“METHOD FOR PRODUCING TRANS-1, 4-BIS (AMINOMETHYL) CYCLOHEXANE”
MITSUI CHEMICALS, INC. of the address: 5-2, Higashi-Shimbashi 1-chome, Minato-ku,
Tokyo 105-7117, Japan; Nationality: Japan.
The following specification particularly describes and ascertains the nature of this invention
and the manner in which it has to be performed:
DESCFUPTION
TITLE OF THE INVENTION
METHOD FOR PRODUCING TRANS- 1,4-BIS(AMN0METHYL)CYCLOHEXANE
TECHNICAL FIELD
[OOOl]
The present invention relates to a method for producing trans-1,4-
bis(aminomethyl)cyclohexane.
BACKGROUND ART
[0002]
Heretofore, 1,4-bis(aminomethyl)cyclohexane has been well knowa fcr a raw maLeGa1-
/
of polyaxmide wed fofibm~i;liTetc~Klso1, ,4-bis(isocyanatomethyl)cyclohexane derived
from 1,4-bis(aminomethyl)cyclohexane is useful as a raw material of polyurethane used for, for
example, paints, adhesives, plastic lenses, etc.
[0003]
Such 1,4-bis(aminomethyl)cyclohexane includes two types of stereo isomers, i.e., trans-
,4-bis(aminomethyl)cyclohexane (hereinafter may be referred to as trans isomer) and cis-1,4-
bis(aminomethyl)cyclohexane (hereinafter may be referred to as cis isomer), and it has been
known that the ratio of the cis isomer to the trans isomer in 1,4-bis(aminomethyl)cyclohexane
affects various physical properties of polyamide or polyurethane produced by using the 1,4-
For example, in the case of polyamide, the higher the ratio of the trans isomer in the raw
material 1,4-bis(aminomethyl)cyclohexane is, the better the physical properties of melting point
or thermal stability are, allowing production of polyamide suitable for fiber, film, etc.
[OOOS]
In the case of polyurethane, by using, as a raw material, 1,4-
bis(isocyanatomethyl)cyclohexane derived from 1,4-bis(aminomethyl)cyclohexane having a high
ratio of trans isomer, polyurethane with excellent heat resistance and solubility in a solvent can
be obtained.
1
1-llF058-PCT
[0006]
Thus, in various industrial fields, a method for producing 1,4-
bis(aminomethyl)cyclohexane having a high ratio of trans isomer has been desired.
[0007]
As methods for producing 1,4-bis(aminomethyl)cyclohexane having a high ratio of trans
isomer, for example, the following has been known: performing nuclear hydrogenation (addition
of hydrogen to aromatic rings) of p-xylylenediamine in the presence of a ruthenium catalyst or a
rhodium catalyst to produce 1,4-bis(aminomethyl)cyclohexane containing the cis isomer and the
trans isomer; heating the 1,4-bis(aminomethyl)cyclohexane containing the cis isomer and the
trans isomer in the presence of a platinum group catalyst to isomerize the cis isomer to the trans
- . - -
~-semxya~d-&ereii&e~~sep-arat- recoveriX@hC1,4-bis(aminomethyl)cyclohexane having a
high trans isomer ratio from the isomerized solution, for example, by distillation (Patent
Document 1) or by crystallization (Patent Document 2).
[OOOS]
For a method for producing p-xylylenediamine used in the above-described method, for
example, Patent Document 3 has proposed arnrnoxidation of p-xylene using a metal oxide
catalyst such as vanadium to produce terephthalonitrile, and hydrogenating the terephthalonitrile
in the presence of a nickel catalyst.
[0009]
Furthermore, as a method for producing trans- l,4-bis(aminomethyl)cyclohexane, for
example, Non-Patent Document 1 (Malachowslu et al.) discloses the following: trans-1,4-
cyclohexanedicarboxylic acid is allowed to react with thionyl chloride and followed by the
reaction with ammonia to produce trans-l,4-cyclohexanedicarboxamidev ia acid chloride; and
the trans-l,4-cyclohexanedicarboxamideis further allowed to react with thionyl chloride to
obtain trans- l,4-dicyanocyclohexane, and then the obtained trans- l,4-dicyanocyclohexane is
hydrogenated to produce trans- 1,4-bis(aminomethyl)cyclohexane.
Citation List
Patent Document
[OOlO]
Patent Document 1
Japanese Unexamined Patent Publication No. H11-33 5335
Patent Document 2
Japanese Unexamined Patent Publication No. H10-306066
Patent Document 3
Japanese Unexamined Patent Publication No. 2003-26638
Non-Patent Document
[OOll]
Non-Patent Document 1
Berichte Der Deutschen Chemischen Gesellschaft, vol. 71, No. 4, p 759 (1938)
--
S ~ R T O ~ - m v E N T I o i
PROBLEM TO BE SOLVED BY THE INVENTION
[0012]
However, when p-xylylenediamine is produced as a raw material of trans-1,4-
bis(aminomethyl)cyclohexane by the method described in Patent Document 3, p-xylene has to be
subjected to arnrnoxidation at a very high temperature of 420°C to produce terephthalonitrile,
and thereafter, the obtained terephthalonitrile has to be hydrogenated under a very high pressure
of 12MPa (Patent Document 3 (ref: Example 1)).
[0013]
Furthermore, when 1,4-bis(aminomethyl)cyclohexane is produced by the method
described in Patent Document 1 or 2 from the thus obtained p-xylylenediamine, nuclear
hydrogenation of p-xylylenediamine under a very high pressure of 100 kg/cm2 (1 0MPa) has to be
performed (ref: Patent Document 1 and 2 (Reference Examples)).
[0014]
That is, in the methods described in Patent Documents 1 to 3, the components have to
be reacted at a high temperature and under a high pressure, and therefore improvements in terms
of equipment and safety are desired.
Furthermore, with the methods described in Patent Document 1 or 2, isomerization of
3
1-115'058-PCT
the obtained cis-l,4-bis(aminomethyl)cyclohexane to the trans isomer requires use of an
expensive catalyst of the platinum group, and moreover, the trans isomer ratio after the reaction
is 80% or less, and therefore to improve the trans isomer ratio, further separation steps, for
example, distillation and crystallization are necessary (ref: Patent Documents 1 and 2
(CLAIMS)).
[OO 161
Thus, the methods described in Patent Documents 1 to 2 involve high production costs,
and therefore improvements in terms of economy are desired.
[0017]
Also, the method described in Non-Patent Document 1 includes steps of multiple stages,
and furthermore, rsq~ireus se cif a 1a1:g~~amo~tlt-ef-t~~ny>I-cwh'-lh~-i~-ia .s e h ighly corrosive
and thus hard to handle, and on top of that, the reaction yield in each of the steps is low.
[0018]
Thus, in the method described in Non-Patent Document 1, in view of industrial
production, improvements in terms of many aspects are desired.
[0019]
The present invention was achieved in view of those disadvantages, and its object is to
provide a method that is excellent in terms of equipment, safety, and economy for producing
trans- l,4-bis(aminomethyl)cyclohexane.
MEANS FOR SOLVING THE PROBLEM
[0020]
To achieve the above object, a method for producing trans-1,4-
bis(aminomethyl)cyclohexane of the present invention includes:
a nuclear hydrogenation step of producing a hydrogenated terephthalic acid or
terephthalic acid derivative by nuclear hydrogenation of a terephthalic acid or terephthalic acid
derivative,
the terephthalic acid or terephthalic acid derivative being at least one selected
kom the group consisting of terephthalic acid, terephthalic acid ester, and terephthalic acid
amide;
4
a cyanation step of treating the hydrogenated terephthalic acid or terephthalic acid
derivative obtained in the nuclear hydrogenation step with ammonia to produce 1,4-
dicyanocyclohexane, and producing trans- l,4-dicyanocyclohexane from the obtained 1,4-
dicyanocyclohexane; and
an aminomethylation step of treating the trans- l,4-dicyanocyclohexane obtained in the
cyanation step with hydrogen, thereby producing trans-1,4-bis(aminomethyl)cyclohexane,
wherein metal oxide is used as a catalyst in the cyanation step, and the obtained trans-
1,4-dicyanocyclohexane has a metal content of 3000 ppm or less.
[0021]
A method for producing trans-l,4-bis(aminomethyl)cyclohexane of the present
- -- - - - inxv~er;tisn-indii&
a cyanation step of treating a hydrogenated terephthalic acid or terephthalic acid
derivative with ammonia, thereby producing 1,4-dicyanocyclohexane, and producing trans- 1,4-
dicyanocyclohexane from the obtained 1,4-dicyanocyclohexane; and
an aminomethylation step of treating the trans-l,4-dicyanocyclohexane obtained in the
cyanation step with hydrogen, thereby producing trans- 1,4-bis(aminomethyl)cyclohexane,
wherein metal oxide is used as a catalyst in the cyanation step, and the obtained trans-
1,4-dicyanocyclohexane has a metal content of 3000 ppm or less.
[0022]
In the above-described production method, it is preferable that the hydrogenated
terephthalic acid or terephthalic acid derivative is obtained by a nuclear hydrogenation step of
nuclear hydrogenation of a terephthalic acid or terephthalic acid derivative,
the terephthalic acid or terephthalic acid derivative being at least one selected
from the group consisting of terephthalic acid, terephthalic acid ester, and terephthalic acid
amide.
[0023]
In the method for producing trans- 1,4-bis(aminomethyl)cyclohexane of the present
invention, it is preferable that in the cyanation step, the cis isomer and the trans isomer in the
1,4-dicyanocyclohexane obtained from the reaction with ammonia are separated, and the
separated trans- l,4-dicyanocyclohexane is used in the aminomethylation step.
[0024]
In the method for producing trans- l,4-bis(aminomethyl)cyclohexane of the present
invention, it is preferable that in the cyanation step, trans- l,4-dicyanocyclohexane is separated
from 1,4-dicyanocyclohexane by crystallization using an aqueous solvent, and in the
crystallization step of the cyanation step and in the aminomethylation step, the same aqueous
solvent is used.
[0025]
In the method for producing trans- l,4-bis(aminomethyl)cyclohexane of the present
invention, it is preferable that in the cyanation step, the separated cis- l,4-dicyanocyclohexane is
broughtinto contact again with ammonia in the presence of or in the absence of the
hydrogenated terephthalic acid or terephthalic acid derivative.
In the method for producing trans- 1,4-bis(aminomethyl)cyclohexane of the present
invention, it is preferable that in the cyanation step, the reaction with ammonia is performed at
the temperature from 200 to 350°C.
[0027]
In the method for producing trans- 1,4-bis(aminomethyl)cyclohexane of the present
invention, it is preferable that in the cyanation step, the reaction with ammonia is performed in
the presence of a solvent having a boiling point of 180°C to 350°C.
[0028]
In the method for producing trans-1,4-bis(arninomethyl)cyclohexane of the present
invention, it is preferable that in the cyanation step, the contact with ammonia is performed in
the presence of 3 to 20 parts by weight of a solvent relative to 100 parts by weight of the
hydrogenated terephthalic acid or terephthalic acid derivative.
[0029]
In the method for producing trans- l,4-bis(aminomethyl)cyclohexane of the present
invention, it is preferable that a solvent is used in the cyanation step, the solvent being selected
from o-dichlorobenzene, triethylene glycol dimethylether, tetraethylene glycol dimethylether, N-
6
1-llF058-PCT
methyl-2-pyrrolidinone, N,N1-dimethylimidazolidinoneN, ,Nt-diethylirnidazolidinone,N ,N1-
dipropylimidazolidinone, N,N1,4-trimethylimidazolidinone,a nd N,N1-dimethylpropyleneurea.
[0030]
In the method for producing trans- l,4-bis(aminomethyl)cyclohexane of the present
invention, it is preferable that in the cyanation step, the ammonia to be brought into contact with
is fed at a rate greater than 0.5 mol equivalentlhydrogenated terephthalic acid or terephthalic acid
derivativelhr.
EFFECTS OF THE INVENTION
[003 11
The method for producing trans- 1,4-bis(aminomethyl)cyclohexane of the present
1- - 1 .. _--2- i m e ~ i n ~ ~ i ~ x c e e 1 1 e n t - i n -eqt ~~:si-p~~mf- t~~-fety~nd-e~:oacnnorerv~eas srarrea, low costs,
and high yield production of trans-1,4-bis(arninomethyl)cyclohexane. Thus, the present
invention can be suitably used as an industrial method for producing trans-1,4-
bis(aminomethyl)cyclohexane.
EMBODIMENT OF THE INVENTION
[0032]
A method for producing trans-l,4-bis(aminomethyl)cyclohexane of the present
invention includes
a nuclear hydrogenation step of producing a hydrogenated terephthalic acid or
terephthalic acid derivative by nuclear hydrogenation of a terephthalic acid or terephthalic acid
derivative,
the terephthalic acid or terephthalic acid derivative being at least one selected
from the group consisting of terephthalic acid, terephthalic acid ester, and terephthalic acid
amide;
a cyanation step of treating the hydrogenated terephthalic acid or terephthalic acid
derivative obtained in the nuclear hydrogenation step with ammonia to produce 1,4-
dicyanocyclohexane, and producing trans-l,4-dicyanocyclohexane from the obtained 1,4-
dicyanocyclohexane; and
an aminomethylation step of treating the trans-l,4-dicyanocyclohexane obtained in the
7
1- llF058-PCT
cyanation step with hydrogen, thereby producing trans- 1,4-bis(aminomethyl)cyclohexane.
Each step is described in detail in the following.
[Nuclear Hydrogenation Step]
In the nuclear hydrogenation step, nuclear hydrogenation of a terephthalic acid or
terephthalic acid derivative is performed, the terephthalic acid or terephthalic acid derivative
being at least one selected fkom the group consisting of terephthalic acid, terephthalic acid ester,
and terephthalic acid amide, to produce a corresponding hydrogenated terephthalic acid or
terephthalic acid derivative (that is, hydrogenated terephthalic acid or terephthalic acid derivative
of at least one selected from the group consisting of cyclohexane-l,4-dicarboxylic acid,
cyclohexane- l,4-dicarboxylic acid ester, and cyclohexane- l,4-dicarboxylic acid amide).
In the nuclear hydrogenation step, for example, the method described in Japanese
Unexamined Patent Publication No. 200 1 - 18 1223 may be used.
[0034]
The terephthalic acid or terephthalic acid derivative used as a raw material in the present
invention may be one having quality of industrially available products, and also undried
(containing water) terephthalic acid or terephthalic acid derivative that has undergone the
purification in the hydrogenation step generally performed in production of terephthalic acid
may be used.
100351
The reaction in the nuclear hydrogenation step is exothermic reaction, and therefore to
suitably suppress the temperature increase due to the heat of reaction, and also to increase
conversion, it is preferable that a solvent that is inactive in such a reaction is added as a diluent
to the raw material terephthalic acid or terephthalic acid derivative so that the terephthalic acid or
terephthalic acid derivative concentration in the reaction solution is, for example, 1 to 50 wt%,
preferably 2 to 30 wt%. When the concentration in the reaction solution is within the range, it
is advantageous in that the reaction rate is not reduced, and the temperature increase in the
reactor is small.
1-llF058-PCT
Examples of such a solvent include aqueous solvents such as water, methanol, ethanol,
1 -propanol, isopropanol, 1 -butanol, 2-butanol, t-butanol, and 1,4-dioxane.
[0037]
Use of such an aqueous solvent is advantageous in that the reaction mixture in the
nuclear hydrogenation step can be cooled as necessary, and re-circulated for use.
[0038]
In this case, water is used preferably because it can be recovered by separation operation
thereafter; it does not allow unwanted components to be mixed into the reaction system; and
undried terephthalic acid that underwent the purification step of terephthalic acid can be used.
[0039]
- h the mcletir h~~~gcn&i~~-stsp~h-y&ogen~nsuceldea~r hheyd rogenation may be
of industrial use quality. For example, the hydrogen may contain inactive gas (e.g., nitrogen,
methane, etc.) but its hydrogen concentration is preferably 50% or more.
[0040]
The hydrogen amount is preferably about 3 to 50 times the raw material terephthalic
acid or terephthalic acid derivative in molar ratio.
[0041]
When the hydrogen amount is within such a range, the amount of unreacted materials is
small, the reaction rate is sufficient, and it is advantageous economically.
[0042]
In the nuclear hydrogenation step, a known catalyst may be added.
[0043]
The catalyst used in the nuclear hydrogenation step is a general noble metal catalyst for
nuclear hydrogenation. To be specific, examples of such a catalyst include palladium, platinum,
ruthenium, and rhodium, and preferably, palladium or ruthenium is used.
These catalysts are preferably prepared as a supported catalyst. Examples of carriers
for such catalysts include activated carbon, alumina, silica, and kieselguhr, and preferably,
activated carbon or silica is used.
9
The amount of metal (e.g., palladium, platinum, ruthenium, rhodium, etc.) supported is
in the range of, for example, 0.1 to 10 wt%, preferably 0.5 to 10 wt%, of the total amount
including the catalyst carrier.
[0046]
When the amount of metal supported is within such a range, it is preferable because the
activity of catalyst per weight is high.
The catalyst is used in the form of, for example, powder, granular, or may be supported
on a pellet carrier. Preferably, the catalyst is in the form of powder. When the catalyst has an
j r i a t esi ze,~o~xam~pie,-whe~-t-Beez-t-z~~~~-is~p~wd-ercatacioynstati~nfs naenc at~yst
internal portion that effectively contributes to reaction in a large amount, and therefore the
reaction rate does not easily decrease.
[0048]
The catalyst amount relative to 100 parts by weight of terephthalic acid or terephthalic
acid derivative is in the range of, for example, 0.1 to 50 parts by weight, preferably 0.5 to 20
parts by weight.
[0049]
The terephthalic acid or terephthalic acid derivative is not highly soluble in general
solvents such as water, and therefore the reaction is preferably performed in a suspension of the
raw material and the solvent.
[OOSO]
The reactor is preferably a pressure-resistant vessel.
[0051.]
A raw material slurry and hydrogen are introduced from the reactor top or bottom, and
brought into contact with the catalyst in a suspension. After the reaction, the product, i.e.,
hydrogenated terephthalic acid or terephthalic acid derivative, is highly soluble in a general
solvent such as water at high temperature, and therefore separation from the catalyst can be
performed by filtration.
10
1-llF058-PCT
[0052]
In the filtration, the above-described product is dissolved in, for example, a known
alkaline solution (e.g., aqueous sodium hydroxide solution, etc.), and after the solution is filtered,
the solution can be neutralized by a known acid solution (e.g., aqueous hydrogen chloride
solution, etc.).
[0053]
Thereafter, by drying or concentrating the mixture, or by crystallizing the product by
cooling, hydrogenated terephthalic acid or terephthalic acid derivative can be obtained.
[0054]
The reaction temperature is usually in the range of 50 to 200°C, and preferably 100 to
The reaction temperature within such a range is advantageous in that the amount of
unreacted materials and by-products is less, hydrogenolysis does not occur easily, and as a result,
the yield increases.
[0056]
The reaction pressure is usually in the range of 0.5 to 1 SMPa, preferably 2 to 1 SMPa,
more preferably 2 to 8MPa, even more preferably 2 to 5MPa.
[0057]
The reaction pressure within such a range is advantageous in that the reaction rate does
not easily decrease, and the amount of by-products is less.
[0058]
The conversion of terephthalic acid or terephthalic acid derivative is usually 90% or
more, preferably 95% or more, and more preferably 98% or more.
[0059]
When the amount of the unreacted terephthalic acid or terephthalic acid derivative is
small as described above, it is advantageous in that after treatment such as separation and
purification of the product from the reaction mixture become not so complicated.
1-llF058-PCT
The hydrogenated terephthalic acid or terephthalic acid derivative obtained in the
nuclear hydrogenation step is a mixture of a cis isomer (that is, cis-cyclohexane-l,4-dicarboxylic
acid, cis-cyclohexane- l,4-dicarboxylic acid ester, andlor cis-cyclohexane- l,4-dicarboxylic acid
amide) and a trans isomer (that is, trans-cyclohexane-l,4-dicarboxylic acid, trans-cyclohexane-
1,4-dicarboxylic acid ester, andlor trans-cyclohexane- l,4-dicarboxylic acid amide).
[Cyanation Step]
In the cyanation step, the above-described hydrogenated terephthalic acid or terephthalic
acid derivative obtained in the nuclear hydrogenation step is treated with ammonia to produce
1,4-dicyanocyclohexane, and the trans and cis isomers are separated from the produced 1,4-
dicyanocyclohexane to obtain trans- l,4-dicyanocyclohexane.
In the cyanation step, for example, the method described in Japanese Unexamined
Patent Publication No. S63-10752 may be used.
[0062]
To be more specific, in the cyanation step, the hydrogenated terephthalic acid or
terephthalic acid derivative obtained in the nuclear hydrogenation step is allowed to react with a
compound capable of serving as an ammonia source (e.g., ammonia, urea, ammonium carbonate,
etc.)(hereinafter may be referred to as an ammonia source) by heating at, usually 200°C or more
and below 350°C, preferably 230°C or more and below 320°C.
[0063]
The reaction temperature within such a range is advantageous in that the reaction rate
does not decrease, and decomposition due to excessive heating occurs less.
[0064]
In the present invention, metal oxide is used as a catalyst in the cyanation step.
[0065]
Examples of metal oxide include silica, alumina, phosphorus pentoxide, tin oxide,
titanium oxide, zinc oxide, iron oxide, zirconium oxide, and cobalt oxide.
[0066]
Of these metal oxides, in view of easy separation after reaction, silica, alumina, tin
12
1-11F058-PCT
oxide, titanium oxide, zinc oxide, iron oxide, zirconium oxide, or cobalt oxide is preferably used.
[0067]
In this step, furthermore, metal oxide and other catalysts can be used in combination,
and examples of such a catalyst include mineral acids such as hydrochloric acid, phosphoric acid,
and sulfuric acid, and organic acids such as acetic acid, propionic acid, and benzoic acid.
[0068]
When metal oxide and other catalyst are used in combination, the mixing ratio of these
is not particularly limited, and is set suitably in accordance with the purpose and application.
[0069]
The catalyst is used in the form of, for example, powder, granular, or may be supported
[0070]
When the catalyst has a suitable size, for example, when the catalyst is powder, the
internal portion in the catalyst that effectively contributes to reaction is large, and reaction rate
does not easily decrease.
[0071]
The amount of catalyst relative to 100 parts by weight of hydrogenated terephthalic acid
or terephthalic acid derivative is in the range of, for example, 0.1 to 50 parts by weight,
preferably 0.5 to 20 parts by weight.
[0072]
In the reaction, a solvent is preferably used as appropriate.
[0073]
Examples of the solvent include, although any solvent that does not inhibit the purpose
of the method of the present invention can be used, aliphatic or alicyclic hydrocarbons such as
decane, undecane, dodecane, tridecane, tetradecane, pentadecane, and decalin; aromatic
hydrocarbons such as mesitylene, tetralin, butylbenzene, p-cymene, diethylbenzene,
diisopropylbenzene, triethylbenzene, cyclohexylbenzene, dipentylbenzene, and dodecylbenzene;
alcohols such as hexanol, 2-ethylhexanol, octanol, decanol, dodecanol, ethylene glycol,
diethylene glycol, and triethylene glycol; ethers such as diethylene glycol dimethylether,
13
triethylene glycol dimethylether, tetraethylene glycol dimethylether, o-dimethoxybenzene,
ethylphenylether, butylphenylether, and o-diethoxybenzene; halogenated aromatic hydrocarbons
such as iodobenzene, o-dichlorobenzene, m-dichlorobenzene, 1,2,4-trichlorobenzene, odibromobenzene,
bromochlorobenzene, o-chlorotoluene, p-chlorotoluene, p-chloroethylbenzene,
and 1 -chloronaphthalene; polar aprotic solvents such as dimethyl sulfoxide, N,Ndimethylformamide,
N,N-dimethylacetamide, hexamethylphosphoramide, N-methyl-2-
pyrrolidinone, N,N'-dimethylimidazolidinone,N ,N'-diethylimidazolidinone,N ,N'-
dipropylimidazolidinone, N,N1,4-trimethylimidazolidinonea,n d N,N'-dimethylpropyleneurea;
and the product in this step, i.e., 1,4-dicyanocyclohexane. These solvents may be used singly or
in a combination of two or more.
As the solvent, in view of suppressing crystallization of 1,4-dicyanocyclohexane to the
gas purge line of the reactor, and to apparatuses at downstream of the reactor such as a condenser,
the solvent is preferably selected from, for example, ethers such as diethylene glycol
dimethylether, triethylene glycol dimethylether, tetraethylene glycol dimethylether, odimethoxybenzene,
ethylphenylether, butylphenylether, and o-diethoxybenzene; halogenated
aromatic hydrocarbons such as iodobenzene, o-dichlorobenzene, m-dichlorobenzene, 1,2,4-
trichlorobenzene, o-dibromobenzene, bromochlorobenzene, o-chlorotoluene, p-chlorotoluene, pchloroethylbenzene,
and 1-chloronaphthalene; and polar aprotic solvents such as dimethyl
sulfoxide, N,N-dimethylformamide, N,N-dimethylacetarnide, hexamethylphosphoramide, Ndipropylimidazolidinone,
N,Nt,4-trimethylimidazolidinone, and N,N'-dimethylpropyleneurea.
[0075]
Of the above-described solvents, those solvents having a boiling point of 180°C to
350°C is preferably used. Use of the solvent having a boiling point lower than 180°C is not
preferable because the energy load on the reactor increases. Use of the solvent having a boiling
point higher than 350°C is not preferable because the effects of suppressing the crystallization of
1,4-dicyanocyclohexane to the reactor gas purge line and to apparatuses at downstream of the
reactor such as a condenser decreases.
14
1-llF058-PCT
[0076]
In view of the above, of the above-described solvents, selection is made preferably from
o-dichlorobenzene, triethylene glycol dimethylether, tetraethylene glycol dimethylether, Nmethyl-
methyl-2-pyrrolidinone, N,N'-dimethylimidazolidinone, N,Nt-diethylimidazolidinoneN, ,Ntdipropylimidazolidinone,
N,Nt,4-trimethylimidazolidinonea,n d N,N1-dimethylpropyleneurea.
[0077]
The amount of solvent used is not particularly limited, and usually is 10 times or less by
weight the reactant (including the above-described hydrogenated terephthalic acid or terephthalic
acid derivative obtained in the nuclear hydrogenation step), preferably 1 time or less by weight
the reactant, and more preferably 3 to 20 parts by weight relative to 100 parts by weight of the
hydrogenated terephthalic ~ c iodr terep~tiza'Iksaci&ds~~~~v+Wamn~ouen t of the solvent
is small, or when no solvent is used, suppression of crystallization of 1,4-dicyanocyclohexane to
the gas purge line of the reactor and to apparatuses at downstream of the reactor such as a
condenser becomes difficult, and when the amount of the solvent is large, it is not preferable
because energy load on the reactor increases.
[0078]
The reaction method is not particularly limited, and examples thereof include slurry-bed
batch process, semi-batch process, and continuous process; and also fixed-bed continuous
process. Preferably, liquid-phase slurry reaction is used.
[0079]
The reactor is preferably a pressure-resistant vessel.
[OOSO]
For example, a hydrogenated terephthalic acid or terephthalic acid derivative, and a
catalyst are introduced from the reactor top or bottom, and the hydrogenated terephthalic acid or
terephthalic acid derivative is dissolved by heating to be suspended; and an ammonia supply
source compound such as ammonia is fed intermittently or continuously to the reactor, to allow
reaction at a predetermined temperature.
[OOSl]
The amount of the ammonia supply source compound to be fed is, in view of making
15
1-llF058-PCT
ammonia easy to treat and recover after reaction, for example, 1 to 20 mol, preferably 2 to 20
rnol relative to 1 rnol of hydrogenated terephthalic acid or terephthalic acid derivative.
[0082]
The rate of the feeding of the ammonia source is not particularly limited, and preferably
0.1 rnol to 2 rnol relative to 1 rnol of hydrogenated terephthalic acid or terephthalic acid
derivative per 1 hour, and more preferably, more than 0.5 rnol and 2 rnol or less (that is, more
than 0.5 rnol equivalenthydrogenated terephthalic acid or terephthalic acid derivativeh and 2
rnol equivalent/hydrogenated terephthalic acid or terephthalic acid derivativelhr or less).
[0083]
The feeding rate lower than 0.5 rnol relative to 1 rnol of hydrogenated terephthalic acid
or terephthalic acid derivzti.jp, per - !h our~~-o~p~s~~ab~e-"oree~acati'ocn ~re~qtui"rense a long
time. The feeding rate higher than 2 rnol relative to 1 rnol of hydrogenated terephthalic acid or
terephthalic acid derivative per 1 hour is disadvantageous economically in that the unreacted
ammonia source increase in volume, and therefore, for example, when ammonia is to be
recovered and reused, the burden is substantial.
[0084]
The feeding time is suitably selected depending on the feeding rate. For example, the
feeding time is 1 to 80 hours, preferably 2 to 50 hours.
[OOSS]
Water is produced as a by-product in this reaction, and therefore in view of accelerating
the reaction, water is preferably removed out of the system. To remove water out of the system,
for example, an inactive gas such as nitrogen can be fed to the reactor.
[0086]
The reaction may be performed under any pressure condition, for example, under
elevated pressure, ambient pressure, and reduced pressure, which is suitably selected.
After the reaction, the product, i.e., 1,4-dicyanocyclohexane, is obtained as a mixture
(stereoisomers) of cis- l,4-dicyanoc yclohexane (cis isomer) and trans- l,4-dicyanocyclohexane
(trans isomer).
16
The cis isomer/trans isomer ratio of the 1,4-dicyanocyclohexane obtained converges to
the equilibrium composition ratio of I ,4-dicyanocyclohexane at the reaction temperature,
approximately, to cis isomer/trans isomer = 40160 to 60/40, regardless of the stereo isomer ratio
of the hydrogenated terephthalic acid or terephthalic acid derivative.
[0089]
From the mixture of the cis- and trans-1,4-dicyanocyclohexanea fter reaction, the
catalyst used is removed by a known method, for example, such as filtration and adsorption, and
thereafter, trans-l,4-dicyanocyclohexaneis separated therefrom, for example, by fractional
crystallization using the difference in their solubility, or by distillation using the difference in
- their boiling poi~ts. Gf these meiho&,s~~p~e-~~~~~~y-~"acti~nai-~ry~tisa p'rfefieiraZbalte.i on
[0090]
Separation of the trans isomer and the cis isomer from the mixture of cis- and trans-1,4-
dicyanocyclohexane is preferable for excellent operability and separation efficiency to the
separation of the trans isomer (trans- 1,4-bis(aminomethyl)cyclohexane) and the cis isomer (cis-
1,4-bis(aminomethyl)cyclohexane) from the mixture of cis- and trans-1,4-
bis(aminomethyl)cyclohexane, for example.
[0091]
The solvent used in the fractional crystallization is preferably a solvent in which the
solubility of the cis isomer and its of the trans isomer of 1,4-dicyanocyclohexane is greatly
different, and examples thereof include water; lower fatty acids such as acetic acid; alcohols such
as methanol, ethanol, 1 -propanol, isopropanol, 1 -butanol, 2-butanol, t-butanol, and ethylene
glycol; and ethers such as diethylether and 1,4-dioxane.
[0092]
The above-described solvent is preferably the same as the solvent used in the
aminomethylation step to be described later, particularly because it does not necessitates the
drying step of the product, and specifically, selected from aqueous solvents such as water and
alcohols.
1-113'058-PCT
In the fractional crystallization, first, 1,4-dicyanocyclohexane is dissolved in the abovedescribed
solvent, and the mixture is heated. Thereafter, the mixture is cooled to ambient
temperature. This allows 1,4-dicyanocyclohexane having a high proportion of trans isomer to
be crystallized (crystallization step). Thereafter, the crystallized 1,4-dicyanocyclohexane can
be separated by filtration.
[0094]
After the separation, as necessary, the mixture is washed and dried so that trans-1,4-
dicyanocyclohexane in solid state can be obtained. The thus obtained trans-1,4-
dicyanocyclohexane is preferably used in the aminomethylation step to be described later.
[0095]
- The parity (trans isome~/1_t_i-r3~f-t~a;i~4~=dicyanocyclcoahne bxea nseu itably
controlled by the conditions in fractional crystallization. The purity (trans isomer ratio) of
trans-l,4-dicyanocyclohexanei s approximately 85% or more, preferably 90% or more.
[0096]
When metal oxide is used as a catalyst in the above-described cyanation reaction, a
metal component of the catalyst used may be contaminated in the obtained trans-1,4-
dicyanocyclohexane as an impurity. The metal content is 3000 ppm or less, preferably 2000
ppm or less, and more preferably, 1500 ppm or less relative to trans- 1,4-dicyanocyclohexane.
[0097]
More than 3000 ppm metal contents are not preferable because resulting metal might
inhibit the reaction in the aminomethylation step to be described later.
[0098]
As necessary, the metal content is preferably reduced by various methods, for example,
by a method in which catalyst removal operation such as filtration and adsorption after reaction
are repeated; a method in which the solution of 1,4-dicyanocyclohexane before crystallization is
brought into contact with activated carbon, synthetic adsorbent, etc. and then separated by
filtration, and thereafter crystallized; and a method in which the trans- l,4-dicyanocyclohexane
having a large amount of metal contents is re-dissolved in the above-described solvent, then
brought into contact with activated carbon, synthetic adsorbent, etc. then separated by filtration,
18
and thereafter, the solvent is distilled off.
[0099]
Meanwhile, in the filtrate after the filtration, the 1,4-dicyanocyclohexane having a high
cis isomer ratio is dissolved.
[OlOO]
The 1,4-dicyanocyclohexane having a high cis isomer ratio obtained by distilling off the
solvent from the filtrate is again fed into the reactor in the cyanation step, to be treated again
with ammonia in the presence of or in the absence of hydrogenated terephthalic acid or
terephthalic acid derivative.
[OlOl]
Tn th;n ---- . . . .
- bLun ~ ~ ~ ~ ~ ~ ~ ~ ~ r ~ ~ n e r m a ~ ~ ~ 0 ~ e ~ - ~temapter-atu1re~ inn th-e~ c ~ i i ~ ~ - & reactor of the cyanation step to form an equilibrium composition mixture of cis isomerltrans
isomer, therefore this is advantageous in that trans- 1,4-dicyanocyclohexane can be obtained with
a small loss.
[0102]
When 1,4-dicyanocyclohexane having a high cis isomer ratio is fed again in the absence
of hydrogenated terephthalic acid or terephthalic acid derivative to the reactor of the cyanation
step, only the isomerization reaction is performed at a predetermined temperature. At that time,
the presence of metal oxide andlor ammonia is not necessary, but in view of shortening the
reaction time, ammonia is preferably present.
[0 1031
The amount of ammonia to be present is sufficient when the amount allows the
ammonia concentration of the reaction solution in the reactor to be saturated continuously, and
the amount of ammonia source to be fed is, in view of making ammonia easy to treat or recover
after the reaction, for example, 0.1 to 10 mol, preferably 0.1 to 5 mol relative to 1 mol of 1,4-
dicyanocyclohexane.
[0 1041
The rate of the ammonia source to be fed is not particularly limited, and in view of
feeding the amount that allows for the ammonia concentration in the reaction solution in the
19
1-llF058-PCT
reactor is saturated during the reaction continuously as described above, the rate is 0.01 mol to 1
mol relative to 1 mol of 1,4-dicyanocyclohexane per 1 hour.
[Aminomethylation Step]
In the aminomethylation step, the trans- l,4-dicyanocyclohexane obtained in the
cyanation step is treated with hydrogen, thereby producing trans- 1,4-
bis(aminomethyl)cyclohexane.
[OlOS]
In the aminomethylation step, for example, the method described in, for example,
Japanese Unexamined Patent Publication No. 200 1-187765 can be used.
[0106]
indiistriaiwse-hydr-~ge~s-s::%zient-'I~~-tem-~o~~i~~huyseddr oing tehne
aminomethylation step, and the hydrogen may contain inactive gas (e.g., nitrogen, methane, etc.).
The hydrogen concentration is preferably 50% or more.
[0107]
As the hydrogenation catalyst used in the aminomethylation step, a known
hydrogenation catalyst, for example, any of a cobalt catalyst, a nickel catalyst, a copper catalyst,
and a noble metal catalyst can be used.
[Ol 081
In view of reactivity and selectivity, a catalyst mainly composed of nickel, cobalt andlor
ruthenium is preferably used, and more preferably, Raney catalyst or a catalyst supported on
porous metal oxides such as silica, alumina, silica alumina, lueselguhr, and activated carbon is
preferably used.
[0 1091
The catalyst may further contain metals such as aluminum, zinc, and silicon.
[OllO]
These hydrogenation catalysts may contain, as a reaction accelerator, a metal selected
from chromium, iron, cobalt, manganese, tungsten, and molybdenum.
[Olll]
The hydrogenation catalyst can be used as a perfect solid catalyst, or can be used as a
20
supported solid catalyst, for example, nickel, cobalt, or ruthenium supported on aluminum oxide,
titanium oxide, zirconium oxide, magnesia/alumina, etc.
[0112]
The catalyst is in the form of, for example, powder, granular, or may be supported on a
pellet carrier may be used. Preferably, the catalyst is powder. When the catalyst has an
appropriate size, for example, when the catalyst is powder catalyst, the catalyst contains an
internal portion that effectively contributes to reaction in a large amount, and therefore the
reaction rate does not easily decrease.
[0113]
The amount of catalyst used is, in view of reactivity and selectivity, for example, 0.1 to
20 parts by-Y~~&ht,+refer-zB~~8,53,~45-p~t~-b~eipgahrtts ~byi ~wteiig~ht~ oOfD tr ans-
1,4-dicyanocyclohexane.
[0114]
For the reaction, a solvent can be used suitably, and examples of such a solvent include
aqueous solvents such as water; alcohols such as methanol, ethanol, 1-propanol, isopropanol, 1
butanol, 2-butanol, and t-butanol; and 1,4-dioxane.
[0115]
For the solvent, preferably, those solvents used in the fractional crystallization in the
above-described cyanation step can be used.
[0116]
The trans-l,4-dicyanocyclohexanec oncentration in the reaction solution is, for example,
1 to 50 wt%, preferably 2 to 40 wt%.
[0117]
The trans-l,4-dicyanocyclohexanec oncentration in the reaction solution within such a
range is advantageous in that the reaction rate does not decrease, and the temperature increase in
the reactor is small.
[0118]
The reaction is preferably performed in the presence of ammonia.
1-llF058-PCT
The ammonia works to suppress production of by-products such as secondary amine,
tertiary amine, and polyamine, i.e., products other than the target trans-1,4-
bis(aminomethyl)cyclohexane, that is, works to improve reaction selectivity.
[0120]
The amount of ammonia used is, in view of suppressing production of the abovedescribed
by-products, preventing decrease in the hydrogenation rate, and making ammonia easy
to treat or recover after reaction, for example, 0.05 to 5 moly preferably 0.1 to 2.5 mol relative to
1 mol of trans- l,4-dicyanocyclohexane.
[0121]
The reaction method is not particularly limited, and examples thereof include a slurrybed
batch process, a - semi-batch p r o c e s s 3 _ a - c o n t i n u s u s i j i a c z s s ~ d ~ i x e d process. Preferably, liquid-phase sluny reaction is used.
I01221
The reactor is preferably a pressure-resistant vessel.
[0123]
For example, trans- l,4-dicyanocyclohexane, catalyst, hydrogen, and as necessary a
solvent and ammonia are introduced from the reactor top or bottom, and the mixture is allowed
to react at a predetermined temperature.
[0124]
The reaction pressure is usually 0.1 to 20MPa, preferably 0.5 to lOMPa, more
preferably 0.5 to SMPa, and particularly preferably 0.5 to 5MPa.
[0125]
The reaction temperature is, in view of reactivity and selectivity, for example, 50 to
250°C, preferably 50 to 200°C, more preferably 70 to 150°C, and preferably, the reaction
temperature is increased during the hydrogenation reaction continuously or stepwise.
[0126]
After the reaction, trans-l,4-bis(aminomethyl)cyclohexane can be separated from the
reaction mixture by a known method, for example, by filtration, distillation, etc.
1-llF058-PCT
The purity (trans isomer ratio) of trans-l,4-bis(aminomethyl)cyclohexane can be
suitably controlled by the conditions of the reaction and the separation. The purity (trans
isomer ratio) of trans- l,4-bis(aminomethyl)cyclohexane is approximately 80% or more,
preferably 85% or more.
[0128]
The method for producing trans- l,4-bis(aminomethyl)cyclohexane of the present
invention is excellent in terms of equipment, safety, and economy, and achieves safe, low costs,
and high yield production of trans- l,4-bis(aminomethyl)cyclohexane.
[0129]
Thus, the method can be suitably used as an industrial method for producing trans- 1,4-
The above-described method for producing trans- 1,4-bis(aminomethyl)cyclohexane
includes the nuclear hydrogenation step, the cyanation step, and the aminomethylation step.
However, in the method for producing trans- l,4-bis(arninomethyl)cyclohexane, for example,
hydrogenated terephthalic acid or terephthalic acid derivative is used as a starting material to
omit the nuclear hydrogenation step, and the cyanation step and the aminomethylation step can
be performed.
[0131]
In such a case, the hydrogenated terephthalic acid or terephthalic acid derivative as a
starting material is not limited to the above-described hydrogenated terephthalic acid or
terephthalic acid derivative obtained in the nuclear hydrogenation step. However, with the
above-described nuclear hydrogenation step, hydrogenated terephthalic acid or terephthalic acid
derivative can be obtained safely at low costs and with high yields, and therefore the
hydrogenated terephthalic acid or terephthalic acid derivative as a starting material is preferably
obtained by the above-described nuclear hydrogenation step.
EXAMPLES
Hereinafter, the present invention will be described more specifically with reference to
23
1-llF058-PCT
Examples. However, the present invention is not limited to those Examples. Analysis in the
nuclear hydrogenation step was performed by high-performance liquid chromatography, and
analyses in the cyanation step and the aminomethylation step were performed by gas
chromatography. The metal component amount was analyzed by ICP (inductively coupled
plasma) emission spectroscopy.
(Example 1)
[Nuclear Hydrogenation Step]
A 100 mL stainless steel-made autoclave equipped with a stirrer was charged with 25.0
g of terephthalic acid, 2.8 g of a catalyst (10% PdlC, manufactured by NE Chemcat Corporation),
and 100 mL of water. The autoclave was purged with nitrogen introduced from the autoclave
nozzle inlet thee times at S~SIPa,anbt~n~-rrri~$~re-~as-heateci-stti~rrii~ngO a~t 4e0 0 rpm.
[0133]
When the temperature reached 150°C, hydrogen supply was started intermittently to
achieve a pressure of 3.5 MPa, and the reaction was performed until there is no hydrogen
absorption.
[0134]
After the completion of reaction, the product was cooled to room temperature. The
reaction mixture was taken out, and after a 5N aqueous NaOH solution containing sodium
hydroxide of 2.5 times mol the charged terephthalic acid amount was added thereto, the mixture
was filtered to remove the catalyst.
[0135]
The filtrate was neutralized with a 5N aqueous HC1 solution, and then analyzed by highperformance
liquid chromatography. It was found that the conversion rate of terephthalic acid
was loo%, the yield of 1,4-cyclohexanedicarboxylic acid was 99%, and the trans isomer/cis
isomer ratio was 33/67.
[Cyanation Step]
A four-neck flask equipped with a stirrer, a gas inlet tube, a thermometer, a gas purge
line, and a condenser was charged with 9.3 g of 1,4-cyclohexanedicarboxylic acid obtained by
concentrating the filtered reaction solution obtained in the nuclear hydrogenation step and 0.13 g
24
of tin (11) oxide, and the mixture was heated to 170°C while stirring at 300 rpm, thereby
dissolving carboxylic acid.
Thereafter, ammonia gas was introduced at a rate of 16 mL/min (0.8 1 mol
equivalent/1,4-cyclohexanedicarboxylica cidlhr) to increase the temperature to 280°C, and while
the temperature was kept constant, reaction was performed. After four hours, the reaction
mixture was cooled to room temperature.
[0 13 71
The solid product was suspended in methanol, and then the suspension was filtered to
remove the catalyst.
The filtrate was analyzed by gas chromatography, and it was found that the conversion
of 1,4-cyclohexanedicarboxylic acid was 99.5%, the yield of 1,4-dicyanocyclohexane was 94.7%,
and the trans isomerlcis isomer ratio was 58/42.
[0139]
Next, to 8 g of 1,4-dicyanocyclohexane containing a mixture of the trans isomer and the
cis isomer obtained by distilling off the solvent from the filtrate obtained as described above,
18.7 g of 1 -butan01 was added, and heated to 80°C to dissolve the 14-dicyanocyclohexane.
Thereafter, as the mixture was cooled to room temperature, a precipitate was appeared.
[0140]
The suspension was filtered, and the residue was further washed with 18.7 g of 1-
butanol. Thereafter, the residue was dried, and 3.8 g of white solid was obtained (yield 48%).
[0141]
The obtained white solid was analyzed by gas chromatography, and it was found that
the solid was 1,4-dicyanocyclohexane having a purity of 99.5% or more, and the trans isomerlcis
isomer ratio was 9416.
A metal (tin) content of the solid was 10 ppm or less, which is 9.95 (10 x 0.995) ppm or
less relative to 1,4-dicyanocyclohexane (including trans isomer and cis isomer), and 9.35 (9.95 x
25
0.94) ppm or less relative to trans-1,4-dicyanocyclohexane.
[0143]
Meanwhile, the solvent was distilled off from the filtrate after the filtration, and 4.2 g of
a yellow solid was obtained. The obtained yellow solid was analyzed by gas chromatography,
and it was found that the solid was 1,4-dicyanocyclohexane having a purity of 87%, and the trans
isomerlcis isomer ratio was 16/84.
[Aminomethylation Step]
A 100 rnL stainless steel-made autoclave equipped with a stirrer was charged with 3.5 g
of 1,4-dicyanocyclohexane having a trans isomerlcis isomer ratio of 9416 obtained in the
cyanation step, 0.35 g of a catalyst (manganese-containing Raney cobalt manufactured by
Ki!?r~zkelnFl ilnle Cherrri~ah-C.o~,-Ltd.~~3~9~~-~f~-2-w8at~e~r,~ aanmd m7o.3n miLa of 1-
butanol. The autoclave was purged with nitrogen introduced from the autoclave nozzle inlet
three times at 2MPa, and the mixture was heated to 80°C while stirring at 400 rpm.
[0144]
When the temperature reached 80°C, hydrogen supply was started intermittently to
achieve a pressure of 0.95 MPa, and the reaction was performed until there is no hydrogen
absorption.
[0145]
After the completion of reaction, the product was cooled to room temperature. The
reaction mixture was taken out, and was filtered to remove the catalyst.
[0146]
The filtrate was analyzed by gas chromatography, and it was found that the conversion
of 1,4-dicyanocyclohexane was loo%, the yield of 1,4-bis(aminomethyl)cyclohexane was 96%,
and the trans isomerlcis isomer ratio was 87113.
[0147]
The filtrate was distilled under a reduced pressure of 10 mmHg, and 1,4-
bis(aminomethyl)cyclohexane having a purity of 99.5% or more and a trans isomerlcis isomer
ratio of 88/12 was obtained with a yield of 97%.
(Example 2)
26
Reaction was performed in the same manner as in the cyanation step of Example 1,
except that 4.0 g of the yellow solid obtained after the reaction in the cyanation step in Example
1 (3.5 g of 1,4-dicyanocyclohexane) was added to the reactor in the cyanation step.
[0148]
After 8 hours, the reaction mixture was cooled to room temperature.
[0149]
The solid product was suspended in methanol, and then the suspension was filtered to
remove the catalyst.
[0150]
The filtrate was analyzed by gas chromatography, and it was found that the conversion
-
of 1,4-cy~l0hexm~dlcarb0x'~~d~wa~_1D.r3~I~~~~~~~d-efw-as1 9~ 14.7~%d,i ~ya~d~he~and the trans isomerlcis isomer ratio was 54/46.
[Examination of Nuclear Hydrogenation Step]
(Example 3)
A 100 mL stainless steel-made autoclave equipped with a stirrer was charged with 12.0
g of terephthalic acid, 1.6 g of a catalyst (5%Pd/C, manufactured by NE Chemcat Corporation),
and 28 mL of water. The autoclave was purged with nitrogen introduced from the autoclave
nozzle inlet three times at 7MPa, and the mixture was heated to 150°C while stirring at 400 rpm.
When the temperature reached 1 50°C, hydrogen supply was started intermittently to
achieve a pressure of 5 MPa, and the reaction was performed until there is no hydrogen
absorption.
[0152]
After the completion of reaction, the mixture was cooled to room temperature. The
reaction mixture was taken out, and after a 5N aqueous NaOH solution containing sodium
hydroxide of 2.5 times mol the charged terephthalic acid amount was added thereto, the mixture
was filtered to remove the catalyst.
[0153]
The filtrate was neutralized with a 5N aqueous HC1 solution, and then analyzed by high-
2 7
1- llF058-PCT
performance liquid chromatography. It was found that the conversion of terephthalic acid was
loo%, the yield of 1,4-cyclohexanedicarboxylic acid was 99.5%, and the trans isomer/cis isomer
ratio was 34/66.
(Example 4)
[0154]
A 100 mL stainless steel-made autoclave equipped with a stirrer was charged with 6.0 g
of terephthalic acid, 0.23 g of a catalyst (5%Pd/C, manufactured by NE Chemcat Corporation),
and 34 mL of water. The autoclave was purged with nitrogen introduced from the autoclave
nozzle inlet three times at 6MPa, and the mixture was heated to 150°C while stirring at 400 rpm.
[0155]
When the ternp~aturerexhd-158 zC7hydro~en-mpfl~~ddintemittentl y to
achieve a pressure of 4 MPa, and reaction was performed for 5.5 hours.
[0156]
After the completion of reaction, the mixture was cooled to room temperature. The
reaction mixture was taken out, 200 ml of water was added thereto, and the mixture was heated
to 90°C to dissolve the product. Thereafter, the mixture was filtered to remove the catalyst.
[0157]
The filtrate was analyzed by gas chromatography, and it was found that the conversion
of terephthalic acid was 99.5%, the yield of 1,4-cyclohexanedicarboxylic acid was 91.9%, and
the trans isomer/cis isomer ratio was 36/64.
(Examples 5 to 13)
The catalyst removed after filtration in Example 4 was recovered, and reaction was
performed repeatedly with the same conditions as those of Example 4. The results are shown in
Table 1. The reaction product did not greatly decrease even after ten times of reaction, and 1,4-
cyclohexanedicarboxylic acid was obtained with a high yield.
Catalyst Recovered
Example 6 Catianl yEsxt Ramec~ovlee5r ed 34/66
Table 1
Catalyst Recovered
Example 7 4-5
in Example 6
34/66
Catalyst Recovered
Example 8 4.5
in Examole 7 100 34/66
Example
No.
Example 4
Catalyst Recovered
v
__5__5---rO-O-o 91.7 36/64 A --
in Examole 10 100 95.7 3 6/64 I
[Examination of Cyanation Step]
(Example 14)
Catalyst Used
5%PdlC
L_- - -
A four-neck flask equipped with a stirrer, a gas inlet tube, a thermometer, a gas purge
line, and a condenser was charged with 15.3 g of 1,4-cyclohexanedicarboxylic acid obtained in
the same manner as in Example 3, 17.5 g of dimethyl 1,4-cyclohexanedicarboxylate,a nd 0.39 g
of tin (11) oxide, and the mixture was heated to 210°C while stirring at 250 rpm.
[0158]
Thereafter, ammonia gas was introduced at a rate of 72 mL/min (1.1 mol equivalent/l,4-
cyclohexanedicarboxylic acid + dimethyl 1,4-cyclohexanedicarboxylate/hr) and the temperature
in the reactor was kept at 210°C for 1 hour. Then the temperature was increased to 280°C, and
Reaction
Time
(hr)
5.5
Terephthalic
Acid
Conversion
(%I
99.5
Example
-12
Example
13
while the temperature was kept constant, reaction was performed. After 8 hours, the reaction
mixture was cooled to room temperature. When the reaction was terminated, a white solid was
1,4-cyclohexanedicarboxylic acid
Catalyst Recovered
in Example 1 1
Catalyst Recovered
in Example 12
observed in the gas purge line and the condenser.
29
Yield (%)
cis isomer/trans isomer
ratio
6
6.5
91.9 1 3 6/64
100
100
96.8
91.7
37/63
3 6/64
[0159]
The solid product and the white solid observed in the gas purge line and the condenser
were together suspended in methanol, and then the suspension was filtered to remove the catalyst.
[0160]
The filtrate was analyzed by gas chromatography, and it was found that the conversion
of 1,4-cyclohexanedicarboxylic acid was 100'76, the conversion of dimethyl 1,4-
cyclohexanedicarboxylate was loo%, the yield of 1,4-dicyanocyclohexane was 90.2%, and the
trans isomerlcis isomer ratio was 53/47.
(Example 15)
A four-neck flask equipped with a stirrer, a gas inlet tube, a thermometer, a gas purge
- !ine,~dciaacnndene~r~~~;;s-&~~edwtgt o'fn T15,41-1c yclohexanedicarboxylica cid obtained in
the same manner as in Example 3, 17.4 g of dimethyl 1,4-cyclohexanedicarboxylate, 4.9 g of
N,N'-dimethylimidazolidinone (boiling point 226OC), and 0.40 g of tin (11) oxide, and the
mixture was heated to 210°C while stirring at 250 rpm.
[0161]
Thereafter, ammonia gas was introduced at a rate of 72 mL/min (1.1 mol equivalent/l,4-
cyclohexanedicarboxylic acid + dimethyl 1,4-cyclohexanedicarboxylatelhr) and the temperature
in the reactor was kept at 210°C for 1 hour. Then the temperature was increased to 280°C, and
while the temperature was kept constant, reaction was performed. After 8 hours, the reaction
mixture was cooled to 90°C. When the reaction was terminated, almost no white solid was
observed in the gas purge line and the condenser.
[0 1621
Then, 3 1.6 g of 1 -butan01 was added thereto and the mixture was stirred to produce a
reaction mixture. The reaction mixture was filtered by hot filtration to remove the catalyst.
The filtrate was analyzed by gas chromatography, and it was found that the conversion of 1,4-
cyclohexanedicarboxylic acid was loo%, the conversion of dimethyl 1,4-
cyclohexanedicarboxylate was 99.9%, the yield of 1,4-dicyanocyclohexane was 89%, and the
trans isomerlcis isomer ratio was 53147.
1-llF058-PCT
Next, 12.6 g of 1-butanol was added to 37.3 g of the filtrate obtained as described above
at 90°C, and as the mixture was cooled while stirring to room temperature, a precipitate was
appeared. The suspension was filtered, and the residue was further washed twice with 17.5 g of
1-butanol. Thereafter, the residue was dried, thereby producing 6.7 g of a light yellow solid
(yield 45%).
[0 1641
The obtained light yellow solid was analyzed by gas chromatography, and it was found
that the solid was 1,4-dicyanocyclohexane having a purity of 99.5% or more, and the trans
isomerlcis isomer ratio was 9515.
[0165]
k m e ~ a ~ ~ i n > ~ o + . t e r - ? t - ~ f t - h e - ~ ~ l i d -x~ 0~.9s95-) p~p-m ~or~ m - ~ ~ ~ ~ ~ less relative to 1,4-dicyanocyclohexane (including trans isomer and cis isomer) and 0.945 (0.995
x 0.95) ppm or less relative to trans- l,4-dicyanocyclohexane.
[0166]
Meanwhile, the solvent was distilled off from the filtrate after the filtration and
washings, and 7.0 g of a yellow solid was obtained. The obtained yellow solid was analyzed by
gas chromatography, and it was found that the solid was 1,4-dicyanocyclohexane having a purity
of 89%, and the trans isomerlcis isomer ratio was 13/87.
(Example 16)
13.5 g of a yellow solid obtained in the same manner as in Example 15 (12.0 g of 1,4-
dicyanocyclohexane) was added to the reactor in the cyanation step, and reaction was performed
in the same manner as in Example 15, except that dimethyl 1,4-cyclohexanedicarboxylatew as
not added, and the rate of the ammonia gas introduction was changed to 36 mLlmin (1.1 mol
After 15 hours, the reaction mixture was treated in the same manner as in Example 15.
As a result of gas chromatography analysis, it was found that the conversion of 1,4-
cyclohexanedicarboxylic acid was loo%, the yield of 1,4-dicyanocyclohexane was 94.5%, and
31
the trans isomerlcis isomer ratio was 53/47. The cyanation reaction proceeded with high yields
even if the recovered solid mainly composed of the separated cis- l,4-dicyanocyclohexane was
fed again in the cyanation step.
(Example 17)
Reaction was performed in the same manner as in Example 15, except that 3.3 g of
tetraethylene glycol dimethylether (boiling point 275°C) was used instead of 4.9 g of N,N'-
dimethylimidazolidinone. When the reaction was terminated, almost no white solid was
observed in the gas purge line and the condenser.
[0169]
The reaction mixture was filtered by hot filtration in the same manner as in Example 15.
The filtrate was maly~ddby~a~-r,h~~mz~og-a~ky~anhdX-hie~ c~on~v~erosiuonn doff 1 ,4-
cyclohexanedicarboxylic acid was loo%, the conversion of dimethyl 1,4-
cyclohexanedicarboxylate was loo%, the yield of 1,4-dicyanocyclohexane was 87%, and the
trans isomer/cis isomer ratio was 52/48.
(Example 18)
Reaction was performed in the same manner as in Example 15, except that 3.3 g of
triethylene glycol dimethylether (boiling point 216°C) was used instead of 4.9 g of N,N'-
dimethylimidazolidinone. When the reaction was terminated, almost no white solid was
observed in the gas purge line and the condenser.
[0 1701
The reaction mixture was filtered by hot filtration in the same manner as in Example 15.
The filtrate was analyzed by gas chromatography, and it was found that the conversion of 1,4-
cyclohexanedicarboxylic acid was loo%, the conversion of dimethyl 1,4-
cyclohexanedicarboxylate was loo%, the yield of 1,4-dicyanocyclohexane was 85%, and the
trans isomer/cis isomer ratio was 5 1/49.
(Example 19)
A four-neck flask equipped with a stirrer, a gas inlet tube, a thermometer, a gas purge
line, and a condenser was charged with 42.2 g of commercially available 1,4-
cyclohexanedicarboxylic acid, 49.1 g of dimethyl 1,4-cyclohexanedicarboxylate, 13.7 g of N,N'-
32
1-llF058-PCT
dimethylimidazolidinone, and 1.06 g of tin (11) oxide, and the mixture was heated to 210°C while
stirring at 250 rpm.
[0171]
Thereafter, ammonia gas and nitrogen were mixedly introduced at a rate of 100 mL/min
(0.55 mol equivalent/l,4-cyclohexanedicarboxylic acid + dimethyl 1,4-
cyclohexanedicarboxylate/hr) and a rate of 100 mL/min, respectively. The temperature of the
reactor was kept at 2 1 O°C for 1 hour, then increased to 280°C, and while the temperature was
kept constant, reaction was performed. After 16 hours, the reaction mixture was cooled to 90°C.
When the reaction was terminated, almost no white solid was observed in the gas purge line and
the condenser.
Then, 100 g of 1-butanol was added thereto and stirred. The reaction mixture was
filtered by hot filtration to remove the catalyst. The filtrate was analyzed by gas
chromatography, and it was found that the conversion of 1,4-cyclohexanedicarboxylic acid was
loo%, the conversion of dimethyl 1,4-cyclohexanedicarboxylate was 98.8%, the yield of 1,4-
dicyanocyclohexane was 86.0%, and the trans isomerlcis isomer ratio was 52/48.
to1731
Next, as the filtrate obtained as described above was cooled while stirring to room
temperature, a precipitate was appeared. The suspension liquid was filtered, and the residue
was further washed with 50 g of 1-butanol twice. Thereafter, the residue was dried, thereby
producing a light yellow solid. The obtained light yellow solid was analyzed by gas
chromatography, and it was found that the solid was 1,4-dicyanocyclohexane having a purity of
96.9%, and the trans isomer/cis isomer ratio was 8911 1.
[0174]
A metal (tin) content of the solid was 4.3 ppm, which is 4.17 (4.3 x 0.969) ppm relative
to 1,4-dicyanocyclohexane (including trans isomer and cis isomer) and 3.7 (4.17 x 0.89) ppm
relative to trans- 1,4-dicyanocyclohexane.
Meanwhile, the solvent was distilled off from the filtrate after the filtration and
3 3
washings, and a yellow solid was obtained. The obtained yellow solid was analyzed by gas
chromatography, and it was found that the solid was 1,4-dicyanocyclohexane having a purity of
90%, and the trans isomerlcis isomer ratio was 21/79.
(Example 20)
Reaction was performed in the same manner as in Example 19, except that 35.2 g of the
yellow solid obtained in Example 19 was added to the reactor in the cyanation step, and dimethyl
1,4-cyclohexanedicarboxylate was not added.
[O 1761
After 16 hours, and the reaction mixture was treated in the same manner as in Example
19.
As a result of gas chromatography analysis, it was found that the conversion of 1,4-
cyclohexanedicarboxylic acid was loo%, the yield of 1,4-dicyanocyclohexane was 93.4%, and
the trans isomerlcis isomer ratio was 52/48. The cyanation reaction proceeded with high yields
even if the recovered solid mainly composed of the separated cis-l,4-dicyanocyclohexanew as
fed again in the cyanation step.
[0178]
Furthermore, the product was filtered by hot filtration and cooled; and the appeared
precipitant was filtered, washed, and dried in the same manner as in Example 19, thereby
producing a light yellow solid. The obtained light yellow solid was analyzed by gas
chromatography, and it was found that the solid was 1,4-dicyanocyclohexane having a purity of
93%, and the trans isomer/cis isomer ratio was 9515.
[0179]
A metal (tin) content of the solid was 44 ppm, which is 40.9 ppm (44 x 0.93) relative to
1,4-dicyanocyclohexane (including trans isomer and cis isomer) and 38.8 ppm (40.9 x 0.95)
relative to trans- 1,4-dicyanocyclohexane.
(Example 2 1)
A four-neck flask equipped with a stirrer, a gas inlet tube, a thermometer, a gas purge
line, and a condenser was charged with 143.3 g of commercially available 1,4-
34
1-11F058-PCT
cyclohexanedicarboxylic acid, 166.7 g of dimethyl 1,4-cyclohexanedicarboxylate, 55.7 g of
N,N'-dimethylimidazolidinone,a nd 3.6 g tin (11) oxide. Ammonia gas and nitrogen were
mixedly introduced thereto at a rate of 90 mL1min (0.14 mol equivalent/l,4-
cyclohexanedicarboxylic acid + dimethyl 1,4-cyclohexanedicarboxylate/hr) and 10 mllmin,
respectively. The temperature was increased to 280°C, and while the temperature was kept
constant, reaction was performed. After 48 hours, the reaction mixture was cooled to 90°C.
When the reaction was terminated, almost no white solid was observed in the gas purge line and
the condenser.
70 g of 1-butanol was added to 30 g of the mixture and stirred. The reaction mixture
was filtered by hot filtration to remove the catalyst. The filtrate was analyzed by gas
~-, ~ ~ a s _ t " 1 ! ~ ~ f ~ d - t h z t - t - h ~ ~ ~ e ~ d - 0 ~ ~ 4 w~ais 8~6%y. a n 0 ~ y ~ 1 o h e [0180]
The remaining of the mixture was filtered by hot filtration in the same manner as in
Example 15, cooled, and the appeared precipitant was filtered, washed, and dried, thereby
producing a light yellow solid. The obtained light yellow solid was analyzed by gas
chromatography, and it was found that the solid was 1,4-dicyanocyclohexane having a purity of
95.7%, and the trans isomer/cis isomer ratio was 9515.
[0181]
A metal (tin) content of the solid was 10 ppm or less, which is 9.57 ppm or less (10 x
0.957) relative to 1,4-dicyanocyclohexane (including trans isomer and cis isomer) and 9.09 ppm
or less (9.57 x 0.95) relative to trans-l,4-dicyanocyclohexane.
(Comparative Example 1)
Reaction was performed in the same manner as in Example 21, except that the ammonia
gas feeding rate was set to an average of 49 mL/min (0.076 mol equivalent/l,4-
cyclohexanedicarboxylic acid + dimethyl 1,4-cyclohexanedicarboxylatelhr), and the reaction
time was set to 80 hours. The yield of 1,4-dicyanocyclohexane was 68%. The mixture was
filtered by hot filtration and cooled; and the appeared precipitant was filtered, washed, and
dried in the same manner as Example 15, thereby producing a light yellow solid. The obtained
light yellow solid was analyzed by gas chromatography, and it was found that the solid was 1,4-
3 5
dicyanocyclohexane having a purity of 94%, and the trans isomerlcis isomer ratio was 9515.
[O 1821
A metal (tin) content of the solid was 3800 pprn (0.38%), which is 3572 pprn (3800 x
0.94) relative to 1,4-dicyanocyclohexane (including trans isomer and cis isomer), and 3393 pprn
(3572 x 0.95) relative to trans- l,4-dicyanocyclohexane.
(Example 22)
32.5 g of the trans-l,4-dicyanocyclohexaneo btained in Comparative Example 1 and 3 15
g of methanol were dissolved at 60°C, and 0.7 g of activated carbon (manufactured by Wako
Pure Chemical Industries, Ltd.) was added thereto. The mixture was stirred for 2 hours. The
mixture was filtered at 60°C to remove the activated carbon, and the solvent was distilled off
-.- from the filtr~tet,h ereby- p roclilcing~~~~~-g-%f~~~k~+,~8~d~s-ohlied -w~abs t~dwhite
analyzed by gas chromatography, and it was found that the solid was 1,4-dicyanocyclohexane
having a purity of 96.4%, and the trans isomerlcis isomer ratio was 9515.
[0183]
A metal (tin) content of the solid was 130 ppm, which is 125 pprn (130 x 0.964) relative
to I ,4-dicyanocyclohexane (including trans isomer and cis isomer), and 1 19 pprn (1 25 x 0.95)
relative to trans-1,4-dicyanocyclohexane.
(Example 23)
The treatment was performed in the same manner as in Example 22, except that
activated carbon was not used. The obtained light yellow solid was analyzed by gas
chromatography, and it was found that the solid was 1,4-dicyanocyclohexane having a purity of
95.8%, and the trans isomerlcis isomer ratio was 9515.
[O 1841
A metal (tin) content of the solid was 1200 ppm (0.12%), which is 11 50 pprn (1200 x
0.94) relative to 1,4-dicyanocyclohexane (including trans isomer and cis isomer), and 1092 pprn
(1 150 x 0.95) relative to trans- l,4-dicyanocyclohexane.
(Example 24)
Reaction was performed in the same manner as in Example 14, except that ammonia gas
was introduced at a rate of 48 mllmin (0.73 mol equivalent/l,4-cyclohexanedicarboxylic acid +
36
1-llF058-PCT
dimethyl 1,4-cyclohexanedicarboxylate/hr). When the reaction was terminated, a white solid
was observed. in the gas purge line and the condenser.
[0185]
The solid product and the white solid observed in the gas purge line and the condenser
were together treated in the same manner as in Example 14. The filtrate was analyzed by gas
chromatography, and it was found that the conversion of 1,4-cyclohexanedicarboxylic acid was
loo%, the conversion of dimethyl 1,4-cyclohexanedicarboxylate was 99%, the yield of 1,4-
dicyanocyclohexane was 84%, and the trans isomerlcis isomer ratio was 54/46.
(Example 25)
Reaction was performed in the same manner as in Example 14, except that ammonia gas
/?-was introd~cec2! t 2 rzte of 24 mL/ I? -1;-a i,un.3 6 moieq~~~i~_a~~nt~~~~~~~~~h8xa::edie~i~b8'fij~~dimethyl 1,4-cyclohexanedicarboxylatelhr). When the reaction was terminated, a white solid
was observed in the gas purge line and the condenser.
[0186]
The solid product and the white solid observed in the gas purge line and the condenser
were together treated in the same manner as in Example 14. The filtrate was analyzed by gas
chromatography, and it was found that conversion of dimethyl 1,4-cyclohexanedicarboxylate
was 98%, the yield of 1,4-dicyanocyclohexane was 54%, and the trans isomerlcis isomer ratio
was 52/48.
[Examination of Aminomethylation Step]
(Example 26)
A 100 mL stainless steel-made autoclave equipped with a stirrer was charged with 5.5 g
of 1,4-dicyanocyclohexane having a trans isomerlcis isomer ratio of 9614 obtained in the same
manner as in Example 15,0.3 g of a catalyst (Raney nickel manufactured by Kawaken Fine
Chemicals Co., Ltd.), 5.6 mL of a 28 wt% ammonia water, and 10.5 mL of 1-butanol. The
autoclave was purged with nitrogen introduced from the autoclave nozzle inlet three times at
2MPa, and the mixture was heated to 80°C while stirring at 400 rpm.
[0187]
When the temperature reached 80°C, hydrogen supply was started intermittently to
3 7
1-llF058-PCT
achieve a pressure of 0.95 MPa, and the reaction was performed until there is no hydrogen
absorption.
[0 1881
After the completion of reaction, the mixture was cooled to room temperature. The
reaction mixture was taken out, and was filtered to remove the catalyst.
[0189]
The filtrate was analyzed by gas chromatography, and it was found that the conversion
of 1,4-dicyanocyclohexane was loo%, the yield of 1,4-bis(aminomethyl)cyclohexane was 99%,
and the trans isomerlcis isomer ratio was 88/12.
[0190]
The reaction mixkxe was distiiiehl~~der-~-~e&~eed-p~essur~f~O
bis(aminomethyl)cyclohexane having a trans isomer/cis isomer ratio of 86/14 and a purity of
99.5% or more was obtained with a yield of 95%.
(Example 27)
A 100 mL stainless steel-made autoclave equipped with a stirrer was charged with 5.3 g
of trans-l,4-dicyanocyclohexane (purity 99.5% or more, trans isomer/cis isomer ratio = 9515, tin
content 1 ppm or less) obtained in the same manner as in Example 15,0.26 g of a catalyst
(manganese-containing Raney cobalt manufactured by Kawaken Fine Chemicals Co., Ltd.), 6.4
mL of a 28 wt% ammonia water, and 10.8 mL of 1-butanol. The autoclave was purged with
nitrogen introduced from the autoclave nozzle inlet three times at 5MPa, and the mixture was
heated to 80°C while stirring at 400 rpm.
[0191]
When the temperature reached 80°C, hydrogen supply was started intermittently to
achieve a pressure of 3.5 MPa, and the reaction was performed until there is no hydrogen
absorption. The reaction time was 3 hours.
[0192]
After the completion of reaction, the mixture was cooled to room temperature. The
reaction mixture was taken out, and was filtered to remove the catalyst.
1-llF058-PCT
The filtrate was analyzed by gas chromatography, and it was found that the conversion
of 1,4-dicyanocyclohexane was 96.3%, the yield of 1,4-bis(aminomethyl)cyclohexane was
94.3%, and the trans isomerlcis isomer ratio was 9317.
(Examples 28 to 3 1)
The catalyst removed after filtration in Example 23 was recovered, and reaction was
performed repeatedly with the same conditions as those of Example 27. The results are shown
in Table 2. The reaction product did not greatly decrease even after five times of reaction, and
trans-1,4-bis(aminomethyl)cyclohexane was obtained with high yields.
Table 2 - . . - - - -
Example
I Example 28 Catalyst Recovered in
Example 27
Catalyst Recovered in 29
Example 28
96.1 9317
(Example 32)
Example 30
Example 3 1
A 100 rnL stainless steel-made autoclave equipped with a stirrer was charged with 9.0 g
of trans-l,4-dicyanocyclohexane (purity 99.5% or more, trans isomerlcis isomer ratio = 9416, tin
Catalyst Used
Time
No.
(hr) Conversion (%)
Manganese-
Example 27 containing Raney 3 96.3
cobalt I
Reaction
content 1 ppm or less) obtained in the same manner as in Example 15,0.45 g of a catalyst
(manganese-containing Raney cobalt manufactured by Kawaken Fine Chemicals Co., Ltd.), 4.6
mL of a 28 wt% ammonia water, and 14.6 mL of methanol. The autoclave was purged with
Catalyst Recovered in
Exam~le29
Catalyst Recovered in
Example 30
nitrogen introduced from the autoclave nozzle inlet three times at 5MPa, and the mixture was
heated to 80°C while stirring at 400 rpm.
[0194]
When the temperature reached 80°C, hydrogen supply was started intermittently to
achieve a pressure of 4.5 MPa, and reaction was performed for 2.5 hours.
[0 1951
1,4-dicyanocyclohexane
After the completion of reaction, the mixture was cooled to room temperature. The
reaction mixture was taken out, and was filtered to remove the catalyst.
[0196]
The filtrate was analyzed by gas chromatography, and it was found that the conversion
of 1,4-dicyanocyclohexane was 95.2%, the yield of 1,4-bis(aminomethyl)cyclohexane was
89.2%, and the trans isomerlcis isomer ratio was 9317.
40
1,4-bis(aminomethyl)cyclohexane
3.5
4
96
96.6
89.4
92.8
9317
9317
(Examples 33 to 37 and Comparative Example 2)
[0197]
Reaction was performed in the same manner as in Example 32, except that trans-1,4-
dicyanocyclohexane used was changed as shown in Table 3. The results are shown in Table 3.
When trans-l,4-dicyanocyclohexaneh aving a smaller tin content was used, 1,4-
bis(aminomethyl)cyclohexane was produced with a high yield. I
[0198]
Table 3
Ex. and
Comp. Ex.
No.
v o%r“nIInPJIUo -
3 2
33
Example
34

(Example 38)
A four-neck flask equipped with a stirrer, a gas inlet tube, a thermometer, a gas purge
line, and a condenser was charged with 287 g of commercially available 1,4-
cyclohexanedicarboxylic acid, 55.7 g of N,N'-dimethylimidazolidinone, and 3.6 g of tin (11)
oxide, and ammonia gas and nitrogen were mixed.1i~n troduced thereto at a rate of 43 mWmin
(0.07 mol equivalent/l,4-cyclohexanedicarboxylic acidlhr), and 5 mllmin, respectively. The
temperature was increased to 280°C, and while the temperature was kept constant, reaction was
performed. After 60 hours, the reaction mixture was cooled to 90°C. When the reaction was
Example
35
Comp.Ex.
2
3 6
37
trans- l,4-dicyanocyclohexane 1,4-bis(aminomethyl)cyclohexane
Example 2 1
Comp.Ex.
1
Example 22
Example 23
Production
Method
Example 15
Example 19
Example 20
9.09
3393
119
1092
Metal Content
( P P ~ )
>99
80.8
94.5
91.6
0.945
3.7
38.8
95.1
25.9
87.7
62.3
95.2
>99
>99
88/12
9515
9218
9515
89.2
>99
>99
9317
8911 1
9218
terminated, almost no white solid was observed in the gas purge line and the condenser.
101991
70 g of 1-butanol was added to 30 g of the product and stirred. The reaction mixture
was filtered by hot filtration to remove the catalyst. The filtrate was analyzed by gas
chromatography, and it was found that the yield of 1,4-dicyanocyclohexane was 70%.
(Examples 39 to 4 1)
Reaction was performed in the same manner as in Example 38, except that the rate of
ammonia gas and nitrogen supply and the reaction time were changed. The results are shown in
Table 4.
r02001
(Example 42)
T-Ll- 4
A four-neck flask equipped with a stirrer, a gas inlet tube, a thermometer, a gas purge
-
line, and a condenser was charged with 74 g of commercially available 1,4-
cyclohexanedicarboxylic acid, 14.8 g of N,N'-dimethylimidazolidinone,a nd 0.93 g of tin (11)
oxide, and ammonia gas and nitrogen were mixedly introduced thereto at a rate of 135 mL/min
(0.84 mol equivalent/l,4-cyclohexanedicarboxylic acid/hr), and 15 mL/min, respectively. The
1,4-dicyanocyclohexane
Yield (%)
70
85
90
91
temperature was increased to 280°C, and while the temperature was kept constant, reaction was
Reaction
Time
(hr)
60
48
32
20
L ~ U I G
performed. After 13 hours, the reaction mixture was cooled to 90°C. When the reaction was
Example
No.
Example 38
Example 39
-
Example 40
Example 41
terminated, almost no white solid was observed in the gas purge line and the condenser.
Ammonia Gas Feeding
Rate
(mL/min)
43
90
180
360
-
Nitrogen
Feeding Rate
(mL1min)
5
10
20
40
1-llF058-PCT
[0201]
70 g of 1-butanol was added to 30 g of the product and stirred. The reaction mixture
was filtered by hot filtration to remove the catalyst. The filtrate was analyzed by gas
chromatography, and it was found that the yield of 1,4-dicyanocyclohexane was 91%.
(Example 43)
Reaction was performed in the same manner as in Example 42, except that the rate of
ammonia gas and nitrogen supply was set to 180 mL/min and 20 mL/min, respectively, and the
reaction time was set to 9 hours. The yield of 1,4-dicyanocyclohexane was 93%.
[0202]
These Examples show that the greater the ammonia gas feeding rate is, the shorter the
reaction time is and the higher the jie!d of i ~ z d i ~ p n ~ ~ ~ ~ ~ ! ~ h s ~ ~ e - i ~ .
[0203]

(Examples 44 to 49 and Comparative Example 3)
Reaction was performed in the same manner as in Example 42, except that the metals
and amounts of metal oxide used were changed as shown in Table 5 from 0.93 g of tin (11) oxide,
and the reaction time was also changed. The results are shown in Table 5.
Table 5
I
Ex. and
Comp. Ex.
No.
I
Example 42
I Example 46 / Iron (111) Oxide / 1.11 / 14 / 9 1
Metal Oxide
Type
Example 44
Example 45
Tin (11) Oxide
Metal Oxide
Amount
Used(g)
Zinc Oxide
Cobalt (111) Oxide
Example 47
These Examples show that metal oxides accelerate the reaction.
to2051

(Example 50)
Reaction was performed in the same manner as in Example 42, except that 12.9 g of Nmethyl-
2-pyrrolidinone (boiling point 202°C) was used instead of 14.8 g of N,Ntdimethylimidazolidinone.
When the reaction was terminated, almost no white solid was
observed in the gas purge line and the condenser.
[0206]
70 g of 1-butanol was added to 30 g of the product and stirred. The reaction mixture
was filtered by hot filtration to remove the catalyst. The filtrate was analyzed by gas
chromatography, and it was found that the yield of 1,4-dicyanocyclohexane was 91 %.
0.93
Example 49
Comp. Ex. 3
Reaction
Time
(hr)
0.56
1.14
i ~ ~ ~ ~ - ~ d i ~ ~ ~ - - l
I
1 Example 48 / Pentoxide 1 1.26 / 18 1 93
Manganese Dioxide
1,4-dicyanocyclohexane
Yield (%)
13
Titanium Dioxide
None
9 1
16
14
0.60 1 16
92
86
89
0.55
-
15
26
89
78
[0207]

I (Examples 52 to 53)
In Example 42, the remaining of the mixture was also filtered by hot filtration in the
same manner as in Example 42 to separate the catalyst. The separated catalyst was recovered
together with 30 g of the previously filtered product by hot filtration. The recovered catalyst
was used repeatedly instead of 0.93 g of tin (11) oxide, and reaction was performed in the same
manner as in Example 42. The results are shown in Table 6. The reaction product did not
I greatly decrease even after three times of reaction, and 1,4-dicyanocyclohexane was obtained
I with a high yield.
1 Table 6
Catalyst (Metal 1,4-dicyanocyclohexane
Example No.
Yield (%)
I Example 42 / Tin (11) oxide ( 13 (
Cyanation: Isomerization of 1,4-dicyanocyclohexane in the Absence of Hydrogenated
Carboxylic Acid Derivative>
(Example 54)
78.1 g of 1-butanol was added to the product obtained in the same manner as in
Example 42 and stirred. The reaction mixture was filtered by hot filtration to remove the
catalyst. The filtrate was analyzed by gas chromatography, and it was found that the yield of
1,4-dicyanocyclohexane was 89%, and the trans isomerlcis isomer ratio was 53/47.
Example 52
Example 53
[0209]
Next, 3 1 g of 1-butanol was added to 92 g of the filtrate obtained as described above at
90°C, and as the reaction mixture was cooled to room temperature while stirring, a precipitate
45
Catalyst Recovered in
Example 42
Catalyst Recovered in
Example 52
13
13
90
90
1- llF058-PCT
was appeared. The suspension was filtered, and the residue was further washed with 43.2 g of
1 -butan01 twice. Thereafter, the residue was dried, thereby producing 16.5 g of a light yellow
solid (yield 45%).
[0210]
The obtained light yellow solid was analyzed by gas chromatography, and it was found
that the solid was 1,4-dicyanocyclohexane having a purity of 99.5% or more, and the trans
isomer/cis isomer ratio was 9614.
[0211]
A metal (tin) content of the solid was 1 ppm or less, which is 0.995 (1 x 0.995) ppm or
less relative to 1,4-dicyanocyclohexane (including trans isomer and cis isomer) and 0.955 (0.995
[0212]
Meanwhile, the solvent was distilled off from the filtrate after the filtration and
washngs, and 17.3 g of a yellow solid was obtained. The obtained yellow solid was analyzed
by gas chromatography, and it was found that the solid was 1,4-dicyanocyclohexane having a
purity of 90%, and the trans isomer/cis isomer ratio was 13/87.
[0213]
Using the thus obtained 1,4-dicyanocyclohexane having a hgh cis isomer ratio, thermal
isomerization reaction was performed in the absence of hydrogenated carboxylic acid or a
derivative thereof.
(Example 5 5)
A four-neck flask equipped with a stirrer, a gas inlet tube, a thermometer, a gas purge
line, and a condenser was charged with 3 g of 1,4-dicyanocyclohexane (purity 90%, trans
isomer/cis isomer ratio 13/87) having a high cis isomer ratio obtained in the same manner as in
Example 54, and 0.8 g of N,N1-dimethylimidazolidinone. Ammonia gas was introduced thereto
while stirring at a rate of 17 mL/min (0.2 mol equivalent/l,4-dicyanocyclohexanekr)to increase
the temperature to 280°C, and while the temperature was kept constant, reaction was performed
for 10 hours, and then cooled. The obtained product was analyzed by gas chromatography, and
it was found that 1,4-dicyanocyclohexane had a purity of 90% (1,4-dicyanocyclohexane recovery
46
of 99% or more), and the trans isomerlcis isomer ratio was 53/47.
(Examples 56 to 58)
Reaction was performed in the same manner as in Example 55, except that use or nonuse
of tin (11) oxide, and ammonia gas feeding rate were changed. The results are shown in I
Table 7.
[0214]
Table 7
Tin (11) Ammonia Gas I Reaction 1,4- Example / Oxide / Feeding Rate / Time 1 dicyanocyclohexane
1,4-
dicyanocyclohexane
These Examples show that, thermal isomerization reaction progresses in the absence of
1 No.
Example
5 7
Example
58
hydrogenated carboxylic acid or a derivative thereof.
[0215]

(Example 59)
Amount
Used(g)
0
--
78 g of 1-butanol was added to the product obtained in the same manner as in Example
44 and stirred. The reaction mixture was filtered by hot filtration to remove the catalyst. The
68
Example
55
0
0.5
filtrate was analyzed by gas chromatography, and it was found that the yield of 1,4-
dicyanocyclohexane was 92%, and the trans isomer/cis isomer ratio was 53/47.
[0216]
Next, 3 1 g of 1-butanol was added to 92 g of the filtrate obtained as described above at
90°C, and as the reaction product was cooled while stirring to room temperature, a precipitate
(mL/min)
17
was appeared. The suspension liquid was filtered, and the residue was further washed with 42
47
90
0
0
(hr)
10
53/47
20
20
Purity(%)
90
trans isomerlcis
isomer ratio
53/47
90
8 9
53/47
53/47
1-llF058-PCT
g of 1-butanol twice. Thereafter, the residue was dried, thereby producing 17 g of a light
yellow solid (yield 46%).
(02 171
The obtained light yellow solid was analyzed by gas chromatography, and it was found
that the solid was 1,4-dicyanocyclohexane having a purity of 99.5% or more, and the trans
isomerlcis isomer ratio was 9317.
[0218]
The metal (zinc) content of the solid was 340 ppm, which is 338 (340 x 0.995) ppm
relative to 1,4-dicyanocyclohexane (including trans isomer and cis isomer) and 3 15 (338 x 0.93)
pprn relative to trans- l,4-dicyanocyclohexane.
,/f~l-p-&-- yeIaxampiec4->
Reaction was performed in the same manner as in Example 44, except that the reaction
time was set to 12 hours. The yield of 1,4-dicyanocyclohexane was 82%. The mixture was
filtered by hot filtration and cooled; and the appeared precipitant was filtered, washed, and dried
in the same manner as in Example 59, thereby producing a light yellow solid. The obtained
light yellow solid was analyzed by gas chromatography, and it was found that the solid was 1,4-
dicyanocyclohexane having a purity of 99%, and the trans isomerlcis isomer ratio was 9416.
[0219]
The metal (zinc) content of the solid was 10000 pprn (1.0%), which is 9900 pprn (10000
x 0.99) relative to 1,4-dicyanocyclohexane (including trans isomer and cis isomer) and 9306
pprn (9900 x 0.94) relative to trans-1,4-dicyanocyclohexane.
(Example 60)
The mixture obtained in the same manner as in Example 46 was filtered by hot filtration
and cooled; and the appeared precipitant was filtered, washed, and dried in the same manner as
in Example 59, thereby producing a light yellow solid. The obtained light yellow solid was
analyzed by gas chromatography, and it was found that the solid was 1,4-dicyanocyclohexane
having a purity of 99.5% or more, and the trans isomerlcis isomer ratio was 9119. The metal
(iron) content of the solid was 21 ppm, which is 21 (21 x 0.995) pprn relative to 1,4-
dicyanocyclohexane (including trans isomer and cis isomer) and 19 (2 1 x 0.9 1) pprn relative to
48
trans- l,4-dicyanocyclohexane.
(Example 6 1)
The mixture obtained in the same manner as in Example 46 was filtered by hot filtration
and cooled; and the appeared precipitant was filtered, washed, and dried in the same manner as
in Example 59, except that washing with 1-butanol was performed once, thereby producing a
light yellow solid. The obtained light yellow solid was analyzed by gas chromatography, and it
was found that the solid was 1,4-dicyanocyclohexane having a purity of 99.5% or more, and the
trans isomer/cis isomer ratio was 9317. The metal (iron) content of the solid was 350 ppm,
which is 348 (350 x 0.995) pprn relative to 1,4-dicyanocyclohexane (including trans isomer and
cis isomer) and 324 (348 x 0.93) pprn relative to trans- l,4-dicyanocyclohexane.
- (c~mpara?&sE~ap~i;i+53
Reaction was performed in the same manner as in Example 46, except that the reaction
time was set to 12 hours. The yield of 1,4-dicyanocyclohexane was 84%. The mixture was
filtered by hot filtration and cooled; and the appeared precipitant was filtered, washed, and dried
in the same manner as in Example 59, thereby producing a light yellow solid. The obtained
light yellow solid was analyzed by gas chromatography, and it was found that the solid was 1,4-
dicyanocyclohexane having a purity of 99.5% or more, and the trans isomerlcis isomer ratio was
9218.
[0220]
The metal (iron) content of the solid was 3500 pprn (0.35%), which is 3483 pprn (3500
x 0.995) relative to 1,4-dicyanocyclohexane (including trans isomer and cis isomer) and 3204
pprn (3483 x 0.92) relative to trans- 1,4-dicyanocyclohexane.
(Example 62)
A 100 mL stainless steel-made autoclave equipped with a stirrer was charged with 9.0 g
of trans-l,4-dicyanocyclohexane( purity 99.5% or more, trans isomerlcis isomer ratio = 9614, tin
content 1 pprn or less) obtained in Example 54, 0.45 g of a catalyst (manganese-containing
Raney cobalt manufactured by Kawaken Fine Chemicals Co., Ltd.), 14.6 g of a solution of
ammonia in methanol (containing 2.4 g of ammonia), and 0.7 g of water. The autoclave was
purged with nitrogen introduced from the autoclave nozzle inlet three times at 5MPa, and the
49
mixture was heated to 80°C while stirring at 400 rpm.
[0221]
When the temperature reached 80°C, hydrogen supply was started continuously to
achieve a pressure of 4.5MPa, and the reaction was performed under a constant pressure until
there is no hydrogen absorption.
After the completion of reaction, the mixture was cooled to room temperature. The
reaction mixture was taken out, and was filtered to remove the catalyst.
[0223]
The filtrate was analyzed by gas chromatography, and it was found that the conversion !
- o f - ' e - d ( = n o m e t h y l ) c y c l o h e x a n e was
96.6%, and the trans isomerlcis isomer ratio was 9317.
(Examples 63 to 65 and Comparative Examples 6 to 7)
Reaction was performed in the same manner as in Example 62, except that trans-1,4-
dicyanocyclohexane used was changed as shown in Table 8. The results are shown in Table 8.
When trans- l,4-dicyanocyclohexane having a smaller metal content was used, 1,4-
bis(aminomethyl)cyclohexane was produced with a high yield.

(Example 66)
Table 8
A 100 mL stainless steel-made autoclave equipped with a stirrer was charged with 9.0 g
Ex. and
Comp.
of trans- 1,4-dicyanocyclohexane (purity 99.4%, trans isomerlcis isomer ratio = 9614, tin content
1 ppm or less) obtained in the same manner as in Example 42, 0.09 g of a catalyst (manganesetrans-
1,4-dicyanocyclohexane
containing Raney cobalt manufactured by Kawaken Fine Chemicals Co., Ltd.), 9.6 mL of a 25
wt% ammonia water, and 11.3 g of 1-butanol. The autoclave was purged with nitrogen
Reaction
Time
introduced from the autoclave nozzle inlet three times at SMPa, and the mixture was heated to
120°C while stirring at 400 rpm.
[0225]
1,4-bis(aminomethyl)cyclohexane
hr
2.5
4.5
5'0
3 .O
4.2
Ex. No. Production
Method
When the temperature reached 120°C, hydrogen supply was started continuously to
Metal
Content(ppm)
tin 0.955
zinc 3 15
P
zinc 9306
iron 19
iron 324
Example
62
Example
63
Comp.
Ex. 6
Example
64
Example
65
achieve a pressure of 3.5 MPa, and the reaction was perfonned under constant pressure until
Conversion
(%)
99.1
98.7
87.3
>99
>99
Yield
(%I
96.6
93.6
Trace
Amount
98.5
93.7
Example
54
Example
59
Comp. Ex.
6
Example
60
Example
6 1
there is no hydrogen absorption. The reaction time was 3.3 hours.
trans isomerlcis isomer
ratio
9317
9317
-
88/12
9317
After the completion of reaction, the mixture was cooled to room temperature and
allowed to stand. The supernatant liquid of the reaction mixture was taken out.
1-llF058-PCT
[0227]
The obtained liquid was analyzed by gas chromatography, and it was found that the
conversion of 1,4-dicyanocyclohexane was 99.9% or more, the yield of 1,4-
bis(aminomethyl)cyclohexane was 96.7%, and the trans isomer/cis isomer ratio was 91/9.
(Examples 67 to 3 1)
The catalyst remained in the autoclave after taking out the supernatant liquid in
Example 66 was used as is, recovered, and reaction was performed repeatedly under the same
reaction conditions as those of Example 66, using new trans-1,4-dicyanocyclohexane,a mmonia
water, and 1-butanol. The results are shown in Table 9. In Example 72,0.09 g of a catalyst
(manganese-containing Raney cobalt manufactured by Kawaken Fine Chemicals Co., Ltd.) was
added.
[0228]
The reaction was repeated 20 times, and trans-1,4-bis(aminomethyl)cyclohexane was
obtained with a high yield.

(Example 87)
A four-neck flask equipped with a stirrer, a gas inlet tube, a thermometer, a gas purge
line, and a condenser was charged with 286.6 g of commercially available 1,4-
cyclohexanedicarboxylic acid, 55.7 g of N,N'-dirnethylimidazolidinone,a nd 3.6 g of tin (11)
oxide. Ammonia gas and nitrogen were mixedly introduced thereto while stirring at a rate of 90
5 3
1-
Table 9 -
Example
72
--
Example
73
Example
74
Example
No.
66
-
Example
67
Example
68
1,4-
bis(aminomethyl)cyclohexane
Reaction
Time
(h-)
3.3
-
4.2
4.8
catalyst used
--
Manganesecontaining
Raney
cobalt
Catalyst
Recovered in
Example 66
Catalyst
Recovered in
Example 67
Catalyst
Example
69
Example
70
Example
7 1
Yield
(%I
96.7
94.7
95.8
---
1,4-
dicyanocyclohexane
Conversion (%)
>99
>99
>99
-----
trans isomerlcis
isomer ratio
9119
9119
9119
9218
9218
---
9218
Recovered in 1 5.3 1 >99 1-94-3- I 9W10
Catalyst
Recovered in
Example- 7 1
Catalyst
Recovered in
Example 72
Catalyst
Recovered in
Example 73
Catalyst
2.5
2.8
3 .O
>99
>99
>99
- --
9011 0
90110
>99 1 9 6 . 9 1 -71 Recovered in
Example 74
95.6
93.4
97.8
95.6
3.3
>99
--
- - & X
Catalyst
Recovered in
Example 69
5.8
--
>99 98 .O
---
Catalyst
Recovered in
Example 70
6.5
mllmin (0.14 mol equivalent1 l,4-cyclohexanedicarboxylic acidihr) and 10 mLImin, respectively.
The temperature was increased to 280°C, and while the temperature was kept constant, reaction
was performed. After 48 hours, the reaction mixture was cooled to 90°C.
[0230]
520 g of 1 -butan01 was added to the mixture and stirred. The mixture was filtered by
hot filtration to remove the catalyst. The filtrate was analyzed by gas chromatography, and it
was found that the yield of 1,4-dicyanocyclohexane was 86%.
[023 11
Next, as the filtrate obtained as described above was cooled while stirring to room
temperature, a precipitate was appeared. The suspension was filtered, and 230 g of 1-butanol
was added to the residge ttikec out.
as the reaction mixture was cooled while stirring to room temperature, a precipitate was appeared
again. The suspension was filtered, and washed twice with 1-butanol. Thereafter, the residue
was dried, thereby producing 100 g of white solid (yield 45%).
The obtained white solid was analyzed by gas chromatography, and it was found that
the solid was 1,4-dicyanocyclohexane having a purity of 99.5% or more, and the trans isomerlcis
isomer ratio was 9911.
(Example 8 8)
A 0.5L stainless steel-made autoclave equipped with a stirrer was charged with 55 g of
1,4-dicyanocyclohexane having a trans isomerlcis isomer ratio of 9911 obtained in Example 87,
3.0 g of a catalyst (Raney nickel manufactured by Kawaken Fine Chemicals Co., Ltd.), 56 mL of
a 28 wt% ammonia water, and 105 mL of 1-butanol. The autoclave was purged with nitrogen
introduced fiom the autoclave nozzle inlet three times at 5MPa, and the mixture was heated to
80°C while stirring at 400 rpm.
[0233]
When the temperature reached 80°C, hydrogen supply was started to achieve a pressure
of 4.5MPaY and the reaction was performed until there is no hydrogen absorption. The reaction
time was 3 hours.
5 4
1-11F058-PCT
[0234]
After the completion of reaction, the mixture was cooled to room temperature. The
reaction mixture was taken out, and was filtered to remove the catalyst.
[0235]
The filtrate was analyzed by gas chromatography, and it was found that the conversion
of 1,4-dicyanocyclohexane was LOO%, the yield of 1,4-bis(aminomethy1)cyclohexane was 98%,
and the trans isomerlcis isomer ratio was 9812.
[0236]
The reaction mixture was distilled under a reduced pressure of 10 rnmHg, and 1,4-
bis(aminomethyl)cyclohexane having a purity of 99.5% or more and a trans isomerlcis isomer
ratio of 9812 was oStained~~aayeId-cf93-0//o.
[0237]
While the illustrative embodiments of the present invention are provided in the above
description, such is for illustrative purpose only and it is not to be construed restrictively.
Modification and variation of the present invention that will be obvious to those skilled in the art
is to be covered by the following claims.
Industrial Applicability
, [0238]
The present invention allows for an industrially advantageous production of 1,4-
bis(aminomethyl)cyclohexane having a high trans isomer ratio using a raw material cheaper than
conventional ones: the raw material such as terephthalic acid or terephthalic acid derivative of at
least one selected fi-om the group consisting of terephthalic acid, terephthalic acid ester, and
terephthalic acid amide.
[0239]
The compound is used suitably for improvement in characteristics of polyamide and
polyurethane.

CLAIMS
1. A method for producing trans- 1,4-bis(aminomethyl)cyclohexane, the method
comprising:
a nuclear hydrogenation step of producing a hydrogenated terephthalic acid or
terephthalic acid derivative by nuclear hydrogenation of a terephthalic acid or terephthalic acid
derivative,
the terephthalic acid or terephthalic acid derivative being at least one selected
from the group consisting of terephthalic acid, terephthalic acid ester, and terephthalic acid
amide;
- a cymat:loil s'tepofirz~tir?gthe-hy-&oge~at~-~~ackida loir cte rephthalic acid
derivative obtained in the nuclear hydrogenation step with ammonia, thereby producing 1,4-
dicyanocyclohexane, and producing trans-l,4-dicyanocyclohexane from the obtained 1,4-
dicyanocyclohexane; and
an aminomethylation step of treating the trans-1,4-dicyanocyclohexaneo btained in the
cyanation step with hydrogen, thereby producing trans-l,4-bis(aminomethyl)cyclohexane,
wherein metal oxide is used as a catalyst in the cyanation step, and the obtained trans-
1,4-dicyanocyclohexane has a metal content of 3000 ppm or less.
2. A method for producing trans-l,4-bis(aminomethyl)cyclohexane, the method
comprising:
a cyanation step of treating a hydrogenated terephthalic acid or terephthalic acid
derivative with ammonia, thereby producing 1,4-dicyanocyclohexane, and producing trans- 1,4-
dicyanocyclohexane from the obtained 1,4-dicyanocyclohexane; and
an aminomethylation step of treating the trans- 1,4-dicyanocyclohexane obtained in the
cyanation step with hydrogen, thereby producing trans-l,4-bis(aminomethyl)cyclohexane,
wherein metal oxide is used as a catalyst in the cyanation step, and the obtained trans-
1,4-dicyanocyclohexane has a metal content of 3000 ppm or less.
1-llF058-PCT
3. The method for producing trans- 1,4-bis(aminomethyl)cyclohexane according to
Claim 2, wherein
the hydrogenated terephthalic acid or terephthalic acid derivative is obtained by a
nuclear hydrogenation step of nuclear hydrogenation of a terephthalic acid or terephthalic acid
derivative,
the terephthalic acid or terephthalic acid derivative being at least one selected
from the group consisting of terephthalic acid, terephthalic acid ester, and terephthalic acid
amide.
4. The method for producing trans- 1,4-bis(aminomethyl)cyclohexane according to
Claim 1, wherein
in the cyanation step, the cis isomer and the trans isomer in the 1,4-
dicyanocyclohexane obtained by the reaction with ammonia are separated, and
the separated trans-l,4-dicyanocyclohexane is used in the aminomethylation step.
5. The method for producing trans-l,4-bis(arninomethyl)cyclohexane according to
Claim 1, wherein
in the cyanation step, trans-l,4-dicyanocyclohexane is separated from 1,4-
dicyanocyclohexane by crystallization using an aqueous solvent, and
in the crystallization step of the cyanation step and in the aminomethylation step, the
same aqueous solvent is used.
6. The method for producing trans- 1,4-bis(aminomethyl)cyclohexane according to
Claim 1, wherein
in the cyanation step, the separated cis-l,4-dicyanocyclohexane is treated again with
ammonia in the presence of or in the absence of the hydrogenated terephthalic acid or
terephthalic acid derivative.
7. The method for producing trans- l,4-bis(aminomethyl)cyclohexane according to
57
1-11F058-PCT
Claim 1, wherein
in the cyanation step, the reaction with ammonia is performed while heating to 200 to
350°C.
8. The method for producing trans- l,4-bis(aminomethyl)cyclohexane according to
Claim 1, wherein
in the cyanation step, the reaction with ammonia is performed in the presence of a
solvent having a boiling point of 180°C to 350°C.
9. The method for producing trans- l,4-bis(aminomethyl)cyclohexane according to
Claim I, wherein
in the cyanation step, the reaction with ammonia is performed in the presence of 3 to
20 parts by weight of a solvent relative to 100 parts by weight of the hydrogenated terephthalic
acid or terephthalic acid derivative.
10. The method for producing trans- l,4-bis(aminomethyl)cyclohexane according to
Claim 1, wherein
a solvent is used in the cyanation step, the solvent being selected from odichlorobenzene,
triethylene glycol dimethylether, tetraethylene glycol dimethylether, N-methyl-
2-pyrrolidinone, N,N'-dimethylimidazolidinone, N,Nt-diethylimidazolidinone, N,Ntdipropylimidazolidinone,
N,N1,4-trimethylimidazolidinonea,n d N,Nt-dimethylpropyleneurea.
1 1. The method for producing trans-l,4-bis(aminomethyl)cyclohexane according to
Claim 1, wherein
in the cyanation step, the ammonia to be brought into contact with is fed at a rate
greater than 0.5 mol equivalenthydrogenated terephthalic acid or terephthalic acid derivativelhr.
12. The method for producing trans- l,4-bis(aminomethyl)cyclohexane according to
Claim 2, wherein
58
1-11F058-PCT
in the cyanation step, the cis isomer and the trans isomer in the 1,4-
dicyanocyclohexane obtained by the reaction with ammonia are separated, and
the separated trans-l,4-dicyanocyclohexane is used in the aminomethylation step.
13. The method for producing trans- 1,4-bis(aminomethyl)cyclohexane according to
Claim 2, wherein
in the cyanation step, trans-l,4-dicyanocyclohexane is separated from 1,4-
dicyanocyclohexane by crystallization using an aqueous solvent, and
in the crystallization step of the cyanation step and in the aminomethylation step, the
same aqueous solvent is used.
14. The method for producing trans-1,4-bis(aminomethyl)cyclohexane according to
Claim 2, wherein
in the cyanation step, the separated cis-l,4-dicyanocyclohexanei s treated again with
ammonia in the presence of or in the absence of the hydrogenated terephthalic acid or
terephthalic acid derivative.
15. The method for producing trans-l,4-bis(aminomethyl)cyclohexane according to
Claim 2, wherein
in the cyanation step, the reaction with ammonia is performed while heating to 200 to
350°C.
16. The method for producing trans-l,4-bis(aminomethyl)cyclohexane according to
Claim 2, wherein
in the cyanation step, the reaction with ammonia is performed in the presence of a
solvent having a boiling point of 180°C to 350°C.
17. The method for producing trans-l,4-bis(aminomethyl)cyclohexane according to
Claim 2, wherein
1-11F058-PCT
in the cyanation step, the reaction with ammonia is performed in the presence of 3 to
20 parts by weight of a solvent relative to 100 parts by weight of the hydrogenated terephthalic
acid or terephthalic acid derivative.
18. The method for producing trans-l,4-bis(aminomethyl)cyclohexane according to
Claim 2, wherein
a solvent is used in the cyanation step, the solvent being selected from odichlorobenzene,
triethylene glycol dimethylether, tetraethylene glycol dimethylether, N-methyl-
2-pyrrolidinone, N^-dimethylimidazolidmone, N,N'-diethylimidazolidinone3 N,N'-
dipropylimidazolidinone, N,N',4-trimethylimidazolidinone, and N>N*-dimethylpropyleneurea.
19. The method for producing trans-i,4-bis(aminomethyl)cyclohexane according to
Claim 2, wherein
in the cyanation step, the ammonia to be brought into contact with is fed at a rate
greater than 0.5 mol equivalent/hydrogenated terephthalic acid or terephthalic acid derivative/hr.