 100 ml per 1 g of the compound which is
expressed by the formula (6).
[0101] The oxidizing agent which is used for the oxidation reaction
with the compound which is expressed by the formula (7) is not
particularly limited, but organic peroxide such as acetic
acid-hydrogen peroxide and m-chloroperbenzoic acid may be
mentioned.
[0102] The amount of use of the oxidizing agent is 2 to 10 moles
per 1 mole of the compound which is expressed by the formula
(7).
[0103] Further, as the suitable solvent for such an oxidation
reaction, a solvent similar to the one used in the oxidation
reaction of the above-mentioned method of production (1) which uses
the reaction method .alpha. may be used.
[0104] Furthermore, this reaction can be performed continuously by
adding to a reaction solution which contains the compound which is
expressed by the formula (7) predetermined amounts of acetic acid
and hydrogen peroxide.
[0105] Each of the reactions of the above reaction method .alpha.,
reaction method .beta., and reaction method .gamma. proceeds
smoothly in the temperature range from 0.degree. C. up to the
boiling point of the solvent which is used. The reaction time is
usually several minutes to several hours.
[0106] Further, in each reaction of the reaction method .alpha.,
reaction method .beta., and reaction method .gamma., after the end
of the reaction, the usual post-treatment operations in organic
synthetic chemicals are performed. If desired, the column
chromatography, recrystallization method, distillation method, and
other known separating and refining means can be applied to isolate
the target substance.
[0107] The structure of the target substance can be identified by
measurement of the NMR spectrum, IR spectrum, mass spectrum, etc.
and by elementary analysis etc.
[0108] The condensed heterocyclic compound which was obtained in
the above way can give high processing stability and heat
resistance, and long life to a polymer or other organic material
which is susceptible to oxidation, heat, or light induced
breakdown.
[0109] The fact that the condensed heterocyclic compound of the
present invention is superior in antiaging performance for organic
materials can for example be confirmed as follows:
[0110] That is, a condensed heterocyclic compound of the present
invention, an acrylic elastomer, carbon black, and stearic acid
were kneaded in predetermined amounts, a cross-linking agent and a
cross-linking accelerator in predetermined amounts are further
added and kneaded to obtain a rubber composition, and the obtained
rubber composition is formed into a sheet and cross-linked. Next,
the obtained sheet is used as a test piece. This test piece is
allowed to stand in a 190.degree. C. environment for 504 hours in a
heat degradation test. Before and after the test, the elongation is
measured in accordance with JIS K6301. The rate of change of
elongation which is calculated by the following calculation formula
is usually -90 to -60(%) and is a value close to zero compared with
the case of using a conventional antiaging agent. From this, it is
learned that the condensed heterocyclic compound of the present
invention has a superior stabilizing action (antiaging
performance).
Rate of change (%)=[(elongation after test (%))-(elongation before
test (%))]/(elongation before test (%)).times.100
[0111] The condensed heterocyclic compound of the present invention
acts as an antiaging agent.
[0112] Specifically, the condensed heterocyclic compound of the
present invention has the function of stabilizing an organic
material against oxidation, heat, or light induced breakdown. In
particular, the condensed heterocyclic compound of the present
invention can suppress the natural oxidation and heat degradation
of an organic material which is used in a high temperature so as to
improve the heat resistance and processing stability of the organic
material and increase the lifetime.
[0113] When using the condensed heterocyclic compound of the
present invention as a stabilizing agent of an organic material,
the amount of the condensed heterocyclic compound of the present
invention is, with respect to 100 g of the organic material, 0.5 to
100 mmoles, preferably 1 to 50 mmoles, particularly preferably 1 to
30 mmoles. If the amount of the condensed heterocyclic compound of
the present invention is smaller than 0.5 mmole, the effect as a
stabilizing agent is not exhibited. If greater than 100 mmoles, no
improvement in effect as a stabilizing agent is seen, contrariwise,
there is a possibility of bleedout or discoloration of the molded
product. This is not preferable.
[0114] Further, the condensed heterocyclic compound of the present
invention may be used alone or may be used as two or more types
combined. Furthermore, it can be used combined with a
conventionally used stabilizing agent in a range not detracting
from the effect of the invention.
[0115] 2) Composition which Contains Organic Material and Condensed
Heterocyclic Compound
[0116] A second aspect of the present invention is a composition
which contains an ingredient (a) of an organic material and an
ingredient (b) of a condensed heterocyclic compound of the present
invention.
[0117] The organic material of the ingredient (a) which is used in
the present invention is not particularly limited. It may be a
natural organic material or a synthetic organic material. Among
these, as the organic material of the ingredient (a), due to the
large effect of addition of the condensed heterocyclic compound of
the present invention, a synthetic rubber, polyolefin,
polystyrene-based resin, polyester, polycarbonate, polyamide, or
other synthetic polymer which is used for applications where heat
resistance is demanded are preferable, while a synthetic rubber is
more preferable.
[0118] The synthetic rubber which can form the composition of the
present invention is not particularly limited, but for example,
rubber in which conjugated diene units are contained such as
isoprene rubber, butadiene rubber, butyl rubber, chloroprene
rubber, styrene-butadiene copolymer rubber, acrylonitrile-butadiene
copolymer rubber (nitrile rubber), styrene-butadiene-isoprene
copolymer rubber, butadiene-isoprene copolymer rubber, and
acrylonitrile-styrene-butadiene copolymer rubber; Acrylic rubber,
hydrin rubber, ethylenepropylene rubber; etc. may be mentioned.
These synthetic rubbers may also have hydroxyl groups, carboxyl
groups, alkoxysilyl groups, amino groups, epoxy groups, etc.
Further, these rubbers may also be hydrogenated. For example,
Hydrogenated acrylonitrile-butadiene copolymer rubber (hydrogenated
nitrile rubber) may be mentioned. These synthetic rubbers may be
used alone or may be used as two or more types combined. Among
these as well, in particular, application to an acrylic rubber or
hydrogenated nitrile rubber from which a high heat resistance is
sought is preferable from the viewpoint of the effect of
improvement of the heat resistance, while application to acrylic
rubber is more preferable.
[0119] (Acrylic Rubber)
[0120] The acrylic rubber which can be used in the present
invention is rubber which has (meth)acrylic acid ester monomer
units in 50 to 100 wt % and cross-linkable monomer units in 10 to 0
wt % and, units of other monomers which are copolymerizable with
the monomers which form these monomer units in 50 to 0 wt % added
in accordance with need. By adjusting the ratios of the monomer
units which form the acrylic rubber, it is possible to adjust the
rubber physical properties. Further, in the present invention,
"(meth)acryl" indicates acryl and/or methacryl.
[0121] An acrylic rubber is known as a rubber which is superior in
oil resistance, in particular oil resistance under a high
temperature, and which is excellent in heat resistance. Demand has
been increasing for it for automobile-use hoses, oil seals, and
O-rings and for conveyor belts built into equipment and
facilities.
[0122] The (meth)acrylic acid ester monomer which forms the
(meth)acrylic acid ester monomer units as the main ingredient of an
acrylic rubber, is not particularly limited, but, for example, as
preferable ones, a (meth)acrylic acid alkyl ester monomer,
(meth)acrylic acid alkoxyalkyl ester monomer, etc. may be
mentioned.
[0123] The (meth)acrylic acid alkyl ester monomer is not
particularly limited, but esters of C.sub.1 to C.sub.8 alkanols and
(meth)acrylic acid are preferable, specifically, methyl
(meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate,
n-butyl (meth)acrylate, isopropyl (meth)acrylate, isobutyl
(meth)acrylate, n-hexyl(meth)acrylate, 2-ethylhexyl (meth)acrylate,
cyclohexyl (meth)acrylate, etc. may be mentioned. Among these as
well, ethyl (meth)acrylate and n-butyl (meth)acrylate are
preferable, while ethyl acrylate and n-butyl acrylate are more
preferable. These may be used as single type alone or two or more
types combined.
[0124] The (meth)acrylic acid alkoxyalkyl ester monomer is not
particularly limited, but esters of C.sub.2 to C.sub.8 alkoxyalkyl
alcohols and (meth)acrylic acid are preferable, specifically,
methoxymethyl (meth)acrylate, ethoxymethyl (meth)acrylate,
2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate,
2-propoxyethyl(meth)acrylate, 2-butoxyethyl(meth)acrylate,
3-methoxypropyl (meth)acrylate, 4-methoxybutyl(meth)acrylate, etc.
may be mentioned. Among these as well, 2-ethoxyethyl (meth)acrylate
and 2-methoxyethyl (meth)acrylate are preferable, while
2-ethoxyethyl acrylate and 2-methoxyethyl acrylate are particularly
preferable. These may be used as single type alone or two or more
types combined.
[0125] In the acrylic rubber, the content of the (meth)acrylic acid
ester monomer units is 50 to 100 wt %, preferably 60 to 99.5 wt %,
more preferably 70 to 99.5 wt %. If the content of the
(meth)acrylic acid ester monomer units is too small, the obtained
cross-linked rubber is liable to fall in weather resistance, heat
resistance, and oil resistance.
[0126] The (meth)acrylic acid ester monomer units are preferably
comprised of (meth)acrylic acid alkyl ester monomer units in 30 to
100 wt % and (meth)acrylic acid alkoxyalkyl ester monomer units in
70 to 0 wt %.
[0127] The cross-linkable monomer which forms the cross-linkable
monomer units is not particularly limited, but an
.alpha.,.beta.-ethylenically unsaturated carboxylic acid monomer; a
monomer which has halogen atom or epoxy group; a diene monomer;
etc. may be mentioned.
[0128] These cross-linkable monomers can be used as single type
alone or as two or more types combined. In the acrylic rubber, the
content of the cross-linkable monomer units is 0 to 10 wt %,
preferably 0.5 to 7 wt %, more preferably 0.5 to 5 wt %. If the
content of these cross-linkable monomer units is too great, the
obtained cross-linked rubber product may fall in elongation or
increase in the rate of compression set.
[0129] Other monomers which is copolymerizable with the above
monomers are not particularly limited, but, for example, an
aromatic vinyl monomer, .alpha.,.beta.-ethylenically unsaturated
nitrile monomer, a monomer which has two or more acryloyloxy
groups, olefin-based monomer, vinyl ether compound, etc. may be
mentioned.
[0130] These copolymerizable other monomers may be used as a single
type alone or two or more types combined. In the acrylic rubber,
the content of the units of the other monomer is 0 to 50 wt %,
preferably 0 to 39.5 wt %, more preferably 0 to 29.5 wt %.
[0131] The acrylic rubber which is used in the present invention
can be obtained by polymerizing the above monomers. As the type of
the polymerization reaction, any of the emulsion polymerization
method, suspension polymerization method, bulk polymerization
method, and solution polymerization method can be used, but from
the viewpoint of the ease of control of the polymerization reaction
and other factors, use of the emulsion polymerization method under
ordinary pressure, which is generally used as the method of
production of conventional known acrylic rubber, is preferable.
[0132] The emulsion polymerization may be either of the batch type,
semi batch type, or continuous type. The polymerization is usually
performed at 0 to 70.degree. C., preferably 5 to 50.degree. C. in
temperature range.
[0133] The thus produced acrylic rubber which is used in the
present invention has a Mooney viscosity (ML.sub.1+4, 100.degree.
C.) (Polymer Mooney) of preferably 10 to 80, more preferably 20 to
70, furthermore preferably 25 to 60.
[0134] (Hydrogenated Nitrile Rubber)
[0135] The hydrogenated nitrile rubber which can be used in the
present invention is a nitrile rubber which has
.alpha.,.beta.-ethylenically unsaturated nitrile monomer units and
conjugated diene monomer units, and monomer units which are derived
from other monomer which is copolymerizable with the monomers which
form the monomer units added in accordance with need and which is
hydrogenated (hydrogenation reaction). Hydrogenated nitrile rubber,
which is obtained by hydrogenating at least part of the
carbon-carbon unsaturated bonds which the conjugated diene monomer
units have, so is known as rubber which is superior in heat
resistance, sour gasoline resistance, and ozone resistance and is
known as a high performance material at a high temperature in
applications such as seals, hoses and packing.
[0136] The .alpha.,.beta.-ethylenically unsaturated nitrile monomer
which forms the .alpha.,.beta.-ethylenically unsaturated nitrile
monomer units is not particularly limited, but, for example,
acrylonitrile, methacrylonitrile, .alpha.-chloroacrylonitrile, etc.
may be mentioned. Among these as well, acrylonitrile is preferable.
These may be used as single type alone, but may also be used
jointly as several types. The content of the
.alpha.,.beta.-ethylenically unsaturated nitrile monomer units in
the hydrogenated nitrile rubber is preferably 10 to 60 wt %, more
preferably 12 to 55 wt %, furthermore preferably 15 to 50 wt %.
Depending on the content of the .alpha.,.beta.-ethylenically
unsaturated nitrile monomer units, the oil resistance, cold
resistance, heat resistance, sour gasoline resistance, ozone
resistance, and other properties differ, it can be widely selected
in accordance with the applications.
[0137] The conjugated diene monomer which forms the conjugated
diene monomer units is not particularly limited, but for example,
1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene,
1,3-pentadiene, etc. may be mentioned, while 1,3-butadiene is
preferable. The content of the conjugated diene monomer units in
the hydrogenated nitrile rubber is preferably 40 to 90 wt %, more
preferably 45 to 88 wt %, furthermore preferably 50 to 85 wt %.
[0138] Further, the other monomer described above is not
particularly limited, but a diene monomer other than a conjugated
diene monomer, .alpha.-olefin, .alpha.,.beta.-ethylenically
unsaturated carboxylic acid ester, aromatic vinyl-based monomer,
fluorine-containing vinyl-based monomer,
.alpha.,.beta.-ethylenically unsaturated monocarboxylic acid,
.alpha.,.beta.-ethylenically unsaturated dicarboxylic acid,
anhydride of an .alpha.,.beta.-ethylenically unsaturated
dicarboxylic acid, copolymerizable antiaging agent, etc. may be
illustrated. These copolymerizable other monomers may be jointly
used in a plurality of types.
[0139] The method of production of the nitrile rubber is not
particularly limited. In general, the method of copolymerizing the
.alpha.,.beta.-ethylenically unsaturated nitrile monomer,
conjugated diene monomer, and other monomer, which is added in
accordance with need, copolymerizable with these is simple and
preferable. As the polymerization method, any of the known emulsion
polymerization method, suspension polymerization method, bulk
polymerization method, and solution polymerization method may be
employed, but due to the ease of control of the polymerization
reaction, the emulsion polymerization method is preferable.
[0140] The nitrile rubber which is produced is hydrogenated to make
it a hydrogenated nitrile rubber whereby the heat resistance, sour
gasoline resistance, and ozone resistance are further improved. The
method of performing the hydrogenation (hydrogenation reaction) is
not particularly limited. A known method can be employed.
[0141] The hydrogenated nitrile rubber is also not particularly
limited in iodine value (measured in accordance with JIS K6235).
When performing a hydrogenation reaction, it is preferably 120 or
less, more preferably 60 or less, furthermore preferably 30 or
less. If the iodine value is too high, the heat resistance becomes
poor.
[0142] The hydrogenated nitrile rubber has a Mooney viscosity
(ML.sub.1+4, 100.degree. C.) (Polymer Mooney) of preferably 15 to
200, more preferably 30 to 150, particularly preferably 45 to 120.
If the hydrogenated nitrile rubber is too low in Mooney viscosity,
the cross-linked rubber is liable to fall in mechanical properties,
while conversely if it is too high in Mooney viscosity, the
workability may fall.
[0143] The composition of the present invention may contain, in
addition to the ingredient (a) and the ingredient (b), other
additives.
[0144] As the other additives, additives which are usually used in
the field of synthetic polymer materials may be mentioned. For
example, reinforcing fillers such as carbon black, and silica;
nonreinforcing fillers such as calcium carbonate, and clay; photo
stabilizers; scorch retarders; plasticizers; processing aids; slip
agents; tackifiers; lubricants; flame retardants; antifungal
agents; antistatic agents; coloring agents; silane coupling agents;
cross-linking agents; cross-linking accelerators; cross-linking
retardants; etc. may be mentioned.
[0145] The amounts of these additives are not particularly limited
so long as in ranges not detracting from the object and effects of
the present invention. Amounts in accordance with the purpose of
compounding can be suitably blended.
[0146] The composition of the present invention can be prepared by
mixing and kneading the ingredient (a), ingredient (b), and other
additives as desired in predetermined amounts by a Bambury mixer,
kneader, etc., next, further kneading them by a kneading roll.
[0147] The order of blending in the ingredients is not particularly
limited, but it is preferable to first fully mix the ingredients
which are resistant to reaction and decomposition by heat, then mix
in the ingredients which easily react or decompose due to heat such
as the cross-linking agent etc. in a short time at a temperature at
which the reaction or decomposition will not occur.
[0148] According to the composition of the present invention, it is
possible to impart high processing stability and heat resistance,
and long life to a polymer or other organic material which is
susceptible to oxidation, heat, or light induced breakdown.
EXAMPLES
[0149] Below, examples, manufacturing examples, and comparative
examples will be give to explain the present invention more
specifically, but the present invention is not limited to these
examples.
Example 1
Synthesis of Compound 1
[0150] The following method was followed to synthesize the compound
1 of the following formula (X).
##STR00009##
[0151] That is, first, a three-necked reactor which was equipped
with a thermometer was charged with, in a nitrogen stream,
phenothiazine 50.0 g (250.92 mmol), then this was made to dissolve
in toluene 200 ml. Next, to this solution, .alpha.-methylstyrene
59.31 g (501.83 mmol) and p-toluenesulfonic acid monohydrate 1.19 g
(6.27 mmol) were added and the result made to react at 80.degree.
C. for 1 hour. After that, the reaction solution was returned to
room temperature, then acetic acid 48 ml and 30% hydrogen peroxide
solution 85.34 g (752.7 mmol) were added and the result further
made to react at 80.degree. C. for 2 hours. The reaction solution
was returned to room temperature, then was charged into methanol
630 ml. The precipitated crystal was filtered and was rinsed by 320
ml of methanol to thereby obtain a white crystal compound 1 in 85.7
g for a yield of 73%. The structure was identified by
.sup.1H-NMR.
[0152] .sup.1H-NMR (500 MHz, DMSO-d6, TMS, .delta.ppm): 1.67 (s,
12H), 7.15-7.32 (m, 12H), 7.43 (dd, 2H, J=9.0, 2.0 Hz), 7.68 (d,
2H, J=1.5 Hz), 10.84 (s, 1H).
Example 2
Synthesis of Compound 2
[0153] The following method was followed to synthesize the compound
2 which is shown in the following formula (XI).
##STR00010##
[0154] That is, first, a three-necked reactor which was equipped
with a thermometer was charged, in a nitrogen stream, with
phenothiazine 30.0 g (150.55 mmol), then this was made to dissolve
in toluene 175 ml. Next, to this solution, .alpha.-methylstyrene
35.58 g (301.10 mmol) and p-toluenesulfonic acid monohydrate 0.72 g
(3.76 mmol) were added and the result reacted at 80.degree. C. for
1 hour. The reaction solution was returned to room temperature,
then acetic acid 60 ml was added, 30% hydrogen peroxide solution
17.07 g (150.55 mmol) was slowly added dropwise over 30 minutes,
and the result was further reacted at room temperature for 2 hours.
After that, the reaction solution was charged with methanol 760 ml
and the precipitated crystal was filtered, then rinsed by 380 ml of
methanol to thereby obtain a white crystal compound 2 in 55.5 g for
a yield of 82%. The structure was identified by .sup.1H-NMR.
[0155] .sup.1H-NMR (500 MHz, DMSO-d6, TMS, .delta.ppm): .delta.
1.68 (s, 6H), 1.70 (s, 6H), 7.15-7.32 (m, 12H), 7.38 (dd, 2H,
J=9.0, 2.0 Hz), 7.70 (d, 2H, J=1.5 Hz), 10.85 (s, 1H).
Example 3
Synthesis of Compound 3
[0156] The following method was followed to synthesize the compound
3 of the following formula (XII). Note that, when synthesizing the
compound 3, this was synthesized by first obtaining the
intermediate A which is shown by the following formula (XIII) and
oxidizing the obtained intermediate A.
##STR00011##
[0157] First, the following method was used to produce the
intermediate A. That is, a two-necked reactor was charged with
phenothiazine 13.34 g (66.94 mmol) and sodium p-toluenesulfinate
13.12 g (73.63 mmol), then these were made to dissolve in methanol
500 ml. To this solution, potassium acetate 13.14 g (133.9 mmol)
and iron trichloride 86.87 g (538.6 were added and the total volume
was made to react under refluxing conditions for 3 hours. After
that, the reaction solution was concentrated by an evaporator down
to 50 ml or so, then 0.2N hydrochloric acid aqueous solution 300 ml
and saturated sodium chloride solution 500 ml were added and the
result was extracted by ethyl acetate 800 ml. The extracted organic
phase was further washed by 0.1N sodium hydroxide aqueous solution
200 ml, dried over anhydrous sodium sulfate, then concentrated by a
rotary evaporator. The concentrate was made to dissolve in
tetrahydrofuran (THF) and methanol was added to cause it to
reprecipitate to thereby obtain a white crystal intermediate A in
12.07 g (yield 51%). The structure of the obtained intermediate A
was identified by .sup.1H-NMR.
[0158] .sup.1H-NMR (500 MHz, DMSO-d6, TMS, .delta.ppm): 2.36 (s,
3H), 6.66 (d, 1H, J=7.5 Hz), 6.72 (d, 1H, J=8.5 Hz), 6.80 (t, 1H,
J=7.5 Hz), 6.90 (d, 1H, J=7.5 Hz), 7.00 (t, 1H, J=7.5 Hz), 7.37 (d,
1H, J=1.5 Hz), 7.39 (d, 2H, J=8.0 Hz), 7.48 (dd, 1H, J=8.5, 1.5
Hz), 7.77 (d, 2H, J=8.0 Hz), 9.17 (s, 1H).
[0159] Next, the obtained intermediate A was used in accordance
with the following method to obtain the compound 3. That is, first,
a two-necked reactor was charged with the intermediate A 11.0 g
(31.12 mmol) which was obtained above, then this was made to
dissolve in THF 800 ml. Next, to this solution, acetic acid 600 ml
and 30% hydrogen peroxide solution 21.17 g (186.7 mmol) were added
and the total volume was made to react at 80.degree. C. for 2
hours. The reaction solution was returned to room temperature, then
was charged into distilled water 4 liters. The precipitated crystal
was filtered. The obtained crystal was made to dissolve in THF and
n-hexane was added to cause it to reprecipitate to thereby obtain a
white crystal compound 3 in 11.05 g for a yield of 93%. The
structure of the obtained compound 3 was identified by
.sup.1H-NMR.
[0160] .sup.1H-NMR (500 MHz, DMSO-d6, TMS, .delta.ppm). 2.37 (s,
3H), 7.36 (t, 1H, J=7.5 Hz), 7.41 (d, 1H, J=8.5 Hz), 7.44 (d, 2H,
J=8.0 Hz), 7.51 (d, 1H, J=9.0 Hz), 7.73 (t, 1H, J=8.0 Hz), 7.84 (d,
2H, J=8.0 Hz), 7.99 (d, 1H, J=8.0 Hz), 8.12 (dd, 1H, J=9.0, 1.5
Hz), 8.34 (d, 1H, J=1.5 Hz), 11.53 (s, 1H).
Example 4
Synthesis of Compound 4
[0161] The following method was followed to synthesize the compound
4 of the following formula (XIV). Note that, when synthesizing the
compound 4, this was synthesized by first obtaining the
intermediate B which is shown by the following formula (XV), next
obtaining the intermediate C which is shown by the following
formula (XVI) from the obtained intermediate B, and finally
oxidizing the obtained intermediate C.
##STR00012##
[0162] First, the following method was used to produce the
intermediate B. That is, a two-necked reactor was charged with
carbazole 25.0 g (149.5 mmol) and iodine 30.36 g (239.2 mmol), then
these were made to dissolve in ethanol 600 ml. Next, to this
solution, sodium periodate 12.8 g (59.80 mmol) was added. Further,
concentrated sulfuric acid 1 g was slowly added dropwise, then the
total volume was made to react at 65.degree. C. for 3 hours. After
that, the reaction solution was returned to room temperature, was
concentrated by a rotary evaporator down to 150 ml or so, then the
concentrated solution was charged with distilled water 500 ml and
saturated sodium chloride solution 300 ml and the result was
extracted by chloroform 1000 ml. The organic layer was made to dry
over anhydrous sodium sulfate, was concentrated by a rotary
evaporator, then the concentrate was charged with n-hexane to
recrystallize it and thereby obtain the intermediate B in 34.4 g
for a yield of 55%. The structure of the obtained intermediate B
was identified by .sup.1H-NMR.
[0163] .sup.1H-NMR (500 MHz, DMSO-d6, TMS, .delta.ppm): 7.35 (d,
2H, J=8.5 Hz), 7.66 (dd, 2H, J=8.5, 1.5 Hz), 8.57 (d, 2H, J=1.5
Hz), 11.54 (s, 1H).
[0164] Next, the obtained intermediate B was used in accordance
with the following method to obtain the intermediate C. That is,
first, a two-necked reactor was charged with, in a nitrogen stream,
the intermediate B 15.0 g (35.80 mmol) which was obtained above and
p-toluenethiol 9.34 g (75.18 mmol), then these were made to
dissolve in toluene 350 ml. Next, to this solution, sodium
tert-butoxide 17.20 g (179.0 mmol), [1,1'-bis(diphenylphosphino)
ferrocene]palladium (II) dichloride dichloromethane adduct 0.73 g
(0.895 mmol) were added and the total volume was made to react at
80.degree. C. for 4 hours. After that, the reaction solution was
returned to room temperature, distilled water 1000 ml and saturated
sodium chloride solution 500 ml were added, and the result was
extracted by ethyl acetate 500 ml. The organic layer was made to
dry over anhydrous sodium sulfate, was concentrated by a rotary
evaporator, then was purified by silica gel column chromatography
(n-hexane:tetrahydrofuran=3:1 (volume ratio)) to thereby obtain the
intermediate C in 9.14 g for a yield of 62%. The structure of the
obtained intermediate C was identified by .sup.1H-NMR.
[0165] .sup.1H-NMR (500 MHz, CDCl3, TMS, .delta.ppm): 2.29 (s, 6H),
7.05 (d, 4H, J=8.0 Hz), 7.15 (d, 4H, J=8.0 Hz), 7.37 (d, 2H, J=8.5
Hz), 7.51 (dd, 2H, J=8.5, 1.5 Hz), 8.12 (d, 2H, J=1.5 Hz), 8.18 (s,
1H).
[0166] Next, the obtained intermediate C was used in accordance
with the following method to obtain the compound 4. That is, first,
a two-necked reactor was charged with the intermediate C 8.00 g
(19.44 mmol) which was obtained above, then this was made to
dissolve in THF 160 ml. To this solution, acetic acid 240 ml and
30% hydrogen peroxide solution 13.22 g (116.6 mmol) were added, and
the total volume was made to react at 80.degree. C. for 10 hours.
The reaction solution was returned to room temperature, then was
charged into distilled water 1.5 liters. The precipitated crystal
was filtered, made to dissolve in THF, and reprecipitated by adding
methanol to thereby obtain a white crystal compound 4 in 8.04 g for
a yield of 87%. The structure of the obtained compound 4 was
identified by .sup.1H-NMR.
[0167] .sup.1H-NMR (500 MHz, DMSO-d6, TMS, .delta.ppm): 2.34 (s,
6H), 7.40 (d, 4H, J=8.0 Hz), 7.71 (d, 2H, J=8.5 Hz), 7.89 (d, 4H,
J=8.0 Hz), 7.99 (dd, 2H, J=8.5, 1.5 Hz), 9.11 (d, 2H, J=1.5 Hz),
12.33 (s, 1H).
Manufacturing Example 1
Synthesis of Compound 5
[0168] The following method was followed to synthesize the compound
5 which is shown in the following formula (XVII).
##STR00013##
[0169] That is, first, a two-necked reactor was charged with
phenothiazine 20.0 g (100.4 mmol), then this was made to dissolve
in acetic acid 200 ml. Next, to this solution, 30% hydrogen
peroxide solution 34.13 g (301.1 mmol) was added, and the total
volume was made to react at 80.degree. C. for 2 hours. After that,
the reaction solution was returned to room temperature, charged
with distilled water 100 ml, and further was stirred for 1 hour.
The precipitated crystal was filtered and made to dry to thereby
obtain an orange colored crystal of the compound 5 in 20.5 g for a
yield of 88%. The structure of the obtained compound 5 was
identified by .sup.1H-NMR.
[0170] .sup.1H-NMR (500 MHz, DMSO-d6, TMS, .delta.ppm): 7.25 (t,
2H, J=8.0 Hz), 7.35 (d, 2H, J=8.0 Hz), 7.66 (t, 2H, J=8.0 Hz), 7.93
(d, 2H, J=8.0 Hz), 10.94 (s, 1H).
Examples 5 to 10
Preparation of Rubber Compositions
[0171] The compounds 1 to 4 which were produced in Examples 1 to 4
(antiaging agents) were used in the amounts described in the
following Table 1 and kneaded together with an acrylic elastomer
(made by Zeon Corporation, Nipol AR22) 100 g, carbon black (made by
Tokai Carbon, Seast SO) 60 g, and stearic acid 2 g using a Bambury
mixer at 50.degree. C., then the obtained mixtures were charged
with predetermined amounts of a cross-linking agent and
cross-linking accelerator and the results kneaded by open rolls to
prepare the rubber compositions of Examples 5 to 10.
[0172] Note that, as the cross-linking agent, hexamethylenediamine
carbamate (made by Dupont Dow Elastomer Japan, Diak No. 1) (below,
referred to as the "cross-linking agent A") was used.
[0173] Further, as the cross-linking accelerator,
1,3-di-o-tolylguanidine (made by Ouchi Shinko Chemical Industrial,
Nocceler DT) (below, referred to as the "cross-linking accelerator
A") was used.
TABLE-US-00001 TABLE 1 Table 1 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10
Antiaging agent Compound 1 Compound 1 Compound 1 Compound 2
Compound 3 Compound 4 Amount added (g) 1.58 4.12 5.96 5.75 4.91
6.05 moles (mmol) 3.39 8.81 12.73 12.73 12.73 12.73
Comparative Examples 1 to 10
Preparation of Rubber Compositions
[0174] The antiaging agents which are shown in the following Table
2 were used in the amounts which are described in the following
Table 3 and kneaded with an acrylic elastomer (made by Zeon
Corporation, Nipol AR22) 100 g, carbon black (made by Tokai Carbon,
Seast SO) 60 g, and stearic acid 2 g using a Bambury mixer at
50.degree. C., then the obtained mixtures were charged with
predetermined amounts of the cross-linking agent A and
cross-linking accelerator A and kneaded by open rolls to prepare
the rubber compositions of Comparative Examples 1 to 10.
TABLE-US-00002 TABLE 2 Antiaging agent Compound (manufacturer name,
product name) A Diphenylamine B 4,4'-di-t-butyldiphenylamine (made
by Seiko Chemical, Stearer STAR) C
4,4'-bis(.alpha.-methylbenzyl)diphenylamine and
4-(.alpha.-methylbenzyl)diphenylamine in mixture (made by Seiko
Chemical, Nonflex LAS-P) D N,N'-di-2-naphthyl-p-phenylenediamine
(made by Ouchi Shinko Chemical Industrial, Nocrac White) E
N,N'-diphenyl-p-phenylenediamine (made by Ouchi Shinko Chemical
Industrial, Nocrac DP) F 4,4'-di-n-octyldiphenylamine (made by
Ouchi Shinko Chemical Industrial, Nocrac AD-F) G Carbazole H
Compound 5 I 4,4'-bis(.alpha.,.alpha.-dimethylbenzyl)diphenylamine
(made by Chemtura, Nauguard 445)
TABLE-US-00003 TABLE 3 Comp. Ex. 1 Comp. Ex. 2 Comp. Ex. 3 Comp.
Ex. 4 Comp. Ex. 5 Antiaging agent None Antiaging Antiaging
Antiaging Antiaging agent A agent B agent C agent D Amount added
(g) -- 0.84 1.12 1.94 1.78 moles (mmol) -- 4.93 4.93 4.93 4.93
Comp. Ex. 6 Comp. Ex. 7 Comp. Ex. 8 Comp. Ex. 9 Comp. Ex. 10
Antiaging agent Antiaging Antiaging Antiaging Antiaging Antiaging
agent E agent F agent G agent H agent I Amount added (g) 1.28 1.94
2.13 2.94 6.05 moles (mmol) 4.93 4.93 12.73 12.73 12.73
[0175] The rubber compositions which were obtained in Examples 5 to
10 and Comparative Examples 1 to 10 were molded by a press and
cross-linked at 170.degree. C. for 20 minutes to prepare 15
cm.times.15 cm.times.2 cm sheets. Further, these sheets were heated
at 170.degree. C. for 4 hours to cause secondary cross-linking. The
sheets were used as test pieces.
[0176] <Test for Evaluation of Heat Resistance>
[0177] The test pieces which were prepared in Examples 5 to 10 and
Comparative Examples 1 to 10 were measured for elongation in
accordance with JIS K6301 before and after a heat degradation test
where they were allowed to stand in an environment of 190.degree.
C. for 504 hours. The following calculation formula was used to
calculate the rates of change. The closer the rate of change to
zero, the higher the heat resistance is judged and the more
preferable the result.
Rate of change (%)=[(elongation after test (%))-(elongation before
test (%))]/(elongation before test (%))].times.100
[0178] The results of evaluation of the heat resistance are
summarized in Table 4. Note that, in Table 4, the elongation at
break before the heat degradation test (%) and the rate of change
of the elongation at break before and after the heat degradation
test (%) are shown.
TABLE-US-00004 TABLE 4 Rate of change in elongation after 504
Elongation at break (%) hours (%) Example 5 260 -65 Example 6 260
-63 Example 7 270 -62 Example 8 270 -63 Example 9 240 -75 Example
10 230 -78 Comparative Example 1 250 -93 Comparative Example 2 260
-89 Comparative Example 3 260 -88 Comparative Example 4 250 -89
Comparative Example 5 260 -87 Comparative Example 6 270 -87
Comparative Example 7 260 -86 Comparative Example 8 235 -90
Comparative Example 9 240 -89 Comparative Example 10 280 -84
[0179] From Table 4, the rubber compositions of Examples 5 to 10
which contain the compounds 1 to 4 of Examples 1 to 4 (condensed
heterocyclic compounds of the present invention) had rates of
change of elongation before and after heat degradation tests of
-78% to -62% and values close to zero compared with a rubber
composition not containing any antiaging agent (Comparative Example
1) and rubber compositions containing conventional antiaging agents
(Comparative Examples 2 to 10).
[0180] Accordingly, it is learned that the compounds 1 to 4 of
Examples 1 to 4 (condensed heterocyclic compounds of present
invention) have excellent stabilizing actions on acrylic elastomers
compared with conventional antiaging agents (antiaging
performance).
* * * * *