U.S. patent application number 15/129248 was filed with the patent office on 2017-04-06 for alkylene oxide polymer production method.
The applicant listed for this patent is SUMITOMO SEIKA CHEMICALS CO., LTD.. Invention is credited to Toru Ido, Noboru Yamaguchi.
Application Number | 20170096527 15/129248 |
Document ID | / |
Family ID | 54239937 |
Filed Date | 2017-04-06 |
United States Patent
Application |
20170096527 |
Kind Code |
A1 |
Ido; Toru ; et al. |
April 6, 2017 |
ALKYLENE OXIDE POLYMER PRODUCTION METHOD
Abstract
Provided is an alkylene oxide polymer production method, whereby
it becomes possible to produce an alkylene oxide polymer having a
high polymerization degree on an industrial scale and with high
reproducibility. An alkylene oxide polymer production method
comprising carrying out a polymerization reaction of an alkylene
oxide in an inert hydrocarbon solvent in the presence of a zinc
catalyst to produce an alkylene oxide polymer, wherein the zinc
catalyst is produced by reacting an organozinc compound with a
monohydric alcohol in an amount of 12-fold equivalent or less
relative to the amount of the organozinc compound and an aliphatic
polyhydric alcohol in an amount of 0.2- to 1.1-fold equivalent
relative to the amount of the organozinc compound, and the
polymerization reaction is carried out under such a condition that
the amount of the monohydric alcohol in the polymerization reaction
system becomes 0.01-fold equivalent or less relative to the amount
of the organozinc compound.
Inventors: |
Ido; Toru; (Himeji-shi,
Hyogo, JP) ; Yamaguchi; Noboru; (Himeji-shi, Hyogo,
JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SUMITOMO SEIKA CHEMICALS CO., LTD. |
Hyogo |
|
JP |
|
|
Family ID: |
54239937 |
Appl. No.: |
15/129248 |
Filed: |
February 12, 2015 |
PCT Filed: |
February 12, 2015 |
PCT NO: |
PCT/JP2015/053777 |
371 Date: |
September 26, 2016 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G 65/266 20130101;
C08G 65/12 20130101; C08G 65/10 20130101 |
International
Class: |
C08G 65/12 20060101
C08G065/12 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 31, 2014 |
JP |
2014-072760 |
Claims
1. A method for the production of an alkylene oxide polymer
comprising polymerizing an alkylene oxide in the presence of a zinc
catalyst in an inert hydrocarbon solvent to produce an alkylene
oxide polymer, wherein the zinc catalyst is prepared by reacting an
organozinc compound with a monohydric alcohol in an amount of 12
equivalents or less relative to the organozinc compound and an
aliphatic polyhydric alcohol in an amount of 0.2 to 1.1 equivalents
relative to the organozinc compound, and the polymerization
reaction is performed under conditions such that the amount of the
monohydric alcohol in the polymerization reaction is 0.01
equivalents or less relative to the organozinc compound.
2. A method for the production of an alkylene oxide polymer
comprising polymerizing an alkylene oxide in the presence of a zinc
catalyst in an inert hydrocarbon solvent to produce an alkylene
oxide polymer, wherein the method comprises: reacting an organozinc
compound with a monohydric alcohol in an amount of 12 equivalents
or less relative to the organozinc compound and an aliphatic
polyhydric alcohol in an amount of 0.2 to 1.1 equivalents relative
to the organozinc compound to prepare a reaction liquid, distilling
the reaction liquid under normal pressure at a temperature of
100.degree. C. or less to prepare a zinc catalyst in which the
amount of the monohydric alcohol is adjusted to 0.01 equivalents or
less relative to the organozinc compound, and polymerizing the
alkylene oxide in the presence of the zinc catalyst in which the
amount of the monohydric alcohol has been adjusted to 0.01
equivalents or less relative to the organozinc compound.
3. The method for the production of an alkylene oxide polymer
according to claim 1, wherein the organozinc compound is a
dialkylzinc.
4. The method for the production of an alkylene oxide polymer
according to claim 1, wherein the monohydric alcohol is an
aliphatic alcohol having 1 to 3 carbon atoms.
5. The method for the production of an alkylene oxide polymer
according to claim 1, wherein the aliphatic polyhydric alcohol is
an aliphatic polyhydric alcohol having 2 or more carbon atoms and
having two or more hydroxy groups in each molecule thereof
6. A method for the production of a zinc catalyst to be used for a
polymerization reaction of an alkylene oxide, the method
comprising: reacting an organozinc compound with a monohydric
alcohol in an amount of 12 equivalents or less relative to the
organozinc compound and an aliphatic polyhydric alcohol in an
amount of 0.2 to 1.1 equivalents relative to the organozinc
compound, and distilling the reaction liquid obtained in the
reaction step under normal pressure at a temperature of 100.degree.
C. or less to adjust the amount of the monohydric alcohol to 0.01
equivalents or less relative to the organozinc compound.
7. A zinc catalyst to be used for a polymerization reaction of an
alkylene oxide, prepared by reacting an organozinc compound with a
monohydric alcohol in an amount of 12 equivalents or less relative
to the organozinc compound and an aliphatic polyhydric alcohol in
an amount of 0.2 to 1.1 equivalents relative to the organozinc
compound, then distilling the resulting reaction liquid under
normal pressure at a temperature of 100.degree. C. or less, thereby
having adjusted the amount of the monohydric alcohol to 0.01
equivalents or less relative to the organozinc compound.
8. The method for the production of an alkylene oxide polymer
according to claim 2, wherein the organozinc compound is a
dialkylzinc.
9. The method for the production of an alkylene oxide polymer
according to claim 2, wherein the monohydric alcohol is an
aliphatic alcohol having 1 to 3 carbon atoms.
10. The method for the production of an alkylene oxide polymer
according to claim 2, wherein the aliphatic polyhydric alcohol is
an aliphatic polyhydric alcohol having 2 or more carbon atoms and
having two or more hydroxy groups in each molecule thereof.
Description
TECHNICAL FIELD
[0001] The present invention relates to a method for producing an
alkylene oxide polymer., More particularly, it relates to a method
for the production of an alkylene oxide polymer by which an
alkylene oxide polymer having a high degree of polymerization can
be produced industrially and reproducibly.
BACKGROUND ART
[0002] Conventionally, there are much studies regarding
polymerization of an alkylene oxide, especially ethylene oxide,
propylene oxide, etc. For example, it is known that a product
prepared by reacting a monohydric alcohol further to a product
obtained by reacting an organozinc compound to a polyhydric
alcohol, or a product prepared by reacting a polyhydric alcohol
further to a product obtained by reacting an organozinc compound to
a monohydric alcohol (see, for example, Patent Documents 1 and 2)
exhibits an excellent catalytic activity for homopolymerization of
an alkylene oxide or copolymerization of two or more alkylene
oxides and a polymer having a high degree of polymerization can be
obtained.
[0003] However, there have been noted problems in that production
stable on an industrial scale cannot be carried out by these
methods, for example, reproducibility of polymerization speed or
degree of polymerization of a resulting polymer is poor, resulting
in failure to attain a sufficiently high yield, or a polymerized
product agglomerates. Moreover, those methods are not fully
satisfactory in degree of polymerization. On the other hand, there
have been attempted methods of obtaining a polymer reproducibly by
using a product prepared by reacting an organozinc compound and a
polyhydric alcohol with each other (see, for example, Patent
Document 3) as a catalyst in contact with various types of fine
particulate metal oxide as a dispersion aid and a nonionic
surfactant, but there has been noted a drawback that the operation
of catalyst preparation is very complicated.
[0004] As a solution to the above-described problems, it is
proposed, for example in Patent Document 4, to use as a
polymerization catalyst a material prepared by heat-treating within
a certain temperature range a product obtained by reacting an
organozinc compound with an aliphatic polyhydric alcohol and a
monohydric alcohol in a certain equivalent ratio.
PRIOR ART DOCUMENTS
Patent Documents
[0005] Patent Document 1: JP-B-45-7751
[0006] Patent Document 2: JP-B-53-27319
[0007] Patent Document 3: JP-A-62-232433
[0008] Patent Document 4: JP-A-5-17566
SUMMARY OF THE INVENTION
Problems to be Solved by the Invention
[0009] Through diligent effort, however, the present inventors have
found that the reproducibility of a polymerization reaction may be
deteriorated even if the method disclosed in Patent Document 4, for
example, is used.
[0010] The present invention is an invention devised in view of
such a problem. That is, a main object of the present invention is
to provide a method for the production of an alkylene oxide polymer
by which an alkylene oxide polymer having a high degree of
polymerization can be produced industrially and reproducibly.
Means for Solving the Problem
[0011] The present inventors have researched earnestly in order to
solve the above-mentioned problems. As a result, it has become
apparent that despite performing the production of a catalyst under
the same conditions using the method disclosed in Patent Document
4, if removal of unreacted monohydric alcohol by heat treatment is
not attained uniformly, the catalytic activity may vary due to
remaining monohydric alcohol and the polymerization time or the
like may vary. Through further diligent effort, it has been found
that an alkylene oxide polymer having a high degree of
polymerization can be produced industrially and reproducibly by a
method for the production of an alkylene oxide polymer including
making an alkylene oxide undergo a polymerization reaction in the
presence of a zinc catalyst in an inert hydrocarbon solvent to
produce an alkylene oxide polymer, wherein the zinc catalyst is one
prepared by reacting an organozinc compound with a monohydric
alcohol in an amount of 12 equivalents or less relative to the
organozinc compound and an aliphatic polyhydric alcohol in an
amount of 0.2 to 1.1 equivalents relative to the organozinc
compound, and the polymerization reaction is performed under such
conditions that the amount of the monohydric alcohol in a
polymerization reaction system may be 0.01 equivalents or less
relative to the organozinc compound. The present invention has been
accomplished by further repeating studies based on these
findings.
[0012] That is, the present invention provides inventions of the
following aspects. [0013] Item 1. A method for the production of an
alkylene oxide polymer including making an alkylene oxide undergo a
polymerization reaction in the presence of a zinc catalyst in an
inert hydrocarbon solvent to produce an alkylene oxide polymer,
wherein
[0014] the zinc catalyst is one prepared by reacting an organozinc
compound with a monohydric alcohol in an amount of 12 equivalents
or less relative to the organozinc compound and an aliphatic
polyhydric alcohol in an amount of 0.2 to 1.1 equivalents relative
to the organozinc compound, and
[0015] the polymerization reaction is performed under such
conditions that the amount of the monohydric alcohol in a system of
the polymerization reaction may be 0.01 equivalents or less
relative to the organozinc compound. [0016] Item 2. A method for
the production of an alkylene oxide polymer including making an
alkylene oxide undergo a polymerization reaction in the presence of
a zinc catalyst in an inert hydrocarbon solvent to produce an
alkylene oxide polymer, wherein the method includes:
[0017] the step of reacting an organozinc compound with a
monohydric alcohol in an amount of 12 equivalents or less elative
to the organozinc compound and an aliphatic polyhydric alcohol in
an amount of 0.2 to 1.1 equivalents relative to the organozinc
compound to prepare a reaction liquid,
[0018] the step of distilling the reaction liquid under normal
pressure at a temperature of 100.degree. C. or lower to prepare a
zinc catalyst in which the amount of the monohydric alcohol is
adjusted to 0.01 equivalents or less relative to the organozinc
compound, and
[0019] the step of making the alkylene oxide undergo a
polymerization reaction using the zinc catalyst in which the amount
of the monohydric alcohol has been adjusted to 0.01 equivalents or
less relative to the organozinc compound. [0020] Item 3. The method
for the production of an alkylene oxide polymer according 1 or 2,
wherein the organozinc compound is a dialkylzinc. [0021] Item 4.
The method for the production of an alkylene oxide polymer
according to any one of Items 1 to 3, wherein the monohydric
alcohol aliphatic alcohol having 1 to 3 carbon atoms. [0022] Item
5. The method for the production of an alkylene oxide polymer
according to any or e of Items 1 to 4, wherein the aliphatic
polyhydric alcohol is an aliphatic polyhydric alcohol having 2 or
more carbon atoms and having two or more hydroxy groups in each
molecule thereof. [0023] Item 6. A method for the production of a
zinc catalyst to be used for a polymerization reaction of an
alkylene oxide, the method including:
[0024] the reaction step of reacting an organozinc compound with a
monohydric alcohol in an amount of 12 equivalents or less relative
to the organozinc compound and an aliphatic polyhydric alcohol in
an amount of 0.2 to 1.1 equivalents relative to the organozinc
compound, and
[0025] the step of distilling the reaction liquid obtained in the
reaction step under normal pressure at a temperature of 100.degree.
C. or lower to adjust the amount of the monohydric alcohol to 0.01
equivalents or less relative to the organozinc compound. [0026]
Item 7. A zinc catalyst to be used for a polymerization reaction of
an alkylene oxide, prepared by reacting an organozinc compound with
a monohydric alcohol in an amount of 12 equivalents or less
relative to the organozinc compound and an aliphatic polyhydric
alcohol in an amount of 0.2 to 1.1 equivalents relative to the
organozinc compound, then distilling the resulting action liquid
under normal pressure at a temperature of 100.degree. C. or lower,
thereby having adjusted the amount of the monohydric alcohol to
0.01 equivalents or less relative to the organozinc compound.
Advantages of the Invention
[0027] According to the method for the production of an alkylene
oxide polymer of the present invention, an alkylene oxide polymer
having a high degree of polymerization can be produced industrially
and reproducibly.
EMBODIMENTS OF THE INVENTION
1. Method for the Production of an Alkylene Oxide Polymer
[0028] The method for the production of an alkylene oxide polymer
of the present invention is a method for the production of an
alkylene oxide polymer including making alkylene oxide undergo a
polymerization reaction in the presence of a zinc catalyst in an
inert hydrocarbon solvent to produce an alkylene oxide polymer,
Characterized in that the zinc catalyst is one prepared by reacting
an organozinc compound with a monohydric alcohol in an amount of 12
equivalents or less relative to the organozinc compound and an
aliphatic polyhydric alcohol in an amount of 0.2 to 1.1 equivalents
relative to the organozinc compound, and the polymerization
reaction is performed under such conditions that the amount of the
monohydric alcohol in a polymerization reaction system may be 0.01
equivalents or less relative to the organozinc compound. Hereafter,
the method for the production of an alkylene oxide polymer of the
present invention is described in detail.
[0029] In the method for the production of an alkylene oxide
polymer of the present invention, the alkylene oxide to be
subjected to a polymerization reaction as a raw material is not
particularly limited, and examples thereof include ethylene oxide,
propylene oxide, butylene oxide, cyclohexene oxide, styrene oxide,
and epichlorohydrin. Of these alkylene oxides, ethylene oxide,
propylene oxide, etc. are preferably used in terms of high
solubility of a resulting alkylene oxide polymer in water. These
alkylene oxides may be used individually or two or more of them may
be used in combination. A polymer prepared using an alkylene oxide
singly is a homopolymer of the alkylene oxide, and a polymer
prepared using two or more alkylene oxides in combination is a
copolymer of these alkylene oxides. The alkylene oxide polymer to
be produced by the production method of the present invention may
be either a block copolymer or a random copolymer.
[0030] The inert hydrocarbon solvent to be subjected to the
polymerization reaction is not particularly limited, and preferable
examples thereof include aliphatic hydrocarbons, such as n-pentane,
n-hexane, n-heptane, and cyclohexane; and aromatic hydrocarbons,
such as benzene, toluene, and xylene. Of these solvents, n-hexane,
n-heptane, and the like are preferably used because they are easily
available in the industry. These solvents may be used individually
or two or more of them may be used in combination.
[0031] While the amount of the inert hydrocarbon solvent to be used
in the polymerization reaction is not particularly limited, it is
preferably 200 to 10000 parts by mass, more preferably 300 to 1000
parts by mass, even more preferably 400 to 600 parts by mass,
relative to 100 parts by mass of the alkylene oxide from the
viewpoint of advancing the polymerization reaction efficiently and
the viewpoint of inhibiting a product alkylene oxide polymer from
forming a mass.
[0032] The zinc catalyst to be used for a polymerization reaction
in the present invention is one obtained by reacting an organozinc
compound with a monohydric alcohol in an amount of 12 equivalents
or less relative to the organozinc compound and an aliphatic
polyhydric alcohol in an amount of 0.2 to 1.1 equivalents relative
to the organozinc compound. As described below, in the present
invention, a zinc catalyst in which the amount of the monohydric
alcohol has been adjusted to 0.01 equivalents or less relative to
the organozinc compound can be obtained by preparing such a
reaction liquid and then distilling the reaction liquid under
normal pressure at a temperature of 100.degree. C. or lower,
thereby evaporating unreacted monohydric alcohol, and the product
can be used for a polymerization reaction by the zinc catalyst. At
this time, the amount of the monohydric alcohol in the
polymerization reaction system is 0.01 equivalents or less relative
to the organozinc compound. In the present invention, performing a
polymerization reaction under such conditions makes it possible to
produce an alkylene oxide polymer having a high degree of
polymerization industrially and reproducibly.
[0033] The organozinc compound to be used for the preparation of
the zinc catalyst is a compound denoted by the formula: ZnR.sub.2 .
In the formula, R each independently may be an alkyl group having 1
to 6 carbon atoms, a phenyl group, a cycloalkyl group having 4 to 6
carbon atoms, or the like. Specific examples of the organozinc
compound include dialkylzinc, such as dimethylzinc, diethylzinc,
di-n-propyizinc, and dibutylzinc; diphenylzinc, and
dicyclobutylzinc. Of these, a dialkylzinc is preferred, and diethyl
zinc is particularly preferred.
[0034] The monohydric alcohol to be used for the preparation of the
zinc catalyst is an alcohol having one hydroxy group in each
molecule thereof and having no other active hydrogen. Specific
examples of the monohydric alcohol include primary alcohols such as
methanol, ethanol, 1-propanol, and 1-butanol; secondary alcohol
such as 2-propanol and 2-butanol and tertiary alcohol such as
tert-butanol. Of these, a monohydric alcohol having 1 to 3 carbon
atoms and having a boiling point under normal pressure of
100.degree. C. or lower is preferred because it is necessary to
efficiently remove unreacted monohydric alcohol to the outside of
the system during the distillation described below, and
specifically, an aliphatic alcohol having 1 to 3 carbon atoms, such
as methanol, ethanol and 2-propanol, is preferably used. These
monohydric alcohols may be used individually or two or more of them
may be used in combination.
[0035] In the preparation of the zinc catalyst, it is necessary to
adjust the upper limit of the use amount of the monohydric alcohol
to 12 equivalents or less relative to the organozinc compound from
the viewpoint of removing unreacted monohydric alcohol by the
distillation described below, thereby reproducibly performing a
polymerization reaction under such conditions that the amount of
unreacted monohydric alcohol may be 0.01 equivalents or less
relative to the organozinc compound. The upper limit of the use
amount of the monohydric alcohol is preferably 10 equivalents or
less, more preferably 8 equivalents or less. From the viewpoint of
maintaining the activity of the zinc catalyst obtained, the lower
limit of the use amount of the monohydric alcohol is preferably 1
equivalent or more, more preferably 2 equivalents or more, even
more preferably 3 equivalents or more, relative to the organozinc
compound. A preferable range of the use amount of the monohydric
alcohol is preferably 1 to 12 equivalents, more preferably 2 to 10
equivalents, even more preferably 3 to 8 equivalents, relative to
the organozinc compound.
[0036] The aliphatic polyhydric alcohol to be used for the prep
anon of the zinc catalyst is an aliphatic polyhydric alcohol having
2 or more carbon atoms and having 2 or more hydroxy groups in each
molecule thereof. Specific examples of the aliphatic polyhydric
alcohol include ethylene glycol, propylene glycol, 1, 2-butanediol,
1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanetriol,
2,3,4-pentanetriol 1,6-hexanediol, glycerol, and pentaerythritol.
Of these, aliphatic polyhydric alcohols having 4 carbon atoms are
preferable from the viewpoint of the activity of a zinc catalyst to
be obtained, and specifically, 1,3-butanediol and 1,4-butariediol
are suitably used.
[0037] The upper limit of the use amount of the aliphatic
polyhydric alcohol is required to be 0.2 to 1.1 equivalents
relative to the organozinc compound from the viewpoint of
preventing the formation of a mass of an alkylene oxide polymer in
the production of an alkylene oxide polymer using the resulting
zinc catalyst. A preferable range of the use amount of the
aliphatic polyhydric alcohol may be 0.3 to 1.0 equivalent relative
to the organozinc compound.
[0038] In the preparation of the zinc catalyst, it is preferable to
use a reaction solvent in reacting the organozinc compound, the
monohydric alcohol, and the aliphatic polyhydric alcohol together
from the viewpoint of performing the reaction smoothly. The
reaction solvent is not particularly limited and examples thereof
include aliphatic hydrocarbons such as n-pentane, n-hexane,
n-heptane, and cyclohexane; and aromatic hydrocarbons such as
benzene, toluene and xylene. In the above-mentioned polymerization
reaction, it is preferable to use the same solvent as the solvent
to be used for the preparation of the zinc catalyst and the inert
hydrocarbon solvent to be used for the polymerization reaction of
the alkylene oxide, from the viewpoint of producing the alkylene
oxide polymer efficiently.
[0039] In the preparation of the zinc catalyst, the use amount of
the solvent may be preferably 200 to 1500 parts by mass, more
preferably 300 to 1200 parts by mass, even more preferably 400 to
1000 parts by mass relative to 100 parts by mass of the organozinc
compound from an economical point of view and the viewpoint of
controlling heat of reaction.
[0040] When reacting the organozinc compound, the monohydric
alcohol, and the aliphatic polyhydric alcohol together in the
preparation of the zinc catalyst, it is preferable to perform the
reaction in an inert gas atmosphere, such as nitrogen, argon, and
helium, from the viewpoint of holding the activity of a zinc
catalyst to be obtained.
[0041] In the preparation of the zinc catalyst, the method of
reacting the organozinc compound, the monohydric alcohol, and the
aliphatic polyhydric alcohol together is not particularly limited,
and examples thereof include (a) a method in which a solvent and
the organozinc compound are charged, then reacted with part of the
monohydric alcohol, and subsequently reacted with the remainder of
the monohydric alcohol and the aliphatic polyhydric alcohol, (b) a
method in which a solvent and the organozinc compound are charged,
then reacted with part of the aliphatic polyhydric alcohol, and
subsequently reacted with the monohydric alcohol and the remainder
of the aliphatic polyhydric alcohol, and (c) a method in which a
solvent and the organozinc compound are charged, and then the
monohydric alcohol and the aliphatic polyhydric alcohol are reacted
simultaneously.
[0042] In the above method (a), the amount of the part of the
monohydric alcohol to be reacted first may be preferably 0.2
equivalents or more, more preferably 0.4 equivalents or more
relative to the organozinc compound. In the above method (b), the
amount of the part of the aliphatic polyhydric alcohol to be
reacted first may be preferably 0.1 equivalents or more, more
preferably 0.2 equivalents or more relative to the organozinc
compound.
[0043] As described above, in the production method of the present
invention, as a result of distilling the reaction liquid prepared
by the method described above, under normal pressure at a
temperature of 100.degree. C. or lower, thereby removing the
monohydric alcohol until the amount of the monohydric alcohol in
the reaction liquid becomes 0.01 equivalents or less relative to
the organozinc compound, there is obtained a zinc catalyst in which
the amount of the monohydric alcohol has been adjusted to 0.01
equivalents or less relative to the organozinc compound. In the
present invention, the use of such a zinc catalyst makes it
possible to perform a polymerization reaction under such conditions
that the amount of the monohydric alcohol in a polymerization
reaction system is adjusted to 0.01 equivalents or less relative to
the organozinc compound, and an alkylene oxide polymer having a
high degree of polymerization can be produced industrially and
reproducibly.
[0044] The upper limit of the temperature in distilling the
reaction liquid is preferably 100.degree. C. or lower under normal
pressure in order to hold the number of active points of a zinc
catalyst to be obtained and hold the activity thereof. The upper
limit of the distillation temperature may more preferably be
90.degree. C. On the other hand, the lower limit of the
distillation temperature is preferably 70.degree. C. from the
viewpoint of fully removing unreacted monohydric alcohol and
aliphatic polyhydric alcohol to the outside of the system to
prevent deterioration and variation in the activity of a zinc
catalyst. The range of the distillation temperature may preferably
be 70.degree. C. to 90.degree. C. In the present invention, the
distillation temperature is the temperature of a heating medium
that is heating a reaction vessel.
[0045] The number of times of performing distillation is not
particularly limited, and it may preferably be twice or more, more
preferably three times or more from the viewpoint of fully removing
unreacted monohydric alcohol and aliphatic polyhydric alcohol to
the outside of the system to prevent deterioration and variation in
the activity of a zinc catalyst. In the case of performing
distillation twice or more, it is preferable to add a proper amount
of a solvent to be used for the polymerization reaction before each
of the second or later distillations. The addition amount of the
solvent is not particularly limited, and it may preferably be 400
to 1000 parts by mass relative to 100 parts by mass of the
organozinc compound from the purpose of the distillation and the
economical point of view.
[0046] Moreover, in the present invention, the zinc catalyst may
further be heat treated after performing the above-mentioned
distillation. The upper limit of the heat treatment temperature may
preferably be 200.degree. C. or lower, more preferably 150.degree.
C. or lower from the viewpoint of holding the activity of a zinc
catalyst to be obtained. The lower limit of the heat treatment
temperature may preferably be 100.degree. C. or higher, more
preferably 120.degree. C. or higher from the viewpoint of fully
removing unreacted monohydric alcohol and aliphatic polyhydric
alcohol to the outside of the system to prevent deterioration and
variation in the activity of a zinc catalyst. The range of the heat
treatment temperature may preferably be 100 to 200.degree. C., more
preferably 120 to 150.degree. C. in the present invention, the heat
treatment temperature is the temperature of a heating medium that
is heating a reaction vessel.
[0047] The time necessary for the heat treatment varies depending
on the heating temperature, and it is properly determined usually
within a range of 5 to 180 minutes, preferably within a range of 10
to 60 minutes from the viewpoint of preventing deterioration in the
activity of a zinc catalyst to be obtained and variation in the
activity.
[0048] In the method for the production of an alkylene oxide
polymer of the present invention, it is required that the amount of
the monohydric alcohol in the polymerization reaction system be
equal to or less than 0.01 equivalents relative to the
above-described organozinc compound. That is, it is necessary to
use for the polymerization reaction the zinc catalyst in which the
amount of the monohydric alcohol is equal to o less than 0.01
equivalents relative to the organozinc compound. When the amount of
the monohydric alcohol exceeds 0.01 equivalents relative to the
organozinc compound, variation in the activity of the zinc catalyst
results, leading to variation in the polymerization time of the
alkylene oxide and variation in the performance (especially,
viscosity) of an alkylene oxide to be obtained. The amount of the
monohydric alcohol in the zinc catalyst is a value determined by
the measuring method described below.
[0049] The zinc catalyst prepared as described above may be used
for a polymerization reaction of an alkylene oxide as received and
can be used by adjusting its concentration through the adjustment
of the amount of a solvent. The adjustment of the concentration can
be performed, for example, by removing or adding the solvent in the
distillation described above or the like.
[0050] The method of making an alkylene oxide undergo a
polymerization reaction in the presence of a zinc catalyst in an
inert hydrocarbon solvent is not particularly limited, and it may
be, for example, a method in which the inert hydrocarbon solvent
and the zinc catalyst are added to a polymerization reaction
vessel, the alkylene oxide is further added, and they are
polymerized in an inert gas atmosphere. It is preferable to perform
the polymerization reaction under stirring or shaking from the
viewpoint of performing the polymerization reaction smoothly.
[0051] The amount of the zinc catalyst o be used in the
polymerization reaction is not particularly limited, it may
preferably be 0.01 to 1 mol %, more preferably 0.02 to 0.8 mol %
based on the zinc atoms in the zinc catalyst relative to the number
of moles of the alkylene oxide from the viewpoint of efficient
advance of the polymerization reaction.
[0052] The temperature of the polymerization reaction can
arbitrarily be set according to reaction conditions such as the
type d the concentration of the alkylene oxide and the
concentration of the zinc catalyst, and it is usually 5 to
100.degree. C., preferably 20 to 50.degree. C. The pressure in the
polymerization reaction is not particularly limited, and it may,
for example, be 0.0 MPa to 1.0 MPa, preferably 0.01 MPa to 0.5
MPa.
[0053] As to the endpoint of the polymerization reaction, for
example, the time when the internal pressure in the polymerization
system has come to no longer change continuously for 15 minutes can
be regarded as the endpoint of the reaction. An alkylene oxide
polymer is obtained by performing drying, etc. after the completion
of the polymerization reaction. The thus-obtained alkylene oxide
polymer is usually in the form of line particulates which do not
agglomerate, and an alkylene oxide polymer having a viscosity of
300 mPas or more as measured by the measurement method described
below can be obtained reproducibly.
[0054] While the mechanism of it becoming possible to produce an
alkylene oxide polymer having a high degree of polymerization
industrially and reproducibly in the present invention by
performing a polymerization reaction using the zinc catalyst
prepared as described above under such conditions that the amount
of a monohydric alcohol in the polymerization reaction system is
adjusted to 0.01 equivalents or less relative to the organozinc
compound is not clear in detail, the mechanism can, for example, be
considered as follows: That is, generally, there can be considered
a mechanism in which in polymerization of an alkylene oxide using
an organozinc compound, alkylene oxide molecules coordinate to zinc
and undergo ring-opening addition successively. It is expected that
owing to the fact that the amount of unreacted monohydric alcohol
remaining after the polymerization reaction is very small as in the
present invention, the catalytic activity of the zinc catalyst is
improved and stabilized and, as a result, an alkylene oxide polymer
having a high degree of polymerization is produced
reproducibly.
[0055] The alkylene oxide polymer to be produced by le production
method of the present invention is a useful polymer to be used for
a variety of applications. For example, an ethylene oxide polymer
can be used as a useful, water-soluble polymer in various fields
including a dispersing agent for paper making, a coagulant, a
water-soluble film, a water-soluble fiber, a sizing agent for
printing, and a plasticizer.
2. Zinc Catalyst
[0056] In the present invention, the production of an alkylene
oxide polymer can be performed using the above-described zinc
catalyst. The zinc catalyst is characterized in that by reacting an
organozinc compound with a monohydric alcohol in an amount of 12
equivalents or less relative to the organozinc compound and an
aliphatic polyhydric alcohol in an amount of 0.2 to 1.1 equivalents
relative to the organozinc compound, then distilling the resulting
reaction liquid under normal pressure at a temperature of
100.degree. C. or lower, the amount of the monohydric alcohol has
been adjusted to 0.01 equivalents or less relative to the
organozinc compound. The zinc catalyst can be produced via the
following steps.
[0057] The reaction step of reacting an organozinc compound with a
monohydric alcohol in an amount of 12 equivalents or less relative
to the organozinc compound and an aliphatic polyhydric alcohol in
an amount of 0.2 to 1.1 equivalents relative to the organozinc
compound to prepare a reaction liquid.
[0058] The step of distilling the reaction liquid obtained in the
action step under normal pressure at a temperature of 100.degree.
C. or lower to prepare a zinc catalyst in which the amount of the
monohydric alcohol is adjusted to 0.01 equivalents or less relative
to the organozinc compound.
[0059] In the zinc catalyst of the present invention, the alkylene
oxide to be used for polymerization, the organozinc compound, the
monohydric alcohol, and the aliphatic polyhydric alcohol to be used
for the production of the zinc catalyst, the reaction conditions,
etc. are as described above.
[0060] By the use of the zinc catalyst of the present invention for
a polymerization reaction of an alkylene oxide, an alkylene oxide
polymer having a high degree of polymerization can be produced
industrially and reproducibly.
EXAMPLES
[0061] The present invention is described below in detail by
providing Examples and Comparative Examples. However, the present
invention is not limited to the Examples.
[Evaluation Methods]
[0062] The performance of the alkylene oxide polymer obtained in
each of the Examples and the Comparative Examples was measured and
evaluated by the following methods. The results are shown in Table
1 and Table 2.
(1) Measurement of Viscosity
[0063] A 1-liter beaker was charged with 497.5 g of ion-exchanged
water, and 2.5 g of an alkylene oxide polymer was charged thereinto
under stirred with a flat board of 80 mm in width and 25 mm in
length at a tip peripheral speed of 1.0 m/s, and the stirring was
continued for 3 hours to prepare an aqueous solution. The resulting
aqueous solution was immersed in a 25.degree. C. thermostatic bath
for 30 minutes or more, and the viscosity of the aqueous solution
was determined with a B type rotary viscometer (a B-type viscometer
manufactured by TOKIMEC INC., rotor number =2, rotation speed =12
rpm, 3 minutes, 25.degree. C.).
[0064] If the viscosity is 300 mPas or more, the polymer can be
judged to be an alkylene oxide polymer having a high degree of
polymerization.
(2) Measurement of the Amount of Monohydric Alcohol
[0065] The amount of a monohydric alcohol was measured using a gas
chromatography (GC-2014 manufactured by Shimadzu Corporation;
hereinafter GC) under conditions including an injection temperature
of 200.degree. C., a column to be used being Thermon 1000 (length:
3 meters) a column temperature of 100.degree. C., and a detector
temperature of 200.degree. C., and a concentration was calculated
from a peak area. The amount of a monohydric alcohol was calculated
from an analytical curve prepared beforehand.
Example 1-1
[Production of Zinc Catalyst]
[0066] There was prepared a round-bottomed flask of 80 mm in inner
diameter and 500 mL capacity equipped with a condenser, a dropping
funnel, a nitrogen gas inlet tube, and stirring blades having four
paddle blades (45 degrees inclined) having a blade diameter of 53
mm as a stirrer.
[0067] Into the flask replaced with nitrogen, 87.1 g of n-hexane
and 9.90 g of diethyl zinc (Et.sub.2Zn) were placed, and as a first
step, a reaction was carried out while dropping 11.03 g (0.240 mol)
of ethyl alcohol (EtOH) at a rate of 0.2 g/minute at an internal
temperature of 20.degree. C. under stirring at a tip peripheral
speed of 0.97 m/second (the rotational speed of stirring =350 rpm).
As a second step, a mixture liquid of 6.49 g (0.072 mol) of
1,4-butanediol (1,4-BDO) and 13.27 g (0.288 mol) of ethyl alcohol
was dropped at a rate of 0.2 g/minute to the reaction liquid cooled
to an internal temperature of 10.degree. C. After the completion of
the dropping, the temperature of the inside of the flask was raised
to 30.degree. C. and a reaction was carried out for 1 hour, and
subsequently the temperature was raised to 50.degree. C. and the
reaction was carried out for 1 hour. Then, heating was performed at
an oil bath temperature of 80.degree. C. and unreacted components
were removed by distillation. Following the distillation, the
residue was allowed to cool to room temperature and 52.4 g of
n-hexane was added, and second distillation was carried out by
heating at an oil bath temperature of 80.degree. C. This operation
was performed further once again and distillation was carried out
three times in total. After the three-time distillation, the
residue was moved to a pressure-resistant vessel thoroughly
replaced with nitrogen, and was subjected to heat treatment at an
oil bath temperature of 130.degree. C. for 15 minutes with the
vessel stoppered. After cooling, the residue was diluted with 264 g
of n-hexane, thereby obtaining 297 g of a zinc catalyst containing
1.8% by mass of zinc. When the n-hexane of the supernatant liquid
of this zinc catalyst was measured by GC, the amount of ethyl
alcohol was found to be 0.0033 equivalents relative to an
organozinc compound.
[Production of Alkylene Oxide Polymer]
[0068] There was prepared a pressure-resistant reaction vessel of
94 mm in inner diameter and 1 L in capacity equipped with a
dropping funnel, a nitrogen gas inlet tube, and stirring blades
having an anchor-shaped paddle blades having a blade diameter of 47
mm as a stirrer.
[0069] A pressure-resistant vessel thoroughly replaced with
nitrogen was charged with 340 g of n-hexane and 0.975 g (0.0004 mol
terms of zinc) of the zinc catalyst obtained above was dispersed
uniformly, and 81 g (1.84 mol) of ethylene oxide was added and the
vessel was stoppered, followed by polymerization under stirring in
a thermostatic bath at 40.degree. C. After the completion of the
polymerization, a white product was taken out by filtration and
dried at 40.degree. C. under reduced pressure, thereby obtaining
81.0 g of polyethylene oxide.
[0070] The polymerization time was 6 hours and the yield was 100%
by mass. The viscosity of a 0.5% by mass aqueous solution of the
resulting polyethylene oxide was 855 mPas.
Example 1-2
[0071] A zinc catalyst was produced in analogy to Example 1-1,
thereby obtaining 297 g of a zinc catalyst containing 1.8% by mass
of zinc. When the n-hexane of the supernatant liquid of this zinc
catalyst was measured by GC, the amount of ethanol was found to be
0.0038 equivalents relative to an organozinc compound.
[0072] 81 g (1.84 mol) of ethylene oxide was polymerized using the
zinc catalyst in analogy to Example 1-1 and, as a result, 79.5 g of
polyethylene oxide was obtained.
[0073] The polymerization time was 6 hours and the yield was 98% by
mass. The viscosity of a 0.5% by mass aqueous solution of the
resulting polyethylene oxide was 825 mPas, and reproducibility was
good.
Example 1-3
[0074] A zinc catalyst was produced in analogy to Example 1-1,
thereby obtaining 297 g of a zinc catalyst containing 1.8% by mass
of zinc. When the n-hexane of the supernatant liquid of this zinc
catalyst was measured by GC, the amount of ethyl alcohol was found
to be 0.0047 equivalents relative to an organozinc compound.
[0075] 81 g (1.84 mol) of ethylene oxide was polymerized using the
zinc catalyst in analogy to Example 1-1 and, as a result, 80.7 a of
polyethylene oxide was obtained.
[0076] The polymerization time was 6 hours and 45 minutes and the
yield was 100% by mass. The viscosity of a 0.5% by mass aqueous
solution of the resulting polyethylene oxide was 865 mPas, and
reproducibility was good.
Example 2
[Production of Zinc Catalyst]
[0077] There was prepared a round-bottomed flask of 80 mm in inner
diameter and 500 mL in capacity equipped with a condenser, a
dropping funnel, a nitrogen gas inlet tube, and stirring blades
having four paddle blades (45 degrees inclined) having a blade
diameter of 53 mm as a stirrer.
[0078] Into the flask replaced with nitrogen, 87.1 g of n-hexane
and 9.90 g of diethyl zinc were placed, and as a first step, a
reaction was carried out while dropping 11.03 g (0.240 mol) of
ethyl alcohol at a rate of 0.2 g/minute at an internal temperature
of 20.degree. C. under stirring at a tip peripheral speed of 0.97
m/second (the rotational speed of stirring =350 rpm). As a second
step, a mixture liquid of 6.49 g (0.072 mol) of 1,4-butanediol and
13.27 g (0.288 mol) of ethyl alcohol was dropped at a rate of 0.2
g/minute to the reaction liquid cooled to an internal temperature
of 10.degree. C. After the completion of the dropping, the
temperature of the inside of the flask was raised to 30.degree. C.
and a reaction was carried out for 1 hour, and subsequently the
temperature was raised to 50.degree. C. and the reaction was
carried out for 1 hour. Then, heating was performed at an oil bath
temperature of 80.degree. C. and unreacted components were removed
by distillation. Following the distillation, the residue was
allowed to cool to room temperature and 52.4 g of n-hexane was
added, and second distillation was carried out by heating at an oil
bath temperature of 80.degree. C. After the two-times distillation,
the residue was moved to a pressure-resistant vessel thoroughly
replaced with nitrogen, and was subjected to h at treatment at an
oil bath temperature of 130.degree. C. for 15 minutes/the vessel
stoppered. After cooling, the residue was diluted with 264 g of
n-hexane, thereby obtaining 297 g of a zinc catalyst containing
1.8% by mass of zinc. When the n-hexane of the supernatant liquid
of this zinc catalyst was measured by GC, the amount of ethyl
alcohol was found to be 0.0093 equivalents relative to an
organozinc compound.
[Production of Alkylene Oxide Polymer]
[0079] There was prepared a pressure-resistant reaction vessel of
94 mm in inner diameter and 1 L in capacity equipped with a
dropping funnel, a nitrogen gas inlet tube, and stirring blades
having an anchor-shaped paddle blades having a blade diameter of 47
mm as a stirrer.
[0080] A pressure-resistant vessel thoroughly replaced with
nitrogen was charged with 340 g of n-hexane and 0.975 g (0.0004 mol
in terms of zinc) of the zinc catalyst obtained above was dispersed
uniformly, and 81 g (1.84 mol) of ethylene oxide was added and the
vessel was stoppered, followed by polymerization under stirring in
a thermostatic bath at 40.degree. C. After the completion of the
polymerization, a white product was taken out by filtration and
dried at 40.degree. C. under reduced pressure, thereby obtaining
78.6 g of polyethylene oxide.
[0081] The polymerization time was 6 hours and 45 minutes and the
yield was 97% by mass. The viscosity of a 0.5% by mass aqueous
solution of the resulting polyethylene oxide was 820 mPas.
Example 3
[Production of Zinc Catalyst]
[0082] There was prepared a round-bottomed flask of 80 mm in inner
diameter and 500 mL in capacity equipped with a condenser, a
dropping funnel, a nitrogen gas inlet tube, and stirring blades
having four paddle blades (45 degrees inclined) haying a blade
diameter of 53 mm as a stirrer.
[0083] Into the flask replaced with nitrogen, 87.1 g of n-hexane
and 9.90 g of diethyl zinc were placed, and as a first step, 1.47 g
(0.030 mol) of ethyl alcohol was reacted while being dropped at a
rate of 0.2 g/minute at an internal temperature of 20.degree. C.
under stirring at a tip peripheral speed of 0.97 in/second (the
rotational speed of stirring =350 rpm). As a second step, a mixture
liquid of 6.49 g (0.072 mot) of 1,4-butariediol and 13.27 g (0.288
mol) of ethyl alcohol was dropped at a rate of 0.2 g/minute to the
reaction liquid cooled to an internal temperature of 10.degree. C.
After the completion of the dropping, the temperature of the inside
of the flask was raised to 30.degree. C. and a reaction was carried
out for 1 hour, and subsequently the temperature was raised to
50.degree. C. and the reaction was carried out for 1 hour. Then,
heating was performed at an oil bath temperature of 80.degree. C.
and unreacted components were removed by distillation. Following
the distillation, the residue was allowed to cool to room
temperature and 52.4. g of n-hexane was added, and second
distillation was carried out by heating at an oil bath temperature
of 80.degree. C. This operation was performed further once again
and distillation was carried out three times in total. After
cooling, the residue was diluted with 264 g of n-hexane, thereby
obtaining 297 g of a zinc catalyst containing 1.8% by mass of zinc.
When the n-hexane of the supernatant liquid of this zinc catalyst
was measured by GC, the amount of ethyl alcohol was found to be
0.0013 equivalents relative to an organozinc compound.
[Production of Alkylene Oxide Polymer]
[0084] There was prepared a pressure-resistant reaction vessel of
94 mm in inner diameter and 1 L in capacity equipped with a
dropping funnel, a nitrogen gas inlet tube, and stirring blades
having an anchor-shaped paddle blades having a blade diameter of 47
mm as a stirrer.
[0085] A pressure-resistant vessel thoroughly r placed with
nitrogen was charged with 340 g of n-hexane and 3.38 g (0.0013 mol
in terms of zinc) of the zinc catalyst obtained above was dispersed
uniformly, and 81 g (1.84 mol) of ethylene oxide was added and the
vessel was stoppered, followed by polymerization under stirring in
a thermostatic bath at 40.degree. C. After the completion of the
polymerization, a white product was taken out by filtration and
dried at 40.degree. C. under reduced pressure, thereby obtaining
80.9 g of polyethylene oxide.
[0086] The polymerization time was 4 hours and 15 minutes and the
yield was 100% by mass. The viscosity of a 0.5% by mass aqueous
solution of the resulting polyethylene oxide was 810 mPas.
Example 4
[0087] A zinc catalyst was produced in analogy to Example 3 except
that all the distillation temperatures where changed from
80.degree. C. to 70'C in the production of the zinc catalyst of
Example 3, thereby obtaining 297 g of a zinc catalyst containing
1.8% by mass of zinc. When the n-hexane of the supernatant liquid
of this zinc catalyst was measured by GC, the amount of ethyl
alcohol was found to be 0.0058 equivalents relative to an
organozinc compound.
[0088] 81 g (1.84 mol) of ethylene oxide was polymerized using the
zinc catalyst in analogy to Example 3 and, as a result, 77.9 g of
an alkylene oxide was obtained.
[0089] The polymerization time was 4 hours and 30 minutes and the
yield was 96% by mass. The viscosity of a 0.5% by mass aqueous
solution of the resulting polyethylene oxide was 595 mPas.
Example 5
[0090] A zinc catalyst was produced in analogy to Example 3 except
that all the distillation temperatures where changed from 80''C to
100.degree. C. in the production of the zinc catalyst of Example 3,
thereby obtaining 297 g of a zinc catalyst containing 1.8% by mass
of zinc. When the it-hexane of the supernatant liquid of this zinc
catalyst was measured by GC, the amount of ethyl alcohol was found
to be 0.001 equivalents relative to an organozinc compound.
[0091] 81 g (1.84 mol) of ethylene oxide was polymerized using the
zinc catalyst in analogy to Example 3 and, as a result, 80.2 g of
an alkylene oxide polymer was obtained.
[0092] The polymerization time was 5 hours and the yield was 99% by
mass. The viscosity of a 0.5% by mass aqueous solution of the
resulting polyethylene oxide was 720 mPas.
Example 6
[Production of Zinc Catalyst]
[0093] There was prepared around-bottomed flask of 80 mm in inner
diameter and 500 mL in capacity equipped with a condenser, a
dropping funnel, a nitrogen gas inlet tube, and stirring blades
having four paddle blades (45 degrees inclined) having a blade
diameter of 53 mm as a stirrer.
[0094] Into the flask replaced with nitrogen, 87.1 g of n-hexane
and 9.90 g of diethyl zinc were placed, and as a first step, 14.42
g (0.240 mot) of isopropyl alcohol (2-PrOH) was reacted while being
dropped at a rate of 0.2 g/minute at an internal temperature of
20.degree. C. under stirring at a tip peripheral speed of 0.97
m/second (the rotational speed of stirring =350 rpm). As a second
step, a mixture liquid of 6.49 g (0.072 mol) of 1,4-butanediol and
17.31 g (0.288 mol) of isopropyl alcohol was dropped at a rate of
0.2 g/minute to the reaction liquid cooled to an internal
temperature of 10.degree. C. After the completion of the dropping,
the temperature of the inside of the flask was raised to 30.degree.
C. and a reaction was carried out for 1 hour, and subsequently the
temperature was raised to 50.degree. C. and the reaction was
carried out for 1 hour. Then, heating was performed at an oil bath
temperature of 80.degree. C. and unreacted components were removed
by distillation. Following the distillation, the residue was
allowed to cool to room temperature and 52.4 g of n-hexane was
added, and second distillation was carried out by heating at an oil
bath temperature of 80.degree. C. This operation was performed
further once again and distillation was carried out three times in
total. After the three-times distillation, the residue was moved to
a pressure-resistant vessel thoroughly replaced with nitrogen, and
was subjected to heat treatment at an oil bath temperature of
130.degree. C. for 15 minutes with the vessel stoppered. After
cooling, the residue was diluted with 264 g of n-hexane, thereby
obtaining 297 g of a zinc catalyst containing 1.8% by mass of zinc.
When the n-hexane of the supernatant liquid of this zinc catalyst
was measured by GC, the amount of isopropyl alcohol was found to be
0.0001 equivalents relative to an organozinc compound.
[Production of Alkylene Oxide Polymer]
[0095] There was prepared a pressure-resistant reaction vessel of
94 mm in inner diameter and 1 L in capacity equipped with a
dropping funnel, a nitrogen gas inlet tube, and stirring blades
having an anchor-shaped paddle blades having a blade diameter of 47
mm as a stirrer.
[0096] A pressure-resistant vessel thoroughly replaced with
nitrogen was charged with 340 g of n-hexane and 0.975 g (0.0004 mol
in terms of zinc) of the zinc catalyst obtained above was dispersed
uniformly, and 81 g (1.84 mol) of ethylene oxide was added and the
vessel was stoppered, followed by polymerization under stirring in
a thermostatic bath at 40.degree. C. After the completion of the
polymerization, a white product was taken out by filtration and
dried at 40.degree. C. under reduced pressure, thereby obtaining
75.7 g of polyethylene oxide.
[0097] The polymerization time was 6 hours and 45 minutes and the
yield was 93% by mass. The viscosity of a 0.5% by mass aqueous
solution of the resulting polyethylene oxide was 575 mPas.
Example 7
[Production of Zinc Catalyst]
[0098] There was prepared a round-bottomed flask of 80 mm in inner
diameter and 500 mL in capacity equipped with a condenser, a
dropping funnel, a nitrogen gas inlet tube, and stirring blades
having four paddle blades (45 degrees inclined) having a blade
diameter of 53 mm as a stirrer.
[0099] Into the flask replaced with nitrogen, 87.1 g of n-hexane
and 9.90 g of diethyl zinc were placed, and as a first step, 1.02 g
(0.030 mol) of methyl alcohol was reacted while being dropped at a
rate of 0.2 g/minute at an internal temperature of 20.degree. C.,
under stirring at a tip peripheral speed of 0.97 m/second (the
rotational speed of stirring =350 rpm). As a second step, a mixture
liquid of 6.49 g (0.072 mol) of 1,4-butanediol and 9.22 g (0.288
_op of methyl alcohol (MeOH) was dropped at a rate of 0.2 g/minute
to the reaction liquid cooled to an internal temperature of
10.degree. C. After the completion of the dropping, the temperature
of the inside of the flask was raised to 30.degree. C. and a
reaction was carried out for 1 hour, and subsequently the
temperature was raised to 50.degree. C. and the reaction was
carried out for 1 hour. Then, heating was performed at an oil bath
temperature of 80.degree. C. and unreacted components were removed
by distillation. Following the distillation, the residue was
allowed to cool to room temperature and 52.4 g of n-hexane was
added, and second distillation was carried out by heating at an oil
bath temperature of 80.degree. C. This operation was performed
further once again and distillation was carried out three times in
total. After cooling, the residue was diluted with 264 g of
n-hexane, thereby obtaining 297 g of a zinc catalyst containing
1.8% by mass of zinc. When the n-hexane of the supernatant liquid
of this zinc catalyst was measured by GC, the amount of methyl
alcohol was found to be 0.0008 equivalents relative to an
organozinc compound.
[Production of Alkylene Oxide Polymer]
[0100] There was prepared a pressure-resist, reaction vessel of 94
mm in inner diameter and 1 L in capacity equipped with a dropping
funnel, a nitrogen gas inlet tube, and stirring blades having an
anchor-shaped paddle blades having a blade diameter of 47 mm as a
stirrer.
[0101] A pressure-resistant vessel thoroughly replaced with
nitrogen was charged with 340 g of n-hexane and 3.38 g (0.0013 mol
in terms of zinc) of the zinc catalyst obtained above was dispersed
uniformly, and 81 g (1.84 mol) of ethylene oxide was added and the
vessel was stoppered, follow d by polymerization wider stirring in
a thermostatic bath at 40.degree. C. After the completion of the
polymerization, a white product was taken out by filtration and
dried at 40.degree. C. under reduced pressure, thereby obtaining
79.1 g of polyethylene oxide.
[0102] The polymerization time was 5 hours and 30 minutes and the
yield was 98% by mass. The viscosity of a 0.5% by mass aqueous
solution of the resulting polyethylene oxide was 425 mPas.
Example 8
[Production of Zinc Catalyst]
[0103] There was prepared a round-bottomed flask of 80 mm in inner
diameter and 500 mL in capacity equipped with a condenser, a
dropping funnel, a nitrogen gas inlet tube, and stirring blades
haying four paddle blades (45 degrees inclined) having a blade
diameter of 53 mm as a stirrer.
[0104] Into the flask replaced with nitrogen, 87.1 g of n-hexane
and 9.90 g of diethyl zinc were placed, and as a first step, a
reaction was carried out while dropping 11.03 g (0.240 mol) of
ethyl alcohol at a rate of 0.2 g/minute at an internal temperature
of 20.degree. C. under stirring at a tip peripheral speed of 0.97
m/second (the rotational speed of stirring =350 rpm). As a second
step, a mixture liquid of 2.16 g (0.30 mol) of 1,4-butanediol and
26.54 g (0.576 mol) of ethyl alcohol was dropped at a rate of 0.2
g/minute to the reaction liquid cooled to an internal temperature
of 10.degree. C. After the completion of the dropping, the
temperature of the inside of the flask was raised to 30.degree. C.
and a reaction was carried out for 1 hour, and subsequently the
temperature was raised to 50.degree. C. and the reaction was
carried out for 1 hour. Then, heating was performed at an oil bath
temperature of 80.degree. C. and unreacted components were removed
by distillation. Following the distillation, the residue was
allowed to cool to room temperature and 52.4 g of n-hexane was
added, and second distillation was carried out by heating at an oil
bath temperature of 80.degree. C. This operation was performed
further once again and distillation was carried out three times in
total. After cooling, the residue was diluted with 264 g of
n-hexane, thereby obtaining 297 g of a zinc catalyst containing
1.8% by mass of zinc. When the n-hexane of the supernatant liquid
of this zinc catalyst was measured by GC, the amount of ethyl
alcohol was found to be 0.0048 equivalents relative to an
organozinc compound.
[Production of Alkylene Oxide Polymer]
[0105] There was prepared a pressure-resistant reaction vessel of
94 mm in inner diameter and 1 L in capacity equipped with a
dropping funnel, a nitrogen gas inlet tube, and stirring blades
having an anchor-shaped paddle blades having a blade diameter of 47
mm as a stirrer.
[0106] A pressure-resistant vessel thoroughly replaced with
nitrogen was charged with 340 g of n-hex and 3.38 g (0.0013 mol in
terms of zinc) of the zinc catalyst obtained above was dispersed
uniformly, and 81 g (1.84 mol) of ethylene oxide was added and the
vessel was stoppered, followed by polymerization under stirring in
a thermostatic bath at 40.degree. C. After the completion of the
polymerization, a white product was taken out by filtration and
dried at 40.degree. C. under reduced pressure, thereby obtaining
79.4 g of polyethylene oxide.
[0107] The polymerization time was 3 hours and the yield was 98% by
mass. The viscosity of a 0.5% by mass aqueous solution of the
resulting polyethylene oxide was 700 mPas.
Example 9
[Production of Zinc Catalyst]
[0108] There was prepared a round-bottomed flask of 80 mm in inner
diameter and 500 mL in capacity equipped with a condenser, a
dropping funnel, a nitrogen gas inlet tube, and stiffing blades
having four paddle blades (45 degrees inclined) having a blade
diameter of 53 mm as a stirrer.
[0109] Into the flask replaced with nitrogen, 87.1 g of n-hexane
and 9.90 g of diethyl zinc were placed, and as a first step, 1.45 g
(0.016 mol) of 1,4-butanediol was reacted while being dropped at a
rate of 0.2 g/minute at an internal temperature of 20.degree. C.
under stirring at a tip peripheral speed of 0.97 m/second (the
rotational speed of stirring =350 rpm). As a second step, a mixture
liquid of 5.04 g (0.056 mol) of 1,4-butariediol and 24.3 g (0.528
mol) of ethyl alcohol was dropped at a rate of 0.2 g/minute to the
reaction liquid cooled to an internal temperature of 10.degree. C.
After the completion of the dropping, the temperature of the inside
of the flask was raised to 30.degree. C. and a reaction was carried
out for 1 hour, and subsequently the temperature was raised to
50.degree. C. and the reaction was carried out for 1 hour. Then,
heating was performed at an oil bath temperature of 80.degree. C.
and unreacted components were removed by distillation. Following
the distillation, the residue was allowed to cool to room
temperature and 52.4 g of n-hexane was added, and second
distillation was carried out by heating at an oil bath temperature
of 80.degree. C. This operation was performed further once again
and distillation was carried out three times in total. After the
three-time distillation, the residue was moved to a
pressure-resistant vessel thoroughly replaced with nitrogen, and
was subjected to heat treatment at an oil bath temperature of
130.degree. C. for 15 minutes with the vessel stoppered. After
cooling, the residue was diluted with 264 g of n-hexane, thereby
obtaining 297 g of a zinc catalyst containing 1.8% by mass of zinc.
When the n-hexane of the supernatant liquid of this zinc catalyst
was measured by GC, the amount of ethyl alcohol was found to be
0.0007 equivalents relative to an organozinc compound.
[Production of Alkylene Oxide Polymer]
[0110] There was prepared a pressure-resistant reaction vessel of
94 mm in inner diameter and 1 L in capacity equipped with a
dropping funnel, a nitrogen gas inlet tube, and stirring blades
having an anchor-shaped paddle blades having a blade diameter of 47
mm as a stirrer.
[0111] A pressure-resistant vessel thoroughly replaced with
nitrogen was charged with 340 g of n-hexane and 3.38 g (0.0013 mol
in terms of zinc) of the zinc catalyst obtained. above was
dispersed uniformly, and 81.0 g(1.84 mol) of ethylene oxide was
added and the vessel was stoppered, followed by polymerization
under stirring in a thermostatic bath at 40.degree. C. After the
completion of the polymerization, a white product was taken out by
filtration and dried at 40.degree. C. under reduced pressure,
thereby obtaining 80.8 g of polyethylene oxide.
[0112] The polymerization time was 4 hours and 30 minutes and the
yield was 100% by mass. The viscosity of a 0.5% by mass aqueous
solution of the resulting polyethylene oxide was 815 mPas.
Example 10
[Production of Zinc Catalyst]
[0113] There was prepared a round-bottomed flask of 80 mm in inner
diameter and 500 mL in capacity equipped with a condenser, a
dropping funnel, a nitrogen gas inlet tube, and stirring blades
having four paddle blades (45 degrees inclined) having a blade
diameter of 53 mm as a stirrer.
[0114] Into the flask replaced with nitrogen, 87.1 g of n-hexane
and 9.90 g of diethyl zinc were placed, and a mixture liquid of
6.49 g (0.072 mol) of 1,4-butanediol and 24.3 g (0.528 mol) of
ethyl alcohol was dropped at a rate of 0.2 g/minute at an internal
temperature of 10.degree. C. under stirring at a tip peripheral
speed of 0.97 m/second (the rotational speed of stirring =350 rpm).
After the completion of the dropping, the temperature of the inside
of the flask was raised to 30.degree. C. and a reaction was carried
out for 1 hour, and subsequently the temperature was raised to
50.degree. C. and the reaction was carried out for 1 hour. Then,
heating was performed at an oil bath temperature of 80.degree. C.
and unreacted components were removed by distillation. Following
the distillation, the residue was allowed to cool to room
temperature and 52.4 g of n-hexane was added, and second
distillation was carried out by heating at an oil bath temperature
of 80.degree. C. This operation was performed further once again
and distillation was carried out three times in total. After
cooling, the residue was diluted with 264 g of n-hexane, thereby
obtaining 297 g of a zinc catalyst containing 1.8% by mass of zinc.
When the n-hexane of the supernatant liquid of this zinc catalyst
was measured by GC, the amount of ethyl alcohol was found to be
0.0038 equivalents relative to an organozinc compound.
[Production of Alkylene Oxide Polymer]
[0115] There was prepared a pressure-resistant reaction vessel of
94 mm in inner diameter and 1 L in capacity equipped with a
dropping funnel, a nitrogen gas inlet tube, and stirring blades
having an anchor-shaped paddle blades having a blade diameter of 47
mm as a stirrer.
[0116] A pressure-resistant vessel thoroughly replaced with
nitrogen was charged with 340 g of n-hexane and 3.38 g (0.0013 mol
in terms of zinc) of the zinc catalyst obtained above was dispersed
uniformly, and 81 g (1.84 mol) of ethylene oxide was added and the
vessel was stoppered, followed by polymerization under stirring in
a thermostatic bath at 40.degree. C. After the completion of the
polymerization, a white product was taken out by filtration and
dried at 40.degree. C. under reduced pressure, thereby obtaining
76.3 g of polyethylene oxide.
[0117] The polymerization time was 7 hours and the yield was 94% by
mass. The viscosity of a 0.5% by mass aqueous solution of the
resulting polyethylene oxide was 530 mPas.
Comparative Examples 1-1
[Production of Zinc Catalyst]
[0118] There was prepared a round-bottomed flask of 80 mm in inner
diameter and 500 mL in capacity equipped with a condenser, a
dropping funnel, a nitrogen gas inlet tube, and stirring blades
having four paddle blades (45 degrees inclined) having a blade
diameter of 53 mm as a stirrer.
[0119] Into the flask replaced with nitrogen, 55.9 g of n-hexane,
21.2 g of high-boiling point aliphatic hydrocarbon (trade name: No.
0 Solvent produced by Nippon Oil Corporation) and 9.90 g of diethyl
zinc were placed, and as a first step, a reaction was carried out
while dropping 11.03 g (0.240 mol) of ethyl alcohol at a rate of
0.2 g/minute at an internal temperature of 20.degree. C. under
stirring at a tip peripheral speed of 0.97 m/second (the rotational
speed of stirring =350 rpm). As a second step, a mixture liquid of
6.49 (0.072 mol) of 1,4-butariediol and 13.27 g (0.288 mol) of
ethyl alcohol was dropped at a rate of 0.2 g/minute to the reaction
liquid cooled to an internal temperature of 10.degree. C. After the
completion of the dropping, the temperature of the inside of the
flask was raised to 30.degree. C. and a reaction was carried out
for 1 hour, and. subsequently the temperature was raised to
50.degree. C. and the reaction was carried out for 1 hour. Then,
heat treatment was carried out without stoppering at an oil bath
temperature of 130.degree. C. for 15 minutes. After cooling, the
residue was diluted with 264 g of n-hexane, thereby obtaining 297 a
of a zinc catalyst containing 1.8% by mass of zinc. When the
n-hexane of the supernatant liquid of this zinc catalyst was
measured by GC, the amount of ethyl alcohol was found to be 0.0116
equivalents relative to an organozinc compound.
[Production of Alkylene Oxide Polymer]
[0120] There was prepared a pressure-resist, reaction vessel of 94
mm in inner diameter and 1 L in capacity equipped with a dropping
funnel, a nitrogen gas inlet tube, and stirring blades having an
anchor-shaped paddle blades having a blade diameter of 47 mm as a
stirrer.
[0121] A pressure-resistant vessel thoroughly replaced with
nitrogen was charged with 340 g of n-hexane and 0.975 g (0.0004 mol
in terms of zinc) of the zinc catalyst obtained above was dispersed
uniformly, and 81 g (1.84 mol) of ethylene oxide was added and the
vessel was stoppered, followed by polymerization under stirring in
a thermostatic bath at 40.degree. C. After the completion of the
polymerization, a white product was taken out by filtration and
dried at 40.degree. C. under reduced pressure, thereby obtaining
80.2 g of polyethylene oxide.
[0122] The polymerization time was 7 hours and 30 minutes and the
yield was 99% by mass. The viscosity of a 0.5% by mass aqueous
solution of the resulting polyethylene oxide was 825 mPas.
Comparative Examples 1-2
[0123] A zinc catalyst was produced in analogy to Comparative
Example 1-1, thereby obtaining 297 g of a zinc catalyst containing
1.8% by mass of zinc. When the n-hexane of the supernatant liquid
of this zinc catalyst was measured by GC, the amount of ethyl
alcohol was found to be 0.0334 equivalents relative to an
organozinc compound.
[0124] 81 g (1.84 mol) of ethylene oxide was polymerized using the
zinc catalyst in analogy to Comparative Example 1-1 and, as a
result, 79.8 g of polyethylene oxide was obtained.
[0125] The polymerization time was 11 hours and 15 minutes and the
yield was 99% by mass. The viscosity of a 0.5% by mass aqueous
solution of the resulting polyethylene oxide was 625 mPas.
Comparative Examples 1-3
[0126] A zinc catalyst was produced in analogy to Comparative
Example 1-1, thereby obtaining 297 g of a zinc catalyst containing
1.8% by mass of zinc. When the n-hexane of the supernatant liquid
of this zinc catalyst was measured by GC, the amount of ethyl
alcohol was found to be 0.00221 equivalents relative to an
organozinc compound.
[0127] 81 g (1.84 mol) of ethylene oxide was polymerized using the
zinc catalyst in analogy to Comparative Example 1-1 and, as a
result, 78.3 g of polyethylene oxide was obtained.
[0128] The polymerization time was 9 hours and 45 minutes and the
yield was 97% by mass. The viscosity of a 0.5% by mass aqueous
solution of the resulting polyethylene oxide was 785 mPas.
TABLE-US-00001 TABLE 1 Monohydric alcohol Polyhydric alcohol
Organozinc First step Second step Total Second step compound [eq
[eq [eq [eq [-] [g] [mol] [-] [g] [mol] ratio] [-] [g] [mmol]
ratio] ratio] [-] [g] [mmol] ratio] Example 1-1 Et.sub.2Zn 9.9
0.080 EtOH 11.03 0.240 3.0 EtOH 13.27 0.288 3.6 6.6 1,4-BDO 6.49
0.072 0.90 Example 1-2 Et.sub.2Zn 9.9 0.080 EtOH 11.03 0.240 3.0
EtOH 13.27 0.288 3.6 6.6 1,4-BDO 6.49 0.072 0.90 Example 1-3
Et.sub.2Zn 9.9 0.080 EtOH 11.03 0.240 3.0 EtOH 13.27 0.288 3.6 6.6
1,4-BDO 6.49 0.072 0.90 Example 2 Et.sub.2Zn 9.9 0.080 EtOH 11.03
0.240 3.0 EtOH 13.27 0.288 3.6 6.6 1,4-BDO 6.49 0.072 0.90 Example
3 Et.sub.2Zn 9.9 0.080 EtOH 1.47 0.030 0.4 EtOH 13.27 0.288 3.6 4.0
1,4-BDO 6.49 0.072 0.90 Example 4 Et.sub.2Zn 9.9 0.080 EtOH 1.47
0.030 0.4 EtOH 13.27 0.288 3.6 4.0 1,4-BDO 6.49 0.072 0.90 Example
5 Et.sub.2Zn 9.9 0.080 EtOH 1.47 0.030 0.4 EtOH 13.27 0.288 3.6 4.0
1,4-BDO 6.49 0.072 0.90 Example 6 Et.sub.2Zn 9.9 0.080 2-PrOH 14.42
0.240 3.0 2-PrOH 17.31 0.288 3.6 6.6 1,4-BDO 6.49 0.072 0.90
Example 7 Et.sub.2Zn 9.9 0.080 MeOH 1.02 0.030 0.4 MeOH 9.22 0.288
3.6 4.0 1,4-BDO 6.49 0.072 0.90 Example 8 Et.sub.2Zn 9.9 0.080 EtOH
11.03 0.240 3.0 EtOH 26.54 0.576 7.2 10.2 1,4-BDO 2.16 0.024 0.30
Example 9 Et.sub.2Zn 9.9 0.080 1,4-BDO* 1.45 0.016 0.2 EtOH 24.3
0.528 6.6 6.6 1,4-BDO 5.04 0.056 0.70 Example 10 Et.sub.2Zn 9.9
0.080 -- -- -- -- EtOH 24.3 0.528 6.6 6.6 1,4-BDO 6.49 0.072 0.90
Comparative Et.sub.2Zn 9.9 0.080 EtOH 11.03 0.240 3.0 EtOH 13.27
0.288 3.6 6.6 1,4-BDO 6.49 0.072 0.90 Example 1-1 Comparative
Et.sub.2Zn 9.9 0.080 EtOH 11.03 0.240 3.0 EtOH 13.27 0.288 3.6 6.6
1,4-BDO 6.49 0.072 0.90 Example 1-2 Comparative Et.sub.2Zn 9.9
0.080 EtOH 11.03 0.240 3.0 EtOH 13.27 0.288 3.6 6.6 1,4-BDO 6.49
0.072 0.90 Example 1-3 *1: In Table 1, 1,4-BDO is written in the
column of monohydric alcohol for convenience thought it is not a
monohydric alcohol.
TABLE-US-00002 TABLE 2 Residual Amount of Viscosity Distillation
monohydric catalyst during Polymerization Yield (0.5% by Number of
Heat treatment alcohol polymerization time [% by mass) [.degree.
C.] distillations [.degree. C.] Time [eq ratio] [mol] Time mass]
[mPa s] Example 1-1 80 3 130 15 min 0.0033 0.0004 6 hr 100 855
Example 1-2 80 3 130 15 min 0.0038 0.0004 6 hr 98 825 Example 1-3
80 3 130 15 min 0.0047 0.0004 6 hr 45 min 100 865 Example 2 80 2
130 15 min 0.0093 0.0004 6 hr 45 min 97 820 Example 3 80 3 -- --
0.0013 0.0013 4 hr 15 min 100 810 Example 4 70 3 -- -- 0.0058
0.0013 4 hr 30 min 96 595 Example 5 100 3 -- -- 0.0010 0.0013 5 hr
99 720 Example 6 80 3 130 15 min 0.0001 0.0004 6 hr 45 min 93 575
Example 7 80 3 -- -- 0.0008 0.0013 5 hr 30 min 98 425 Example 8 80
3 -- -- 0.0048 0.0013 3 Hr 98 700 Example 9 80 3 130 15 min 0.0007
0.0013 4 hr 30 min 100 815 Example 10 80 3 -- -- 0.0038 0.0013 7 Hr
94 530 Comparative -- -- 130 15 min 0.0116 0.0004 7 hr 30 min 99
825 Example 1-1 Comparative -- -- 130 15 min 0.0334 0.0004 11 hr 15
min 99 625 Example 1-2 Comparative -- -- 130 15 min 0.0221 0.0004 9
hr 45 min 97 785 Example 1-3
[0129] As is apparent from the results shown in Tables 1 and 2, it
is understood from the comparison of Examples 1-1, 1-2 and 1-3 with
Comparative Examples 1-1, 1-2 and 1-3 that an alkylene oxide
polymer can be obtained reproducibly by adjusting the amount of a
monohydric alcohol in a zinc catalyst to 0.01 equivalents or less
relative to an organozinc compound by performing distillation
treatment during the production of the zinc catalyst. In other
words, these results show that in order to reproducibly obtain an
alkylene oxide polymer having a high degree of polymerization, it
is necessary to remove a monohydric alcohol to a prescribed value
or less by performing distillation before heat treatment of a zinc
catalyst. It has also been confirmed that an alkylene oxide polymer
having a high degree of polymerization can be produced industrially
and efficiently also in Examples 2 to 10 by likewise adjusting that
amount to 0.01 equivalents or less.
* * * * *