U.S. patent application number 09/270017 was filed with the patent office on 2001-12-13 for process for preparing an alkylcyclohexanol alkylene oxide adduct.
Invention is credited to FUKUOKA, DAISUKE, INOUE, YOSHIHISA, MOTOYAMA, YOSHIO, OKITA, MASUMI, ONO, YASUKO, SHIMAMOTO, KENJI, WATANABE, HIROYOSHI.
Application Number | 20010051752 09/270017 |
Document ID | / |
Family ID | 27524474 |
Filed Date | 2001-12-13 |
United States Patent
Application |
20010051752 |
Kind Code |
A1 |
INOUE, YOSHIHISA ; et
al. |
December 13, 2001 |
PROCESS FOR PREPARING AN ALKYLCYCLOHEXANOL ALKYLENE OXIDE
ADDUCT
Abstract
The invention is a preparation process of alkylcyclohexanol
alkylene oxide adduct which contains almost no alkylphenol alkylene
oxide adduct 1) in the absence of a solvent, 2) in the presence of
a saturated hydrocarbon solvent, or 3) in the presence of water.
The invention can prepare alkylcyclohexanol alkylene oxide having a
200 ppm or less content of alkylphenol and alkylphenol alkylene
oxide adduct. The alkylcyclohexanol alkylene oxide adduct obtained
in the process of the invention has less ultraviolet absorption and
fluorescence due to alkylphenol alkylene oxide adduct and is thus
useful for spectrometric analysis of protein and further has
excellent properties in the field of detergent and other common
uses of surface active agents.
Inventors: |
INOUE, YOSHIHISA; (OSAKA-FU,
JP) ; WATANABE, HIROYOSHI; (OSAKA-FU, JP) ;
ONO, YASUKO; (OSAKA-FU, JP) ; OKITA, MASUMI;
(OSAKA-FU, JP) ; FUKUOKA, DAISUKE; (YAMAGUCHI-KEN,
JP) ; MOTOYAMA, YOSHIO; (HIROSHIMA-KEN, JP) ;
SHIMAMOTO, KENJI; (YAMAGUCHI-KEN, JP) |
Correspondence
Address: |
BURNS DOANE SWECKER & MATHIS L L P
POST OFFICE BOX 1404
ALEXANDRIA
VA
22313-1404
US
|
Family ID: |
27524474 |
Appl. No.: |
09/270017 |
Filed: |
March 16, 1999 |
Current U.S.
Class: |
568/606 ;
568/670 |
Current CPC
Class: |
C07C 41/20 20130101;
C07C 41/42 20130101; C07C 43/196 20130101; C07C 2601/14 20170501;
C08G 65/322 20130101; C07C 41/20 20130101; C07C 43/196 20130101;
C07C 41/42 20130101; C07C 43/196 20130101 |
Class at
Publication: |
568/606 ;
568/670 |
International
Class: |
C07C 043/00 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 23, 1998 |
JP |
HEI 10-073940 |
Apr 8, 1998 |
JP |
HEI 10-095734 |
Sep 1, 1998 |
JP |
HEI 10-247453 |
Sep 1, 1998 |
JP |
HEI 10-247454 |
Oct 15, 1998 |
JP |
HEI 10-293149 |
Claims
What is claimed is:
1. An alkylcyclohexanol alkylene oxide adduct which has a 200 ppm
or less content of alkylphenol and alkylphenol alkylene oxide
adduct and is represented by the formula (1): 22wherein R.sup.1 is
an alkyl group having 6 to 20 carbon atoms, R.sup.2 is a hydrogen
atom, methyl or ethyl group, and n is an integer of 1 or more.
2. The alkylcyclohexanol alkylene oxide adduct according to claim
1, wherein the content of alkylphenol and alkylphenol alkylene
oxide adduct is 10 ppm by weight or less.
3. A process for preparing an alkylcyclohexanol alkylene oxide
adduct represented by the formula (1): 23wherein R.sup.1 is an
alkyl group having 6 to 20 carbon atoms, R.sup.2 is a hydrogen
atom, methyl or ethyl group, and n is an integer of 1 or more,
comprising reacting alkylphenol alkylene oxide adduct represented
by the formula (2): 24wherein R.sup.1, R.sup.2 and n are the same
as above, with hydrogen in the presence of a supported catalyst of
ruthenium or rhodium in the absence of a solvent under hydrogen
pressure exceeding gauge pressure 2.0 MPa, at temperature of 80 to
150.degree. C.
4. A process for preparing an alkylcyclohexanol alkylene oxide
adduct represented by the formula (1): 25wherein R.sup.1 is an
alkyl group having 6 to 20 carbon atoms, R.sup.2 is a hydrogen
atom, methyl or ethyl group, and n is an integer of 1 or more,
comprising reacting alkylphenol alkylene oxide adduct represented
by the formula (2): 26wherein R.sup.1, R.sup.2 and n are the same
as above, with hydrogen in the presence of water by using a
supported catalyst of ruthenium, rhodium, palladium or
platinum.
5. A process for preparing an alkylcyclohexanol alkylene oxide
adduct represented by the formula (1): 27wherein R.sup.1 is an
alkyl group having 6 to 20 carbon atoms, R.sup.2 is a hydrogen
atom, methyl or ethyl group, and n is an integer of 1 or more,
comprising reacting alkylphenol alkylene oxide adduct represented
by the formula (2): 28wherein R.sup.1 , R.sup.2 and n are the same
as above, with hydrogen in a saturated hydrocarbon solvent in the
presence of a supported catalyst of ruthenium, rhodium, palladium
or platinum.
6. A process for preparing a high purity alkylcyclohexanol alkylene
oxide adduct which has a narrow addition distribution of alkylene
oxide and is represented by the formula (1): 29wherein R.sup.1 is
an alkyl group having 6 to 20 carbon atoms, R .sup.2 is a hydrogen
atom, methyl or ethyl group, and n is an integer of 1 or more,
comprising the step consisting of: 1) the first alkylene oxide
addition step for reacting one mole of alkylphenol represented by
the formula (4): 30wherein R.sup.1 is an alkyl group having 6 to 20
carbon atoms, with 0.9 to 1.2 moles of alkylene oxide in the
presence of a basic catalyst to obtain a formed product primarily
consisting of one molar alkylene oxide adduct of alkylphenol, 2) a
hydrogenation step for reacting the formed product obtained in the
first alkylene oxide addition step with hydrogen in the presence of
a hydrogenation catalyst to obtain a resulting product primarily
consisting of one molar alkylene oxide adduct of alkylcyclohexanol,
3) a distillation step for distillating the resulting product
obtained in the hydrogenation step to obtain a fraction primarily
consisting of alkylcyclohexanol alkylene oxide adduct and having a
content of 10 ppm by weight or less in the sum of alkylphenol and
alkylphenol alkylene oxide adduct, and 4) the second alkylene oxide
addition step for reacting the fraction obtained in the
distillation step and primarily consisting of one molar alkylene
oxide adduct of cyclohexanol with alkylene oxide having 2 to 4
carbon atoms in the presence of a basic catalyst.
7. A process for preparing a high purity alkylcyclohexanol alkylene
oxide adduct which has a narrow addition distribution of
alkylene-oxide and is represented by the formula (1): 31wherein
R.sup.1 is an alkyl group having 6 to 20 carbon atoms, R.sup.2 is a
hydrogen atom, methyl or ethyl group, and n is an integer of 1 or
more, comprising the step consisting of: 1) a hydrogenation step
for reacting alkylphenol represented by the formula (4): 32wherein
R.sup.1 is an alkyl group having 6 to 20 carbon atoms, with
hydrogen in the presence of a hydrogenation catalyst to obtain a
formed product primarily consisting of alkylcyclohexanol
represented by the formula (3): 33wherein R.sup.1 is the same as
above, 2) the first distillation step for distillating the formed
product obtained in the hydrogenation step to give a fraction
primarily consisting of alkylcyclohexanol and having an alkylphenol
content 10 ppm by weight or less, 3) an alkylene oxide addition
step for reacting one mole of alkylcyclohexanol obtained in the
first distillation step with 1 to 5 moles of alkylene oxide having
2 to 4 carbon atoms in the presence of an acid catalyst to give
alkylcyclohexanol alkylene oxide adduct, and 4) the second
distillation step for separating unreacted alkylcyclohexanol and
low boiling-point by product of the reaction from alkylcyclohexanol
alkylene oxide adduct obtained in the alkylene oxide addition step.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to an alkylcyclohexanol
alkylene oxide adduct, and a preparation process and uses of the
same. More particularly, the invention relates to an
alkylcyclohexanol alkylene oxide adduct which contains a trace
amount or less of alkylphenol and alkylphenol alkylene oxide
adduct, and a preparation process and uses of the same.
[0003] The alkylcyclohexanol alkylene oxide adduct of the invention
is useful in the field of surfactant.
[0004] 2. Description of the Related Art
[0005] Higher primary alcohol ethylene oxide adducts and
nonylphenol alkylene oxide adduct have been conventionally known as
nonionic surfactants. However, higher primary alcohol ethylene
oxide adducts have a higher pour point, change to solid when the
added molar numbers of ethylene oxide is increased, and become
difficult to handle.
[0006] Alkylcyclohexanol alkylene oxide adducts have also excellent
properties as a nonionic surfactant. Ethylene oxide adducts in
particular have a lower pour point, can maintain a liquid sate even
in a relatively high addition mole number of ethylene oxide, can be
handles with ease and thus have been focused attention as an
excellent surfactant.
[0007] These alkylcyclohexanol alkylene oxide adducts are
specifically useful for protein extraction from cell membrane in
the biochemical field. When analyzing the extracted protein by
ultraviolet or fluorescent spectrum, conventional alkylcyclohexanol
alkylene oxide adduct contains much amount of remained alkylphenol
and alkylphenol alkylene oxide adduct and thus the ultraviolet or
fluorescent spectrum of these compounds overlaps spectrum of
extracted protein. As a result, it has a problem of impairing
analysis accuracy, and the development of alkylcyclohexanol
alkylene oxide adduct containing a less amount of residual
alkylphenol and alkylphenol alkylene oxide adduct has been strongly
desired.
[0008] As to the process for preparing alkylcyclohexanol ethylene
oxide adducts and other alkylcyclohexanol alkylene oxide adducts
having a higher alkyl group on a side chain of a cyclohexane ring,
several processes have been known as shown below.
[0009] For example, German Laid-Open Patent 4417947 has disclosed a
process for obtaining alkylcyclohexanol by hydrogenation of
alkylphenol and successively reacting with ethylene oxide in the
presence of a basic catalyst to prepare alkylcyclohexanol ethylene
oxide adducts. However, the process leads to a relatively broad
addition distribution of ethylene oxide, increases proportion of
high molar adduct, and thus results in a solid reaction product
which is unfavorable because of difficulty in handling as a
surfactant. Further, the reaction of alkylcyclohexanol and other
secondary alcohols with ethylene oxide in the presence of a basic
catalyst has been generally known to have a very low reaction rate.
For example, it has been described in H. Horiguchi ("New
Surfactants", page 626, published by Sankyo Shuppan Co. (1975) that
ethylene oxide generally reacts very quickly with primary alcohol
whereas slowly with secondary alcohol in the presence of a basic
catalyst. Consequently, in the preparation of an alkylcyclohexanol
ethylene oxide adduct by reaction of alkylcyclohexanol with
ethylene oxide in the presence of a basic catalyst, a small amount
of alkylcyclohexanol ethylene oxide adduct (primary alcohol) formed
in the initial stage of the reaction preferentially reacts with
ethylene oxide. As a result, unreacted alkylcyclohexanol remains in
an extremely large quantity.
[0010] H. Stache et al. have obtained one molar ethylene oxide
adduct of isooctylcyclohexanol by hydrogenation of one molar
ethylene oxide adduct of isooctylphenol and have successively
reacted the product with ethylene oxide to obtain
isooctylcyclohexanol ethylene oxide adduct (Tr.-Mezhdunar. Kongr.
Poverkhn.-Akt Veshchestvam 7th, Vol. 1(1977), 378-391). However, as
to the hydrogenation reaction of one molar ethylene oxide adduct of
isooctylphenol, no description can be found at all on the species
of the catalyst used and the reaction conditions carried out.
Further, no specific purification has been carried out after the
hydrogenation reaction. Quite no description has been found on the
amount of isooctylphenol ethylene oxide adduct remained in the
isooctylcyclohexanol ethylene oxide adduct thus obtained.
[0011] Further, German Patent No. 626965 has also obtained
alkylcyclohexanol alkylene oxide adduct by the same process as that
of H. Stache et al. The process also did not carry out specific
purification of hydrogenation product. No description is found at
all on the amount of alkylphenol alkylene oxide adduct remained in
the resulting alkylcyclohexanol alkylene oxide adduct.
[0012] Further, George E. Tillar et al. have obtained
octylcyclohexanol ethylene oxide adduct by hydrogenation of
octylphenol ethylene oxide adduct (Trade Mark: Triton X-100) in an
ethanol solvent in the presence of a rhodium carbon catalyst
(Analytical Biochemistry 141, 262-266 (1984)). The cited example
has suggested that such a process remains 600 ppm of octylphenol
ethylene oxide adduct even though the reaction time of
hydrogenation is extended.
[0013] As mentioned above, several suggestions have been found on
the preparation process of alkylcyclohexanol alkylene oxide
adducts. However, in the present state of the art, almost no
information has been obtained on the preparation process of
alkylcyclohexanol alkylene oxide adducts which contain a reduced
amount of residual alkylphenol and alkylphenol alkylene oxide
adduct, have higher purity and narrow addition distribution of
alkylene oxide.
[0014] Therefore, the object of the invention is to provide a high
purity alkylcyclohexanol alkylene oxide adduct which has a narrow
addition distribution of alkylene oxide and contains a trace amount
or less of alkylphenol and alkylphenol alkylene oxide adduct, a
simple and efficient preparation process of alkylcyclohexanol
alkylene oxide adduct, and uses of the same.
SUMMARY OF THE INVENTION
[0015] As a result of an intensive investigation in order to solve
the above subjects, the present inventors have found a process for
efficiently preparing an alkylcyclohexanol alkylene oxide adduct
which has a narrow addition distribution of alkylene oxide,
contains a trace amount or less of impurities including alkylphenol
and alkylphenol alkylene oxide adduct, and is represented by the
formula (1). Thus the present invention has been completed. 1
[0016] That is, the first aspect of the invention is an
alkylcyclohexanol alkylene oxide adduct which contains 200 ppm or
less of alkylphenol and alkylphenol alkylene oxide adduct and is
represented by the formula (1): 2
[0017] wherein R.sup.1 is an alkyl group having 6 to 20 carbon
atoms, R.sup.2 is a hydrogen atom, methyl or ethyl group, and n is
an integer of 1 or more.
[0018] The second aspect of the invention is a preparation process
of an alkylcyclohexanol alkylene oxide adduct which contains a
trace amount or less of alkylphenol alkylene oxide adduct and is
represented by the formula (1), comprising hydrogenating
alkylphenol alkylene oxide adduct represented by the formula (2):
3
[0019] wherein R.sup.1 is an alkyl group having 6 to 20 carbon
atoms, R.sup.2 is a hydrogen atom, methyl or ethyl group, and n is
an integer of 1 or more, 1) in the absence of a solvent, 2) in the
presence of a saturated hydrocarbon solvent, or 3) in the presence
of water.
[0020] The third aspect of the invention is a preparation process
of a high purity alkylcyclohexanol alkylene oxide adduct which has
a narrow addition distribution of alkylene oxide and is represented
by the formula (1), comprising adding one mole of alkylene oxide
having 2 to 4 carbon atoms to alkylphenol represented by the
formula (4): 4
[0021] wherein R.sup.1 is an alkyl group having 6 to 20 carbon
atoms, thereafter hydrogenating and distillating to obtain alkylene
oxide one molar adduct of alkylcyclohexanol which contains a trace
amount of alkylphenol and alkylphenol alkylene oxide adduct, and
successively adding alkylene oxide in the presence of a basic
catalyst.
[0022] The fourth aspect of the invention is a preparation process
of a high purity alkylcyclohexanol alkylene oxide adduct which has
a narrow addition distribution of alkylene oxide and is represented
by the formula (1), comprising hydrogenating alkylphenol
represented by the formula (4), thereafter distillating to obtain
alkylcyclohexanol which contains a trace amount of alkylphenol, and
successively adding alkylene oxide having 2 to 4 carbon atoms in
the presence of an acid catalyst, and further distillating the
reaction product.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0023] Alkylcyclohexanol alkylene oxide of the present invention is
represented by the formula (1): 5
[0024] wherein R.sup.1 is an alkyl group having 6 to 20 carbon
atoms, R.sup.2 is a hydrogen atom, methyl or ethyl group, and n is
an integer of 1 or more, and corresponds to the nuclear
hydrogenation product of alkylphenol alkylene oxide represented by
the formula (2): 6
[0025] wherein R.sup.1 is an alkyl group having 6 to 20 carbon
atoms, R.sup.2 is a hydrogen atom, methyl or ethyl group, and n is
an integer of 1 or more.
[0026] On the formula (2) of alkylphenol alkylene oxide adduct in
the invention, R.sup.1 is an alkyl group having 6 to 20 carbon
atoms. No particular restriction is imposed upon the structure of
R.sup.1. R.sup.1 can be a straight chain structure or branched
structure or any isomeric structure of an alkyl group. The attached
position of R.sup.1 can be any of the 2, 3 or 4 position to the
alkoxylate group (--O(CH.sub.2CHR.sup.2O- ).sub.n H group) on the
benzene ring. Further, R.sup.2in the oxyalkylene units
(--CH.sub.2CHR.sup.2O--units) is a hydrogen atom, methyl or ethyl
group. Oxyalkylene units are specifically oxyethylene units
(--CH.sub.2CH.sub.2O--units), oxypropylene units
(--CH.sub.2CH(CH.sub.3)O- -- units) or oxybutylene units
(--CH.sub.2CH(CH.sub.2CH.sub.3)O-- units). n is an integer of 1 or
more. When n is 2 or more, recurring units can have only one of the
oxyethylene units, oxypropylene units or oxybutylene units, or can
have 2 or more oxyalkylene units. When 2 or more species of
oxyalkylene units are present, the units can be in a random
addition or block addition. No particular limitation is imposed
upon the range of n. However, n is usually in the range of 1 to 50.
When n is 1, the compound can be specifically one molar adduct of
alkylene oxide or one molar alkylene oxide adduct.
[0027] Alkylphenol alkylene oxide adduct represented by the formula
(2) includes structural isomers of R.sup.1 and an alkoxylate group,
and compounds which differ in the species and numbers and numbers
of the oxyalkylene group. These compounds can be used singly and
are usually used as a mixture. Further, these compounds can be a
mixture of two species or more alkylphenol alkylene oxide adducts
which are represented by the formula (2) and differ in the carbon
numbers of the alkyl group R.sup.1.
[0028] Specific alkylphenol alkylene oxide adducts represented by
the formula (2) include, for example, ethylene oxide adduct of
hexylphenol, heptylphenol, octylphenol, nonylphenol, decylphenol,
undecylphenol, tridecylphenol, tetradecylphenol, pentadecylphenol,
hexadecylphenol, heptadecylphenol. octadecylphenol,
nonadecylphenol, eicosylphenol and other alkylphenols; for example,
propylene oxide adduct of hexylphenol, heptylphenol, octyphenol,
nonylphenol, decylphenol, undecylphenol, tridecylphenol,
tetradecylphenol, pentadecylphenol, hexadecylphenol,
heptadecylphenol, octadecylphenol, nonadecylphenol eicosylphenol
and other alkylphenols; for example, butyleneoxide adduct of
hexylphenol, heptylphenol, octylphenol, nonylphenol, decylphenol,
undecylphenol, tridecylphenol, tetradecylaphenol, pentadecylphenol,
hexadecylphenol, heptadecylphenol, octadecylphenol,
nonadecylphenol, eicosylphenol and other alkylphenols; for example,
octylphenol(ethylene oxide/propylene oxide) random copolymer,
octylphenol(ethylene oxide/butylene oxide) random copolymer,
octylphenol(propylene oxide/butylene oxide) random copolymer,
nonylphenol(ethylene oxide/propylene oxide) random copolymer
nonylphenol(ethylene oxide/butylene oxide) random copolymer,
nonylphenol(propylene oxide/butylene oxide) random copolymer and
other alkylphenol alkylene oxide random copolymers; and for
example, octylphenol(ethylene oxide/propylene oxide) block
copolymer, octylphenol(ethylene oxide/butylene oxide) block
copolymer, octylphenol(propylene oxide/butylene oxide) block
copolymer, nonylphenol(ethylene oxide/propylene oxide) block
copolymer, nonylphenol(ethylene oxide/butylene oxide) block
copolymer, nonylphenol(propylene oxide/butylene oxide) block
copolymer and other alkylphenol alkylene oxide block
copolymers.
[0029] Further, alkylcyclohexanol of the invention is represented
by the formula (3): 7
[0030] wherein R.sup.1 is an alkyl group having 6 to 20 carbon
atoms, and corresponds to the hydrogenation product of alkylphenol
represented by the formula (4): 8
[0031] wherein R.sup.1 is an alkyl group having 6 to 20 carbon
atoms.
[0032] One the formula (4) of alkylphenol in the invention, R.sup.1
is an alkyl group having 6 to 20 carbon atoms. No particular
restriction is imposed upon the structure of R.sup.1. R.sup.1 can
be a straight chain structure or branched structure or any isomeric
structure of an alkyl group. The attached position of R.sup.1 can
be any of the 2, 3 or 4 position to the hydroxyl group (--OH group)
on the benzene ring. Alkylphenol represented by the formula (3) has
structural isomers of R.sup.1 and hydroxyl group. These isomers can
be usually used as a mixture and can also be used singly. Further,
a mixture of alkylphenols which differ in the number of carbon atom
on the alkyl group R.sup.1 can also be used.
[0033] Representative alkylphenols represented by the formula (3)
include, for example, hexylphenol, heptylphenol, octylphenol
nonylphenol, decylphenol, undecylphenol, tridecylphenol,
tetradecylphenol, pentadecylphenol, hexadecylphenol,
heptadecyplphenol octadecylphenol, nonadecylphenol, eicosylphenol,
and other alkylphenols.
[0034] Further, alkylene oxides having 2 to 4 carbon atoms in the
invention specifically include ethylene oxide, propylene oxide and
butylene oxide. These alkylene oxides can be used singly or as a
mixture. When two or more alkylene oxides are used as a mixture
both random addition and block addition can be carried out.
[0035] The alkylcyclohexanol alkylene oxide adduct which has a
narrow addition distribution of alkylene oxide, and contains a
trace amount or less of alkylphenol and alkylphenol alkylene oxide
adduct can be prepared by the preparation processes (A) to (E)
below.
Preparation Process (A)
[0036] The alkylcyclohexanol alkylene oxide adduct of the invention
represented by the formula (1); 9
[0037] wherein R.sup.1 is an alkyl group having 6 to 20 carbon
atoms, R.sup.2 is a hydrogen atom, methyl or ethyl group, and n is
an integer of 1 or more, is prepared by reacting alkylphenol
alkylene oxide adduct represented by the formula (2): 10
[0038] wherein R.sup.1, R.sup.2 and n are the same as above, with
hydrogen under hydrogen gauge pressure exceeding 2.0 MPa, at
temperature of 50 to 150.degree. C., in the absence of a solvent,
and in the presence of a supported catalyst of ruthenium or
rhodium.
[0039] The process is characterized by reacting alkylcyclohexanol
alkylene oxide adduct with hydrogen in the absence of a solvent.
The reaction in the absence of a solvent can provide the desired
alkylcyclohexanol alkylene oxide adduct in a high degree of
conversion merely by removing the catalyst without solvent recovery
procedure.
[0040] The process reacts alkylphenol alkylene oxide adduct with
hydrogen in the presence of a supported catalyst of ruthenium or
rhodium. Representative supported catalysts of ruthenium or rhodium
include, for example, ruthenium carbon, rhodium carbon and other
carbon supported catalysts of these metals; ruthenium alumina,
rhodium alumina and other alumina supported catalysts of these
metals; and ruthenium titania and other titania supported catalyst
of these metals. No particular limitation is imposed upon the
supported amount of these metals. The amount is usually in the
range of 0.01 to 20% by weight. These catalysts can be crushed or
powdered or molded into pellet or sphere. In these catalysts,
ruthenium or rhodium catalyst supported on carbon or alumina is
preferred in view of excellent activity and selectivity.
[0041] In the process, the reaction is carried out at temperature
of 80 to 150.degree. C. under hydrogen gauge pressure exceeding 2.0
MPa in order to prepare alkylcyclohexanol alkylene oxide adduct in
good efficiency and high selectivity. When the hydrogen gauge
pressure is 2.0 MPa or less, the hydrogenation reaction is very
slow. On the other hand, the gauge pressure exceeding 15 Mpa
requires very high pressure resistance to the reactor and thus the
upper limit of the hydrogen pressure is preferably gauge pressure
of 15 Mpa. Further, the reaction temperature less than 80.degree.
C. leads to very low reaction rate of hydrogenation reaction. On
the other hand, the reaction temperature exceeding 150.degree. C.
tends to cause side reactions such as cleavage of ether bonds due
to a hydrogenation decomposition reaction, and unfavorably lowers
selectivity of alkylcyclohexanol alkylene oxide adduct. More
preferred hydrogen pressure and reaction temperature differ
depending upon species and amount of the catalyst used and numbers
of oxyalkylene units in the alkylcyclohexanol alkylene oxide adduct
and are suitably selected in the specified ranges of hydrogen
pressure and reaction temperature.
[0042] No particular restriction is imposed upon the procedures for
carrying out the reaction. Batch procedure, semi-batch procedure
and continuous procedure can be carried out. No particular
limitation is put upon the amount of the catalyst in the batch and
semi-batch procedures. The amount of the catalyst is usually in the
range of 0.5 to 50% by weight for the alkylphenol alkylene oxide
adduct used as a raw material. The reaction time is usually in the
range of 0.5 to 50 hours. When the reaction is carried out by the
continuous procedure, reaction conditions differ depending upon the
species of the catalyst and other factors. LHSV is usually in the
range of 0.01 to 50 hr.sup.-1.
Preparation Process (B)
[0043] Alkylcyclohexanol alkylene oxide adduct of the invention
represented by the formula (1): 11
[0044] wherein R.sup.1 is an alkyl group having 6 to 20 carbon
atoms, R.sup.2 is a hydrogen atom, methyl or ethyl group, and n is
an integer of 1 or more, can also be prepared by reacting
alkylphenol alkylene oxide adduct represented by the formula (2):
12
[0045] wherein R.sup.1, R.sup.2 and n are the same as above, with
hydrogen in the presence of water by use of a supported catalyst of
ruthenium, rhodium, palladium or platinum.
[0046] Alkylcyclohexanol alkylene oxide adduct of the invention is
characterized by reacting alkylphenol alkylene oxide adduct with
hydrogen in the presence of water by use of a supported catalyst of
ruthenium, rhodium, palladium or platinum.
[0047] The catalyst used for the process can be a supported
catalyst of ruthenium, rhodium, palladium or platinum.
Representative supported catalysts of ruthenium, rhodium, palladium
and platinum include, for example, ruthenium carbon, rhodium
carbon, palladium carbon, platinum carbon and other carbon
supported catalysts of these metals; ruthenium alumina, rhodium
alumina and other alumina supported catalysts of these metals;
palladium silica alumina, platinum silica alumina and other silica
alumina supported catalysts of these metals; palladium silica
magnesia, and other silica magnesia supported catalyst of these
metals; palladium zeolite and other zeolite supported catalyst of
these metals; palladium barium sulfate and other barium sulfate
supported catalysts of these metals; and ruthenium titania and
other titania supported catalysts of these metals. Further,
catalysts supported by two species or more metals at the same time
in an arbitrary proportion can also be used. Exemplary catalysts of
such type include, for example, ruthenium-rhodium carbon,
palladium-platinum carbon and other carbon supported catalysts of
these metals; and ruthenium-rhodium alumina, palladium-platinum
alumina and other alumina supported catalysts of these metals.
These supported catalysts can be used singly or as a mixture of any
proportion. No particular limitation is put upon the supported
amount of these metals. The supported amount is usually in the
range of 0.01 to 20% by weight. These catalysts can be powdered,
crushed or molded into pellet or globe. Further, water containing
catalyst which can be commonly obtained with ease in the market can
preferably be used.
[0048] In these supported catalysts, carbon or alumina supported
catalyst of ruthenium is preferably used in view of excellent
activity and selectivity.
[0049] The process carries out reaction in the presence of water.
The water charged to the reaction system can be previously
dissolved, dispersed or impregnated into the raw material such as
alkylphenol alkylene oxide adduct, catalyst or solvent, when used,
or can also be independently charged to the reaction system.
[0050] No particular limitation is imposed upon the amount of
water. The amount of water is usually in the range of 1 to 50% by
weight, preferably 1 to 40% by weight for the amount of alkylphenol
alkylene oxide adduct used for the raw material.
[0051] The process can be carried out in the presence or absence of
a solvent. Any type of a solvent can be used so long as the
solvent, when used, can dissolve or disperse the raw material
alkylphenol alkylene oxide adduct and the solvent itself cannot be
hydrogenated.
[0052] Exemplary solvents which can be used include, for example,
methanol, ethanol, isopropyl alcohol, t-butylalcohol, cyclohexanol,
4-methylcyclohexanol, 1,2-ethanediol, glycerol and ether alcohol
compounds; pentane, hexane, heptane, 2-methylpentane and other
aliphatic hydrocarbon compounds; cyclopentane, cyclohexne,
methylcyclohexane, ethylcyclohexane, bicyclohexyl, decalin and
other aliphatic cyclic hydrocarbon compounds; dichloromethane,
carbon tetrachloride, butyl chloride, propyl bromide,
chlorocyclohexanol and other halogenated hydrocarbon compounds;
diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran
1,2-dimethoxyethane and other ether compounds; acetone, methyl
ethyl ketone, diisobutyl ketone, acetylacetone and other ketone
compounds; methyl formate, ethyl acetate, ethylene carbonate and
other ester compounds; and nitromethane, acetonitrile and other
nitrogen compounds. These solvents can be used singly or as a
mixture.
[0053] Specifically, when alcohol compounds such as ethanol are
used as a solvent, the hydrogenating reaction in the absence of
water has a very low rate of reaction and remains a large amount of
unreacted alkylphenol alkylene oxide adduct. However, it is
surprising that, when the hydrogenation reaction is carried out in
alcohol compounds in the presence of water, the reaction rate is
extremely accelerated and almost no unreacted alkylphenol alkylene
oxide adduct is remained after the hydrogenation reaction.
[0054] The reaction is usually carried out at reaction temperature
of 30 to 200.degree. C., preferably 50 to 150.degree. C. under the
hydrogen gauge pressure of 0 to 20 MPa, preferably 0.5 to 15 MPa.
More preferred hydrogen pressure and reaction temperature differ
depending upon the species and amount of the catalyst used and the
numbers of oxyalkylene units in the alkylphenol alkylene oxide
adduct, and are suitably selected.
[0055] No particular restriction is put upon the procedures for
carrying out the reaction. Batch procedure, semi-batch procedure
and continuous procedure can be carried out. No particular
limitation is imposed upon the amount of the catalyst in the batch
and semi-batch procedures. The amount of the catalyst is usually in
the range of 0.5 to 50% by weight for the alkylphenol alkylene
oxide adduct used as a raw material. The reaction time is usually
in the range of 0.5 to 50 hours. When the reaction is carried out
by the continuous procedure, reaction conditions differ depending
upon the species of the catalyst and other factors. LHSV is usually
in the range of 0.01 to 50 hr.sup.-1.
Preparation Process (C)
[0056] Alkylcyclohexanol alkylene oxide adduct of the invention
represented by the formula (1): 13
[0057] wherein R.sup.1 is an alkyl group having 6 to 20 carbon
atoms, R.sup.2 is a hydrogen atom, methyl or ethyl group, and n is
an integer of 1 or more, can also be prepared by reacting
alkylphenol alkylene oxide adduct represented by the formula (2):
14
[0058] wherein R.sup.1, R.sup.2 and n are the same as above, with
hydrogen in the saturated hydrocarbon solvent in the presence of a
hydrogenation catalyst.
[0059] The hydrogenation catalyst used in the process can be the
same supported catalyst of ruthenium, rhodium, palladium or
platinum which can be used in the preparation process (B), as
mentioned above. These supported catalysts can be used singly or as
a mixture of any proportion. No particular limitation is put upon
the supported amount of these metals. The supported amount is
usually in the range of 0.01 to 20% by weight. These catalysts can
be powdered, crushed or molded into pellet or globe. Further, water
containing catalyst which can be commonly obtained with ease in the
market can preferably be used.
[0060] In these catalysts, the ruthenium catalyst supported on
carbon or alumina is preferred in view of excellent catalytic
activity and selectivity.
[0061] The process is characterized by carrying out in the presence
of a saturated hydrocarbon solvent. No particular restriction is
imposed upon the structure of the saturated hydrocarbon solvent
used. The solvents having straight chain structure, branched
structure and cyclic structure can be used. Any type of solvent can
be used so long as the solvent can dissolve or disperse the raw
material alkylphenol alkylene oxide adduct of the formula (2) and
the product alkylcyclohexanol alkylene oxide adduct of the formula
(1) and the solvent itself cannot be hydrogenated. Representative
solvents which can be used in the process include, for example,
n-pentane, n-hexane, n-heptane, n-octane, n-dodecane and other
straight chain saturated hydrocarbons; 2-methylbutane,
2-methylpentane, 2-methylhexane, 2-methylheptane, 3-methylpentane,
3- ethylpentane, 3-methylhexane, 3-ethylhexane, 3-methylheptane,
2,2-dimethylpropane, 2,2-dimethylbutane, 2,2-dimethylhexane,
2,3-dimethylbutane, 3-methyl-3-ethylpentane, 2,2,3-trimethylbutane
and other branched saturated hydrocarbons; and cyclopentane,
cyclohexane, decalin, methylcyclopentane, methylcyclohexane,
p-menthane and other cyclic saturated hydrocarbons. These solvents
can be used singly or as a mixture. In these saturated hydrocarbon
solvents, cyclic saturated hydrocarbon is particularly preferred in
view of reactivity and selectivity. No particular limitation is
imposed upon the amount of the saturated hydrocarbon solvent. The
amount of the solvent used is commonly in the range of providing a
concentration of 5 to 80% by weight, preferably 20 to 60% by weight
for the raw material alkylphenol alkylene oxide adduct.
[0062] In proceeding the reaction, presence of water is preferred
because reaction rate is enhanced without giving an adverse effect
on the selectivity of the reaction. Water, when used, can be
previously dissolved, dispersed or impregnated in the raw material
alkylphenol alkylene oxide adduct of the formula (2), catalyst or
solvent, or can be independently charged to the reaction system. No
particular limitation is imposed on the amount of water. The amount
of water is usually in the range of 0.1 to 50% by weight,
preferably 1 to 40% by weight for the raw material alkylphenol
alkylene oxide adduct of the formula (2).
[0063] Hydrogen pressure and reaction temperature of the process
are the same as those used in the preparation process (B). More
preferred hydrogen pressure and reaction temperature differ
depending upon the species and amount of the catalyst used and
numbers of oxyethylene units in the alkylphenol alkylene oxide
adduct of the formula (2), and thus these reaction conditions are
arbitrarily selected.
[0064] No particular restriction is imposed upon the procedure of
the reaction. Batch procedure, semi-batch procedure and continuous
procedure can be carried out. When the reaction is carried out by
batch or semi-batch procedures, no particular limitation is imposed
upon the amount of catalyst. The amount is usually in the range of
0.5 to 50% by weight for the raw material alkylphenol alkylene
oxide adduct of the formula (2). The reaction time is commonly in
the range of 0.5 to 50 hours. When the reaction is carried out by
continuous procedures, the reaction conditions differ depending
upon the species of the catalyst. LHSV is usually in the range of
0.01 to 50 hr.sup.-1.
[0065] Preparation processes (A), (B) and (C) can provide
alkylcyclohexanol alkylene oxide adduct containing 200 ppm or less
of unreacted alkylphenol alkylene oxide adduct.
[0066] Alkylcyclohexanol alkylene oxide adduct having further
decreased content of alkylphenol alkylene oxide adduct and
alkylphenol can be obtained by below described preparation
processes (D) and (E) which have an added step of distillation.
Preparation Process (D)
[0067] In the process, the preparation of high purity
alkylcyclohexanol alkylene oxide adduct represented by the formula
(1); 15
[0068] wherein R.sup.1 is an alkyl group having 6 to 20 carbon
atoms, R.sup.2 is a hydrogen atom, methyl or ethyl group, and n is
an integer of 1 or more, is characterized by consisting of below
described four steps;
[0069] 1) the first alkylene oxide addition step for reacting 1
mole of alkylphenol represented formula (4); 16
[0070] wherein R.sup.1 is an alkyl group having 6 to 20 carbon
atoms, with 0.9 to 1.2 moles of alkylene oxide having 2 to 4 carbon
atoms in the presence of a basic catalyst to obtain a formed
product primarily consisting of one molar alkylene oxide adduct of
alkylphenol,
[0071] 2) the hydrogenation step for reacting the formed product of
the first alkylene oxide addition step with hydrogen in the
presence of a hydrogenation catalyst to obtain a formed product
primarily consisting of one molar alkylene oxide adduct of
alkylcyclohexanol,
[0072] 3) the distillation step for distillating the formed product
of the hydrogenation step to obtain a fraction primarily consisting
of one molar alkylene oxide adduct of alkylcyclohexanol and
containing 10 ppm by weight or less in the sum of alkylphenol and
alkylphenol alkylene oxide adduct, and
[0073] 4) the second alkylene oxide addition step for reacting the
fraction obtained in the distillation step and primarily consisting
of one molar alkylene oxide adduct of alkylcyclohexanol with
alkylene oxide in the presence of a basic catalyst.
[0074] The alkylene oxide having 2 to 4 carbon atoms which can be
used in the first and second alkylene oxide addition steps
includes, for example, ethylene oxide, propylene oxide and butylene
oxide. Alkylene oxide can be used singly or as a mixture. When
alkylene oxide is used as a mixture, both random and block addition
can be carried out.
[0075] Exemplary, basic catalysts which are used in the first
alkylene oxide addition step include, for example, sodium
hydroxide, potassium hydroxide, cesium hydroxide and other alkali
metal hydroxides; sodium ethoxide, lithium ethoxide, potassium
phenoxide and other alkali metal alkoxides or phenoxides; calcium
hydroxide, barium hydroxide, strontium hydroxide and other alkali
earth metal hydroxides; calcium methoxide, calcium phenoxide and
other alkali earth metal alcoxides or phenoxides; magnessium oxide,
barium oxide and other alkali earth metal oxides. In these basic
catalysts, alkali metal hydroxides are preferably used. Amount of
the catalyst differs depending upon the species of the catalyst and
reaction temperature and reaction temperature and is usually in the
range of 10 to 5,000 ppm by weight for the raw material
alkylphenol.
[0076] The basic catalyst which is soluble in the reaction product
can be converted to a soluble salt of organic acid by neutralizing
with an organic acid after the reaction, or can be neutralized with
a mineral acid such as sulfuric acid and the precipitated mineral
acid salt is removed by filtration. Alternatively, the reaction
mass can be used as intact to the next hydrogenation step without
neutralization. Further, the catalyst which is insoluble in the
reaction product can be usually removed by filtration and
successively the next hydrogenation step is carried out.
[0077] The first alkylene oxide addition step reacts 1 mole of
alkylphenol with 0.9 to 1.2 moles of alkylene oxide having 2 to 4
carbon atoms and primarily prepares one molar alkylene oxide adduct
of alkylphenol. When addition amount of alkylene oxide is less than
the above range, an increased amount of unreacted alkylphenol is
remained after the reaction. On the other hand, the addition amount
of alkylene oxide more than the above range increases formation of
compounds having two moles or more alkylene oxide addition to
alkylphenol.
[0078] The object of the first alkylene oxide addition step is to
prepare one molar ethylene oxide adduct of alkylphenol which can
maintain primary alcohol even after the hydrogenation step and can
be readily purified by distillation. Thus, it is unfavorable to
remain much amount of alkylphenol which converts to secondary
alcohol after the hydrogenation step, or to form much amount of two
or more molar alkylene oxide adduct of alkylphenol which has a high
boiling point and is difficult to purify by distillation.
[0079] The reaction temperature in the first alkylene oxide
addition step is usually in the range of 60 to 230.degree. C.,
preferably 120 to 200.degree. C. The reaction time is usually in
the range of 0.1 to 30 hours, preferably 0.3 to 20 hours. The gauge
pressure in the reaction is usually in the range of 0 to 2 MPa,
preferably 0.1 to 0.7 MPa. Any of the batch procedure, semi-batch
procedure and continuous procedure can be carried out.
[0080] The hydrogenation catalysts which are used in the
hydrogenation step of the process can be any species of the
catalyst so long as the catalysts is capable of hydrogenating the
aromatic ring of the formed product which is obtained in the first
alkylene oxide addition step and primarily consisting of one molar
alkylene oxide adduct of alkylphenol, with hydrogen to obtain a
cyclohexane ring. Representative such catalysts include, for
example, supported catalysts of ruthenium, rhodium, palladium and
platinum, complex catalysts of these metals, and Raney nickel and
Raney cobalt. Specific supported catalysts of ruthenium, rhodium
palladium, and platinum include, for example, ruthenium carbon,
rhodium carbon, palladium carbon, platinum carbon and other carbon
supported catalysts of metals, ruthenium alumina, rhodium alumina
and other alumina supported catalysts of metals; palladium silica
alumina and other silica alumina supported catalysts of metals;
palladium zeolite and other zeolite supported catalysts of metals;
palladium barium sulfate and other barium sulfate supported
catalysts of metals; and ruthenium titania and other titania
supported catalysts of metals. No particular limitation is imposed
upon the supported amount of metals. The amount is usually in the
range of 0.01 to 20% by weight. These catalysts can be powdered,
crushed or molded into pellet or sphere.
[0081] Representative complex catalysts of ruthenium, rhodium,
palladium and platinum include, for example, ruthenium chloride,
palladium bromide and other halogenides of metal; palladium
acetate, rhodium propionate and other carboxylates of metal;
palladium acetylacetonate, ruthenium acetylacetonate and other
acetylacetonate complexes of metal; and
dichlorotris-(triphenylphosphine) ruthenium,
chlorotris(triphenylphosphin- e) rhodium,
dichlorobis(triphenylphosphine) palladium,
dichlorobis(triphenylphosphine) platinum and other phosphine
complex of these metals. These complex catalysts can be used singly
or as a mixture.
[0082] In these catalysts, carbon or alumina supported catalysts of
ruthenium or rhodium and Raney nickel are preferred in view of
excellent catalytic activity and selectivity.
[0083] In the hydrogenation step of the process, hydrogen pressure
is usually in the range of gauge pressure of 0 to 20 MPa,
preferably 0.5 to 15 MPa in the gauge pressure. Reaction
temperature is usually in the range of 30 to 200.degree. C.,
preferably 50 to 150.degree. C.
[0084] The reaction can be carried out in the presence or absence
of a solvent. Any solvent can be used for the process so long as
the solvent can dissolve or disperse the raw material, one molar
alkylene oxide adduct of alkylphenol and one molar alkylene oxide
adduct of corresponding alkylcyclohexanol which is a formed product
and the solvent itself does not react with hydrogen in the above
reaction conditions. The solvents used in the preparation process
(B) can be used as intact for the process.
[0085] In these solvents, aliphatic hydrocarbon compounds and
aliphatic cyclic hydrocarbon compounds are preferably used, and
aliphatic cyclic hydrocarbon compounds are preferred in particular.
No particular limitation is imposed upon the amount of solvents.
The amount is usually in the range of providing a concentration of
usually 5 to 80% by weight, preferably 20 to 60% by weight for the
raw material, one molar alkylene oxide adduct of alkylphenol.
[0086] When one molar alkylene oxide adduct of alkylphenol is
reacted with hydrogen in the presence of a solvent, the reaction
rate is sometimes low and preferable yield cannot be obtained in
the reaction. Particularly, ethanol and other alcohol solvents
require a long reaction time and lead to inferior productivity. In
such a case, the reaction can be preferably carried out in the
presence of water because the reaction rate is preferably
accelerated without giving an adverse effect on the selectivity.
Water, when used, can be previously dissolved, dispersed or
impregnated into the raw material, one molar alkylene oxide adduct
of alkylphenol, catalyst or solvent, or can be independently
charged to the reaction system. No particular limitation is imposed
upon the amount of water. The amount is usually in the range of 0.1
to 50% by weight, preferably 1 to 40% by weight for the raw
material, one molar alkylene oxide adduct of alkylphenol.
[0087] No particular restriction is put upon the procedures for
carrying out the reaction. Any of batch procedure, semi-batch
procedure and continuous procedure can be carried out. No
particular limitation is imposed upon the amount of catalyst when
the reaction is carried out by batch or semi-batch procedure. The
amount of catalyst is usually in the range of 0.5 to 50% by weight
for the raw material one molar alkylene oxide adduct of
alkylphenol. The reaction time is usually in the range of 0.5 to 50
hours. When the reaction is carried out by the continuous
procedure, reaction conditions differ depending upon the species of
the catalyst used and is usually in the range of 0.01 to 50
hr.sup.-1 in LHSV. After finishing the reaction, the formed product
which is primarily consisting of one molar alkylene oxide adduct of
alkylcyclohexanol can be obtained by removing the catalyst with a
common solid-liquid separation method. When the solvent is used,
the formed product desired can be obtained by separating the
catalyst from the reaction mass and distilling off the solvent from
the filtrate.
[0088] In the process, the formed product obtained in the
hydrogenation step is distilled to provide a fraction consisting
primary of one molar alkylene oxide adduct of alkylcyclohexanol and
containing 10 ppm by weight or less in the sum of unreacted
alkylphenol and alkylphenol alkylene oxide adduct. The term
alkylphenol alkylene oxide adduct refers to any compounds obtained
by adding one molar or more alkylene oxide to alkylphenol. The
object of the distillation step is to fractionate alkylphenol and
alkylphenol alkylene oxide adduct and to obtain a fraction which is
almost free from these compounds and primarily consists of one
molar alkylene oxide adduct of alkylcyclohexanol. The fraction can
contain a small amount of alkylcyclohexanol and two molar or more
alkylene oxide adduct of alkylcyclohexanol. The distillation can be
carried out by batch or continuous procedures.
[0089] In the second alkylene oxide addition step, a fraction of
distillation step consisting primarily of one molar alkylene oxide
adduct of alkylcyclohexanol is reacted with alkylene oxide having 2
to 4 carbon atoms in the presence of a basic catalyst to obtain
high purity alkylene oxide adduct of alkylcyclohexanol.
[0090] The basic catalysts used in the step are the same as used in
the first alkylene oxide addition step. Alkali metal hydroxide is
preferred in these basic catalysts. The amount of the catalyst is
usually in the range of 10 to 5,000 ppm by weight for the raw
material fraction consisting primarily of one molar alkylene oxide
adduct of alkylcyclohexanol. No particular restriction is imposed
upon the addition numbers of alkylene oxide. The numbers are
suitably selected depending upon uses of the alkylene oxide adduct
obtained. Reaction temperature and reaction pressure are usually
the same as those in the first alkylene oxide addition step.
Reaction time differs depending upon the amount of alkylene oxide
to be added and is usually in the range of 0.5 to 50 hours.
[0091] The alkylcyclohexanol alkylene oxide adduct obtained in the
preparation processes (D) and represented by the formula (1) has a
10 ppm or less content of alkylphenol and alkylphenol alkylene
oxide adduct, has a narrow addition distribution, and can be used
as a material of surface active agents.
Preparation Process (E)
[0092] The process for preparing high purity alkylcyclohexanol
alkylene oxide adduct represented by the formula (1); is
characterized by consisting of below described four steps; 17
[0093] wherein R.sup.1 is an alkyl group having 6 to 20 carbon
atoms, R.sup.2 is a hydrogen atom, methyl or ethyl group, and n is
an integer of 1 or more,
[0094] 1) the hydrogenation step for reacting alkylphenol
represented by the formula (4); 18
[0095] wherein R.sup.1 is an alkyl group having 6 to 20 carbon
atoms, with hydrogen in the presence of a hydrogenation catalysts
to obtain a formed product primarily consisting of corresponding
alkylcyclohexanol represented by the formula (3); 19
[0096] wherein R1 is the same as above,
[0097] 2) the first distillation step for distillating the formed
product obtained in the hydrogenation step to provide alkylphenol
content of 10 ppm by weight or less in the fraction primarily
consisting of alkylcyclohexanol,
[0098] 3) an alkylene oxide addition step for reacting one mole of
alkylcyclohexanol obtained in the first distillation step with 1 to
5 moles of alkylene oxide having 2 to 4 carbon atoms in the
presence of an acid catalyst to prepare alkylcyclohexanol alkylene
oxide adduct, and
[0099] 4) the second distillation step for separating unreacted
alkylcyclohexanol and low boiling-point byproduct of the reaction
from alkylcyclohexanol alkylene oxide adduct obtained in the
alkylene oxide addition step.
[0100] The hydrogenation step of the process can use the same
catalyst as used in the preparation process (D).
[0101] Hydrogen pressure in the hydrogenation step of the process
is usually in the range of gauge pressure 0 to 20 MPa, preferably
0.5 to 15 MPa. Reaction temperature is usually in the range of 30
to 200.degree. C., preferably 50 to 150.degree. C.
[0102] The reaction can be carried out in the presence or absence
of a solvent. Any solvent can be used for the process so long as
the solvent can dissolve or disperse the raw material alkylphenol
and corresponding alkylcyclohexanol which is a formed product and
the solvent itself does not react with hydrogen in the above
reaction conditions. The solvents used in the preparation process
(B) can be used as intact for the process.
[0103] In these solvents, aliphatic hydrocarbon compounds and
aliphatic cyclic hydrocarbon compounds are preferably used, and
aliphatic cyclic hydrocarbon compounds are preferred in particular.
No particular limitation is imposed upon the amount of solvents.
The amount is usually in the range of providing a concentration of
usually 5 to 80% by weight, preferably 20 to 60% by weight for the
raw material alkylphenol.
[0104] When alkylphenol is reacted with hydrogen in the presence of
a solvent, the reaction rate is sometimes low and preferable yield
cannot be obtained in the reaction. Particularly, ethanol and other
alcohol solvents require a long reaction time and lead to inferior
productivity. In such a case, the reaction can be preferably
carried out in the presence of water because the reaction rate is
preferably accelerated without giving an adverse effect on the
selectivity. Water, when used, can be previously dissolved,
dispersed or impregnated into the raw material alkylphenol of the
formula (3), catalyst or solvent, or can be independently charged
to the reaction system. No particular limitation is imposed upon
the amount of water. The amount is usually in the range of 0.1 to
50% by weight, preferably 1 to 40% by weight for the raw material
alkylphenol.
[0105] No particular restriction is imposed upon the reaction
procedures in the hydrogenation step. Any of batch procedure,
semi-batch procedure and continuous procedure can be carried out.
When the reaction is carried out by batch or semi-batch procedure,
no particular limitation is put upon the amount of the catalyst.
The amount is usually in the range of 0.5 to 50% by weight for the
raw material alkylphenol. The reaction time is usually in the range
of 0.5 to 50 hours. When the reaction is carried out by the
continuous procedure, the reaction conditions differ depending upon
the species of the catalyst used and LHSV is usually in the range
of 0.01 to 50 hr.sup.-1. After finishing the reaction, the formed
product which consists primarily of alkylcyclohexanol can be
obtained by separating the catalyst with a usual solid-liquid
separation method. When a solvent is used, the desired product can
be obtained by distillating off the solvent after separating the
catalyst from the reaction mixture.
[0106] In a formed product obtained in the hydrogenation step and
composed primarily of alkylcyclohexanol, unreacted alkylphenol
remains though in a trace amount. The residual alkylphenol
influences the successive reaction and leads to quality reduction
of the final product alkylcyclohexanol alkylene oxide adduct.
Accordingly, the first distillation step below is carried out.
[0107] The first distillation step of the invention distillates the
formed product in the hydrogenation step and reduces the content of
alkylphenol to 10 ppm by weight or less in the fraction consisting
of alkylcyclohexanol. The object of the distillation step is to
obtain an alkylcyclohexanol fraction containing a trace amount or
less of impurity by separating alkylphenol with distillation.
Accordingly, a distillation apparatus equipped with a rectifying
column and a reflux condenser can be used. The distillation can be
carried out at atmospheric pressure or under reduced pressure.
[0108] Further, a high purity alkylcyclohexanol fraction containing
a trace amount or less of alkylphenol can be obtained by carrying
out the distillation step in the presence of a basic compound
without using the rectification, column, reflux condenser and other
high grade distillation equipment. The basic compounds which can be
used in the distillation step are organic and inorganic compounds
having basicity and include, for example, sodium hydroxide,
potassium hydroxide, cesium hydroxide and other alkali metal
hydroxides; sodium ethoxide, lithium ethoxide, potassium phenoxide
and other alkali metal alkoxides and phnoxides; calcium hydroxide,
barium hydroxide, strontium hydroxide and other alkali earth metal
hydroxides; calcium methoxide, calcium phenoxide and other alkali
earth metal alkoxides and phenoxides; magnesium oxide, barium oxide
and other alkali earth metal oxides; and triethylamine,
dimethylamine, aniline, morpholine, pyridine and other organic
amino compounds. In these basic compounds, alkali metal hydroxides
are preferably used due to low price and handling with ease. No
particular limitation is imposed upon the amount of basic
compounds. The amount is usually in the range of 1 to 1,000 moles
per mole of the raw material alkylphenol contained in the formed
product consisting primarily of alkylcyclohexanol.
[0109] Distillation can be carried out by both batch and continuous
procedures.
[0110] The alkylene oxide addition step mentioned below is carried
out by using the high purity alkylcyclohexanol thus obtained to
provide alkylcyclohexanol alkylene oxide adduct containing a trace
amount or less of alkylphenol.
[0111] In the alkylene oxide addition step of the invention,
alkylcyclohexanol obtained in the first distillation step reacts
with alkylene oxide having 2 to 4 carbon atoms in the presence of
an acid catalyst to give alkylcyclohexanol alkylene oxide
adduct.
[0112] The alkylene oxide having 2 to 4 carbon atoms which can be
used in the alkylene oxide addition step includes, for example,
ethylene oxide, propylene oxide and butylene oxide. Alkylene oxide
can be used singly or as a mixture. When alkylene oxide is used as
a mixture, both random and block addition can be carried out.
Addition mole numbers of alkylene oxide is in the range of 1 to 5
moles for 1 mole of alkylcyclohexanol.
[0113] Alkylene oxide addition mole numbers less than the range
increases amount of alkylcyclohexanol which remains unreacted. On
the other hand, mole numbers higher than the range increases
unfavorably formation of byproducts such as dioxane.
[0114] The acid catalyst used in the alkylene oxide addition step
can be soluble or insoluble in the raw material alkylcyclohexanol
used, and both Br.o slashed.nsted acid and Lewis acid can be used
for the catalyst. Specific acids include, for example, hydrochloric
acid, sulfuric acid, phosphoric acid, boric acid and other mineral
acids; formic acid, acetic acid, propionic acid, benzoic acid and
other carboxylic acids; sulfate of aluminum, chromium, cobalt and
other metals; phosphate of zirconium, iron, manganese and other
metals; aluminum chloride, tin tetrachloride, antimony trichloride
and other halogenide of metals; BF.sub.3,
(C.sub.2H.sub.5).sub.3OBF.sub.4, (C.sub.2H.sub.5).sub.3OBF.sub.3
and other fluorinated boron compounds; tungstosilicic acid,
tungstophosphoric acid and other hetero polyacids; aluminum oxide,
SiO.sub.4-Al.sub.2O.sub.- 3, zinc oxide. tungsten oxide and other
metal oxides; activated clay, zeolite, montmorillonite and other
H-type or metal substituted type ion exchangers; and cation
exchange resins having a sulfonate group, fluoroalkylsulfonate
group, fluorinated alkylsulfonate group and carboxylic acid group.
Preferred catalysts are aluminum chloride, tin tetrachloride,
antimony trichloride and other metal halogenides, and Lewis acid
base catalysts such as BF.sub.3, (C.sub.2H.sub.5).sub.3OBF.sub- .4,
(C.sub.2H.sub.5).sub.3OBF.sub.3 and other fluorinated boron
compounds.
[0115] The amount of the catalyst used in the process differs
depending upon the species of the catalyst and reaction
temperature. The amount is usually in the range of 100 to 10,000
ppm by weight for the raw material alkylcyclohexanol. The acid
catalyst soluble in the reaction mass can be removed by
neutralizing with a basic compound such as alkali metal hydroxide
or water-soluble amine and successively washing with water. When
the salt is separated the catalyst can be completely removed by
filtering off the precipitate and further washing the filtrate with
water, when necessary. Further, the catalyst insoluble in the
reaction mass can be usually removed by filtration. Further, the
catalyst can also be separated by distillation without
neutralization operation.
[0116] The reaction temperature in the first alkylene oxide
addition step is usually in the range of 20 to 120.degree. C.,
preferably 30 to 70.degree. C. The reaction time is usually in the
range of 0.1 to 30 hours, preferably 0.3 to 20 hours. The reaction
pressure is usually in the range of gauge pressure 0 to 2 MPa,
preferably 0.1 to 0.7 MPa. No particular restriction is imposed
upon the reaction procedures. Batch procedure, semi-batch procedure
and continuous procedure can be carried out. The alkylcyclohexanol
alkylene-oxide adduct obtained in the step is successively used in
the second distillation step below.
[0117] The object of the second distillation step of the invention
is to remove unreacted alkylcyclohexanol, dioxane, aldehyde and low
boiling-point byproducts of the reaction and to obtain high purity
alkylcyclohexanol alkylene oxide adduct. Accordingly, a
distillation apparatus equipped, when necessary, with a rectifying
column and reflux condenser can be used. Distillation can be
carried out at atmospheric pressure or under reduced pressure. High
purity alkylcyclohexanol alkylene oxide adduct can be obtained as
still residue. The distillation can be carried out both by the
batch procedure and continuous procedure. Recovered, unreacted
alcohol can be recycled into the alkylene oxide addition step.
[0118] The alkylcyclohexanol alkylene oxide adduct obtained in the
preparation processes (E) and represented by the formula (1) has a
10 ppm or less content of alkylphenol and alkylphenol alkylene
oxide adduct, has a narrow addition distribution essentially
consisting of adduct having alkylene oxide addition numbers of 1 to
5, is liquid, and can be used as a material of surface active
agents or a raw material of alkylcyclohexanol alkylene oxide adduct
having a high addition numbers of alkylene oxide.
[0119] Alkylcyclohexanol alkylene oxide adduct of the invention
which is represented by the formula (1) has excellent properties as
a nonionic surface active agent and can be used for a surfactant by
utilizing its dominant penetrating ability, dispersing ability and
emulsifying ability. The adduct can be used as an effective
ingredient in many fields. Representative fields which can use the
adduct include, for example, scouring cleaner, spinning agent,
process oil, knitting oil, scotching oil, textile softener, dyeing
auxiliaries and other uses in textile industry; deresination
disparsant for DP, digestion auxiliaries, pitch dispersant in paper
making, antifoaming agent, deinking agent, felt cleaner, agent for
coated paper and other uses in paper-pulp industry; emulsifier in
emulsion polymerization, antistatic agent, antifogging agent and
other uses in synthetic rubber and resin industries; emulsifier,
solubilizing agent, spreading agent, hydrating agent, dispersant,
lubricant and other uses in agricultural chemicals industry; metal
cleaner, rust preventive and other uses in metal industry; and
garment working agent, kitchen detergent, residence cleaner and
other household detergents.
EXAMPLES
Reference Example 1
Synthesis of Nonylphenol Ethylene Oxide Adduct
[0120] To a 1,000 ml autoclave equipped with an ethylene oxide
inlet tube, 220 g (0.998 mole) of nonylphenol having a branched
nonyl group and an ortho/para ratio of 1/9, and 0.55 g of 40%
aqueous sodium hydroxide solution (5.5 mmoles of sodium hydroxide)
were charged. The reaction system was substituted with nitrogen and
thereafter heated to 120.degree. C. Successively the reaction
system was evacuated to 50 mmHg and dehydrated for an hour. After
dehydration, the system was returned to atmospheric pressure with
nitrogen and heated to 150.degree. C. While maintaining the same
temperature, 220 g (4.99 moles) of ethylene oxide were charged to
the reaction system over 5 hours under the pressure of 0.2 to 0.4
MPa (gauge). After finishing ethylene oxide charge, the reaction
mixture was kept at the same temperature for an hour. After
cooling, the reaction mixture was neutralized with 0.0.35 g (5.8
mmoles) of acetic acid to obtain 440 g of nonylphenol ethylene
oxide adduct. The adduct obtained had an ethylene oxide addition
mole numbers of 5.0 for one mole of nonylphenol.
[0121] Nonylphenol ethylene oxide adducts having arbitrary addition
mole numbers of ethylene oxide were similarly, prepared with
similar procedures described above by changing the ratio of
ethylene oxide to nonylphenol to be reacted.
Example 1
[0122] To a 70 ml autoclave, 20 g (45.4 mmoles, mole numbers of
nonylphenoxy skeleton, hereinafter the same shall apply) of
nonylphenol ethylene oxide adduct having an ethylene oxide addition
mole number of 5.0 and 2.0 g of 5%-ruthenium carbon powder were
charged. The reaction system was substituted with nitrogen,
successively substituted with hydrogen and heated to 120.degree. C.
Hydrogenation reaction was carried out for 6 hours under hydrogen
gauge pressure of 5.0 MPa while controlling the pressure by
continuously feeding hydrogen so as to maintain the constant
pressure. After the reaction, the catalyst was filtered at
70.degree. C. under increased pressure to obtain colorless liquid.
As a result of .sup.1H and .sup.13C-NMR, elementary analysis, mass
spectrometry and IR spectrum measurement, the liquid was identified
as nonylcyclohexanol ethylene oxide adduct having an ethylene oxide
addition mole number of 5.0 for nonylcyclohexanol.
[0123] The consumed amount of hydrogen during the reaction was
136.6 mmoles and was 3.01 moles per 1 mole of charged nonylphenol
ethylene oxide adduct. Nonylphenol ethylene oxide adduct remained
in nonylcyclohexanol ethylene oxide adduct was determined by liquid
chromatography. The amount was 120 ppm by weight. Further,
nonylcyclohexane formed by hydrogenation decomposition reaction was
determined by gas chromatography. The amount was 150 ppm by
weight.
Examples 2 and 3
[0124] The same reaction and filtration procedures as Example 1
were carried out except that nonylphenol ethylene oxide adduct
having the ethylene oxide addition mole numbers shown in Table 1
was used and the reaction was carried out for the time shown in
Table 1. Nonylcyclohexanol ethylene oxide adducts having different
ethylene oxide addition mole numbers were obtained. Amounts of
consumed hydrogen, remained nonylphenol ethylene oxide adduct and
nonylcyclohexane are shown in Table 1.
1 TABLE 1 Example 1 Example 2 Example 3 Ethylene oxide addition
mole number 5.0 10.0 15.0 Reaction time (hr) 6 6 5 Consumed
hydrogen (mmole) 136.6 90.8 68.2 Mole ratio to nonylphenol ethylene
(3.01) (3.00) (3.00) oxide adduct Remained nonylphenol ethylene 120
130 120 oxide adduct (ppm by weight) Nonylcyclohexane (ppm by
weight) 150 120 100
Example 4
[0125] The same reaction and filtration procedures as Example 1
were carried out except that monoethylene glycol monononylphenyl
ether was used in place of nonylphenol ethylene oxide adduct having
an ethylene oxide addition mole number of 5.0 and the catalyst
amount was changed to 4.0 g. Monoethylene glycol
monononylcyclohexyl ether was obtained.
[0126] Consumed hydrogen was 226.8 mmoles which corresponded to
3.00 mole ratio to monoethylene glycol monononylphenyl ether used,
remained monoethylene glycol monononylphenyl ether was 100 ppm by
weight, and nonylcyclohexane was 100 ppm by weight.
Examples 5.about.8 and Comparative Example 1
[0127] To 70 ml autoclave, 20 g (45.4 mmoles) of nonylphenol
ethylene-oxide adduct having an ethylene oxide addition mole number
of 5.0 and 2.0 g of powdery 5%-ruthenium alumina were charged. The
reaction system was substituted with nitrogen, successively with
hydrogen, and heated to 100.degree. C. Hydrogen pressure was
respectively controlled to the pressure shown in Table 2.
Hydrogenation reaction was carried out for the time and at the
temperature shown in Table 2 while feeding hydrogen so as to
maintain the hydrogen pressure constant. After the reaction, the
catalyst was filtered at 90.degree. C. under increased pressure to
obtain nonylcyclohexanol ethylene oxide adduct having an ethylene
oxide addition mole number of 5.0. Table 2 shows amounts of
consumed hydrogen, remained nonylphenol ethylene oxide adduct and
nonylcyclohexane.
[0128] As shown in the results of Comparative Example 1, too low
hydrogen pressure unfavorably leads to very slow reaction rate.
2TABLE 2 Comparative Example 1 Example 5 Example 6 Hydrogen
pressure 0.5 5.0 7.0 (gauge pressure, MPa) Reaction time (hr) 30 10
8 Consumed hydrogen (mmole) 49.0 136.1 136.3 Mole ratio to
nonylphenol (1.08) (3.00) (3.00) ethylene oxide adduct Remained
nonylphenol ethylene 63.90% 150 ppm 120 ppm oxide adduct (ppm or %
by weight) Nonylcyclohexane 50 100 150 (ppm by weight) Example 7
Example 8 Hydrogen pressure (gauge pressure, MPa) 9.0 12.0 Reaction
time (hr) 6 6 Consumed hydrogen (mmole) 136.7 136.7 Mole ratio to
nonylphenol ethylene oxide adduct (3.01) (3.01) Remained
nonylphenol ethylene oxide adduct (ppm or % by weight) 100 ppm 100
ppm Nonylcyclohexane (ppm by weight) 150 180
Examples 9 and Comparative Examples 2 and 3
[0129] The same reaction and filtration procedures as Example 5
were carried out except that the reaction temperature and reaction
time were employed as shown in Table 3. Nonylcyclohexanol ethylene
oxide adduct thus obtained had amounts of consumed hydrogen,
remained nonylphenol ethylene oxide adduct and nonylcyclohexane as
shown in Table 3.
[0130] As shown in the results of Comparative Example 2, too low
reaction temperature unfavorably leads to react very slowly. On the
other hand, too high reaction temperature is unfavorably liable to
cause hydrogenation decomposition.
3 TABLE 3 Comparative Comparative Example 2 Example 5 Example 9
Example 3 Reaction temperature (.degree. C.) 30 100 120 180
Reaction Time (hr) 40 10 7 5 Consumed hydrogen (mmole) 7.6 136.1
136.2 138.5 Mole ratio to nonylphenol ethylene (0.17) (3.00) (3.00)
(3.05) oxide adduct Remained nonyiphenol ethylene oxide 94.50% 150
ppm 120 ppm 120 ppm adduct (ppm by weight) Nonylcyclohexane (ppm by
weight) 10 ppm or less 120 ppm 180 ppm 0.80%
Examples 10 and 11
[0131] The same reaction and filtration procedures were carried out
as Example 1 except that the catalyst, hydrogen pressure, reaction
temperature and reaction time were changed as shown in Table 4.
Nonylcyclohexanol ethylene oxide adduct was obtained. Amounts of
consumed hydrogen, remained nonylphenol ethylene oxide adduct and
nonylcyclohexane are shown in Table 4.
4 TABLE 4 Example 10 Example 11 Catalyst 5% Rh/C 5%
Rh/Al.sub.2O.sub.3 Hydrogen pressure 5.0 5.0 (gauge pressure, MPa)
Reaction temperature (.degree. C.) 70 70 Reaction time (hr) 8 10
Consumed hydrogen (mmole) 136.2 137.1 Mole ratio to nonylphenol
ethylene (3.00) (3.02) oxide adduct Remained nonylphenol ethylene
oxide 130 100 adduct (ppm by weight) Nonylcyclohexane (ppm by
weight) 160 140
Example 12
[0132] To a 70 ml autoclave, 20 g (45.5 mmoles) of nonylphenol
ethylene-oxide adduct having an ethylene oxide addition mole number
of 5.0, 4.0 g of wet powder of 5%-ruthenium carbon having a
moisture content of 50% by weight and 20 g of ethanol were charged.
The system was substituted with nitrogen, thereafter with hydrogen
and heated to 60.degree. C. Hydrogen pressure was controlled to the
gauge pressure of 6.0 MPa and hydrogenation reaction was carried
out at the same temperature for 5 hours while feeding hydrogen so
as to maintain the same pressure. After the reaction, the catalyst
was filtered at 50.degree. C. and successively water and solvent
were removed to obtain a colorless liquid fraction. As a result of
determination by .sup.1H and .sup.13C-NMR, elementary analysis,
mass spectrometry and IR-spectrum, the liquid was identified as
nonylcyclohexanol ethylene oxide adduct having an ethylene oxide
addition number of 5.0.
[0133] The amount of hydrogen consumed during the reaction was
136.6 mmoles which corresponded to 3.01 mole per one mole of the
nonylphenol ethylene oxide adduct charged. The amount of remained
nonylphenol ethylene oxide adduct in nonylcyclohexanol
ethylene-oxide adduct was determined by liquid chromatography. The
amount was 40 ppm by weight. Nonylcyclohexane formed by the
hydrogenation decomposition reaction was determined by gas
chromatography. The amount was 90 ppm by weight.
Examples 13.about.17
[0134] Nonylphenol ethylene oxide adduct having an ethylene oxide
addition mole number shown in Table 5 and Table 6 was used. The
reaction, filtration, dehydration and solvent removal were carried
out by the same procedures Example 12 except that the reaction time
was changed to the time shown in Table 6. Nonylcyclohexanol
ethylene oxide adduct having different addition mole numbers of
ethylene oxide was obtained. The amounts of consumed hydrogen,
remained nonylphenol ethylene oxide adduct and nonylcyclohexane are
shown in Table 5 and Table 6.
[0135] As clearly shown in Table 5 and Table 6, the reaction was
almost completed in 3 hours in any addition mole number of ethylene
oxide.
5 TABLE 5 Example 12 Example 13 Example 14 Ethylene oxide addition
5.0 10.0 15.0 mole number Reaction time (hr) 5 5 5 Consumed
hydrogen (mmole) 136.6 90.8 68.2 Mole ratio to nonylphenol (3.01)
(3.00) (3.00) ethylene oxide adduct Remained nonylphenol 40 40 50
ethylene oxide adduct (ppm by weight) Nonylcyclohexane 90 90 100
(ppm by weight)
[0136]
6 TABLE 6 Example 15 Example 16 Example 17 Ethylene oxide addition
5.0 10.0 15.0 mole number Reaction time (hr) 3 3 3 Consumed
hydrogen (mmole) 136.1 90.8 68.4 Mole ratio to nonylphenol (3.00)
(3.00) (3.01) ethylene oxide adduct Remained nonylphenol 40 45 50
ethylene oxide adduct (ppm by weight) Nonylcyclohexane 95 90 100
(ppm by weight)
Example 18
[0137] The reaction, filtration, dehydration and solvent removal
were carried out by the same procedures as Example 12 except that
nonylphenol propylene oxide adduct having a propylene oxide
addition mole number of 5.0 was used in place of nonylphenol
ethylene oxide adduct having an ethylene oxide addition mole number
of 5.0. Nonylcyclohexanol propylene oxide adduct was obtained.
[0138] Consumed amount of hydrogen was 117.5 mmoles which
corresponded to 3.00 mole ratio to nonylphenol propylene oxide
adduct used, the amount of remained nonylphenol propylene oxide
adduct was 50 ppm by weight, and the amount of formed
nonylcyclohexane was 80 ppm by weight.
Example 19
[0139] The reaction, filtration, dehydration and solvent removal
were carried out by the same procedures as Example 12 except that
n-octylphenol ethylene oxide adduct having an ethylene oxide
addition mole number of 5.0 was used in place of nonylphenol
ethylene oxide adduct having an ethylene oxide addition mole number
of 5.0. n-Octylcyclohexanol ethylene oxide adduct was obtained.
[0140] Consumed amount of hydrogen was 141.3 mmoles which
corresponded to 3.01 mole ratio to n-octylphenol ethylene oxide
adduct used, the amount of remained n-octylphenol ethylene oxide
adduct was 50 ppm by weight, and the amount of n-octylcyclohexanol
was 95 ppm by weight.
Example 20
[0141] The reaction, filtration, dehydration and solvent removal
were carried out by the same procedures as Example 12 except that
2.0 g of dried powder of 5%-ruthenium carbon and 2 g of water were
used in place of 4.0 g of wet powder of 5%-ruthenium carbon having
a moisture content of 50% by weight. Nonylcyclohexanol ethylene
oxide adduct was obtained.
[0142] Consumed amount of hydrogen was 136.1 mmoles which
corresponded to 3.00 mole ratio to nonylphenol ethylene oxide
adduct used, the amount of remained nonylphenol ethylene oxide
adduct was 40 ppm by weight, and the amount of nonylcyclohexane was
85 ppm by weight.
Comparative Example 4
[0143] The reaction, filtration, dehydration and solvent removal
were carried out by the same procedures as Example 12 except that
2.0 g of dried powder of 5%-ruthenium carbon was used in place of
4.0 g of wet powder of 5%-ruthenium carbon having a moisture
content of 50% by weight. Nonylcyclohexanol ethylene oxide adduct
was obtained. The amount of hydrogen consumed during the reaction
was 68.1 mmoles which corresponded to a mole ratio of 1.50 to the
amount of nonylphenol ethylene oxide adduct charged. The amount of
remained nonylphenol ethylene oxide adduct in nonylcyclohexanol
ethylene oxide adduct was determined by liquid chromatography. The
amount was 50.1% by weight. Further, nonylcyclohexane formed by the
hydrogenation decomposition reaction was determined by gas
chromatography. The amount was 150 ppm by weight. As clearly shown
in those results, when the reaction was carried out in the absence
of water, the reaction rate was very low and satisfactory degree of
addition could not be obtained.
Example 21
[0144] To a 70 ml autoclave, 20 g (45.5 mmoles) of nonylphenol
ethylene oxide adduct having an ethylene oxide addition mole number
of 5.0, 20 g of dried powder of 5%-ruthenium carbon, and 20 g of
cyclohexane were charged. The system was substituted with nitrogen,
thereafter with hydrogen and heated to 60.degree. C. Hydrogen
pressure was controlled to gauge pressure of 6.0 MPa and
hydrogenation reaction was carried out for 3 hours at the same
temperature, while continuously feeding hydrogen so as to maintain
the same pressure. After the reaction, the catalyst was filtered at
50.degree. C. under increased pressure and the solvent was removed
by distillation to obtain a fraction of colorless liquid.
Measurement of .sup.1H and .sup.13C-NMR, elementary analysis, mass
spectrometry and IR-spectrum analysis identified the liquid as
nonylcyclohexanol ethylene oxide adduct having an ethylene oxide
addition mole number of 5.0.
[0145] The amount of hydrogen consumed during the reaction was
136.1 mmoles which corresponded to 3.00 mole ratio to the
nonylphenol ethylene oxide adduct used. Nonylphenol ethylene oxide
adduct remained in nonylcyclohexanol ethylene oxide adduct was
determined by liquid chromatography. The amount was 60 ppm by
weight. Nonylcyclohexane formed by the hydrogenation decomposition
reaction was determined by gas chromatography. The amount was 90
ppm by weight.
Comparative Example 5
[0146] The reaction, filtration, and solvent removal were carried
out by the same procedures as Example 21 except ethanol was used in
place of cyclohexane. Nonylcyclohexanol ethylene oxide adduct was
obtained. The amount of hydrogen consumed during the reaction was
54.4 mmoles which amount corresponded to a mole ratio of 1.19 to
the charged nonylphenol ethylene oxide adduct. The amount of
nonylphenol ethylene-oxide adduct remained in the nonylcyclohexanol
ethylene oxide adduct was determined by liquid chromatography. The
amount was 60.2% by weight. Further, nonylcyclohexane formed by the
hydrogenation decomposition reaction was determined by gas
chromatography. The amount was 140 ppm by weight. These results
clearly show that, when the reaction was carried out by using a
solvent other than saturated hydrocarbon, the reaction rate was
very low and satisfactory results could not be obtained.
Example 22
[0147] The reaction, filtration, dehydration and solvent removal
were carried out by the same procedures as Example 21 except that
4.0 g (moisture content was 50% by weight) of wet powder of
5%-ruthenium carbon was used in place of 2.0 g of dried powder of
5%- ruthenium carbon. Nonylcyclohexanol ethylene oxide adduct was
obtained.
[0148] The amount of consumed hydrogen was 136.1 mmoles which
corresponded to a mole ratio of 3.00 to nonylphenol ethylene oxide
adduct used, the amount of remained nonylphenol ethylene oxide
adduct was 30 ppm by weight, and the amount of nonylcyclohexane was
55 ppm by weight.
Example 23.about.27
[0149] The same reaction, filtration, dehydration and solvent
recovery procedures were carried out as Example 22 except that
nonylphenol ethylene oxide adduct having an ethylene oxide addition
mole number shown in Table 7 and Table 8, was used and reaction was
carried out for the time shown in Table 7 and Table 8.
Nonylcyclohexanol ethylene oxide adduct which differs in the
ethylene oxide addition mole number was obtained. Amounts of
consumed hydrogen, remained nonylphenol ethylene oxide adduct and
nonylcyclohexane are shown in Table 7 and Table 8.
[0150] As clearly shown in Table 7 and Table 8, when a saturated
hydrocarbon solvent is used, the reaction rate is very high and the
reaction can almost complete within 1.5 hours in any addition mole
numbers of ethylene oxide.
7 TABLE 7 Example 22 Example 23 Example 24 Ethylene addition 5.0
10.0 15.0 mole number Ereaction time (hr) 3 3 3 Consumed hydrogen
(mmole) 136.1 91.1 68.2 Mol ratio to nonylphenol (3.00) (3.01)
(3.00) ethylene oxide adduct Remained nonylphenol 40 45 50 ethylene
oxide adduct (ppm by weight) Nonylcyclohexane 55 55 60 (ppm by
weight)
[0151]
8 TABLE 8 Example 25 Example 26 Example 27 Ethylene oxide addition
5.0 10.0 15.0 mole number Reaction time (hr) 1.5 1.5 1.5 Consumed
hydrogen (mmole) 136.1 90.8 68.4 Mol ratio to nonylphenol (3.00)
(3.00) (3.01) ethylene oxide adduct Remained nonylphenol 45 45 55
ethylene oxide adduct (ppm by weight) Nonylcyclohexane 65 60 60
(ppm by weight)
Example 28
[0152] The reaction, filtration and solvent removal were carried
out by the same procedures as Example 21 except that cyclohexane
was replaced by n-heptane to obtain nonylcyclohexanol ethylene
oxide adduct. Amount of consumed hydrogen was 136.6 mmoles which
corresponded to a mole ratio of 3.01 to nonylphenol ethylene oxide
used, amount of remained nonylphenol ethylene oxide adduct was 120
ppm by weight, and the amount of nonylcyclohexane was 95 ppm by
weight.
Example 29
The First Ethylene Oxide Addition Step
[0153] To a 1,000 ml autoclave equipped with an ethylene oxide
inlet tube, 440 g (2.00 moles) of nonylphenol and 0.66 g (6.6
mmoles as sodium hydroxide) of a 40% aqueous sodium hydroxide
solution were charged. The system was substituted with nitrogen and
heated to 120.degree. C. Thereafter the system was evacuated to 50
mmHg and dehydration was carried out for an hour under reduced
pressure. After the dehydration, the system was returned to
atmospheric pressure by feeding nitrogen and heated to 150.degree.
C. While maintaining the temperature, 92 g (2.09 moles) of ethylene
oxide was charged to the reaction system over 3 hours under
increased gauge pressure of 0.2 to 0.4 MPa. The ethylene oxide
addition reaction of nonylphenol was thus carried out to react 1.05
moles of ethylene oxide with 1 mole of nonylphenol. After ethylene
oxide charge, the reaction mixture was kept at the same temperature
for an hour, cooled and neutralized the catalyst with 0.47 g (7.0
mmoles) of acetic acid to obtain 532 g of colorless liquid. The
liquid was analyzed with liquid chromatography. The liquid
contained, 1.2% by weight of nonylphenol, 96.7% by weight of one
molar ethylene oxide adduct of nonylphenol, and 2.1% by weight of
two molar ethylene oxide adduct of nonylphenol, respectively.
Hydrogenation Step
[0154] To a 1,000 ml autoclave, 520 g (1.95 moles) of the formed
product obtained in the first ethylene oxide addition step and
composed primarily of nonylphenol one molar ethylene oxide adduct,
and 30 g of powdery 5%-ruthenium carbon were charged. The system
was substituted with nitrogen, successively with hydrogen and
heated to 120.degree. C. Hydrogen pressure was controlled to gauge
pressure of 5.0 MPa, and the hydrogenation reaction was carried out
for 6 hours at the same temperature while continuously feeding
hydrogen so as to maintain the same pressure. After the reaction,
the catalyst was filtered at 70.degree. C. under increased pressure
to obtain 532 g of colorless liquid. The amount of hydrogen
consumed over the reaction was 5.88 moles which corresponded to a
molar ratio of 3.01 to nonylphenol ethylene oxide adduct charged.
As a result of measurement on .sup.1H and .sup.13C-NMR, mass
spectrometry and elementary analysis, the liquid was composed
primarily of one molar ethylene oxide adduct of nonylcyclohexanol
and most of nonylphenol and its ethylene oxide adduct were found to
become hydrogenation products. As a result of liquid
chromatography, the sum of remained nonylphenol and nonylphenol
ethylene oxide adduct was 150 ppm by weight.
Distillation Step
[0155] By using a batch type vacuum distillation apparatus equipped
with a rectifying column and reflux condenser, 520 g of the
colorless liquid obtained in the hydrogenation step and composed
primarily of one molar ethylene oxide adduct of nonylcyclohexanol
was distilled under reduced pressure. As an initial fraction, 10.3
g of the fraction composed mainly of nonylcyclohexanol was
obtained. As a main fraction, 462.2 g of the fraction composed
mainly of one molar ethylene oxide adduct of nonylcyclohexanol. The
remainder was disposed as still residue. According to the analysis
by liquid chromatography, the main fraction was one molar ethylene
oxide adduct of nonylcyclohexanol which contains 0.06% by weight of
nonylcyclohexanol. The sum of nonylphenol and nonylphenol ethylene
oxide adduct was 0.1 ppm by weight or less.
The Second Ethylene Oxide Addition Step
[0156] To a 1,000 ml autoclave equipped with an ethylene oxide
inlet tube, 270 g (1.00 mole) of one molar ethylene oxide adduct of
nonylcyclohexanol, obtained in the distillation step and 0.67 g
(6.7 mmoles as sodium hydroxide) of a 40% aqueous solution of
sodium hydroxide were charged. The reaction system was substituted
with nitrogen, heated to 120.degree. C., successively evacuated to
50 mmHg and dehydrated for an hour under reduced pressure. After
dehydration, the system was returned to atmospheric pressure by
feeding nitrogen, and heated to 150.degree. C. Successively
ethylene oxide addition reaction of one molar ethylene oxide adduct
of nonylcyclohexanol was carried out by feeding 265 g (6.02 moles)
of ethylene oxide into the reaction system over 6 hours under
increased gauge pressure of 0.2 to 0.4 MPa while maintaining the
same temperature. After ethylene oxide feeding, the reaction system
was kept at the same temperature for an hour, cooled and
neutralized the catalyst with 0.42 g (7.0 mmoles) of acetic acid to
obtain nonylcyclohexanol ethylene oxide adduct as colorless liquid.
According to analysis by liquid chromatography, the colorless
liquid was nonylcyclohexanol ethylene oxide adduct having an
average ethylene oxide addition mole number of 7.0. The colorless
liquid had 0.1 ppm by weight or less in the sum of nonylphenol and
nonylphenol ethylene oxide adduct.
Example 30
The First Ethylene Oxide Addition Step
[0157] The same procedures were carried out as Example 29.
Hydrogenation Step
[0158] The same procedures were carried out as Example 29 except
that 5%-rhodium alumina was used in place of 5%-ruthenium carbon
and the reaction was carried out at 100.degree. C. After the
reaction, the catalyst was filtered at 70.degree. C. under
increased pressure to obtain 532 g of colorless liquid consisting
primarily of one molar ethylene oxide adduct of nonylcyclohexanol.
Amount of hydrogen consumed during the reaction was 5.86 moles
which corresponded 3.01 mole ratio to nonylphenol ethylene oxide
adduct charged.
[0159] .sup.1H-NMR measurement proved that most of nonylphenol and
nonylphenol ethylene oxide adduct was hydrogenated. The remained
amount of nonylphenol and nonylphenol ethylene oxide adduct was
measured by liquid chromatography. The sum of remained amount was
130 ppm by weight.
Distillation Step
[0160] The same procedures as Example 29 were carried out. The main
fraction was primarily composed of ethylene oxide one molar adduct
of nonylcyclohexanol and was obtained in an amount of 458.9 g .
According to the analysis by liquid chromatography, the main
fraction was one molar ethylene oxide adduct of nonylcyclohexanol
containing 0.07% by weight of nonylcyclohexanol. The sum of
nonylphenol and nonylphenol ethylene oxide adduct was 0.1 ppm by
weight or less.
The Second Ethylene Oxide Addition Step
[0161] The same procedures were carried out as Example 29.
[0162] Nonylcyclohexanol ethylene-oxide adduct having an average
ethylene oxide addition mole number of 7.0 was obtained. According
to the analysis by liquid chromatography, the sum of nonylphenol
and nonylphenol ethylene oxide adduct was 0.1 ppm by weight or
less.
Example 31
The First Ethylene Oxide Addition Step
[0163] The same procedures were carried out as Example 29.
Hydrogenation Step
[0164] The same procedures as Example 29 were carried out except
that Raney nickel was used in place of 5%-ruthenium carbon, 200 g
of ethanol was added as a solvent, reaction temperature was
100.degree. C., hydrogen gauge pressure was 8.0 MPa, and reaction
time was 8 hours. After the reaction, the catalyst was filtered at
70.degree. C. under increased pressure, and distilling off ethanol
with a thin film still to obtain 532 g colorless liquid principally
composed of one molar ethylene oxide adduct of nonylcyclohexanol.
The amount of hydrogen consumed during the reaction was 5.78 moles
which corresponded 2.97 mole ratio to nonylphenol ethylene oxide
adduct charged.
[0165] As a result of .sup.1H-NMR measurement, nonylphenol and
nonylphenol ethylene oxide adduct are revealed to be mostly
hydrogenated. Residual amount of nonylphenol and nonylphenol
ethylene oxide adduct were determined by liquid chromatography. The
sum of these amounts was 320 ppm by weight.
Distillation Step
[0166] The same procedures as Example 29 were carried out. The main
fraction, 447.3 g of a fraction principally consisting of one molar
ethylene oxide adduct of nonylcyclohexanol was obtained. Analysis
by liquid chromatography revealed that the main fraction was one
molar ethylene oxide adduct of nonylcyclohexanol containing 0.05%
by weight of nonylcyclohexanol. The amount of nonylphenol and
nonylphenol ethylene oxide adduct was 0.1 ppm by weight or
less.
The Second Ethylene Oxide Addition Step
[0167] The same procedures as Example 29 were carried out to obtain
nonylcyclohexanol ethylene oxide adduct having an average ethylene
oxide addition mole number of 7.0. As a result of liquid
chromatography measurement, the sum of nonylphenol and nonylphenol
ethylene oxide adduct was 0.1 ppm by weight or less.
Comparative Example 6
The First Ethylene Oxide Addition Step
[0168] The same procedures as Example 29 were carried out.
Hydrogenation Step
[0169] The same procedures as Example 29 were carried out.
Distillation Step
[0170] The procedures were omitted.
The Second Ethylene Oxide Addition Step
[0171] The same procedures as Example 29 were carried out for
reacting 270 g of the reaction product which was obtained in the
hydrogenation step and composed primarily of one molar ethylene
oxide adduct of nonylcyclohexanol with 265 g of ethylene oxide.
Nonylcyclohexanol ethylene oxide adduct thus obtained was analyzed
with liquid chromatography. The product contained 80 ppm by weight
or less in the sum of nonylphenol and nonylphenol ethylene oxide
adduct.
Comparative Example 7
[0172] The same procedures as the first ethylene oxide addition
step of Example 29 were carried out except that the amount of
ethylene oxide was changed to 61 g (1.38 moles). That is, 0.69 mole
of ethylene oxide was reacted with 1 mole of nonylphenol. Colorless
liquid thus obtained was analyzed with liquid chromatography. The
liquid contained 27.3% by weight of nonylphenol, 72.7% by weight of
one molar ethylene oxide adduct, and trace amount of two molar
ethylene oxide adduct of nonylphenol, respectively. The reaction
product unfavorably formed a large amount of nonylcyclohexanol in
the next hydrogenation step.
Comparative Example 8
[0173] The same reaction and neutralization procedures as the first
ethylene oxide addition step of Example 29 were carried out except
that 132 g (3.00 moles) of ethylene oxide was reacted in the step.
That is, 1.5 moles of ethylene oxide were reacted with 1 mole of
nonylphenol. Colorless liquid thus obtained was analyzed with
liquid chromatography. No nonylphenol was contained in the liquid
and the amounts of nonylphenol ethylene oxide adduct contained were
49.0% by weight in one molar adduct, 48.5% by weight in two molar
adduct, and 2.5% by weight in 3 molar adduct, respectively.
[0174] The reaction product unfavorably generated a large amount of
two moles or more ethylene oxide adducts of nonylcyclohexanol in
the next hydrogenation step.
Example 32
Hydrogenation Step
[0175] To a 1,000 ml autoclave, 506.8 g (2.30 moles) of nonylphenol
and 30 g of 5%-ruthenium carbon powder were charged. The reaction
system was substituted with nitrogen and thereafter with hydrogen
and heated to 120.degree. C. Hydrogen pressure was controlled to
gauge pressure of 5.0 MPa, and hydrogenation reaction was carried
out for 6 hours at the same temperature, while continuously feeding
hydrogen so as to maintain the same pressure. After the reaction,
the catalyst was filtered at 70.degree. C. under increased pressure
to obtain 521.0 g of colorless liquid. Amount of consumed hydrogen
during the reaction was 6.94 moles which corresponded to 3.02 mole
ratio to nonylphenol charged. Measurement by .sup.1H and
.sup.13C-NMR, mass spectrometry and elementary analysis revealed
that the liquid consisted primarily of nonylcyclohexanol and most
of nonylphenol were hydrogenated. Amount of remainder nonylphenol
was determined with liquid chromatography. The amount was 150 ppm
by weight in the sum.
The First Distillation Step
[0176] With a batch type reduced pressure distillation apparatus
equipped with a rectifying column and reflux condenser, 510 g of
colorless liquid obtained in the hydrogenation step was distilled
under reduced pressure. Initial fraction was 5.3 g and composed of
nonylcyclohexanol containing low boiling fraction. Main fraction
was 480 g . The main fraction was analyzed by liquid chromatography
and was revealed to be nonylcyclohexanol. The amount of nonylphenol
was 0.1 ppm by weight or less by liquid chromatography.
Alkylene Oxide Addition Step
[0177] To a 1,000 ml autoclave equipped with an ethylene oxide
inlet tube, 453 g (2.00 moles) of nonylcyclohexanol, and 2.5 g of a
catalyst (C.sub.2H.sub.5).sub.2OBF.sub.3 were charged. The system
was substituted with nitrogen and warmed to 30.degree. C. While
maintaining the reaction temperature at 40 to 60.degree. C., 176 g
(4.0 moles; 2.0 moles per mole of charged nonylcyclohexanol) of
ethylene oxide was charged to the system under gauge pressure of
0.2 to 0.4 MPa, over 1.5 hours to carry out the ethylene oxide
addition reaction of nonylcyclohexanol. That is, 2.0 moles of
ethylene oxide was reacted with 1 mole of nonylcyclohexanol. After
ethylene oxide charge, the system was further kept at the same
temperature for an hour. After cooling, the reaction mixture was
neutralized with a 25% aqueous sodium hydroxide solution and the
catalyst was removed by washing twice with water. A colorless
liquid thus obtained was 629.2 g. The liquid was analyzed by liquid
chromatography. The content of unreacted nonylcyclohexanol was
24.1% by weight, formed one molar ethylene oxide adduct of
nonylcyclohexanol was 16.9% by weight, two molar adduct of 17.5% by
weight, 3 molar adduct of 16.0% by weight, 4 molar adduct of 12.3%
by weight, 5 molar adduct of 7.7% by weight, and 5 or more molar
adduct of 5.5% by weight, respectively. As a result of liquid
chromatography, the sum of nonylphenol and nonylphenol ethylene
oxide adduct was less than 0.1 ppm by weight.
The Second Distillation Step
[0178] With a batch type vacuum distillation apparatus equipped
with a rectifying column and reflux condenser, 610 g of colorless
liquid obtained in the alkylene oxide addition step was distilled
under reduced pressure. 147.3 g of unreacted nonylcyclohexanol was
distilled out and 458.1 g of residue was remained in the bottom.
The residue was analyzed by gas chromatography and no
nonylcyclohexanol was detected. Average addition mole number
calculated from measured hydroxyl value was 3.00. Hydroxyl value
was measured in accordance with JIS K-0070.
Example 33
Hydrogenation Step
[0179] The same procedures as Example 32 were carried out except
that 5%-rhodium alumina was used in place of 5%-ruthenium carbon
and the reaction temperature was changed to 100.degree. C. After
the reaction, the catalyst was filtered at 70.degree. C. under
increased pressure to obtain 521.0 g of colorless liquid consisting
primarily of nonylcyclohexanol. .sup.1H-NMR measurement revealed
that most of nonylphenol was hydrogenated. The sum of remained
nonylphenol was 170 ppm by weight by liquid chromatography.
Distillation Step
[0180] The same procedures as Example 32 were carried out. The
initial fraction was 7. g and composed of nonylcyclohexanol
containing low boiling fraction. Main fraction was 475 g and was a
nonylcyclohexanol fraction. The main fraction was revealed to be
nonylcyclohexanol by analysis with liquid chromatography. The
amount of nonylphenol was less than 0.1 ppm by weight by liquid
chromatography.
Alkylene Oxide Addition Step
[0181] The same procedures as Example 32 were carried out except
that ethylene oxide feeding amount was 132 g (3.00 moles; 1.5 moles
per mole of nonylcyclohexanol charged). After cooling, the reaction
mass was neutralized 25% aqueous sodium hydroxide solution and the
catalyst was removed by washing twice with water to obtain 585.6 g
of colorless liquid. Liquid chromatography analysis found 21.2% by
weight of unreacted nonylcyclohexanol, 21.9% by weight of one molar
adduct, 20.9% by weight of two molar adduct, 15.9% by weight of
three molar adduct, 10.3% by weight of four molar adduct, 7.3% by
weight of five molar adduct, and 2.5% by weight of six or more
molar adduct, respectively. Liquid chromatography measurement
revealed that the sum of nonylphenol and nonylphenol ethylene oxide
adduct was 0.1 ppm by weight or less.
The Second Distillation Step
[0182] With a batch type vacuum distillation apparatus equipped
with a rectifying column and reflux condenser, 500 g of colorless
liquid obtained in the alkylene oxide addition step was distilled
under reduced pressure to distil off 106.2 g of unreacted
nonylcyclohexanol and to obtain 390.8 g of residue in the bottom.
The residue was analyzed by gas chromatography. No
nonylcyclohexanol was detected. The average addition mole number
calculated from a hydroxyl value measured was 2.06.
Example 34
Hydrogenation Step
[0183] The same reaction procedures as Example 32 were carried out
except that 5%-palladium carbon was used in place of 5%-ruthenium
carbon, reaction temperature was 100.degree. C., hydrogen gauge
pressure was 8.0 MPa and reaction time was 8 hours. After finishing
the reaction, the catalyst was hot filtered at 70.degree. C. under
reduced pressure to obtain 520.8 g of colorless liquid consisting
primarily of nonylcyclohexanol. Amount of hydrogen consumed during
the reaction was 6.95 moles which amount corresponded to a mole
ratio of 3.02 to nonylphenol charged. .sup.1H-NMR measurement
revealed that most of nonylphenol was hydrogenated. The remained
nonylphenol was 190 ppm by weight by liquid chromatography.
Distillation Step
[0184] The same procedures as Example 32 were carried out. Initial
fraction was 4.5 g and was nonylcyclohexanol containing low boiling
fraction. Main fraction was 477 g and composed of
nonylcyclohexanol. The main fraction was analyzed by liquid
chromatography. The fraction was nonylcyclohexanol. According to
liquid chromatography, the amount of nonylphenol was 0.1 ppm by
weight or less.
Alkylene Oxide Addition Step
[0185] The same procedures as Example 32 were carried out except
that feed amount of ethylene oxide was 264.5 g (6.00 moles: 3.0
mole ratio to charged cyclohexanol). After cooling, the reaction
mass was neutralized 25% aqueous sodium hydroxide solution, and the
catalyst was removed by washing twice with water to obtain 717.2 g
of colorless liquid. Liquid chromatographic analysis revealed that
unreacted nonylcyclohexanol was 18.1% by weight, formed one mole
ethylene oxide adduct of nonylcyclohexanol was 13.6% by weight, two
molar adduct was 17.4% by weight, 3 molar adduct was 16.5% by
weight, 4 molar adduct was 15.3% by weight, 5 molar adduct was
12.1% by weight, and 6 or more molar adduct was 7.0% by weight,
respectively. As a result of liquid chromatographic determination,
the sum of nonylphenol and nonylphenol ethylene oxide adduct was
0.1 ppm by weight or less.
The Second Distillation Step
[0186] With a batch type vacuum distillation apparatus equipped
with a rectifying column and reflux condenser, 500 g of colorless
liquid obtained in the alkylene oxide addition step and was
distilled under reduced pressure, 90.8 g of unreacted
nonylcyclohexanol was distilled off and 406.1 g of residue was
obtained in the bottom. As a result of gas chromatography, no
nonylcyclohexanol was detected from the residue. The average
addition mole number calculated from the hydroxyl value was
4.20.
Example 35
Hydrogenation Step
[0187] In Example 32, the reaction was carried out by using 603.6 g
(2.3 moles) of n-dodecylphenol in place of the raw material
nonylphenol, using Raney nickel in place of 5 %-ruthenium carbon
powder, adding 200 g of ethanol as a solvent and at a reaction
temperature of 100.degree. C. and for a reaction time of 8 hours.
After the reaction, the catalyst was filtered at 70.degree. C.
under increased pressure, ethanol was distilled off with a thin
film evaporator to obtain 617.7 g of colorless liquid consisting
primarily of n-dodecylcyclohexanol. The amount of hydrogen consumed
during the reaction was 6.99 moles which corresponded to a mole
ratio of 3.04 to dodecylphenol charged. As a result of .sup.1H-NMR
measurement, most of n-dodecylphenol was found to be hydrogenated.
Remained n-dodecylphenol was determined by liquid chromatography,
and the amount of remained n-dodecylphenol was 145 ppm by
weight.
The First Distillation Step
[0188] The same procedures as Example 32 were carried out except
that 600 g of n-dodecylcyclohexanol obtained in the hydrogenation
step was used. An initial fraction composed of
n-dodecylcyclohexanol and a low boiling fraction was 6.3 g , and a
main fraction composed of n-dodecylcyclohexanol was 566.8 g . The
main fraction was analyzed by liquid chromatography. The fraction
was n-dodecylcyclohexanol and n-dodeylphenol content was 0.1 ppm by
weight or less.
Alkylene Oxide Addition Step
[0189] The same reaction procedures Example 32 were carried out
except that 537.0 g (2.0 moles) of dodecylcyclohexanol was charged.
After cooling, the reaction mass was neutralized 25% aqueous sodium
hydroxide solution, and the catalyst was removed by washing twice
with water to obtain 713.4 g of colorless liquid. The liquid was
analyzed by liquid chromatography. The liquid contained 29.4% by
weight of unreacted dodecylcyclohexanol, 16.7% by weight of formed
one molar ethylene oxide adduct of dodecylcyclohexanol, 17.4% by
weight of two molar adduct, 15.3% by weight of three molar adduct,
12.7% by weight of four molar adduct, 5.9% by weight of five molar
adduct, and 2.6% by weight of six or more molar ethylene oxide
adduct of dodecylcyclohexanol. As a result of liquid
chromatography, the sum of dodecylphenol and dodecylphenol ethylene
oxide adduct was 0.1 ppm by weight or less.
The Second Distillation Step
[0190] With a batch type vacuum distillation apparatus equipped
with a rectifying column and reflux condenser, 500 g of colorless
liquid obtained in the alkylene oxide addition step and consisting
of dodecylcyclohexanol ethylene oxide adduct was distilled under
reduced pressure, and 147.4 g of unreacted dodecylcyclohexanol was
distilled off and 348.9 g of residue was obtained in the bottom.
The residue was analyzed by gas chromatography. As a result, no
dodecylcyclohexanol was detected. The average addition mole number
calculated from the measured hydroxyl value was 3.28.
Example 36
Hydrogenation Step
[0191] The same procedures were carried out was Example 32. After
the reaction, the catalyst was filtered at 70.degree. C. under
increased pressure to obtain 520.8 g of colorless liquid. The
amount of hydrogen consumed during the reaction was 6.94 moles
which corresponded to a mole ratio of 3.02 to nonylphenol charged.
As a result of .sup.1H-NMR measurement, most of nonylphenol was
found to be hydrogenated. The residual amount of nonylphenol was
determined by liquid chromatography. The sum of residual amount was
165 ppm by weight.
Distillation Step
[0192] The same procedures as Example 32 were carried out. As an
initial fraction, 4.3 g of nonylcyclohexanol fraction containing a
low boiling fraction was obtained. A s a main fraction, 470 g of
nonylcyclohexanol fraction was obtained. The main fraction was
analyzed by liquid chromatography. The liquid was
nonylcyclohexanol, and nonylphenol content was 0.1 ppm by weight or
less.
Alkylene Oxide Addition Step
[0193] The same procedures as Example 32 were carried out except
that 232.3 g (4.0 moles) of propylene oxide was used in place of
ethylene oxide. After cooling, the reaction mass was neutralized
25% aqueous sodium hydroxide solution and the catalyst was removed
by washing twice with water to obtain 685.2 g of colorless liquid.
The liquid was analyzed by liquid chromatography. The liquid
contained 27.9% by weight of unreacted nonylcyclohexanol, 15.5% by
weight of formed one molar propylene oxide adduct of
nonylcyclohexanol, 17.2% by weight of two molar adduct, 15.6% by
weight of three molar adduct, 12.7% by weight of four molar adduct,
6.7% by weight of five molar adduct, and 4.4% by weight of six or
more molar propylene oxide adduct of nonylcyclohexanol. As a result
of liquid chromatographic analysis, the sum of nonylphenol and
nonylphenol propylene oxide adduct was 0.1 ppm by weight or
less.
The Second Distillation Step
[0194] With a batch type vacuum distillation apparatus equipped
with a rectifying column and reflux condenser, 500 g of colorless
liquid obtained in the alkylene oxide addition step was distilled
under reduced pressure to distil off 139.1 g of unreacted
nonylcyclohexanol and 356.7 g of still residue liquid was obtained
in the bottom. The residue was analyzed by gas chromatography. No
nonylcyclohexanol was detected. The average addition mole number
calculated from the measured hydroxyl value was 3.45.
Example 37
The Second Alkylene Oxide Addition Step
[0195] To a 1,000 ml autoclave equipped with an ethylene oxide
inlet tube, 352.5 g (1.0 mole: average addition mole number of
3.00) of nonylcyclohexanol ethylene oxide adduct obtained in the
second distillation step of Example 32 and 0.67 g (6.7 mmoles as
sodium hydroxide) of a 40% aqueous sodium hydroxide solution were
charged. The reaction system was substituted with nitrogen, heated
to 120.degree. C., successively evacuated to 50 mmHg and dehydrated
for an hour under reduced pressure. After dehydration, the system
was returned to atmospheric pressure by feeding nitrogen and heated
to 150.degree. C. While maintaining the temperature, 308.4 g (7.0
moles) of ethylene oxide was fed into the system during 3 hours at
gauge pressure of 0.2 to 0.4 MPa to carry out ethylene oxide
addition reaction of nonylcyclohexanol ethylene oxide adduct. After
finishing the ethylene oxide charge, the reaction mass was further
at the same temperature for an hour, cooled and neutralized the
catalyst with 0.42 g (7.0 mmoles) of acetic acid to obtain 661.6 g
of nonylcyclohexanol ethylene oxide adduct as colorless liquid.
According to hydroxyl value measurement, the liquid was
nonylcyclohexanol ethylene oxide adduct having an average ethylene
oxide addition mole number of 9.99. As a result of liquid
chromatography, the sum of nonylphenol and nonylphenol ethylene
oxide adduct was 0.1 ppm by weight or less.
Example 38
The Second Alkylene Oxide Addition Step
[0196] To a 1,000 ml autoclave equipped with an ethylene oxide
inlet tube, 264.4 g (0.75 mole) of nonylcyclohexanol ethylene oxide
adduct which was obtained in the second distillation step of
Example 32 and had an average addition mole number of 3.00, and
0.67 g (6.7 mmoles as sodium hydroxide) of 40% aqueous sodium
hydroxide solution were charged. The reaction system was
substituted with nitrogen, heated to 120.degree. C., successively
evacuated to 50 mmHg, and dehydrated for an hour under reduced
pressure. After dehydration, the reaction system was returned to
atmospheric pressure by feeding nitrogen and heated to 150.degree.
C. While maintaining the temperature, 484.6 g (11.0 moles) of
ethylene oxide was fed into the reaction system over 4 hours under
gauge pressure of 0.2 to 0.4 MPa to carry out ethylene oxide
addition reaction of nonylcyclohexanol ethylene oxide adduct. After
the ethylene oxide feed, the reaction system was further at the
same temperature for an hour, cooled, neutralized the catalyst with
0.42 g (7.0 mmoles) of acetic acid to obtain 750.7 g of
nonylcyclohexanol ethylene oxide adduct as colorless liquid.
According to hydroxyl value measurement, the adduct obtained had an
average ethylene oxide addition mole number of 14.05. As a result
of liquid chromatography, the sum of nonylphenol and nonylphenol
ethylene oxide adduct was 0.1 ppm by weight or less.
Comparative Example 9
[0197] The same alkylene oxide addition step as the alkylene oxide
addition step of Example 32 were carried out without the first
distillation step. As a result, the reaction mass contained 25.7%
by weight of unreacted nonylcyclohexanol, 16.7% by weight of formed
ethylene oxide one molar adduct of nonylcyclohexanol, 17.1% by
weight of 2 molar adduct, 15.7% by weight of three molar adduct,
11.6% by weight of four molar adduct, 7.7% by weight of five molar
adduct, 5.5% by weight of six molar or more adduct of ethylene
oxide of nonylcyclohexanol, respectively. The unreacted
nonylcyclohexanol was removed according to the second distillation
step of the Example 32. According to hydroxyl value measurement,
the residue in the bottom had an average ethylene oxide addition
mole number of 3.10. As a result of liquid chromatography, the sum
of nonylphenol and nonylphenol ethylene oxide adduct was 110 ppm by
weight.
Comparative Example 10
[0198] The same reaction and catalyst removal procedures as the
alkylene oxide addition step of Example 32 were carried out except
that 226.5 g (1.00 mole) of nonylcyclohexanol was used, 308.4 g
(7.00 moles) of ethylene oxide was reacted, and reaction time was 8
hours. As a result, 534.5 g of white solid was obtained at room
temperature. As a result of liquid chromatography analysis, the
white solid contained 2.1% by weight of unreacted
nonylcyclohexanol, 5.7% by weight of formed ethylene oxide one
molar adduct of nonylcyclohexanol, 6.2% by weight of 2 molar
adduct, 7.9% by weight of three molar adduct, 8.2% by weight of
four molar adduct, 8.8% by weight of five molar adduct, 9.2% by
weight of six molar adduct, 9.6% by weight of seven molar adduct,
8.9% by weight of 8 molar adduct, 8.3% by weight of nine molar
adduct, 6.8% by weight of ten molar adduct, 6.1% by weight of
eleven molar adduct, and 7.9% by weight of twelve or more molar
adduct of ethylene oxide of nonylcyclohexanol, respectively. The
white solid was analyzed by gas chromatography and was detected
3.2% by weight of dioxane and 1.1% by weight of other low boiling
compounds.
Comparative Example 11
[0199] To a 1,000 ml autoclave equipped with an ethylene oxide
inlet tube, 226.5 g (1.0 mole) of nonylcyclohexanol and 0.67 g (6.7
mmoles as sodium hydroxide) of 40% aqueous sodium hydroxide
solution were charged. The reaction system was substituted with
nitrogen, heated to 120.degree. C., successively evacuated to 50
mmHg, and carry out dehydration for an hour under reduced pressure.
After dehydration, the system was returned to atmospheric pressure
by feeding nitrogen, and heated to 150.degree. C. While maintaining
the temperature, 396.5 g (9.0 moles) of ethylene oxide was fed into
the reaction system over 3 hours under gauge pressure of 0.2 to 0.4
MPa to carry out ethylene oxide addition reaction of
nonylcyclohexanol. After finishing ethylene oxide charge, the
reaction system was further kept at the same temperature for an
hour and the catalyst was neutralized after cooling with 0.42 g
(7.0 mmoles) of acetic acid to obtain 623.4 g of nonylcyclohexanol
ethylene oxide adduct as white solid at room temperature. The white
solid was analyzed by liquid chromatography. The solid contained
38.8% by weight of unreacted nonylcyclohexanol, 0.5% by weight of
formed one molar ethylene oxide adduct of nonylcyclohexanol, 1.1%
by weight of two molar adduct, 1.6% by weight of three molar
adduct, 2.3% by weight of four molar adduct, 3.4% by weight of five
molar adduct, 4.3% by weight of six molar adduct, 5.2% by weight of
seven molar adduct, 6.3% by weight of eight molar adduct, 7.4% by
weight of nine molar adduct, 6.6% by weight of ten molar adduct,
5.8% by weight of eleven molar adduct, and 4.7% by weight of twelve
molar adduct, 4.1% by weight of thirteen molar adduct, 3.2% by
weight of fourteen molar adduct, and 4.7% by weight of fifteen or
more molar adduct.
[0200] As mentioned above, when ethylene oxide addition reaction is
carried out in the presence of a base catalyst alone, a large
amount of unreacted nonylcyclohexanol remains, mole distribution of
ethylene oxide addition becomes considerably broad, and high molar
adduct increases. Thus the reaction product unfavorably becomes a
solid.
[0201] Hereinafter illustrated tests were carried out in order to
prove that alkylcyclohexanol alkylene oxide adducts of the
invention can be applied to various uses.
Reference Example 2
[0202] To a 1,000 ml autoclave equipped with an ethylene oxide
inlet tube, 220 g (0.998 moles) of nonylphenol having a branched
mixture of nonyl group and an ortho/para ratio of 1/9 and 0.83 g
(8.3 mmoles as sodium hydroxide) of 40% aqueous sodium hydroxide
solution were charged. The reaction system was substituted with
nitrogen, heated to 120.degree. C., successively evacuated to 50
mmHg, and dehydrated for an hour under reduced pressure. After the
dehydration, the reaction system was returned to atmospheric
pressure by feeding nitrogen and heated to 150.degree. C. While
maintaining the temperature, 440 g (9.99 moles) of ethylene oxide
was fed to the reaction system over 8 hours under increased gauge
pressure of 0.2 to 0.4 MPa to carry out ethylene oxide addition
reaction of nonylphenol. After ethylene oxide charge, the reaction
system was further kept at the same temperature for an hour. After
cooling the reaction system, the reaction system was neutralized
with 0.52 g (8.7 mmoles) of acetic acid to obtain 660 g of
nonylphenol ethylene oxide adduct. Nonylphenol ethylene oxide
adduct thus obtained had an average ethylene oxide addition mole
number of 10.0.
[0203] Successively, to a 1,000 ml autoclave, 200 g (302.6 mmoles)
of nonylphenol ethylene oxide adduct having an ethylene oxide
addition mole number of 10.0, and 20.0 g of powdery 5%-ruthenium
carbon were charged. The reaction system was substituted with
nitrogen, successively with hydrogen, and heated to 120.degree. C.
The hydrogen pressure was controlled to gauge pressure of 5.0 MPa,
and the hydrogenation reaction was carried out for 6 hours at the
same temperature while continuously feeding hydrogen so as to
maintain the pressure constant. After the reaction, the catalyst
was filtered at 70.degree. C. under increased pressure to obtain
colorless liquid.
[0204] As a result of .sup.1H- and .sup.13C-NMR, elementary
analysis, mass spectrometry and IR spectrum measurement, the liquid
was identified as nonylcyclohexanol ethylene oxide adduct having an
ethylene oxide addition mole number of 10.0 to
nonylcyclohexanol.
[0205] The consumed amount of hydrogen during the reaction was
914.0 mmoles which amount corresponded to 3.02 mole ratio to
nonylphenol ethylene oxide adduct charged. Further, the amount of
nonylphenol ethylene oxide adduct remained in the nonylcyclohexanol
ethylene oxide adduct was determined by liquid chromatography. The
amount was 120 ppm by weight. Further, nonylcyclohexane formed by
hydrogenation decomposition reaction was determined by gas
chromatography. The amount was 10 ppm by weight.
[0206] With a Model-B viscosimeter, viscosity was measured at
25.degree. C. on nonylcyclohexanol ethylene oxide adduct which was
obtained in the present Reference Example 2 and had an ethylene
oxide addition mole number of 10 and on intermediate product
nonylphenol ethylene oxide adduct having an ethylene oxide addition
mole number of 10. The former viscosity was 210 cps and the latter
viscosity was 250 cps. Nonylcyclohexanol ethylene oxide adduct had
lower viscosity.
Reference Example 3
[0207] The same procedures as Reference Example 2 were carried out
to obtain nonylcyclohexanol ethylene oxide adduct having an
ethylene oxide addition mole number of 6.0.
Reference Example 4
[0208] The same procedures as Reference Example 2 were carried out.
Nonylcyclohexanol ethylene oxide adduct having an ethylene oxide
addition mole number of 30.0 was obtained.
Test Example 1
Fiber Washing Test
[0209] As an artificial soil, a mixture of 23.6 g of Kanto clay
loam, 0.4 g of carbon black, 56.2 g of synthetic sebum, and 4 kg
carbon tetrachloride was used. Synthetic sebum composed of
following ingredients;
[0210] Palmitic acid 5.6 g , stearic acid 2.8 g , oleic acid 5.6 g
, linolic acid 2.8 g , coconut oil 8.4 g , olive oil 11.2 g ,
paraffin (m.p. 48.about.50.degree. C.) 5.6 g , spermaceti 8.6 g ,
squalene 2.8 g , and cholesterol 2.8 g .
[0211] The above artificial soil was vigorously stirred with a
homomixer in the bath. A standard cotton fabric (JIS L-0803) was
dipped into the bath with a continuous automatic soiling machine.
The soiled fabric was subjected to natural drying for 3 weeks and
successively cut into dimensions of 10 cm square to prepare
artificially soiled fabric.
[0212] Terg-O-Tometer was used for the detergency test. Washing was
carried out at 30.degree. C. for 10 minutes by immersing four
soiled fabrics in 1 liter of 0.25% by weight of aqueous solution of
nonylcyclohexanol ethylene oxide adduct prepared in Reference
Example 2. After washing, rinsing was carried out twice with one
liter each of pure water for 3 minutes each. After subjecting the
test fabric to air-drying, successively to ironing, surface
reflectance of the fabric was measured with a color difference
meter for used in colorimetry. Detergency (D) was calculated from
the following equation.
D(%)=[1-(Ro-Rw)/(Ro-Rs)].times.100
[0213] wherein Rw, Rs and Ro are surface reflectance of washed
fabric, soiled fabric and original white fabric, respectively.
Detergency was 84%, which illustrated good washing ability.
Test Example 2
Metal Washing Test
[0214] A test piece was prepared by coating fiber grease on a
wrought iron plate. To 96.0 g of water, 3.0 g of sodium carbonate
and 1.0 g of nonylcyclohexanol ethylene oxide adduct prepared in
Reference Example 2 was added and warmed to 40.degree. C. The test
piece was washed for 10 minutes by moving up and down the test
piece in the solution. Weight of the test piece was measured and
detergency (D) was calculated from the following equation.
D(%)=[1-(Ww-Wo)/(Ws-Wo)].times.100
[0215] wherein Ww, Ws, and Wo are weight of test piece after
washing, weight of test piece before washing and weight of test
piece before coating the fiber grease, respectively.
[0216] Detergency was 99.2%, which illustrated good washing
ability.
Test Example 3
Tableware Washing Test
[0217] Test was carried out by washing a glass piece adhered with
model soil in accordance with Method for Evaluating Detergency for
Synthetic Kitchen Detergent in JIS K-3362, Testing Method of
Synthetic Detergent. The test detergent was prepared by mixing
polyoxyethylene alkylether sulfate, nonylcyclohexanol ethylene
oxide adduct prepared in Reference Example 2, ethanol and water in
a weight ratio of 16:3:6:75. Washing water was prepared by
dissolving 1.5 g of the test detergent in 1 liter of water. As a
result, the test detergent containing nonylcyclohexanol ethylene
oxide adduct had excellent detergency as compared with an index
detergent.
Test Example 4
Fiber Scouring Test
[0218] A scouring agent was prepared by mixing nonylcyclohexanol
ethylene oxide adduct prepared in Reference Example 2, 40% aqueous
solution of n-octylalcohol sulfate ester sodium salt, palm oil
fatty acid and water in a ratio of 10:14:5. A scouring bath was
prepared by dissolving 2 g of the scouring agent in 1 liter of
water. A green ware of wool serge was immersed in the scouring bath
in a bath ratio of 1:20. Scouring was carried out in a stainless
steel beaker at 80.degree. C. for 20 minutes. After scouring, rinse
was carried out twice with warm water at 40.degree. C. for 2
minutes each and flowing rinse was carried out with water for 2
minutes. Thereafter the wool serge was dehydrated, dried and
extracted with diethyl ether for 4 hours in a Soxhlet extractor.
The ratio of remaining lipid was measured on the resulting
specimen. The ratio of remaining lipid was 0.11%, which illustrated
good scouring ability.
Test Example 5
Deinking Test
[0219] Waste paper consisting of 70% by weight of waste newspaper
elapsed two or three months after printing and 30% by weight of
folded leaflet was shredded. To a bench disaggregation apparatus,
100 g of the shredded matter, 3 liter of water, 0.3% by weight of
sodium hydroxide for waste paper, and 0.1% by weight of
nonylcyclohexanol ethylene oxide adduct obtained in Reference
Example 3 for waste paper as a deinking agent were charged and
disaggregated for 10 minutes. The above was a disaggregation
step.
[0220] The disaggregated sample was dehydrated with a Buchner
funnel and concentrated to a waste paper concentration of 25 to
30%. Thereafter, 0.2% by weight for the waste paper of the same
deinking agent as in the desaggregation step, 0.7% by weight for
the waste paper of sodium hydroxide, 2.0% by weight for the waste
paper of sodium silicate, and 0.7% by weight for the waste paper of
hydrogen peroxide were added, thoroughly mixed and kneaded with a
twin screw laboratory kneader at 300 rpm. The resulting sample was
placed in a polyethylene bag and aged at 60.degree. C. for 2 hours
in a water bath. After aging, the sample was diluted to a waste
concentration of 1% by addition of water, disaggregated for 10
minutes with the bench disaggregator, poured into a floatator to
carry out floatation for 10 minutes. After floatation, the slurry
of pulp was concentrated to 4% by 50 mesh wire, diluted to 1%
concentration by addition of water, and a pulp sheet was prepared
with a TAPPI standard sheet machine.
Measurement of Brightness
[0221] By using a photoelectric reflectance meter, blue reflectance
of the pulp sheet obtained was measured at 457 .mu.m.
Measurement of Residual Ink)
[0222] By using a microscope having a magnification of 200 times,
numbers of ink remained in one visual field (0.1 cm.sup.2) of the
pulp sheet were measured. Measurement was carried out at different
10 points and measured values were averaged.
Measurement of Froth Amount
[0223] Amount of froth removed in floatation was measured as a
guide for formability and yield. Increase in the froth amount
indicates reduction of pulp yield.
[0224] The deinked pulp obtained in the test had a small amount
(602 g ) of froth, high brightness (57.6%) and small numbers of
residual ink (12 particles)
Test Example 6
Yarn-making Ability Test
[0225] Fiber lubricating oil was prepared by mixing 45 parts by
weight of lauryl laurate, 10 parts by weight of mineral oil, 35
parts by weight of nonylcyclohexanol ethylene oxide adduct prepared
by Reference Example 3, 2 parts by weight of aliphatic
diethanol-amide, 4 parts by weight of
polyoxyethylenelaurylphosphate amine having an average ethylene
oxide addition mole number of 3 and 4 parts by weight of sodium
alkanesulfonate. Yarn making ability was evaluated by the following
methods.
[0226] (1) Filament prepared: polyester filament, 75 denier, 36
filaments.
[0227] (2) Yarn making condition: spinning velocity 1500 mpm, wind
up velocity 4500 mpm.
[0228] (3) Oil charge: An aqueous emulsion wherein the lubrication
oil composition has a concentration of 15% by weight was prepared
and charged on the roller. The oiling roller had a rotation
velocity of 15 rpm.
[0229] (4) Evaluation: By using the above aqueous emulsion,
filaments were spun with a spin-draw type spinning machine and
numbers of fluff outside the pirn were counted.
[0230] Fluff numbers were 8, which illustrated good yarn-making
ability.
Test Example 7
Test as an Emulsifier for Agricultural Chemicals
[0231] To a homomixer, 6 parts by weight of nonylcyclohexanol
ethylene oxide adduct obtained in Reference Example 2, 36 parts by
weight of fenthion, and 21 parts by weight of water were charged
and stirred at 10,000 rpm for 10 minutes.
[0232] The agricultural chemicals were dispersed and an emulsified
composition of agricultural chemicals formulation was obtained.
Storage stability of the composition was examined by allowing to
stand in a constant temperature chamber at 20.degree. C. for 30
days. As a result, no separation was found at all and a good
emulsified state was maintained.
Test Example 8
Test as an Emulsifier of Agricultural Chemicals
[0233] To a homomixer, 9 parts by weight of nonylcyclohexanol
ethylene oxide adduct obtained in Reference Example 2, 36 parts by
weight of chloropyriphosmethyl, 6 parts by weight of propylene
glycol and 53 parts by weight of water were charged and stirred at
10,000 rpm for 10 minutes to obtain and emulsion of agricultural
chemicals formulation.
[0234] Storage stability was examined by allowing to stand in a
constant temperature chamber at 20.degree. C. for 30 days. After
the test, no separation was found at all and a good emulsified
state was maintained.
Test Example 9
Test for an Emulsifier of Emulsion Polymerization
[0235] To a 500 ml flask equipped with a thermometer, stirrer, gas
inlet tube, reflux condenser, and three dropping funnels, 120 g of
water and 2 g of emulsifier nonylcyclohexanol ethylene oxide adduct
obtained in Reference Example 4 were charged and heated to
60.degree. C. under nitrogen ventilation. Thereafter, while
maintaining the same temperature, 16 g of an unsaturated monomer
mixture composed of butyl acrylate and styrene in a weight ratio of
1/1, 1.0 g of an aqueous solution containing 5% by weight of sodium
persulfate, and 1.0 g of an aqueous solution containing 2.5% by
weight of sodium hydrogen sulfate were dropwise added individually
from each funnel at the same time to initiate polymerization.
Thereafter, 64 g of the unsaturated monomer mixture was further
added dropwise over 2 hours and simultaneously 5.7 g of an aqueous
solution containing 5% by weight of sodium persulfate and 5.7 g of
an aqueous solution containing 2.5% by weight of sodium hydrogen
sulfate were dropwise added over 3 hours. After the dropwise
addition, the reaction mass was maintained at the same temperature
for 2 hours to complete the reaction. A high polymer emulsion was
thus obtained.
Stability in the Polymerization Stage
[0236] The obtained high polymer emulsion was filtered through an
80 mesh metal net. The resulting solid portion was washed with
water and dried. The weight of the dried solid was measured. As a
result, 0.38% by weight of solid portion was formed for the
unsaturated monomer charged.
Chemical Stability
[0237] The high polymer emulsion thus obtained was diluted with
water to a concentration of 1% by weight and dropwise incorporated
with a 0.5 mole/l aqueous calcium chloride solution. Concentration
of calcium chloride in the emulsion was measured at the initiation
time of coagulating emulsion particles. The concentration was 42
mmoles/l.
Test Example 10
Test for Dyeing Auxiliaries
[0238] Into a bath containing 0.25 g /l of a dyestuff represented
by the following formula: 20
[0239] 1 g/l of dinaphthylmethanedisulfonate and 0.2 g/l of dyeing
auxiliaries nonylcyclohexanol ethylene oxide adduct obtained in
Reference Example 2, a cloth of polyethyleneglycol terephthalate
fiber was introduced at 60.degree. C. in a bath-ratio of 1:40.
Successively the bath was heated to 125.degree. C. over 30 minutes
and maintained the temperature for 60 minutes. The colored material
thus obtained was uniformly dyed without unevenness and had high
fixing ability.
Test Example 11
Test for Dyeing Auxiliaries
[0240] Into a bath containing 0.25 g/l of a dyestuff represented by
the following formula: 21
[0241] and 0.2 g/l of dyeing auxiliaries nonylcyclohexanol ethylene
oxide adduct obtained in Reference Example 2, a cloth of
polyethyleneglycol terephthalate fiber was introduced at 60.degree.
C. in a bath ratio of 1:40. The bath was heated to 125.degree. C.
over 30 minutes and maintained at the temperature for 60 minutes.
The colored material thus obtained was uniformly dyed without
unevenness and had high fixing ability.
Test Example 12
Test for an Antistatic Agent
[0242] A mixture was prepared from 100 g of polyvinyl chloride
powder, 45 g of DOP, 2 g of a cadmium barium base stabilizer and 2
g of nonylcyclohexanol ethylene oxide adduct obtained in Reference
example 2. The mixture thus obtained was kneaded with a baby roll
at 180.degree. C. for 1 minutes and formed into a film. The film
was allowed to stand in a constant temperature and humidity room at
20.degree. C., 60% RH, for 48 hours. After the test, the film had
surface resistivity of 1.6.times.10.sup.11 .OMEGA..
[0243] As a comparative test, the same procedures were carried out
without using nonylcyclohexanol ethylene oxide adduct obtained in
Reference Example 2. The film thus obtained had surface resistivity
2.5.times.10.sup.16 .OMEGA..
Test Example 13
Test for an Antifogging Agent
[0244] A mixture was prepared from 100 parts by weight of polyvinyl
chloride resin, 30 parts by weight of dioctyl phthalate, 10 parts
by weight of dioctyl adipate, 5 parts by weight of tricresyl
phosphate, 4 parts by weight of epoxy resin, 3 parts by weight of
calcium-zinc based liquid stabilizer, 2 parts by weight of
calcium-zinc base powder stabilizer and 2.5 parts by weight of
antifogging agent nonylcyclohexanol ethylene oxide adduct obtained
in Reference Example 2. The mixture thus obtained was kneaded on a
hot roll at 180.degree. C. to obtain a film having a thickness of
0.1 mm. The film was mounted on a head inclined box and allowed to
stand for 12 hours at the outside air temperature of 5.degree. C.
at water temperature of 15.degree. C. with an inclined angle of 10
degrees. Thereafter the wet state of the film was observed. Overall
film surface was uniformly moistened into a transparent state.
Further, the film was applied to an outdoor house and the wet state
of the film was observed after 5 hours. Overall film surface was
uniformly moistened into a transparent state.
Effect of the Invention
[0245] According to the process of the present invention,
alkylcyclohexanol alkylene oxide adduct having 200 ppm or less
content of alkylphenol and alkylphenol alkylene oxide adduct.
Alkylcyclohexanol alkylene oxide adduct obtained by the process of
the invention has less ultraviolet absorption and fluorescence due
to alkylphenol alkylene oxide adduct, and thus the adduct is useful
for spectrochemical analysis of protein and further has excellent
properties also in the uses such as detergents and other common
surfactant applications.
* * * * *