U.S. patent application number 14/482698 was filed with the patent office on 2015-05-14 for polyamine and method for producing thereof.
The applicant listed for this patent is RHODIA OPERATIONS. Invention is credited to Hiroyuki KITAYAMA, Yasunari MONGUCHI, Hironao SAJIKI.
Application Number | 20150133628 14/482698 |
Document ID | / |
Family ID | 44226449 |
Filed Date | 2015-05-14 |
United States Patent
Application |
20150133628 |
Kind Code |
A1 |
KITAYAMA; Hiroyuki ; et
al. |
May 14, 2015 |
POLYAMINE AND METHOD FOR PRODUCING THEREOF
Abstract
A method for producing a polyamine is described that provides
excellent safety, a lot of flexibility regarding a variety of its
productions, and that can produce a polyamine of high-molecular
weight easily and inexpensively. The polyamine includes a
combination of units of formula (1) or (2):
--(NH--(CH.sub.2).sub.m--NH--(CH.sub.2).sub.n)-- (1) (in the
formula (1), independently in every unit, "m" indicates an integral
number of 0 or more and "n" indicates an integral number of 3 or
more.) --(NH--Y--NH--Z)-- (2) (in the formula (2), independently in
every unit, "Y" and "Z" are the same as or different from each
other, and they indicate substituted or unsubstituted groups
including unsaturated aliphatic, cyclic aliphatic or aromatic
hydrocarbon radicals that can include hetero atoms.).
Inventors: |
KITAYAMA; Hiroyuki; (Osaka,
JP) ; SAJIKI; Hironao; (Gifu-shi, JP) ;
MONGUCHI; Yasunari; (Gifu-shi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
RHODIA OPERATIONS |
Aubervilliers |
|
FR |
|
|
Family ID: |
44226449 |
Appl. No.: |
14/482698 |
Filed: |
September 10, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13520770 |
Sep 26, 2012 |
8853457 |
|
|
PCT/JP2010/072794 |
Dec 17, 2010 |
|
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14482698 |
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Current U.S.
Class: |
528/347 ;
528/332; 528/335 |
Current CPC
Class: |
C08G 73/0266 20130101;
C08G 73/0206 20130101; C08G 73/0213 20130101 |
Class at
Publication: |
528/347 ;
528/335; 528/332 |
International
Class: |
C08G 73/02 20060101
C08G073/02 |
Foreign Application Data
Date |
Code |
Application Number |
Jan 4, 2010 |
JP |
2010-000211 |
Claims
1. A polyamine comprising a combination of units of formula (1) or
(2): --(NH--(CH.sub.2).sub.m--NH--(CH.sub.2).sub.n)-- (1) (in the
formula (1), independently in every unit, "m" indicates an integral
number of 0 or more and "n" indicates an integral number of 3 or
more.) --(NH--Y--NH--Z)-- (2) (in the formula (2), independently in
every unit, "Y" and "Z" are the same as or different from each
other, and they indicate substituted or unsubstituted groups
comprising unsaturated aliphatic, cyclic aliphatic or aromatic
hydrocarbon radicals that can include hetero atoms.)
2. The polyamine according to claim 1, wherein m and/or n of the
formula (1) are the same as each other among the combined
units.
3. The polyamine as defined by claim 1, wherein the and/or Z of the
formula (2) are the same as each other among combined units.
4. The polyamine as defined by claim 1, wherein the polyamine
comprises a polymer with a molecular weight of 1,000 or more as it
is measured by a mass spectrum.
5. A polyamine obtained by a reductive polycondensation
polymerization of diamine and dinitrile, wherein the diamine is at
least one member selected from the group consisting of a
substituted diamine, an unsubstituted diamine, an aliphatic
diamine, an aromatic diamine and an aliphatic-aromatic combined
diamine.
6. The polyamine according to claim 5, wherein the aliphatic
diamine is at least one member selected from the group consisting
of ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine,
1,2-butylenediamine, 1,3-butylenediamine, 1,4-butylenediamine,
2,3-butylenediamine, 1,2-cyclohexanediamine,
1,3-cyclohexanediamine, 1,4-cyclohexanediamine, hydrazine,
pentamethylenediamine, hexamethylenediamine, heptamethylenediamine,
octamethylenediamine, nonamethylenediamine, decamethylenediamine,
undecamethylenediamine, dodecamethylenediamine, piperazine,
diaminopiperazine, imidazolidine, diethylenetriamine,
triethylenetetramine, 3-oxa-1,5-diaminopentane,
1,3-diamino-2-propanol, 2-acetoxy-1,3-propanediamine, lysine,
2,4-diaminobutanoic acid and 2,3-diaminosuccinic acid, the aromatic
diamine is at least one member selected from the group consisting
of 1,2-phenylenediamine, 1,3-phenylenediamine,
1,4-phenylenediamine, tolylenediamine, naphthalenediamine,
N,N-diphenylethylenediamine, 3,3'-methylenedianiline,
4,4'-methylenedianiline, 1,1'-binaphthyl-2,2'-diamine,
diaminoferrocene, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl,
2,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 3,4'-diaminobiphenyl,
benzidine, 2,7-diamino-9H-fluorene, 2,3-diaminopyridine,
2,4-diaminopyridine, 2,5-diaminopyridine, 2,6-diaminopyridine,
3,4-diaminopyridine, 3,5-diaminopyridine, 2,3-diaminophenol,
2,4-diaminophenol, 2,5-diaminophenol, 2,6-diaminophenol,
3,4-diaminophenol, 3,5-diaminophenol, 2,4-diaminopyrimidine,
2,5-diaminopyrimidine, 4,5-diaminopyrimidine,
4,6-diaminopyrimidine, 2,3-diaminobenzotrifluoride,
2,4-diaminobenzotrifluoride, 2,5-diaminobenzotrifluoride,
2,6-diaminobenzotrifluoride, 3,4-diaminobenzotrifluoride,
3,5-diaminobenzotrifluoride, 2,3-diaminobenzoic acid,
2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid,
2,6-diaminobenzoic acid, 3,4-diaminobenzoic acid,
3,5-diaminobenzoic acid, 2,3-diaminobenzamide,
2,4-diaminobenzamide, 2,5-diaminobenzamide, 2,6-diaminobenzamide,
3,4-diaminobenzamide and 3,5-diaminobenzamide, the
aliphatic-aromatic combined diamine is at least one member selected
from the group consisting of o-xylenediamine, m-xylenediamine,
p-xylenediamine and methylaminoaniline, and the substituted group
is at least one member selected from the group consisting of an
alkyl group, a carboxyl group, an ester group, an alkoxy group, a
hydroxyl group, a tertiary amine, an aromatic hydrocarbon group and
a perfluoro alkyl group.
7. The polyamine as defined by claim 5, wherein the dinitrile is at
least one selected member from the group consisting of an aliphatic
dinitrile, an aromatic dinitrile and an aliphatic-aromatic combined
dinitrile.
8. The polyamine according to claim 7, wherein the aliphatic
dinitrile is at least one member selected from the group consisting
of malononitrile, succinonitrile, trimethylenedinitrile,
adiponitrile, 2-methylglutaronitirile, pimelonitrile,
suberonitrile, decanedinitrile, undecanedinitrile,
dodecanedinitrile, 3-oxaglutaronitrile, 1,2-cyclopentanedinitirle,
1,3-cyclopentanedinitirle, 1,2-cyclohexanedinitrile,
1,3-cyclohexanedinitrile, 1,4-cyclohexanedinitrile,
2,4-dicyano-3-methylglutaramide, 4-azaheptanedinitirle and
N-alkyl-4-azaheptanedinitrile, the aromatic dinitrile is at least
one member selected from the group consisting of phthalonitrile,
isophthalonitrile, terephthalonitrile, toluylenediamine,
naphthalenedinitirle, 2,4-dicyanoimidazole, 2,5-dicyanoimidazole,
4,5-dicyanoimidazole, 2,3-dicyanopyridine, 2,4-dicyanopyridine,
2,5-dicyanopyridine, 3,4-dicyanopyridine, 3,5-dicyanopyridine and
tetrafluorophthalonitile, the aliphatic-aromatic combined dinitrile
is at least one member selected from the group consisting of
1,2-phenylenediacetonitrile, 1,3-phenylenediacetonitrile,
1,4-phenylenediacetonitrile, 1,2-cyanomethylbenzonitrile,
1,3-cyanomethylbenzonitrile, 1,4-cyanomethylbenzonitrile,
3-(2-cyanophenoxy)propionitrile, 3-(3-cyanophenoxy)propionitrile,
3-(4-cyanophenoxy)propionitrile, 1,2-di(2-cyanoethoxy)benzene,
1,3-di(2-cyanoethoxy)benzene and 1,4-di(2-cyanoethoxy)benzene, and
the substituted group is at least one member selected from the
group consisting of an alkyl group, a carboxyl group, an ester
group, an alkoxy group, a hydroxyl group, a tertiary amine, an
aromatic hydrocarbon group and a perfluoro alkyl group.
9.-25. (canceled)
Description
FIELD OF THE INVENTION
[0001] The present invention relates to polyamine and method for
producing thereof.
BACKGROUND OF THE INVENTION
[0002] Polyamine can have a wide variety of application in both
industrial and personal application fields, and it is used in, for
example, a wide variety of neutralizing agents, hardening agents of
epoxy, processing agents of textiles, paper chemicals, coating
agents, moisturizing agents of cosmetics, settling agents,
reformation agents for flowability of concrete, and the like.
DESCRIPTION OF THE RELATED ART
[0003] The method for producing polyamine of synthetic polymer are
well-known as disclosed in, for example, Japanese Patent
Application Laid-Open Publication No.11-158271. However, its
synthetic approaches are limited. Polyamines of high-molecular
weight that are industrially produced are only polyethylene imine,
polyvinyl amine and polyallyl amine.
[0004] However, with regard to polyethylene imine that is a typical
representative of polyamine of synthetic polymer, its basic
ingredients include ethylene imine that is highly toxic.
Accordingly, there is a problem in the light of safety and
environmental protection. Therefore, it is not allowed to leave its
monomer in productions. As a result, it is necessary to conduct a
cleaning operation of the monomer at the production and at
replacement of facilities, and then it drives up the cost of the
production.
[0005] In addition, cyclic amines that can be used as the monomer
are not produced. Accordingly, with regard to monomer unit, a
carbon number of the monomer is limited to two. Therefore, in the
light of the variety of polyamine that can be produced, there is
few flexibility.
[0006] Further, with regard to conventional methods for producing
ethylene diamine, though a small quantity of polymer can be
produced in a reaction of ammonia and ethylene dichloride, most of
its molecular weight is 200 to 300, and therefore it cannot be
deemed to be a high polymers. In addition, its appearance is
similar to that of pitch or tar component that includes polymers of
a wide variety of isomeric forms and molecular weight.
[0007] Further, there is a method of reacting ammonia and
dihalogeno compound other than ethylene dichloride in order to
change alkylene chain. However, as with producing of ethylene
diamine, polymer that can be produced is mostly that of
low-molecular weight. Even in the case of trying to produce polymer
of high-molecular weight, only polymer of low-molecular weight that
has complicated composition like tar is produced because it is
difficult to control the reaction.
[0008] With regard to other methods for producing polyalkylene
amine polymer, there is a method of producing Schiff base polymer
by reacting diamine and dialdehyde, and then reducing it. However,
it is difficult to accomplish the reaction because the method
relates to a reduction of polymer. Accordingly, there are problems
in solubility and reactivity of substrate, and efficiency of the
reduction. Therefore, it is difficult to produce the polyamine of
high-molecular weight, though it is possible to produce the polymer
that has the molecular weight of oligomer.
SUMMARY OF THE INVENTION
[0009] An object of the present application is to provide novel
polyamine and a method for producing thereof that has excellent
safety, a lot of flexibility regarding a variety of its products,
and that can produce the polyamine of high-molecular weight easily
and inexpensively.
[0010] In a production of polyamine, polyamine in the form of white
powder and viscous liquid can be produced by reductive condensation
of diamine and dinitrile in water/alcohol solution by hydrogen with
appropriately controlling pH of the reaction solution in the
presence of a supported platinum group metal catalyst. However, in
the above synthesis of amine by the reductive condensation, the
platinum group metal catalyst constitutes inert complexes as
described in the following formula (A). Therefore, the reaction
does not proceed and only products of low-molecular weight can be
provided. In addition, it is difficult to recover and reuse the
supported platinum group metal catalyst because the complexes as
described in the formula (A) elutes into the reaction solution.
##STR00001##
[0011] The inventors have drawn attention to the above problems and
extensively investigated to overcome them. As a result, they have
found the facts that it is necessary for amino groups related to
the reaction to be not in the condition of salt but in the
condition of free as functional groups. They also have found the
facts that the catalytic activity deteriorates enormously because
metal catalyst and diamine that is a basic ingredient and/or
ammonia form a complex in the high pH condition where the ammonia
by-product in the reaction of the amine and nitrile that are basic
ingredients exists. Further, they found the facts that the novel
polyamine of high-molecular weight can be provided by a method for
producing polyamine that can solve the above problems.
[0012] In one aspect, the present invention completed as the basis
of the above knowledge is:
[0013] a polyamine comprising a combination of units of the general
formula (1) or (2):
--(NH--(CH.sub.2).sub.m--NH--(CH.sub.2).sub.n)-- (1)
(in the formula (1), independently in every unit, "m" indicates an
integral number of 0 or more and "n" indicates an integral number
of 3 or more.)
--(NH--Y--NH--Z)-- (2)
(in the formula (2), independently in every unit, "Y" and "Z" are
the same as or different from each other, and they indicate
substituted or unsubstituted groups comprising unsaturated
aliphatic, cyclic aliphatic or aromatic hydrocarbon radical that
may includes hetero atoms.)
[0014] In one embodiment, the present invention is:
[0015] the polyamine wherein the "m"s and/or "n"s of the formula
(1) are the same as each other among the combined units.
[0016] In preferred embodiment, the present invention is:
[0017] the polyamine wherein the "Y"s and/or "Z"s of the formula
(2) are the same as each other among the combined units.
[0018] In another preferred embodiment, the present invention is:
the polyamine wherein the polyamine comprises a polymer of
molecular weight of 1000 or more as it is measured by a mass
spectrum.
[0019] In another aspect, the present invention is:
[0020] a polyamine obtained by a reductive polycondensation
polymerization of diamine and dinitrile, the diamine being at least
one selected from the group consisting of substituted or
unsubstituted diamine, aliphatic diamine, aromatic diamine and
aliphatic-aromatic combined diamine.
[0021] In one embodiment, the present invention is: The polyamine
wherein
[0022] the aliphatic diamine is at least one selected from the
group consisting of ethylenediamine, 1,2-propylenediamine,
1,3-propylenediamine, 1,2-butylenediamine, 1,3-butylenediamine,
1,4-butylenediamine, 2,3-butylenediamine, 1,2-cyclohexanediamine,
1,3-cyclohexanediamine, 1,4-cyclohexanediamine, hydrazine,
pentamethylenediamine, hexamethylenediamine, heptamethylenediamine,
octamethylenediamine, nonamethylenediamine, decamethylenediamine,
undecamethylenediamine, dodecamethylenediamine, piperazine,
diaminopiperazine, imidazolidine, diethylenetriamine,
triethylenetetramine, 3-oxa-1,5-diaminopentane,
1,3-diamino-2-propanol, 2-acetoxy-1,3-propanediamine, lysine,
2,4-diaminobutanoic acid and 2,3-diaminosuccinic acid, the aromatic
diamine is at least one selected from the group consisting of
1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine,
tolylenediamine, naphthalenediamine, N,N-diphenylethylenediamine,
3,3'-methylenedianiline, 4,4'-methylenedianiline,
1,1'-binaphthyl-2,2'-diamine, diaminoferrocene,
2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 2,4'-diaminobiphenyl,
3,3'-diaminobiphenyl, 3,4'-diaminobiphenyl, benzidine,
2,7-diamino-9H-fluorene, 2,3-diaminopyridine, 2,4-diaminopyridine,
2,5-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine,
3,5-diaminopyridine, 2,3-diaminophenol, 2,4-diaminophenol,
2,5-diaminophenol, 2,6-diaminophenol, 3,4-diaminophenol,
3,5-diaminophenol, 2,4-diaminopyrimidine, 2,5-diaminopyrimidine,
4,5-diaminopyrimidine, 4,6-diaminopyrimidine,
2,3-diaminobenzotrifluoride, 2,4-diaminobenzotrifluoride, 2,
5-diaminobenzotrifluoride, 2,6-diaminobenzotrifluoride,
3,4-diaminobenzotrifluoride, 3,5-diaminobenzotrifluoride,
2,3-diaminobenzoic acid, 2,4-diaminobenzoic acid,
2,5-diaminobenzoic acid, 2,6-diaminobenzoic acid,
3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid,
2,3-diaminobenzamide, 2,4-diaminobenzamide, 2,5-diaminobenzamide,
2,6-diaminobenzamide, 3,4-diaminobenzamide and
3,5-diaminobenzamide,
[0023] the aliphatic-aromatic combined diamine is at least one
selected from the group consisting of o-xylenediamine,
m-xylenediamine, p-xylenediamine and methylaminoaniline, and
[0024] the substituted group is at least one selected from the
group consisting of alkyl group, carboxyl group, ester group,
alkoxy group, hydroxyl group, tertiary amine, aromatic hydrocarbon
group and perfluoro alkyl group.
[0025] In preferred embodiment, the present invention is:
[0026] The polyamine wherein the dinitrile is at least one selected
from the group consisting of aliphatic dinitrile, aromatic
dinitrile and aliphatic-aromatic combined dinitrile.
[0027] In another preferred embodiment, the present invention is:
The polyamine wherein
[0028] the aliphatic dinitrile is at least one selected from the
group consisting of malononitrile, succinonitrile,
trimethylenedinitrile, adiponitrile, 2-methylglutaronitirile,
pimelonitrile, suberonitrile, decanedinitrile, undecanedinitrile,
dodecanedinitrile, 3-oxaglutaronitrile, 1,2-cyclopentanedinitirle,
1,3-cyclopentanedinitirle, 1,2-cyclohexanedinitrile,
1,3-cyclohexanedinitrile, 1,4-cyclohexanedinitrile,
2,4-dicyano-3-methylglutaramide, 4-azaheptanedinitirle and
N-alkyl-4 -azaheptanedinitrile,
[0029] the aromatic dinitrile is at least one selected from the
group consisting of phthalonitrile, isophthalonitrile,
terephthalonitrile, toluylenediamine, naphthalenedinitirle,
2,4-dicyanoimidazole, 2,5-dicyanoimidazole, 4,5-dicyanoimidazole,
2,3-dicyanopyridine, 2,4-dicyanopyridine, 2,5-dicyanopyridine,
3,4-dicyanopyridine, 3,5-dicyanopyridine and
tetrafluorophthalonitile,
[0030] the aliphatic-aromatic combined dinitrile is at least one
selected from the group consisting of 1,2-phenylenediacetonitrile,
1,3-phenylenediacetonitrile, 1,4-phenylenediacetonitrile,
1,2-cyanomethylbenzonitrile, 1,3-cyanomethylbenzonitrile,
1,4-cyanomethylbenzonitrile, 3-(2-cyanophenoxy)propionitrile,
3-(3-cyanophenoxy)propionitrile, 3-(4-cyanophenoxy)propionitrile,
1,2-di(2-cyanoethoxy)benzene, 1,3-di(2-cyanoethoxy)benzene and
1,4-di(2-cyanoethoxy)benzene, and
[0031] the substituted group is at least one selected from the
group consisting of alkyl group, carboxyl group, ester group,
alkoxy group, hydroxyl group, tertiary amine, aromatic hydrocarbon
group and perfluoro alkyl group.
[0032] In another aspect, the present invention is:
[0033] a method for producing a polyamine comprising a reductive
polycondensation polymerization of diamine and dinitrile with
elimination of ammonia in the condition of keeping pH of a reaction
system more basic than the neutralization point of the diamine and
more acidic than the pH to form a complex of a diamine and a metal
catalyst.
[0034] In one embodiment, the present invention is:
[0035] the method wherein the diamine is provided by a reduction of
dinitrile.
[0036] In preferred embodiment, the present invention is: a method
for producing a polyamine comprising a reductive polycondensation
polymerization of aminonitrile with elimination of ammonia in the
condition of keeping pH of a reaction system more basic than the
neutralization point of the amine and more acidic than the pH to
form a complex of a diamine and a metal catalyst.
[0037] In another preferred embodiment, the present invention
is:
[0038] the method wherein the aminonitrile is at least one selected
from the group consisting of glycinonitrile, aminopropionitorile,
2-aminobenzonitrile, 3-aminobenzonitrile, 4-aminobenzonitrile,
2-aminomethylbenzonitrile, 3-aminomethylbenzonitrile and
4-aminomethylbenzonitrile.
[0039] In another preferred embodiment, the present invention
is:
[0040] the method wherein the elimination of ammonia is conducted
by providing hydrogen to the reaction system in the presence of a
platinum group metal catalyst.
[0041] In another preferred embodiment, the present invention
is:
[0042] the method wherein the platinum group metal catalyst is
palladium or rhodium.
[0043] In another preferred embodiment, the present invention
is:
[0044] the method wherein the pH of the reaction system is kept at
10 or less.
[0045] In another preferred embodiment, the present invention
is:
[0046] the method wherein the pH of the reaction system is kept at
7 to 9.
[0047] In another preferred embodiment, the present invention
is:
[0048] the method wherein solvent used in the reaction system is
water or hydrophilic solvent.
[0049] In another preferred embodiment, the present invention
is:
[0050] the method wherein the hydrophilic solvent is a solvent
selected from the group consisting of alcohol, tetrahydrofuran,
dioxane and dimethylformamide.
[0051] In another preferred embodiment, the present invention
is:
[0052] the method wherein initial pH of the reaction system is
controlled by a pH-adjusting agent.
[0053] In another preferred embodiment, the present invention
is:
[0054] the method wherein the pH of the reaction system is
controlled by a neutralization of ammonia produced in the reaction
system.
[0055] In another preferred embodiment, the present invention
is:
[0056] the method wherein mineral acid is used in the
neutralization of ammonia.
[0057] In another preferred embodiment, the present invention
is:
[0058] the method wherein the pH of the reaction system is
controlled by a degassing of ammonia produced in the reaction
system with hydrogen.
[0059] In another preferred embodiment, the present invention
is:
[0060] the method wherein the hydrogen used in the degassing of
ammonia is reused in the elimination of ammonia.
[0061] In another preferred embodiment, the present invention
is:
[0062] the method wherein the metal catalyst used in the reductive
polycondensation polymerization is a metal catalyst that was used
in the other reductive polycondensation polymerization.
[0063] In another preferred embodiment, the present invention
is:
[0064] the method wherein the metal catalyst used in the reductive
polycondensation polymerization is a metal catalyst that was used
in the other reductive polycondensation polymerization and washed
by acid.
DESCRIPTION OF THE DRAWINGS
[0065] FIG. 1 is a IT-TOF-MASS chart of the polymer of Example
2.
[0066] FIG. 2 is a proton NMR chart of the
poly(ethyleneiminotetramethyleneimine) of Example 2, which was
measured by heavy methanol.
[0067] FIG. 3 is a proton NMR chart of the poly(hexamethyleneimine)
of Example 3, which was measured by heavy methanol.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0068] (Polyamine)
[0069] In the preferred embodiment, the polyamine of the present
invention comprises:
[0070] a combination of units of the general formula (1) or
(2):
--(NH--(CH.sub.2).sub.m--NH--(CH.sub.2).sub.n)-- (1)
[0071] (in the formula (1), independently in every unit, "m"
indicates an integral number of 0 or more and "n" indicates an
integral number of 3 or more.)
--(NH--Y--NH--Z)-- (2)
[0072] (in the formula (2), independently in every unit, "Y" and
"Z" are the same as or different from each other, and they indicate
substituted or unsubstituted groups comprising unsaturated
aliphatic, cyclic aliphatic or aromatic hydrocarbon radical that
may includes hetero atoms.)
[0073] The polyamine may be a linear polymer composed of repeated
units of the formula (1) or (2). The polyamine may be a branched
polymer composed of repeated units of the formula (1) or (2). The
"m"s and/or "n"s of the formula (1) may be the same as each other
among the combined units. The "Y"s and/or "Z"s of the formula (2)
may be the same as each other among the combined units. The "m" is
about 0 to 20 and the "n" is about 3 to 20 because available
monomers as basic ingredients are actually limited at this moment.
However, if the number of kinds of the available monomers increases
in the future, the numbers of the "m" and "n" also increase
accordingly as a matter of course. Both ends of the polyamine have,
for example, NH.sub.2 group.
[0074] The linear polyamine of high-molecular weight can have a
wide variety of application in both industrial and personal
application fields. However, only polyethyleneimine is produced as
a main-chain type polyamine so far. Correspondingly, the present
invention can provide the wide variety of the main-chain type
linear polyamines as described above.
[0075] The branched polyamine composed of the repeated units may
have a repeated unit of the following general formula (3) or (4) in
its branched parts:
##STR00002##
[0076] (in the formula (3), "m" indicates an integral number of 1
or more, "n" indicates an integral number of 3 or more. R1 and R2
are the same as or different from each other and they are groups
further comprising H or the repeated unit of the formula (3).)
##STR00003##
[0077] (in the formula (4), "Y" and "Z" are the same as or
different from each other, and they indicate substituted or
unsubstituted groups comprising unsaturated aliphatic, cyclic
aliphatic or aromatic hydrocarbon radical that may includes hetero
atoms. R3 and R4 are the same as or different from each other and
they are groups further comprising H or the repeated unit of the
formula (4).)
[0078] The branched polyamine composed of the repeated units may
have a net-like structure including, for example, primary,
secondary and tertiary amines.
[0079] The polyamine of the present invention may be a block
polymer, a graft polymer or random polymer.
[0080] The polyamine of the present invention may be a polyamine of
high-molecular weight being 1,000 or more, preferably 10,000 or
more, more preferably 30,000 or more, further preferably 70,000 or
more, further preferably 100,000 or more. The polyamine of the
present invention has advantages of suppressed hazardousness to a
human body and broad availability because it is a polymer of
high-molecular weight as described above.
[0081] It is difficult to measure an absolute molecular weight of
the polyamine directly. However, it is deemed that the polyamine is
a polymer of high-molecular weight being distributed in a range of
several tens of thousands or more because it is found when measured
by a mass spectrum that polymers of molecular weight being less
than 30,000 do not exist and it is found when measured by a
IT-TOF-MASS that a lot of polyvalent ions exist in 3,000 to 4,000
(mass number).
[0082] The polyamine of the present invention may be a polyamine
obtained by a reductive polycondensation polymerization of diamine
and dinitrile. The diamine is at least one selected from the group
consisting of substituted or unsubstituted diamine, aliphatic
diamine, aromatic diamine and aliphatic-aromatic combined diamine.
The aliphatic diamine is not limited particularly, but may be, for
example, at least one selected from the group consisting of
ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine,
1,2-butylenediamine, 1,3-butylenediamine, 1,4-butylenediamine,
2,3-butylenediamine, 1,2-cyclohexanediamine,
1,3-cyclohexanediamine, 1,4-cyclohexanediamine, hydrazine,
pentamethylenediamine, hexamethylenediamine, heptamethylenediamine,
octamethylenediamine, nonamethylenediamine, decamethylenediamine,
undecamethylenediamine, dodecamethylenediamine, piperazine,
diaminopiperazine, imidazolidine, diethylenetriamine,
triethylenetetramine, 3-oxa-1,5-diaminopentane,
1,3-diamino-2-propanol, 2-acetoxy-1,3-propanediamine, lysine,
2,4-diaminobutanoic acid and 2,3-diaminosuccinic acid. The aromatic
diamine is not limited particularly, but may be, for example, at
least one selected from the group consisting of
1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine,
tolylenediamine, naphthalenediamine, N,N-diphenylethylenediamine,
3,3'-methylenedianiline, 4,4'-methylenedianiline,
1,1'-binaphthyl-2,2'-diamine, diaminoferrocene,
2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 2,4'-diaminobiphenyl,
3,3'-diaminobiphenyl, 3,4'-diaminobiphenyl, benzidine,
2,7-diamino-9H-fluorene, 2,3-diaminopyridine, 2,4-diaminopyridine,
2,5-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine,
3,5-diaminopyridine, 2,3-diaminophenol, 2,4-diaminophenol,
2,5-diaminophenol, 2,6-diaminophenol, 3,4-diaminophenol,
3,5-diaminophenol, 2,4-diaminopyrimidine, 2,5-diaminopyrimidine,
4,5-diaminopyrimidine, 4,6-diaminopyrimidine,
2,3-diaminobenzotrifluoride, 2,4-diaminobenzotrifluoride, 2,
5-diaminobenzotrifluoride, 2,6-diaminobenzotrifluoride,
3,4-diaminobenzotrifluoride, 3,5-diaminobenzotrifluoride,
2,3-diaminobenzoic acid, 2,4-diaminobenzoic acid,
2,5-diaminobenzoic acid, 2,6-diaminobenzoic acid,
3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid,
2,3-diaminobenzamide, 2,4-diaminobenzamide, 2,5-diaminobenzamide,
2,6-diaminobenzamide, 3,4-diaminobenzamide and
3,5-diaminobenzamide. The aliphatic-aromatic combined diamine is
not limited particularly, but may be, for example, at least one
selected from the group consisting of o-xylenediamine,
m-xylenediamine, p-xylenediamine and methylaminoaniline. The
substituted group is not limited particularly, but may be, for
example, at least one selected from the group consisting of alkyl
group, carboxyl group, ester group, alkoxy group, hydroxyl group,
tertiary amine, aromatic hydrocarbon group and perfluoro alkyl
group.
[0083] The dinitrile is not limited particularly, but may be, for
example, at least one selected from the group consisting of
aliphatic dinitrile, aromatic dinitrile and aliphatic-aromatic
combined dinitrile. The aliphatic dinitrile is not limited
particularly, but may be, for example, at least one selected from
the group consisting of malononitrile, succinonitrile,
trimethylenedinitrile, adiponitrile, 2-methylglutaronitirile,
pimelonitrile, suberonitrile, decanedinitrile, undecanedinitrile,
dodecanedinitrile, 3-oxaglutaronitrile, 1,2-cyclopentanedinitirle,
1,3-cyclopentanedinitirle, 1,2-cyclohexanedinitrile,
1,3-cyclohexanedinitrile, 1,4-cyclohexanedinitrile,
2,4-dicyano-3-methylglutaramide, 4-azaheptanedinitirle and
N-alkyl-4-azaheptanedinitrile. The aromatic dinitrile is not
limited particularly, but may be, for example, at least one
selected from the group consisting of phthalonitrile,
isophthalonitrile, terephthalonitrile, toluylenediamine,
naphthalenedinitirle, 2,4-dicyanoimidazole, 2,5-dicyanoimidazole,
4,5-dicyanoimidazole, 2,3-dicyanopyridine, 2,4-dicyanopyridine, 2,
5-dicyanopyridine, 3,4-dicyanopyridine, 3,5-dicyanopyridine and
tetrafluorophthalonitile. The aliphatic-aromatic combined dinitrile
is not limited particularly, but may be, for example, at least one
selected from the group consisting of 1,2-phenylenediacetonitrile,
1,3-phenylenediacetonitrile, 1,4-phenylenediacetonitrile,
1,2-cyanomethylbenzonitrile, 1,3-cyanomethylbenzonitrile,
1,4-cyanomethylbenzonitrile, 3-(2-cyanophenoxy)propionitrile,
3-(3-cyanophenoxy)propionitrile, 3-(4-cyanophenoxy)propionitrile,
1,2-di(2-cyanoethoxy)benzene, 1,3-di(2-cyanoethoxy)benzene and
1,4-di(2-cyanoethoxy)benzene. The substituted group is not limited
particularly, but may be, for example, at least one selected from
the group consisting of alkyl group, carboxyl group, ester group,
alkoxy group, hydroxyl group, tertiary amine, aromatic hydrocarbon
group and perfluoro alkyl group.
[0084] The polyamine of the present invention has primary,
secondary and/or tertiary amines and then excellent water
solubility. A nonhazardous polyamine can be provided by selecting
substituent groups and the like of its monomer. Therefore, the
polyamine of the present invention can have a wide variety of
application, and it is useful as, for example, a moisturizing agent
of shampoo, cosmetics and the like, a neutralizing agent, an ink
adherence improving agent, a dispersing agent of pigment, a
hardening agent of epoxy and the like, a aggregating agent, a water
processing agent, a flowability improving agent of concrete, an
additive agent for metal plating, a bubble maintaining agent for
extinguisher, paper, fabric, a laminate anchoring agent of film, a
heavy metal chelating agent, a coating agent for inhibition of
metal oxidation, and further a substrate of DDS (Drug Delivery
System) that recently attracts attention.
[0085] (Method for Producing the Polyamine)
[0086] The method for producing the polyamine of the present
invention comprises a reductive polycondensation polymerization of
diamine and dinitrile with elimination of ammonia in the condition
of keeping pH of a reaction system more basic than the
neutralization point of the diamine and more acidic than the pH to
form a complex of a diamine and a metal catalyst.
[0087] Theoretical summary of a hypothetical reaction mechanism of
the reductive polycondensation polymerization of diamine and
dinitrile with elimination of ammonia can be explained by the
following general formula (7) where a palladium catalyst is used as
an example. In the formula (7), for the sake of simplicity, diamine
is shown as "R--NH.sub.2" that is described about only one of
terminal amino groups, and dinitrile is shown as "R'--CN" that is
described about only one of terminal nitrile groups. In this case,
Pd is used as a metal catalyst.
##STR00004##
[0088] Firstly, the dinitrile R'--CN is reduced to the imine
intermediate (E) by the first hydrogen contact reduction in the
reaction mechanism in the formula (7). As a result of this, a
polymerization reaction begins. The imine intermediate (E)
eliminates ammonia by a nucleophilic attack in priority to the
second hydrogen contact reduction. Then the second hydrogen contact
reduction is conducted and the reaction proceeds. Then
R--NHCH.sub.2--R' that has an amino group in one end and a nitrile
group in the other end is provided. The amino group and the nitrile
group in each end further reacts in the reaction mechanism of the
formula (7) and then the linear polyamine of high-molecular weight
is provided.
[0089] Further, in the reaction mechanism of the formula (7), the
nucleophilic attack by the secondary amine of the provided
R--NHCH.sub.2--R' to an analog of the imine intermediate
((R)(R'CH.sub.2)N(+).dbd.CH--R') produces the branched polyamine,
and the polyamine that has a net-like structure is provided by
repeat of the reaction.
[0090] However, the imine intermediate (E) is coordinated with
palladium. Accordingly, the primary amine is likely to react in
priority to the bulky secondary amine. Therefore, it is basically
deemed that the linear polymer is provided dominantly.
[0091] As mentioned above, the method for producing the polyamine
of the present invention makes use of the reaction with the amino
group in the end of the diamine and the nitrile in the end of the
dinitrile which are starting materials, and the method is
impervious to constructions between the amino groups in both ends
of the diamine and between the nitrile groups in both ends of the
dinitrile. Therefore, polyamines of desired constitutions can be
produced by selecting predetermined diamines and dinitriles.
[0092] In the method for producing the polyamine of the present
invention, a formation of a complex of the catalyst used in the
reaction and the diamine or the ammonia produced in the reaction
can be inhibited by keeping pH of the reaction system more basic
than the neutralization point of the diamine and keeping the amine
free, and simultaneously by keeping pH of the reaction system more
acidic than the pH to form a complex of a diamine and a metal
catalyst. This can ensure the reactivity of the diamine and can
enable the polymerization reaction to proceed gradely. Therefore,
polyamines of high-molecular weight being several tens of thousands
or more can be easily produced, though it is difficult to produce
them conventionally. The pH of the reaction system has an optimum
value according to used diamines and dinitriles, and the pH of the
reaction system is preferably kept at 10 or less. Further, it is
necessary to keep the pH more basic than the neutralization point
of the diamine in order for the amine to proceed its nucleophilic
reaction because the reactivity of the amine deteriorates in the
form of salt. Further, it is necessary to keep the pH more acidic
than the pH to form the complex of the diamine and the metal
catalyst. Accordingly, the pH of the reaction system is more
preferably kept at 7 to 9.
[0093] The pH at starting to form the complex of the diamine and
the metal catalyst is not measured strictly. However, in cases
where the reaction solution is left overnight (for example, for 12
hours at a room temperature) on an experimental basis, a coloration
of red to brown peculiar to the metal complex can be seen at pH of
9 or more. Accordingly, the pH at starting to form the complex is
estimated to be in the vicinity. Therefore, the pH at starting to
form a complex is defined to be pH when the solvent is colored
during leaving the diamine and dinitrile in the solvent in the
presence of the metal catalyst.
[0094] In the method for producing the polyamine of the present
invention, the diamine may be provided by a reduction of dinitrile.
In this case, a starting material of the reaction is a dinitrile
only. When a part of the dinitrile is reduced to diamine, the
reductive condensation of the diamine and the residual dinitrile
proceeds on the basis of the reaction mechanism of the formula (7).
By repeating these reactions, desired polyamines can be
provided.
[0095] In the method for producing the polyamine of the present
invention, an aminonitrile may be used as the starting material. In
this case, the reductive condensation of an amino group in one
aminonitrile molecule and a nitrile group in the other aminonitrile
molecule proceeds on the basis of the reaction mechanism of the
formula (7). By repeating these reactions, desired polyamines can
be provided. The aminonitrile is not limited particularly, but may
be, for example, at least one selected from the group consisting of
glycinonitrile, aminopropionitorile, 2-aminobenzonitrile,
3-aminobenzonitrile, 4-aminobenzonitrile,
2-aminomethylbenzonitrile, 3-aminomethylbenzonitrile and
4-aminomethylbenzonitrile. In the case of using a-aminonitrile such
as glycinonitrile, its monomer is unstable and six-membered ring
piperazine derivatives which have stable structure are
preferentially produced. Therefore, small quantity of polymers is
provided. However, if .beta.-aminonitrile and the like are used,
they do not have a six-membered ring structure and the reaction can
proceed gradely. Further, various kinds of polyamines can be
synthesized because aminonitriles of the starting materials are
reflected in the structures between the amino groups.
[0096] In the method for producing the polyamine of the present
invention, the elimination of ammonia is conducted by providing
hydrogen in the presence of the metal catalyst. The metal catalyst
used in this case is not limited particularly, but may be, for
example, a platinum group metal catalyst such as palladium or
rhodium. The examination results by the inventors provide the fact
that polyalkylene polyamine can be provided at a low cost and high
yield in using palladium as the platinum group metal catalyst, but
branched polyamines are produced as by-products in small quantity.
Further, the examination results by the inventors provide the fact
that linear polyamines can be provided at a high cost but
selectively in using rhodium.
[0097] The platinum group metal catalyst can be supported by a
support such as carbon, silica or alumina. By the support, the
platinum group metal disperses finely, a function as a catalyst
improves and a recovery of the catalyst after the reaction becomes
easy. The examination results by the inventors provide the fact
that desired polyamines can be provided at high yield and high
selectively in using carbon as the support.
[0098] If an acid or an ammonium salt thereof is added to the
reaction solution as a reaction accelerator, the reaction proceeds
more efficiently. The added acid is not limited particularly, but
may be, for example, at least one selected from the group
consisting of organic acid such as trifluoroacetic acid, acetic
acid and benzoic acid, inorganic acid such as hydrochloric acid and
ammonium salt thereof. Among them, the addition of the ammonium
salt of the organic acid enables the reaction to proceed more
gradely.
[0099] In the method for producing the polyamine of the present
invention, the solvent used in the reaction system is not limited
particularly, but may be water or hydrophilic solvent such as
alcohol, tetrahydrofuran, dioxane or dimethylformamide.
[0100] In the method for producing the polyamine of the present
invention, it is very important to control the pH of the reaction
system from the early period. A pH-adjusting agent can be used as
the controlling of the pH. The pH-adjusting agent is not limited
particularly, but may be, for example, inexpensive mineral acids
and the like in using the free amine, and caustic soda, caustic
potash, calcium hydrate, sodium carbonate and the like in using the
salt of amine. In the case of using the salt, salts produced by a
neutralizing may be removed by a filtration in order to proceed the
reaction effectively.
[0101] The pH of the above reaction system is increased by ammonia
produced in the reaction system. Accordingly, the pH may be
controlled by a neutralizing. For the neutralizing of ammonia, it
is not limited particularly, but for example, mineral acid and the
like can be used.
[0102] The pH of the above reaction system may be controlled by a
degassing of ammonia produced in the reaction system with hydrogen.
In this case, the hydrogen used in the degassing of ammonia may be
reused in the elimination of ammonia in the reaction mechanism of
the formula (7) after separating ammonia.
[0103] The metal catalyst used in the reductive polycondensation
polymerization may be a metal catalyst that was used in the other
reductive polycondensation polymerization. In this case, it is
effective that the metal catalyst that was used in the other
reductive polycondensation polymerization is washed by inexpensive
strong acid such as hydrochloric acid and the like and then reused
in order to exclude an influence of the residual amine.
[0104] Typical polyamines of the present invention are, for
example, produced by the reductive polycondensation polymerization
with the elimination of ammonia between hexamethylenediamine,
2-methyl-1,5-pentanediamine that is an isomeric form of
hexamethylenediamine and a mixture of these compounds used as the
amine, and adiponitrile, methylglutaronitirile that is an isomeric
form of adiponitrile and a mixture of these compounds used as the
nitrile.
[0105] The method for producing the polyamine of the present
invention enables polyamines of all kinds of constitutions to be
produced easily by selecting constitutions of the parts between the
amino groups in the both ends of the diamine, constitutions of the
parts between the nitrile groups in the both ends of the dinitrile
and constitutions of the parts other than amino group and the
nitrile group of the aminonitrile because the reaction mechanism
depends almost exclusively on the reaction between the amino group
in the end of the diamine and the nitrile group in the end of the
dinitrile.
EXAMPLES
[0106] Examples of the present invention are described below.
However, they are provided for a better understanding of the
present invention, and do not intend to limitations of the present
invention.
Example 1
[0107] 6.0 g of ethylenediamine (0.1 mol), 10.8 g of adiponitrile
(0.1 mol), 1.7 g of ammonium acetate, 1.2 g of 10% palladium carbon
(50% hydroscopic compound) and 30 ml of methanol were added in a 50
ml, four-necked round bottom flask, fitted with a stirrer,
thermometer, a hydrogen blowing tube, a pH meter electrode, an
dropping funnel and a condenser, and then an atmosphere in the
reaction system was replaced by argon for explosion protection.
[0108] Concentrated hydrochloric acid was then added in the
reaction system from the dropping funnel and pH of the reaction
solution was controlled to 8.9.
[0109] Fine bubbles of hydrogen was then injected by using a
sintered glass at normal pressures (pressure of 10 cm of liquid
paraffin) with stirring the reaction solution at ambient
temperature. The blow-by gas was diffused after bubbling with water
for explosion protection. The pH of the reaction solution was
monitored all the time and was controlled by adding hydrochloric
acid in order no to be over 9. The water used in the bubbling of
the blow-by hydrogen during the reaction has strong alkalinity. The
blow-by gas stands indicates strong alkalinity in the same way by
checking with a litmus paper, and ammonia odor was felt.
[0110] The reaction solution was clear and colorless after reacting
for 10 hours and leaving it overnight.
[0111] Methanol in the reaction solution was evaporated after
filtrating a catalyst in the solution, and at the same time,
unreacted ethylenediamine in the solution was recovered.
[0112] The residue was then dissolved in 30 ml of 10% hydrochloric
acid. In this case, an extraction was conducted three times with 20
ml of ethyl acetate, and then acetic acid detached from the
reaction accelerator and unreacted adiponitrile were removed
because small quantity of unreacted oil layer was separated.
[0113] The hydrochloric acid solution was then neutralized to pH
6.9 with 15% of caustic soda, and then pH was controlled to 10 or
more by adding sodium carbonate powder. Undissolved sodium
carbonate was dissolved by adding small quantity of water.
[0114] Using caustic soda only and controlling pH to 10 or more had
no effect on the above alkalization.
[0115] An extraction was then conducted three times with 30 ml of
ethyl acetate and residual unreacted ethylenediamine was
removed.
[0116] An aqueous layer was evaporated by an evaporator and the
pressure was reduced to constant mass with oil-sealed rotary
pump.
[0117] The residue was a mixture of brown liquid and solid powder.
50 ml of ethanol was then added to the residue and dissolve organic
matters. Then sodium chloride and excess sodium carbonate were
separated by filtration and the residue was washed by 10 ml of
ethanol twice.
[0118] The residue in ethanol was then evaporated and 50 ml of cold
isopropanol was added. Then white powder precipitated.
[0119] The white powder was separated by the filtration, washed by
10 ml of cold isopropanol twice and then evaporated. Then 8.6 g of
the white powder was provided.
[0120] The layer of isopropanol was evaporated by the evaporator
and the pressure was reduced to constant mass with oil-sealed
rotary pump. Then 4.6 g of viscous liquid was provided. This was
poly(ethyleneiminohexamethyleneimine) and its total yield was
98.5%.
[0121] Further, the separated catalyst was washed by 10%
hydrochloric acid, and then the above reaction was conducted by
using the catalyst again. However, its catalytic activity did not
deteriorate and the same result of the reaction was provided.
Example 2
[0122] As substitute for adiponitrile in Example 1, succinonitrile
was used. As for the rest, Example 2 was conducted just like
Example 1. As the result, poly(ethyleneiminotetramethyleneimine)
was provided at a total yield of 95.4%.
Example 3
[0123] As substitute for ethylenediamine in Example 1,
hexamethylenediamine was used. As for the rest, Example 3 was
conducted just like Example 1. As the result,
poly(hexamethyleneimine) was provided at a yield of 88.3% as white
to gray wax solid material.
Example 4
[0124] As substitute for ethylenediamine in Example 1,
4,4'-dianilinomethane was used. As for the rest, Example 4 was
conducted just like Example 2. As the result,
poly(4,4'-diphenylmethyleneiminohexamethyleneimine) was provided at
a yield of 41%.
Example 5
[0125] 10.5 g of sulfate salt of glycinonitrile (0.05 mol) and 50
ml of methanol were added in a 300 ml, four-necked round bottom
flask and the solution was stirred and suspended. 25% of caustic
soda solution was gradually added in the solution with the flask
cooled in an ice bath and then pH of the solution was controlled to
10 or more.
[0126] The solution was suspended in white at first. However, the
solution became suspended solution in black-red as soon as the
neutralizing stared.
[0127] The solution was stirred for 30 minutes, precipitate sodium
sulfate was filtrated and then washed by small quantity of
methanol. Then the methanol solution of glycinonitrile was
provided.
[0128] The above prepared glycinonitrile solution, 1.7 g of
ammonium acetate, and 1.2 g of 10% palladium carbon (50%
hydroscopic compound) were added in a 100 ml, four-necked round
bottom flask, fitted with a stirrer, thermometer, a hydrogen
blowing tube, a pH meter electrode, an dropping funnel and a
condenser, and then an atmosphere in the reaction system was
replaced by argon for explosion protection.
[0129] Concentrated hydrochloric acid was then added in the
reaction system from the dropping funnel and pH of the reaction
solution was controlled to 8.5.
[0130] Fine bubbles of hydrogen was then injected by using a
sintered glass at normal pressures (pressure of 10 cm of liquid
paraffin) with stirring the reaction solution at ambient
temperature. The blow-by gas was diffused after bubbling with water
for explosion protection. The pH of the reaction solution was
monitored all the time just like Example 1 and was controlled by
adding hydrochloric acid in order no to be over 9.
[0131] The solution was brown after reacting for 24 hours. However,
the solution changed to be black-red after shutdown of providing
hydrogen and then leaving for a while.
[0132] Methanol in the reaction solution was evaporated after
filtrating a catalyst in the solution.
[0133] The residue was then dissolved in 30 ml of 10% hydrochloric
acid. An extraction was then conducted three times with 20 ml of
ethyl acetate, and then acetic acid detached from the reaction
accelerator was removed. The hydrochloric acid solution was then
neutralized to pH of 10 or more with 15% caustic soda.
[0134] An extraction was then conducted three times with 30 ml of
ethyl acetate. Massive amount of piperazine was detected in the
solution by a gas chromatography.
[0135] An aqueous layer was evaporated by an evaporator and the
pressure was reduced to constant mass with oil-sealed rotary
pump.
[0136] The residue was a mixture of brown liquid and solid powder.
50 ml of ethanol was then added to the residue and dissolve organic
matters. Then sodium chloride was separated by filtration and the
residue was washed by 10 ml of ethanol twice.
[0137] The residue in ethanol was then evaporated. 50 ml of cold
isopropanol was then added, a soluble part was separated by the
filtration and then evaporated. Then 1.3 g of brown viscous liquid
was provided.
[0138] The yield was 30.2%.
[0139] (Analysis)
[0140] The polymers provided in the above Examples were white
powders that precipitated from alcohol in alkalinity and high
viscosity (just like starch syrup) liquid. Accordingly, it cannot
be deemed that the polymer is at low-molecular weight and
hydrochloride salt or carbonate. Therefore, the analysis for
polymer of high-molecular weight was conducted.
[0141] The analysis was conducted on GPC, MASS and NMR.
[0142] It is well-known that the analysis of molecular weight of
polyamines by GPC is difficult because amines was adsorbed to
carbonyl group or --OH that remain at a filler. The polymer
provided by in the above Examples also indicated their single peak
at vicinity of molar weight 1,000.
[0143] Accordingly, the analysis was conducted by FAB-MASS (maximum
molar weight 30,000). However, outstanding mass number was 800 to
900 that fell far short of expectations. Therefore, the analysis
was then conducted by IT-TOF-MASS.
[0144] As an example, a IT-TOF-MASS chart of the polymer of Example
2 is indicated in FIG. 1. By the IT-TOF-MASS, a lot of polyvalent
ions are detected in mass number between 3,000 and 4,000 in the
spectrum, and as a result, it suggests that the polyamines are
polymers of high-molecular weight being distributed in a range of
several tens of thousands or more. However, the molecular weight
could not be identified.
[0145] As a measurement example, a proton NMR chart of the
poly(ethyleneiminotetramethyleneimine) of Example 2, which was
measured by heavy methanol is indicated in Fig.2, and a proton NMR
chart of the poly(hexamethyleneimine) of Example 3, which was
measured by heavy methanol is indicated in Fig.3. The belongingness
of signals are indicated in the figures.
[0146] Almost same NMR charts are obtained regarding the viscous
parts and the powdered parts. The signals of the viscous parts are
broader than those of the powdered parts. Therefore, it is deemed
that branched polymers mix in the viscous parts.
Comparative Example 1
[0147] 0.6 g of ethylenediamine (100 mmol), 1.1 g of adiponitrile
(100 mmol), 0.2 g of ammonium acetate, 0.12 g of 10% palladium
carbon (50% hydroscopic compound) and 3 ml of methanol were added
in a 10 ml autoclave, and then at a pressure of 5kg/cm.sup.2 of
hydrogen, the reaction was conducted at room temperature. The
reaction solution then changed to be black-red. The post treatment
was conducted on the amine component of the provided solution.
However, both viscous parts and powdered parts could not be
provided and all of them were extracted in the layer of ethyl
acetate. Though the catalyst was then filtrated and the reaction
was conducted in the same way, the reaction did not proceed.
* * * * *