Polyether glycols and alcohols derived from 3,4-epoxy-1-butene

Disclosed are novel saturated polyether compounds comprised of n units of residue (1) and m units of residue (2), wherein (i) residues (1) and (2) have the structures: ##STR1## (ii) the total value of n+m is 2 to 70 and m/(n+m) is 0.05 to 0.98; (ii) at least 98 percent of the terminal hydroxyl groups of the polyether have the structure: ##STR2## The polyethers are obtained by first polymerizing 3,4-epoxy-1-butene to produce unsaturated polyether precursors comprising residues (1A) and (2A) having the structures: ##STR3## and then hydrogenating the unsaturated polyether precursors. The hydrogenation advantageously is performed in the presence of a nickel hydrogenation catalyst.

This invention pertains to certain novel saturated polyether glycols and 
alcohols. More specifically, this invention pertains to saturated 
polyether glycols and alcohols comprising repeating units of the 
structure: 
##STR4## 
This invention also pertains to a process for the preparation of the novel 
polyether compounds by catalytic hydrogenation of unsaturated polyether 
glycols and alcohols prepared from 3,4-epoxy-1-butene and comprising 
repeating units of the structure: 
##STR5## 
A series of papers [L. P. Blanchard, et al., J. Polym. Sci., Part A-1, 
9(12), 3547-54 (1971); L. P. Blanchard, et al., Kinet. Mech. 
Polyreactions, Int. Symp. Macromol. Chem., Prepr., Volume 1, 395-9. Akad. 
Kiado: Budapest, Hung. (1969); and J. M. Hammond, J. Polym. Sci., Part 
A-1, 9(2), 265-79, (1971)] teach that a mixture of cyclic oligomers and 
polyether glycols containing residues (1) and (2) can be prepared by the 
copolymerization of 1,2-butylene oxide and tetrahydrofuran in the presence 
of boron trifluoride etherate and a glycol initiator. However, only minor 
amounts of residue (2), in the range of about 20 to 55 percent, may be 
incorporated by this method, and, according to the description of 
Blanchard, et al., the resulting polyether glycol cannot be terminated 
with residue (2). Our investigation of this chemistry showed that a 
copolymer of 1,2-butylene oxide and tetrahydrofuran, prepared as described 
by Blanchard, et al., is terminated with residue (1) only. Furthermore, as 
is shown in Comparative Example 1 hereof, about 75% of the terminal 
hydroxyl groups of the copolymer are secondary and 25% of the terminal 
hydroxyl groups are primary hydroxyl groups. 
The presence of secondary hydroxyl groups in the polymers referred to in 
the preceding paragraph is not unexpected in view of a number of 
publications [P. Kubisa, Makromol. Chem., Macromol. Symp., 13/14,203 
(1988); K. Brzezinska, R. Szymanski, P. Kubisa, and S. Penczek, Makromol. 
Chem., Rapid Commun., 7, 1 (1986); M. Bednarek, P. Kubisa, and S. Penczek, 
Makromol. Chem., Suppl., 15 49 (1989); P. Kubisa and S. Penczek, Am. Chem. 
Soc., Div. Polym. Chem., Polym. Preprints, 31(1), 89-90 (1990); and T. 
Biedron, R. Szymanski, P. Kubisa, and S. Penzcek, Makromol. Chem., 
Macromol. Symp., 32, 155 (1990)] which teach that the polymer 
microstructure from copolymerization of propylene oxide and 
tetrahydrofuran using boron trifluoride etherate and a glycol initiator is 
determined by interplay of steric and electronic factors, with steric 
factors prevailing to give copolyethers with about 55 percent secondary 
hydroxyl groups and 45 percent primary hydroxyl groups. Further, they 
teach that the major contribution of the electronic effects of the side 
group is its influence on the basicity of the secondary hydroxyl of the 
growing chain. Butylene oxide gives a greater amount of secondary hydroxyl 
than does propylene oxide due to greater steric effects of the ethyl group 
compared to the methyl group. 
E. J. Vandenberg, U.S. Pat. No. 3,509,118, discloses unsaturated polyether 
glycols containing residue (1A) and prepared by n-butyl lithium cleavage 
of the alkyl-capped, high molecular weight polyether prepared by the 
polymerization of 3,4-epoxy-1-butene in benzene using triethylaluminum 
prereacted with water. However, hydrogenation of the polyether glycols is 
neither disclosed nor contemplated. 
M. A. Hillmyer, et al; Macromolecules, 25, 3345-3350 (1992), disclose the 
hydrogenation of a high molecular weight, unsaturated polyether using 
Crabtree's catalyst, a soluble, iridium complex, in methylene chloride 
under an atmosphere of hydrogen for 1 hour. However, the production of 
hydroxyl-terminated polyether is neither disclosed nor contemplated. 
The polyether compounds provided by the present invention are comprised of 
n units of residue (1) and m units of residue (2), wherein (i) residues 
(1) and (2) have the structures: 
##STR6## 
(ii) the total value of n+m is 2 to 70 and m/(n+m) is 0.05 to 0.98, i.e., 
residue (2) constitutes from 5 to 98 mole percent of the total moles of 
residues (1) and (2), and (iii) and at least 98 percent of the 
terminal-hydroxyl groups of the polyether compounds have the structure: 
##STR7## 
i.e., at least 98 percent of the terminal hydroxyl groups are primary 
(rather than secondary) hydroxyl groups. The polyether compounds normally 
have a polydispersity value of less than 4, preferably in the range of 1 
to 2.5, and most preferably in the range of 1 to 1.7. Furthermore, the 
total value of n+m preferably is 7 to 50. 
The provision in the above description that at least 98 percent of the 
terminal hydroxyl groups of the polyether compounds have the structure: 
##STR8## 
means that the polyethers are essentially free of residues of ethylene 
oxide and oxetane as terminal groups. See, for example U.S. Pat. Nos. 
4,183,821 and 4,299,993 which describe the preparation of intermediate 
polyethers containing tetrahydrofuran residues and the subsequent reaction 
of the intermediate polyether with ethylene oxide to obtain an ethoxylated 
polyether having a high content of primary, terminal hydroxyl groups. 
The saturated polyether compounds and polymers may be used in the 
preparation or formulation of condensation polymers, surfactants, and 
other compositions analogous to compositions derived from known polyether 
polymers. It is known that hydroxyl-terminated polyethers wherein all, or 
substantially all, of the terminal hydroxyl groups are primary are more 
reactive and thus produce superior products when compared to analogous 
hydroxyl-terminated polyethers wherein a significant portion of the 
terminal hydroxyl groups are secondary hydroxyl groups. For example, 
Wolfe, Rubber Chemistry and Technology, 50(4), 688-703, September/October 
1977, teaches that titanate-ester-catalyzed melt condensation 
polymerizations of poly(propylene glycol) having a number-average 
molecular weight of about 1000 with dimethyl terephthalate and 
1,4-butanediol give copolyester-ethers having low inherent viscosities and 
poor properties compared to copolyester/ethers prepared using 
poly(tetramethylene glycol) and poly(ethylene glycol) having similar 
molecular weights. The low inherent viscosities and poor properties are 
due to the relatively high secondary hydroxyl group content of the 
poly(propylene glycol). Wolfe also discloses that the use of 
poly(propylene glycol) end-capped with 10-20 weight percent of ethylene 
oxide does not overcome the problem, as only a marginal improvement in 
inherent viscosity was realized. Due to the higher reactivity of the 
formed primary hydroxyl, end-capping polyethers having secondary terminal 
hydroxyl groups with ethylene oxide to increase primary hydroxyl content 
typically is only partially successful. In order to achieve a majority of 
primary hydroxyl end groups, e.g., greater than 65 percent, large amounts 
of ethylene oxide are needed and usually give concomittant formation of 
long ethylene blocks and causes the resulting polyether to have reduced 
hydrophobicity and thus limits the usefulness of the polyethers in the 
manufacture of condensation polymers. The high content of primary, 
terminal hydroxyl groups possessed by the polyether polymers of the 
present invention renders the polyethers more reactive, and thus more 
useful, for condensation reactions in general. 
Poly(tetramethylene ether) glycol is the industry standard for the 
preparation of high performance condensation polymers such as Hytrel 
polymer and polyurethane ethers such as Lycra spandex polymer. Efforts to 
incorporate a substiuted oxirane such as propylene oxide and butylene 
oxide for purposes of price and performance give increased concentrations 
of secondary hydroxyl groups. The polyethers of this invention overcome 
this difficulty without the incorporation of ethylene oxide or oxetane. 
The polyethers of this invention are fundamentally different from 
ethoxylated copolyethers of tetrahydrofuran and butylene oxide, which are 
expected to have increased hydrophobicity and decreased thermal stability 
compared to poly(tetramethylene ether) glycol. 
The polyether polymers of this invention may be ethoxylated by methods 
known in the art to form copolymers containing one or more ethylene oxide 
blocks and such block copolyethers are expected to have surfactant 
properties. The primary, terminal hydroxyl groups of the novel polyethers 
of this invention offer the potential advantage of adding very short 
ethylene oxide blocks to the polyethers to produce polyether derivatives 
having unique properties. Generally, the addition of short ethylene oxide 
blocks to polyethers having a significant content of secondary, terminal 
hydroxyl groups is not possible. 
The polyether polymers of the present invention may be prepared by first 
polymerizing 3,4-epoxy-1-butene in the presence of a hydroxyl initiator 
compound and a catalyst to obtain the corresponding unsaturated polymer 
comprising n' units of residue (1A) and m' units of residue (2A), wherein 
the total value of n'+m' is 2 to 70 and m'/(n'+m') is 0.05 to 0.98 and 
residues (1A) and (2A) have the structures: 
##STR9## 
The unsaturated polymer then may be catalytically hydrogenated to obtain 
the novel polyether polymers of the invention. 
The unsaturated precursor polymers wherein m'/(n'+m') is in the range of 
0.05 to 0.30 are prepared by polymerizing 3,4-epoxy-1-butene in the 
presence of a catalytic amount of certain acidic compounds and a hydroxyl 
initiator compound. The acidic catalysts may be selected from strong acids 
such as sulfuric acid; perchloric acid; fluoroboric acid; strongly acidic 
ion exchange resins, e.g., Amberlyst resins; and fluorosulfonic acids such 
as perfluoroalkanesulfonic acids containing up to about 6 carbon atoms, 
e.g., trifluoromethanesulfonic acid and fluorosulfonic acid and 
perfluorosulfonic acid polymers, e.g., Nafion resins, e.g., Nafion NR-50 
acidic resin. Although strong acids generally are capable of effecting 
reaction of 3,4-epoxy-1-butene and an initiator, most exhibit limited 
activity and result in the formation of low molecular weight products. The 
most effective catalysts are the perfluoroalkanesulfonic acids such as 
trifluoromethanesulfonic acid and, especially, Nafion NR-50 acidic resin 
which has been cryogenically ground to 60 to 100 mesh (particles having an 
average diameter of 170 to 250 microns), available from C. G. Processing 
of Rockland, Del. The amount of the acidic catalyst which may be used can 
vary substantially depending, for example, on process conditions and the 
particular strong acid employed. In batch operation of the process, the 
amount of catalyst used typically is in the range of 0.5 to 1.5 mole 
percent based on the equivalents of initiator. 
The acid-catalyzed polymerization normally is conducted in the presence of 
a solvent, e.g., an inert, organic solvent such as a hydrocarbon, 
chlorinated hydrocarbon, acyclic ether, and the like. Specific examples of 
such solvents include benzene, toluene, xylene, heptane, methylene 
chloride, chloroform, diethyl ether, and the like. The polymerization may 
be carried out at temperatures in the range of about 0.degree. to 
150.degree. C., depending upon the choice of initiator, solvent, and 
catalyst. Temperatures of about 20.degree. to 60.degree. C. are preferred. 
Reaction pressure is not an important part of our novel process, and, 
therefore, the process typically is performed at approximately atmospheric 
pressure although pressure moderately above or below atmospheric may be 
used. 
The unsaturated precursor polymers wherein m'/(n'+m') is in the range of 
0.30 to 0.75 are prepared by polymerizing 3,4-epoxy1-butene in the 
presence of a catalytic amount of a palladium(O) complex and a hydroxyl 
initiator compound. The palladium catalyst comprises palladium(O) in 
complex association with about 2 to 4 ligands, such as the catalysts 
disclosed in Published International PCT Application WO 89/02883. The 
palladium-ligand catalyst may be preformed or formed in situ, and those 
skilled in the art recognize that the palladium-ligand catalyst can be 
generated in a variety of ways. Suitable ligands include trihydrocarbyl 
phosphines and trihydrocarbylarsines, e.g., triphenylphosphine, 
tributylphosphine, trimethylphosphine, 1,2-bis(diphenylphosphino)ethane, 
triphenylarsine, tributylarsine, the trisodium salt of 
tri(m-sulfophenyl)phosphine, and the like. Those skilled in the art 
recognize that palladium(O) complexes also can be stabilized by other 
ligands such as, for example, olefins, phosphites, and the like. 
Tris(dibenzylideneacetone)dipalladium(O) is an example of a specific 
palladium(O) catalyst containing another type of ligand. The catalyst also 
may be formed in situ by adding palladium(O) and a ligand separately, 
e.g., 5% palladium on carbon and triphenylphosphine or 
tris(dibenzylideneacetone)dipalladium(O) and 
1,2-bis(diphenylphosphino)ethane. 
The palladium(O) complex may be supported on a polymer substrate. In this 
form, one substituent of at least one of the ligands is a repeating unit 
of a polymer. An example of a commercially available palladium complex 
supported on a polymer substrate is polymer-supported 
tetrakis(triphenylphosphine)palladium(O) available from Aldrich Chemical 
Co., Inc. The amount of the palladium(O) catalyst which may be used can 
vary substantially depending, for example, on process conditions and the 
particular palladium compound employed. In batch operation of the process, 
the amount of catalyst used typically is in the range of 0.4 to 1.0 mole 
percent based on the moles of palladium(O) metal and equivalents of 
initiator. 
The palladium-catalyzed polymerization normally is conducted in the absence 
of solvent. However, inert solvents such as hydrocarbons, chlorinated 
hydrocarbons, and the like may be used if desired. Examples of such 
solvents include benzene, toluene, xylene, heptane, methylene chloride, 
chloroform, and the like. The palladium-catalyzed polymerization may be 
carried out at temperatures in the range of about -40.degree. to 
60.degree. C., depending upon the choice of initiator, solvent, and 
catalyst. The polymerization temperature affects the ratio of repeating 
units (1A) and (2A) set forth above, with lower polymerization 
temperatures generally favoring the formation of residues (2A): 
EQU --O--CH.sub.2 --CH.dbd.CH--CH.sub.2 -- (2A) 
Temperatures of about -10.degree. to 50.degree. C. are preferred. Reaction 
pressure is not an important part of our novel process and, therefore, the 
process typically is performed at approximately atmospheric pressure 
although pressure moderately above or below atmospheric may be used. 
The unsaturated precursor polymers wherein m'/(n'+m') is in the range of 
0.75 to 0.98 may be obtained by polymerizing 3,4-epoxy-1-butene in the 
presence of a catalyst system comprising an onium iodide compound such as 
an ammonium or phosphonium iodide and an organotin compound such as a 
trihydrocarbyltin iodide. The onium iodide component of the catalyst 
system may be selected from a variety of tetra(hydrocarbyl)ammonium 
iodides and tetra(hydrocarbyl)phosphonium iodides, preferably having a 
total carbon atom content of about 16 to 72 carbon atoms. Such compounds 
have the formulas: 
##STR10## 
wherein 
each R.sup.1 substituent independently is selected from alkyl of up to 
about 20 carbon atoms and each R.sup.2 substituent is independently 
selected from R.sup.1, benzyl, phenyl or phenyl substituted with up to 3 
substituents selected from lower alkyl, e.g., alkyl of up to about 4 
carbon atoms, lower alkoxy or halogen; or 
two R.sup.1 substituents collectively may represent alkylene of 4 to 6 
carbon atoms including alkylene of 4 to 6 carbon atoms substituted with 
lower alkyl; provided, as specified above, that the quaternary iodide 
compounds contain about 16 to 72 carbon atoms. Specific examples of the 
onium iodide catalyst component include tetra-n-octylphosphonium iodide, 
tri-n-octyl(n-dodecyl)phosphonium iodide, 
tri-n-octyl(n-hexadecyl)phosphonium iodide, 
tri-n-octyl(n-octadecyl)phosphonium iodide, tetra-n-dodecylphosphonium 
iodide, tetra-n-hexadecylphosphonium iodide, tetra-n-octadecylphosphonium 
iodide, tetra-n-dodecylammonium iodide, tetra-n-hexadecylammonium iodide, 
and tetra-n-octadecylammonium iodide. The preferred onium iodides are 
tetra-n-alkylphosphonium iodides containing about 32 to 72 carbon atoms, 
especially compounds of formula (II) above wherein each R.sup.2 is 
straight-chain alkyl of about 4 to 18 carbon atoms. 
Tetra-n-dodecylphosphonium iodide, tetra-n-hexadecylphosphonium iodide, 
and tri-n-octyl(n-octa-decyl)phosphonium iodide are especially preferred. 
The organotin catalyst component may be selected from organotin (IV) 
iodides such as hydrocarbyltin triiodides, di(hydrocarbyl)tin diiodides, 
and tri(hydrocarbyl)tin iodides. Examples of such organotin (IV) iodide 
compounds have the general formula 
EQU (R.sup.3).sub.n --Sn--I.sub.(4-n) (III) 
wherein 
each R.sup.3 independently is selected from alkyl or substituted alkyl 
moieties having up to about 20 carbon atoms, cycloalkyl or substituted 
cycloalkyl having about 5 to 20 carbon atoms, carbocyclic aryl or 
substituted carbocyclic aryl having about 6 to 20 carbon atoms, or 
heteroaryl or substituted heteroaryl moieties having about 4 up to 20 
carbon atoms; and 
EQU n is 1, 2, or 3. 
Specific examples of the organotin compounds include di-n-butyltin 
diiodide, tri-n-butyltin iodide, tri-n-octyltin iodide, triphenyltin 
iodide, trimethyltin iodide, n-butyltin triiodide, tricyclohexyltin 
iodide, tris(2-methyl-2-phenylpropyl)tin iodide, tribenzyltin iodide, 
dimethyltin diiodide and diphenyltin diiodide. Other organotin halides 
such as chlorides and bromides may be used in the process wherein they are 
converted to the iodide compounds. The preferred organotin iodide 
compounds have the general formula: 
EQU (R.sup.3).sub.3 --Sn--I (IV) 
wherein 
each R.sup.3 independently is selected from alkyl having about 4 to 10 
carbon atoms, phenyl, or 2-methyl-2-phenylpropyl. 
The ratio of the onium iodide and organotin iodide components of the 
catalyst system can vary substantially depending, for example, upon the 
particular compounds used. Generally, the quaternary onium 
iodide:organotin iodide mole ratio is within the range of about 20:1 to 
0.05:1. For the preferred catalyst system comprising a phosphonium iodide 
and an organotin iodide, a phosphonium iodide:organotin iodide mole ratio 
of about 5:1 to 0.2:1 is especially preferred. 
In the synthesis of the unsaturated polyether precursor compounds by each 
of the 3 processes described herein, the primary reactant, 
3,4-epoxy-1-butene is added to a mixture of the catalyst or catalysts, a 
hydroxyl initiator compound, and, optionally, a solvent. The 
3,4-epoxy-1-butene monomer may be added all at once or, preferably, slowly 
or in stepwise increments to a mixture of the catalyst and the initiator. 
Slow addition of 3,4-epoxy-1-butene is preferred for controlling the 
conversion, controlling the product molecular weight, and minimizing side 
reaction. Stepwise addition of the 3,4-epoxy-1-butene monomer gives 
stepwise increase in polymer molecular weight. Thus, molecular weight 
control is achieved by the stoichiometry of monomer to initiator. A wide 
variety of molecular weights may be achieved, but the molecular weights 
are generally controlled to provide polymers with molecular weights of 
about 500 to 3000 for use as condensation polymer intermediates. The 
process may be carried out in a batch, semi-continuous, or continuous mode 
of operation. 
The hydroxyl initiator compound useful in the preparation of the 
unsaturated polyether precursors by each of the 3 processes described 
herein may be selected from a vast number and broad variety of mono- and 
poly-hydroxy compounds. Normally, the residue of the hydroxyl initiator 
compound constitutes at least 0.5 weight percent of the polyether. The 
mono-hydroxy initiators include low molecular weight organic alcohols and 
polymeric alcohols which may be linear or branched chain, aliphatic, 
alicyclic, or aromatic. The mono-hydroxy initiators preferably are 
selected from alkanols containing up to about 20 carbon atoms. When an 
alcohol is used as the initiator, the polyether polymeric product obtained 
has a primary hydroxyl group on one end of the polymer chain and thus is a 
polymeric alcohol. The other end of the polymer chain is terminated with 
the residue of the alcohol initiator, e.g., a residue having the formula 
--O--R.sup.4 wherein R.sup.4 is the residue of an alcohol, preferably an 
alkyl group, containing up to about 20 carbon atoms. Although secondary or 
tertiary alcohols may be used, primary alcohols are preferred. The 
secondary alcohols are converted to primary hydroxyls and, thus, this 
invention provides a novel method of converting secondary hydroxyls to 
primary hydroxyls without the use of ethylene oxide. Some typically useful 
alcohol initiators include methanol, ethanol, n-butanol, iso-butanol, 
2-ethylhexanol, n-decanol, stearyl alcohol, cetyl alcohol, allyl alcohol, 
benzyl alcohol, phenol, and the like. Water also may be used as the 
initiator. Also, an inorganic hydroxide such as litium hydroxide may be 
used as the initiator in the polymerization of 3,4-epoxy-1-butene in the 
presence of a palladium(O) complex. 
The poly-hydroxyl initiators contain 2 or more hydroxyl groups and may be 
monomeric or polymeric compounds. Examples of the poly-hydroxyl initiators 
include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 
1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 
1,4-cyclohexanedimethanol, 2,2-dimethyl-1,3-propanediol, 
2,2,4-trimethyl-1,3-pentanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 
2-butene-1,4-diol, 1-butene-3,4-diol, hydroquinone, resorcinol, 
bis-phenol-A, glycerol, trimethylolpropane, starch, sucrose, glucose, 
pentaerythritol, polyethylene glycol, polypropylene glycol, polybutylene 
glycol, poly(tetramethylene ether) glycol, and hydroxyl-terminated, low 
molecular weight polyesters. When a poly-hydroxyl compound is used as the 
initiator, the polyether polymer typically grows from at least 2 of the 
hydroxyl groups of the initiator and the subsequently-obtained polymer is 
a poly-hydroxyl polymer. The residue of the poly-hydroxyl initiators may 
be represented by the formula --O--R.sup.5 --O-- wherein R.sup.5 is the 
residue of a poly-hydroxyl initiator. The diols having 2 to 6 carbon atoms 
constitute the preferred initiators. 
The residues of the hydroxyl initiator compounds may constitute a minor or 
major portion of the molecular weight of the unsaturated polyether 
precursor polymers as well as the saturated polyether polymers of the 
invention. For example, if a polymeric initiator, such as a 
hydroxyl-terminated polyoxyalkylene polymer, is employed and the number of 
repeat units of 3,4-epoxy-1-butene residue is relatively low, the 
initiator residue content of the polymer may be greater than 90 weight 
percent. On the other hand, if the initiator employed is a low molecular 
weight compound such as methanol or water, the initiator residue may 
constitute as low as 0.5 weight percent of the polymer. Both the 
unsaturated and saturated polyether polymers typically comprise at least 
80 weight percent, preferably at least 90 weight percent, 
3,4-epoxy-1-butene residues. Both the unsaturated and saturated polyether 
polymers preferably comprise 5 to 20 weight percent, most preferably 5 to 
10 weight percent, of residues derived from the hydroxyl initiator 
compounds, e.g., residues --O--R.sup.4 and --O--R.sup.5 --O--. 
The saturated polyether polymers of the present invention comprising 
residues (1) and (2) are prepared by contacting the unsaturated polyether 
precursors described hereinabove with hydrogen in the presence of a 
hydrogenation catalyst at elevated temperature and pressure. The 
hydrogenation catalyst may be selected from a wide variety of known 
materials such as catalysts containing one or more metals selected from 
palladium, rhodium, platinum, ruthenium, iridium, nickel, cobalt, copper, 
and the like. The catalyst may consist of one or more of the metals 
deposited on the surface of a suitable catalyst support material such as 
carbon, alumina, silica, silica-alumina, titania, kieselguhr, molecular 
sieves, zeolites, and the like. 
The use of nickel catalysts in the hydrogenation of the unsaturated 
polyether precursors to the polyether polymers of the present invention is 
particularly advantageous. It has been found that nickel hydrogenation 
catalysts are effective to give complete, or essentially complete, 
hydrogenation of the olefinic unsaturation of the polyether precursors 
without concomitant hydrogenolysis of the polyether linkages and 
subsequent decrease in molecular weight, i.e., without causing degradation 
of the polymer. Thus, another embodiment of the present invention is a 
process for the preparation of a saturated polyether polymer which 
comprises contacting an unsaturated polyether precursor with hydrogen in 
the presence of a nickel hydrogenation catalyst under hydrogenation 
conditions of pressure and temperature, wherein (i) the saturated 
polyether polymer is comprised of n units of residue (1) and m units of 
residue (2) wherein residues (1) and (2) have the structures: 
##STR11## 
(ii) the total value of n+m is 2 to 70 and m/(n+m) is in the range of 
about 0.05 and 0.98; (iii) the saturated polyether polymer comprises at 
least 1 weight percent of the residue of a hydroxyl initiator compound; 
and (iv) the unsaturated polyether precursor is comprised of residues (1A) 
and (2A): 
##STR12## 
The nickel hydrogenation catalyst may be Raney-nickel or a supported nickel 
catalyst, e.g., a catalyst comprising about 10 to 80, preferably 25 to 65, 
weight percent nickel, based on the total weight of the catalyst, 
deposited on the surface of a suitable catalyst support material. Typical 
catalyst support materials include carbon, alumina, silica, 
silica-alumina, titania, kieselguhr, molecular sieves, zeolites, and the 
like. Nickel catalysts modified or promoted with, for example, molybdenum, 
chromium, iron, zirconium, and/or cobalt also may be used. 
The hydrogenation conditions of temperature and pressure can vary 
substantially depending on several factors such as contact time with the 
catalyst, the amount of catalyst, the choice of catalyst, and the mode of 
operation. Hydrogenation temperatures of about 20.degree. to 200.degree. 
C. may be used although temperatures in the range of about 50.degree. to 
80.degree. C. are preferred. The hydrogenation process may be carried out 
using total pressures in the range of about 2.4 to 414.5 bars absolute (20 
to 6000 psig), preferably 35.5 to 70 bars (500 to 1000 psig). As noted 
above, the optimum combination of temperature and pressure depends on 
other process variables but can be readily ascertained by those skilled in 
the art. 
The hydrogenation process optionally may be carried out in the presence of 
inert solvents such as aliphatic and aromatic hydrocarbons, ketones, 
ethers, alcohols, water, and the like. For example, benzene, toluene, 
tetrahydrofuran, methanol, ethanol, butanol, methyl isoamyl ketone, and 
the like may be used individually or in combination as solvent. 
For the unsaturated polyether precursors prepared by the 
palladium-catalyzed polymerization of 3,4-epoxy-1-butene, the palladium(O) 
polymerization catalyst may be removed by pretreatment with hydrogen 
pressure alone to precipitate the palladium with minimal concomitant 
hydrogenation of the unsaturated polyether, followed by filtration of the 
precipitated palladium metal. Also, if a water soluble phosphine ligand, 
such as a sulfonated triphenylphosphine, is used, such phosphine ligand 
and complexed palladium(O) may be removed from the polymer by aqueous 
washings. After the removal of the catalyst components as described, the 
unsaturated polyether precursor may be hydrogenated in the presence of a 
nickel hydrogenation catalyst. 
Alternatively, the unsaturated polyether precursors prepared by the 
palladium-catalyzed polymerization of 3,4-epoxy-1-butene may be 
hydrogenated directly, i.e., without the above-described removal of 
catalyst components, by contacting the precursor polymer with hydrogen in 
the presence of a supported palladium catalyst. The supported palladium 
catalyst may consist of about 0.5 to 15, preferably about 5, weight 
percent palladium deposited on a catalyst support material such as carbon, 
alumina, silica, silica-alumina, titania, kieselguhr, molecular sieves, 
zeolites, and the like. The palladium catalysts also may contain 
molybdenum, chromium, zinc, zirconium and or cobalt as catalyst modifiers 
or promoters. An especially preferred catalyst is 5% palladium on carbon. 
The hydrogenation process may be carried out in a batch, semi-continuous, 
or continuous mode of operation. For example, batch operation may comprise 
agitating a slurry of catalyst and unsaturated polyether precursor 
comprised of residues (1A) and (2A), and, optionally, a solvent in a 
pressure vessel for a time sufficient to hydrogenate essentially all of 
the olefinic unsaturation. The catalyst can be separated from the 
hydrogenated mixture by filtration and the saturated polyether compound 
isolated by evaporation of solvent. 
Another mode of operation uses a fixed bed of a catalyst wherein the 
unsaturated polyether compound is hydrogenated by feeding a solution of 
the compound in an inert solvent to the top of a columnar, pressure 
reactor containing one or more fixed beds of a supported nickel catalyst. 
The reactant solution flows (trickles) over the catalyst bed in the 
presence of hydrogen at elevated temperature and pressure, and the 
hydrogenated product exits the bottom of the reactor and is isolated by 
evaporation of solvent. 
Our novel polyether polymers preferably are comprised of n units of residue 
(1) and m units of residue (2), wherein the total value of n+m is about 7 
to 50 and m/(n+m) is a value in the range of 0.15 to 0.30. The polymers 
are further characterized in that at least 99 percent of the terminal 
hydroxyl groups are primary (rather than secondary) hydroxyl groups. The 
primary hydroxyl groups (and thus the polymers) are more reactive for 
condensation polymerization reactions in general. The polyether polymers 
normally have a polydispersity value of less than 4, preferably in the 
range of 1 to 2.5, and most preferably in the range of 1 to 1.7. The 
polyether polymers wherein the total value of n+m is about 10 to 30 are 
particularly preferred. 
The preparation of the unsaturated polyether precursors and the novel 
saturated polyether polymers of the present invention and the operation of 
the hydrogenation process are further illustrated by the following 
examples. Proton NMR spectra are obtained on a 300 MHz NMR spectrometer 
with samples dissolved in deuterated chloroform containing 
tetramethylsilane as an internal standard. The value of m/(n+m) is 
determined by comparison of the integrated proton NMR absorptions of 
residues (1) and (2). The value of m'/(n'+m') is determined by comparison 
of the integrated proton NMR absorptions of residues (1A) and (2A). The 
percent hydrogenation is determined by comparison of the integrated proton 
NMR absorptions of residues (1) and (2) with the integrated proton NMR 
absorptions of remaining residues (1A) and (2A). Number average molecular 
weights (M.sub.n) and polydispersity values (M.sub.w /M.sub.n) are 
determined using size-exclusion chromatography with refractive index 
detection in tetrahydrofuran using four 10 .mu.m PLgel mixed-bed columns 
and calibrated using narrow molecular weight distribution polystyrene 
standards. Hydroxyl numbers are determined from titration of the acetic 
acid formed by the reaction of the sample with acetic anhydride. 
J-resolved NMR and .sup.13 C NMR analyses, obtained from a 400 MHz NMR 
spectrometer, are used to determine the percent of primary hydroxyl end 
groups. Further conformation may be obtained by trifluoroacetylation and 
.sup.19 F NMR analyses.

REFERENCE EXAMPLE 1 
Methylene chloride (400 mL), 18.0 g (0.200 mole) of 1,4 butanediol, and 0.2 
mL of trifluoromethane sulfonic acid are charged to a 3-neck, 1-L, 
round-bottom flask having a nitrogen atmosphere and equipped with a 
thermocouple, mechanical stirrer, septum, and reflux condenser with argon 
inlet. With stirring, 3,4-epoxy-1-butene (392.5 g, 5.60 mole) is added at 
a rate of 60 g/hr by liquid pump. The temperature rises initially to about 
42.degree. C., gently refluxing the solvent, and continued to rise, 
reaching 58.degree. C. near complete addition of the 3,4-epoxy-1-butene. 
After complete addition the reaction is allowed to cool and stirred for 1 
hour. To the reaction mixture is added 100 mL of 5 percent sodium 
carbonate solution, and the mixture is stirred for 30 minutes. Then the 
layers are allowed to separate, and the bottom organic layer is removed, 
dried over anhydrous magnesium sulfate, filtered, and evaporated to give a 
clear, light-yellow oil that is an unsaturated polyether glycol comprising 
n' repeat units of residue (1A) and m' repeat units of residue (2A), 
wherein n'+m' is about 15; m'/(n'+m') is 0.16; M.sub.n =1400 and M.sub.n 
=1.99; and hydroxyl number=103.4. 
REFERENCE EXAMPLE 2 
Methylene chloride (80 mL), 1,4-butanediol (3.62 g, 40.0 mmole), and 3 
drops of trifluoromethane sulfonic acid are charged to a 3-neck, 300-mL, 
round-bottom flask having an argon atmosphere and equipped with a 
thermocouple, mechanical stirrer, and a septum with argon inlet. Stirring 
is begun and the reaction flask is cooled with a cooling bath composed of 
water and ice and having a temperature of 0.degree. to 5.degree. C. 
3,4-Epoxy-1-butene (40 mL, 500 mmole) is added dropwise at a rate of 9 
mL/hour by syringe pump. After the addition of the 3,4-epoxy-1-butene is 
complete, the cooling bath is removed and the reaction is allowed to warm 
to room temperature. Solid calcium oxide is added and the mixture stirred 
for several hours to neutralize the acid. The mixture is then filtered and 
the filtrate evaporated to give 35 g of a clear, colorless oil having a 
n'+m' value of approximately 17 and a m'/(n'+m') value of 0.15; Mn=1270 
and Mw/Mn=1.94; and hydroxyl number=100.5. 
REFERENCE EXAMPLE 3 
The procedure described in Reference Example 2 is repeated in the absence 
of a solvent and at a reaction temperature between 20.degree. and 
30.degree. C. by cooling with cool water and adding small amounts of ice 
as needed. The resulting clear, colorless oil has a n'+m' value of 
approximately 18 and a m'/(n'+m') value of 0.14; Mn=1305 and Mw/Mn=2.00; 
and hydroxyl number=97.18. NMR analysis of this product shows no evidence 
of secondary hydroxyl end groups. 
REFERENCE EXAMPLE 4 
1,4-Butanediol (21.6 g, 0.240 mole) and 10 drops of trifluoromethane 
sulfonic acid dissolved in 250 mL of methylene chloride are charged to a 
3-neck, 1-L, round-bottom flask having an argon atmosphere and equipped 
with a thermocouple, mechanical stirrer, septum, and reflux condenser with 
argon inlet. With stirring, 3,4-epoxy-1-butene (471 g, 6.72 mole) is added 
dropwise at a rate of 60 g/hour by liquid pump. The temperature rises 
initially to about 42.degree. C., gently refluxing the solvent, and 
continued to rise, reaching 58.degree. C. near the completion of the 
addition of the 3,4-epoxy-1-butene. After complete addition the reaction 
is allowed to cool and stir for 1 hour. The reaction mixture is washed 
twice with water, dried over anhydrous magnesium sulfate, filtered, and 
evaporated to give 468 g of a light yellow oil having a n'+m' value of 
approximately 29 and a m'/(n'+m') value of about 0.17; Mn=2100 and 
Mw/Mn=2.64; and hydroxyl number=46.09. 
REFERENCE EXAMPLE 5 
1,4-Butanediol (0.90 g, 0,010 mole) and 1 drop of trifluoromethane sulfonic 
acid dissolved in 10 ml of toluene are charged to a reaction flask having 
a nitrogen atmosphere and equipped with a refluxing condenser. With 
stirring, the reaction solution is heated to 100.degree. C. by an oil 
bath. 3,4-Epoxy-1-butene (9.1 g, 0.13 mole) is added dropwise at a rate of 
0.15 mL/minute by syringe pump. After complete addition the reaction is 
allowed to cool and stir for 15 minutes. The reaction mixture is washed 
twice with water, dried over anhydrous magnesium sulfate, filtered, and 
evaporated to give 8.0 g of a black oil having a n'+m' value of 
approximately 14 and a m'/(n'+m') value of about 0.26; Mn=950 and 
Mw/Mn=2.16; and hydroxyl number=95.0. 
REFERENCE EXAMPLE 6 
3,4-Dihydroxy-1-butene (0.88 g, 0.010 mole) and 1 drop of trifluoromethane 
sulfonic acid dissolved in 10 mL of methylene chloride are charged to a 
reaction flask having a nitrogen atmosphere and an 18.degree. C. chilled 
water cooling bath. With stirring, 3,4-epoxy-1-butene (9.1 g, 0.13 mole) 
is added dropwise at a rate of 0.15 mL/minute by syringe pump. After 
complete addition, the reaction is allowed to cool and stir for 15 
minutes. The reaction mixture is washed with 5% sodium carbonate in water, 
dried over anhydrous sodium carbonate, filtered, and evaporated to give 
8.6 g of a clear, colorless oil having a n'+m' value of approximately 14 
and a m'/(n'+m') value of about 0.13; Mn=1400; and Mw/Mn=1.68. 
REFERENCE EXAMPLE 7 
The procedure described in Reference Example 6 is repeated using 0.18 g 
(0.010 mole) of water as the initiator in place of 1,4-butanediol, 
yielding 8.6 g of a clear, colorless oil having a n'+m' value of 
approximately 15 and a m'/(n'+m') value of about 0.14; Mn=1400; and 
Mw/Mn=1.68. 
REFERENCE EXAMPLE 8 
To a 3-neck, 300-mL, round-bottom flask having an argon atmosphere and 
equipped with a thermocouple, mechanical stirrer, and a septum with argon 
inlet is charged tetrakis(triphenylphosphine)palladium(O) (0.25 g, 0.22 
mmole) and 1,4-butanediol (7.22 g, 80.0 mmole). Stirring is begun and a 
total of 83.2 mL (1040 mmole) of 3,4-epoxy-1-butene is added dropwise at a 
rate of 9 mL/hr by syringe pump. After about 1 mL of 3,4-epoxy-1-butene is 
added, the reaction flask is cooled with a cooling bath composed of water 
and ice and having a temperature of 0.degree. to 5.degree. C. The reaction 
temperature is maintained between 10.degree. and 15.degree. C. by cooling 
for the duration of the 3,4-epoxy-1-butene addition. After complete 
addition, the cooling bath is removed, and the reaction is allowed to warm 
to room temperature. The resulting clear, yellow oil is an unsaturated 
polyether glycol having a n'+m' value of about 15; a m'/(n'+m') value of 
about 0.65; M.sub.n =1300 and M.sub.w /M.sub.n =1.39; and hydroxyl 
number=101.8. 
REFERENCE EXAMPLE 9 
Tetrakis(triphenylphosphine)palladium(O) (0.25 g, 0.22 mmole) and 
1,4-butanediol (3.62 g, 40.0 mmole) are charged to a 3-neck, 100-mL, 
round-bottom flask having an argon atmosphere and equipped with a 
thermocouple, mechanical stirrer, and a septum with argon inlet. Stirring 
is begun and a total of 41.8 mL (520 mmole) of 3,4-epoxy-1-butene is added 
dropwise at a rate of 9 mL/hour by syringe pump. After about 1 mL of 
3,4-epoxy-1-butene is added, the reaction flask is cooled with a cooling 
bath composed of water and ice and having a temperature of 0.degree. to 
5.degree. C. The reaction temperature is maintained between 10.degree. and 
15.degree. C. by cooling for the duration of the 3,4-epoxy-1-butene 
addition. After addition is complete, the cooling bath is removed, and the 
reaction mixture is allowed to warm to room temperature. The resulting 
clear, yellow oil has a n'+m' value of approximately 17, a m'/(n'+m' ) 
value of 0.59, a number average molecular weight (Mn) of 1300, a weight 
average molecular weight (Mw) of 1800, a polydispersity value (Mw/Mn) of 
1.39; and a hydroxyl number of 95.27. NMR analyses of this product showed 
no evidence of secondary hydroxyl. 
REFERENCE EXAMPLE 10 
The procedure of Reference Example 9 is repeated using a cooling bath 
composed of ethylene glycol and Dry Ice and having a temperature of 
-15.degree. to -25.degree. C. The reaction temperature is maintained 
between -5.degree. and 5.degree. C. The resulting clear, yellow oil has a 
n'+m' value of approximately 15 and a m'/(n'+m') value of 0.65; Mn=1110 
and Mw/Mn=1.38; and hydroxyl number=130.9. 
REFERENCE EXAMPLE 11 
The procedure of Reference Example 9 is repeated without using a cooling 
bath. The reaction temperature increases upon the addition of 
3,4-epoxy-1-butene and is maintained between 40.degree. and 50.degree. C. 
by controlling the rate of addition. The resulting clear, yellow oil has a 
n'+m' value of approximately 14 and a m'/(n'+m') value of 0.48; Mn=1038 
and Mw/Mn=1.44; and hydroxyl number=128.7. 
REFERENCE EXAMPLE 12 
The procedure in Reference Example 11 is repeated using 1.67 g (40.0 mmole) 
of lithium hydroxide in place of 1,4-butanediol. The resulting yellow oil 
is dissolved in 100 mL of methylene chloride and 40 mL of water. Enough 
dilute hydrochloric acid is added so that the aqueous layer is neutral or 
slightly acidic to pH paper. The layers are separated, and the methylene 
chloride is washed with water, dried over magnesium sulfate, filtered, and 
evaporated to produce 36.6 g of a clear, yellow oil having a n'+m' value 
of approximately 42 and a m'/(n'+m') value of 0.31; Mn=3245 and 
Mw/Mn=2.73; and hydroxyl number=23.36. 
REFERENCE EXAMPLE 13 
The procedure of Reference Example 9 is repeated using 0.27 g (0.20 mmole) 
of tetrakis(triphenylarsine)palladium(O) in place of 
tetrakis(triphenylphosphine)palladium(O). The resulting clear, colorless 
oil has a n'+m' value of approximately 15 and a m'/(n'+m') value of 0.56; 
Mn=1185 and Mw/Mn=1.23; and hydroxyl number=129.8. 
REFERENCE EXAMPLE 14 
The procedure of Reference Example 13 is repeated using a solution of 80 
parts by volume 3,4-epoxy-1-butene and 20 parts by volume isopropanol. The 
resulting clear, yellow oil has a n'+m' value of approximately 12 and a 
m'/(n'+m') value of 0.60; Mn=950 and Mw/Mn=1.17; and hydroxyl 
number=162.5. 
REFERENCE EXAMPLE 15 
The procedure of Reference Example 9 is repeated using 4.33 g (40.0 mmole) 
of benzyl alcohol in place of 1,4-butanediol. The resulting clear, yellow 
oil has a m'/(n'+m') value of 0.46 and hydroxyl number=48.59. 
REFERENCE EXAMPLE 16 
The procedure of Reference Example 15 is repeated using 100 mL of heptane 
as solvent. The clear, yellow oil is isolated by evaporating the volatiles 
and has a m'/(n'+m') value of 0.32. 
REFERENCE EXAMPLE 17 
The procedure of Reference Example 9 is repeated using a total of 6.4 mL 
(80 mmoles) of 3,4-epoxy-1-butene. The resulting clear, colorless oil has 
a n'+m' value of approximately 2 and a m'/(n'+m') value of 0.63. 
REFERENCE EXAMPLE 18 
The procedure of Reference Example 9 is repeated using a total of 70 g (1.0 
mole) of 3,4-epoxy-1-butene. The resulting clear, yellow oil has a n'+m' 
value of approximately 26 and a m'/(n'+m') value of 0.48. 
REFERENCE EXAMPLE 19 
The procedure of Reference Example 13 is repeated using a total of 6.4 mL 
(80 mmoles) of 3,4-epoxy-1-butene. The resulting clear, colorless oil has 
a n'+m' value of approximately 2 and a m'/(n'+m') value of 0.73. 
REFERENCE EXAMPLE 20 
Tris(2-methyl-2-phenylpropyl)tin iodide [also known as trineophyltin 
iodide] (33.8 g), tri-n-octyl(n-octadecyl)phosphonium iodide (39.0 g), and 
1,4-butanediol (10.0 g) are placed in a 4-neck, 250-mL, round-bottom flask 
equipped with a thermocouple, magnetic stirrer, distillation head, oil 
heating bath, and reactant feed tube. The mixture is heated to 110.degree. 
C., and the 3,4-epoxy-1-butene addition is begun. A total of 816 g of 
3,4-epoxy-1-butene is added over 44 hours. Then the pressure within the 
flask is gradually lowered to about 100 torr to completely distill the 
volatile components from the catalyst/polyether polymer residue. A total 
of 648.5 g of distillate is collected (79.5% weight recovery). The 
composition of the distillate is 21.1% 3,4-epoxy-1-butene, 75.3% 
2,5-dihydrofuran, and 3.6% crotonaldehyde. 
The catalyst/polyether polymer residue and 200 mL of heptane are added to a 
500-mL, jacketed, glass vessel equipped with a mechanical stirrer, 
thermocouple, and bottom stopcock and the mixture is agitated and heated 
to 65.degree.-75.degree. C. by circulating heated glycol/water from a 
constant temperature bath to the jacket. Stirring is discontinued, and the 
mixture is allowed to settle. The layers are separated, and the bottom 
polyether polymer layer is extracted again with 200 mL of heptane then 
once more with 100 mL of heptane. The heptane layers containing the 
extracted catalyst are combined, and the solvent is removed by rotary 
vacuum evaporation (up to about 70.degree. C. and 30 torr) to give a 
catalyst-containing material (80.3 g) with the following approximate 
composition by weight: 31.1% tris(2-methyl-2-phenylpropyl)tin iodide, 
54.9% tri-n-octyl(n-octyldecyl)phosphonium iodide, and 13.9% polyether 
polymer. The recovered catalyst mixture can be returned to the reaction 
flask for continued cycles of polymerization and catalyst separation. 
After removal of residual volatile material by rotary vacuum evaporation 
(up to about 70.degree. C. and 30 torr) the polyether polymer layer weighs 
149.4 g (18.3% yield) and has n'+m' equal to about 11, 
m'/(n'+m')=approximately 0.94, and M.sub.w /M.sub.n =1.59. J-resolved NMR 
and .sup.13 C NMR analyses of the polyether polymer product in deuterated 
acetone show no evidence of secondary hydroxyl carbons. 
EXAMPLE 1 
The unsaturated polyether polymer (10 g) prepared in Reference Example 1, 
Raney-nickel (1.0 g, prewashed with methanol), and methanol (90 mL) are 
charged to a 1-L autoclave equipped with a magnetic stirbar. The autoclave 
is purged with nitrogen, pressurized with 35.5 bar absolute (500 psig) 
hydrogen and then heated to 80.degree. C., with stirring. The reaction 
mixture is stirred at 80.degree. C. and at a total pressure of 35.5 bar 
absolute (500 psig) for 20 hours. After cooling, the pressure is released, 
and the reaction mixture is removed, filtered, and concentrated by 
evaporating the methanol to give a clear, colorless oil. The oil is 
further purified by dissolving in 50 mL methylene chloride, drying over 
anhydrous magnesium sulfate, filtering, and evaporating the volatiles, 
giving 9.0 g of a clear, colorless oil comprising n repeat units of 
residue (1) and m repeat units of residue (2), wherein n+m is about 16 and 
m/(n+m) is 0.21 [These values are higher than the values of n'+m' and 
m'/(n'+m') of the starting material because the 1,4-butanediol initiator 
fragment is identical to repeat unit (2) and is no longer distinguishable 
in the hydrogenated product.]; M.sub.n =1500 and M.sub.w /M.sub.n =1.92; 
hydroxyl number=100.6; and percent hydrogenation&gt;99. 
EXAMPLE 2 
The unsaturated polyether glycol(250 g) prepared in Reference Example 1, 
water-wet Raney-nickel (20.0 g), and tetrahydrofuran (450 g) are charged 
to a 2-L autoclave equipped with a magnetic stirbar. The autoclave is 
purged with nitrogen, pressurized with 35.5 bar absolute (500 psig) 
hydrogen then heated to 60.degree. C., with stirring. The reaction mixture 
is stirred at 60.degree. C. and a total pressure of 35.5 bar absolute (500 
psig) for 20 hours. After cooling, the pressure is released, and the 
reaction mixture is removed, filtered, and concentrated by evaporating the 
volatiles to give a clear, colorless oil. The oil is further purified by 
dissolving in 500 mL of methylene chloride, drying over anhydrous 
magnesium sulfate, filtering, and evaporating the volatiles, giving 200 g 
of a clear, colorless oil having m/(n+m)=0.21; M.sub.n =1300 and M.sub.w 
/M.sub.n =1.73; hydroxyl number=100.3; and percent hydrogenation&gt;99. 
EXAMPLE 3 
The unsaturated polyether glycol (10 g) prepared in Reference Example 1, 
0.8 g of water-wet Raney-nickel, and 100 mL of aqueous tetrahydrofuran (5 
volume percent water) are charged to a 250-mL glass high-pressure bottle 
and placed into a Parr shaker. The bottle is purged with nitrogen, 
pressurized with 4.5 bar absolute (50 psig) hydrogen and heated to 
55.degree. C., with shaking. The reaction mixture is shaken at 55.degree. 
C. and 4.5 bar absolute (50 psig) for 16 hours. After cooling, the 
pressure is released, and the reaction mixture is removed, filtered, and 
concentrated by evaporating the volatiles to give a clear, light-yellow 
oil. The oil is further purified by dissolving in 50 mL methylene 
chloride, drying over anhydrous magnesium sulfate, filtering, and 
evaporating the volatiles, giving 9.1 g of a clear, colorless oil having 
m/(n+m)=0.21; M.sub.n =1200 and M.sub.w /M.sub.n =2.33; percent 
hydrogenation=95. 
EXAMPLE 4 
The unsaturated polyether glycol (10 g) prepared in Reference Example 1, 
1.5 g of 5 percent palladium on charcoal, and 90 mL of aqueous 
tetrahydrofuran (5 volume percent water) are charged to a 1-L autoclave 
equipped with a magnetic stirbar. The autoclave is purged with nitrogen, 
pressurized with 35.5 bar absolute (500 psig) hydrogen then heated to 
80.degree. C., with stirring. The reaction mixture is stirred at 
80.degree. C. and 35.5 bar absolute (500 psig) total pressure for 20 
hours. After cooling, the pressure is released, and the reaction mixture 
is removed, filtered, and concentrated by evaporating the volatiles to 
give a clear, colorless oil. The oil is further purified by dissolving in 
50 mL methylene chloride, drying over anhydrous magnesium sulfate, 
filtering, and evaporating the volatiles, giving a clear, colorless oil 
having m/(n+m)=0.21; M.sub.n =900 and M.sub.w /M.sub.n =1.94; hydroxyl 
number=123.5; and percent hydrogenation&gt;99. 
EXAMPLE 5 
The unsaturated polyether glycol (10 g) prepared in Reference Example 1, 
0.50 g of 5 percent rhodium on charcoal, and 100 mL of aqueous 
tetrahydrofuran (containing 5 volume percent water) are charged to a 
250-mL glass high-pressure bottle and placed into a Parr shaker. The 
bottle is purged with nitrogen, pressurized with 4.5 bar absolute (50 
psig) hydrogen and heated to 55.degree. C. with shaking. The reaction 
mixture is shaken at 55.degree. C. and 4.5 bar absolute (50 psig) total 
pressure for 25 hours. After cooling the pressure is released, and the 
reaction mixture is removed, filtered, and concentrated by evaporating the 
volatiles to give a clear, light-yellow oil. The oil is further purified 
by dissolving in 50 mL of methylene chloride, drying over anhydrous 
magnesium sulfate, filtering, and evaporating the volatiles, giving 9.0 g 
of a clear, colorless oil having m/(n+m)=0.21; M.sub.n =830 and M.sub.w 
/M.sub.n =1.62; hydroxyl number=136.6; and percent hydrogenation&gt;99. 
EXAMPLE 6 
An unsaturated polyether precursor (450 g) prepared according to the 
general procedure described in Reference Example 1 [m'/(n'+m')=0.17, 
M.sub.n =2420, M.sub.w /M.sub.n =1.77, and hydroxyl number=50.66] and 5 
percent palladium on charcoal powder (20 g) are charged to a 1-L autoclave 
equipped with magnetic stirbar and baffles. The autoclave is purged with 
nitrogen, pressurized with 35.5 bar absolute (500 psig) hydrogen and then 
heated to 80.degree. C. with stirring. The reaction mixture is stirred at 
80.degree. C. and 35.5 bar absolute (500 psig) for 20 hours. After 
cooling, the pressure is released and the reaction mixture taken up with 
600 mL methylene chloride, gravity filtered, and evaporated to give 371 g 
of a clear, slightly yellow oil having an n+m of value of about 32; 
m/(n+m)=0.20; M.sub.n =2860 and M.sub.w /M.sub.n =2.61; hydroxyl 
number=53.8; and percent hydrogenation&gt;99. 
EXAMPLE 7 
A 1-L reactor equipped with a glass stirring rod with Teflon paddle and a 
thermocouple is flushed with argon then charged with 1,4-butanediol (32.5 
g, 0.360 moles) and the H.sup.+ form of Nafion 1100 EW acidic resin (10.0 
g, 9.09 meq, 60-100 mesh). With stirring, 500 g (7.13 mole) of 
3,4-epoxy-1-butene is added at a rate of about 130 g/hour by liquid pump. 
Upon addition of the epoxide, the temperature rises and is maintained 
below 40.degree. C. by cooling with an ice-water bath. After complete 
addition the reaction mixture is allowed to cool and stirred for 1 hour. 
Then the catalyst is removed by filtration, and the filtrate is taken up 
in 500 mL of methanol. 
The methanol solution is then hydrogenated over 20 g of water-wet 
Raney-nickel at 35.5 bar absolute (500 psig) hydrogen and 60.degree. C. 
for 24 hours in a 2-L stainless steel stirred autoclave. The Raney-nickel 
catalyst is removed by filtration, and the filtrate is evaporated with 
heating and reduced pressure to give a clear, colorless oil. Low molecular 
weight material, such as cyclic dimers, is removed by passing the oil 
through a wiped-film evaporator at 120.degree. C. and 0.1 torr to give 292 
g of a clear, colorless oil that is a saturated polyether glycol having an 
n+m value of about 9 and an m/(n+m) value of 0.30; M.sub.n =680; M.sub.w 
/M.sub.n =1.16; and hydroxyl number=195. 
EXAMPLE 8 
A 1-L reactor equipped with a glass stirring rod with Teflon paddle, a 
stainless steel cooling coil, and a thermocouple is flushed with argon and 
then charged with distilled water (6.48 g, 0.360 moles) of and the H.sup.+ 
form of Nafion 1100 EW acidic resin (10.0 g, 9.09 meq). The reactor is 
cooled with ice and with chilled water (5.degree.-10.degree. C.) 
circulating through the cooling coil. With stirring, 525 g (7.49 mole) of 
3,4-epoxy-1-butene is added at a rate of about 130 g/hour by liquid pump. 
Upon addition of the epoxide, the temperature rises to about to 34.degree. 
C. and is maintained at about 32.degree. to 36.degree. C. After complete 
addition the reaction mixture is allowed to cool and stir for 1 hour. Then 
the catalyst is removed by filtration, and the filtrate is taken up in 500 
mL of methanol. 
The methanol solution is then hydrogenated over 20 g of water-wet 
Raney-nickel at 35.5 bar absolute (500 psig) hydrogen and 60.degree. C. 
for 24 hours in a 2-L stainless steel stirred autoclave. The Raney-nickel 
catalyst is removed by filtration, and the filtrate is evaporated with 
heating and reduced pressure to give a clear, colorless oil. Low molecular 
weight material, such as cyclic dimers, is removed by passing the oil 
through a wiped-film evaporator at 120.degree. C. and 0.1 torr to give a 
clear, colorless oil that is a saturated polyether glycol having an n+m 
value of about 13 and an m/(n+m) value of 0.25; M.sub.n =1200 and M.sub.w 
/M.sub.n =1.94; and hydroxyl number=98.7. 
EXAMPLE 9 
The unsaturated polyether glycol (10 g) prepared in Reference Example 8, 
1.5 g of 5 percent palladium on carbon, and 90 mL of tetrahydrofuran are 
charged to a 1-L autoclave equipped with a magnetic stirbar. The autoclave 
is purged with nitrogen, pressurized with 21.7 bar absolute (300 psig) 
hydrogen then heated to 90.degree. C., with stirring. The reaction mixture 
is stirred at 90.degree. C. and 21.7 bar absolute (300 psig) for 20 hours. 
After cooling, the pressure is released, and the reaction mixture is 
removed, filtered, and concentrated by evaporating the volatiles to give a 
clear, light yellow oil having m/(n+m) of about 0.64; M.sub.n =1350 and 
M/.sub.w /M.sub.n =1.54; hydroxyl number=104.7; and percent 
hydrogenation&gt;99. 
EXAMPLE 10 
The unsaturated polyether glycol (10 g) prepared in Reference Example 8, 
1.5 g of 5 percent rhodium on alumina, and 90 mL of tetrahydrofuran are 
charged to a 1-L autoclave equipped with a magnetic stirbar. The autoclave 
is purged with nitrogen, pressurized with 21.7 bar absolute (300 psig), 
and then heated to 90.degree. C., with stirring. The reaction mixture is 
stirred at 90.degree. C. and 21.7 bar absolute (300 psig) for 20 hours. 
After cooling, the pressure is released, and the reaction mixture is 
removed, filtered, and concentrated by evaporating the volatiles to give a 
clear, light yellow oil having m/(n+m) of about 0.62; M.sub.n =1330 and 
M.sub.w /M.sub.n =1.29; hydroxyl number=125.0; and percent 
hydrogenation&gt;99. 
EXAMPLE 11 
The unsaturated polyether glycol (10 g) prepared in Reference Example 8 and 
90 mL of tetrahydrofuran are charged to a 1-L autoclave equipped with a 
magnetic stirbar. No catalyst is added and, thus, the residual palladium 
used to catalyze the polymerization serves as the hydrogenation catalyst. 
The autoclave is purged with nitrogen, pressurized with 21.7 bar absolute 
(300 psig) hydrogen then heated to 90.degree. C., with stirring. The 
reaction mixture is stirred at 90.degree. C. and 21.7 bar absolute (300 
psig) for 20 hr. After cooling, the pressure is released, and the reaction 
mixture is removed, filtered, and concentrated by evaporating the 
volatiles to give a clear, light yellow oil having a m/(n+m) value of 
about 0.68; M.sub.n =1230 and M.sub.w /M.sub.n = 1.58; hydroxyl 
number=130.7; and percent hydrogenation=43. 
EXAMPLE 12 
The product of Example 11, 1.0 g of water-wet Raney-nickel, and 90 mL of 
tetrahydrofuran are charged to a 1-L autoclave equipped with a magnetic 
stirbar. The autoclave is purged with nitrogen, pressurized with 21.7 bar 
absolute (300 psig) hydrogen then heated to 90.degree. C., with stirring. 
The reaction mixture is stirred at 90.degree. C. and 21.7 bar absolute 
(300 psig) for 20 hr. After cooling, the pressure is released and the 
reaction mixture is removed, filtered, and concentrated by evaporating the 
volatiles to give a clear, light yellow oil having a m/(n+m) value of 
about 0.68; M.sub.n =1250 and M.sub.w /M.sub.n =1.60; hydroxyl number=129; 
and percent hydrogenation&gt;99. 
EXAMPLE 13 
The unsaturated polyether glycol (10 g) prepared in Reference Example 20, 
2.0 g of water-wet Raney nickel, and 100 mL of tetrahydrofuran (5 volume 
percent water) are charged to a 250-mL, glass, high-pressure bottle and 
placed into a Parr shaker. The bottle is purged with nitrogen, pressurized 
with 4.5 bar absolute (50 psig) hydrogen, and heated to 55.degree. C., 
with shaking. The reaction mixture is shaken at 55.degree. C. and 4.5 bar 
absolute total pressure for 48 hours. After cooling, the pressure is 
released and the reaction mixture is removed, filtered, and concentrated 
by evaporating the volatiles to give a clear, light-yellow oil. The oil is 
further purified by dissolving in 50 mL of methylene chloride, drying over 
anhydrous magnesium sulfate, filtering, and evaporating the volatiles, 
giving 9.61 g of a clear, colorless oil having an m/(n+m) value of 0.94; 
and percent hydrogenation=90. 
COMATIVE EXAMPLE 1 
A 50-mL flask equipped with a magnetic stirbar is flushed with argon then 
cooled with an ice-water bath. To the flask is charged 0.90 g (0.010 mole) 
of 1,4-butanediol, 8.1 mL (7.2 g, 0.10 mole) of tetrahydrofuran, 8.6 mL 
(7.2 g, 0.10 mole) of 1,2-butylene oxide, and 15.8 mL (19.8 g, 0.200 mole) 
of 1,2-dichloroethane. The reaction mixture is stirred for about 15 
minutes to cool. Then 0.20 mL (0.070 mmole) of 0.53 g/mL boron trifluoride 
etherate in ligroin is added, and the reaction mixture is stirred and 
cooled with the ice-water bath for 4 hours. Then the ice-water bath is 
removed, and the reaction mixture warms with stirring, reaching a 
temperature of about 50.degree. C. After stirring overnight, the 
polymerization solution is neutralized by washing with water three times. 
The solution is dried over anhydrous magnesium sulfate, filtered, and 
rotary evaporated to give 10.2 g of a clear, colorless oil. J-resolved NMR 
and .sup.13 C NMR analyses show that the oil is a copolyether having a 
value of m/(n+m) of about 0.20, the hydroxyl groups are on residues (1) 
only, and about 75% of the hydroxyls are secondary hydroxyls and about 25% 
are primary hydroxyls. 
The copolyether polymers of the present invention differ from the above 
copolyether polymer prepared as described by Blanchard, et al., in that 
(i) greater than 95% of the hydroxyls of the copolyether polymers of the 
present invention are primary hydroxyls while only about 25% of the 
hydroxyls of the copolyether polymer prepared as described by Blanchard, 
et al., are primary hydroxyls, (ii) the hydroxyls of the copolyether 
polymers of the present invention reside on terminal residues of (1) and 
(2) while the hydroxyls of the copolyether polymer prepared as described 
by Blanchard, et al., reside only on terminal residues of (1), and (iii) 
the value of m/(n+m) for the copolyether polymers of the present invention 
are controlled and varied in the range of 0.05 to 0.95 while the value of 
m/(n+m) for the copolyether polymers described by Blanchard, et al., are 
controlled and varied in the range of 0.20 to 0.55. 
The invention has been described in detail with particular reference to 
preferred embodiments thereof, but it will be understood that variations 
and modifications will be effected within the spirit and scope of the 
invention.