DESCRIPTION
TITLE OF THE INVENTION
METHOD FOR PRODUCING BIS(AMINOMETHYL)CYCLOHEXANES
TECHNICAL FIELD
[0001]
The present invention relates to a method for producing bis(aminomethyl)cyclohexanes.
BACKGROUND ART
[0002]
Heretofore, bis(aminomethyl)cyclohexanes have been well known for a raw material of
polyamide used for fiber, film, etc. Also, bis(isocyanatomethyl)cyclohexanes derived from
bis(aminomethyl)cyclohexanes are useful as a raw material of polyurethane used for, for
example, paints, adhesives, plastic lenses, etc.
[0003]
As a method for producing such bis(aminomethyl)cyclohexanes, for example, Patent
Document 1 below has proposed a method for producing bis(aminomethyl)cyclohexanes by
nuclear hydrogenation (hydrogen addition to aromatic rings) of xylylenediamine in the presence
of, for example, a ruthenium catalyst using one or more solvents selected from alkylamines and
alkylenediamines.
[0004]
As a method for producing xylylenediamine used in the above-described method, for
example, Patent Document 2 has proposed ammoxidation of xylene using a metal oxide catalyst
such as vanadium to produce phthalonitrile, and then hydrogenation of the phthalonitrile in the
presence of a nickel catalyst.
[0005]
Patent Document 3 below has proposed a method for producing
bis(aminomethyl)cyclohexanes in which hydrogen cyanide is added to 4-cyanocyclohexene to
produce dicyanocyclohexanes, and then the dicyanocyclohexanes are hydrogenated in the
presence of a catalyst.
[0006]
Furthermore, as a method for producing bis(aminomethyl)cyclohexane, for example,
Non-Patent Document 1 (Malachowski et al.) discloses the following: an acid chloride derivative
3
is prepared using cyclohexanedicarboxylic acid with thionyl chloride; cyclohexane diamide is
prepared using the acid chloride derivative with ammonia; and thereafter, the cyclohexane
diamide is further allowed to react with thionyl chloride to obtain dicyanocyclohexane, and then
the obtained dicyanocyclohexane is hydrogenated.
Citation List
Patent Document
[0007]
Patent Document 1
Japanese Unexamined Patent Publication No. H8-143514
Patent Document 2
Japanese Unexamined Patent Publication No. 2003-26638
Patent Document 3
Japanese Unexamined Patent Publication No.H2-202856
[Non-Patent Document]
[0008]
Non-Patent Document 1
Berichte Der Deutschen Chemischen Gesellschaft, vol. 71, No. 4, p 759 (1938)
SUMMARY OF THE INVENTION
PROBLEM TO BE SOLVED BY THE INVENTION
[0009]
However, when xylylenediamine is produced as a raw material of
bis(aminomethyl)cyclohexanes by the method described in Patent Document 2, xylene has to be
subjected to ammoxidation with a very high temperature of 420°C to produce phthalonitrile, and
thereafter, the obtained phthalonitrile has to be hydrogenated at a very high pressure of 12 MPa
(Patent Document 2 above (ref: Example 1)).
[0010]
Furthermore, when bis(aminomethyl)cyclohexane is produced by the method described
in the above Patent Document 1 from the thus obtained xylylenediamine, nuclear hydrogenation
of xylylenediamine at a very high pressure of 100kg/cm2 (10 MPa) has to be performed (ref:
Patent Document 1 above (Reference Examples)).
4
[0011]
Also, when dicyanocyclohexane, i.e., a raw material of bis(aminomethyl)cyclohexane is
produced by the method described in Patent Document 3, hydrogen cyanide is added to 4-
cyanocyclohexene, and hydrogen cyanide is highly poisonous, and its handling requires a great
deal of care, thus being significantly disadvantageous for industrial use.
[0012]
That is, with the methods described in the above-described Patent Documents 1 to 3,
reaction of the components at high temperature and under high pressure may be required, and
there may be disadvantages in terms of handleability, and thus improvement in facilities and
safety has been demanded.
[0013]
Also, the method described in Non-Patent Document 1 includes steps of multiple stages,
and furthermore, requires use of a large amount of thionyl chloride, which is highly corrosive
and thus hard to handle, and on top of that, the reaction yield in each of the steps is low.
[0014]
Thus, in the method described in Non-Patent Document 1, in view of industrial
production, improvements in terms of many aspects are desired.
[0015]
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
bis(aminomethyl)cyclohexanes.
MEANS FOR SOLVING THE PROBLEM
[0016]
A method for producing bis(aminomethyl)cyclohexanes of the present invention
includes:
a nuclear hydrogenation step of producing hydrogenated phthalic acids or phthalic acid
derivatives by nuclear hydrogenation of phthalic acids or phthalic acid derivatives,
the phthalic acids or phthalic acid derivatives being at least one selected from
the group consisting of phthalic acids, phthalic acid esters, and phthalic acid amides;
a cyanation step of treating the hydrogenated phthalic acids or phthalic acid derivatives
obtained in the nuclear hydrogenation step with ammonia to produce dicyanocyclohexanes; and
5
an aminomethylation step of treating the dicyanocyclohexanes obtained in the
cyanation step with hydrogen, thereby producing bis(aminomethyl)cyclohexanes;
wherein metal oxide is used as a catalyst in the cyanation step, and the obtained
dicyanocyclohexanes have a metal content of 3000 ppm or less.
[0017]
A method for producing bis(aminomethyl)cyclohexanes of the present invention
includes
a cyanation step of treating hydrogenated phthalic acids or phthalic acid derivatives
with ammonia, thereby producing dicyanocyclohexanes; and
an aminomethylation step of treating the dicyanocyclohexanes obtained in the
cyanation step with hydrogen, thereby producing bis(aminomethyl)cyclohexanes,
wherein metal oxide is used as a catalyst in the cyanation step, and the obtained
dicyanocyclohexanes have a metal content of 3000 ppm or less.
[0018]
In the above-described production method, it is preferable that the hydrogenated
phthalic acids or phthalic acid derivatives are obtained by a nuclear hydrogenation step of
nuclear hydrogenation of phthalic acids or phthalic acid derivatives of at least one selected from
the group consisting of phthalic acids, phthalic acid esters, and phthalic acid amides.
[0019]
In the method for producing bis(aminomethyl)cyclohexanes 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 equivalent/hydrogenated phthalic acids or phthalic acid derivatives/hr.
[0020]
In the method for producing bis(aminomethyl)cyclohexanes 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.
[0021]
In the method for producing bis(aminomethyl)cyclohexanes of the present invention, it
is preferable that 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 the hydrogenated phthalic
acids or phthalic acid derivatives.
6
[0022]
In the method for producing bis(aminomethyl)cyclohexanes of the present invention, it
is preferable that 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,N'-diethylimidazolidinone, N,N'-
dipropylimidazolidinone, N,N',4-trimethylimidazolidinone, and N,N'-dimethylpropyleneurea.
EFFECT OF THE INVENTION
[0023]
The method for producing bis(aminomethyl)cyclohexanes of the present invention is
excellent in terms of equipment, safety, and economy, and achieves safe, low costs, and high
yield production of bis(aminomethyl)cyclohexanes. Thus, the present invention can be suitably
used as an industrial method for producing bis(aminomethyl)cyclohexanes.
EMBODIMENT OF THE INVENTION
[0024]
A method for producing bis(aminomethyl)cyclohexanes of the present invention
includes
a nuclear hydrogenation step of producing hydrogenated phthalic acids or phthalic acid
derivatives by nuclear hydrogenation of phthalic acids or phthalic acid derivatives,
the phthalic acids or phthalic acid derivatives being at least one selected from
the group consisting of phthalic acids, phthalic acid esters, and phthalic acid amides;
a cyanation step of treating the hydrogenated phthalic acids or phthalic acid derivatives
obtained in the nuclear hydrogenation step with ammonia to produce dicyanocyclohexanes; and
an aminomethylation step of treating the dicyanocyclohexanes obtained in the
cyanation step with hydrogen, thereby producing bis(aminomethyl)cyclohexanes. Each step is
described in detail in the following.
[Nuclear Hydrogenation Step]
In the nuclear hydrogenation step, nuclear hydrogenation of phthalic acids or phthalic
acid derivatives is performed, the phthalic acids or phthalic acid derivatives being at least one
selected from the group consisting of phthalic acids, phthalic acid esters, and phthalic acid
amides, to produce corresponding hydrogenated phthalic acids or phthalic acid derivatives (that
is, hydrogenated phthalic acids or phthalic acid derivatives of at least one selected from the
7
group consisting of cyclohexanedicarboxylic acids, cyclohexanedicarboxylic acid esters, and
cyclohexanedicarboxylic acid amides).
[0025]
Examples of phthalic acids include phthalic acid (ortho-phthalic acid), isophthalic acid
(meta-phthalic acid), and terephthalic acid (para-phthalic acid).
[0026]
These phthalic acids or phthalic acid derivatives may be used singly or in a combination
of two or more.
[0027]
The substituted positions of the functional groups on the cyclohexane ring of the
hydrogenated phthalic acids or phthalic acid derivatives obtained in the nuclear hydrogenation
step correlate with the ortho-, meta-, or para- form of the raw material component of phthalic
acids or phthalic acid derivatives.
[0028]
That is, for example, when isophthalic acid or an isophthalic acid derivative is used as
the phthalic acids or phthalic acid derivatives, the hydrogenated phthalic acids or phthalic acid
derivatives to be produced are hydrogenated phthalic acids or phthalic acid derivatives of at least
one selected from the group consisting of cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,3-
dicarboxylic acid ester, and cyclohexane-1,3-dicarboxylic acid amide; and when terephthalic
acid or a terephthalic acid derivative is used as the phthalic acids or phthalic acid derivatives, the
hydrogenated phthalic acids or phthalic acid derivatives to be produced are hydrogenated
phthalic acids or phthalic acid derivatives of at least one selected from the group consisting of
cyclohexane-1,4-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid ester, and cyclohexane-
1,4-dicarboxylic acid amide.
[0029]
In the nuclear hydrogenation step, for example, the method described in Japanese
Unexamined Patent Publication No. 2001-181223 may be used.
[0030]
The phthalic acids or phthalic acid derivatives used as a raw material in the present
invention may be one having quality of industrially available products, and also undried
(containing water) phthalic acids or phthalic acid derivatives that have undergone the purification
8
in the hydrogenation step generally performed in production of phthalic acids may be used.
[0031]
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 phthalic acids or phthalic acid derivatives for dilution so that the phthalic acid
or phthalic 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.
[0032]
Examples of such a solvent include aqueous solvents such as water, methanol, ethanol,
1-propanol, isopropanol, 1-butanol, 2-butanol, sec-butanol, t-butanol, and 1,4-dioxane.
[0033]
Use of such an aqueous solvent is advantageous in that the reaction mixture in the
nuclear hydrogenation step can be cooled as necessary, and recirculated for use.
[0034]
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 phthalic acids that underwent the purification step of phthalic acids can be used.
[0035]
In the nuclear hydrogenation step, hydrogen used in the nuclear hydrogenation 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.
[0036]
The hydrogen amount is preferably about 3 to 50 times the raw material phthalic acids
or phthalic acid derivatives in molar ratio.
[0037]
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.
9
[0038]
In the nuclear hydrogenation step, a known catalyst may be added.
[0039]
The catalyst used in the nuclear hydrogenation step is a general use 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.
[0040]
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.
[0041]
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.
[0042]
When the amount of metal supported is within such a range, it is preferable because the
activity of catalyst per weight is high.
[0043]
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
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.
[0044]
The catalyst amount relative to 100 parts by weight of phthalic acids or phthalic acid
derivatives is in the range of, for example, 0.1 to 50 parts by weight, preferably 0.5 to 20 parts by
weight.
[0045]
The phthalic acids or phthalic acid derivatives are 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.
10
[0046]
The reactor is preferably a pressure-resistant vessel.
[0047]
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 phthalic acids or phthalic acid derivatives, is highly soluble in a general solvent
such as water at high temperature, and therefore separation from the catalyst can be performed
by filtration.
[0048]
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.).
[0049]
Thereafter, by drying or concentrating the mixture, or by crystallizing the product by
cooling, hydrogenated phthalic acids or phthalic acid derivatives can be obtained.
[0050]
The reaction temperature is usually in the range of 50 to 200°C, and preferably 100 to
160°C.
[0051]
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.
[0052]
The reaction pressure is usually in the range of 0.5 to 15 MPa, preferably 2 to 15 MPa,
more preferably 2 to 8 MPa, even more preferably 2 to 5Mpa.
[0053]
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.
[0054]
The conversion of phthalic acids or phthalic acid derivatives is usually 90% or more,
11
preferably 95% or more, and more preferably 98% or more.
[0055]
When the amount of the unreacted phthalic acids or phthalic acid derivatives 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.
[0056]
The hydrogenated phthalic acids or phthalic acid derivatives obtained in the nuclear
hydrogenation step have functional groups at substituted positions correlating with the ortho-,
meta-, or para- form of the phthalic acids or phthalic acid derivatives used as the raw material,
and are a mixture of cis isomer and trans isomer.
[0057]
To be more specific, for example, when isophthalic acid or an isophthalic acid
derivative (meta-phthalic acid) is used as the raw material, the hydrogenated phthalic acids or
phthalic acid derivatives to be produced are a mixture of 1,3-disubstituted cis isomer (that is, ciscyclohexane-
1,3-dicarboxylic acid, cis-cyclohexane-1,3-dicarboxylic acid ester, and/or ciscyclohexane-
1,3-dicarboxylic acid amide), and 1,3-disubstituted trans isomer (that is, transcyclohexane-
1,3-dicarboxylic acid, trans-cyclohexane-1,3-dicarboxylic acid ester, and/or transcyclohexane-
1,3-dicarboxylic acid amide); and when terephthalic acid or a terephthalic acid
derivative (para-phthalic acid) is used as the raw material, the hydrogenated phthalic acids or
phthalic acid derivatives to be produced are a mixture of 1,4-disubstituted cis isomer (that is, ciscyclohexane-
1,4-dicarboxylic acid, cis-cyclohexane-1,4-dicarboxylic acid ester, and/or ciscyclohexane-
1,4-dicarboxylic acid amide), and 1,4-disubstituted trans isomer (that is, transcyclohexane-
1,4-dicarboxylic acid, trans-cyclohexane-1,4-dicarboxylic acid ester, and/or transcyclohexane-
1,4-dicarboxylic acid amide).
[0058]
Furthermore, for example, when isophthalic acid or an isophthalic acid derivative (metaphthalic
acid), and terephthalic acid or a terephthalic acid derivative (para-phthalic acid) are used
in combination as the raw materials, the hydrogenated phthalic acids or phthalic acid derivatives
to be produced are a mixture of the above-described 1,3-disubstituted cis isomer, 1,3-
disubstituted trans isomer, 1,4-disubstituted cis isomer, and 1,4-disubstituted trans isomer.
[Cyanation Step]
12
In the cyanation step, the above-described hydrogenated phthalic acids or phthalic acid
derivatives obtained in the nuclear hydrogenation step are treated with ammonia to produce
dicyanocyclohexanes.
[0059]
In the cyanation step, for example, the method described in Japanese Unexamined
Patent Publication No. S63-10752 may be used.
[0060]
To be more specific, in the cyanation step, the hydrogenated phthalic acids or phthalic
acid derivatives obtained in the nuclear hydrogenation step are 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 ammonia source) by heating at, usually 200°C or more and
below 350°C, preferably 230°C or more and below 320°C.
[0061]
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.
[0062]
In the present invention, metal oxide is used as a catalyst in the cyanation step.
[0063]
Examples of metal oxide include silica, alumina, phosphorus pentoxide, tin oxide,
titanium oxide, zinc oxide, iron oxide, zirconium oxide, and cobalt oxide.
[0064]
Of these metal oxides, in view of easy separation after reaction, silica, alumina, tin
oxide, titanium oxide, zinc oxide, iron oxide, zirconium oxide, or cobalt oxide is preferably used.
[0065]
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.
[0066]
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.
13
[0067]
The catalyst is used in the form of, for example, powder, granular, or may be supported
on a pellet carrier. Preferably, the catalyst is powder.
[0068]
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.
[0069]
The catalyst amount relative to 100 parts by weight of hydrogenated phthalic acids or
phthalic acid derivatives is in the range of, for example, 0.1 to 50 parts by weight, preferably 0.5
to 20 parts by weight.
[0070]
In the reaction, a solvent is preferably used as appropriate.
[0071]
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,
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,N',4-trimethylimidazolidinone, and 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.
14
[0072]
As the solvent, in view of suppressing crystallization of dicyanocyclohexanes 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, 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; and 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,N',4-trimethylimidazolidinone, and N,N'-dimethylpropyleneurea.
[0073]
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 of 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
dicyanocyclohexanes to the reactor gas purge line and to apparatuses at downstream of the
reactor such as a condenser decreases.
[0074]
In view of the above, of the above-described solvents, selection is made preferably from
o-dichlorobenzene, triethylene glycol dimethylether, tetraethylene glycol dimethylether, polar
aprotic solvents such as N-methyl-2-pyrrolidinone, N,N'-dimethylimidazolidinone, N,N'-
diethylimidazolidinone, N,N'-dipropylimidazolidinone, N,N',4-trimethylimidazolidinone, and
N,N'-dimethylpropyleneurea.
[0075]
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 phthalic acids or phthalic acid
derivatives 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 phthalic acids or phthalic acid derivatives. When the amount of the solvent is
15
small, or when no solvent is used, suppression of crystallization of dicyanocyclohexanes 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.
[0076]
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.
[0077]
The reactor is preferably a pressure-resistant vessel.
[0078]
For example, hydrogenated phthalic acids or phthalic acid derivatives, and a catalyst are
introduced from the reactor top or bottom, and the hydrogenated phthalic acids or phthalic acid
derivatives are dissolved by heating to be suspended; and an ammonia source such as ammonia
is fed intermittently or continuously to the reactor, to allow reaction at a predetermined
temperature.
[0079]
The amount of the ammonia source to be fed is, in view of making ammonia easy to
treat or recover after reaction, for example, 1 to 20 mol, preferably 2 to 20 mol relative to 1 mol
of hydrogenated phthalic acids or phthalic acid derivatives.
[0080]
The rate of the feeding of the ammonia source is not particularly limited, and preferably
0.1 mol to 2 mol per 1 hour relative to 1 mol of hydrogenated phthalic acids or phthalic acid
derivatives, and more preferably, more than 0.5 mol and 2 mol or less (that is, more than 0.5 mol
equivalent/hydrogenated terephthalic acids or terephthalic acid derivatives/hr and 2 mol
equivalent/hydrogenated terephthalic acids or terephthalic acid derivatives/hr or less). The
feeding rate lower than 0.5 mol relative to 1 mol of hydrogenated phthalic acids or phthalic acid
derivatives per 1 hour is not preferable because the reaction requires a long time. The feeding
rate higher than 2 mol relative to 1 mol of hydrogenated phthalic acids or phthalic acid
derivatives 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
16
burden is substantial.
[0081]
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.
[0082]
Water is produced as a by-product in this reaction, and therefore in view of accelerating
the reaction rate, 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.
[0083]
The reaction may be performed under any pressure condition, for example, under
elevated pressure, ambient pressure, and reduced pressure, which is suitably selected.
[0084]
After the reaction, the product dicyanocyclohexanes are obtained as a mixture (mixture
of stereoisomers) of the cis isomer and trans isomer.
[0085]
The dicyanocyclohexanes obtained in the cyanation step have functional groups at
substituted positions correlating with the ortho-, meta-, or para- form of the phthalic acids or
phthalic acid derivatives used as the raw material, and are a mixture of cis isomer and trans
isomer.
[0086]
To be more specific, for example, when isophthalic acid or an isophthalic acid
derivative is used as the raw material, dicyanocyclohexanes to be produced are a mixture of 1,3-
disubstituted cis isomer (that is, cis-1,3-dicyanocyclohexane) and 1,3-disubstituted trans isomer
(that is, trans-1,3-dicyanocyclohexane); and for example, when terephthalic acid or a terephthalic
acid derivative (para-phthalic acid) is used as the raw material, dicyanocyclohexanes to be
produced are a mixture of 1,4-disubstituted cis isomer (that is, cis-1,4-dicyanocyclohexane) and
1,4-disubstituted trans isomer (that is, trans-1,4-dicyanocyclohexane).
[0087]
Furthermore, for example, when isophthalic acid or an isophthalic acid derivative (metaphthalic
acid) and terephthalic acid or a terephthalic acid derivative (para-phthalic acid) are used
in combination as the raw materials, the dicyanocyclohexanes to be produced are a mixture of
17
the above-described 1,3-disubstituted cis isomer, 1,3-disubstituted trans isomer, 1,4-disubstituted
cis isomer, and 1,4-disubstituted trans isomer.
[0088]
The cis isomer/trans isomer ratio of the dicyanocyclohexanes obtained converges to the
equilibrium composition ratio of dicyanocyclohexanes at the reaction temperature,
approximately, to cis isomer/trans isomer = 40/60 to 60/40, regardless of the stereo isomer ratio
of the hydrogenated phthalic acids or phthalic acid derivatives.
[0089]
If necessary, from the stereo isomer mixture of the dicyanocyclohexanes after reaction,
the catalyst used is removed by a known method, for example, such as filtering and adsorption,
and thereafter, the cis and trans isomer can be separated from the mixture, for example, by
fractional crystallization using the difference in their solubility, or by distillation using the
difference in their boiling points.
[0090]
For example, 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 dicyanocyclohexanes 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.
[0091]
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.
[0092]
In the fractional crystallization, first, dicyanocyclohexanes are dissolved in the abovedescribed
solvent, and the mixture is heated. Thereafter, the mixture is cooled to ambient
temperature. This allows dicyanocyclohexanes having a high proportion of trans isomer to be
crystallized (crystallization step). Thereafter, the crystallized dicyanocyclohexanes can be
separated by filtration.
18
[0093]
After the separation, as necessary, the mixture is washed and dried so that transdicyanocyclohexanes
in a viscous liquid or in a solid state can be obtained.
[0094]
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 dicyanocyclohexanes
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 dicyanocyclohexanes.
[0095]
More than 3000 ppm metal contents are not preferable because resulting metal might
inhibit the reaction in the aminomethylation step to be described later.
[0096]
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 dicyanocyclohexanes 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 dicyanocyclohexanes 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, and thereafter,
the solvent is distilled off.
[0097]
Meanwhile, when stereoisomers of dicyanocyclohexanes are separated by fractional
crystallization, in the filtrate after the crystallization and filtration, the dicyanocyclohexanes
having a high cis isomer ratio is dissolved.
[0098]
The dicyanocyclohexanes having a high cis isomer ratio obtained by distilling off the
solvent from the filtrate are again fed into the reactor in the cyanation step, to be treated again
with ammonia along with hydrogenated phthalic acids or phthalic acid derivatives.
[0099]
In this manner, thermal isomerization occurs at a predetermined temperature in the
reactor of the cyanation step to form an equilibrium composition mixture of cis isomer/trans
19
isomer.
[Aminomethylation Step]
In the aminomethylation step, the dicyanocyclohexanes obtained in the cyanation step
are treated with hydrogen, thereby producing bis(aminomethyl)cyclohexanes.
[0100]
In the aminomethylation step, for example, the method described in, for example,
Japanese Unexamined Patent Publication No. 2001-187765 can be used.
[0101]
Quality of hydrogen used in the aminomethylation step is sufficient when the hydrogen
is of industrial use, and the hydrogen may contain inactive gas (e.g., nitrogen, methane, etc.).
The hydrogen concentration is preferably 50% or more.
[0102]
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.
[0103]
In view of reactivity and selectivity, a catalyst mainly composed of nickel, cobalt and/or
ruthenium is preferably used, and more preferably, Raney catalyst or a catalyst supported on
porous metal oxides such as silica, alumina, silica alumina, kieselguhr, and activated carbon is
preferably used.
[0104]
The catalyst may further contain metals such as aluminum, zinc, and silicon.
[0105]
These hydrogenation catalysts may contain, as a reaction accelerator, a metal selected
from chromium, iron, cobalt, manganese, tungsten, and molybdenum.
[0106]
The hydrogenation catalyst can be used as a perfect solid catalyst, or can be used as a
supported solid catalyst, for example, nickel, cobalt, or ruthenium supported on aluminum oxide,
titanium oxide, zirconium oxide, magnesia/alumina, etc.
[0107]
The catalyst is used in the form of, for example, powder, granular, or may be supported
20
on a pellet carrier. 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.
[0108]
The amount of catalyst used is, in view of reactivity and selectivity, for example, 0.1 to
20 parts by weight, preferably 0.5 to 15 parts by weight relative to 100 parts by weight of
dicyanocyclohexanes.
[0109]
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.
[0110]
The dicyanocyclohexanes concentration in the reaction solution is, for example, 1 to 50
wt%, preferably 2 to 40 wt%.
[0111]
The dicyanocyclohexanes concentration 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.
[0112]
The reaction is preferably performed in the presence of ammonia.
[0113]
The ammonia works to suppress production of by-products such as secondary amine,
tertiary amine, and polyamine, i.e., products other than the target bis(aminomethyl)cyclohexanes,
that is, works to improve reaction selectivity.
[0114]
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 mol, preferably 0.1 to 2.5 mol relative to
1 mol of dicyanocyclohexanes.
21
[0115]
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.
[0116]
The reactor is preferably a pressure-resistant vessel.
[0117]
For example, dicyanocyclohexanes, 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.
[0118]
The reaction pressure is usually 0.1 to 20 MPa, preferably 0.5 to 10 MPa, more
preferably 0.5 to 8 MPa, and particularly preferably 0.5 to 5 MPa.
[0119]
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.
[0120]
After the reaction, bis(aminomethyl)cyclohexanes can be separated from the reaction
mixture by a known method, for example, by filtration, distillation, etc.
[0121]
The bis(aminomethyl)cyclohexanes obtained in the aminomethylation step have
functional groups at substitution positions correlating with the ortho-, meta-, or para- form of the
phthalic acids or phthalic acid derivatives used as the raw material, and are a mixture of cis
isomer and trans isomer.
[0122]
To be more specific, for example, when isophthalic acid or an isophthalic acid
derivative is used as the raw material, bis(aminomethyl)cyclohexanes to be obtained is a mixture
of 1,3-disubstituted cis isomer (that is, cis-1,3-bis(aminomethyl)cyclohexane) and 1,3-
disubstituted trans isomer (that is, trans-1,3-bis(aminomethyl)cyclohexane); and for example,
when terephthalic acid or a terephthalic acid derivative (para-phthalic acid) is used as the raw
22
material, a mixture of 1,4-disubstituted cis isomer (that is, cis-1,4-bis(aminomethyl)cyclohexane)
and 1,4-disubstituted trans isomer (that is, trans-1,4-bis(aminomethyl)cyclohexane).
[0123]
Furthermore, for example, when isophthalic acid or an isophthalic acid derivative (metaphthalic
acid) and terephthalic acid or a terephthalic acid derivative (para-phthalic acid) are used
in combination as the raw materials, the dicyanocyclohexanes to be obtained are a mixture of the
above-described 1,3-disubstituted cis isomer, 1,3-disubstituted trans isomer, 1,4-disubstituted cis
isomer, and 1,4-disubstituted trans isomer.
[0124]
The method for producing bis(aminomethyl)cyclohexanes of the present invention is
excellent in terms of equipment, safety, and economy, and achieves safe, low costs, and high
yield production of bis(aminomethyl)cyclohexanes.
[0125]
Thus, the method can be suitably used as an industrial method for producing
bis(aminomethyl)cyclohexanes.
[0126]
The above-described method for producing bis(aminomethyl)cyclohexanes includes the
nuclear hydrogenation step, the cyanation step, and the aminomethylation step. However, in the
method for producing bis(aminomethyl)cyclohexanes, for example, hydrogenated phthalic acids
or phthalic acid derivatives are used as a starting material to omit the nuclear hydrogenation step,
and the cyanation step and the aminomethylation step can be performed.
[0127]
In such a case, the hydrogenated phthalic acids or phthalic acid derivatives as the
starting material is not limited to the above-described hydrogenated phthalic acids or phthalic
acid derivatives obtained in the nuclear hydrogenation step. However, with the abovedescribed
nuclear hydrogenation step, hydrogenated phthalic acids or phthalic acid derivatives
can be obtained safely at low costs and with high yields, and therefore the hydrogenated phthalic
acids or phthalic acid derivatives as a starting material is preferably obtained by the abovedescribed
nuclear hydrogenation step.
EXAMPLES
23
[0128]
Hereinafter, the present invention will be described more specifically with reference to
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%Pd/C, manufactured by NE Chemcat Corporation),
and 100 mL of water. The autoclave was purged with nitrogen introduced from the autoclave
nozzle inlet three times at 5 MPa, and the mixture was heated to 150°C while stirring at 400 rpm
under normal pressure.
[0129]
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.
[0130]
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.
[0131]
The filtrate was neutralized with a 5N aqueous HCl solution, and then analyzed by highperformance
liquid chromatography. It was found that the conversion of terephthalic acid was
100%, 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
24
concentrating the filtered reaction solution obtained in the nuclear hydrogenation step and 0.13 g
of tin (II) oxide, and the mixture was heated to 170°C while stirring at 300 rpm, thereby
dissolving the carboxylic acid.
[0132]
Thereafter, ammonia gas was introduced at a rate of 16 mL/min (0.81 mol
equivalent/1,4-cyclohexanedicarboxylic acid/hr) 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.
[0133]
The solid product was suspended in methanol, and then the suspension was filtered to
remove the catalyst.
[0134]
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 isomer/cis isomer ratio was 58/42.
[0135]
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-butanol was added, and heated to 80°C to dissolve the 1,4-dicyanocyclohexane.
Thereafter, as the mixture was cooled to room temperature, a precipitant was appeared.
[0136]
The suspension liquid 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%).
[0137]
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 isomer/cis
isomer ratio was 94/6.
[0138]
A metal (tin) content of the solid was 10 ppm or less, which is 9.95 (10 × 0.995) ppm or
less relative to dicyanocyclohexane (including trans isomer and cis isomer).
25
[0139]
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
isomer/cis isomer ratio was 16/84.
[Aminomethylation Step]
A 100 mL stainless steel-made autoclave equipped with a stirrer was charged with 3.5 g
of 1,4-dicyanocyclohexane having a trans isomer/cis isomer ratio of 94/6 obtained in the
cyanation step, 0.35 g of a catalyst (manganese-containing Raney cobalt manufactured by
Kawaken Fine Chemicals Co., Ltd.), 3.9 mL of a 28 wt% ammonia water, and 7.3 mL of 1-
butanol. The autoclave was purged with nitrogen introduced from the autoclave nozzle inlet
three times at 2 MPa, and the mixture was heated to 80°C while stirring at 400 rpm.
[0140]
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.
[0141]
After the completion of reaction, the product was cooled to room temperature. The
reaction mixture was taken out, and the mixture was filtered to remove the catalyst.
[0142]
The filtrate was analyzed by gas chromatography, and it was found that the conversion
of 1,4-dicyanocyclohexane was 100%, the yield of 1,4-bis(aminomethyl)cyclohexane was 96%,
and the trans isomer/cis isomer ratio was 87/13.
[0143]
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 isomer/cis isomer
ratio of 88/12 was obtained with a yield of 97%.
(Example 2)
[Nuclear Hydrogenation Step]
A 100 mL stainless steel-made autoclave equipped with a stirrer was charged with 25.1
g of isophthalic acid, 2.8 g of a catalyst (10%Pd/C, manufactured by NE Chemcat Corporation),
26
and 100 mL of water. The autoclave was purged with nitrogen introduced from the autoclave
nozzle inlet three times at 5 MPa, and the mixture was heated to 150°C while stirring at 400 rpm
under normal pressure.
[0144]
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.
[0145]
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 isophthalic acid amount was added thereto, the mixture
was filtered to remove the catalyst.
[0146]
The filtrate was neutralized with a 5N aqueous HCl solution, and then analyzed by highperformance
liquid chromatography. It was found that the conversion of isophthalic acid was
100%, and the yield of 1,3-cyclohexanedicarboxylic acid was 99%.
[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 9.1 g of 1,3-cyclohexanedicarboxylic acid obtained by
filtering and concentrating the reaction solution obtained in the nuclear hydrogenation step and
0.12 g of tin (II) oxide, and the mixture was heated to 170°C while stirring at 300 rpm, thereby
dissolving the carboxylic acid.
[0147]
Thereafter, ammonia gas was introduced at a rate of 16 mL/min (0.81 mol
equivalent/1,3-cyclohexanedicarboxylic acid/hr) 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.
[0148]
The solid product was suspended in methanol, and then the suspension was filtered to
remove the catalyst.
27
[0149]
The filtrate was analyzed by gas chromatography, and it was found that the conversion
of 1,3-cyclohexanedicarboxylic acid was 98.5%, the yield of 1,3-dicyanocyclohexane was 94.7%,
and the trans isomer/cis isomer ratio was 45/55.
[0150]
Then, the solvent was distilled off from the filtrate obtained as described above and the
filtrate was dried, thereby producing 7.8 g of a yellow solid.
[0151]
The yellow solid was analyzed by gas chromatography, and it was found that solid was
1,3-dicyanocyclohexane having a purity of 95.3%.
[0152]
A metal (tin) content of the solid was 10 ppm or less, which was 9.53 (10 × 0.953) ppm
or less relative to dicyanocyclohexane (including trans isomer and cis isomer).
[Aminomethylation Step]
A 100 mL stainless steel-made autoclave equipped with a stirrer was charged with 3.5g
(3.7 g of yellow solid) of 1,3-dicyanocyclohexane having a trans isomer/cis isomer ratio of 45/55
obtained in the cyanation step, 0.35g of a catalyst (manganese-containing Raney cobalt
manufactured by Kawaken Fine Chemicals Co., Ltd.), 3.9 mL of a 28 wt% ammonia water, and
7.3 mL of 1-butanol. The autoclave was purged with nitrogen introduced from the autoclave
nozzle inlet three times at 2 MPa, and the mixture was heated to 80°C while stirring at 400 rpm
under normal pressure.
[0153]
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.
[0154]
After the completion of reaction, the mixture was cooled to room temperature. The
reaction mixture was taken out, and the mixture was filtered to remove the catalyst.
[0155]
The filtrate was analyzed by gas chromatography, and it was found that the conversion
of 1,3-dicyanocyclohexane was 100%, the yield of 1,3-bis(aminomethyl)cyclohexane was 94%,
28
and the trans isomer/cis isomer ratio was 42/58.
[0156]
The filtrate was distilled under a reduced-pressure of 10 mmHg, and 1,3-
bis(aminomethyl)cyclohexane having a purity of 99.5% or more was obtained with a yield of
97%.
(Example 3)
A four-neck flask equipped with a stirrer, a gas inlet tube, a thermometer, a gas purge
line, and a condenser was charged with 15.1 g of 1,4-cyclohexanedicarboxylic acid, 17.4 g of
dimethyl 1,4-cyclohexanedicarboxylate, 4.9 g of N,N'-dimethylimidazolidinone (boiling point
226°C), and 0.40g of tin (II) oxide, and the mixture was heated to 210°C while stirring at
250rpm.
[0157]
Thereafter, ammonia gas was introduced at a rate of 72 mL/min (1.1 mol equivalent/1,4-
cyclohexanedicarboxylic acid + dimethyl 1,4-cyclohexanedicarboxylate/hr). The temperature
inside the reactor was kept at 210°C for 1 hour, and then thereafter, increased to 280°C: 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.
[0158]
Then, 31.6 g of 1-butanol 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 100%, the conversion of dimethyl 1,4-
cyclohexanedicarboxylate was 99.9%, the yield of 1,4-dicyanocyclohexane was 89%, and the
trans isomer/cis isomer ratio was 53/47.
[0159]
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 precipitant was
appeared. The suspension liquid 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%).
29
[0160]
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 95/5.
[0161]
A metal (tin) content of the solid was 1 ppm or less, which is 0.995 (1 × 0.995) ppm or
less relative to 1,4-dicyanocyclohexane (including trans isomer and cis isomer) and 0.945 (0.995
× 0.95) ppm or less relative to trans-1,4-dicyanocyclohexane.
[0162]
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 isomer/cis isomer ratio was 13/87.
(Example 4)
13.5 g of a yellow solid obtained in the same manner as in Example 3 (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 3, except that dimethyl 1,4-cyclohexanedicarboxylate was not
added, and the rate of the ammonia gas introduction was changed to 36 mL/min (1.1 mol
equivalent/1,4-cyclohexanedicarboxylic acid/hr).
[0163]
After 15 hours, the reaction mixture was treated in the same manner as in Example 3.
[0164]
As a result of gas chromatography analysis, it was found that the conversion of 1,4-
cyclohexanedicarboxylic acid was 100%, the yield of 1,4-dicyanocyclohexane was 94.5%, and
the trans isomer/cis isomer ratio was 53/47. The cyanation reaction proceeded with high yields
even if the recovered solid mainly composed of the separated cis-1,4-dicyanocyclohexane was
fed again to be used in the cyanation step.
(Example 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 15.1 g of 1,3-cyclohexanedicarboxylic acid obtained in
the same manner as in Example 2, 17.4 g of dimethyl 1,3-cyclohexanedicarboxylate, 5.0 g of
30
N,N'-dimethylimidazolidinone (boiling point 226°C), and 0.40 g of tin (II) oxide, and the
mixture was heated to 210°C while stirring at 250 rpm.
[0165]
Thereafter, ammonia gas was introduced at a rate of 72 mL/min (1.1 mol equivalent/1,3-
cyclohexanedicarboxylic acid + dimethyl 1,3-cyclohexanedicarboxylate/hr). The temperature
inside the reactor was kept at 210°C for 1 hour, and then thereafter, increased to 280°C: while
the temperature was kept constant, reaction was performed. After 8 hours, the reaction was
terminated, and the reaction product was cooled to 90°C. When the reaction was terminated,
almost no white solid was observed in the gas purge line and the condenser.
[0166]
Then, 31.6 g of 1-butanol 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 1,3-
cyclohexanedicarboxylic acid was 100%, the conversion of dimethyl 1,4-
cyclohexanedicarboxylate was 99%, the yield of 1,3-dicyanocyclohexane was 86%, and the trans
isomer/cis isomer ratio was 47/53.
[0167]
Then, the solvent was distilled off from the filtrate obtained as described above and the
filtrate was dried, thereby producing a yellow solid. The yellow solid was analyzed by gas
chromatography, and it was found that solid was 1,3-dicyanocyclohexane having a purity of
96.1%.
[0168]
A metal (tin) content of the solid was 10 ppm or less, which was 9.61 (10 × 0.961) ppm
or less relative to 1,3-dicyanocyclohexane (including trans isomer and cis isomer).
(Example 6)
[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 75.3 g of 1,3-cyclohexanedicarboxylic acid, 15.1 g of
N,N'-dimethylimidazolidinone, and 0.95 g of tin (II) oxide, and the mixture was heated to 210°C
while stirring at 300 rpm.
31
[0169]
Thereafter, ammonia gas and nitrogen gas were mixedly introduced at a rate of 135
mL/min (0.83 mol equivalent/1,3-cyclohexanedicarboxylic acid/hr) and a rate of 15 mL/min,
respectively. The temperature was increased to 280°C, and while the temperature was kept
constant, reaction was performed. After 35 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.
[0170]
70 g of 1-butanol was added to 30 g of the reaction mixture 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 1,3-cyclohexanedicarboxylic acid was
100%, the yield of 1,3-dicyanocyclohexane was 90%, and the trans isomer/cis isomer ratio was
59/41.
[0171]
The remaining of the mixture was filtered by hot filtration in the same manner as
described above to separate the catalyst. The solvent was distilled off therefrom together with
the filtrate for 30 g of the mixture that previously underwent hot filtration, thereby producing
58g of a yellow viscous liquid. The viscous liquid had a purity of 96%, and a metal (tin)
content of 10 ppm or less, which was 9.6 (10 × 0.96) ppm or less relative to 1,3-
dicyanocyclohexane (including trans isomer and cis isomer).
[0172]
30g of the viscous liquid was distilled under a reduced-pressure of 5 mmHg, thereby
producing 25g of a colorless semi-solid. The semi-solid was analyzed by gas chromatography,
and it was found that 1,3-dicyanocyclohexane had a purity of 99.5% or more, and its trans
isomer/cis isomer ratio was 67/33. A metal (tin) content of the semi-solid was 1 ppm or less,
which was 0.995 (1 × 0.995) ppm or less relative to 1,3-dicyanocyclohexane (including trans
isomer and cis isomer).
[Aminomethylation Step]
A 100 mL stainless steel-made autoclave equipped with a stirrer was charged with 10.0
g of 1,3-dicyanocyclohexane having a trans isomer/cis isomer ratio of 59/41 (10.4 g of yellow
viscous liquid), i.e., a yellow viscous solid before the distillation obtained in the above-described
32
cyanation step, 0.48 g of a catalyst (manganese-containing Raney cobalt manufactured by
Kawaken Fine Chemicals Co., Ltd.), 9.6 g of a 28 wt% ammonia water, and 11.4 g of 1-butanol.
The autoclave was purged with nitrogen introduced from the autoclave nozzle inlet three times at
5 MPa, and the mixture was heated to 80°C while stirring at 400 rpm under normal pressure.
[0173]
When the temperature reached 80°C, hydrogen supply was started continuously to
achieve a pressure of 3.5 MPa, and the reaction was performed under a constant pressure until
there is no hydrogen absorption. The reaction time was 5.2 hours.
[0174]
After the completion of reaction, the mixture was cooled to room temperature. The
reaction mixture was taken out, and the mixture was filtered to remove the catalyst.
[0175]
The filtrate was analyzed by gas chromatography, and it was found that the conversion
of 1,3-dicyanocyclohexane was 100%, the yield of 1,3-bis(aminomethyl)cyclohexane was 93%,
and the trans isomer/cis isomer ratio was 59/41.
[0176]
The filtrate was distilled under a reduced-pressure of 5 mmHg, and 1,3-
bis(aminomethyl)cyclohexane having a purity of 99.5% or more was obtained with a yield of
91%.
(Example 7)
A 100 mL stainless steel-made autoclave equipped with a stirrer was charged with 9.1 g
of 1,3-dicyanocyclohexane having a trans isomer/cis isomer ratio of 67/33 (9.1 g of colorless
semi-solid), i.e., a colorless semi-solid after the distillation obtained in the cyanation step of
Example 6, 0.46 g of a catalyst (manganese-containing Raney cobalt manufactured by Kawaken
Fine Chemicals Co., Ltd.), 9.7g of a 28 wt% ammonia water, and 11.4 g of 1-butanol. The
autoclave was purged with nitrogen introduced from the autoclave nozzle inlet three times at 5
MPa, and the mixture was heated to 80°C while stirring at 400 rpm under normal pressure.
[0177]
When the temperature reached 80°C, hydrogen supply was started continuously to
achieve a pressure of 3.5 MPa, and the reaction was performed under a constant pressure until
there is no hydrogen absorption. The reaction time was 4.4 hours.
33
[0178]
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.
[0179]
The filtrate was analyzed by gas chromatography, and it was found that the conversion
of 1,3-dicyanocyclohexane was 100%, the yield of 1,3-bis(aminomethyl)cyclohexane was 93%,
and the trans isomer/cis isomer ratio was 67/33.
[0180]
The filtrate was distilled under a reduced-pressure of 5 mmHg, and 1,3-
bis(aminomethyl)cyclohexane having a purity of 99.5% or more was obtained with a yield of
90%.
[0181]
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
[0182]
The present invention allows for an industrially advantageous production of
bis(aminomethyl)cyclohexanes using a raw material cheaper than conventional ones: the raw
material such as phthalic acids or phthalic acid derivatives of at least one selected from the group
consisting of phthalic acids, phthalic acid esters, and phthalic acid amides.
[0183]
The compound is used suitably for polyamide, polyimide, polyurethane, and
polyisocyanate, and also for a curing agent of epoxy resins.
34

CLAIMS
1. A method for producing bis(aminomethyl)cyclohexanes, the method comprising:
a nuclear hydrogenation step of producing hydrogenated phthalic acids or phthalic acid
derivatives by nuclear hydrogenation of phthalic acids or phthalic acid derivatives of at least one
selected from the group consisting of phthalic acids, phthalic acid esters, and phthalic acid
amides,
a cyanation step of treating the hydrogenated phthalic acids or phthalic acid derivatives
obtained in the nuclear hydrogenation step with ammonia, thereby producing
dicyanocyclohexanes, and
an aminomethylation step of treating the dicyanocyclohexanes obtained in the
cyanation step with hydrogen, thereby producing bis(aminomethyl)cyclohexanes,
wherein metal oxide is used as a catalyst in the cyanation step, and the obtained
dicyanocyclohexanes have a metal content of 3000 ppm or less.
2. A method for producing bis(aminomethyl)cyclohexanes, the method comprising:
a cyanation step of treating hydrogenated phthalic acids or phthalic acid derivatives
with ammonia, thereby producing dicyanocyclohexanes, and
an aminomethylation step of treating the dicyanocyclohexanes obtained in the
cyanation step with hydrogen, thereby producing bis(aminomethyl)cyclohexanes,
wherein metal oxide is used as a catalyst in the cyanation step, and the obtained
dicyanocyclohexanes have a metal content of 3000 ppm or less.
3. The method for producing bis(aminomethyl)cyclohexanes according to Claim 2,
wherein
the hydrogenated phthalic acids or phthalic acid derivatives are obtained by
a nuclear hydrogenation step of nuclear hydrogenation of phthalic acids or phthalic
acid derivatives of at least one selected from the group consisting of phthalic acids, phthalic acid
esters, and phthalic acid amides.
4. The method for producing bis(aminomethyl)cyclohexanes according to Claim 1,
35
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 phthalic acids or phthalic acid derivatives/hr.
5. The method for producing bis(aminomethyl)cyclohexanes 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.
6. The method for producing bis(aminomethyl)cyclohexanes according to Claim 1,
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 phthalic acids
or phthalic acid derivatives.
7. The method for producing bis(aminomethyl)cyclohexanes 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,N'-diethylimidazolidinone, N,N'-
dipropylimidazolidinone, N,N',4-trimethylimidazolidinone, and N,N'-dimethylpropyleneurea.
8. The method for producing bis(aminomethyl)cyclohexanes 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 phthalic acids or phthalic acid derivatives/hr.
9. The method for producing bis(aminomethyl)cyclohexanes 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.
36
10. The method for producing bis(aminomethyl)cyclohexanes according to Claim 2,
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 phthalic acids
or phthalic acid derivatives.
11. The method for producing bis(aminomethyl)cyclohexanes 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,N'-dimethylimidazolidinone, N,N'-diethylimidazolidinone, N,N'-
dipropylimidazolidinone, N,N',4-trimethylimidazolidinone, and N,N'-dimethylpropyleneurea.