TECHNICAL FIELD
[0001]
The present invention relates to a process for producing a linear
or cyclic aliphatic isocyanate comprising a step of_,reacting a
10 linear or cyclic aliphatic amine with hydrogen chloride (step for
obtaining hydrochloride). The present invention further relates
to a linear or cyclic: aliphatic isocyanate obtained by the
production process and the use of the isocyanate.
15 BACKGROUND ART
[0002]
An isocyanate compound is useful as a raw material, for the
production of a polyurethane material, a polyurea material, a
polyisocyanurate material and the like used in the fields of
20 chemical, resin and paint industries. :.
[000.3]
In particular, since a plastic lens using a polyi_i ethane
9
material containing a sulfur atom or the like is lightweight and
hardly broken as compared to an inorganic lens, and can be dyed,
'25 in late years, it has quickly come into wide use as an optical
element of a spectacle lens, a camera lens and the like.
[0004]
In processes for preparing important isocyanates in the various
applications including a raw material of resin for the
aforementioned plastic lens, further rationalization of such
processes has been in demand. So, various proposals have already
5 been made.
[0005]
As the process for preparing isocyanates, a phosgene process
comprising reacting a raw material amine with phosgene can be cited
as a typical example. As the phosgere process, a direct process
10 comprising directly reacting a raw material amine witt phosgene,
and a hydrochloride process comprising converting a raw material
amine into hydrochloride and then reacting with phosgene have been
widely known.
[0006]
15 The direct process is much simpler as compared to the
hydrochloride process, but urea has been generated as a by-product
by reacting c.arbamoyl chloride or isocyanate that is an
intermediate with a raw material amine in many cases. In case of
the preparation of an aromatic isocyanate, since urea generated
20 as a by-product is further reacted with phosgene to generate an
isocyanate, products is obtained in relatively high yield and
generation of urea is not usually a problem accordingly. However,
when a linear or cyclic aliphatic amine is reacted with phosgene
in the direct process, since the byproduced urea is reacted with
25 phosgene, there has been known that a chlorine derivative is
generated as a by-product (for example, refer to Patent Document
1). The chlorine derivative is usually byproduced in an amount
of 3 to 10% and is sometimes byproduced as high as 20%. Hence the
yield. of the desired product might be decreased and the physical
properties of the resin such as urethane or the like in use might
be also adversely affected, So, the direct process is not usually
5 adopted. Namely, in case of the preparation of a linear or cyclic
aliphatic isocyanate, in order to suppress generation of urea as
a by-product, the hydrochloride process comprising converting a
raw material amine into hydrochloride and then reacting with
phosgene to prepare an isocyanate has been employed (for example,
10 refer to Patent Documents 2 to 5)
[0007].
Of these Patent Documents, in Patent Document 3 to 5, there have
15
been described processes comprising preparing an isocyanate by
converting a raw material amine into hydrochloride in an organic
solvent or the like in advance and then reacting with phosgene,
Patent Document 1: GB Patent No. 1086782
Patent Document 2. Japanese Patent laid-open No. 1975-108239
Patent Document 3:
Patent Document 4:
Japanese Patent Laid-open No.
GB Patent No, 1146664
1999-310567
20 Patent Docuient 5: Japanese Patent Laid-open No. 2003-286241
DISCLOSURE OF THE INVENTION
[0008]
However, in the hydrochloride process, the increased viscosity
25 of the obtained hydrochloride slurry is accompanied by
disadvantages of a decrease of the productivity and the like. So,
it has been demanded to be solved. For example, in the
9_
hydrochloride process, generally used is a process which comprises
blowing hydrogen chloride gas into an organic solvent with a raw
material amine dissolved therein for the production of
hydrochloride. At this time, the concentration of the raw material
5 amine is, for example, not less than 5 weight which is
industrially favorable. When the raw material amine is reacted
with hydrogen chloride gas under a condition such a concentration,
as the reaction is progressed, the viscosity of the hydrochloride
slurry is increased, for example, to 5,000 to 10,000 mPa°s, the
10 fluidity of the hydrochloride slurry is decreased, acid it is
difficult to transfer the hydrochloride by a pump or the like in
some cases. A'decrease of the productivity caused by the
difficulties in transferring the liquid becomes particularly
important when continuously carrying out the halogenation.
15 [0009]
In order to solve the above objects, the present. inventors have
conducted an extensive study and as a result, have found that the
pressure at the time of the production of a hydrochloride of a
linear or cyclic aliphatic amine is higher by 0. 01 MPa or more than
20 the atmospheric pressure, whereby it is possible to lower the
viscosity of the hydrochloride slurry. Thus, the present invention
has been completed. If the fluidity is enhanced by the lowere.d
viscosity o,f the hydrochloride slurry, a hydrochloride having an
excellent liquid transfer property is obtained, which is
25 partid,ularly useful for the improvement of the productivity of the
hydrochloride (particularly the improvement of the productivity
when the reaction for obtaining hydrochloride is continuously
conducted),
[0010]
Furthermore, it was found that the pressure at the time of the
production of a hydrochloride of a linear or cyclic aliphatic amine
5 is in the aforementioned condition, whereby the increase of the
particle diameter of the hydrochloride particle in the
hydrochloride slurry can be suppressed and the increase of the
viscosity of the hydrochloride slurry can be suppressed. It was
also found that the yield of isocyanate is increased through the
]0 improvement of Lhe conversion rate of hydrochloride 1_ the
phosgenation in some cases.
[0011]
That is, the present invention relates to (,1) a process for
producing a linear or cyclic aliphatic isocyanate comprising a step
15 of reacting a linear or cyclic aliphatic amine with hydrogen
chloride to yield a hydrochloride of the linear or cyclic aliphatic
amine, wherein said step is performed under a pressure higher by
0,01 MPa or more than the atmospheric pressure.
[0012]
20 The following (2) to (11) are each one of preferred embodiments
of the present invention;
[0013]
(2) the process for producing a linear or cyclic aliphatic
isocyanate as set forth in (1), wherein said linear or cyclic
25 aliphatic amine is a di- or higher functional linear or cyclic
f -
aliphatic amine;
[0019]
(3) the process for producing a linear or cyclic aliphatic
isocyanate as set forth in (1), wherein said step is a step of
reacting a di- or higher functional linear or cyclic aliphatic
amine with hydrogen chloride in an organic solvent in a tank
5 reactor; -
[0015]
(4) the process for producing a linear or cyclic aliphatic
isocyanate as set forth in (1), wherein said step is a step of
reacting a di- or higher functional linear or cyclic aliphatic
10 amine in an organ i_c solvent with hydrogen chloride blouc into the
organic solvent;
[0016]
(5) the process for producing a linear or cyclic aliphatic
isocyanate as set forth in any one.of (1) to (4), wherein the
15 viscosity of a slurry containing the hydrochloride of the linear
or cyclic aliphatic amine obtained in said step measured at 120
degree centigrade usinq a Brookfield LVT viscometer is not more
than 2,000 mPa°s;
[0017]
20 (6) the process for producing a linear or cyclic aliphatic
isocyanate as set forth in any one of (1). to ( 4) , wherein said step
is performed under a pressure higher by the range of 0.01 MPa or
more and L0 MPa or less than the atmospheric pressure;
[0018]
25 (7) the process for producing a linear or cyclic aliphatic
isocyanate as set forth in any one of (1) to (4), wherein the
reaction temperature in said step is not less than -20 degree
centigrade and not more than 180 degree centigrade;
[0019]
(8) the process for producing a linear or cyclic aliphatic
isocyanate as set forth in any one of (1) to (4) , wherein at least
5 one kind of organic aromatic solvent is used in said step;
[0020]
(9) the process for producing a linear or cyclic aliphatic
isocyanate as set forth in any one of (2) to (4), wherein said di
or higher functional linear or cyclic aliphatic amine is a compound
10 having a primary amino group;
[0021]
(10) the propels for producing a linear or cyclic aliphatic
isocyanate as set forth in any one of (2) to ( 4 ) wherein said di
or higher functional linear or cyclic aliphatic isocyanate is one
15 or more compounds selected from xylylene diisocyanate,
bis(isocyanatomethyl)norbornene, hexamethylene diisocyanate and
bis(isocyanatomethyl)cyclohexane; and
[0022]
(11) the process for producing a linear or cyclic aliphatic
20 isocyanate as set forth in any one of (1) to (4) , wherein the total
amine concentration in the reaction system is not less than 5
weight i% and not more than 40 weight % in said step,
[0023]
The present invention relates to (12) a linear- or cyclic
25 aliphatic isocyanate produced by the process as set forth in any
one of (1) to (11)
[0024]
The present invention relates to (13) a polyurethane resin
produced by using the linear or cyclic aliphatic isocyanate as set
forth in (12) .
[0025]
5 The present invention relates to (14) a lens containing the
polyurethane resin as set forth in (13)0
[0026]
Furthermore, the present invention relates to (15) a process for
producing a hydrochloride of a linear or cyclic aliphatic amine,
10 which comprises reacting a linear or cyclic aliphatio amine with
hydrogen chloride under a pressure higher by 0.01 MPa or more than
the atmospherid pressure. -
[0027]
The following (16) to (18) are each one of preferred embodiments
15 in the process for producing a hydrochloride of a linear or cyclic
aliphatic amine of the present invention:
[0028]
(16) the process for producing a hydrochloride of a linear or
cyclic aliphatic amine as set forth in (15), wherein raid linear
20 or cyclic aliphatic amine is a di- or higher functional linear or
cyclic aliphatic amine;
[0029]
(17) the process for producing a hydrochloride of a linear or
cyclic aliphatic amine as set forth in (15), which comprises
25 reacting a di or higher functional linear or cyclic aliphatic
amine with hydrogen. chloride in an organic solvent in a tank
reactor; anal
9
[0030]
(18) the process for producing a hydrochloride of a linear or
cyclic aliphatic amine as set forth in (15), which comprises
reacting a di- or higher functional linear or cyclic aliphatic
5 amine in an organic solvent with hydrogen chloride blown into the
organic solvent. -
[0031]
According to the present invention, the pressure at the time of
producing a hydrochloride of a linear or cyclic aliphatic amine
10 is higher by 0 . 01 HUn or more than the atmospheric pr_eseu ^e, whereby
it becomes possible to lower the viscosity of the obtained
hydrochloride slurry of the linear or cyclic aliphatic amine. Due
to this, the fluidity and liquid transfer property-of the
hydrochloride slurry are enhanced and it is possible-to produce
15 a hydrochloride having excellent liquid transfer_ property which
is particularly suitably applicable to the continuous reaction for
obtaining hydrochloride. So, the productivity of the
hydrochloride is improved.
20 BEST MODE FOR CARRYING OUT THE INVENTION
[0032]
- The present invention will be illustrated in detail below..
[0033] .
The process for producing a linear or cyclic aliphatic
25 isoc^anate of the present invention- includes a step of reacting
r
a linear or cyclic aliphatic amine with hydrogen chloride to yield
a slurry containing a hydrochloride of a linear or cyclic aliphatic
10
amine (hereinafter referred to as reaction step for obtaining
hydrochloride"). Furthermore, to produce the aforementioned
isocyanate, a step of reacting the amine hydrochloride obtained
by the aforementioned step with phosgene (hereinafter referred to
as "phosgenatior step") is involved, whereby the amine
hydrochloride is phosgenated to produce an isocyanate.
[0034]
Reaction Step for obtaining Hydrochloride
In the present invention, the reaction for obtaining
10 hydrochloride is carried out in a reactor under a preurwre higher
by 0.01 MPa or more than the atmospheric pressure, preferably 0.02
MPa or more, and more preferably 0.03 MPa or more. Due to this,
the viscosity of the hydrochloride slurry obtained in the reaction
for obtaining hydrochloride can be lowered, preferably to not more
15 than 2,000 mPa s, Incidentally, the viscosity of the slurry is
a value measured at 120 degree centigrade by using a Brookfield
LVT viscometer.
[0035]
According to the production process of the present invention
20 comprising carrying out the reaction for obtaining hydrochloride.
under such a pressure, the fluidity and liquid transfer property
are improved because of the lowered viscosity of the hydrochloride
slurry, while a hydrochloride having excellent liquid transfer
property which is particularly suitably applicable to the
25 continuous reaction for obtaining hydrochloride can be produced.
i
Accordingly, the productivity of the hydrochloride can be
improved.
[0036]
Furthermore, according to the production process of the present
invention, since the viscosity of the hydrochloride slurry is in
the above range, an unreacted, raw material amine and a chlorine
5 derivative generated from the unreacted raw material amine can be
decreased in some cases because of the improvement of the mixing
efficiency of the hydrochloride slurry. As a result, the
conversion rate of the raw material amine in the reaction for
obtaining hydrochloride is improved, and the yield of isocyanate
10 is improved, and the like in soi^ie cases. Furthermore, according
to the production process of the present invention, the increase
of the particle diameter of the hydrochloride particle contained
in the hydrochloride slurry can be suppressed and the hydrochloride
particle can be finer in some cases. Due to this, the increase
15 of the viscosity of the hydrochloride slurry can be suppressed,
and the yield of the isocyanate can be improved through the
improvement of the conversion rate of hydrochloride at the
phosgenation in some cases.
[0037]
20 In the present invention, the aforementioned linear or cyclic
aliphatic amine is preferably a di- or higher functional linear
or cyclic aliphatic amine. When the aforementioned linear or
cyclic aliphatic amine is a di_ or higher functional linear or
cyclic aliphatic amine, a hydrochloride of a di- or higher
25 functional linear or cyclic aliphatic amine can be obtained by the
reaction for obtaining hydrochloride. Furthermore, the
hydrochloride is phosgenated, whereby a di- or higher functional
12
linear or cyclic aliphatic isocyanate can be obtained. The dior
higher functional linear or cyclic aliphatic isocyanate is
reacted with a compound having two or more active hydrogen
containing groups, whereby a polymer compound such as polyurethane
5 or the like can be obtained. Thus, it is of practically high value.
[0038]
Furthermore, in the present invention, the aforementioned
reaction step for obtaining hydrochloride is preferably carried
out in an organic solvent from the viewpoints of the stability of
10 the reaction, the ,^;olubility of each component contribiiling to the
reaction, and the like.
[0039]
In the present invention, the reactor used for the
aforementioned reaction step for obtaining hydrochloride is
1.5 preferably a tank reactor, and particularly a tank reactor equipped
with a stirrer for stirring the inside. In the present invention,
a tank 'reactor refers to a reactor equipped with a reaction vessel
in which at least a part of a substance (reaction product,'generrated
product, solvent or the like) involved in the reaction is present
20 in a liquid phase thereinside, and a reactor satisfying the
relationship of D1/D2-0,85 when a diameter of a stirring blade is
- Dl and an internal diameter of the reaction vessel is D2.
Furthermore, in the tank reactor used in the present invention,
the ratio (D/L) of the bath diameter (D) and the bath length (L)
25 is preferably not less than 0.1 and not more than 5.0. ^Ihen D/L
is not less than 0.i, hydrogen chloride gas can be well removed
so that a phenomenon of the obtained hydrochloride exhibiting a
1.3,
whip shape for deteriorating the fluidity can be effectively
suppressed. When D/L is not more than 5.0, it is easy to stir
uniformly. As the result, the problem which unreacted amine is
increased and the like can be effectively suppressed. From the
5 viewpoint of a balance of such effects, the reactor having the
aforementioned ratio of D/L of not less-than 0.5 and not more than
1.5 is further desirable.
[0040]
The reaction for obtaining hydrochloride can be carried out in
10 various processes such as a process comprising introisci-ng an
organic solvent, preferably an organic aromatic solvent in a tank
reactor, subjecting to a temperature elevation to a prescribed
temperature and then adding a solvent with amine dissolved therein
dropwise thereto and at the same time feeding hydrogen chloride
15 gas, a process comprising heating the introduced solvent to a
prescribed temperature, absorbing hydrogen chloride gas in advance
and then adding an amine dissolved solution dropwise thereto and
at the same time feeding hydrogen chloride gas, a process
comprising heating a solvent with amine dissolved therein to a
20 prescribed temperature and then feeding hydrogen chloride gas, or
the like. The reaction for obtaining hydrochloride is preferably
carried out in any of the above-cited processes. However, the
reaction for obtaining hydrochloride carried out in processes
other than the cited processes is not excluded. In any of these
25 processes, when hydrogen chloride gas is inserted, it is preferable
that hydrogen chloride gas is blown into the organic solvent from
the viewpoint of the reaction efficiency.
14
[0041]
The pressure in a tank reactor for carrying out the reaction for
obtaining hydrochloride of the present invention is higher by 0.01
MPa or more than the atmospheric pressure from the viewpoint that
5 the viscosity of the hydrochloride slurry obtained in the reaction
for obtaining hydrochloride is preferably not more than 2, 000 mPa ° s
or the conversion rate of the raw material amine is preferably not
less than 99 mole o . The pressure is more preferably higher by 0.02
MPa or more than the atmospheric pressure. The pressure is further
10 preferably bighei by 0. 0.3 MPa or more than the atmoej1ieric
pressure.
[0042]
On the other hand, when the reaction for obtaining hydrochloride
is carried out under the atmospheric pressure, the particle
15 diameter of the hydrochloride particle in the hydrochloride slurry
becomes large or the viscosity of the hydrochloride slurry is
increased so that the decrease of the mixing efficiency in the.
reactor is resulted due to the decrease of the liquid transfer
property or the fluidity. For that reason, the increase of
20 unreacted amine or the increase of chloride generated in the
reaction with phosgene might be resulted in some cases.
[0043]
In the present invention, when the upper limit of the pressure
at the reaction for obtaining hydrochloride is higher by 1.0 MPa
25 or less than the atmospheric pressure, it is preferable that the
solubility of hydrogen chloride gas in the hydrochloride slurry
is increased so that the reaction speed at the reaction for
15
obtaining hydrochloride is enhanced. Furthermore, since the
fluidity is improved, the liquid transfer property of the
hydrochloride slurry preferably becomes excellent as well. The
pressure condition is more preferably 0.5 MPa or less than the
5 atmospheric pressure, and further preferably 0.3 MPa or, less than
the atmospheric pressure. When the pressure in the reactor for
obtaining hydrochloride is extremely high, there occur some
problems such that release of hydrogen chloride gas becomes worse,
the hydrochloride slurry exhibits a whip shape, and the fluidity
10 is adversely detc,i_rioraLed in some cases.
[0044]
Incidentally', the lower limit and upper limit of the pressure
at the reaction for obtaining hydrochloride can be in any
combination. In the present invention, from the viewpoints of the
15 above effects, the reaction for obtaining hydrochloride is
preferably carried out under a pressure higher by not less than
0.01 MPa and not more than 1.0 MPa than the atmospheric, pressure,
and more preferably carried out under a pressure higher by not less
than 0.01 MPa and not more than 0.5 MPa than the atmospheric
20 pressure.
[0045]
According to the production process, of the present invention,
the conversion rate of the raw material amine can be not less than
99 mole% in some cases. When the conversion rate of the raw material
25 amine 'is not less than 99 mole%, it is preferable that the yield
of isocyanate is high and the influence of the by-product can be
suppressed.
16
[0046]
The conversion rate of the raw material amine is measured in the
following manner. The amine remained in the slurry after the
completion of the reaction for obtaining hydrochloride i.s
5 subjected to neutralization titration to calculate the mole number
of the remained amine. From the mole number of the remained amine
and the mole number of the introduced amine, the amine conversion
rate is calculated according to the following formula.
Formula: Amine conversion rate = ((mole number of introduced
10 amine - mole number of remained ami.r / mole number of irltrod-oced
amine) x 100
[0047]
The total amine concentration in the present invention is
preferably not less than 5 weight % and not more than 40 weight %
15 in consideration of the industrial production efficiency. The
total amine concentration is a value calculated by dividing the
amount of amine introduced into the reactor for obtaining
hydrochloride by the total weight of the raw material introduced
into the reactor for obtaining hydrochloride.
20 [0048]
When the concentration is not less than 5 weight %, it is
preferable that the production efficiency is high. When the
concentration is not more than 40 weight %, problems of the
deteriorated fluidity of the hydrochloride slurry, the reduced
25 mixing efficiency due to the increase of the slurry viscosity,
increased unreacted amine, decreased liquid transfer property,
increased chloride at the reaction with phosgene and the like can
17
be effectively suppressed. For that reason, the total amine
concentration is preferably not less than 5 weight % and not more
than 35 weight %, and more preferably not less than 5 weight % and
not more than 30 weight %.
5 [0049]
The temperature at the reaction for obtaining hydrochloride in
the present invention is preferably not less than -20 degree
centigrade and not more than 180 degree centigrade in consideration
of the decrease of unreacted amine, prevention of a chlorine
10 derivative generated as a by-product derived from the unreacted
amine, fine particle diameter of generated hydrochloride, thermal
balance at the time of shifting to the next reaction with phosgene
or the like.
[0050]
15 When the temperature is not less than -20 degree centigrade,
phenomena such that condensation of the hydrochloride particle is
difficult and hydrochloride in the bulk; state at the halogenation
is generated can be effectively suppressed. When the temperature
is not more than 180 degree centigrade, phenomena such that the
20 generated hydrochloride exhibits a whip shape, the fluidity is
damaged and it is difficult to transfer hydrochloride can be
effectively suppressed. The temperature at the reaction for
obtaining hydrochloride is preferably not less than -20 degree
centigrade and not more than 180 degree centigrade, more preferably
25 not l'^ss than,60 degree centigrade and not more than 175 degree
centigrade, and further preferably not less than 100 degree
centigrade and not more than 170 degree centigrade.
18
[0051]
Phosgenation Step
The,r_eaction of a hydrochloride obtained by the reaction for
obtaining hydrochloride with phosgene can also be carried out under
5 a normal pressure or a pressure, but the phosgenation is preferably
carried out under a normal pressure from the viewpoint of
suppression of side reaction due to byproduced hydrogen chloride
gas. Moreover, the temperature of the reaction with phosgene is
not less than 120 degree centigrade and not more than 180 degree
10 centigrade, preferably not less than 130 degree centig.i tcle and not
more than 175 degree centigrade, and further preferably not less
than 150 degree `centigrade and not more than 170 degree centigrade
from the viewpoints of the reaction speed and suppression of
converting generated iso.cyanate into tar.
15 [0052]
In the present invention, as the equivalent ratio of amine and
hydrogen chloride gas at the reaction for obtaining hydrochloride,
hydrogen chloride gas is not less than 1.0 and not more than 2.5
and preferably not less than 1.1 and not more than 2.0 based on.
20 1.0 of amine. When it is not less than 1.0, the conversion rate
of the raw material amine can be maintained high. When it is not
more than 2. 5, it is industrially more favorable from-the viewpoint
of the economical efficiency.
[0053]
25 The di- or higher linear or cyclic aliphatic amine which is
preferably used in the present invention is not particularly
limited, but typical examples thereof include linear aliphatic
19
amines such as hexamethylene diamine, 2,2-dimethylpentane diamine,
2,2,4-trimethylhexane diamine, butene diamine,
1,3-butadiene-l,4-diamine, 2,4,4-trirnethylhexamethylene diamine,
1,6,11-undecane triamine, 1,3,6-hexamethylene triamine,
5 1,8-diisocyanato-4--isocyanatomethyloctane,
bis(aminoethyl)carbonate, bis (aminoethyl) ether, lysine diamino
methyl ester, lysine triamine, xylylene diamine,
bis(aminoethyl)benzene, bis(aminopropyl)benzene,
n,a,a',a'-tetramethylx_.ylylene diamine, bis(aminobutyl)benzene,
10 bis(aminomethyl)napl-ithalene, bis(aminomethyl)diphenyl ether,
bis(aminoethyl)phthalate, mesitylylene triamine,
2,6-di(aminomethyl)furan and the like; -
cyclic aliphatic amines such as bis(aminomethyl)cyclohexane,
dicyclohexylmethane diamine, cyclohexane diamine,
15 methylcyclohexane diamine, dicyclohexyldimethylmethane diamine,
2,2-dimethyl dicyclohexylmethane diamine,
2,5-bis(aminomethyl)bicyclo-[2,2,1]-heptane,
2,6-bis(aminomethyl)bicyclo-[2,2,1] -heptane,
3,8-bis(aminometlhyl)tricyclodecane,
20 3,9-bis(aminonethyl)tricyclodecane,
4,8-bis(aminomethyl)tricyclodecane,
4,9-bis(aminomethyl)tricyclodecane, bis(aminomethyl)norbornene
and the like; and
sulfur-containing linear aliphatic amines such as
25 bis(aminomethyl)sulfide, bis(aminoethyl)sulfide,
bis(aminopropyl)sul'fide, bis(aminohexyl)sulfide,
bis(aminomethyl)sulfone, bis(aminomethyl)disulfide,
20
bis(aminoethyl)disulfide, bis(aminopropyl)disulfide,
bis(aminomethylthio)methane, bis(aminoethylthio)methane,
bis(aminoethylthio)ethane, bis(aminomethylthio)ethane,
1,5-diamino-2-aminomethyl-3-thiapentane and the like.
5 [0054]
Isocyanate obtained by reacting the amine hydrochloride
obtained in the aforementioned reaction for obtaining
hydrochloride with phosgene is not particularly limited, but
typical examples there-of include linear aliphatic polyisocyanate
10 such as hexamethylene diisocyanate, 2, 2-di_methylpen( itie
diisocyanate, 2,2,4-trimethylhexane diisocyanate, butene
diisocyanate, 113-butadiene-l,4-diisocyanate,
2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecane
triisocyanate, 1,3,6-hexamethylene triisocyanate,
15 1,8-diisocyanato-4-isocyanatomethyloctane,
bis(isocyanatoethyl)carbonate bis(isocyanatoethyl)ether,
lysine' diisocyanatomethyl ester, lysine: triisocyanate, xylylene
diisocyanate, bis(isocyanatoethyl)benzene, _
bis(isocyanatopropyl)benzene, a, a, a' ,e' -tetramethylxylylene
20 diisocyanate, bis(isocyanatobutyl)benzene,
bis(isocyanatomethyl)naphthalene, bis(isocyanatomethyl)diphenyl
ether, bis(isocyanatoethyl)phthalate, mesitylylene
triisocyanate, 2,6-di(isocyanatomethyl)furan and the like;
cyclic aliphatic polyisocyanate such as
25 bis(i'socyanatomethyl)cyclohexane, dicyclohexylmethane,
diisocyanate, cyclohexane diisocyanate, methylcyclohexane
diisocyanate, dicyclohexyl dimethylmethane diisocyanate,
21.
2,2-dimethyldicycloh.exylmethane diisocyanate,
2,5-bis(isocyanatomethyl)bicyclo-[2,2,1]-heptane,
2,6-bis(isocyanatomethyl)bicyclo-[2,2,1]-heptane,
3,8-bis(isocyanatomethyl)tricyclodecane,
5 3,9-bis(isocyanatomethyl)tricyclodecane,
4,8-bis(isocyanatomethyl.)tricyclodecane,
4,9-bis(isocyanatomethyl)tricyclodecane,
bis(isocyanatomethyl)norbornene and the like; and
sulfur-containing linear aliphatic isocyanate such as
10 his (isocyanatomethyl)sulfide, bis(isocyanatoethyl)suIN de,
bis(isocyanatopropyl)sulfide, bis(isocyanatohexyl)sulfi-de,
bis(isocyanatomethyl)sulfone, bis(isocyanatomethyl)disulfide,
bis(isocyanatoethyl)disulfide, bis(isocyanatopropyl)disulfide,
bis(isocyanatomethylthio)metharie,
15 bis(isocyanatoethylthio)methane, bis(isocyanatoethylthio)ethane,
bis(isocyanatomethylthio)ethane,
1,5-diisocvanato-2-isocyanatomethyl-3 thiapentane and the like.
[0055]
Particularly preferable examples of the compound for various
20 applications of optical components among the above-cited compounds
obtained by the production process of the present invention include
xylylene diisocyanate, bis(isocyanatomethyl)norbornene,
hexamethylene diisocyanate and bis (isocyanatomethyl) cyclohexane.
[0056]
25 The solvent{ used in the.present invention is not particularly
limited. However, it is preferable to use an organic.. aromatic
compound with a high boiling point in which the hydrochloric acid
22 .
solubility at the reaction for obtaining hydrochloride is high,
the phosgene solubility at the phosgenation is high, and the
hydrochloric acid solubility is small. Typical examples of the
organic aromatic compound include, though not restricted to,
5 1,2-diethylbenzene, 1,3-diethylbenzene, 1,4-diethylbenzene,
isopropylbenzene, 1,2,4-trimethylbenzene,, amylbenzene,
diamylbenzene, triamylbenzene, dodecylb'enzene, p-cymene, cumene,
dimethyl phthalate, diethyl phthalate, dibutyl phthalate,
di-2-ethylhexyl phthalate, methyl benzoate, ethyl benzoate, butyl
10 benzoate, propyl benzoate, isoamyl benzoate, benzy] I,)eenzoate;
methyl salicylate, methylphenyl ether, ethylphenyl ether,
diisoamyl ether;, n-hexyl ether, orthodichlorobenzene,
p-chlorotoluene, bromobenzene, 1,2,4-trichlorobenzene'and the
like. Of the exemplified solvents, particularly preferably used
15 for carrying out the present invention is an aromatic halogen
compound.
[005'/]
An isocyanate has been widely used in various industrial fields
including optical materials. The process for producing an
20 isocyanate of the present invention is capable of enhancing its
production efficiency and has a technically and industrially high
value.
[0058]
The isocyanate compound obtained by the production process of
25 the present invention is excellent in the economical efficiency,
and it is easy to reduce the unreacted raw material amine and a
chorine derivative generated from the unreacted raw material amine.
23
For that reason, by using the isocyanate compound, resins or
optical products excellent in quality can be obtained with high
economical efficiency.
[0059]
5 The isocyanate compound obtained by the production process of
the present invention is useful as a rawmaterial for the production
of various resins such as a polyurethane resin (including a
polythiourethane resin), a polyurea resin, a,polyisocyanurate
resin and the like, Since a chlorine derivative highly needs to
10 be removed to produce the polyurethane resin, the isocyanate
compound obtained by the production process of the present
invention is particularly useful as a raw material for the
production of a polyurethane resin. That is, the isocyanate
obtained by the present invention is excellent in the economical
15 efficiency, and it is easy to reduce the unreacted raw material
amine and a chorine derivative generated from the unreacted raw
material amine. By using such an isocyanate, resins such as a
polyurethane resin or the like and products such as lens or the
like excellent in quality can be obtained with high economical
20 efficiency.
[0060]
A process for producing a polyurethane resin from the isocyanate
compound and conditions (kind of isocyanate compounds, kind of
compounds reacting with an isocyanate resin, kind of catalysts,
25 kind of other additives, amount ratio thereof, reaction
temperature, reaction time and the like) are not particularly
limited. Conventional processes and conditions known in the art
24
can be properly used in the ranges in which the object of the present
invention is not impaired. For example, those described in
Japanese Patent Laid-open No. 2003-043201 can be preferably used.
[0061]
5 Since molded articles composed of the polyurethane resin
obtained as described above have excellent impact resistance and
dye-affinity, and high transparency in many cases, such articles
are particularly suitable as materials of plastic lenses. Plastic
lenses using the polyurethane materials are particularly useful
10 as optical components of spectacle lenses, camera lenses and the
like.
[0062]
EXAMPLES
15 The present invention is now illustrated in detail below with
reference to Examples. However, the range of the present invention
is not restricted to these Examples in•anv sense.
Incidentally, the following Examples and Comparative Examples
were measured in the following manner.
20 [0063]
(Conversion Rate of Amine)
Amine remained in the slurry after the completion of the reaction
for obtaining hydrochloride was subjected to neutralization
titration to calculate the mole number of the remained amine. From
25 the mole number of the remained amine and the mole number of the
introduced amine, the conversion rate was calculated according to
the following formula.
25
Formula: Amine conversion rate = ((mole number of introduced
amine - mole number of remained amine) / mole number of introduced
amine) x 100
[0064]
5 (Generation Rate of Chloride)
The reaction solution after the completion of the reaction with
phosgene was analyzed by gas chromatography to calculate the mole
number of chloride. The mole number of chloride was divided by
the mole number of the introduced hydrochloride to calculate the
10 generation rate.
[0065]
(Purity of Isocyanate)
The finally obtained isocyanate was analyzed by gas
chromatography to calculate the purity of the isocyanate.
15 [0066]
(Conversion Rate of Hydrochloride)
A residue of the reaction filtrate obtained by filtering after
the reaction with phosgene was subjected to neutralization
titration to calculate the mole number of the remai.ncd
20 hydrochloride. From the mole number of the remained hydrochloride
and the mole number of the introduced hydrochloride, the conversion
rate was calculated according to the following formula.
Formula:, Hydrochloride conversion rate = ((mole-number of
introduced hydrochloride - mole number of remained hydrochloride)
25 / mole number of introduced hydrochloride) x 100
[0067]
(Method for Measurement of Hydrochloride Viscosity)
26
The slurry after the completion of the reaction for obtaining
hydrochloride was weighed in a vessel and the measurement
temperature was elevated to 120 degree centigrade. When the
temperature reached 120 degree centigrade, the viscosity was
5 measured with No. 2 rotor of a Brookfield LVT viscometer and the
indication value was multiplied by a coeff i cient to calculate the
viscosity.
[0068]
(Method for Measurement of Particle Diameter)
10 A small amount of the slurry after the completion of 11ie reaction
for obtaining hydrochloride was picked out and measured by using
SALD-2100, a laser diffraction particle size analyzer,
manufactured by Shimadzu Corporation in an acetonitrile solvent.
The measured particle diameter was a number average-value of the
15 total particle diameter.
[0069]
Example 1
An autoclave (reactor) equipped with a reflux condenser, a
stirring blade, a thermometer, a hydrogen chloride gas inlet tube,
20 a phosgene inlet tube, a raw material bath, a raw material feeding
pump and a pressure regulator was used. In the reactor, a value
of a diameter of the stirring blade (Di) / an internal diameter
of the reaction vessel (D2) was 0.7, a value of the bath diameter
(D) / the bath length (L) was 0.59, and an inner volume of the
25 reaction vessel was 2L. To the reactor was fed 846 g of
orthodichlorobenzene as a reaction solvent, and to the raw material
bath were fed 136.2 g (1.'0 mole) of m-xylylene diamine and 621 g
27
of orthodichlorobenzene (total amine concentration: 8.5 weight o),
Next, the temperature in the reactor was elevated to 120 degree
centigrade and then the internal pressure was regulated by 0.01
MPa higher than the atmospheric pressure. Hydrogen chloride gas
5 started to be fed into the reactor at a rate of 93.8 g/hr from the
hydrogen chloride gas inlet tube and nc-xylylene diam:ine diluted
with a solvent simultaneously started to be fed at a rate of 379
g/hr from the raw material bath by using the raw material feeding
pump.. The total amount was fed over 2 hours. Furthermore, hydrogen
10 chloride gas was fed at a rate of 20 g/hr and matured for 1 hour
After the completion of the reaction, the conversion rate of the
raw material amine was calculated by the neutralization
titrimetric method and as a result, the conversion rate was 99.80
mole%. Further, the viscosity of the obtained hydrochloride slurry
15 was measured at 120 degree centigrade using a Brookfield LVT
viscometer and as a result, it was 201 mPa•s. So, the slurry had
sufficient fluidity. Moreover, a particle diameter of the
hydrochloride particle was measured by using SALD-2100, a laser
diffraction particle size analyzer, manufactured by Shimadzu
20 Corporation in an acetonitrile solvent and as a resul-t, the number
average particle diameter of the hydrochloride particle was 2'5 pin.
The obtained hydrochloride slurry was in a liquid phase and
excellent in the fluidity. So, it was confirmed that when the
hydrochloride was transferred to the next step, the hydrochloride
25 did not remain in the reactor and the liquid transfer property was
excellent accordingly.
Subsequently, the hydrochloride slurry in the reactor was heated
28
to 160 degree centigrade and then phosgene was blown at a rate of
100 g/hr (1.0 mole/hr) from the phosgene inlet tube. The reaction
was carried out for 8 hours while maintaining the temperature.
After the completion of the reaction, nitrogen in the system was
5 purged to remove unreacted phosgene and hydrogen chloride gas The
reaction solution was filtered to remove 0.8 g (dry weight)
unreacted hydrochloride. The obtained filtrate was desolvated to
obtain 188.58 g (purity conversion yield: 98.30 mole%) of m-xylene
diisocyanate having a purity of 98.10° containing 0.1 weight %
10 m-chloromethyl boozyl isocyanate (hereinafter simply eferr_ed 1 o
as CBi). The conversion rate of hydrochloride was 99.620. The
results are shown in Table 1 to 3.
[0070]
Example 2
15 The same reactor as in Example 1 was used. To the reactor was
fed 846 g of orthodichlorobenzene as a reaction solvent, and to
the raw material bath were fed 136.2 g,(1.0 mole) of-m-xylylene
diamine and 621 g of orthod.ichlorobenzene (total amine
concentration: 8 , 5 weight %) . Next, the temperature i.n the reactor
20 was elevated to 120 degree centigrade ahd'then the internal
pressure was regulated by 0.05 MPa higher than the-atmospheric
pressure. Hydrogen chloride gas started to be fed into.the reactor
at a rate of 43.8 g/hr from the hydrogen chloride gas inlet tube
and m-xylylene diamine diluted with a solvent simultaneously
25 started to be fed at a rate of 379 g/hr from the raw material bath
by using the raw material feeding pump. The total amount was fed
over 2 hours. Furthermore, hydrogen chloride gas was fed at a rate
29
of 20 g/hr and matured for 1 hour. After the completion of the
reaction, the conversion rate of the raw material amine was
calculated by the neutralization titrimetri.c method and as a result,
the conversion rate was 99.75 moleo. Further, the viscosity of
5 the obtained hydrochloride slurry was measured at 120 degree
centigrade using a Brookfield LVT viscometer and as-a result, it
was 215 mPa • s. So, the slurry, had sufficient fluidity. Moreover,
a particle diameter of the hydrochloride was measured by using
SALD-2100, a laser diffraction particle size analyzer,
10 manufactured by Shimadzu Corporation in an acetonitr_L_le solvent
and as a result, the number average particle diameter of the
hydrochloride particle was 29 pm. The obtained hydrochloride
slurry was in a liquid phase and excellent in the fluidity. So,
it was confirmed that when the hydrochloride was transferred to
15 the next step, the hydrochloride did not remain in the reactor and
the liquid transfer property was excellent accordingly.
Sub'sequently, the hydrochloride slurry in the reactor was heated
to 160 degree centigrade and then phosgene was blown at a rate of
100 g/hr (1.0 mole/hr) from the phosgene inlet tube. The reaction
20 was carried out for 8 hours while maintaining the temperature.
After the completion of the reaction, nitrogen in the system was
purged to remove unreacted phosgene and hydrogen chloride gas. The
reaction solution was filtered to remove 0.6 g (dry weight) of
unreacted hydrochloride. The obtained filtrate was desolvated to
25 obtain 190.3 (purity conversion yield: 98.50 mole%), of m-xylene
diisocyanate having a purity of 97.40% containing 0.3 weight % of
CBi. The conversion rate of hydrochloride was 99.70 mole%. The
30
results are shown in Table 1 to 3.
[0071]
Example 3
The same reactor as in Example 1 was used. To the reactor was
5 fed 846 g of orthodichlorobenzene as a reaction solvent, and to
the raw material bath were fed 136.2 g (1.0 mole) of m-xylylene
diamine and 621 g of orthodichlorobenzene (total amine
concentration: 8.5 weight %) . Next, the temperature in -the reactor
was elevated to 120 degree centigrade and then the internal
10 pressure was regulated by 0.1 MPa higher than the a' iiiospheric
pressure, Hydrogen chloride gas started to be fed at a rate of
43. 8 g/hr from the hydrogen chloride gas inlet tube and m-xylylene
diamine diluted with a solvent simultaneously started to be fed
at a rate of 379 g/hr from the raw material bath by using the raw
15 material feeding pump. The total amount was fed over 2 hours.
Furthermore, hydrogen chloride gas was fed at a rate of 20 g/hr
and matured for 1 hour. After the completion of the reaction; the
conversion rate of the raw material amine was calculated by the
neutralization titrimetric method and as a result, the conversion
20 rate was 99.81 mole%. Further, the viscosity of the hydrochloride
slurry_ was measured at 120 degree centigrade using a Brookfield
LVT viscometer and as a result, it was 221 mPa•s. So, the slurry
had sufficient fluidity. Moreover, a particle diameter of the
hydrochloride was measured by using SALD-2100, a laser diffraction
25 particle size analyzer, manufactured by Shimadzu Corporation in
an acetonitrile solvent and as a result, the number average
particle diameter of the hydrochloride particle was 31 pm. The
3 1.
obtained hydrochloride slurry was in a liquid phase and excellent
in the fluidity. So, it was confirmed that when the hydrochloride
was transferred to the next step, the hydrochloride did not remain
in the reactor and the liquid transfer property was excellent
5 accordingly.
Subsequently, the hydrochloride slurry in the reactor was heated
to 160 degree centigrade and then phosgene was blown at a rate of
100 g/hr (1.0 mole/hr) from the phosgene inlet tube. The reaction
was carried out for 8.hours while maintaining the temperature.
10 After the completion of the reaction, nitrogen in th(, system was
purged to remove unreacted phosgene and hydrogen chloride gas. The
reaction solution was filtered to remove 0.4 g (dry weight) of
unreacted hydrochloride. The obtained filtrate was desolvated to
obtain 188.9 g (purity conversion yield: 98.80 mole%) of m-xylene
15 diisocyanate having a purity of 98.42% containing 0.2 weight % of
CBi. The conversion rate of hydrochloride was 99.80 mole%. The
results are shown in Table 1 to 3-
0 07 2 ]
Example 4
20 The same reactor as in Example 1 was used. To the reactor was
fed 958 g of orthodichlorobenzene as a reaction solvent, and to
the raw material bath were fed 154.2 g (1.0 mole) of
bis(aminomethyl)norbornene and 702 g of orthodichlorobenzene
(total amine concentration: 8.5 weight %) . Next, the temperature
25 in the' reactor was elevated to 120 degree centigrade and then the
pressure inside the autoclave was regulated by 0. 01 MPa higher than
the atmospheric pressure. Hydrogen chloride gas started to be fed
32
into the reactor at a rate of 43. 8 g/hr from the hydrogen chloride
gas inlet tube and bis(aminomethyl)norbornene diluted with a
solvent simultaneously started to be fed at a rate of 428.1 g/hr
from the raw material bath by using the raw material feeding pump.
5 The total amount was fed over 2 hours. Furthermore, hydrogen
chloride gas was fed at a rate of 20 g/hr and matured for 1 hour.
After the completion of the reaction, the conversion rate of the
raw material amine was calculated by the neutralization
titrimetric method and as a result, the conversion rate was 99.88
10 mole° . Further, the viscosity of the obtained hydrochir)ride slurry
was measured at 120 degree centigrade using a Brookfield LVT
viscometer and as a result, it, was 241 mPa ° s . So, the slurry had
sufficient fluidity. Moreover, a particle diameter of the
hydrochloride was measured by using SALD-2100, a lasex diffraction
15 particle size analyzer, manufactured by Shimadzu Corporation in
an acetonitrile solvent and as a result, the number average
particle diameter of the hydrochloride,particle was 29 pm. The
obtained hydrochloride slurry was in a liquid phase and excellent
in the fluidity. So, it was confirmed that when the hydrochloride
20 was transferred to the next step, the hydrochloride did not remain.
in the reactor and the liquid transfer property was excellent
accordingly.
Subsequently, the hydrochloride slurry in the reactor was heated
to 160 degree centigrade and then phosgene was blown at a rate of
25 100 g/hr (1.0 mole/hr) from the.phosgene inlet tube. The reaction
was carried out for 8 hours while maintaining the temperature.
After the completion of the reaction, nitrogen in the system was
33
purged to remove unreacted phosgene and hydrogen chloride gas. The
reaction solution was filtered to remove 0.5 g (dry weight) of
unreacted hydrochloride. The obtained filtrate was desolvated to
obtain 206.9 g (purity conversion yield: 98.81 mole%) of
5 bi.s(isocyanatomethyl)norbornene having a purity of 98.5%
containing 0.2 weight % of chloromethyl-isocyanatomethvl
norbornene(hereinafter simply referred to as CNi) The conversion
rate of hydrochloride was 99.79 mole%. The results are shown in
Table 1 to 3.
10 [0073]
Example 5
The same reactor as in Example 1 was used. To the reactor was
fed 958g of orthodichlorobenzene as a reaction solvent, and to
the raw material bath were fed 154.2 g (1.0 mole) of
15 bis(aminomethyl)norbornene and 702 g of orthodichlorobenzene
(total amine concentration: 8.5 weight %) . Next, the temperature
in the reactor was elevated to 120 degree. centigrade and then the
internal pressure was regulated by 0.03 T IPa higher than the
atmospheric pressure. Hydrogen chloride gas started to be fed at
20 a rate of 43.R g/hr from the hydrogen chloride gas inlet tube and
bis (aminomethyl) norbornene diluted with a solvent simultaneously
started to be fed at a rate of 428.1 g/hr from the raw material
bath by using the raw material feeding pump. The total amount was
fed over 2 hours. Furthermore, hydrogen chloride gas was fed at
25 a rate of 20 g/hr and matured for 1 hour. After the completion
of the reaction, the conversion rate of the raw material amine was
calculated by the neutralization titrimetric method and as a result,
34
the conversion rate was 99.91 mole%, The viscosity of the
hydrochloride was measured at 1.20 degree centigrade using a
Brookfield LVT viscometer and as a result, it was 196 mPa•s. So,
the hydrochloride had sufficient fluidity. Moreover, a particle
5 diameter of the hydrochloride was measured by using SALD-2100, a
laser diffraction particle size analyzer, manufactured by Shimadzu
Corporation in an acetonitrile solvent and as a result, the number
average particle diameter of the hydrochloride particle was 33 pm.
The obtained hydrochloride slurry was in a liquid phase and
10 excellent in the Fluidity. So, it was confirmed thai when the
hydrochloride was transferred to the next step, the hydrochloride
did not remain in the reactor and the liquid transfer property was
excellent accordingly.
Subsequently, the hydrochloride slurry in the reactor was heated
15 to 160 degree centigrade and then phosgene was blown at a rate of
100 g/hr (1.0 mole/hr) from the phosgene inlet tube. - The reaction
was carried out for 8 hours while maintaining the .temperature.:
After the completion of the reaction, nitrogen in the `system was
purged to remove unreacted phosgene and hydrogen chloride gas. The
20 reaction solution was filtered to remove 0.5 g (dry weight) of
unreacted hydrochloride. The obtained filtrate was desolvated to
obtain 206.3 g (purity conversion yield: 98.32 mole%) of
bis(isocyanatomethyl)norbornene having a purity of 98..30
containing 0.1 weight %'of CNi. The conversion rate of
25 hydrochloride was 99.78 mole%. The results are shown in Table 1
to 3.
[0074]
35
Example 6
The same reactor as in Example 1 was used. To the reactor was
fed 566.8 g of orthodichlorobenzene as a reaction solvent, and to
the raw material bath were fed 142.2 g (1.0 mole) of
5 bis(aminomethyl)cyclohexane and 476.0 g of
o-dichlorochlorobenzene (total amine concentration: 8.5 weight o).
Next, the .temperature in the reactor was elevated to 120 degree
centigrade and then the internal pressure was regulated by 0.01
MPa higher than the atmospheric pressure. Hydrogen chloride gas
10 started to be fed at a rate of 43.8 g/hr from Lhe hydro(p,n chloride
gas inlet tube and amine diluted with a solvent simultaneously
started to be fed at a rate of 309.1 g/hr from the-raw material
bath by using the raw material feeding pump. The total amount was
fed over 2 hours. Furthermore, hydrogen chloride gas was fed at
15 a rate of 20 g/hr and matured for 1 hour. After the completion
of the reaction, the conversion rate of the raw material amine was
calculated by the neutralization titrimetric method and as a result,
the conversion rate was 99.88 mo.leo. The viscosity of the
hydrochloride was measured at 120 degree centigrade using a
20 Brookfield LVT viscometer and as a result, it was 213 mPa•s. So,
the hydrochloride had sufficient fluidity. Moreover, a particle
diameter of the hydrochloride was measured by using SALD-2100,, a
laser diffraction particle size analyzer, manufactured by Shimadzu
Corporation in an acetonitrile solvent and as a result, the number
25 average particle diameter of the hydrochloride particle was 32 pm.
The obtained hydrochloride slurry was in a liquid phase and
excellent in the fluidity. So, it was confirmed that when the
36
hydrochloride was transferred to the next step, the hydrochloride
did not remain in the reactor and the liquid transfer property was
excellent accordingly.
Subsequently, the hydrochloride slurry in the reactor,was heated
to 160 degree centigrade and then phosgene was blown at a rate of
100 g/hr (1.0 mole/hr) from the phosgene inlet tube. The reaction
was carried out for 8 hours while maintaining the temperature.
After the completion of the reaction, nitrogen in the system was
purged to remove unreacted phosgene and hydrogen chloride gas. The
10 reaction solution was filtered to remove 0.4 g (dry w(igh+t-) of
unreacted hydrochloride. The obtained filtrate was desolvated to
obtain 194.0 g(puri_ty conversion yield: 98.60 mole%)
bis(isocyanatomethyl)cyclohexane having a purity of 98.70%
containing 0.2 weight % of chloromethyl-isocyanatomethyl
15 cyclohexane (hereinafter simply referred to as CHi). The
conversion rate of hydrochloride was 99.81%. The results are shown
in Table 1 to 3.
[0075)
Example 7
20 The same reactor as in Example 1 was used. To the reactor was
fed 61„4.6 g of orthodichlorobenzene as a reaction solvent, and to
the raw material bath were fed 154.2 g (1.0 mole) of
bis(aminomethyl)norbornene and 516.2 g of orthodichlorobenzene
(total amine concentration: 12.0 weight %) . Next, the temperature
25 in the reactor was elevated to 120 degree centigrade and then the
internal pressure was regulated by 0.01 MPa higher than the
atmospheric pressure. Hydrogen chloride gas started to be fed
37
a rate of 43. 8 g/hr from the hydrogen chloride gas inlet tube and
bis(aminomethyl)norbornene diluted with a solvent simultaneously
started to be fed at a rate of 335.2 g/hr from the raw material
bath by using the raw material feeding pump. The total amount was
5 fed over 2 hours. Furthermore, hydrogen chloride gas was fed at
arate of 20 g/hr and matured for 1 hour. After the completion
of the reaction, the conversion rate of the raw material amine was
calculated by.the neutralization titrimetric method and as a result,
the conversion rate was 99.86 mole%. The viscosity of the
10 hydrochloride wa;; measured at 120 degree centigrade icing a
Brookfield LVT viscometer and as a result, it was 1, 110 mPa. s. So,
the hydrochloride had sufficient fluidity. Moreover,..a particle
diameter of the hydrochloride was measured by using SALD-2100, a
laser diffraction particle size analyzer, manufactured by Shimadzu
15 Corporation in an acetonitrile solvent and as a result, the number
average particle diameter of the hydrochloride particle was 35 pm.
The obtained hydrochloride slurry was in a liquid phase and
excellent in the fluidity. So, it was confirmed that when the
hydrochloride was transferred to the next step, the hydrochloride
20 did not remain in the reactor and the liquid transfer property was
excellent accordingly.
Subsequently, the hydrochloride slurry in the reactor was heated
to 160 degree centigrade and then phosgene was blown at a rate of
100 g/hr (1.0 mole/hr) from the phosgene inlet tube. The reaction
25 was carried out for 8 hours while maintaining the temperature.
After the completion of the reaction, nitrogen in the system was
purged to remove unreacted phosgene and hydrogen chloride gas. The
38
reaction solution was filtered to remove 0.7 g (dry weight) of
unreacted hydrochloride. The obtained filtrate was desolvated to
obtain 205.4 g (purity conversion yield: 98.00 mole%)
bis(isocyanatomethyl)norbornene having a purity of 98.4%
5 containing 0.1 weight % of CNi. The conversion rate of
hydrochloride was 99.69 mole %.. The results are shown in Table 1
to 3.
[00761
Example ,8
10 A reactor for obtaining hydrochloride (tank reactoi equipped
with a stirrer, a reflux condenser, a thermometer, a 'hydrogen
chloride gas inlet tube, a raw material bath, a raw material feeding
pump, a fluidic pump and a pressure regulator was used. In the
reactor for obtaining hydrochloride, a value of a diameter of the
15 stirring blade (D1) / an internal diameter of the reaction vessel
(D2) was 0.53, a value of the bath diameter (D) / the bath length
(L) was 0,73, and a volume of the reaction vessel was 4 m3, The
reactor for obtaining hydrochloride was filled with 2,000 kg of
orthodichlorobenzene which is a reaction solvent. Next, the
20 temperature in the reactor for obtaining hydrochloride was
elevated to 120 degree centigrade and the internal pressure was
regulated by 0.1 MPa higher than the atmospheric pressure.
Hydrogen chloride as started to be fed into-the reactor for
obtaining hydrochloride at a rate of 172 kg/hr from the hydrogen
25 chloride gas inlet tube, and m-xylylene diamine at a rate of 193
kg/hr (1.42 kmole/hr) and orthodichlorobenzene at a rate of 2,078
kg/hr were continuously fed from the raw material bath (total amine
39
concentrations 8.5 weight °). The hydrochloride slurry kept in
the reactor for obtaining hydrochloride for 1 hour was continuously
flowed into a relay bath equipped with a stirrer and matured for
6 hours. After maturing, the conversion rate of the raw material
5 amine was calculated by the neutralization titrimetric method and
as a result, the conversion rate was 99.83 moleo. The viscosity
of the hydrochloride slurry was measured at 120 degree centigrade
using a Brookfield LVT viscometer and as a result, it was 900 mPa • s.
So, the slurry had sufficient fluidity. Moreover, a ,particle
10 diameter of the hydrochloride was measured by using SRLD-2100, a
laser diffraction particle size analyzer, manufactured by Shimadzu
Corporation in an acetonitrile solvent and as a result; the number
average particle diameter of the hydrochloride particle was 33 pm.
The obtained hydrochloride slurry was in a liquid phase and
15 excellent in the fluidity. So, when the hydrochloride was
transferred to the next step, the hydrochloride did not remain in
the reactor and the liquid transfer property was excellent
accordingly.
Subsequently, the hydrochloride slurry transferred from the
20 relay bath was heated to 160 degree centigrade in the reactor
(phosgenation vessel) and then phosgene was blown at a rate of 1, 129
kg/hr (11..4 kmole/hr) from the phosgene inlet tube. The reaction
was carried out for 6 hours while maintaining the temperature.
After the completion of the reaction, nitrogen in the system was
25 purged to remove unreacted phosgene and hydrogen chloride gas. The
reaction solution was filtered to remove 3.6 kg (dry weight) of
unreacted hydrochloride. The obtained filtrate was desolvated to
4 0
obtain 1, 603 kg (purity conversion yield: 98.50 mole%) of m-xylene
diisocyanate having a purity of 98.3% containing 0.4 weight % of
CBi. The conversion rate of hydrochloride was 99.80 mole%. The
results are shown in Table 1 to 3.
5 [0077]
Example 9
The same reactor for obtaining hydrochloride (tank reactor) as
in Example 8 was used. The reactor for obtaining hydrochloride
was filled with 2, 000 kg of orthodichlorobenzene that is a reaction
10 solvent, and them the temperature in the reactor for obtaining
hydrochloride was elevated to 120 degree centigrade and the
internal pressure was regulated by 0.05 MPa higher than the
atmospheric pressure. Hydrogen chloride gas started to be fed at
a rate of 172 kg/hr from the hydrogen chloride gas inlet tube and
15 m-xylylene diamine at a rate of 193 kg/hr. (1.42 kmole/hr) and
orthodichlorobenzene at a rate of 2,078 kg/hr were continuously
fed from the raw material bath (total amine concentration: 8.5
weight %). The hydrochloride slurry kept in the reactor for
obtaining hydrochloride for 1 hour was continuously flowed into
20 a relay bath equipped with a stirrer and matured for 6 hours. After
maturing, the conversion rate of the raw material amine was
calcult.ed by the neutralization titrimetric method and as a result,
the conversion rate was 99.47 mole%. The viscosity of the
hydrochloride was measured at 120 degree centigrade using a
25 Brookfield LVT viscometer and as a result, it was 1, 400 mPa ° s. So,
the hydrochloride had sufficient fluidity. Moreover, a particle
diameter of the hydrochloride was measured by using SALD-2100, a
91
laser diffraction particle size analyzer, manufactured by Shimadzu
Corporation in an acetonitrile solvent and as a result, the number
average particle diameter of the hydrochloride particle was 38 pm.
The obtained hydrochloride slurry was in a liquid phase and
5 excellent in the fluidity. So, when the hydrochloride was
transferred to the next step, the hydrochloride did not remain in
the reactor and the liquid transfer property was excellent
accordingly.
Subsequently, the hydrochloride slurry transferred from the
10 relay bath was hwated to 160 degree centigrade in the reactor
(phosgenation vessel) and then phosgene was blown at a rate of 1, 129
kg/hr (11.4 kmole/hr) from the phosgene inlet tube. The reaction
was carried out for 6 hours while maintaining the temperature.
After the completion of the reaction, nitrogen in the system was
15 purged to remove unreacted phosgene and hydrogen chloride gas. The
reaction solution was filtered to remove 5.2 kg (dry weight) of
unreacted.hydrochloride. The obtained filtrate was desolvaLed to
obtain 1, 607 kg (purity conversion yield: 98.30 mole%-) of m-xylene
diisocyanate having a purity of 97.9% containing 0.5 weight %
20 CBi. The conversion rate of hydrochloride was 99.70 mole%. The
results are shown in Table 1 to 3.
[0078.]
Comparative Example 1 _
An autoclave (reactor) equipped with a reflux condenser, a
25 stirring blade, a thermometer, a hydrogen chloride gas inlet tube,
a phosgene inlet tube, a raw material bath and a raw material
feeding pump was used. In the reactor, a value of a diameter of
42
the stirring blade (Dl) / an internal diameter of the reaction
vessel (D2) was 0.7, a value of the bath diameter (D) / the bath
length (L) was 0.59, and an inner volume of the reaction vessel
was 2L. To the reactor was fed 846 g of orthodichlor.obenzene as
5 a reaction solvent, and to the raw material bath were fed 136.2
g (1.0 mole) of in-xylylene diamine and 621 g of
orthodichl_orobenzene (total amine concentration: 8.5 weight o).
Next, under the atmospheric pressure, the temperature in the
reactor was elevated to 120 degree centigrade. Thereafter,
10 hydrogen chlorid : gas started to be fed at a rate of 43, 8 g/hr from
the hydrogen chloride gas inlet tube and amine diluted with a
solvent simultaneously started to be fed at a rate of 379 g/hr from
the raw material bath by using the raw material feeding pump. The,
total amount was fed over 2 hours. Furthermore, hydrogen chloride
15 gas was fed at a rate of 20 g/hr and matured for. 1 hour. After
the completion of the reaction, the conversion rate of the raw
material amine was calculated by the neutralization titrimetric
method and as a result, the conversion rate was 97.81 mole%. The
viscosity of the hydrochloride was measured at 120 degree
20 centigrade using a Brookfield LVT viscometer and as a result, it
was 3,320 mPa°s, exhibiting a whip shape. The obtained
hydrochloride slurry was viscous and poor in the fluidity.
it was confirmed that when the hydrochloride was transferred to
the next step, the hydrochloride remained in the reactor in large
25 quantities and the liquid transfer property was bad accordingly.
Moreover, a particle diameter of the hydrochloride was measured
by using SALD-2100, a laser diffraction particle size analyzer,
43
manufactured by Shimadzu Corporation in an acetonitrile solvent
and as a result, the number average particle diameter of the
hydrochloride particle was 100 pm.
Subsequently, the hydrochloride slurry in the reactor was heated
5 to 160 degree centigrade and then phosgene was blown at a rate of
100 g/hr (1.0 mole/hr) from the phosgene inlet tube. The reaction
was carried out for 8 hours while maintaining the temperature.
After the completion of the reaction, nitrogen in the system was
purged to remove unreacted phosgene and hydrogen chloride gas. The
10 reaction solution wan filtered to remove 8.2 g (dry weight)
unreacted hydrochloride by filtering. The obtained filtrate was
desolvated to obtain 183.3 g (purity conversion yield: 93.71 mole o )
of m-xylene diisocyanate having a purity of 96,20% containing 1.1
weight % of CBi. The conversion rate of hydrochloride was 96.10
15 moleo. The results are shown in Table 1 to 3.
[0079]
Comparative Example 2,
The same reactor as in Comparative Example 1 was used. To the
reactor was fed 958 g of orthodichlorobenzene as a reaction solvent,
20 and to the raw material bath were fed 154.2 g (1.0-mole) of
bis(aminomethyl)norbornene and 702 g of orthodichlorobenzene
(totalamine concentration: 8.5 weight o). Next, under the
atmospheric pressure, the temperature in the reactor was elevated
to 100 degree centigrade. Thereafter, hydrogen chloride gas
25 started to be fed at a rate of 43.8 g/h.r from the hydr-ogen chloride
gas inlet tube and amine diluted with a solvent simultaneously
started to;be fed at a rate of 428.1 g/hr from the raw material
44
bath by using the raw material feeding pump. The total, amount was
fed over 2 hours. Furthermore, hydrogen chloride gas was fed at
a rate of 20 g/hr and matured for 1 hour. After the completion
of the reaction, the conversion rate of the raw material amine was
5 calculated by the neutralization titrimetric method and as a result,
the conversion rate was 98.10 mole%. The viscosity of the
hydrochloride was measured at 120 degree centigrade using a
Brookfield LVT viscometer and as a result, it was 5,180 mPa°s,
exhibiting a whip shape. The obtained hydrochloride slurry was
10 viscous and poor in the fluidity. So, it was confirm(,d that when
the hydrochloride was transferred to the next step, the
hydrochloride remained in the reactor in large quantities and the
liquid transfer property was bad accordingly. Moreover, a particle
diameter of the hydrochloride was measured by using SALD-2100, a
15 laser diffraction particle size analyzer, manufactured by Shimadzu
Corporation in an acetonitrile solvent and as a result, the number
average particle diameter of the hydrochloride particle was 150
Pm.
Subsequently, the hydrochloride slurry in the reactor was heated
20 to 160 degree centigrade and then phosgene was blown at a rate of
100 g/hr (1.0 mole/hr) from the phosgene inlet tube. - The reaction
was carried out for 8 hours while maintaining the temperature.
After the completion of the reaction, nitrogen in the system was
purged to remove unreacted phosgene and hydrogen chloride gas. The
25 reaction solution was filtered to remove 7.9 g (dry weight) of
unreacted hydrochloride. The obtained filtrate was desolvated to
obtain 20009 g (purity conversion yield: 93.51 mole%) of
95
bis(isocyanatomethyl)norbornene having a purity of 96,000
containing 0.9 weight % of CNi. The conversion rate of
hydrochloride was 96.52%. The results are shown in Table 1 to 3.
[0080]
5 Comparative Example 3
The same reactor as in Comparative Example 1 was used. To the
reactor was fed 883 g of orthodichlorobenzene as a reaction solvent,
and to the raw material bath were fed 142.2 g (1.0 mole) of
bis(aminomethyl)cyclohex'ane and 647.8 g of orthodichlorobenzene
10 (total amine concentration: 8.5 weight o). Next, under the
atmospheric pressure, the temperature in the reactor was elevated
to 100 degree centigrade. Thereafter, hydrogen chloride gas
started to be fed at a rate of 43.8 g/hr from the hydrogen chloride
gas inlet tube and amine diluted with a solvent simultaneously
15 started to be fed at a rate of 395 g/hr from the raw material bath
by using the raw material feeding pump. The total amount was fed
over 2 hours. Furthermore, hydrogen chloride gas.was fed at a rage
of 20 g/hr and matured for 1 hour. After the completion of the
reaction, the conversion rate of the raw material amine was
20 calculated by the neutralization titrimetric method and as a result,
the conversion rate was 97.85 mole:. The viscosity of the
hydrochloride was measured at 120 degree centigrade using a
Brookfield LVT viscometer and as a result, it was 4,100 mPa-s,
exhibiting a whip shape. The obtained hydrochloride slurry was
25 viscous and poor in the fluidity. So, it was confirmed that when
the hydrochloride was transferred to the next step, the
hydrochloride remained in the reactor in large quantities and the
46
5
liquid transfer property was bad accordingly. Moreover, a particle
diameter of the hydrochloride was measured by using-SALD-2100, a
laser diffraction particle size analyzer, manufactured by Shimadzu
Corporation in an acetonitrile solvent and as a result, the number
average particle diameter of the hydrochloride particle was 120
Subsequently, the hydrochloride slurry in the reactor was heated
to 160 degree centigrade and then phosgene was blown at a rate of
100 g/hr (1,0 mole/hr) from the phosgene inlet tube. The reaction
10 v-'as carried out for. 8 hours while maintaining the temperature.
After the completion of the reaction, nitrogen in the system was
purged to remove unreacted phosgene and hydrogen chloride gas. The
reaction solution was filtered to remove 8.8 g (dry weight) of
unreacted hydrochloride by filtering. The obtained filtrate was
15 desolvated to obtain 188.0 g (purity conversion yield: 94.09 mole%)
of bis(isocyanatomethyl)cyclohexane having a purity of 97.20%
containing 1.0 weight % of CHi. The conversion rate of
hydrochloride was 95.910. The results are shown in Table 1 to 3.
[0081]
20 Comparative Example 4
The same reactor as in Comparative Example 1 was used. To the
reactor was fed 958 g of orthodichlorobenzene as a reaction solvent,
and to the raw material bath were fed 154.2 g (1.0-mole) of
bis(aminomethyl)norbornene and 702 g of orthodichlorobenzene
25 (total amine concentration: 8.5 weight o). Next, the temperature
in the reactor was elevated to 100 degree centigrade and then the
internal pressure was regulated by 0.001 MPa higher than the
47
atmospheric pressure. Hydrogen chloride gas started to be fed at
a rate of 43.8 g/hr from the 'hydrogen chloride gas inlet tube and
amine diluted with a solvent simultaneously started to be fed at
a rate of 428.1 g/hr from the raw material bath by using the raw
5 material feeding pump. The total amount was fed over '2 hours.
Furthermore, hydrogen chloride gas was fed at a rate of 20 g/hr
and matured for 1 hour. After the completion of the reaction, the
conversion rate-of the raw material amine was calculated by the
neutralization titrimetric method and as a result, the conversion
10 rate was 98.90 iunle%. The viscosity of the hydrochloride was
measured at 120 degree centigrade using a Brookfield LVT viscometer
and as a result, it was 3,180 mPa ° s, exhibiting a whip shape. The
obtained hydrochloride slurry was viscous and poor in the fluidity.
So, it was confirmed that when the hydrochloride was transferred
15 to the next step, the hydrochloride remained in the reactor in large
quantities and the liquid transfer property was bad accordingly.
Moreover, a particle diameter of the hydrochloride was measured
by using SALD-2100, a laser diffraction particle size analyzer,
manufactured by Shimadzu Corporation in an acetonitri_le solvent
20 and as a result, the number.average particle diameter of the
hydrochloride particle was 80 pm.
Subsequently, the hydrochloride slurry in the reactor was heated
to 160 degree centigrade and then phosgene was blown at a rate of
100 g/hr (1.0 mole/hr) from the phosgene inlet tube.- The reaction
25 was carried out for 8 hours while maintaining the temperature.
After the completion of the reaction, nitrogen in the system was
purged to remove unreacted phosgene and hydrogen chloride gas. The
48
reaction solution was filtered to remove 5.9 g (dry weight) of
unreacted hydrochloride. The obtained filtrate was desolvated to
obtain,202.0 g (purity conversion yield: 94.51 mole-'O) of
bis(isocyanatomethyl)norbornene having a purity of_96.500
5 containing 0.9 weight % of CNi. The conversion rate-of
hydrochloride was 97.40%. The results are shown in Table 1 to 3.
[0082]
[Table 1]
*:"Pressure" is the internal pressure in reaction for obtaining hydrochloride.
10 [Table 2]

WE CLAIM:
1. A process for producing a hydrochloride of a linear or cyclic aliphatic amine, which
comprises reacting a linear or cyclic aliphatic amine with hydrogen chloride under a pressure
between 0.01 MPa to 0.1 MPa higher than the atmospheric pressure.
2. The process for producing a hydrochloride of a linear or cyclic aliphatic amine as set forth
in claim 1, wherein said linear or cyclic aliphatic amine is a di- or higher functional linear or
cyclic aliphatic amine.
3. The process for producing a hydrochloride of a linear or cyclic aliphatic amine as set forth
in claim 1, which comprises reacting a di- or higher functional linear or cyclic aliphatic amine
with hydrogen chloride in an organic solvent in a tank reactor.
4. The process for producing a hydrochloride of a linear or cyclic aliphatic amine as set forth
in claim 1, which comprises reacting a di- or higher functional linear or cyclic aliphatic amine
in an organic solvent with hydrogen chloride blown into the organic solvent.