Process for producing a polyoxyalkylene compound

The present invention has an object of producing a polyoxyalkylene compound by ring-opening polymerization of an alkylene oxide to a certain specific highly hydrophobic initiator. The present invention provides a process for producing a polyoxyalkylene compound, characterized in that the polyoxyalkylene compound is produced by ring-opening polymerization of an alkylene oxide, in the presence of a plural metal cyanide complex catalyst, with an initiator selected from an organopolysiloxane compound having an active hydrogen-containing functional group to which an alkylene oxide is reactive, and a fluorine-containing compound having such an active hydrogen-containing functional group and a fluorinated hydrocarbon group.

TECHNICAL FIELD 
The present invention relates to a process for producing a polyoxyalkylene 
compound having an organopolysiloxane residue and a fluorinated 
hydrocarbon group. 
BACKGROUND ART 
A polyoxyalkylene compound produced by ring-opening polymerization of an 
alkylene oxide such as propylene oxide or ethylene oxide to an initiator 
having at least one active hydrogen-containing functional group to which 
an alkylene oxide is reactive, is industrially useful, for example, as a 
polyol component to be used in the polyurethane industry or as a 
surfactant and a starting material thereof. Such a polyoxyalkylene 
compound may be prepared to have various characteristics by selecting the 
initiator to be used. 
As the initiator, a compound having a hydroxyl group is the commonest 
compound. As a catalyst for the ring-opening polymerization of an alkylene 
oxide, an alkali catalyst such as an alkali metal hydroxide is widely 
employed. The alkali catalyst reacts with a hydroxyl group of the 
initiator or with a hydroxyl group formed afresh by a reaction of an 
alkylene oxide, to form an alkali metal alkoxide, and this alkali metal 
ion is believed to serve as a catalyst. 
A polyoxyalkylene compound obtainable by ring-opening polymerization of an 
alkylene oxide to an initiator having an organopolysiloxane structure or 
to an initiator having a fluorinated hydrocarbon group, is useful as a 
starting material for various synthetic resins, as a modifier or as an 
additive, and it is expected to provide such characteristics as 
improvement of weather resistance or water resistance, a tack-reducing 
effect or improvement of self-releasing properties. However, when such a 
highly hydrophobic initiator is used, the ring-opening addition reaction 
of an alkylene oxide to the active hydrogen-containing functional group of 
the initiator tends to be remarkably disadvantageous with the conventional 
alkali catalyst. 
When an alkali catalyst is added to a highly hydrophobic initiator, the 
compatibility of the initiator and the alkali catalyst is poor, and the 
two do not easily react to each other. Therefore, the hydroxyl group of 
the initiator tends to be hardly converted to an alkali metal alkoxide, 
and an alkylene oxide is hardly reactive to such a hydroxyl group. 
Therefore, the alkali catalyst itself such as the alkali metal hydroxide 
or the existing water is likely to act as an initiator, whereby it happens 
that a polyoxyalkylene glycol which is not bonded to the highly 
hydrophobic initiator, will form as a by-product. Further, there is a 
problem that if the temperature in the system is brought to a high level 
of at least 100.degree. C. in the presence of an alkali metal hydroxide, a 
decomposition reaction of the organopolysiloxane is likely to occur. 
Further, there is a compound instable to an alkali catalyst, such as a 
partially fluorinated alkanol. 
It is known to use an acid catalyst such as boron trifluoride instead of 
the alkali catalyst. However, use of an acid catalyst has a problem such 
that a homopolymer of the alkylene oxide is likely to be formed as a 
byproduct, and it is difficult to obtain a polyoxyalkylene compound of a 
high molecular weight. 
DISCLOSURE OF THE INVENTION 
The present invention has an object of producing a polyoxyalkylene compound 
by ring-opening polymerization of an alkylene oxide to such a highly 
hydrophobic initiator as mentioned above. 
The present invention is the following invention relating to a process for 
producing a polyoxyalkylene compound by ring-opening polymerization of an 
alkylene oxide, in the presence of a plural metal cyanide complex, to an 
initiator composed of an organopolysiloxane compound or a 
fluorine-containing compound having a fluorinated hydrocarbon group: 
A process for producing a polyoxyalkylene compound, characterized in that 
the polyoxyalkylene compound is produced by ring-opening polymerization of 
an alkylene oxide, in the presence of a plural metal cyanide complex 
catalyst, to an initiator selected from an organopolysiloxane compound 
having an active hydrogen-containing functional group to which an alkylene 
oxide is reactive, and a fluorine-containing compound having such an 
active hydrogen-containing functional group and a fluorinated hydrocarbon 
group. 
The plural metal cyanide complex catalyst in the present invention is a 
complex containing at least two metals and having cyan ions on part or all 
of ligands and the one having an ability of catalyzing the ring-opening 
polymerization reaction of an alkylene oxide. Specifically, it includes, 
for example, a hexacyanocobaltzinc complex such as a 
hexacyanocobaltzinc-glyme complex as disclosed in Japanese Examined Patent 
Publication No. 15336/1984 and other plural metal cyanide complex 
catalysts as disclosed in U.S. Pat. Nos. 3,278,457, 3,278,458 and 
3,278,459. Such a catalyst is known to show a high catalytic activity to 
ring-opening polymerization of an alkylene oxide. However, such a catalyst 
has not been known as a catalyst for polymerization of an alkylene oxide 
in which a highly hydrophobic initiator is employed which has an 
organopolysiloxane structure or a fluorinated hydrocarbon group in its 
molecule. 
The plural metal cyanide complex in the present invention is believed to 
have a structure of the following formula (1) as disclosed in the above 
prior art references: 
EQU M.sup.1.sub.a [M.sup.2.sub.x (CN).sub.y ].sub.b (H.sub.2 O).sub.c R.sub.d 
wherein M.sup.1 is a metal ion such as Zn(II), Fe(II), Fe(III), Co(II), 
Ni(II), Al(III), Sr(II), Mn(II), Cr(III), Cu(IgI), Sn(II), Pb(II), Mo(IV), 
Mo(VI), W(IV) or W(VI), and M.sup.2 is a metal ion such as Fe(II), 
Fe(III), Co(II), Co(III), Cr(II), Cr(III), Mn(II), Mn(III), Ni(II), V(IV) 
or V(V), and R is an organic ligand, a, b, x and y are positive integers 
which vary depending upon the valence and the number of coordination of 
the metal. 
In the plural metal cyanide complex of the above chemical formula, M.sup.1 
is preferably Zn(II), and M.sup.2 is preferably Fe(II), Fe(III), Co(II) or 
Co(III). The organic ligand may be, for example, a ketone, an ether, an 
aldehyde, an ester, an alcohol, an amide, a nitrile or a sulfide. 
Particularly preferred as the plural metal cyanide complex is a 
hexacyanocobaltzinc complex. Further, a catalyst having a 
hexacyanocobaltzinc complex combined with other plural metal cyanide 
complex, may be employed. Such a combination may be a combination of metal 
components or may be a mixture of at least two catalysts. 
The plural metal cyanide complex of the above chemical formula can be 
prepared by mixing aqueous solutions or solutions in a solvent mixture of 
water and an organic solvent of a metal salt M.sup.1 Y.sub.a (M.sup.1 and 
a are as defined above, and Y is an anion which forms a salt with M.sup.1) 
and a polycyano metalate (salt) Ze[M.sup.2.sub.x (CN).sub.y ].sub.f 
(M.sup.2, x and y are as defined above, Z is hydrogen, an alkali metal, an 
alkaline earth metal, etc., and e and f are positive integers determined 
by the valence of Z and M.sup.2 and the number of coordination), 
contacting a plural metal cyanide thereby obtained, with an organic ligand 
R, and then removing any excess solvent and organic ligand R. 
In the polycyano metalate (salt) Ze[M.sup.2.sub.x (CN).sub.y ].sub.f, 
hydrogen or various metals including alkali metals, may be used for Z. As 
an alkali metal salt, a lithium salt, a sodium salt, a potassium salt, a 
magnesium salt or a calcium salt is preferred. Particularly preferred is a 
usual alkali metal salt such as a sodium salt or a potassium salt. As a 
metal salt, a metal halide compound is preferred, and, for example, zinc 
chloride or the like is suitable. 
The alkylene oxide useful for the ring opening polymerization reaction in 
the present invention may be any alkylene oxide which can be polymerized 
by the plural metal cyanide complex catalyst. Specifically, it may be, for 
example, ethylene oxide, propylene oxide, 1-butene oxide, 2-butene oxide, 
isobutene oxide, 1-hexene oxide, cyclohexene oxide, phenylglycidyl ether, 
allylglycidyl ether or styrene oxide. A particularly preferred alkylene 
oxide is a C.sub.2-4 alkylene oxide such as ethylene oxide, propylene 
oxide, 1-butene oxide, 2-butene oxide or isobutene oxide. Two or more of 
such alkylene oxides may be used in combination. In such a case, two or 
more alkylene oxides may be reacted in a mixed state or may be 
sequentially reacted separately. 
The compound which is used as an initiator in the present invention and 
which has an active hydrogen-containing functional group to which an 
alkylene oxide is reactive, is a compound having in its molecule at least 
one active hydrogen-containing functional group which serves as an 
initiation point of the polymerization of the alkylene oxide. This active 
hydrogen-containing functional group is a functional group having one or 
two hydrogen atoms to which an alkylene oxide is reactive, such as a 
hydroxyl group, a mercapto group, a primary amino group, a secondary amino 
group and a carboxyl group. The number of functional groups per molecule 
of this compound is preferably at most 10. Particularly preferred is a 
compound having from 1 to 6 such functional groups. The alkylene oxide is 
reacted in an amount of at least one molecule, particularly at least two 
molecules, per the active hydrogen of such an active hydrogen-containing 
functional group. 
The organopolysiloxane compound is a polymer of a siloxane having at least 
one organic group bonded thereto, and at least one such organic group is 
an organic group having an active hydrogen-containing functional group. 
The organic group having an active hydrogen-containing functional group 
may be present at least at one of two terminals of the molecule, or may be 
present at an intermediate position of the molecular chain. This 
polyorganosiloxane compound may be a low polymer of e.g. an 
organodisiloxane compound There is no particular limit as to the upper 
limit in the number of polymerization units, but the number is preferably 
500, particularly 200. 
It is preferred that two organic groups are bonded to a silicon atom other 
than at both terminals of the organopolysiloxane compound. As such organic 
groups other than organic groups having active hydrogen-containing 
functional groups, hydrocarbon groups are preferred. As such hydrocarbon 
groups, alkyl groups, alkenyl groups or aryl groups are preferred. 
Particularly preferred are alkyl groups having at most 4 carbon atoms 
(hereinafter referred to also as lower alkyl groups) and phenyl groups. 
Most preferred are methyl groups. It is preferred that three organic 
groups are bonded to a silicon atom at each terminal, and the organic 
groups other than organic groups having active hydrogen-containing 
functional groups are preferably hydrocarbon groups as mentioned above. 
Further, at least one of the three organic groups may be a long chain 
hydrocarbon group. 
The organic group having an active hydrogen-containing functional group is 
preferably a C.sub.3-10 hydrocarbon group containing one or more 
functional groups of at least one type selected from --OH, SH, --NH.sub.2 
--NHR.sup.4 and --CO.sub.2 H. Further, it may contain a linking group such 
as an ether bond, a thioether bond or an amino bond. This organic group 
preferably has from 1 to 4 active hydrogen-containing functional groups. 
Specifically, as such an organopolysiloxane compound, compounds of the 
following formulas (1) to (3) are preferred: 
##STR1## 
(in the formulas, X.sup.1 is a C.sub.3-10 hydrocarbon group containing at 
least one functional group of at least one type selected from --OH, --SH, 
--NH.sub.2, --NHR.sup.10 and --CO.sub.2 H, which may contain an ether 
bond, a thioether bond or an amino bond, R.sup.1, R.sup.2, R.sup.3, 
R.sup.4, R.sup.6, R.sup.7, R.sup.8 and R.sup.10 are, respectively, the 
same or different C.sub.1-6 hydrocarbon groups, R.sub.5 and R.sup.9 are 
C.sub.1-18 hydrocarbon groups, n is 0 or an integer of from 1 to 200, and 
m is an integer of from 1 to 10.) 
In the above formulas, each of R.sup.1 and R.sup.2 is preferably a lower 
alkyl group, particularly a methyl group. Likewise, each of R.sup.3 to 
R.sup.10 is preferably a lower alkyl group. X.sup.1 is, for example, 
preferably a hydroxyalkyl group, a dihydroxyalkyl group, a 
hydroxyalkoxy-substituted alkyl group, a mercaptoalkyl group, an 
aminoalkyl group, an N-aminoalkyl-substituted aminoalkyl group or a 
carboxyalkyl group. 
In the present invention, the initiator made of a fluorine-containing 
compound having an active hydrogen-containing functional group to which an 
alkylene oxide is reactive and a fluorinated hydrocarbon group, is a 
compound having an active hydrogen-containing functional group as 
described above and a monovalent or higher valent hydrocarbon group having 
at least one fluorine atom. A preferred fluorinated hydrocarbon group is a 
monovalent or bivalent fluorinated hydrocarbon group having at least two 
fluorine atoms. Specifically, for example, a polyfluoroalkyl group, a 
polyfluoroalkylene group or a polyfluoroaryl group is preferred. The 
number of carbon atoms thereof is preferably from 1 to 20, particularly 
from 3 to 16. 
The polyfluoroalkyl group is preferably a polyfluoroalkyl group having a 
perfluoroalkyl moiety. This polyfluroalkyl group having a perfluoroalkyl 
moiety is a polyfluoroalkyl group f the formula R.sub.f.sup.1 --.sup.11 
--. This R.sub.f.sup.1 is a linear or branched perfluoroalkyl group having 
at least one carbon atom, particularly a linear C.sub.3-20 perfluoroalkyl 
group. R.sup.11 is an alkylene group containing no fluorine atom, 
particularly preferably a C.sub.2-6 polymethylene group. Further, the 
polyfluoroalkyl group may be a perfluoroalkyl moiety (R.sub.f.sup.1 --) of 
a perfluorocarboxylic acid (R.sub.f.sup.1 --COOH) or its derivative such 
as an an ester or amide. 
The polyfluoroalkylene group is preferably a polyfluoroalkylene group 
having a perfluoroalkylene moiety. This polyfluoroalkylene group having a 
perfluoroalkylene moiety is a polyfluoroalkylene group of the formula 
--R.sup.12 --R.sub.f.sup.2 --R.sup.13 --. This R.sub.f.sup.2 is a 
perfluoroalkylene group having at least two carbon atoms, particularly 
preferably a C.sub.2-12 perfluoroalkylene group. Each of R.sup.12 and 
R.sup.13 which are independent from each other, is an alkylene group 
containing no fluorine atom, particularly preferably a C.sub.2-6 
polymethylene group. 
The polyfluoroaryl group may be a phenyl group or an alkyl-substituted 
phenyl group, with at least two fluorine atoms bonded to the phenyl group, 
particularly preferably a polyfluorophenyl group having all unsubstituted 
positions of the phenyl group substituted by fluorine atoms. Further, the 
substituent may be a polyfluoroalkyl group such as a trifluoromethyl 
group. 
Further, the polyfluoroalkyl group or the polyfluoroalkylene group may be 
in such a form that part of carbon atoms of the carbon chain is 
substituted by an ether-type oxygen atom or a thioether-type sulfur atom, 
such as a polyfluoroxalkyl group, a polyfluoroxalkylene group, 
polyflorothioxalkyl group or a polyfluorothioxalkylene group. For example, 
it may be a perfluoroxalkyl group of the formula R.sub.f.sup.1 --OCF.sub.2 
CF(CF.sub.3)--k-- (k is an integer of at least 1). 
The active hydrogen-containing functional group and the fluorinated 
hydrocarbon group may be directly bonded or may be bonded by an organic 
group such as a hydrocarbon group interposed therebetween. Such an organic 
group may contain an ether group, an ester group, an amide group, a 
carbamate group, a urea group, a carbonate group, etc. 
More preferred compounds are compounds of the following formulas (4) to 
(8): 
EQU R.sub.f.sup.1 --R.sup.11 --X.sup.2 (4) 
EQU R.sub.f.sup.1 --COOX.sup.3 (5) 
EQU R.sub.f.sup.1 --CON(R.sup.14)--X.sup.3 (6) 
EQU X.sup.2 --R.sup.12 R.sub.f.sup.2 --R.sup.13 --X.sup.2 (7) 
EQU (R.sub.f.sup.1).sub.t --C.sub.6 --F.sub.5-t --X.sup.2 (8) 
(in the formulas, X.sup.2 is an active hydrogen-containing functional group 
selected from --OH, --SH, --NH.sub.2, --NHR.sup.4 and --CO.sub.2 H, or a 
hydrocarbon group having at least one such functional group, X.sup.3 is a 
hydrogen atom or a hydrocarbon group having at least one of the above 
mentioned active hydrogen-containing functional groups, R.sup.14 is a 
hydrogen atom or a C.sub.1-6 hydrocarbon group, R.sub.f.sup.1, 
R.sub.f.sup.2, R.sup.11, R.sup.12 and R.sup.13 are the above mentioned 
groups, and t is 0 or an integer of from 1 to 3.) 
Specific fluorine-containing compounds include, for example, 
4,4'-(hexafluoroisopropylidene)diphenol, tetrafluorohydroquinone, 
pentafluorophenol, pentafluorothiophenol, pentafluorobenzoic acid, 
pentafluorobenzyl alcohol, pentafluoroaniline and hexafluoro-2-propanol. 
Further, there are compounds of the following formulas (9) to (13): 
##STR2## 
(in the formulas, X.sup.4 is an active hydrogen-containing functional 
group selected from --OH, --SH, --NH.sub.2, --NHR.sup.15 and --CO.sub.2 H, 
R.sup.15 is a C.sub.1-6 hydrocarbon group, p is 0 or an integer of from 1 
to 16, and each of q and r is an integer of from 2 to 6.) 
Further, a compound obtained by bonding the above-mentioned specific 
fluorine-containing compound as a starting material to other active 
hydrogen-containing compound by an ester group, an amide group, a 
carbamate group, a urea group or a carbonate group, can also be used as an 
initiator for the polymerization of an alkylene oxide. As such a compound, 
for example, the following reaction products may be mentioned. 
A hydroxyl group-containing compound obtained by reacting the above 
fluorine-containing compound with a polyisocyanate compound in an excess 
of isocyanate groups, followed by reacting with a polyhydroxy compound 
under such a condition that hydroxyl groups are in excess. A carboxyl 
group-containing compound obtained by reacting the above-mentioned 
fluorine-containing compound containing a hydroxyl group with an excess 
equivalent of a polycarboxylic acid compound or an acid anhydride. A 
hydroxyl group-containing ester compound obtained by condensing a 
polyfluoroalkylenecarboxylic acid or its ester compound with a polyhydroxy 
compound under such a condition that hydroxyl groups are in excess. A 
hydroxyl group-containing amide compound obtained by condensing a 
polyfluoroalkylcarboxylic acid or its ester compound with an alkanolamine 
under such a condition that hydroxyl groups are in excess. 
The actual polymerization reaction may be conducted by heating a mixture 
comprising the initiator, the plural metal cyanide complex and the 
alkylene oxide in a nitrogen atmosphere to the polymerization reaction 
temperature. At that time, the alkylene oxide may be added at once or may 
be gradually added while watching the progress of the reaction. Further, 
as mentioned above, when two or more alkylene oxides are polymerized, a 
block copolymer or a random copolymer may optionally be produced by 
controlling the method of their addition. Namely, when a mixture of two or 
more alkylene oxides is added, a random copolymer will be obtained. On the 
other hand, when two or more alkylene oxides are added one after another 
after completion of the respective polymerization reactions, a block 
copolymer can be produced. 
The temperature for the polymerization reaction is suitably from 20.degree. 
to 180.degree. C., preferably from 60.degree. to 130.degree. C. This 
polymerization reaction may be conducted by using or not using a solvent. 
As the solvent useful in the present invention, an ether-type, 
hydrocarbon-type, halogenated hydrocarbon-type, ketone-type, amide-type or 
ester-type solvent may be mentioned. Particularly preferred is an 
ether-type or ketone-type solvent. Specifically, tetrahydrofuran, diethyl 
ether, 1,2-dimethoxyethane, 1,2-dimethoxypropane, diethylene glycol 
dimethyl ether, methyltetrahydrofuran, dioxane, acetone or methyl ethyl 
ketone may be mentioned. The solvent can be recovered after completion of 
the reaction by distillation from the reaction mixture. 
It is believed that since the plural metal cyanide complex catalyst is 
likely to coordinate with an active hydrogen group in the present 
invention, it is possible to easily conduct the polymerization of an 
alkylene oxide even in a case where an initiator having in its molecule a 
highly hydrophobic organopolysiloxane structure or a fluorinated 
hydrocarbon group is used, which used to be hardly useful for the ring 
opening polymerization of an alkylene oxide where the conventional alkali 
metal hydroxide is used as a catalyst. Further, with the plural metal 
cyanide complex catalyst of the present invention, decomposition of the 
organopolysiloxane structure or decomposition of the partially fluorinated 
alkanol will not occur.

EXAMPLES 
The present invention will be described in detail with reference to the 
following Examples. However, it should be understood that the present 
invention is by no means restricted to such Examples. 
Example 1 
500 g of .alpha.,.omega.-bis[3-(2-hydroxyethoxy)propyl]polydimethylsiloxane 
of the following formula having a molecular weight of about 1,800 and 0.1 
g of hexacyanocobaltzinc-glyme complex were charged into an autoclave and 
heated to bring the internal temperature to 100.degree. C. under a 
nitrogen atmosphere. Then, 1.5 kg of propylene oxide was introduced so 
that the internal temperature would not exceed 120.degree. C., and 
reacted. After completion of the introduction of propylene oxide, the 
mixture was further stirred at the same temperature for one hour. Then, an 
unreacted monomer was distilled off under reduced pressure to obtain 2.5 
kg of a slightly turbid oily substance. 
By the GPC analysis, the product showed a single peak which is different 
from the starting material polydimethylsiloxane, and its hydroxyl value 
was 12.9 mgKOH/g. The obtained oily substance did not undergo separation 
even after being stored for three months at 25.degree. C. 
##STR3## 
Example 2 
25 g of 1-(3-mercaptopropyl)-1,1,3,3,3-pentamethyldisiloxane was dissolved 
in 25 g of tetrahydrofuran, and 0.05 g of hexacyanocobaltzinc-glyme 
complex was added thereto, and the mixture was charged into an autoclave. 
Further, 50 g of propylene oxide was added thereto, and the mixture was 
heated to 100.degree. C. under a nitrogen atmosphere, whereby an 
exothermic reaction took place. After completion of the heat generation, 
the mixture was further heated for 30 minutes at 100.degree. C. Then, an 
unreacted monomer was removed under reduced pressure to obtain 74.8 g of 
an oily substance. By the GPC analysis, the product showed a single peak. 
Example 3 
0.02 g of hexacyanocobaltzinc-glyme complex was added to a mixture 
comprising 100 g of 
.alpha.,.omega.-bis(3-mercaptopropyl)-polydimethylsiloxane having an 
average molecular weight of 876 and 100 g of tetrahydrofuran, and the 
mixture was heated in an autoclave at 100.degree. C. under a nitrogen 
atmosphere. To the autoclave, a mixture comprising 200 g of propylene 
oxide and 100 g of ethylene oxide, was gradually introduced so that the 
internal temperature would not exceed 120.degree. C. After completion of 
the introduction of the monomer, the mixture was heated for further one 
hour. Then, the solvent was distilled off under reduced pressure to obtain 
498 g of an oily substance. 
By the GPC analysis, the product showed a single peak, and the hydroxyl 
value was 26.5 mgKOH/g. The obtained oily substance did not undergo 
separation even after being stored for 3 months at 25.degree. C. 
Example 4 
A mixture comprising 25 g of 
.alpha.,.omega.-bis(3-aminopropyl)polydimethylsiloxane having an average 
molecular weight of 800 and 5 g of propylene oxide, was heated in an 
autoclave at 120.degree. C. for 2 hours. An unreacted monomer was removed, 
and the reaction mixture was cooled to room temperature. Then, 0.01 g of 
hexacyanocobaltzinc-glyme complex and 50 g of tetrahydrofuran were added 
thereto, and 50 g of propylene oxide was gradually introduced under a 
nitrogen atmosphere so that the internal temperature would not exceed 
120.degree. C. After completion of the introduction of the monomer, the 
mixture was heated for further one hour. Then, the solvent and an 
unreacted monomer were distilled off under reduced pressure to obtain 75.1 
g of an oily substance. 
By the GPC analysis, the product showed a single peak, and its hydroxyl 
value was 95.0 mgKOH/g. 
Example 5 
50 g of 
.alpha.-methyl-.omega.-3-(2,2-bis(hydroxymethyl)butoxy)propylpolydimethyls 
iloxane of the following formula having an average molecular weight of 
2,000 and 0.02 g of hexacyanocobaltzinc-glyme complex were charged into an 
autoclave and heated to 100.degree. C. under a nitrogen atmosphere. A 
mixture comprising 100 g of propylene oxide and 30 g 1-butene oxide was 
gradually introduced so that the internal temperature would not exceed 
120.degree. C. and reacted. After completion of the introduction of the 
alkylene oxides, the mixture was heated at the same temperature for 
further one hour. Then, an unreacted monomer was removed to obtain 180 g 
of an oily substance. 
By the GPC analysis, the product showed a single peak, and its hydroxyl 
value was 14.5 mgKOH/g. The obtained oily substance did not underwent 
separation even after being stored at 25.degree. C. for three months. 
##STR4## 
Example 6 
50 g of 
.alpha.,.omega.-bismethylpolydimethylsilyloxy-polymethyl-3-(2-hydroxyethyl 
)propylsiloxane of the following formula having a molecular weight of of 
5,000 and a hydroxyl value of 27 mgKOH/g and 0.02 g of 
hexacyanocobaltzinc-glyme complex were charged into an autoclave and 
heated to 100.degree. C. under a nitrogen atmosphere. 150 g of propylene 
oxide was gradually added so that the internal temperature would not 
exceed 120.degree. C. and reacted. After completion of the introduction of 
propylene oxide, the mixture was heated at the same temperature for 
further one hour. Then, an unreacted monomer was removed to obtain 200 g 
of an oily substance. 
By the GPC analysis, the product showed a single peak, and its hydroxyl 
value was 7.0 mgKOH/g. The obtained oily substance did not undergo 
separation even after being stored at 25.degree. C. for three months. 
##STR5## 
Example 7 
5 g of 1,1,1-trifluoroethanol was dissolved in 30 g of tetrahydrofuran, and 
the solution was charged into an autoclave. 20 mg of 
hexacyanocobaltzinc-glyme complex was added, and 25 g of propylene oxide 
was added. The autoclave was substituted by nitrogen and heated to 
100.degree. C., whereby the internal temperature rose to 140.degree. C. by 
an exothermic reaction. Thereafter, the mixture was heated at 100.degree. 
C. for further 30 minutes, and then cooled to room temperature. The 
solvent was distilled off under reduced pressure to obtain 29.95 g of an 
oily substance. By the GPC analysis, the product showed a single peak, and 
its hydroxyl value was 94.5 mgKOH/g. 
Example 8 
15.0 g of tridecafluoroctanol (C.sub.6 F.sub.13 C.sub.2 H.sub.4 OH), was 
dissolved in 50 g of tetrahydrofuran, and the solution was charged into an 
autoclave. 30 mg of hexacyanocobaltzinc-glyme complex was added, and 25 g 
of propylene oxide was added. Then, in accordance with Example 7, the 
mixture was reacted at 100.degree. C. to obtain 40.0 g of an oily product. 
By the GPC analysis, this product showed a single peak, and its hydroxyl 
value was 58.2 mgKOH/g. 
Example 9 
30.0 g of tridecafluoroctanol (C.sub.6 F.sub.13 C.sub.2 H.sub.4 OH), was 
dissolved in 100 g of tetrahydrofuran, and the solution was charged into 
an autoclave. 50 mg of hexacyanocobaltzinc-glyme complex was added, and 
the autoclave was substituted by nitrogen and pressurized under a nitrogen 
pressure of 1 kg/cm.sup.2. The autoclave was heated to 100.degree. C., and 
a mixture comprising 30 g of propylene oxide and 70 g of ethylene oxide 
was gradually introduced so that the internal temperature would not exceed 
110.degree. C. and reacted. After completion of the introduction of 
alkylene oxides, the mixture was left to stand at the same temperature for 
one hour. Then, the solvent was distilled off under reduced pressure to 
obtain 129.5 g of an oily product. By the GPC analysis, the product showed 
a single peak, and its hydroxyl value was 58.2 mgKOH/g. 
Example 10 
5 g of 3,3,4,4,5,5,6,6-octafluoro-1,8-octanediol was dissolved in 40 g of 
1,2-dimethoxyethane, and the solution was charged into an autoclave. 25 mg 
of hexacyanocobaltzinc-glyme complex was added, and the autoclave was 
substituted by nitrogen. The autoclave was heated to 100.degree. C., and 
200 g of propylene oxide was gradually introduced so that the internal 
temperature would not exceed 120.degree. C. and reacted. After completion 
of the introduction of propylene oxide, the mixture was left at the same 
temperature for one hour. Then, the solvent was distilled off under 
reduced pressure to obtain 203.5 g of an oily product. By the GPC 
analysis, the product showed a single peak, and its hydroxyl value was 9.8 
mgKOH/g. 
Example 11 
20 g of pentadecafluorodecanediol [CF.sub.3 (CF.sub.2).sub.6 CH.sub.2 
CH(OH)CH.sub.2 OH] was dissolved in 60 g of tetrahydrofuran, and the 
solution was charged into an autoclave. Then, 100 mg of 
hexacyanocobaltzinc-glyme complex was added, and the autoclave was 
substituted by nitrogen. The autoclave was heated to 100.degree. C., and 
340 g of propylene oxide was gradually introduced so that the internal 
temperature would not exceed 120.degree. C., and reacted. After the 
introduction of propylene oxide, the mixture was left at the same 
temperature for 30 minutes. Then, 90 g of 1-butene oxide was further added 
so that the internal temperature would not exceed 120.degree. C. and 
reacted. After completion of the introduction of 1-butene oxide, the 
mixture was heated at the same temperature for further one hour. The 
solvent was distilled off under reduced pressure to obtain 448 g of an 
oily product. By the GPC analysis, the product showed a single peak, and 
its hydroxyl value was 11.7 mgKOH/g. 
Example 12 
5 g of pentafluoroaniline (C.sub.6 F.sub.5 NH.sub.2) was dissolved in 50 g 
of tetrahydrofuran, and the solution was charged into an autoclave. 50 g 
of hexacyanocobaltzinc-glyme complex was added, and the autoclave was 
substituted by nitrogen. The autoclave was heated to 100.degree. C., and 
340 g of propylene oxide was gradually added so that the internal 
temperature would not exceed 120.degree. C. and reacted. After the 
introduction of the propylene oxide, the mixture was left at the same 
temperature for one hour. Then, the solvent was distilled off under 
reduced pressure to obtain 104.5 g of an oily product. By the GPC 
analysis, the product showed a single peak, and its hydroxyl value was 
30.5 mgKOH/g. 
Example 13 
5 g of pentafluorothiophenol (C.sub.6 F.sub.5 SH) was dissolved in 50 g of 
tetrahydrofuran, and the solution was charged into an autoclave. 50 mg of 
hexacyanocobaltzinc-glyme complex was added and the autoclave was 
substituted by nitrogen. The autoclave was heated to 100.degree. C., and 
50 g of propylene oxide was gradually added so that the internal 
temperature would not exceed 120.degree. C., and reacted. After the 
introduction of propylene oxide, the mixture was left at the same 
temperature for one hour. Then, the solvent was distilled off under 
reduced pressure to obtain 54.2 g of an oily product. By the GPC analysis, 
the product showed a single peak, and its hydroxyl value was 26.3 mgKOH/g. 
Example 14 
15.0 g of tridecafluoroctylic acid (C.sub.6 F.sub.13 CH.sub.2 CO.sub.2 H) 
was dissolved in 50 g of tetrahydrofuran, and the solution was charged 
into an autoclave. 50 mg of hexacyanocobaltzinc-glyme complex was added 
and the autoclave was substituted by nitrogen. The autoclave was heated to 
100.degree. C., and 50 g of propylene oxide was gradually introduced so 
that the internal temperature would not exceed 120.degree. C., and 
reacted. After completion of the introduction, the mixture was left at the 
same temperature for one hour. Then, the solvent was distilled off under 
reduced pressure to obtain 64.8 g of an oily product. By the GPC analysis, 
the product showed a single peak, and its hydroxyl value was 35.0 mgKOH/g. 
Example 15 
5 g of N-tridecafluoropentanoyl-1,1-dihydroxymethylpropylamide [CF.sub.3 
(CF.sub.2).sub.5 CONC(CH.sub.2 OH).sub.2 CH.sub.2 CH.sub.3 ] was dissolved 
in 30 g of tetrahydrofuran, and the solution was charged into an 
autoclave. 0.1 g of hexacyanocobaltzinc-glyme complex was added, and 30 g 
of propylene oxide was added, and the autoclave was substituted by 
nitrogen. Then, in the same operation as in Example 7, 34.8 g of a product 
was obtained. By the GPC analysis, the product showed a single peak, and 
its hydroxyl value was 35.8 mgKOH/g.