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Cyclic Carbodiimide Compound
Abstract: Disclosed is a cyclic carbodiimide compound represented by formula (i) the compound being useful as a terminal blocking agent for polymers. (In formula (i) X is a specific di or tetravalent group; q is 0 when X is the divalent group and is 1 when X is the tetravalent group; and Ar to Ar each independently is selected from optionally substituted aromatic groups depending on the group X.)
Notices, Deadlines & Correspondence
Patent Information
Applicants
TEIJIN LIMITED
Inventors
1. SHOJI Shinichiro
Specification
Description
CYCLIC CARBODIIMIDE COMPOUND
Technical Field
The present invention relates to a carbodiimide
compound. More specifically, the invention relates to a cyclic carbodiimide compound.
Background Art
Polyesters, polyamides, polyimides, polycarbonates,
polyurethanes, and the like have excellent mechanical
physical properties and thus have been used for a wide
variety of applications. These polymers have a
hydrolyzable ester bond, amide bond, imide bond, carbonate
bond, or urethane bond in the molecule. Accordingly, when
they are used in a more severe environment, a problem with
reliability may occur, against which urgent
countermeasures have been demanded.
The catalytic hydrolysis of a hydrolyzable bond such
as an ester bond is promoted by the presence of a polar
group such as a carboxyl group in the molecule. Therefore,
a method for suppressing such a disadvantage by applying a
carboxyl-group-capping agent to reduce the carboxyl group
concentration has been proposed (Patent Document 1 and
1
m
Patent Document 2).
As a capping agent for carboxyl groups and like
acidic groups, a mono- or polycarbodiimide compound has
been used considering the stability and reactivity of the
capping agent, the color tone of the resulting product,
and the like, and this has been effective to a certain
degree. However, mono- and polycarbodiimide compounds are
both linear carbodiimide compounds and thus have an
intrinsic defect in that when they are used, a volatile
isocyanate compound is by-produced, generating an
offensive odor, whereby the working environment is
deteriorated. There is a demand for the development of a
capping agent that is free of such a defect and has higher
reactivity.
Patent Document 3 describes a macrocyclic
carbodiimide compound having a urethane bond and a polymer
chain with a molecular weight of 100 to 7,000.
Macrocyclic carbodiimide compounds have high molecular
weight and thus are inefficient as acidic-group-capping
agents. In addition, the prevention of an offensive odor
is not considered in Patent Document 3.
[Patent Document 1] JP-A-2004-332166
[Patent Document 2] JP-A-2005-350829
[Patent Document 3] WO 2008/081230
2
Disclosure of the Invention
An object of the inveniton is to provide a cyclic
carbodiimide compound useful as a stabilizer for polymers
having a hydrolyzable functional group, such as polyesters.
Another object of the inveniton is to provide a method for
producing the cyclic carbodiimide compound. Another
object of the inveniton is to provide an end-capping agent
for polymer compounds, which contains the cyclic
carbodiimide compound as an active ingredient. Still
another object of the inveniton is to provide an acidic
group scavenger, which contains the cyclic carbodiimide
compound as an active ingredient.
Means for Solving the Problems
The present inventors conducted extensive research
on capping agents whose reaction with an acidic group,
such as a carboxyl group, does not causes the release of
an isocyanate compound. As a result, they have found that
the reaction of a carbodiimide compound having a ring I
structure with an acidic group does not cause the release
of an isocyanate compound, whereby an offensive odor is
not generated and the working environment is not
deteriorated. The invention has thus been accomplished.
That is, the invention includes the following
inventions.
3
1. A cyclic carbodiimide compound represented by the
following formula (i):
^ \ / II
Y x' C
N /O \ ^N
^Ar^ L V J„
^ (i)
wherein
X is a divalent group represented by any one of the
following formulae (i-1) to (i-6) or a tetravalent group
represented by any one of the following formulae (i-7) and
(i-8) ,
when X is a divalent group, q is 0, and in the case
where X is selected from (i-1) and {i-2) , Ar^ and Ar^ are
each independently an aromatic group substituted with a
substituent other than a Ci-g alkyl group and a phenyl
group, while in the case where X is selected from (i-3) to
(i-6) , Ar^ and Ar^ are each independently an aromatic
group optionally substituted with a substituent, and
when X is a tetravalent group, q is 1, and Ar^ to Ar^
are each independently an aromatic group substituted with
a substituent other than a Ci-e alkyl group and a phenyl
group:
( i - 1 )
4
wherein h is an integer of 1 to 6,
_(_CH,4-^-(-CH,^
(i-2)
wherein m and n are each independently an integer of 0 to
3,
m'
(i-3)
wherein in' and n' are each independently an integer of 0
to 3, Q
-i—cA H2cJ—
(i-4)
wherein m'' and n'' are each independently an integer of 0
to 3,
(i-5)
wherein Y and Z are each an oxygen atom or a sulfur atom,
j, k, and r are each independently an integer of 1 to 4,
5
and i is an integer of 0 to 3,
-(-c')^0—Ar^-0-(-c')^
(i-6)
wherein Ar^ is an aromatic group, and s and t are each
independently an integer of 1 to 3,
V
/ CH2 H2C (i-7)
wherein R^ and R^ each independently represent a Ci-e alkyl
group or a phenyl group,
H2 H2
/ —CH2 c—
"2 (i-8) .
2. The compound according to the item 1 above, wherein
Ar^ to Ar^ are each independently an o-phenylene group or
1,2-naphthalene-diyl group substituted with a substituent
other than a Ci-e alkyl group and a phenyl group.
3. A method for producing the cyclic carbodiimide
compound of the item 1 above, including:
(1) a step (la) of allowing a compound of the I
following formula (a-1) and a compound of the following
formula (a-2) to react with a compound of the following
6
#
formula (b-1) to give a nitro compound of the following
formula (c):
HO Ar^ NO2 (^_i)
HO Ar^ NO2 (^_2)
E^ X E^ (^.,)
O X O
Ar^ Ar2
NO2 NO2 (^)
wherein
X, Ar^, and Ar^ are as defined in formula (i), with
the proviso that X is a divalent group, and in the case
where X is selected from (i-1) and (i-2) , Ar^ and Ar^ are
each independently an aromatic group substituted with a i
substituent other than a Ci-6 alkyl group and a phenyl
group, while in the case where X is selected from (i-3) to
(i-6) , Ar''" and Ar^ are each independently an aromatic
group optionally substituted with a substituent, and
E""" and E^ are each independently a group selected
from the group consisting of a halogen atom, a
toluenesulfonyloxy group, a methanesulfonyloxy group, a
benzenesulfonyloxy group, and a p-bromobenzenesulfonyloxy
group;
(2) a step (2a) of reducing the obtained nitro
compound to give an amine compound represented by the
7
#
following formula (d):
O X O
Ari Ar2
NH, NH^ ^^^ ,
(3) a step (3a) of allowing the obtained amine i
compound to react with triphenylphosphine dibromide to
give a triphenylphosphine compound represented by the
following formula (e-1):
/ I
N N
PAr-3 PAr^3 (e-i)
wherein Ar^ is a phenyl group; and
(4) a step (4a) of isocyanating the obtained
triphenylphosphine compound in a reaction system, followed
by direct decarboxylation to give a compound of the
following formula (f):
o-x-o
A? Ar2
\ /
N:^C=N (f) .
4. The method for producing the cyclic carbodiimide
compound of the item 1 above according to the item 3 above,
wherein the step (la) is replaced with a step (lb) of
8
allowing a compound of the following formula (a-i) and a
compound of the following formula (a-ii) to react with a
compound of the following formula (b-i):
E' Ar^ NO2 (,_ii)
HO X OH (b-i)
wherein
X, Ar^, and Ar^ are as defined in formula (i) , X is
divalent, and in the case where X is selected from (i-1)
and (i-2), Ar^ and Ar^ are each independently an aromatic
group substituted with a substituent other than a Ci-6
alkyl group and a phenyl group, while in the case where X
is selected from (i-3) to (i-6), Ar^ and Ar^ are each
independently an aromatic group optionally substituted
with a substituent, and
E^ and E* are each independently a group selected
from the group consisting of a halogen atom, a
toluenesulfonyloxy group, a methanesulfonyloxy group, a
benzenesulfonyloxy group, and a p-bromobenzenesulfonyloxy
group.
5. The method for producing the cyclic carbodiimide
compound of the item 1 above according to the item 3 above,
wherein
the step (3a) is replaced with a step (3b) of
9
allowing the amine compound to react with carbon dioxide
or carbon disulfide to give a urea compound or thiourea
compound represented by the following formula (e-2):
^o—x-o
\ /
HN C NH
Z (e-2)
wherein
X, Ar""", and Ar^ are as defined in formula (i) , X is
divalent, and in the case where X is selected from (i-1)
and (i-2) , Ar""" and Ar^ are each independently an aromatic
group substituted with a substituent other than a Ci-g
alkyl group and a phenyl group, while in the case where X
is selected from (i-3) to (i-6), Ar^ and Ar^ are each
independently an aromatic group optionally substituted
with a substituent, and
Z is an oxygen atom or a sulfur atom, and
the step (4a) is replaced with a step (4b) of
dehydrating the obtained urea compound or desulfurizing
the obtained thiourea compound.
6. A method for producing the cyclic carbodiimide
compound of the item 1 above, including:
(1) a step (lA) of allowing a compound of any one of
the following formulae (A-1) to (A-4) to react with a
10
compound of the following formula (B-1) to give a nitro
compound of the following formula (C):
HO Ar' NO2 (A-l)
HO k? NO2 (A_2)
HO Ar^ NO2 (A_3)
HO Ar^ NO2 (A_4)
wherein
Ar^ to Ar^ are as defined in formula (i) and are each
independently an aromatic group substituted with a
substituent other than a Ci-s alkyl group and a phenyl
group, and 1
E^ to E"* are each independently a group selected from
the group consisting of a halogen atom, a
toluenesulfonyloxy group, a methanesulfonyloxy group, a
benzenesulfonyloxy group, and a p-bromobenzenesulfonyloxy
group,
/ E' E^ (B-1)
H2 H2
wherein Xi is '^2 ,
I
!
11
N02 N02
n N NO2
O2N (^)
wherein X is as defined in formula (i) , with the proviso
that X is a tetravalent group represented by any one of
formulae (i-7) and (i-8);
(2) a step (2A) of reducing the obtained nitro
compound to give an amine compound of the following
formula (D):
NH2 NH2
Ar^~^^ ^Ar^
°^ ^O
(3) a step (3A) of allowing the obtained amine
compound to react with triphenylphosphine dibromide to
give a triphenylphosphine compound of the following
formula (E-1):
i
i
I
12
%
{
#
N=PAr-3 N=PAr«3
Ari-°^''"°^Ar^
N^PAi^3 N=PAi^3 (g_^j
wherein Ar^ is a phenyl group; and
(4) a step (4A) of isocyanating the obtained
triphenylphosphine compound in a reaction system, followed
by direct decarboxylation to give a compound (F) of the
following formula:
N=C^N
Afi >,r2
N=C=N (F) .
7. The method for producing the cyclic carbodiimide
compound of the item 1 above according to the item 6 above,
wherein the step (lA) is replaced with a step (IB) of
allowing a compound of any one of the following formulae
(A-i) to (A-iv) to react with a compound of the following
formula (B-i) to give a nitro compound of formula (C):
E' Ar^ NO2 (^_i)
E« Ar' NO2 (;,_ii) I
E^ Ar^ NO2 (^_iii) I
13
#
E« Ar^ NO2 (;,_i^)
wherein
Ar""" to Ar^ are as defined in formula (i) and are each
independently an aromatic group substituted with a
substituent other than a Ci-g alkyl group and a phenyl
group, and
E^ to E^ are each independently a group selected from
the group consisting of a halogen atom, a
toluenesulfonyloxy group, a methanesulfonyloxy group, a
benzenesulfonyloxy group, and a p-bromobenzenesulfonyloxy
group,
HO OH
HO OH (B-i)
Hj H2
wherein Xi is ^^ ,
NO2 NO2
Ar^ ^Ar
n M NO2
O2N ((.)
wherein X is as defined in formula (i) , with the proviso
that X is a tetravalent group represented by any one of
formulae (i-7) and (i-8). I
14
I
8. The method for producing the cyclic carbodiimide
compound of the item 1 above according to the item 6 above,
wherein i
the step (3A) is replaced with a step (3B) of
allowing the amine compound to react with carbon dioxide
or carbon disulfide to give a urea compound or thiourea
compound of the following formula (E-2):
Z
HN C NH
3 / \^
Arl Ar
Ar^ \r2
\ /
HN C NH
Z (E-2)
wherein
Ar^ to Ar* are as defined in formula (i) and are each
independently an aromatic group substituted with a
substituent other than a Ci-g alkyl group and a phenyl
group,
X is as defined in formula (i) and is a tetravalent
group represented by any one of formulae (i-7) and (i-8) ,
and
Z is an oxygen atom or a sulfur atom, and
the step (4A) is replaced with a step (4B) of
15
#
dehydrating the obtained urea compound or desulfurizing j
the obtained thiourea compound. I
9. An end-capping agent for polymer compounds, containing
the cyclic carbodiimide compound represented by formula
(i) of the item 1 above as an active ingredient.
10. An acidic group scavenger, containing the cyclic
carbodiimide compound represented by formula (i) of the
item 1 above as an active ingredient.
Advantage of the Invention
The cyclic carbodiimide compound of the invention is
capable of effectively stabilizing a hydrolyzable
component of a polymer compound. At the same time, the
by-production of a free isocyanate compound can also be
suppressed. Even when the cyclic carbodiimide compound of
the invention is used to end-cap a polymer compound, the
generation of an offensive odor from an isocyanate
compound can be suppressed, whereby the working
environment is not deteriorated.
In addition, when a polymer compound is end-capped
with the cyclic carbodiimide compound, isocyanate groups
are produced at the ends of the polymer compound. The
reaction of such isocyanate groups allows the molecular j
16 5
i
I
i
weight of the polymer compound to be increased. |
In addition, the cyclic carbodiimide compound of the
invention also has the function of scavenging free
monomers or other acidic-group-containing compounds in the
polymer compound.
Further, the cyclic carbodiimide compound of the
invention has a ring structure and thus is advantageous in
that ends can be capped under milder conditions as
compared with linear carbodiimide compounds.
According to the production method of the invention,
a cyclic carbodiimide can be easily produced. The cyclic
carbodiimide compound of the invention is useful as an
end-capping agent for polymer compounds. The cyclic
carbodiimide compound of the invention is useful as an
acidic group scavenger, particularly as a scavenger for
free compounds in a polymer compound.
The difference in end-capping reaction mechanism
between a linear carbodiimide compound and a cyclic
carbodiimide compound is as follows.
When a linear carbodiimide compound (R^-N=C=N-R^) is
I
used as an end-capping agent for a polymer compound j
terminated with carboxyl groups, the reaction is as shown
i
in the formula below. In the formula, W is the main chain !
I
of the polymer compound. Through the reaction of the
linear carbodiimide compound with a carboxyl group, an
17
amide group is formed at the end of the polymer compound,
and an isocyanate compound (R'''NCO) is released.
W'wx.cOOH + Ri N=C=N—R2 ^^ W^^CONH—R2 + R1NCO
Meanwhile, when a cyclic carbodiimide compound is
used as an end-capping agent for a polymer compound j
terminated with carboxyl groups, the reaction is as shown
in the formula below. Through the reaction of the cyclic |
I
carbodiimide compound with a carboxyl group, an isocyanate «
group (-NCO) is formed at the end of the polymer compound
via an amide group. It will be understood that no
isocyanate compound is released.
W-wvcOOH + C ^ ^ ^ ^" W'w>cONH-Q-NCO |
N=C=N^ I
In the formula, Q is a divalent to tetravalent I
linking group that is an aliphatic group, an alicyclic
group, an aromatic group, or a combination thereof and
optionally contains a heteroatom and a substituent. j
In addition, when two or more carbodiimides are
present in one ring, this leads to a disadvantage in that I
!
an isocyanate compound is released during the carbodiimide
I!
group reaction.
I
i
Mode for Carrying Out the Invention I
i
s
Hereinafter, the invention will be described in j
I
detail. j
18 I
The invention is a cyclic carbodiimide compound
represented by the following formula (i):
ff \ / \i / \ I
N\r2 L V J^ I
wherein
X is a divalent group represented by any one of the
following formulae (i-1) to (i-6) or a tetravalent group
represented by any one of the following formulae (i-7) and
(i-8) ,
when X is a divalent group, q is 0, and in the case
where X is selected from (i-1) and (i-2) , Ar'^ and Ar^ are
each independently an aromatic group substituted with a
substituent other than a Ci-g alkyl group and a phenyl
group, while in the case where X is selected from (i-3) to
(i-6) , Ar""" and Ar^ are each independently an aromatic
group optionally substituted with a substituent, and
when X is a tetravalent group, q is 1, and Ar"^ to Ar^
are each independently an aromatic group substituted with
a substituent other than a Ci-s alkyl group and a phenyl
group: j
19 j
(i-1)
wherein h is an integer of 1 to 6,
_(_CH,^^-(-CH,^
(i-2)
wherein m and n are each independently an integer of 0 to
3,
m'
\ /n'
(i-3)
wherein m' and n' are each independently an integer of 0
to 3, o
—l—C] HocJ
(i-4)
wherein m'' and n'' are each independently an integer of 0
to 3,
20 j
(i-5)
wherein Y and Z are each an oxygen atom or a sulfur atom,
j, k, and r are each independently an integer of 1 to 4, j
I
and i is an integer of 0 to 3,
-(-c')^0—Ar^-O-fc')^
(i-6)
i
wherein Ar^ is an aromatic group, and s and t are each
independently an integer of 1 to 3,
V
/ CH2 H2C (i-7)
wherein R^ and R^ each independently represent a Ci-e alkyl
group or a phenyl group,
H2 H2
/ V
CH2 C
"2 (i-8) .
In the formula, when X is a divalent group selected
from (i-1) and (i-2) , Ar^ and Ar^ are each independently
an aromatic group substituted with a substituent other
than a Ci-s alkyl group and a phenyl group. Examples of
substituents other than a Ci-g alkyl group and a phenyl
group include an alkoxy group and a halogen group.
Specific examples thereof include a methoxy group, an i
21 j
I
ethoxy group, a chloro group, and a fluoro group.
In the formula, when X is a divalent group selected
from (i-3) to (i-6), Ar^ and Ar^ are each independently an
optionally substituted aromatic group. In the case where
they are substituted, a Ci-g alkyl group, a phenyl group,
and also conventionally known substituents are applicable j
I
I
as such substituents. Examples thereof include an alkyl i
j
group having 7 or more carbon atoms, an aryl group other 5
"I
than a phenyl group, an alkoxy group, a hydroxy group, an
aldehyde group, an acyl group, a carboxyl group, an ester
group, a nitro group, an amino group, a sulfo group, a
sulfonyloxy group, a halogeno group, a silyl group, a
vinyl group, an allyl group, a cyano group, an isonitrile
group, an amide group, an imide group, and a thiol group.
The substituent may also be a linking group to another
polymer or cyclic carbodiimide compound. The presence of
such a substituent is expected to be effective in
increasing compatibility with a polymer such as a
polyester and enhancing the effect of the cyclic
carbodiimide compound of the invention. Its presence is
also expected to be effective in suppressing the
volatility of the cyclic carbodiimide compound.
In the formula, when X is a tetravalent group, Ar'"'
to Ar"* are each independently an aromatic group
substituted with a substituent other than a Ci-g alkyl
I
i
22 !
group and a phenyl group. Examples of substituents other
than a Ci-6 alkyl group and a phenyl group include an j
alkoxy group and a halogen group. Specific examples
thereof include a methoxy group, an ethoxy group, a chloro
group, and a fluoro group.
Examples of aromatic groups include C5-15 aromatic
groups such as a phenylene group and a naphthalenediyl j
j
group. j
X is a divalent or tetravalent group. When X is
divalent, q is 0. When X is tetravalent, q is 1. It is
preferable that X is a divalent group represented by the
following formula (i-l) .
(i-l)
In the formula, h is an integer of 1 to 6.
Preferred examples of groups represented by (i-l) include
a methylene group, an ethylene group, a 1,3-propylene
group, a 1,4-butylene group, a 1,5-pentane group, and a
1,6-hexane group. In a 1,3-propylene group, a 1,4-
butylene group, a 1,5-pentane group, or a 1,6-hexane group,
carbon that is not directly attached to oxygen may be
substituted with at least one member selected from the
group consisting of a Ci-e alkyl group and a phenyl group.
Examples of Ci-g alkyl groups include a methyl group, an I
23
ethyl group, an n-propyl group, a sec-propyl group, an
iso-propyl group, an n-butyl group, a tert-butyl group, a
sec-butyl group, an isobutyl group, an n-pentyl group, a
sec-pentyl group, an iso-pentyl group, an n-hexyl group, a
sec-hexyl group, and an iso-hexyl group. i
It is preferable that X is a group represented by j
!
the following formula (i-2). j
In the formula, m and n are each independently an
integer of 0 to 3. When m = 0, the methylene group
represents a single bond. When X has a 1,3-phenylene
group, the stability of the cyclic carbodiimide compound
of the invention is further enhanced, leading to an
advantage in that a polymer compound can be applied at a
higher process temperature.
It is preferable that X is a group represented by
the following formula (i-3) and/or (i-4):
m'
\ /n
(i-3)
wherein m' and n' are each independently an integer of 0
24 j
j
to 3,
Q
(i-4)
wherein m'' and n'' are each independently an integer of 0
to 3.
Here, when m' = 0 or m' ' = 0, the methylene group
represents a single bond. When X has a phenylene group,
the stability of the cyclic carbodiimide compound of the
invention is further enhanced, leading to an advantage in
that a polymer compound can be applied at a higher process
temperature.
It is preferable that X is a group represented by
the following formula (i-5).
(i-5)
In the formula, Y and Z are each an oxygen atom or a
sulfur atom, j, k, and r are each independently an integer
of 1 to 4, and i is an integer of 0 to 3. The presence of
an oxygen atom or a sulfur atom in X is expected to be
effective in increasing compatibility with a polymer such
j
2 5 I
i
as a polyester and enhancing the effect of the cyclic
carbodiimide compound of the invention.
It is preferable that X is a divalent group
represented by the following formula (i-4).
-(-c')i-0—Ar^-0-(-?)p
(i-6)
1
I
In the formula, Ar is an aromatic group, and s and
t are each independently an integer of 1 to 3.
Examples of aromatic groups include an o-phenylene
group, a m-phenylene group, and a p-phenylene group.
It is preferable that X is a group represented by
the following formula (i-7) .
V
/ CH2 H2C (i-7)
In the formula, R""" and R^ are each independently a
Ci-6 alkyl group or a phenyl group. Examples of Ci-g alkyl
groups include a methyl group, an ethyl group, an n-propyl
group, a sec-propyl group, an iso-propyl group, an n-butyl
group, a tert-butyl group, a sec-butyl group, an iso-butyl
group, an n-pentyl group, a sec-pentyl group, an isopentyl
group, an n-hexyl group, a sec-hexyl group, and an
iso-hexyl group.
It is preferable that X is a group represented by
I
26 j
the following formula (i-8) .
H2 H2
/ —CH2 c—
"2 (i_8)
I
I
The cyclic carbodiimide compound of the invention j
i
may be a monocyclic compound of the following formula (f) I
or a bicyclic compound of the following formula (F). J
\ /
N^C^N (f)
In the formula, Ar''", Ar^ and X are as defined in
formula (i). It is preferable that Ar^ and Ar^ are each a
substituted o-phenylene group. X is a divalent group.
N=C=N I
ArV Ar^ i
^'\ ' i
N=C=N (F)
j
In the formula, Ar^ to Ar'* and X are as defined in
formula (i) . It is preferable that Ar'"' to Ar^ are each a
i
substituted o-phenylene group. X is a tetravalent group. j
I
It is preferable that the cyclic carbodiimide i
i
1
compound of the invention has two o-phenylene groups at i
27 i
the 1- and 3-positions of the carbodiimide group, the ophenylene
groups each have ether oxygen at the orthoposition
of the carbodiimide group, and the ether oxygen
atoms are linked by X to form a ring structure.
That is, a compound represented by the following
formula is preferable.
P (ii)
In the formula, X is as defined in formula (i) . 7}
and 7? are each independently a substituent.
Conventionally known substituents are applicable as such
substituents, examples thereof including an alkyl group,
an aryl group, an alkoxy group, a hydroxy group, an
aldehyde group, an acyl group, a carboxyl group, an ester
group, a nitro group, an amino group, a sulfo group, a
sulfonyloxy group, a halogeno group, a silyl group, a
vinyl group, an allyl group, a fluoroalkyl group, a cyano
group, an isonitrile group, an amide group, an imide group,
and a thiol group.
Examples of cyclic carbodiimide compounds according
28
to the invention include the following compounds.
^^^°^°\^^
Meo \ / ^^^ OMe
N = C = N
(n = an integer of 1 to 6)
MeOOC ^ - ^ \ / ^ - ^ COOMe
M r. M
(m = an integer of 0 to 3, n == an integer of 0 to 3)
O ^^-^ O
( Om y) n
N C ^N
(m = an integer of 1 to 3, n = an integer of 1 to 3)
29
( rim > 1 )n
\..^ N = C = N ^-^
(m = an integer of 1 to 4, n = an integer of 1 to 4)
( r ^
The monocyclic carbodiimide compound (f) of the
invention can be produced through the following steps (1)
to (4) .
The step (1) is a step for obtaining a nitro
compound (c) . The step (1) has two modes, a step (la) and !
a step (lb) . The step (2) is a step for obtaining an
amide compound (d) from the nitro compound (c) . The step
(3) and the step (4) are steps for obtaining a monocyclic
carbodiimide compound (f) from the amide compound (d) .
The steps (3) and (4) have a mode that goes through a step
(3a) and a step (4a) and a mode that goes through a step
(3b) and a step (4b).
Specifically, the carbodiimide compound (f) can be
produced as follows.
(Scheme 1): Step (la)-step (2a)-step (3a)-step (4a)
(Scheme 2): Step (la)-step (2a)-step (3b)-step (4b)
(Scheme 3): Step (lb)-step (2a)-step (3b)-step (4b)
(Scheme 4): Step (lb)-step (2a)-step (3a)-step (4a)
(Step (la))
The step (la) is a step of allowing a compound of
the following formula (a-1) and a compound of the
following formula (a-2) to react with a compound of the
following formula (b-1) to give a nitro compound (c) of
33
the following formula.
HO Ar^ NO2 (^_l)
HO Ar^ NO2 (^_2)
t X E (b-i)
O X O I I
Ar^ Ar^
NO2 NO2 (c)
In the formulae, X, Ar""", and Ar^ are as defined in
formula (i). X is a divalent group.
E^ and E^ are each independently a group selected
from the group consisting of a halogen atom, a
toluenesulfonyloxy group, a methanesulfonyloxy group, a
benzenesulfonyloxy group, and a p-bromobenzenesulfonyloxy
group. Examples of halogen atoms include a chlorine atom,
a bromine atom, and an iodine atom.
The reaction may be a conventionally known ether
synthesis method. For example, it is possible to use the
Williamson reaction in which a compound represented by
formula (a-1) and a compound represented by formula (a-2)
are allowed to react with a compound represented by
formula (b-1) in a solvent in the presence of a basic
compound, etc.
Examples of basic compounds include sodium hydride,
metallic sodium, sodium hydroxide, potassium hydroxide,
34
and potassium carbonate. Examples of solvents include
N,N-dimethylformamide, N-methyl-2-pyrrolidone, and
tetrahydrofuran. The reaction temperature is suitably
selected within a range of 25°C to 150°C. In addition,
although the reaction proceeds rapidly enough under the
above conditions, it is also possible to add a phasetransfer
catalyst in order to promote the reaction.
(Step (lb))
The step (lb) is a step of allowing a compound of
the following formula (a-i) and a compound of the
following formula (a-ii) to react with a compound of the
following formula (b-i) to give a nitro compound of the
following formula (c).
E' Ar^ NO2 (^_i)
E' Ar^ NO2 (^_ii)
HO X OH (b-i)
O X O
NO2 NO2 (c)
In the formulae, Ar""", Ar^, and X are as defined in
formula (i) . X is a divalent group. E^ and E^ are each
independently a group selected from the group consisting
of a halogen atom, a toluenesulfonyloxy group, a
methanesulfonyloxy group, a benzenesulfonyloxy group, and
35
#
a p-bromobenzenesulfonyloxy group.
The reaction may be a conventionally known ether
synthesis method. For example, it is possible to use the I
Williamson reaction in which a compound represented by i
formula (a-i) and a compound represented by formula (a-ii)
are allowed to react with a compound represented by
formula (b-i) in a solvent in the presence of a basic
compound, etc.
Examples of basic compounds include sodium hydride,
metallic sodium, sodium hydroxide, potassium hydroxide,
and potassium carbonate. Examples of solvents include
N,N-dimethylformamide, N-methyl-2-pyrrolidone, and
tetrahydrofuran. The reaction temperature is suitably
selected within a range of 25°C to 150°C. In addition,
although the reaction proceeds under the above conditions,
it is preferable to add a phase-transfer catalyst in order
to promote the reaction. Examples of phase-transfer
catalysts include a tetrabutylammonium salt, a
trioctylmethylammonium salt, a
benzyldimethyloctadecylammonium salt, and crown ether.
(Step (2))
The step (2) is a step of reducing the obtained
nitro compound (c) to give an amine compound (d) of the
following formula.
I
36
O X O
NH2 NH2 (d)
Ar^, Ar^, and X are as defined in formula (i) . X is
a divalent group.
The reaction may be a conventionally known method.
For example, it is possible to use a method in which the
nitro compound (c) is catalytically reduced in a solvent
in the presence of hydrogen and a catalyst.
Examples of catalysts include palladium carbon,
palladium carbon-ethylenediamine composites, palladiumfibroin,
palladium-polyethyleneimine, nickel, and copper.
Examples of solvents include methanol, ethanol,
isopropyl alcohol, dioxane, tetrahydrofuran, ethyl acetate,
dichloromethane, chloroform, and N,N-dimethylformamide.
The reaction temperature is suitably selected within a
range of 25°C to 100°C. In addition, although the reaction
proceeds at normal pressure, it is preferable to apply
pressure in order to promote the reaction.
The reaction to produce an amine compound (d) may
also be a method in which the nitro compound (c) is
allowed to react with an acid and a metal, a method in
which the nitro compound (c) is allowed to react with
hydrazine and a catalyst, etc.
37
(Step (3a))
The step (3a) is a step of allowing the obtained
amine compound (d) to react with triphenylphosphine
dibromide to give a triphenylphosphine compound (e-1) of
the following formula.
I I
N N
I
r^Ar 3 h-Ar 3 (e-l)
In the formula, Ar^, Ar^, and X are as defined in
formula (i) , and Ar^ is a phenyl group.
The reaction may be a conventionally known method.
For example, it is possible to use a method in which the
amine compound represented by formula (d) is allowed to
react with triphenylphosphine dibromide in a solvent in
the presence of a basic compound, etc. Examples of basic
compounds include triethylamine and pyridine. Examples of
solvents include dichloroethane, chloroform, and benzene.
The reaction temperature is suitably selected within a
range of 0°C to 80°C.
(Step (4a))
The step (4a) is a step of isocyanating the obtained
triphenylphosphine compound in a reaction system, followed
by direct decarboxylation to give a cyclic carbodiimide
compound (f).
38
m
The reaction may be a conventionally known method.
For example, it is possible to use a method in which the
triphenylphosphine compound of formula (e-1) is allowed to
react in a solvent in the presence of di-tert-butyl
dicarbonate and N,N-dimethyl-4-aminopyridine, etc.
Examples of solvents include dichloromethane and
chloroform. The reaction temperature is suitably selected
within a range of 10°C to 4 0°C.
(Step (3b))
The step (3b) is a step of allowing the amine
compound (d) to react with carbon dioxide or carbon
disulfide to give a urea compound or thiourea compound
represented by the following formula (e-2).
/ O — X —O
\ /
HN C NH
Z (e-2)
In the formula, Ar^, Ar^, and X are as defined in
formula (i), and Z is an oxygen atom or a sulfur atom.
The reaction to produce a urea compound (e-2) may be
a conventionally known method. For example, it is
possible to use a method in which the amine compound (d)
is allowed to react in a solvent in the presence of carbon
dioxide, a phosphorus compound, and a basic compound.
Examples of phosphorus compounds include phosphite
39
and phosphonate. Examples of basic compounds include
triethylamine, pyridine, imidazole, and picoline.
Examples of solvents include pyridine, N,Ndimethylformamide,
acetonitrile, chlorobenzene, and
toluene. The reaction temperature is suitably selected
within a range of 0°C to 80°C.
The reaction to produce a urea compound (e-2) may
also be a method in which the amine compound (d) is
allowed to react with carbon monoxide, a method in which
the amine compound (d) is allowed to react with phosgene,
etc.
The reaction to produce a thiourea compound (e-2)
may be a conventionally known method. For example, it is
possible to use a method in which the amine compound (d)
is allowed to react in a solvent in the presence of carbon
disulfide and a basic compound, etc.
Examples of basic compounds include triethylamine,
pyridine, imidazole, and picoline. Examples of solvents
include acetone, methanol, ethanol, isopropyl alcohol, 2-
butanone, pyridine, N,N-dimethylformamide, and
acetonitrile. The reaction temperature is suitably
selected within a range of 25°C to 90°C. Although the
reaction proceeds rapidly enough under the above
conditions, it is also possible to use carbon tetrabromide
or the like together in order to promote the reaction.
I
40 j
(Step (4b)) j
The step (4b) is a step of dehydrating the obtained
urea compound (e-2) or desulfurizmg the obtained thiourea
compound (e-2) to give a cyclic carbodiimide compound (f).
The reaction may be a conventionally known method.
For example, it is possible to use a method in which the
urea compound or thiourea compound (e-2) is allowed to
react in a solvent in the presence of toluenesulfonyl
chloride or methylsulfonyl chloride to dehydrate the urea
compound (e-2) or desulfurize the thiourea compound (e-2).
Examples of solvents include dichloromethane,
chloroform, and pyridine. The reaction temperature is
suitably selected within a range of 0°C to 80°C.
The reaction to produce a cyclic carbodiimide
compound (f) may also be a method in which the urea
compound (e-2) is allowed to react with mercury oxide, a
method in which the thiourea compound (e-2) is allowed to
react with sodium hypochlorite, etc.
The bicyclic carbodiimide compound (F) of the
invention can be produced through the following steps (1)
to (4) .
The step (1) is a step for obtaining a nitro
compound (C) . The step (1) has two modes, a step (lA) and
a step (IB) . The step (2) is a step for obtaining an
I
j
41
I
I
I
amide compound (D) from the nitro compound (C) . The step
(3) and the step (4) are steps for obtaining a bicyclic
carbodiimide compound (F) from the amide compound (D) .
The steps (3) and (4) have a mode that goes through a step
(3A) and a step (4A) and a mode that goes through a step
(3B) and a step (4B).
The carbodiimide compound (F) can be produced as
!
follows. i
I
I
(Scheme 1) Step (lA)-step (2A)-step (3A)-step (4A) j
I
(Scheme 2) Step (lA)-step (2A)-step (3B)-step (4B) 1
(Scheme 3) Step (IB)-step (2A)-step (3B)-step (4B)
(Scheme 4) Step (IB)-step (2A)-step (3A)-step (4A)
(Step (lA) )
The step (lA) is a step of allowing a compound of j
any one of the following formulae (A-1) to (A-4) to react
with a compound of the following formula (B-1) to give a
nitro compound of the following formula (C).
HO Ar^ NO2 (A_i)
HO Ar^ NO2 (;,_2)
HO Ar^ NO2 (A-3)
HO Ar^ NO2 (;,_4)
/ E^ E^ (B-1)
i
42 I
H2 H2
CHo C
(Xi i s ^ H, .)
NO2 NO2
1 I
In the formulae, Ar^ to Ar'* and X are as defined in
formula (i) . X is a tetravalent group. E^ to E^ are each
independently a group selected from the group consisting
of a halogen atom, a toluenesulfonyloxy group, a
methanesulfonyloxy group, a benzenesulfonyloxy group, and
a p-bromobenzenesulfonyloxy group.
The reaction conditions are the same as in the step
(la) mentioned above.
(Step (IB))
The step (IB) is a step of allowing a compound of
any one of the following formulae (A-i) to (A-iv) to react
with a compound of the following formula (B-i) to give a
nitro compound of the following formula (C).
E^ Ar^ NO2 (;,_i)
E' Ar^ NO2 (;,_ii)
E' Ar^ NO2 (;,_iii)
E« Ar^ NO2 (^_i^)
43
HO OH
/ HO OH (B-i)
I
H2 H2 S
/ V i
(X, is ~^"^ H. .) I
NO2 NO2 I
°^^\ ^ O f
1 I i
OoN NO2 I
U2N (C)
i
In the formulae, Ar^ to Ar^ and X are as defined in I
formula (i) . E^ to E® are each independently a group i
selected from the group consisting of a halogen atom, a j
toluenesulfonyloxy group, a methanesulfonyloxy group, a J
I benzenesulfonyloxy group, and a p-bromobenzenesulfonyloxy i
group.
The reaction conditions are the same as in the step
(lb) mentioned above.
(Step (2A))
The step (2A) is a step of reducing the obtained
nitro compound to give an amine compound (D) of the
following formula.
I
i
44 i
I
I
I
f
I
I
I
NH2 NH2 i
I
A r - ^ ^Ar
H2N NH2 (P) I
Ar""" to Ar^ and X are as defined in formula (i) . j
The reaction conditions are the same as in the step {
i
i
(2a) mentioned above. 1
I
I
(Step (3A)) I
i
The step (3A) is a step of allowing the obtained j
amine compound (D) to react with triphenylphosphine j
j
dibromide to give a triphenylphosphine compound (E-1) of i
the following formula.
i
N=PAr\ N=PAr'3
Ar^ ^Ar
N=PAr% N=PAr^ (E-i)
In the formula, Ar^ to Ar^ and X are as defined in
formula (i), and Ar^ is a phenyl group.
The reaction conditions are the same as in the step
(3a) mentioned above.
(Step (4A))
The step (4A) is a step of isocyanating the obtained
I
triphenylphosphine compound in a reaction system, followed
by direct decarboxylation to give a compound (F) of the
following formula.
\ Ar
< >
N^C^N (F)
In the formula, Ar^ to Ar^ and X are as defined in
formula (i).
The reaction conditions are the same as in the step
(4a) mentioned above.
(Step (3B))
The step (3B) is a step of allowing the amine
compound to react with carbon dioxide or carbon disulfide
to give a urea compound or thiourea compound (E-2) of the
following formula.
Z
HN C NH
3 / \.
o o
\ /
HN C NH
Z (E-2)
In the formula, Ar''' to Ar^ and X are as defined in
f I
46 I
I
#
formula (i), and Z is an oxygen atom or a sulfur atom.
The reaction conditions are the same as in the step
(3b) mentioned above.
(Step (4B))
The step (4B) is a step of dehydrating the obtained
urea compound or desulfurizing the obtained thiourea
compound to give a compound (F) of the following formula.
Ar\ ^Ar^
\ Ar
N : ^ C ^ N (F)
In the formula, Ar to Ar and X are as defined in
formula (i).
The reaction conditions are the same as in the step
(4b) mentioned above.
(Other Production Methods)
In addition to the above production methods, the
cyclic carbodiimide compound of the invention can also be
produced by conventionally known methods. Examples of
methods include production from an amine compound via an
isocyanate compound, production from an amine compound via
an isothiocyanate compound, and production from a
carboxylic acid compound via an isocyanate compound.
Although the cyclic carbodiimide compound is capable
47
of effectively capping acidic groups of a polymer compound,
if desired, without departing from the gist of the
invention, for example, a conventionally known carboxylgroup-
capping agent for polymers can be used together.
Examples of such conventionally known carboxyl-groupcapping
agents include agents described in JP-A-2005-2174,
such as an epoxy compound, an oxazoline compound, and an
oxazine compound.
In the invention, a polymer compound to which the
cyclic carbodiimide compound is applied has acidic groups.
The acidic group may be at least one member selected from
the group consisting of a carboxyl group, a sulfonic acid
group, a sulfinic acid group, a phosphonic acid group, and
a phosphinic acid group. The polymer compound may be at
least one member selected from the group consisting of
polyesters, polyamides, polyamideimides, polyimides, and
polyester amides.
Examples of polyesters include polymers and
copolymers obtained by the polycondensation of at least
one member selected from a dicarboxylic acid or an esterforming
derivative thereof with a diol or an ester-forming
derivative thereof, a hydroxycarboxylic acid or an esterforming
derivative thereof, and a lactone. Thermoplastic
polyester resins are preferable, for example. For
48
moldability, etc., such a thermoplastic polyester resin
may have a crosslinked structure formed by treatment with
a radical-generating source, such as active energy rays or
an oxidizing agent.
Examples of dicarboxylic acids and ester-forming
derivatives thereof include aromatic dicarboxylic acids
such as terephthalic acid, isophthalic acid, phthalic acid,
2,6-naphthalenedicarboxylic acid, 1,5-
naphthalenedicarboxylic acid, bis(p-carboxyphenyl)methane,
anthracenedicarboxylic acid, 4,4'-diphenyl ether
dicarboxylic acid, 5-tetrabutylphosphonium isophthalic
acid, and 5-sodium sulfoisophthalic acid, as well as
ester-forming derivatives thereof. Examples also include
aliphatic dicarboxylic acids such as oxalic acid, succinic
acid, adipic acid, sebacic acid, azelaic acid,
dodecanedioic acid, malonic acid, glutaric acid, and dimer
acid, as well as ester-forming derivatives thereof.
Examples also include alicyclic dicarboxylic acids such as
1,3-cyclohexanedicarboxylic acid and 1,4-
cyclohexanedicarboxylic acid, as well as ester-forming
derivatives thereof.
Examples of diols and ester-forming derivatives
thereof include C2-20 aliphatic glycols, i.e., ethylene
glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol,
neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol,
49
decamethylene glycol, cyclohexane dimethanol,
cyclohexanediol, dimer diol, and the like. Examples also
include long-chain glycols having a molecular weight of
200 to 100,000, i.e., polyethylene glycol,
polytrimethylene glycol, poly(1,2-propylene glycol),
polytetramethylene glycol, and the like. Examples also
include aromatic dioxy compounds, i.e., 4,4'-
dihydroxybiphenyl, hydroquinone, tert-butyl hydroquinone,
bisphenol-A, bisphenol-S, bisphenol-F, and the like, as
well as ester-forming derivatives thereof.
Examples of hydroxycarboxylic acids include glycolic
acid, lactic acid, hydroxypropionic acid, hydroxybutyric
acid, hydroxyvaleric acid, hydroxycaproic acid,
hydroxybenzoic acid, p-hydroxybenzoic acid, and 6-hydroxy-
2-naphthoic acid, as well as ester-forming derivatives
thereof. Examples of lactones include caprolactone,
valerolactone, propiolactone, undecalactone, and 1,5-
oxepan-2-one.
Examples of aromatic polyesters obtained by the
polycondensation of, as main components, an aromatic
dicarboxylic acid or an ester-forming derivative thereof
and an aliphatic diol or an ester-forming derivative
thereof include polymers obtained by the polycondensation
of, as main components, an aromatic carboxylic acid or an
ester-forming derivative thereof, preferably terephthalic
50
#
acid, naphthalene-2,6-dicarboxylic acid, or an esterforming
derivative thereof, and an aliphatic diol selected
from ethylene glycol, 1,3-propanediol, and butanediol or
an ester-forming derivative thereof.
Specific preferred examples thereof include
polyethylene terephthalate, polyethylene naphthalate,
polytrimethylene terephthalate, polytrimethylene
naphthalate, polybutylene terephthalate, polybutylene
naphthalate, polyethylene(terephthalate/isophthalate),
polytrimethylene(terephthalate/isophthalate),
polybutylene(terephthalate/isophthalate), polyethylene
terephthalate-polyethylene glycol, polytrimethylene
terephthalate-polyethylene glycol, polybutylene
terephthalate-polyethylene glycol, polybutylene
naphthalate-polyethylene glycol, polyethylene
terephthalate-poly(tetramethylene oxide) glycol,
polytrimethylene terephthalate-poly(tetramethylene oxide)
glycol, polybutylene terephthalate-poly(tetramethylene
oxide) glycol, polybutylene naphthalatepoly(
tetramethylene oxide) glycol,
polyethylene(terephthalate/isophthalate)-
poly(tetramethylene oxide) glycol,
polytrimethylene(terephthalate/isophthalate)-
poly(tetramethylene oxide) glycol,
polybutylene(terephthalate/isophthalate)-
51
poly(tetramethylene oxide) glycol,
polybutylene(terephthalate/succinate),
polyethylene(terephthalate/succinate),
polybutylene(terephthalate/adipate), and
polyethylene(terephthalate/adipate).
Examples of aliphatic polyesters include polymers
containing an aliphatic hydroxycarboxylic acid as a main
component, polymers obtained by the polycondensation of an
aliphatic polycarboxylic acid or an ester-forming
derivative thereof and an aliphatic polyalcohol as main
components, and copolymers thereof.
Examples of polymers containing an aliphatic
hydroxycarboxylic acid as a main component inclucde
polycondensates of glycolic acid, lactic acid,
hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric
acid, hydroxycaproic acid, and the like, as well as
copolymers thereof. In particular, polyglycolic acid,
polylactic acid, poly(3-hydroxycarboxybutyric acid) ,
poly(4-polyhydroxybutyric acid), poly(3-hydroxyhexanoic
acid), polycaprolactone, copolymers thereof, and the like
are mentioned. Poly(L-lactic acid), poly(D-lactic acid),
stereocomplex polylactic acid, and racemic polylactic acid
are particularly suitable.
Examples of polyesters also include polymers
containing an aliphatic polycarboxylic acid and an
52
aliphatic polyalcohol as main components. Examples of
polycarboxylic acids include aliphatic dicarboxylic acids
such as oxalic acid, succinic acid, adipic acid, sebacic
acid, azelaic acid, dodecanedioic acid, malonic acid,
glutaric acid, and dimer acid. Examples also include
alicyclic dicarboxylic acid units such as 1,3-
cyclohexanedicarboxylic acid and 1,4-
cyclohexanedicarboxylic acid, as well as ester derivatives
thereof.
Examples of diol components include C2-20 aliphatic
glycols, i.e., ethylene glycol, 1,3-propanediol, 1,4-
butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-
hexanediol, decamethylene glycol, cyclohexane dimethanol,
cyclohexanediol, dimer diol, and the like. Examples also
include condensates containing as a main component a longchain
glycol having a molecular weight of 200 to 100,000,
i.e., polyethylene glycol, polytrimethylene glycol,
poly(1,2-propylene glycol), or polytetramethylene glycol.
Specific examples thereof include polyethylene adipate,
polyethylene succinate, polybutylene adipate, and
polybutylene succinate, as well as copolymers thereof.
Further, examples of wholly aromatic polyesters
include polymers obtained by the polycondensation of, as
main components, an aromatic carboxylic acid or an esterforming
derivative thereof, preferably terephthalic acid,
53
naphthalene-2,6-dicarboxylic acid, or an ester-forming
derivative thereof, and an aromatic polyhydroxy compound
or an ester-forming derivative thereof.
Specific examples thereof include poly(4-
oxyphenylene-2,2-propylidene-4 -oxyphenylene-terephthaloylco-
isophthaloyl).
Such a polyester has, as carbodiimide-reactive
components, terminal carboxyl and/or hydroxyl groups at
its molecular ends in an amount of 1 to 50 eq/ton. Such
terminal groups, especially carboxyl groups, reduce the
stability of the polyester and thus are preferably capped
with a cyclic carbodiimide compound.
In the capping of terminal carboxyl groups with a
carbodiimide compound, the application of the cyclic
carbodiimide compound of the invention allows the carboxyl
groups to be capped without producing toxic, free
isocyanates. This is greatly advantageous.
Further, as an additional effect, because of chain
extension by the terminal isocyanate groups that are not
released but formed in the polyester during capping with
the cyclic carbodiimide compound and the terminal hydroxyl
or carboxyl groups that are present in the polyester, the
molecular weight of the polyester can be increased or
prevented from decreasing more efficiently as compared
with conventional linear carbodiimide compounds. This is
54
of great industrial significance.
The polyesters mentioned above can be produced by a
well known method (e.g., described in "Howa-Poriesuteru-
Jushi Handobukku (Handbook of Saturated Polyester Resin)"
written by Kazuo YUKI, Nikkan Kogyo Shimbun (published on
December 22, 1989), etc.).
In the invention, examples of polyesters further
include, in addition to the above polyesters, unsaturated
polyester resins obtained by the copolymerization of
unsaturated polycarboxylic acids or ester-forming
derivatives thereof and also polyester elastomers
containing a low-melting-point polymer segment.
Examples of unsaturated polycarboxylic acids include
maleic anhydride, tetrahydromaleic anhydride, fumaric acid,
and endomethylene tetrahydromaleic anhydride. Various
monomers are added to such an unsaturated polyester in
order to control curing properties, and the unsaturated
polyester is cured and molded by heat curing, radical
curing, or curing with active energy rays such as light or
electron beams. The control of carboxyl groups in such an
unsaturated resin is an important technical problem
related to rheological properties such as thixotropy,
resin durability, etc. However, the cyclic carbodiimide
compound allows the carboxyl groups to be capped and
controlled without producing toxic, free isocyanates, and
55
also allows the molecular weight to be more effectivelyincreased.
These advantages are of great industrial
significance.
Further, in the invention, the polyester may also be
a polyester elastomer obtained by the copolymerization of
soft components. A polyester elastomer is a copolymer
containing a high-melting-point polyester segment and a
low-melting-point polymer segment having a molecular
weight of 400 to 6,00 0, as described in known documents,
for example, JP-A-11-92636.
In the case where the copolymer is made solely of a
high-melting-point polyester segment, the melting point
thereof is 150°C or more. In the case where the copolymer
is made solely of a low-melting-point polymer segment, the
melting point or softening point thereof is 80°C or less.
It is preferable that a low-melting-point polymer segment
is made of a polyalkylene glycol or a C2-12 aliphatic
dicarboxylic acid and a C2-10 aliphatic glycol. Such an
elastomer has a problem with hydrolytic stability.
However, its carboxyl groups can be controlled by the
cyclic carbodiimide compound without any safety problem,
which is of great significance, and also its molecular
weight can be prevented from decreasing or can be
increased by the cyclic carbodiimide compound, which is of
great industrial significance.
56
As a polyamide, a thermoplastic polymer having an
amide bond and containing an amino acid, a lactam, or a
diamine and a dicarboxylic acid or an amide-forming
derivative thereof as main raw materials is mentioned.
In the invention, polycondensates obtained by the
condensation of a diamine and a dicarboxylic acid or an
acyl activator thereof, polymers obtained by the
polycondensation of an aminocarboxylic acid, a lactam, or
an amino acid, and copolymers thereof are usable as
polyamides.
Examples of diamines include aliphatic diamines and
aromatic diamines. Examples of aliphatic diamines include
tetramethylenediamine, hexamethylenediamine,
undecamethylenediamine, dodecamethylenediamine, 2,2,4-
trimethylhexamethylenediamine, 2,4,4-
trimethylhexamethylenediamine, 5-
methylnonamethylenediamine, 2,4-
dimethyloctamethylenediamine, m-xylylenediamine, pxylylenediamine,
1,3-bis(aminomethyl)cyclohexane, 1-amino-
3-aminomethyl-3,5,5-trimethylcyclohexane, 3,8-
bis(aminomethyl)tricyclodecane, bis(4-
aminocyclohexyl)methane, bis(3-methyl-4 -
aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane,
bis(aminopropyl)piperazine, and aminoethylpiperazine.
Examples of aromatic diamines include p-
57
phenylenediamine, m-phenylenediamine, 2,6-
naphthalenediamine, 4,4'-diphenyldiamine, 3,4'-
diphenyldiamine, 4,4'-diaminodiphenyl ether, 3,4'-
diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4'-
diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ketone,
3,4'-diaminodiphenyl ketone, and 2,2-bis(4-
aminophenyl)propane.
Examples of dicarboxylic acids include adipic acid,
suberic acid, azelaic acid, sebacic acid, dodecanoic acid,
terephthalic acid, isophthalic acid,
naphthalenedicarboxylic acid, 2-chloroterephthalic acid,
2-methylterephthalic acid, 5-methylisophthalic acid, 5-
sodium sulfoisophthalic acid, hexahydroterephthalic acid,
hexahydroisophthalic acid, and diglycolic acid.
Specific examples of polyamides include aliphatic
polyamides such as polycaproamide (Nylon 6) ,
polytetramethylene adipamide (Nylon 46), polyhexamethylene
adipamide (Nylon 66) , polyhexamethylene sebacamide (Nylon
610), polyhexamethylene dodecamide (Nylon 612),
polyundecamethylene adipamide (Nylon 116) ,
polyundecanamide (Nylon 11) , and polydodecanamide (Nylon
12) .
Examples also include aliphatic-aromatic polyamides
such as polytrimethylhexamethylene terephthalamide,
polyhexamethylene isophthalamide (Nylon 61) ,
58
polyhexamethylene terephthal/isophthalamide (Nylon 6T/6I),
poly[bis(4-aminocyclohexyl)methane dodecamide] (Nylon
PACM12), poly[bis(3-methyl-4-aminocyclohexyl)methane
dodecamide] (Nylon Dimethyl PACM12), poly(m-xylylene
adipamide) (Nylon MXD6) , polyundecamethylene
terephthalamide (Nylon IIT), polyundecamethylene
hexahydroterephthalamide (Nylon IIT(H)), and copolyamides
thereof, as well as copolymers and mixtures thereof.
Examples further include poly(p-phenylene terephthalamide)
and poly(p-phenylene terephthalamide-co-isophthalamide).
Examples of amino acids include co-aminocaproic acid,
co-aminoenanthic acid, co-aminocaprylic acid, roaminopergonic
acid, co-aminocapric acid, 11-aminoundecanoic
acid, 12-aminododecanoic acid, and p-aminomethylbenzoic
acid. Examples of lactams include co-caprolactam, coenantholactam,
co-capryllactam, and co-laurolactam.
The molecular weight of such a polyamide resin is
not particularly limited. However, it is preferable that
its relative viscosity measured at 25°C in a 98%
concentrated sulfuric acid solution having a polyamide
resin concentration of 1% by weight is within a range of
2.0 to 4.0.
These amide resins can be produced according to a
well known method, for example, "Poriamido-Jusi Handohukku
(Polyamide Resin Handbook)" (written by Osamu FUKUMOTO,
59
Nikkan Kogyo Shimbun, published on January 30, 1988), etc.
Polyamid.es in the invention further include
polyamides known as polyatnide elastomers. Examples of
such polyamides include graft and block copolymers
obtained by a reaction of a polyamide-forming component
having 6 or more carbon atoms with a poly(alkylene oxide)
glycol. The linkage between the polyamide-forming
component having 6 or more carbon atoms and the
poly(alkylene oxide) glycol component is usually an ester
bond or an amide bond. However, the linkage is not
particularly limited thereto, and it is also possible to
use a third component, such as a dicarboxylic acid or a
diamine, as a reaction component for the two.
Examples of poly(alkylene oxide) glycols include
polyethylene oxide glycol, poly(1,2-propylene oxide)
glycol, poly(1,3-propylene oxide) glycol,
poly(tetramethylene oxide) glycol, poly(hexamethylene
oxide) glycol, block and random copolymers of ethylene
oxide and propylene oxide, and block and random copolymers
of ethylene oxide and tetrahydrofuran. In terms of
polymerizability and rigidity, the number average
molecular weight of the poly(alkylene oxide) glycol is
preferably 200 to 6,000, and more preferably 300 to 4,000.
As a polyamide elastomer for use in the invention, a
polyamide elastomer obtained by the polymerization of
60
1
caprolactam, polyethylene glycol, and terephthalic acid is
preferable.
As can be easily understood from the raw materials,
such a polyamide resin has carboxyl groups in an amount of
30 to 100 eq/ton and amino groups in an amount of 30 to
100 eq/ton, approximately, but it is well known that
carboxyl groups have an unfavorable effect on the
stability of a polyamide.
By the cyclic carbodiimide compound of the invention,
the carboxyl groups are controlled to 2 0 eq/ton or less or
to 10 eq/ton or less, preferably further to a lower degree,
without any safety problems, and also the molecular weight
is more effectively prevented from decreasing; such a
composition is of great significance.
A polyamideimide resin for use in the invention has
a main repeating structural unit represented by the
following formula (I).
/ 0 I / II c \ H II / \ N C R2 N R^—j—
\ i >
(I)
In the formula, R^ represents a trivalent organic
group, R'^ represents a divalent organic group, and n
represents a positive integer.
Examples of typical methods for synthesizing such a
61
m
polyamideimide resin include (1) a method in which a
diisocyanate is allowed to react with a tribasic acid
anhydride, (2) a method in which a diamine is allowed to
react with a tribasic acid anhydride, and (3) a method in
which a diamine is allowed to react with a tribasic acid
anhydride chloride. However, the method for synthesizing
a polyamideimide resin for use in the invention is not
limited thereto. Typical compounds used in the above
synthesizing methods are listed hereinafter.
First, preferred examples of diisocyanates include
4,4'-diphenylmethane diisocyanate, xylylene diisocyanate,
3 , 3'-diphenylmethane diisocyanate, 4,4'-diphenylether
diisocyanate, 3,3'-diphenylether diisocyanate, and pphenylene
diisocyanate.
Preferred examples of diamines include 4,4'-
diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone,
4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether,
4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane,
xylylenediamine, and phenylenediamine.
Among these, 4,4'-diphenylmethane diisocyanate,
3 , 3'-diphenylmethane diisocyanate, 4 , 4'-diphenylether
diisocyanate, 3,3'-diphenylether diisocyanate, 4,4'-
diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-
diaminodiphenylmethane, and 3,3'-diaminodiphenylmethane
are more preferable.
62
#
Preferred examples of tribasic acid anhydrides
include trimellitic anhydride, and examples of tribasic
acid anhydride chlorides include trimellitic anhydride
chloride.
In the synthesis of a polyamideimide resin, a
dicarboxylic acid, a tetracarboxylic dianhydride, or the
like may be simultaneously subjected to the reaction
without impairing the properties of the polyamideimide
resin. Examples of dicarboxylic acids include
terephthalic acid, isophthalic acid, and adipic acid.
Examples of tetracarboxylic dianhydrides include
pyromellitic dianhydride, benzophenone tetracarboxylic
dianhydride, and biphenyl tetracarboxylic dianhydride. It
is preferable that they are used in an amount of 50 eq% or
less based on the total acid components.
The durability of a polyamideimide resin may
decrease depending on the concentration of carboxyl groups
contained in the polymer. Therefore, it is preferable
that the carboxyl group content is controlled preferably
to 1 to 10 eq/ton or less. In the cyclic carbodiimide
compound of the invention, the above carboxyl group
concentration range can be suitably achieved.
As a polyimide resin, it is preferable to select a
thermoplastic polyimide. An example of a polyimide resin
is a polyimide containing the following diamine component
63
and tetracarboxylic acid:
H2N-R*-NH2
wherein R^ is (i) a single bond; (ii) a C2-12 aliphatic
hydrocarbon group; (iii) a C4-30 alicyclic group; (iv) a Cs-
30 aromatic group; (v) a -Ph-0-R^-O-Ph- group (in the
formula, R^ represents a phenylene group or a Ph-W^-Phgroup
wherein W''' represents a single bond, a C1-4 alkylene
group optionally substituted with a halogen atom, a -0-Ph-
O- group, -0-, -CO-, -S-, -SO-, or a -SO2- group; or (vi)
a -R^-(SiR'20)m-SiR^2-R^- group (in the formula, R^
represents -(CH2)s-, -(CH2)s-Ph-, - (CH2) s-O-Ph-, or -Phwherein
m is an integer of 1 to 10 0, s represents an
integer of 1 to 4, and R' represents a Ci-e alkyl group, a
phenyl group, or a Ci-g alkylphenyl group) ,
O O
O Y O
c c
o o
wherein Y is a C2-12 tetravalent aliphatic group, a C4-8
tetravalent alicyclic group, a C6-14 monocyclic or fusedring
polycyclic tetravalent aromatic group, or a >Ph-W^-
Ph< group (in the formula, W^ represents a single bond, a
Ci-4 alkylene group optionally substituted with a halogen
atom, -O-Ph-0-, -0-, -CO-, -S-, -SO-, or a -SO2- group).
Specific examples of tetracarboxylic anhydrides for
64
0
use in the production of a polyamide acid include, but are
not limited to, pyromellitic anhydride (PMDA), 4,4'-
oxydiphthalic anhydride (ODPA) , biphenyl-3,3',4,4'-
tetracarboxylic anhydride (BPDA) , benzophenone-3,3',4,4'-
tetracarboxylic anhydride (BTDA), ethylenetetracarboxylic
anhydride, butanetetracarboxylic anhydride,
cyclopentanetetracarboxylic anhydride, benzophenone-
2 , 2',3,3'-tetracarboxylic anhydride, biphenyl-2,2',3,3'-
tetracarboxylic anhydride, 2,2-bis(3,4-
dicarboxyphenyl)propane anhydride, 2,2-bis(2,3-
dicarboxyphenyl)propane anhydride, bis(3,4-
dicarboxyphenyl)ether anhydride, bis(3,4-
dicarboxyphenyl)sulfone anhydride, l,l-bis(2,3-
dicarboxyphenyl)ethane anhydride, bis(2,3 -
dicarboxyphenyl)methane anhydride, bis(3,4-
dicarboxyphenyl)methane anhydride, 4,4'-(pphenylenedioxy)
diphthalic anhydride, 4,4'-(mphenylenedioxy)
diphthalic anhydride, naphthalene-2,3,6,7-
tetracarboxylic anhydride, naphthalene-1,4,5,8-
tetracarboxylic anhydride, naphthalene-1,2,5,6-
tetracarboxylic anhydride, benzene-1,2,3,4-tetracarboxylic
anhydride, perylene-3,4,9,10-tetracarboxylic anhydride,
anthracene-2,3,6,7-tetracarboxylic anhydride, and
phenanthrene-1,2,7,8-tetracarboxylic anhydride.
These dicarboxylic anhydrides may be used alone, and
65
it is also possible to use a mixture of two or more kinds.
Among them, it is preferable to use pyromellitic anhydride
(PMDA), 4,4'-oxydiphthalic anhydride (ODPA), biphenyl-
3 , 3',4,4'-tetracarboxylic anhydride (BPDA), benzophenone-
3,3',4,4'-tetracarboxylic anhydride, or biphenylsulfone-
3,3',4,4'-tetracarboxylic anhydride (DSDA).
Specific example of diamines for use in the
production of a polyimide include, but are not limited to,
4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane,
4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl
thioether, 4,4'-di(m-aminophenoxy)diphenyl sulfone, 4,4'-
di (p-aminophenoxy)diphenyl sulfone, o-phenylenediamine, mphenylenediamine,
p-phenylenediamine, benzidine, 2,2'-
diaminobenzophenone, 4,4'-diaminobenzophenone, 4,4'-
diaminodiphenyl-2,2'-propane, 1,5-diaminonaphthalene, 1,8-
diaminonaphthalene, trimethylenediamine,
tetramethylenediamine, hexamethylenediamine, 4,4-
dimethylheptamethylenediamine, 2,11-dodecadiamine, di(paminophenoxy)
dimethylsilane, 1,4-di(3-
aminopropyldiaminosilane)benzene, 1,4-diaminocyclohexane,
o-tolyldiamine, m-tolyldiamine, acetoguanamine,
benzoguanamine, 1,3-bis(3-aminophenoxy)benzene (APB),
bis [4-(3-aminophenoxy)phenyl]methane, l,l-bis[4-(3-
aminophenoxy)phenyl]ethane, 1,2-bis[4-(3-
aminophenoxy)phenyl]ethane, 2,2-bis[4-(3-
66
aminophenoxy)phenyl]ethane, 2,2-bis[4-(3-
aminophenoxy)phenyl]propane, 2,2-bis[4-(3-
aminophenoxy)phenyl]butane, 2,2-bis[4-(3-
aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 4,4'-
di(3 -aminophenoxy)biphenyl, di[4 -(3 -
aminophenoxy)phenyl] ketone, di[4 -(3 -
aminophenoxy)phenyl]sulfide, di[4-(3-
aminophenoxy)phenyl]sulfoxide, di[4-(3-
aminophenoxy)phenyl]sulfone, and di(4 -(3 -
amionohpenoxy)phenyl)ether. The above diamines may be
used alone, and it is also possible to use a mixture of a
large number of them.
Examples of thermoplastic polyimides include
polyimide resins containing a tetracarboxylic anhydride
represented by the below formula and a known diamine such
as p-phenylenediamine, cyclohexanediamine, or hydrogenated
bisphenol-A type diamine. Further, examples also include
those commercially available from General Electric under
the trade name Ultem, such as Ultem 1000, Ultera 1010,
Ultem CRS5001, and Ultem XH6050, and also AURUM 250AM
manufactured by Mitsui Chemicals.
67
o
\ ( -^'jn
O
( R« )m I
In the formulae, R^ and R^ each independently
represent a hydrogen atom, a linear or branched Ci-io alkyl
group, or an aryl group, R^° represents a Cg-so arylene
group or a C2-20 alkylene group, m and n are each an
integer of 0 to 5, and k is an integer of 1 to 3.
Examples of polyester amide resins include
conventionally known polyester amide resins obtained by
the copolymerization of a polyester component and a
polyamide component. In particular, it is preferable to
68
select a thermoplastic polyester amide resin.
A polyester amide resin can be synthesized by a
known method, etc. For example, it is possible to employ
a method in which the polyamide component is first
subjected to a polycondensation reaction to synthesize a
polyamide terminated with functional groups, and then the
polyester component is polymerized in the presence of the
polyamide, etc. This polycondensation reaction usually
takes place through the first stage in which an amidation
reaction proceeds and then the second stage in which an
esterification reaction proceeds. The polyester component
is preferably selected from the polyester components
mentioned above. In addition, the polyamide component is
preferably selected from the polyamide components
mentioned above.
In the invention, the cyclic carbodiimide compound
is mixed with a polymer compound having acidic groups to
cause a reaction therebetween, whereby the acidic groups
can be capped. The method for mixing the cyclic
carbodiimide compound into the polymer compound is not
particularly limited and may be a conventionally known
method. It is possible to employ a method in which the
cyclic carbodiimide compound is added in the form of a
solution, a melt, or a masterbatch of a polymer to be
69
treated, a method in which a polymer compound in solid
state is brought into contact with a liquid having the
cyclic carbodiimide compound dissolved, dispersed, or
melted therein, thereby impregnating the polymer compound
with the cyclic carbodiimide compound, or the like.
In the case where a method in which the cyclic
carbodiimide compound is added in the form of a solution,
a melt, or a masterbatch of a polymer to be treated is
employed, it is possible to employ a method in which a
conventionally known kneading apparatus is used for
addition. For kneading, kneading in the form of a
solution or kneading in the form of a melt is preferable
in terms of uniform kneading. The kneading apparatus is
not particularly limited and may be a conventionally known
vertical reaction vessel, mixing tank, kneading tank, or a
single-screw or multi-screw horizontal kneading apparatus
such as a single-screw or multi-screw extruder or kneader,
for example. The mixing time with a polymer compound is
not particularly limited. Although this depends on the
mixing apparatus and the mixing temperature, the mixing
time is preferably 0.1 minutes to 2 hours, more preferably
0.2 minutes to 60 minutes, and still more preferably 0.2
minutes to 3 0 minutes.
The solvent may be one that is inert to the polymer
compound and the cyclic carbodiimide compound. In
70
#
particular, a solvent that has affinity for both of them
and at least partially dissolves both of them is
preferable.
Examples of usable solvents include hydrocarbonbased
solvents, ketone-based solvents, ester-based
solvents, ether-based solvents, halogen-based solvents,
and amide-based solvents.
Examples of hydrocarbon-based solvents include
hexane, cyclohexane, benzene, toluene, xylene, heptane,
and decane. Examples of ketone-based solvents include
acetone, methyl ethyl ketone, diethyl ketone,
cyclohexanone, and isophorone. Examples of ester-based
solvents include ethyl acetate, methyl acetate, ethyl
succinate, methyl carbonate, ethyl benzoate, and
diethylene glycol diacetate. Examples of ether-based
solvents include diethyl ether, dibutyl ether,
tetrahydrofuran, dioxane, diethylene glycol dimethyl ether,
triethylene glycol diethyl ether, and diphenyl ether.
Examples of halogen-based solvents include
dichloromethane, chloroform, tetrachloromethane,
dichloroethane, 1, 1', 2 , 2'-tetrachloroethane, chlorobenzene,
and dichlorobenzene. Examples of amide-based solvents
include formamide, N,N-dimethylformamide, N,Ndimethylacetamide,
and N-methyl-2-pyrrolidone. These
solvents may be used alone. They may also be used as a
71
#
mixed solvent if desired.
In the invention, the solvent is used in an amount
within a range of 1 to 1,000 parts by weight per 100 parts
by weight of the total of the polymer compound and the
cyclic carbodiimide compound. When the amount is less
than 1 part by weight, the application of the solvent has
no significance. Although there is no particular upper
limit on the amount of the solvent to be used, in terms of
operativity and reaction efficiency, the upper limit is
about 1,0 00 parts by weight.
In the case where a method in which a polymer
compound in solid state is brought into contact with a
liquid having the cyclic carbodiimide compound dissolved,
dispersed, or melted therein, thereby impregnating the
polymer compound with the cyclic carbodiimide compound, is
employed, it is possible to employ a method in which the
polymer compound in solid state is brought into contact
with the carbodiimide compound dissolved in the solvent, a
method in which the polymer compound in solid state is
brought into contact with an emulsion of the cyclic
carbodiimide compound, or the like. As a contact method,
it is preferable to employ a method in which the polymer
compound is immersed in the cyclic carbodiimide compound,
a method in which the cyclic carbodiimide compound is
applied or sprayed to the polymer compound, or the like.
72
The capping reaction of the cyclic carbodiimide
compound of the invention can take place at a temperature
of room temperature (25°C) to 300°C, approximately.
However, in terms of reaction efficiency, the temperature
is preferably within a range of 50 to 280°C, more
preferably 100 to 280°C, whereby the reaction is further
promoted. The reaction easily proceeds at a temperature
where the polymer compound is molten. However, in order
to prevent the cyclic carbodiimide compound from
sublimation, decomposition, or the like, it is preferable
to carry out the reaction at a temperature of less than
300°C. The application of a solvent is also effective in
reducing the polymer melting temperature and increasing
stirring efficiency.
Although the reaction proceeds rapidly enough in the
absence of a catalyst, it is also possible to use a
catalyst to promote the reaction. As the catalyst,
catalysts used for conventional linear carbodiimide
compounds (JP-A-2005-2174) are applicable. Examples
thereof include alkali metal compounds, alkaline-earth
metal compounds, tertiary amine compounds, imidazole
compounds, quaternary ammonium salts, phosphine compounds,
phosphonium salts, phosphoric acid esters, organic acids,
and Lewis acid. They may be used alone, and it is also
possible to use two or more kinds. The amount of the
73
catalyst to be added is not particularly limited, but is
preferably 0.001 to 1 part by weight, more preferably 0.01
to 0.1 parts by weight, and most preferably 0.02 to 0.1
parts by weight per 100 parts by weight of the total of
the polymer compound and the cyclic carbodiimide compound.
The amount of the cyclic carbodiimide compound to be
applied is selected such that the amount of carbodiimide
groups contained in the cyclic carbodiimide compound is
within a range of 0.5 to 100 equivalents per equivalent of
acidic groups. When the amount is less than 0.5
equivalents, the application of the carbodiimide may have
no significance. When the amount is more than 100
equivalents, the properties of the substrate may change.
From such a point of view, based on the above basis, the
amount is preferably selected within a range of 0.6 to 75
equivalents, more preferably 0.65 to 50 equivalents, still
more preferably 0.7 to 30 equivalents, and particularly
preferably 0.7 to 20 equivalents.
Examples
Hereinafter, the invention will be described in
further detail through examples. Physical properties were
measured by the following methods.
(1) Identification of Cyclic Carbodiimide Structure by
74
NMR:
A synthesized cyclic carbodiimide compound was
confirmed by ^H-NMR and ^^C-NMR. JNR-EX270 manufactured by
JEOL was used for NMR. Deuterated chloroform was used as
the solvent.
(2) Identification of Carbodiimide Backbone of Cyclic
Carbodiimide by IR:
The presence of the carbodiimide backbone of a
synthesized cyclic carbodiimide compound was confirmed by
FT-IR at 2,100 to 2,200 cm"^, which is characteristic to a
carbodiimide. Magna-750 manufactured by Thermo Nicolet
was used for FT-IR.
(3) Carboxyl Group Concentration
A sample was dissolved in purified o-cresol,
dissolved in a nitrogen stream, and titrated with an
ethanol solution of 0.05 N potassium hydroxide using
bromocresol blue as an indicator.
Example 1: Synthesis of Cyclic Carbodiimide CCl (Scheme 1)
CCl: MW = 312
75
MeO. ^^^ N^=^^^^^^^^^^^^^^N ^^^ OMe
O O
Step (la)
4-Methoxy-2-nitrophenol (0.11 mol), 1,2-
dibromoethane (0.05 mol), potassium carbonate (0.33 mol),
and 200 ml of N,N-dimethylf ormamide were placed in a
reactor equipped with a stirrer and a heater in a N2
atmosphere and allowed to react at 130°C for 12 hours.
DMF was then removed under reduced pressure. The
resulting solid was dissolved in 200 ml of dichloromethane,
followed by partitioning with 100 ml of water three times.
The organic layer was dried over 5 g of sodium sulfate,
and dichloromethane was removed under reduced pressure to
give an intermediate product A (nitro compound).
Step (2a)
Next, the intermediate product A (0.1 mol), 5%
palladium carbon (Pd/C) (1 g) , and 200 ml of
ethanol/dichloromethane (70/30) were placed in a reactor
equipped with a stirrer. The reactor was purged with
hydrogen five times, and the mixture was allowed to react
at 2 5°C under constant supply of hydrogen. The reaction
76
is terminated when hydrogen stops decreasing. Pd/C was
recovered, and the mixed solvent was removed to give an
intermediate product B (amine compound).
Step (3a)
Next, triphenylphosphine dibromide (0.11 mol) and
150 ml of 1,2-dichloroethane are placed in a reactor
equipped with a stirrer, a heater, and a dropping funnel
in a N2 atmosphere and stirred. Then, a solution of the
intermediate product B (0.05 mol) and triethylamine (0.25
mol) dissolved in 50 ml of 1,2-dichloroethane is slowly
added dropwise at 25°C. After the completion of dropping,
the mixture is allowed to react at 70°C for 5 hours.
Subsequently, the reaction solution was filtered, and the
filtrate was partitioned with 100 ml of water five times.
The organic layer was dried over 5 g of sodium sulfate,
and 1,2-dichloroethane was removed under reduced pressure
to give an intermediate product C (triphenylphosphine
compound).
Step (4a)
Next, di-tert-butyl dicarbonate (0.11 mol), N,Ndimethyl-
4-aminopyridine (0.055 mol), and 150 ml of
dichloromethane are placed in a reactor equipped with a
stirrer and a dropping funnel in a N2 atmosphere and
77
stirred. Then, 100 ml of dichloromethane having dissolved
therein the intermediate product C (0.05 mol) is slowly
added dropwise at 2 5°C. After dropping, the mixture is
allowed to react for 12 hours. Subsequently,
dichloromethane was removed, and the resulting solid was
purified to give CCl. The structure of CCl was confirmed
by NMR and IR.
Example 2: Synthesis of Cyclic Carbodiimide CC2 (Scheme 1)
CC2: MW = 636
MeO OMe
O O
O O
MeO OMe
Step (lA)
4-Methoxy-2-nitrophenol (0.11 mol), pentaerythrityl
tetrabromide (0.025 mol), potassium carbonate (0.33 mol),
and 200 ml of N, N-dimethylformamide were placed in a
78
reactor equipped with a stirrer and a heater in a N2
atmosphere and allowed to react at 130°C for 12 hours.
DMF was then removed under reduced pressure. The
resulting solid was dissolved in 200 ml of dichloromethane,
followed by partitioning with 100 ml of water three times.
The organic layer was dried over 5 g of sodium sulfate,
and dichloromethane was removed under reduced pressure to
give an intermediate product D (nitro compound).
Step (2A)
Next, the intermediate product D (0.1 mol), 5%
palladium carbon (Pd/C) (2 g) , and 400 ml of
ethanol/dichloromethane (70/30) were placed in a reactor
equipped with a stirrer. The reactor was purged with
hydrogen five times, and the mixture was allowed to react
at 2 5°C under constant supply of hydrogen. The reaction
is terminated when hydrogen stops decreasing. Pd/C was
recovered, and the mixed solvent was removed to give an
intermediate product E (amine compound).
Step (3A)
Next, triphenylphosphine dibromide (0.11 mol) and
150 ml of 1,2-dichloroethane are placed in a reactor
equipped with a stirrer, a heater, and a dropping funnel
in a N2 atmosphere and stirred. Then, a solution of the
79
intermediate product E (0.02 5 raol) and triethylamine (0.25
mol) dissolved in 50 ml of 1,2-dichloroethane is slowlyadded
dropwise at 25°C. After the completion of dropping,
the mixture is allowed to react at 70°C for 5 hours.
Subsequently, the reaction solution was filtered, and the
filtrate was partitioned with 100 ml of water five times.
The organic layer was dried over 5 g of sodium sulfate,
and 1,2-dichloroethane was removed under reduced pressure
to give an intermediate product F (triphenylphosphine
compound).
Step (4A)
Next, di-tert-butyl dicarbonate (0.11 mol), N,Ndimethyl-
4-aminopyridine (0.055 mol), and 150 ml of
dichloromethane are placed in a reactor equipped with a
stirrer and a dropping funnel in a N2 atmosphere and
stirred. Then, 10 0 ml of dichloromethane having dissolved
therein the intermediate product F (0.025 mol) is slowly
added dropwise at 2 5°C. After dropping, the mixture is
allowed to react for 12 hours. Subsequently,
dichloromethane was removed, and the resulting solid was
purified to give CC2. The structure of CC2 was confirmed
by NMR and JR.
Example 3: Synthesis of Cyclic Carbodiimide CC2 (Scheme 2)
80
step (lA)
4-Methoxy-2-nitrophenol (0.11 mol), pentaerythrityl
tetrabromide (0.025 mol), potassium carbonate (0.33 mol),
and 200 ml of N,N-dimethyl formamide were placed in a
reactor equipped with a stirrer and a heater in a N2
atmosphere and allowed to react at 130°C for 12 hours.
N,N-dimethylformamide was then removed under reduced
pressure. The resulting solid was dissolved in 200 ml of
dichloromethane, followed by partitioning with 100 ml of
water three times.
The organic layer was dried over 5 g of sodium
sulfate, and dichloromethane was removed under reduced
pressure to give an intermediate product D (nitro
compound).
Step (2A)
Next, the intermediate product D (0.1 mol), 5%
palladium carbon (Pd/C) (1.25 g) , and 500 ml of N,Ndimethylformamide
were placed in a reactor equipped with a
stirrer. The reactor was purged with hydrogen five times,
and the mixture was allowed to react at 2 5°C under
constant supply of hydrogen. The reaction is terminated
when hydrogen stops decreasing. Pd/C is recovered by
filtration, and the filtrate is placed in 3 L of water to
precipitate a solid. The solid was recovered and dried to
81
give an intermediate product E (amine compound).
Step (3B)
Next, the intermediate product E (0.025 mol) ,
imidazole (0.2 mol), carbon disulfide (0.2 mol), and 150
ml of 2-butanone are placed in a reactor equipped with a
stirrer, a heater, and a gas washing bottle containing
alkaline water in a N2 atmosphere. The reaction solution
is heated to a temperature of 80°C and allowed to react
for 15 hours. After the reaction, the precipitated solid
was recovered by filtration and washed to give an
intermediate product G (thiourea compound).
Step (4B)
Next, the intermediate product G (0.02 5 mol), ptoluenesulfonyl
chloride (0.1 mol), and 50 ml of pyridine
are placed in a reactor equipped with a stirrer in a N2
atmosphere and stirred. The mixture is allowed to react
at 25°C for 3 hours, and then 150 ml of methanol is added
and further stirred at 2 5°C for 1 hour. The precipitated
solid was recovered by filtration and washed to give CC2.
The structure of CC2 was confirmed by NMR and IR.
Example 4: Synthesis of Cyclic Carbodiimide CC2 (Scheme 2)
Step (lA)
82
4-Methoxy-2-nitrophenol (0.11 mol) , pentaerythrityl
tetrabromide (0.025 mol), potassium carbonate (0.33 mol),
and 200 ml of N,N-dimethyl formamide were placed in a
reactor equipped with a stirrer and a heater in a N2
atmosphere and allowed to react at 130°C for 12 hours.
N,N-dimethylformamide was then removed under reduced
pressure. The resulting solid was dissolved in 200 ml of
dichloromethane, followed by partitioning with 10 0 ml of
water three times.
The organic layer was dried over 5 g of sodium
sulfate, and dichloromethane was removed under reduced
pressure to give an intermediate product D (nitro
compound).
Step (2A)
Next, the intermediate product D (0.1 mol), 5%
palladium carbon (Pd/C) (1.25 g) , and 500 ml of N,Ndimethylformamide
were placed in a reactor equipped with a
stirrer. The reactor was purged with hydrogen five times,
and the mixture was allowed to react at 25°C under
constant supply of hydrogen. The reaction is terminated
when hydrogen stops decreasing. Pd/C is recovered by
filtration, and the filtrate is placed in 3 L of water to
precipitate a solid. The solid was recovered and dried to
give an intermediate product E (amine compound).
83
step (3B)
Next, the intermediate product E (0.025 mol) ,
imidazole (0.2 mol), and 125 ml of acetonitrile were
placed in a reactor equipped with a stirrer, a heater, and
a dropping funnel in a N2 atmosphere, and diphenyl
phosphite (0.1 mol) was placed in the dropping funnel.
After purging with carbon dioxide five times, diphenyl
phosphite is slowly added dropwise with stirring at 2 5°C
under constant supply of carbon dioxide to allow the
mixture to react for 15 hours. After the reaction, the
precipitated solid was recovered by filtration and washed
to give an intermediate product H (urea compound).
Step (4B)
Next, the intermediate product H (0.025 mol), ptoluenesulfonyl
chloride (0.1 mol), and 50 ml of pyridine
are placed in a reactor equipped with a stirrer in a N2
atmosphere and stirred. The mixture is allowed to react
at 2 5°C for 3 hours, and then 150 ml of methanol is added
and further stirred at 2 5°C for 1 hour. The precipitated
solid was recovered by filtration and washed to give CC2.
The structure of CC2 was confirmed by NMR and IR.
Example 5: Synthesis of Cyclic Carbodiimide CC2 (Scheme 3)
84
m
step (IB)
4-Chloro-3-nitroanisole (0.125 mol), pentaerythritol
(0.025 mol), potassium carbonate (0.25 mol),
tetrabutylammonium bromide (0.018 mol), and 50 ml of N,Ndimethylformamide
were placed in a reactor equipped with a
stirrer and a heater in a N2 atmosphere and allowed to
react at 13 0°C for 12 hours. After the reaction, the
solution was added to 20 0 ml of water, and the
precipitated solid was recovered by filtration. The solid
was washed and dried to give an intermediate product D
(nitro compound).
Step (2A)
Next, the intermediate product D (0.1 mol), 5%
palladium carbon (Pd/C) (1.25 g) , and 500 ml of N,Ndimethylformamide
were placed in a reactor equipped with a
stirrer. The reactor was purged with hydrogen five times,
and the mixture was allowed to react at 2 5°C under
constant supply of hydrogen. The reaction is terminated
when hydrogen stops decreasing. Pd/C is recovered by
filtration, and the filtrate is placed in 3 L of water to
precipitate a solid. The solid was recovered and dried to
give an intermediate product E (amine compound).
Step (3B)
85
Next, the intermediate product E (0.025 mol) ,
imidazole (0.2 mol), and 125 ml of acetonitrile were
placed in a reactor equipped with a stirrer, a heater, and
a dropping funnel in a N2 atmosphere, and diphenyl
phosphite (0.1 mol) was placed in the dropping funnel.
After purging with carbon dioxide five times, diphenyl
phosphite is slowly added dropwise with stirring at 2 5°C
under constant supply of carbon dioxide to allow the
mixture to react for 15 hours. After the reaction, the
precipitated solid was recovered by filtration and washed
to give an intermediate product H (urea compound).
Step (4B)
Next, the intermediate product H (0.025 mol), ptoluenesulfonyl
chloride (0.1 mol), and 50 ml of pyridine
are placed in a reactor equipped with a stirrer in a N2
atmosphere and stirred. The mixture is allowed to react
at 25°C for 3 hours, and then 150 ml of methanol is added
and further stirred at 2 5°C for 1 hour. The precipitated
solid was recovered by filtration and washed to give CC2.
The structure of CC2 was confirmed by NMR and IR.
Example 6: Synthesis of Cyclic Carbodiimide CC2 (Scheme 3)
Step (IB)
4-Chloro-3-nitroanisole (0.125 mol), pentaerythritol
86
(0.025 mol), potassium carbonate (0.25 mol),
tetrabutylammonium bromide (0.018 mol), and 50 ml of N,Ndimethylformamide
were placed in a reactor equipped with a
stirrer and a heater in a N2 atmosphere and allowed to
react at 130°C for 12 hours. After the reaction, the
solution was added to 200 ml of water, and the
precipitated solid was recovered by filtration. The solid
was washed and dried to give an intermediate product D
(nitro compound).
Step (2A)
Next, the intermediate product D (0.1 mol), 5%
palladium carbon (Pd/C) (1.25 g) , and 500 ml of N,Ndimethylformamide
were placed in a reactor equipped with a
stirrer. The reactor was purged with hydrogen five times,
and the mixture was allowed to react at 25°C under
constant supply of hydrogen. The reaction is terminated
when hydrogen stops decreasing. Pd/C is recovered by
filtration, and the filtrate is placed in 3 L of water to
precipitate a solid. The solid was recovered and dried to
give an intermediate product E (amine compound).
Step (3B)
Next, the intermediate product E (0.025 mol),
imidazole (0.2 mol), carbon disulfide (0.2 mol), and 150
87
I
ml of 2-butanone are placed in a reactor equipped with a
stirrer, a heater, and a gas washing bottle containing
alkaline water in a N2 atmosphere. The reaction solution
is heated to a temperature of 80°C and allowed to react
for 15 hours. After the reaction, the precipitated solid
was recovered by filtration and washed to give an
intermediate product G (thiourea compound).
Step (4B)
Next, the intermediate product G (0.02 5 mol), ptoluenesulfonyl
chloride (0.1 mol), and 50 ml of pyridine
are placed in a reactor equipped with a stirrer in a N2
atmosphere and stirred. The mixture is allowed to react
at 2 5°C for 3 hours, and then 150 ml of methanol is added
and further stirred at 25°C for 1 hour. The precipitated
solid was recovered by filtration and washed to give CC2.
The structure of CC2 was confirmed by NMR and IR.
Example 7: Synthesis of Cyclic Carbodiimide CC2 (Scheme 4)
Step (IB)
4-Chloro-3-nitroanisole (0.125 mol), pentaerythritol
(0.025 mol), potassium carbonate (0.25 mol),
tetrabutylammonium bromide (0.018 mol), and 50 ml of N,Ndimethylformamide
were placed in a reactor equipped with a
stirrer and a heater in a N2 atmosphere and allowed to
88
I
react at 13 0°C for 12 hours. After the reaction, the
solution was added to 20 0 ml of water, and the
precipitated solid was recovered by filtration. The solid
was washed and dried to give an intermediate product D
(nitro compound).
Step (2A)
Next, the intermediate product D (0.1 mol), 5%
palladium carbon (Pd/C) (1.25 g) , and 500 ml of N,Ndimethylformamide
were placed in a reactor equipped with a
stirrer. The reactor was purged with hydrogen five times,
and the mixture was allowed to react at 2 5°C under
constant supply of hydrogen. The reaction is terminated
when hydrogen stops decreasing. Pd/C is recovered by
filtration, and the filtrate is placed in 3 L of water to
precipitate a solid. The solid was recovered and dried to
give an intermediate product E (amine compound).
Step (3A)
Next, triphenylphosphine dibromide (0.11 mol) and
150 ml of 1,2-dichloroethane are placed in a reactor
equipped with a stirrer, a heater, and a dropping funnel
in a N2 atmosphere and stirred. Then, a solution of the
intermediate product E (0.025 mol) and triethylamine (0.25
mol) dissolved in 50 ml of 1,2-dichloroethane is slowly
89
I
added dropwise at 25°C. After the completion of dropping,
the mixture is allowed to react at 70°C for 5 hours.
Subsequently, the reaction solution was filtered, and the
filtrate was partitioned with 100 ml of water five times.
The organic layer was dried over 5 g of sodium sulfate,
and 1,2-dichloroethane was removed under reduced pressure
to give an intermediate product F (triphenylphosphine
compound).
Step (4A)
Next, di-tert-butyl dicarbonate (0.11 mol), N,Ndimethyl-
4-aminopyridine (0.055 mol), and 150 ml of
dichloromethane are placed in a reactor equipped with a
stirrer and a dropping funnel in a N2 atmosphere and
stirred. Then, 100 ml of dichloromethane having dissolved
therein the intermediate product F (0.025 mol) is slowly
added dropwise at 2 5°C. After dropping, the mixture is
allowed to react for 12 hours. Subsequently,
dichloromethane was removed, and the resulting solid was
purified to give CC2. The structure of CC2 was confirmed
by NMR and IR.
Example 8: End-Capping of Polylactic Acid with CCl
0.005 parts by weight of tin octylate was added to
10 0 parts by weight of L-lactide (manufactured by
90
Musashino Chemical Laboratory, optical purity: 100%), and
the mixture was allowed to react in a nitrogen atmosphere
in a reactor equipped with a stirring blade at 180°C for 2
hours. As a catalyst deactivator, phosphoric acid was
added in an amount of 1.2 equivalents of tin octylate,
then the residual lactide was removed at 13.3 Pa, and the
resulting product was formed into chips to give poly(Llactic
acid). The obtained poly(L-lactic acid) had a
carboxyl group concentration of 14 eq/ton.
100 parts by weight of the obtained poly(L-lactic
acid) and 0.5 parts by weight of CCl were melt-kneaded in
a twin-screw extruder (cylinder temperature: 230°C) for a
residence time of 3 minutes. The carboxyl group
concentration had decreased to 0.4 eq/ton or less. In
addition, no isocyanate odor was detected at the outlet of
the extruder after kneading.
Example 9: End-Capping of Polylactic Acid with CC2
A reaction was carried out under the same conditions
as in Example 8, except that the cyclic carbodiimide CCl
was replaced with the cyclic carbodiimide CC2. As a
result, the carboxyl group concentration decreased to 0.3
eq/ton or less. In addition, no isocyanate odor was
detected at the outlet of the extruder after kneading.
91
i
4
Comparative Example 1: End-Capping of Polylactic Acid with
Linear Carbodiiraide Compound
A reaction was carried out under the same conditions
as in Example 8, except that the cyclic carbodiimide
compound CCl was replaced with a linear carbodiimide
"Stabaxol" I manufactured by Rhein Chemie Japan. As a
result, although the carboxyl group concentration was 0.4
eq/ton, a strong, offensive isocyanate odor was generated
at the outlet of the extruder.
Example 10: End-Capping of Polyamide with CC2
Poly(m-xylene adipamide) ("MX Nylon S6001"
manufactured by Mitsubishi Gas Chemical), a polyamide made
of m-xylylenediamine and adipic acid and having a carboxyl
group concentration of 70 eq/ton, was used. 100 parts by
weight of this poly(m-xylene adipamide) and 2.0 parts by
weight of CC2 were melt-kneaded in a twin-screw extruder
(cylinder temperature: 260°C) for a residence time of 3
minutes. The carboxyl group concentration had decreased
to 1.2 eq/ton or less. In addition, no isocyanate odor
was detected at the outlet of the extruder after kneading.
Comparative Example 2: End-capping of Polyamide with
Linear Carbodiimide Compound
A reaction was carried out under the same conditions
92
as in Example 10, except that the cyclic carbodiimide
compound CC2 was replaced with a linear carbodiimide
"Stabaxol" I manufactured by Rhein Chemie Japan. As a
result, although the carboxyl group concentration was 2.2
eq/ton, a strong, offensive isocyanate odor was generated
at the outlet of the extruder.
Example 12: Synthesis of Cyclic Carbodiimide CC3 (Scheme
1)
CCS: MW = 328
N C ^=N
Step (la)
o-Nitrophenol (0.11 mol), 1,4-
bis(bromomethyl)benzene (0.05 mol), potassium carbonate
(0.33 mol), and 200 ml of N, N-dimethyl formamide were
placed in a reactor equipped with a stirrer and a heater
in a N2 atmosphere and allowed to react at 13 0°C for 12
hours. DMF was then removed under reduced pressure. The
resulting solid was dissolved in 200 ml of dichloromethane,
93
I
followed by partitioning with 100 ml of water three times.
The organic layer was dried over 5 g of sodium sulfate,
and dichloromethane was removed under reduced pressure to
give an intermediate product I (nitro compound).
Step (2a)
Next, the intermediate product I (0.1 mol), 5%
palladium carbon (Pd/C) (1.5 g) , and 300 ml of
ethanol/dichloromethane (70/30) were placed in a reactor
equipped with a stirrer. The reactor was purged with
hydrogen five times, and the mixture was allowed to react
at 2 5°C under constant supply of hydrogen. The reaction
is terminated when hydrogen stops decreasing. Pd/C was
recovered, and the mixed solvent was removed to give an
intermediate product J (amine compound).
Step (3a)
Next, triphenylphosphine dibromide (0.11 mol) and
150 ml of 1,2-dichloroethane are placed in a reactor
equipped with a stirrer, a heater, and a dropping funnel
in a N2 atmosphere and stirred. Then, a solution of the
intermediate product J (0.05 mol) and triethylamine (0.25
mol) dissolved in 50 ml of 1,2-dichloroethane is slowly
added dropwise at 25°C. After the completion of dropping,
the mixture is allowed to react at 70°C for 5 hours.
94
Subsequently, the reaction solution was filtered, and the
filtrate was partitioned with 100 ml of water five times.
The organic layer was dried over 5 g of sodium sulfate,
and 1,2-dichloroethane was removed under reduced pressure
to give an intermediate product K (triphenylphosphine
compound).
Step (4a)
Next, di-tert-butyl dicarbonate (0.11 mol), N,Ndimethyl-
4-aminopyridine (0.055 mol), and 150 ml of
dichloromethane are placed in a reactor equipped with a
stirrer and a dropping funnel in a N2 atmosphere and
stirred. Then, 100 ml of dichloromethane having dissolved
therein the intermediate product K (0.05 mol) is slowly
added dropwise at 2 5°C. After dropping, the mixture is
allowed to react for 12 hours. Subsequently,
dichloromethane was removed, and the resulting solid was
purified to give CC3. The structure of CC3 was confirmed
by NMR and JR.
Example 13: Synthesis of Cyclic Carbodiimide CC3 (Scheme
2)
Step (la)
o-Nitrophenol (0.11 mol), 1,4-
bis(bromomethyl)benzene, 1,4-bis(bromomethyl)benzene (0.05
95
mol) , potassium carbonate (0.33 mol) , and 200 ml of N,Ndimethylformamide
were placed in a reactor equipped with a
stirrer and a heater in a N2 atmosphere and allowed to
react at 130°C for 12 hours. DMF was then removed under
reduced pressure. The resulting solid was dissolved in
200 ml of dichloromethane, followed by partitioning with
100 ml of water three times. The organic layer was dried
over 5 g of sodium sulfate, and dichloromethane was
removed under reduced pressure to give an intermediate
product I (nitro compound).
Step (2a)
Next, the intermediate product I (0.1 mol), 5%
palladium carbon (Pd/C) (1.5 g), and 200 ml of N,Ndimethylformamide
were placed in a reactor equipped with a
stirrer. The reactor was purged with hydrogen five times,
and the mixture was allowed to react at 2 5°C under
constant supply of hydrogen. The reaction is terminated
when hydrogen stops decreasing. Pd/C is recovered by
filtration, and the filtrate is placed in 600 ml of water
to precipitate a solid. The solid was recovered and dried
to give an intermediate product J (amine compound).
Step (3b)
Next, the intermediate product J (0.025 mol),
96
imidazole (0.1 mol), carbon disulfide (0.1 mol), and 100
ml of 2-butanone are placed in a reactor equipped with a
stirrer, a heater, and a gas washing bottle containing
alkaline water in a N2 atmosphere. The reaction solution
is heated to a temperature of 80°C and allowed to react
for 15 hours. After the reaction, the precipitated solid
was recovered by filtration and washed to give an
intermediate product L (thiourea compound).
Step (4b)
Next, the intermediate product L (0.02 5 mol), ptoluenesulfonyl
chloride (0.05 mol), and 40 ml of pyridine
are placed in a reactor equipped with a stirrer in a N2
atmosphere and stirred. The mixture is allowed to react
at 2 5°C for 3 hours, and then 12 0 ml of methanol is added
and further stirred at 2 5°C for 1 hour. The precipitated
solid was recovered by filtration and washed to give CC3.
The structure of 3 was confirmed by NMR and IR.
Example 14: Synthesis of Cyclic Carbodiimide CC4 (Scheme
1)
CC4: Mw = 388
97
o^^^>^ o
( Om ()) „
^^^ r^
N C N
Compound wherein m = 2 and n = 2
Step (lb)
o-Chloronitrobenzene (0.0625 mol), l,3-bis(2-
hydroxyethoxy)benzene (0.025 mol), potassium carbonate
(0.12 5 mol), tetrabutylammonium bromide (0.012 mol), and
40 ml of N,N-dimethylformamide were placed in a reactor
equipped with a stirrer and a heater in a N2 atmosphere
and allowed to react at 130°C for 15 hours. After the
reaction, the solution was added to 160 ml of water, and
the precipitated solid was recovered by filtration. The
solid was washed and dried to give an intermediate product
M (nitro compound).
Step (2a)
Next, the intermediate product M (0.1 mol), 5%
palladium carbon (Pd/C) (1.0 g) , and 200 ml of N,N-
98
I
m
dimethylformamide were placed in a reactor equipped with a
stirrer. The reactor was purged with hydrogen five times,
and the mixture was allowed to react at 2 5°C under
constant supply of hydrogen. The reaction is terminated
when hydrogen stops decreasing. Pd/C is recovered by
filtration, and the filtrate is placed in 600 ml of water
to precipitate a solid. The solid was recovered and dried
to give an intermediate product N (amine compound).
Step (3b)
Next, the intermediate product N (0.025 mol) ,
imidazole (0.1 mol), and 100 ml of acetonitrile were
placed in a reactor equipped with a stirrer, a heater, and
a dropping funnel in a N2 atmosphere, and diphenyl
phosphite (0.05 mol) was placed in the dropping funnel.
After purging with carbon dioxide five times, diphenyl
phosphite is slowly added dropwise with stirring at 2 5°C
under constant supply of carbon dioxide to allow the
mixture to react for 15 hours. After the reaction, the
precipitated solid was recovered by filtration and washed
to give an intermediate product O (urea compound).
Step (4b)
Next, the intermediate product 0 (0.025 mol), ptoluenesulfonyl
chloride (0.05 mol), and 40 ml of pyridine
99
are placed in a reactor equipped with a stirrer in a N2
atmosphere and stirred. The mixture is allowed to react
at 2 5°C for 3 hours, and then 12 0 ml of methanol is added
and further stirred at 2 5°C for 1 hour. The precipitated
solid was recovered by filtration and washed to give CC4.
The structure of CC4 was confirmed by NMR and IR.
Example 15: Synthesis of Cyclic Carbodiimide CCS (Scheme
1)
CC5: Mw = 2 96
^;;>.^ O O ^x;>^ ^ ^ ^ N = ^ C = N ^^^^
Compound wherein m = 2 and n = 2
Step (lb)
o-Chloronitrobenzene (0.0625 mol) , diethylene glycol
(0.025 mol), potassium carbonate (0.125 mol),
tetrabutylammonium bromide (0.012 mol), and 4 0 ml of N,Ndimethylformamide
were placed in a reactor equipped with a
stirrer and a heater in a N2 atmosphere and allowed to
react at 130°C for 15 hours. After the reaction, the
solution was added to 160 ml of water, and the
100
precipitated solid was recovered by filtration. The solid
was washed and dried to give an intermediate product P
(nitro compound).
Step (2a)
Next, the intermediate product P (0.1 mol), 5%
palladium carbon (Pd/C) (1.0 g) , and 150 ml of N,Ndimethylformamide
were placed in a reactor equipped with a
stirrer. The reactor was purged with hydrogen five times,
and the mixture was allowed to react at 2 5°C under
constant supply of hydrogen. The reaction is terminated
when hydrogen stops decreasing. Pd/C is recovered by
filtration, and the filtrate is placed in 450 ml of water
to precipitate a solid. The solid was recovered and dried
to give an intermediate product Q (amine compound).
Step (3a)
Next, triphenylphosphine dibromide (0.11 mol) and
150 ml of 1,2-dichloroethane are placed in a reactor
equipped with a stirrer, a heater, and a dropping funnel
in a N2 atmosphere and stirred. Then, a solution of the
intermediate product Q (0.05 mol) and triethylamine (0.25
mol) dissolved in 50 ml of 1,2-dichloroethane is slowly
added dropwise at 25°C. After the completion of dropping,
the mixture is allowed to react at 70°C for 5 hours.
101
Subsequently, the reaction solution was filtered, and the
filtrate was partitioned with 100 ml of water five times.
The organic layer was dried over 5 g of sodium sulfate,
and 1,2-dichloroethane was removed under reduced pressure
to give an intermediate product R (triphenylphosphine
compound).
Step (4a)
Next, di-tert-butyl dicarbonate (0.11 mol), N,Ndimethyl-
4-aminopyridine (0.055 mol), and 150 ml of
dichloromethane are placed in a reactor equipped with a
stirrer and a dropping funnel in a N2 atmosphere and
stirred. Then, 100 ml of dichloromethane having dissolved
therein the intermediate product R (0.05 mol) is slowly
added dropwise at 2 5°C. After dropping, the mixture is
allowed to react for 12 hours. Subsequently,
dichloromethane was removed, and the resulting solid was
purified to give CC5. The structure of CC5 was confirmed
by NMR and IR.
Example 16: End-Capping of Polylactic Acid with CC3
0.005 parts by weight of tin octylate was added to
100 parts by weight of L-lactide (manufactured by
Musashino Chemical Laboratory, optical purity: 100%) , and
the mixture was allowed to react in a nitrogen atmosphere
102
#
in a reactor equipped with a stirring blade at 180°C for 2
hours. As a catalyst deactivator, phosphoric acid was
added in an amount of 1.2 equivalents of tin octylate,
then the residual lactide was removed at 13.3 Pa, and the
resulting product was formed into chips to give poly(Llactic
acid). The obtained poly(L-lactic acid) had a
carboxyl group concentration of 14 eq/ton.
100 parts by weight of the obtained poly(L-lactic
acid) and 1.0 part by weight of CC3 were melt-kneaded in a
twin-screw extruder (cylinder temperature: 230°C) for a
residence time of 3 minutes. The carboxyl group
concentration had decreased to 0.7 eq/ton or less. In
addition, no isocyanate odor was detected at the outlet of
the extruder after kneading.
Example 17: End-Capping of Polylactic Acid with CC5
A reaction was carried out under the same conditions
as in Example 16, except that the cyclic carbodiimide CC3
was replaced with the cyclic carbodiimide CC5. As a
result, the carboxyl group concentration decreased to 0.4
eq/ton or less. In addition, no isocyanate odor was
detected at the outlet of the extruder after kneading.
Example 18: End-Capping of Polyamide with CC4
Poly(m-xylene adipamide) ("MX Nylon S6001"
103
i
manufactured by Mitsubishi Gas Chemical), a polyamide made
of m-xylylenediamine and adipic acid and having a carboxyl
group concentration of 70 eq/ton, was used. 100 parts by
weight of this poly(m-xylene adipamide) and 3.0 parts by
weight of CC4 were melt-kneaded in a twin-screw extruder
(cylinder temperature: 260°C) for a residence time of 3
minutes. The carboxyl group concentration had decreased
to 1.9 eq/ton or less. In addition, no isocyanate odor
was detected at the outlet of the extruder after kneading.
Examplel9: Synthesis of Cyclic Carbodiimide CC6 (Scheme 1)
CC6: MW = 324
( (ff>\ )n
Me^"^^-^^"'^ N = C = N ^'^^^-^"'^ Me
Compound wherein m = 2 and n = 2
Step (lb)
4-Chloro-3-nitrotoluene (0.11 mol), diethylene
glycol (0.05 mol), potassium carbonate (0.33 mol), and 200
ml of N,N-dimethylformamide were placed in a reactor
equipped with a stirrer and a heater in a N2 atmosphere
and allowed to react at 130°C for 12 hours. DMF was then
104
removed under reduced pressure. The resulting solid was
dissolved in 200 ml of dichlorome thane, followed bypartitioning
with 100 ml of water three times. The
organic layer was dried over 5 g of sodium sulfate, and
dichloromethane, was removed under reduced pressure to give
an intermediate product P (nitro compound).
Step (2a)
Next, the intermediate product P (0.1 mol), 5%
palladium carbon (Pd/C) (1 g) , and 200 ml of
ethanol/dichloromethane (70/30) were placed in a reactor
equipped with a stirrer. The reactor was purged with
hydrogen five times, and the mixture was allowed to react
at 2 5°C under constant supply of hydrogen. The reaction
is terminated when hydrogen stops decreasing. Pd/C was
recovered, and the mixed solvent was removed to give an
intermediate product Q (amine compound).
Step (3a)
Next, triphenylphosphine dibromide (0.11 mol) and
150 ml of 1,2-dichloroethane are placed in a reactor
equipped with a stirrer, a heater, and a dropping funnel
in a N2 atmosphere and stirred. Then, a solution of the
intermediate product Q (0.05 mol) and triethylamine (0.25
mol) dissolved in 50 ml of 1,2-dichloroethane is slowly
105
added dropwise at 25°C. After the completion of dropping,
the mixture is allowed to react at 70°C for 5 hours.
Subsequently, the reaction solution was filtered, and the
filtrate was partitioned with 100 ml of water five times.
The organic layer was dried over 5 g of sodium sulfate,
and 1,2-dichloroethane was removed under reduced pressure
to give an intermediate product R (triphenylphosphine
compound).
Step (4a)
Next, di-tert-butyl dicarbonate (0.11 mol), N,Ndimethyl-
4-aminopyridine (0.055 mol), and 150 ml of
dichloromethane are placed in a reactor equipped with a
stirrer and a dropping funnel in a N2 atmosphere and
stirred. Then, 100 ml of dichloromethane having dissolved
therein the intermediate product R (0.05 mol) is slowly
added dropwise at 2 5°C. After dropping, the mixture is
allowed to react for 12 hours. Subsequently,
dichloromethane was removed, and the resulting solid was
purified to give CC6. The structure of CC6 was confirmed
by NMR and IR.
106
Claims
1. A cyclic carbodiimide compound represented by the
following formula (i):
/ < r /"^ 1
°\ / II
I \ / 11
C X C I / \ I
N /O \ ^N
^ (i)
wherein
X is a divalent group represented by any one of the
following formulae (i-1) to (i-6) or a tetravalent group
represented by any one of the following formulae (i-7) and
(i-8) ,
when X is a divalent group, q is 0, and in the case
where X is selected from (i-1) and (i-2), Ar^ and Ar^ are
each independently an aromatic group substituted with a
substituent other than a Ci-s alkyl group and a phenyl
group, while in the case where X is selected from (i-3) to
(i-6) , Ar'"' and Ar^ are each independently an aromatic
group optionally substituted with a substituent, and
when X is a tetravalent group, q is 1, and Ar^ to Ar*
are each independently an aromatic group substituted with
a substituent other than a Ci-6 alkyl group and a phenyl
group:
107
(i-1)
wherein h is an integer of 1 to 6,
(i-2)
wherein m and n are each independently an integer of 0 to
3,
m'
\ /«
(i-3)
wherein m' and n' are each independently an integer of 0
to 3,
Q
(i-4)
wherein m'' and n'' are each independently an integer of 0
to 3,
(i-5)
108
#
wherein Y and Z are each an oxygen atom or a sulfur atom,
j, k, and r are each independently an integer of 1 to 4,
and i is an integer of 0 to 3,
^ C ' ) ^ 0 — A r ^ - O - f c ' )^
(i-6)
wherein Ar^ is an aromatic group, and s and t are each
independently an integer of 1 to 3,
V" / CH2 H2C (i-7)
wherein R'"' and R^ each independently represent a Ci-g alkyl
group or a phenyl group,
H2 H2
/ CH2 C
^2 (i-8).
2. The compound according to claim 1, wherein Ar^ to Ar^
are each independently an o-phenylene group or 1,2-
naphthalene-diyl group substituted with a substituent
other than a Ci-e alkyl group and a phenyl group.
3. A method for producing the cyclic carbodiimide
compound of claim 1, comprising:
(1) a step (la) of allowing a compound of the
109
following formula (a-1) and a compound of the following
formula (a-2) to react with a compound of the following
formula (b-1) to give a nitro compound of the following
formula (c) :
HO Ar^ NO2 (^_-L)
HO Ar^ NO2 (^_2)
E^ X E^ (^_,)
O X O
Ar^ Ar2
NO2 NO2 (^)
wherein
X, Ar''', and Ar^ are as defined in formula (i) , with
the proviso that X is a divalent group, and in the case
where X is selected from (i-1) and (i-2) , Ar^ and Ar^ are
each independently an aromatic group substituted with a
substituent other than a Ci-g alkyl group and a phenyl
group, while in the case where X is selected from (i-3) to
(i-6) , Ar^ and Ar^ are each independently an aromatic
group optionally substituted with a substituent, and
E^ and E^ are each independently a group selected
from the group consisting of a halogen atom, a
toluenesulfonyloxy group, a methanesulfonyloxy group, a
benzenesulfonyloxy group, and a p-bromobenzenesulfonyloxy
group;
110
m
(2) a step (2a) of reducing the obtained nitro
compound to give an amine compound represented by the
following formula (d):
O X O
Ar^ Ar2
(3) a step (3a) of allowing the obtained amine
compound to react with triphenylphosphine dibromide to
give a triphenylphosphine compound represented by the
following formula (e-1):
/ I
N N
PAr-3 PAr^3 (e-i)
wherein Ar^ is a phenyl group; and
(4) a step (4a) of isocyanating the obtained
triphenylphosphine compound in a reaction system, followed
by direct decarboxylation to give a compound of the
following formula (f):
o-x-o
AT' >r2
\ /
N^C^N (f) .
4. The method for producing the cyclic carbodiimide
111
m
compound of claim 1 according to claim 3, wherein the step
(la) is replaced with a step (lb) of allowing a compound
of the following formula (a-i) and a compound of the
following formula (a-ii) to react with a compound of the
following formula (b-i):
E' Ar^ NO2 (^_i)
E' Ar^ NO2 (^_ii)
HO X OH (b-i)
wherein
X, Ar''", and Ar^ are as defined in formula (i) , X is
divalent, and in the case where X is selected from (i-1)
and (i-2), Ar^ and Ar^ are each independently an aromatic
group substituted with a substituent other than a Ci-e
alkyl group and a phenyl group, while in the case where X
is selected from (i-3) to (i-6), Ar''" and Ar^ are each
independently an aromatic group optionally substituted
with a substituent, and
E^ and E^ are each independently a group selected
from the group consisting of a halogen atom, a
toluenesulfonyloxy group, a methanesulfonyloxy group, a
benzenesulfonyloxy group, and a p-bromobenzenesulfonyloxy
group.
5. The method for producing the cyclic carbodiimide
compound of claim 1 according to claim 3, wherein
112
the step (3a) is replaced with a step (3b) of
allowing the amine compound to react with carbon dioxide
or carbon disulfide to give a urea compound or thiourea
compound represented by the following formula (e-2):
^o—x-o
\ /
HN C NH
Z (e-2)
wherein
X, Ar"'", and Ar^ are as defined in formula (i) , X is
divalent, and in the case where X is selected from (i-1)
and (i-2), Ar^ and Ar^ are each independently an aromatic
group substituted with a substituent other than a Ci-g
alkyl group and a phenyl group, while in the case where X
is selected from (i-3) to (i-6), Ar^ and Ar^ are each
independently an aromatic group optionally substituted
with a substituent, and
Z is an oxygen atom or a sulfur atom, and
the step (4a) is replaced with a step (4b) of
dehydrating the obtained urea compound or desulfurizing
the obtained thiourea compound.
6. A method for producing the cyclic carbodiimide
compound of claim 1, comprising:
(1) a step (lA) of allowing a compound of any one of
113
the following formulae (A-1) to (A-4) to react with a
compound of the following formula (B-l) to give a nitro
compound of the following formula (C):
HO Ar' NO2 (;^_i)
HO Ar^ NO2 (;^_2)
HO Ar^ NO2 (^_3)
HO Ar^ NO2 (A_4)
wherein
Ar^ to Ar* are as defined in formula (i) and are each
independently an aromatic group substituted with a
substituent other than a Ci-e alkyl group and a phenyl
group, and
E^ to E* are each independently a group selected from
the group consisting of a halogen atom, a
toluenesulfonyloxy group, a methanesulfonyloxy group, a
benzenesulfonyloxy group, and a p-bromobenzenesulfonyloxy
group,
E^ V (B-l)
H2 Hj
/ V
wherein Xi is ^^2 ,
114
N02 N02
n N NO2
O2N (^)
wherein X is as defined in formula (i) , with the proviso
that X is a tetravalent group represented by any one of
formulae (i-7) and (i-8);
(2) a step (2A) of reducing the obtained nitro
compound to give an amine compound of the following
formula (D):
NH2 NH2
Ari-°'^''^°--Ar2
(3) a step (3A) of allowing the obtained amine
compound to react with triphenylphosphine dibromide to
give a triphenylphosphine compound of the following
formula (E-1):
115
N=PAr^3 N=PAra3
Ar3-^ ^Ar^
Ar^ ^Ar
N-=PAi^3 N=PAi^3 (g_^)
wherein Ar^ is a phenyl group; and
(4) a step (4A) of isocyanating the obtained
triphenylphosphine compound in a reaction system, followed
by direct decarboxylation to give a compound (F) of the
following formula:
N=C=N
Ari ^Ar2
N=C^N (F) .
7. The method for producing the cyclic carbodiimide
compound of claim 1 according to claim 6, wherein the step
(lA) is replaced with a step (IB) of allowing a compound
of any one of the following formulae (A-i) to (A-iv) to
react with a compound of the following formula (B-i) to
give a nitro compound of formula (C):
E' Ar^ NO2 (;,_i)
E' Ar^ NO2 (;,_ii)
E' Ar^ NO2 (;,_iii)
116
E' Ar^ NO2 (;,_i^)
wherein
Ar'"' to Ar"* are as defined in formula (i) and are each
independently an aromatic group substituted with a
substituent other than a Ci_6 alkyl group and a phenyl
group, and
E^ to E^ are each independently a group selected from
the group consisting of a halogen atom, a
toluenesulfonyloxy group, a methanesulfonyloxy group, a
benzenesulfonyloxy group, and a p-bromobenzenesulfonyloxy
group,
HO OH
/ HO OH (B_i)
Hj H2
wherein Xi is "2 ,
NO2 NO2
Ar ^Ar
oj
wherein X is as defined in formula (i) , with the proviso
that X is a tetravalent group represented by any one of
formulae (i-7) and (i-8).
117
8. The method for producing the cyclic carbodiimide
compound of claim 1 according to claim 6, wherein
the step (3A) is replaced with a step (3B) of
allowing the amine compound to react with carbon dioxide
or carbon disulfide to give a urea compound or thiourea
compound of the following formula (E-2):
Z
II
HN C NH
3 / \^
Arl Ar
o o
\ /
HN C NH
Z (E-2)
wherein
Ar"'' to Ar* are as defined in formula (i) and are each
independently an aromatic group substituted with a
substituent other than a Ci-s alkyl group and a phenyl
group,
X is as defined in formula (i) and is a tetravalent
group represented by any one of formulae (i-7) and (i-8) ,
and
Z is an oxygen atom or a sulfur atom, and
the step (4A) is replaced with a step (4B) of
dehydrating the obtained urea compound or desulfurizing
118
the obtained thiourea compound.
9. An end-capping agent for polymer compounds,
comprising the cyclic carbodiimide compound represented by
formula (i) of claim 1 as an active ingredient.
10. An acidic group scavenger, comprising the cyclic
carbodiimide compound represented by formula (i) of claim
1 as an active ingredient.
Documents
Application Documents
| # | Name | Date |
|---|---|---|
| 1 | 11397-DELNP-2012.pdf | 2013-01-07 |
| 2 | 11397-delnp-2012-Form-3-(10-06-2013).pdf | 2013-06-10 |
| 3 | 11397-delnp-2012-Correspondence-Others-(10-06-2013).pdf | 2013-06-10 |
| 4 | 11397-delnp-2012-GPA.pdf | 2013-08-20 |
| 5 | 11397-delnp-2012-Form-5.pdf | 2013-08-20 |
| 6 | 11397-delnp-2012-Form-3.pdf | 2013-08-20 |
| 7 | 11397-delnp-2012-Form-2.pdf | 2013-08-20 |
| 8 | 11397-delnp-2012-Form-1.pdf | 2013-08-20 |
| 9 | 11397-delnp-2012-Description(Complete).pdf | 2013-08-20 |
| 10 | 11397-delnp-2012-Correspondence-others.pdf | 2013-08-20 |
| 11 | 11397-delnp-2012-Claims.pdf | 2013-08-20 |
| 12 | 11397-delnp-2012-Abstract.pdf | 2013-08-20 |
| 13 | 11397-delnp-2012-Form-3-(18-11-2013).pdf | 2013-11-18 |
| 14 | 11397-delnp-2012-Correspondence Others-(18-11-2013).pdf | 2013-11-18 |
| 15 | 11397-delnp-2012-Form-18-(27-12-2013).pdf | 2013-12-27 |
| 16 | 11397-delnp-2012-Correspondence-Others-(27-12-2013).pdf | 2013-12-27 |
| 17 | 11397-delnp-2012-Form-3-(20-05-2014).pdf | 2014-05-20 |
| 18 | 11397-delnp-2012-Correspondence-Others-(20-05-2014).pdf | 2014-05-20 |
| 19 | 11397-delnp-2012-Correspondence-Others-(01-10-2014).pdf | 2014-10-01 |
| 20 | 11397-DELNP-2012 petition.pdf | 2014-10-07 |
| 21 | 11397-DELNP-2012-FORM 3 [10-10-2017(online)].pdf | 2017-10-10 |
| 22 | 11397-DELNP-2012-FER.pdf | 2017-11-02 |
| 23 | 11397-DELNP-2012-Verified English translation (MANDATORY) [06-03-2018(online)].pdf | 2018-03-06 |
| 24 | 11397-DELNP-2012-OTHERS-070318.pdf | 2018-03-14 |
| 25 | 11397-DELNP-2012-Correspondence-070318.pdf | 2018-03-14 |
| 26 | 11397-DELNP-2012-OTHERS [30-04-2018(online)].pdf | 2018-04-30 |
| 27 | 11397-DELNP-2012-Informationundersection8(2)(MANDATORY) [30-04-2018(online)].pdf | 2018-04-30 |
| 28 | 11397-DELNP-2012-FORM3 [30-04-2018(online)].pdf | 2018-04-30 |
| 29 | 11397-DELNP-2012-FORM-26 [30-04-2018(online)].pdf | 2018-04-30 |
| 30 | 11397-DELNP-2012-FER_SER_REPLY [30-04-2018(online)].pdf | 2018-04-30 |
| 31 | 11397-DELNP-2012-CORRESPONDENCE [30-04-2018(online)].pdf | 2018-04-30 |
| 32 | 11397-DELNP-2012-CLAIMS [30-04-2018(online)].pdf | 2018-04-30 |
| 33 | 11397-DELNP-2012-ABSTRACT [30-04-2018(online)].pdf | 2018-04-30 |
| 34 | 11397-DELNP-2012-Power of Attorney-030518.pdf | 2018-05-09 |
| 35 | 11397-DELNP-2012-Correspondence-030518.pdf | 2018-05-09 |
| 36 | 11397-DELNP-2012-RELEVANT DOCUMENTS [01-02-2019(online)].pdf | 2019-02-01 |
| 37 | 11397-DELNP-2012-PETITION UNDER RULE 137 [01-02-2019(online)].pdf | 2019-02-01 |
| 38 | 11397-DELNP-2012-Written submissions and relevant documents (MANDATORY) [19-03-2019(online)].pdf | 2019-03-19 |
| 39 | 11397-DELNP-2012-Written submissions and relevant documents (MANDATORY) [02-04-2019(online)].pdf | 2019-04-02 |
| 40 | 11397-DELNP-2012-PatentCertificate10-04-2019.pdf | 2019-04-10 |
| 41 | 11397-DELNP-2012-IntimationOfGrant10-04-2019.pdf | 2019-04-10 |
| 42 | 11397-DELNP-2012-RELEVANT DOCUMENTS [28-02-2020(online)].pdf | 2020-02-28 |
| 43 | 11397-DELNP-2012-FORM-26 [22-01-2021(online)].pdf | 2021-01-22 |
| 44 | 11397-DELNP-2012-RELEVANT DOCUMENTS [24-09-2021(online)].pdf | 2021-09-24 |
| 45 | 11397-DELNP-2012-RELEVANT DOCUMENTS [19-09-2022(online)].pdf | 2022-09-19 |
| 46 | 11397-DELNP-2012-RELEVANT DOCUMENTS [12-09-2023(online)].pdf | 2023-09-12 |
Search Strategy
| 1 | search_02-11-2017.pdf |