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(11) EP 2 809 703 B1

(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.:

of the grant of the patent: C08G 65/00 (2006.01)
03.08.2016 Bulletin 2016/31
(86) International application number:
(21) Application number: 13702181.2 PCT/US2013/022385

(22) Date of filing: 21.01.2013 (87) International publication number:

WO 2013/116027 (08.08.2013 Gazette 2013/32)

(54) PROCESS FOR PREPARING HIGH MOLECULAR WEIGHT POLYMERS BY POLYMERIZING

EPOXIDE MONOMERS
VERFAHREN ZUR HERSTELLUNG VON POLYMEREN MIT HOHEM MOLEKULARGEWICHT
DURCH POLYMERISIERUNG VON EPOXIDMONOMEREN
PROCÉDÉ DE PRÉPARATION DE POLYMÈRES DE POIDS MOLÉCULAIRE ÉLEVÉ PAR LA
POLYMÉRISATION DE MONOMÈRES D’ÉPOXYDE

(84) Designated Contracting States: (56) References cited:

AL AT BE BG CH CY CZ DE DK EE ES FI FR GB EP-A1- 0 008 131 WO-A2-2008/145579
GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO US-A- 1 539 650 US-A- 3 499 847
PL PT RO RS SE SI SK SM TR US-A- 4 193 892 US-A- 4 267 309

(30) Priority: 30.01.2012 US 201261592207 P • PORSCH B ET AL: "Distribution analysis of

ultra-high molecular mass poly(ethylene oxide)
(43) Date of publication of application: containing silica particles by size-exclusion
10.12.2014 Bulletin 2014/50 chromatography with dual light-scattering and
refractometric detection", JOURNAL OF
(73) Proprietor: Dow Global Technologies LLC CHROMATOGRAPHY, ELSEVIER SCIENCE
Midland, MI 48674 (US) PUBLISHERS B.V, NL, vol. 1068, no. 2, 18 March
2005 (2005-03-18), pages 249-260, XP027723450,
(72) Inventors: ISSN: 0021-9673 [retrieved on 2005-03-18]
• SIMMS, John, R. • Dow Chemical Company: "Polyox", Polyox Water
Saint Albans, WV 25177 (US) Soluble Resins, 1 March 2002 (2002-03-01), pages
• KENNEY, John, M. 1-24, XP55040540, internet Retrieved from the
Scott Depot, WV 25560 (US) Internet:
• LANDON, Robert, S. URL:http://msdssearch.dow.com/PublishedLit
Livingston, TX 77399 (US) eratureDOWCOM/dh_0031/0901b80380031a4a.p
• HIPPLER, Jeffrey, G. df ?filepath=polyox/pdfs/noreg/326-00001.pdf&
South Charleston, WV 25309 (US) fromPage=GetDoc [retrieved on 2012-10-10]

(74) Representative: f & e patent

Fleischer, Engels & Partner mbB, Patentanwälte
Braunsberger Feld 29
51429 Bergisch Gladbach (DE)
EP 2 809 703 B1

Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent
Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the
Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been
paid. (Art. 99(1) European Patent Convention).

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 EP 2 809 703 B1

Description

FIELD

5 [0001] This invention relates to a process for polymerizing an epoxide monomer such as ethylene oxide in the presence
of a novel catalyst resulting in exceptionally high molecular weight polymer products.

INTRODUCTION

10 [0002] The catalytic polymerization of olefin oxides has been practiced for the past decades, one of the commercial
processes being the suspension polymerization of ethylene oxide in a hydrocarbon solvent such as isopentane using
as a catalyst calcium hexammine (Ca(NH3)6) modified with a mixture of propylene oxide and acetonitrile. In this process,
it is believed that a living polymer is generated and is eventually terminated by impurities which build up in the medium.
However, the actual structure of the catalytically active species and the mechanism of the polymerization are still unknown.
15 [0003] Various methods to produce the above-mentioned olefin oxide polymerization catalysts are described in the
prior art. Some of those catalysts are said to be active in effecting polymerization of olefin oxides resulting in polymers
having a relatively high molecular weight.
[0004] US 2,969,402 and US 3,037,943 teach the reaction of alkaline earth metal hexammine with an alkylene oxide
and a saturated aliphatic hydrocarbon nitrile in excess liquid ammonia. The process is conducted in a batch type mode
20 by dissolving the calcium metal in liquid ammonia, adding the aliphatic nitrile and the alkylene oxide and subsequently
evaporating the ammonia to obtain a solid residue. Said solid product is used as a catalyst in the polymerization of
ethylene oxide to produce a relatively low molecular weight poly(ethylene oxide).
[0005] US 3,627,702 is directed to a process for the production of high molecular weight polymers of 1,2-alkylene
oxides using a catalyst prepared by reacting an alkaline earth metal hexammine and/or alkaline earth metal amide in
25 liquid ammonia with a 1,2-alkylene oxide and cyanamide and/or dicyandiamide. In the examples the catalysts are
prepared in a one-pot reaction by dissolving calcium in liquid ammonia and then adding ethylene oxide, cyanamide or
its dimer, and an organic solvent, i.e. heptane. After evaporation of ammonia and part of the organic solvent the catalyst
is obtained in the form of a suspension in heptane which is directly employed in the polymerization of ethylene oxide.
In a comparative example a combination of ethylene oxide/acetonitrile is used as modifier in the preparation of the
30 catalyst instead of ethylene oxide in combination with cyanamide or its dimer. However, the ethylene oxide polymer
obtained when using this catalyst has a lower viscosity than those polymers obtained by using the ethylene oxide/cy-
anamide-modified catalyst. This indicates that the described ethylene oxide/acetonitrile-modified catalyst does not serve
to produce exceptionally high molecular polymers.
[0006] US 4,193,892 and US 4,267,309 describe a further development of the catalyst preparation disclosed in US
35 2,969,402 and US 3,037,943 to obtain an olefin oxide polymerization catalyst providing an improvement in the productivity
and/or in the molecular weight picture of the polymer. The modification includes aging the resulting catalyst following
admixing of calcium metal, ammonia, an alkylene oxide and an organic nitrile, which aging is performed at a temperature
of from 150 °C to 225 °C for up to 15 h after evaporation of ammonia. As it is advantageous when the final catalyst
product is in slurry form for direct use in the olefin oxide polymerization, a high or intermediate boiling organic diluent is
40 preferably added after or concurrently with evaporation of ammonia. The complete reaction including the evaporation
of ammonia, addition of diluent and aging is conducted in a single vessel. The ethylene oxide polymers that are prepared
by catalytic polymerization in the examples have 1 weight % solution viscosities at 25 °C of up to 17,000 mPa·s.
[0007] CN 1740209 A teaches the preparation of an ethylene oxide polymerization catalyst by dissolving calcium in
liquid ammonia, adding propylene oxide modifier, acetonitrile and a carrier of a nanoscalic silica or nanoscalic mesoporous
45 molecular sieve, evaporating excessive ammonia after complete reaction and adding a high boiling alkane solvent to
form a catalyst slurry. The catalyst is used in the polymerization of ethylene oxide and results in ethylene oxide polymers
having molecular weight ranges of from 50,000 to 2,000,000.
[0008] There are further references mentioning high molecular weight ethylene oxide polymers.
[0009] Poly(ethylene oxide)s having a weight molecular weight within the range of from 100,000 to 9,000,000 are
50 commercially available from the Dow Chemical Company and various grades are sold under the trade names POLYOX
Water-Soluble Resins (POLYOX WSR) and UCARFLOC Polymers (see Bulletin Form No. 326-00001-0302 AMS, pub-
lished March 2002 by the Dow Chemical Company and entitled "POLYOX Water-Soluble Resins").
[0010] US 3,729,441 teaches how to inhibit degradation of poly(ethylene oxide) and discloses that polymers having
a molecular weight such as 10,000,000 and even higher can be employed. However, in the examples only polymers
55 having a molecular weight of up to 250,000 are used.
[0011] US 5,186,942, US 3,281,312 and US 2007/0269491 refer to the use of poly(ethylene oxide) having a wide
molecular weight range of up to 10,000,000 Dalton in various applications. These references do not describe the pro-
duction of poly(ethylene oxide) but generally refer to commercial availability of the poly(ethylene oxide). In all three cases

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only Union Carbide Corporation is mentioned as a supplier of the poly(ethylene oxide). However, Union Carbide Cor-
poration which is now a wholly owned subsidiary of The Dow Chemical Company has never offered a poly(ethylene
oxide) having a molecular weight of 10,000,000 Dalton or above. In addition, there are no known other commercial
suppliers claiming to offer a poly(ethylene oxide) having a molecular weight of 10,000,000 Dalton.
5 [0012] For several applications including flocculating agents, super swelling tablets, osmotic dosage forms, aqueous
drag reduction/drift control (reduction of the turbulent frictional drag of water in which olefin oxide polymers are dissolved),
e.g. drift control of agricultural sprays, and concrete pumping lubricity olefin oxide polymers having extremely high
molecular weight are desired. Hitherto, olefin oxide polymers having a weight average molecular weight of more than
9,000,000 are not known und thus, the problem addressed by the present invention is to provide a method for preparing
10 extremely high molecular weight olefin oxide polymers, i.e. olefin oxide polymers such as poly(ethylene oxide) having
a weight average molecular weight of more than 9,000,000.

SUMMARY

15 [0013] The problem is solved by a process for polymerizing an epoxide monomer, preferably ethylene oxide, comprising
carrying out the process in the presence of a catalytically active amount of a catalyst obtainable by a preparation process
comprising
admixing at least one alkaline earth metal, liquid ammonia, an alkylene oxide, which is optionally substituted by aromatic
radicals, and an organic nitrile having at least one acidic hydrogen atom to prepare a slurry of modified alkaline earth
20 hexammine in liquid ammonia;
continuously transferring the slurry of modified alkaline earth hexammine in liquid ammonia into a stripper vessel and
continuously evaporating ammonia, thereby accumulating the modified catalyst in the stripper vessel; and
upon complete transfer of the slurry of modified alkaline earth hexammine into the stripper vessel, aging the modified
catalyst to obtain the final polymerization catalyst.
25 [0014] The present invention is also directed to the polymer obtainable by the above process and to its uses.

BRIEF DESCRIPTION OF DRAWINGS

[0015]
30
Fig. 1 illustrates a semi-continuous stirred tank reaction system utilized in the process for producing an olefin oxide
polymerization catalyst.

Fig. 2 illustrates the correlation of viscosities of 0.5 % and 1 % poly(ethylene oxide) solutions.
35
DETAILED DESCRIPTION

[0016] It is surprising that modifying the standard batch type process for preparing an olefin oxide polymerization
catalyst (as for example disclosed in US 4,193,892 and US 4,267,309) by conducting it in a semi-continuous manner
40 leads to a highly active catalyst effective to produce olefin oxide polymers of higher molecular weight than achievable
using current technology.
[0017] It is understood that the technical meaning of the terms "olefin oxide" and "alkylene oxide" is identical. However,
for reasons of clarity the terms "olefin oxide" and "poly(olefin oxide)", respectively, are used in the present application
to refer to the monomers or polymers taking part in the polymerization promoted by the inventive catalyst whereas the
45 term "alkylene oxide" is used to refer to the modifier utilized in the preparation of the catalyst. Two different terms are
used to emphasize that the "olefin oxide" and the "alkylene oxide" need not be identical compounds but can be selected
independently.
[0018] The catalyst is referred to as "modified alkaline earth hexammine" and "modified calcium hexammine" or "mod-
ified alkaline earth hexammoniate" and "modified calcium hexammoniate", the technical terms "ammine" and "ammoniate"
50 being synonymous. However, the fact that the catalyst is complex, pyrophoric, air sensitive, and insoluble in, or reactive
with, most organic solvents makes chemical as well as spectroscopic analysis difficult. Consequently, it is not surprising
that the structure of the catalyst prepared by either the conventional process or the improved process of the present
invention is unknown. The improved new catalyst of the present invention catalyst will have to be, therefore, defined by
the process by which it is made.
55 [0019] First, a slurry of the modified alkaline earth hexammine in liquid ammonia is prepared by admixing the at least
one alkaline earth metal, liquid ammonia, the alkylene oxide and the organic nitrile. This step is carried out in the liquid
phase with ammonia in the liquid state under suitable pressure, preferably it is carried out with agitation.
[0020] The alkaline earth metal used to prepare the alkaline earth hexammine is typically selected from calcium,

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 EP 2 809 703 B1

strontium, barium and its mixtures; most preferably it is calcium.

[0021] The liquid ammonia employed in the process is preferably essentially anhydrous. Reacting the alkaline earth
metal, preferably calcium, with excessive liquid ammonia results in the formation of alkaline earth hexammine dissolved
in liquid ammonia. As two modifiers are also introduced in this step the product of this reaction is a modified alkaline
5 earth hexammine.
[0022] One of the modifiers is an alkylene oxide which is optionally substituted by aromatic radicals. The optionally
substituted alkylene oxides for use in the present invention consist of carbon, hydrogen, and oxirane oxygen atoms. The
oxirane oxygen is bonded to vicinal or adjacent carbon atoms to form an epoxy group. The alkylene oxide can be an
aliphatic, cycloaliphatic or mixed aliphatic/cycloaliphatic alkylene oxide. In some embodiments the alkylene oxide is
10 substituted by one or more aromatic radicals, preferably aromatic radicals having 6 to 12 carbon atoms, e.g. phenyl.
Illustrative alkylene oxides include ethylene oxide, propylene oxide, 1,2-epoxybutane, 2,3-epoxybutane, the epoxypen-
tanes, the epoxyhexanes, the epoxyoctanes, the epoxydecanes, the epoxydodecanes, 2,4,4-trimethyl-1,2-epoxypen-
tane, 2,4,4-trimethyl- 2,3-epoxypentane, cyclohexylepoxythane, 7-oxabicyclo[4.1.0]heptane, 6-oxabicyclo[3.1.0]hex-
ane, 3-methyl-6-oxabicyclo[3.1.0]hexane, and 4-ethyl-6-oxabicyclo[3.1.0]hexane. Exemplary alkylene oxides having
15 aromatic substituents are styrene oxide and 1-phenyl-1,2-epoxypropane. Typically, the number of carbon atoms in the
optionally substituted alkylene oxide ranges from 2 to 20, alkylene oxides having 2 to 5 carbon atoms are preferred, e.g.
ethylene oxide, propylene oxide, 1,2-epoxybutane, and 2,3-epoxybutane. A single alkylene oxide or mixtures of two or
more different alkylene oxides can be used. Propylene oxide is most preferred.
[0023] The second modifier is an organic nitrile consisting of carbon, nitrogen, and hydrogen atoms, at least one
20 hydrogen atom being acidic. Typically, the nitrile is a mononitrile. The nitrile is preferably a saturated aliphatic mononitrile,
more preferably a saturated aliphatic mononitrile wherein the organic moiety has 2 to 10 carbon atoms, e.g. acetonitrile,
propionitrile, and butyronitrile, valeronitrile, isovaleronitrile, capronitrile, caprylonitrile and caprinitrile. Aromatic nitriles,
preferably mononitriles such as benzonitrile and ortho-toluenenitrile are also useful. Acetonitrile is most preferred.
[0024] The order of introduction of the alkaline earth metal, the ammonia, and the modifiers can vary. The preferred
25 procedure is to conduct the preparation of the slurry of modified alkaline earth hexammine in liquid ammonia in two
steps. More preferably, the first step is to add the alkaline earth metal to the ammonia to form a solution of alkaline earth
hexammine and the second step is to add the modifiers. The modifiers may be added subsequently in either sequence
or simultaneously as two separate feeds or preferably as a mixture. Typically, the mixture of alkylene oxide and organic
nitrile comprises 10 to 98 mol % of alkylene oxide and 2 to 90 mol % of organic nitrile, more preferably it is a mixture of
30 40 to 80 mol % of alkylene oxide and 20 to 40 mol % of organic nitrile, and most preferably a mixture of about 60 mol
% of alkylene oxide and about 40 mol % of organic nitrile. One alternative mode of preparation is to introduce the alkaline
earth metal and modifiers first together with a low boiling (and low freezing) organic diluent and then add the ammonia.
Another alternative mode is to add the alkaline earth metal to a mixture of the ammonia and the modifiers.
[0025] In preferred embodiments the preparation of the slurry of modified alkaline earth hexammine in liquid ammonia
35 is conducted in a continuous manner and comprises continually feeding the alkaline earth metal and liquid ammonia
and continuously feeding the alkylene oxide and the organic nitrile. "Continually feeding" the alkaline earth metal includes
both continuously feeding the alkaline earth metal or constantly feeding the alkaline earth metal in repeated single
portions (multiple charges). A similar definition of "continually" feeding or adding applies to "continually" feeding or adding
ammonia. Feeding the alkaline earth metal and ammonia in multiple charges is sometimes practicable in a small scale
40 production process to mimic or approximate a continuous addition.
[0026] If the continuous mode is applied to the preferred two-step process described above this transforms to a process
wherein the slurry of the modified alkaline earth hexammine is prepared in two different vessels: a first vessel ("dissolver
vessel") where the alkaline earth metal and ammonia are combined to form alkaline earth hexammine dissolved in liquid
ammonia and a second vessel ("modifier vessel") where the modifiers are added and the modified alkaline earth hex-
45 ammine slurried in liquid ammonia is formed. More specifically, the continuous process to prepare the slurry of modified
alkaline earth hexammine, preferably modified calcium hexammine, in liquid ammonia in two vessels comprises:

(1a) continually feeding alkaline earth metal, preferably calcium, into the dissolver vessel comprising liquid ammonia
and
50 (1b) continually adding liquid ammonia to form alkaline earth hexammine dissolved in liquid ammonia;
(2a) continuously transferring the alkaline earth hexammine solution into the modifier vessel; and
(2b) continuously feeding the alkylene oxide and the organic nitrile into the modifier vessel to form a slurry of modified
alkaline earth hexammine in liquid ammonia.

55 [0027] Preferably the alkaline earth metal is fed to the dissolver vessel continuously over the duration of the reaction
in order to maintain an appropriate level in the dissolver vessel. Appropriate dosing and feeding systems for solids are
well known to the person skilled in the art. It is preferred to use a system that avoids backwash of the pressurized
ammonia from the dissolver. Typically, the liquid ammonia is added simultaneously with the alkaline earth metal to

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maintain the desired alkaline earth metal concentration in liquid ammonia. If the alkaline earth metal is fed in multiple
charges over the duration of the reaction each alkaline earth metal charge is typically immediately followed by the addition
of sufficient liquid ammonia to maintain the desired alkaline earth metal concentration. In all embodiments agitation
(stirring) of the dissolver vessel is advantageous.
5 [0028] It is preferred to maintain the mole fraction of alkaline earth metal, preferably calcium, in the liquid ammonia in
the dissolver vessel within the range of from 0.1 to 16 mol %, more preferably from 1 to 8 mol %, and most preferably
from 2 to 6 mol %.
[0029] Typically, the dissolver vessel is held at a temperature within the range of from -50 to 25 °C and at a pressure
within the range of from 8 to 1100 kPa, preferably at a temperature within the range of from -25 to 15 °C and at a pressure
10 within the range of from 120 to 750 kPa, more preferably at a temperature within the range of from -15 to 5 °C and at a
pressure within the range of from 200 to 600 kPa, and most preferably at a temperature within the range of from -11 to
1 °C and at a pressure within the range of from 250 to 520 kPa.
[0030] The alkaline earth hexammine solution is continuously drained off from the dissolver vessel and introduced in
the modifier vessel simultaneously with the two modifiers, alkylene oxide and organic nitrile, to form the slurry of modified
15 alkaline earth hexammine in liquid ammonia. As described above the modifiers can be added as separate feeds or as
a mixture (including preferred mixing ratios described above), the latter being the preferred mode. Agitation (stirring) of
the modifier vessel is advantageous.
[0031] Typically, the alkaline earth hexammine solution is transferred to the modifier vessel at a controlled rate. Methods
to control the rate are well known to the person skilled in the art.
20 [0032] In preferred embodiments the alkylene oxide and the organic nitrile are fed into the modifier vessel at a rate to
provide 0.5 to 1.5 mol of total alkylene oxide and organic nitrile, preferably 0.7 to 1.3 mol of total alkylene oxide and
organic nitrile, more preferably 0.9 to 1.1 mol of total alkylene oxide and organic nitrile, and most preferably 1 mol of
total alkylene oxide and organic nitrile for 1 mol of alkaline earth hexammine flowing in from the dissolver vessel.
[0033] Usually, the modifier vessel is held at a temperature within the range of from -45 to 30 °C and at a pressure
25 within the range of from 1 to 1200 kPa, preferably at a temperature within the range of from -20 to 20 °C and at a pressure
within the range of from 90 to 900 kPa, more preferably at a temperature within the range of from -10 to 10 °C and at a
pressure within the range of from 190 to 620 kPa, and most preferably at a temperature within the range of from -6 to
6 °C and at a pressure within the range of from 240 to 540 kPa.
[0034] In the following step the slurry of modified alkaline earth hexammine in liquid ammonia either prepared in a
30 batch type mode or by a continuous process as described directly above is transferred into a further vessel ("stripping
vessel") and the ammonia is continuously evaporated. Thus, the modified catalyst accumulates in the stripping vessel.
Agitation (stirring) of the stripping vessel is advantageous. The simultaneous introduction of the ammoniacal slurry of
modified alkaline earth hexammine into the stripper vessel and evaporation of the ammonia results in an immediate
removal of ammonia from the catalyst. In preferred embodiments of the present invention an accumulation of ammonia
35 in the stripper vessel is avoided.
[0035] Preferably, the stripper vessel is held at a temperature of at least 30 °C, preferably at least 40 °C above the
boiling point of ammonia at the system pressure. Typically, the stripper vessel is held at a temperature within the range
of from 0 to 100 °C and at a pressure within the range of from 30 to 6300 kPa, preferably at a temperature within the
range of from 25 to 100 °C and at a pressure within the range of from 100 to 3300 kPa, more preferably at a temperature
40 within the range of from 25 to 70 °C and at a pressure within the range of from 200 to 520 kPa, and most preferably at
a temperature within the range of from 29 to 41 °C and at a pressure within the range of from 240 to 420 kPa,.
[0036] Upon complete transfer of the ammoniacal slurry of modified alkaline earth hexammine into the stripper vessel
the modified catalyst is aged to obtain the final olefin oxide polymerization catalyst. In case of a continuous production
of the slurry of modified alkaline earth hexammine in liquid ammonia the transfer into the stripper vessel is completed
45 when after a predetermined amount of alkaline earth metal has been used up all feeds are terminated and the dissolver
vessel (via the modifier vessel) and modifier vessel are emptied into the stripper vessel.
[0037] The stripper vessel is heated to reach the aging temperature. Typically, the aging is carried out at a temperature
within the range of from 150 to 225 °C and at a pressure within the range of from 30 to 650 kPa, preferably at a temperature
within the range of from 175 to 225 °C and at a pressure within the range of from 100 to 450 kPa, and more preferably
50 at a temperature within the range of from 190 to 217 °C and at a pressure within the range of from 125 to 380 kPa. In
preferred embodiments the aging is carried out for 0.1 to 15 h, preferably for 1 to 10 h, more preferably for 2 to 5 h, and
most preferably for about 3 h. At the end of the aging period the catalyst is cooled to room temperature by air quenching
or any other conventional quenching means.
[0038] It is desirable when the final catalyst product is in slurry form for transfer to, and direct use, in the olefin oxide
55 polymerization. Thus, it is preferred to carry out at least part of the process in an inert organic liquid diluent. The organic
diluent is one which is inert to any of the reactants or the catalyst product and will not be affected by operating conditions
including evaporation of ammonia. As the diluent will be used to form the slurry used in the polymerization, it also should
be inert to the polymerization reactants and product and the polymerization operating conditions. One advantage of

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using an inert diluent is in the realm of safety in view of the pyrophoric and air sensitive nature of the catalyst.
[0039] Preferably, the inert organic diluent has a boiling point within the range of from 25 to 330 °C and more preferably
it is a C12 to C19 hydrocarbon diluent such as for example dodecane, tridecane, tetradecane, pentadecane and hexa-
decane. A single inert organic diluent or mixtures of two or more different organic diluent can be used. An exemplary
5 inert organic diluent is a mixture of dodecane, tridecane and tetradecane such as NORPAR 13 ® hydrocarbon.
[0040] Typically, the inert organic diluent is contained in the stripper vessel into which the slurry of the modified catalyst
in liquid ammonia is introduced and since the organic diluent does not or not completely evaporate under stripping
conditions a slurry of the modified catalyst in the diluent is formed. Preferably, the weight ratio of inert organic diluent in
the stripper vessel to total alkaline earth metal charged, preferably total calcium charged, is within a range of from 1:1
10 to 20:1, preferably from 2:1 to 15:1, and more preferably from 4:1 to 9:1.
[0041] If an inert organic diluent is used, the catalyst is aged in the form of a slurry in the organic diluent. The stripping
and aging conditions described above are applicable for both cases: a dry catalyst product (no organic diluent present)
and the catalyst product in slurry form. However, if no organic diluent is present the applicable pressure ranges in the
stripping and aging steps are even broadened and include lower pressures up to 0 kPa.
15 [0042] Throughout the preparation of the catalyst, conventional precautions are preferably taken to exclude water,
oxygen, and carbon dioxide from the system. This may be accomplished by using properly sealed apparatus together
with an inert atmosphere such as nitrogen. The inert gas can be used first as a sweep and then the process steps can
be conducted in the same atmosphere.
[0043] In preferred embodiments the present process for the production of an olefin oxide polymerization catalyst
20 comprises:

(1a) continually feeding a predetermined amount of alkaline earth metal, preferably calcium, into a dissolver vessel
comprising liquid ammonia and
(1b) continually adding liquid ammonia to form alkaline earth hexammine dissolved in liquid ammonia;
25 (2a) continuously transferring the alkaline earth hexammine solution into a modifier vessel;
(2b) continuously feeding the alkylene oxide and the organic nitrile into the modifier vessel to form a slurry of modified
alkaline earth hexammine in liquid ammonia;
(3a) continuously transferring the slurry of modified alkaline earth hexammine in liquid ammonia into the stripper
vessel and
30 (3b) continuously evaporating ammonia, thereby accumulating the modified catalyst in the stripper vessel;
(4b) upon consumption of the alkaline earth metal gradually terminating all feeds and emptying the dissolver vessel
via the modifier vessel into the stripper vessel; and
(4c) aging the modified catalyst in the stripper vessel to obtain the final olefin oxide polymerization catalyst.

35 [0044] The preferred compounds and conditions described before are applicable in each of the above process steps.
[0045] The finished catalyst in dry or preferably in slurry form can then used in a conventional process for polymerizing
an epoxide, typically in a suspension polymerization process. The novel catalysts of this invention are useful in effecting
the polymerization of epoxide monomers which contain a cyclic group composed of two carbon atoms and one oxygen
atom. Typically, these epoxide monomers can be characterized by the following formula:
40

45
wherein each R1, individually, can be hydrogen, haloaryl, or a hydrocarbon radical free from ethylenic and acetylenic
unsaturation such as, for example, alkyl, aryl, cycloalkyl, aralkyl, or alkaryl radicals. In addition, both R1 variables together
with the epoxy carbon atoms, i.e. the carbon atoms of the epoxy group can represent a saturated cycloaliphatic hydro-
carbon nucleus which contains from 4 to 10 carbon atoms, preferably from 4 to 8 carbon atoms, for example, a saturated
50 cycloaliphatic hydrocarbon nucleus derived from cycloalkane, alkyl substituted cycloalkane, cyclobutane, cyclopentane,
cyclohexane, cycloheptane, cyclooctane, methylcyclopentane, or amylcyclohexane. Illustrative R1 radicals include,
among others, methyl, ethyl, propyl, butyl, isobutyl, hexyl, isohexyl, 3-propylheptyl, dodecyl, octadecyl, phenyl, halophe-
nyl, chlorophenyl, bromophenyl, benzyl, tolyl, ethylphenyl, butylphenyl, phenethyl, phenylpropyl, cyclopentyl, cyclobexyl,
2-methylcyclohexyl, and cycloheptyl.
55 [0046] A single epoxide monomer or an admixture of at least two different epoxide monomers can be employed as
the monomeric feed. A broad range of epoxide monomers can be used in the polymerization process and representative
expoxide monomers include, for example, ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, the
epoxypentanes, the epoxyhexanes, 2,3-epoxyheptane, nonene oxide, 5-butyl-3,4-epoxyoctane, 1,2-epoxydodecane,

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 EP 2 809 703 B1

1,2-epoxyhexadecane, 1,2-epoxyoctadecane, 5-benzyl-2,3-epoxyheptane, 4-cyclo-hexyl-2,3-epoxypentane, chlorosty-

rene oxide, styrene oxide, ortho-, meta-, and para-ethylstyrene oxide, glycidyl benzene, the oxabicycloalkanes and alkyl-
substituted oxabicycloalkanes, e.g., 7-oxabicyclo[4.1.0]heptane, oxabicyclo[3.1.0]hexane, 4-propyl-7-oxabicyclo[4.1.0]
heptane, and 3-amyl-6-oxabicyclo[3.1.0]hexane.]
5 [0047] It is preferred that the epoxide monomer is an olefin oxide, more preferably an olefin oxide having 2 to 20 carbon
atoms, such as for example ethylene oxide, propylene oxide, 1,2-epoxy-butane, or 2,3-epoxybutane. The most preferred
monomer is ethylene oxide. Outstanding results are achieved in polymerizing ethylene oxide via that suspension po-
lymerization route.
[0048] The novel catalyst can be used in a concentration in the range of 0.02 to 10 percent by weight, such as 0.1 to
10 3 percent by weight, based on the weight of the epoxide monomer feed, preferably olefin oxide feed. Typically, the
catalyst is used in an amount corresponding to 0.0004 to 0.0040 g of alkaline earth metal per g of epoxide monomer,
such as 0.0004 to 0.0040 g of calcium per g of olefin oxide, preferably 0.0007 to 0.0021 g of alkaline earth metal per g
of epoxide monomer, such as 0.0007 to 0.0021 g of calcium per g of olefin oxide, more preferably 0.0010 to 0.0017 g
of alkaline earth metal per g of epoxide monomer, such as 0.0010 to 0.0017 g of calcium per g of olefin oxide, and most
15 preferably 0.0012 to 0.0015 g of alkaline earth metal per g of epoxide monomer, such as 0.0012 to 0.0015 g of calcium
per g of olefin oxide.
[0049] The polymerization reaction can be conducted over a wide temperature range. Polymerization temperatures
can be in the range of from -30 to 150°C and depends on various factors, such as the nature of the epoxide monomer(s)
employed, the particular catalyst employed, and the concentration of the catalyst. A typical temperature range is from
20 0 to 150°C. For the preparation of granular poly(ethylene oxide) (which preparation is a preferred embodiment and is
described hereinafter in detail) a reaction temperature below 70°C is preferred. Though granular poly(ethylene oxide)
can be prepared at a reaction temperature of about 65 to 70°C the poly(ethylene oxide) product tends to accumulate
on the interior surfaces of the reaction equipment. Consequently, it is preferred that the reaction temperature for the
preparation of granular poly(ethylene oxide) be in the range of from -30 to 65°C and more preferably from 0 to 60°C. In
25 an extremely desirable aspect the polymerization reaction is conducted below the softening point of the resulting granular
poly(ethylene oxide) product.
[0050] The pressure conditions are not specifically restricted and the pressure is set by the boiling points of the diluent
and monomer(s) used in the polymerization process.
[0051] In general, the reaction time will vary depending on the operative temperature, the nature of the epoxide oxide
30 reagent(s) employed, the particular catalyst and the concentration employed, the use of an inert diluent, and other factors.
Polymerization times can be run from minutes to days depending on the conditions used. Preferred times are 1 to 10 h.
[0052] When polymerizing an admixture containing two different epoxide monomers, the proportions of said epoxides
can vary over the entire range. Preferably the concentration of either monomeric epoxide is in the range of from 5 to 95
weight percent, based on the total weight of said epoxides.
35 [0053] The polymerization reaction preferably takes place in the liquid phase. Typically, the polymerization reaction
is conducted under an inert atmosphere, e.g. nitrogen. It is also highly desirable to effect the polymerization process
under substantially anhydrous conditions. Impurities such as water, aldehyde, carbon dioxide, and oxygen which may
be present in the epoxide feed and/or reaction equipment should be avoided. The polymers of this invention can be
prepared via the bulk polymerization, suspension polymerization, or the solution polymerization route, suspension po-
40 lymerization being preferred.
[0054] The polymerization reaction can be carried out in the presence of an inert organic diluent such as, for example,
aromatic hydrocarbons, benzene, toluene, xylene, ethylbenzene, and chlorobenzene; various oxygenated organic com-
pounds such as anisole, the dimethyl and diethyl ethers of ethylene glycol, of propylene glycol, and of diethylene glycol;
normally-liquid saturated hydrocarbons including the open chain, cyclic, and alkyl-substituted cyclic saturated hydrocar-
45 bons such as pentane (e.g. isopentane), hexane, heptane, various normally-liquid petroleum hydrocarbon fractions,
cyclohexane, the alkylcyclohexanes, and decahydronaphthalene.
[0055] Unreacted monomeric reagent oftentimes can be recovered from the reaction product by conventional tech-
niques such as by heating said reaction product under reduced pressure. The polymer product also can be recovered
from the reaction product by washing said reaction product with an inert, normally-liquid organic diluent, and subsequently
50 drying same under reduced pressure at slightly elevated temperatures. Another route involves dissolution in a first inert
organic solvent, followed by the addition of a second inert organic solvent which is miscible with the first solvent, but
which is a non-solvent for the polymer product, thus precipitating the polymer product. Recovery of the precipitated
polymer can be effected by filtration, decantation, etc., followed by drying same as indicated previously. Granular po-
ly(ethylene oxide) can be recovered from the reaction product by filtration, decantation, etc., followed by drying said
55 granular poly(ethylene oxide) under reduced pressure at slightly elevated temperatures, e.g. 30 to 40 °C. If desired, the
granular poly(ethylene oxide), prior to the drying step, can be washed with an inert, normally-liquid organic diluent in
which the granular polymer is insoluble, e.g. pentane, heptane, cyclohexane, and then dried as illustrated above.
[0056] As indicated previously the novel catalysts of the instant invention are highly useful in the preparation of granular

7
 EP 2 809 703 B1

poly(ethylene oxide) via the suspension polymerization process. Granular poly(ethylene oxide) results from the suspen-
sion polymerization of an agitated reaction mixture comprising ethylene oxide in contact with a catalytic amount of the
novel catalysts previously described, the suspension polymerization reaction being conducted at a temperature below
the softening point of the resulting granular poly(ethylene oxide) product. A suitable temperature range is from about
5 -30 to + 65°C, and preferably from about 0 to 60°C. Agitation of the reaction mixture is recommended in order to maintain
catalyst suspended in said reaction mixture during the course of the polymerization reaction.
[0057] Unlike the granular poly(ethylene oxide) which directly results from the suspension polymerization route as
illustrated above, the bulk or solution polymerization of ethylene oxide yields non-granular resinous poly(ethylene oxide)
which is substantially an entire polymeric mass or an agglomerated polymeric mass or it is dissolved in the inert, organic
10 diluent. It is understood, of course, that the term "bulk polymerization" refers to polymerization in the absence of an inert,
normally-liquid organic diluent, and the term "solution polymerization" refers to polymerization in the presence of an
inert, normally-liquid organic diluent in which the monomer employed and the polymer produced are soluble.
[0058] Granular poly(ethylene oxide) directly results from effecting the instant invention via the suspension polymer-
ization route. Granular poly(ethylene oxide) possesses several highly desirable characteristics. One can recover granular
15 poly(ethylene oxide) from the reaction product by the mere technique of decantation or filtration, followed by drying at
slightly elevated temperatures, e.g. 30 to 40°C. Further treatment is unnecessary and the granular polymer can be
shipped to customers in bags or drums. Poly(ethylene oxide) prepared via the solution polymerization route necessitates
the complete removal of the inert organic vehicle at elevated temperatures in order to recover the polymer dissolved in
said vehicle. The resulting polymer, of course, is not granular. Mechanical means are necessary to reduce non-granular,
20 resinous poly(ethylene oxide) prepared by the bulk or solution polymerization routes to a particle size which approximately
corresponds to the synthetically formed granular poly(ethylene oxide).
[0059] Granular poly(ethylene oxide) can be produced (as previously indicated) via the suspension polymerization
route by employing an inert, normally-liquid organic diluent in which the ethylene oxide monomer is soluble and the
resulting polymer is insoluble. It is understood, of course, that the diluent employed is non-reactive with ethylene oxide.
25 Illustrative diluents suitable in the suspension polymerization process are the normally-liquid saturated hydrocarbons,
e.g. saturated aliphatic hydrocarbons, saturated cycloaliphatic and alkyl-substituted cycloaliphatic hydrocarbons, and
various normally-liquid saturated ethers. Examples of preferred diluents include, among others, pentane such as iso-
pentane, hexane, heptane, isoheptane, ethylpentane, the octanes, the decanes, various petroleum hydrocarbon frac-
tions, cyclohexane, alkyl-substituted cyclohexanes, and decahydronaphthalene. Other illustrative diluents which can be
30 employed include diethyl, dipropyl, dibutyl, and higher dialkyl ethers; dioxane; and the lower glycol dialkyl ethers of
diethylene glycol. It is to be noted that certain of these ether diluents become solvents for the polymer at elevated
temperatures. Among such ethers are dioxane, the dimethyl and diethyl ethers of ethylene glycol and diethylene glycol.
[0060] A preferred method for producing granular poly(ethylene oxide) is to feed the ethylene oxide into the stirred
diluent which contains the novel catalyst, the reaction temperature being maintained below the softening point of the
35 resulting granular polymer product, e.g. below 65 to 70 °C. When operating in this manner pressure equipment is not
necessary. The ethylene oxide is fed into the stirred diluent and unreacted ethylene oxide, if any, is allowed to pass out
of the reaction vessel, for example, through a vent, an appropriately adjusted blow-off valve, or other means, as desired.
It is highly desirable to conduct the suspension polymerization reaction under a blanket of nitrogen gas, care being taken
to exclude oxygen and carbon dioxide. The suspension polymerization can be conducted as a batch, semi-continuous,
40 or a continuous process.
[0061] The single components of the polymerization reaction, i.e. the epoxide monomer, the catalyst and the diluent,
if used, may be added to the polymerization system in any practicable sequence as the order of introduction is not crucial
for the present invention.
[0062] The use of the novel catalysts in the polymerization of epoxide monomers allows for the preparation of excep-
45 tionally high molecular weight polymers. Without being bound by theory it is believed that the unique capability of the
novel catalysts to produce longer polymer chains than are otherwise obtained in the same polymerization system using
the same raw materials is due to the combination of higher reactive site density (which is considered activity) and the
ability to internally bind catalyst poisons.
[0063] The olefin oxide polymers that are obtained by using the novel catalysts according to the present invention
50 have extremely high (ultrahigh) molecular weight. In case of poly(ethylene oxide) the weight average molecular weight
is equal to or greater than 10,000,000 Dalton. Current technology to directly determine the molecular weight of ultrahigh
molecular weight poly(ethylene oxide) is limited and thus, only the approximate weight average molecular weight can
be measured by an indirect method. Poly(ethylene oxide) is water-soluble and the 1 % and 0.5 % solution viscosities of
the inventive ethylene oxide polymers are compared with the solution viscosities of commercially available high molecular
55 weight ethylene oxide polymers with known weight average molecular weight.
[0064] With the higher molecular weight polymers, viscosity measurements are complicated because of the difficulties
encountered in dissolving the polymers in aqueous systems. During dissolution the mixture assumes a mucous-like
consistency with a high tendency to gel. In addition, the extremely long chains are quite sensitive to shearing forces and

8
 EP 2 809 703 B1

must be stirred under very low shearing conditions in order to minimize mechanical degradation. The procedure for
dissolving the polymers of the present invention may be found in Bulletin Form No. 326-00002-0303 AMS, published
March 2003 by the Dow Chemical Company and entitled "POLYOX Water-Soluble Resins Dissolving Techniques". The
solution viscosity values that are recited throughout this application refer to solutions of ethylene oxide polymers that
5 are prepared according to the procedure set forth in the example.
[0065] The term "1 % aqueous solution viscosity" as used herein means the dynamic viscosity of a 1 weight % solution
of the polymer in a mixture of water and isopropyl alcohol in a weight ratio of about 6:1. Accordingly, the term "0.5 %
aqueous solution viscosity" means the dynamic viscosity of a 0.5 weight % solution of the polymer in a mixture of water
and isopropyl alcohol in a weight ratio of about 6:1. In both cases the weight percentage of polymer is based on the
10 weight of water only, i.e. not including the isopropyl alcohol. Preparing the aqueous solutions of the polymers the isopropyl
alcohol is added first in order to allow the polymer particles to disperse as individuals before water is added. This seems
to greatly minimize gel formation and provides reliable viscosity measurements. The 1 % aqueous solution viscosities
of the ethylene oxide polymers according to the present invention are preferably greater than 20,000 mPa·s at 25 °C.
The 0.5 % aqueous solution viscosities of the ethylene oxide polymers according to the present invention are preferably
15 greater than 5,000 mPa·s at 25 °C. The 1 % and 0.5 % aqueous solution viscosities of the ethylene oxide polymers are
determined at 25 °C using a Brookfield® DV-II + digital viscometer. The Brookfield® guard leg is in place when making
the measurement. RV spindle #2 and a speed of 2 RPM are employed to make the measurement. The spindle is
immersed in the polymer solution, avoiding entrapping air bubbles, and attached to the viscometer shaft. The height is
adjusted to allow the solution level to meet the notch on the spindle. The viscometer motor is activated, and the viscosity
20 reading is taken 5 min after the viscometer motor was started.
[0066] The ultrahigh molecular weight olefin oxide polymers, especially the ultrahigh molecular weight ethylene oxide
polymers find application in a variety of technical fields and any application requiring high solution thickening properties
at low polymer concentration would benefit from the use of the present ultrahigh molecular weight olefin polymers,
especially the ultrahigh molecular weight ethylene oxide polymers. The primary applications of those new ultrahigh
25 molecular polymers are in the area of flocculation (as flocculation agent), for applications such as tissue paper production,
waste treatment and clay sedimentation. They are, for example, able to improve the yield in papermaking. The new
polymers can also be used in pharmaceuticals e.g. in controlled release solid dose matrix systems such as in the
production of super swelling tablets for drug delivery and osmotic dosage forms. They also find use in various personal
care applications, for example as viscosity improver and foam stabilizer. Further applications include aqueous drag
30 reduction/drift control (reduction of the turbulent frictional drag of water in which they are dissolved) such as drift control
of agricultural sprays, and the new polymers may add lubricity to concrete to assist pumpability.
[0067] One embodiment of the invention will now be described in detail in the following example.

EXAMPLE
35
Preparation of modified calcium hexammine catalyst

[0068] The semi-continuous stirred tank reaction system shown in Fig. 1 was utilized to produce a calcium based
catalyst using parallel processing. A K-Tron single screw loss in weight gravimetric solids feeder (model # KCL-24-KQX)
40 fed calcium metal to a lock hopper. The lock hopper was made up of two 1" Kitz ball valves. The lock hopper was
operated as follows: A charge of approximately 2.5 g of calcium was fed on top of the top lock hoper ball valve. The top
ball valve opened, allowing the calcium metal charge to fall into the lock hopper. The top lock hopper valve immediately
closed and the lock hopper was purged with nitrogen gas to remove any traces of oxygen. Upon completion of the
nitrogen purge of the lock hopper, the bottom valve was opened and the calcium metal charge dropped into the liquid
45 ammonia contained in the agitated dissolver vessel. The dissolver vessel was maintained at a temperature range of -10
°C to 0 °C, and a pressure of 482 to 515 kPa (55-60 psig). Calcium metal was fed in multiple charges over the duration
of the reaction in order to maintain an appropriate liquid level in the dissolver vessel. Each calcium charge was immediately
followed by the addition of sufficient liquid ammonia to maintain a calcium concentration of approximately 2 mol %. The
resulting reaction of calcium metal and liquid ammonia was formation of calcium hexammine, dissolved in liquid ammonia.
50 The calcium hexammine solution was continuously transferred into the modifier vessel, at a controlled rate using a
variable speed peristaltic pump. Simultaneously, a mixture of 60 mol % propylene oxide and 40 mol % acetonitrile was
added to the modifier vessel. The propylene oxide/acetonitrile mixture was added to the agitated modifier vessel at a
rate targeting 1 mol total propylene oxide/acetonitrile for 1 mol of calcium hexammine flowing in from the dissolver vessel.
Reaction of the calcium hexammine with the propylene oxide/acetonitrile mixture produced a gray/white precipitate
55 suspended in liquid ammonia. The resulting slurry was continuously pressure transferred from the modifier vessel to the
agitated stripper vessel. The modifier vessel was maintained at a temperature of -5 °C to 5 °C and a pressure of 446 to
482 kPa (50-55 psig). The stripper vessel was charged with approximately 1000 mL of NORPAR13 ® hydrocarbon
(dodecane/tridecane/tetradecane mixture) prior to initiation of the reaction. The slurry formed in the modifier vessel was

9
 EP 2 809 703 B1

continuously transferred to the stripper vessel over the duration of the reaction. The stripper was maintained at a pressure
of 377 to 411 kPa (40-45 psig) and a temperature of 30 °C to 40 °C. Upon completion of the reaction all flows were
terminated, and the stripper vessel pressure was lowered to 129 kPa to 136 kPa (4-5 psig). The stripper was heated at
approximately 3 K/min to a maximum temperature of 205 °C. The slurry was maintained at 205 °C for 3 h. Upon completion
5 of the thermal treating, the stripper was cooled and the catalyst slurry recovered. The resulting slurry was the catalyst
source for the polymerization of ethylene oxide to produce ultrahigh molecular poly(ethylene oxide).

Polymerization of ethylene oxide

10 [0069] A laboratory reaction system for the polymerization of ethylene oxide under pressure was utilized to polymerize
ethylene oxide employing the catalyst slurry prepared as described in the above example. To the polymerization reactor
were charged 443 g of isopentane, 28 g of ethylene oxide and 2 g of hydrophilic silica followed by a quantity of the
catalyst slurry containing 0.26 g of calcium, calculated as the metal. Ethylene oxide flow into the reactor was set to
maintain a 6 wt % concentration of ethylene oxide in isopentane and the reaction temperature was maintained at 38 °C.
15 The reaction was run at a varying pressure around 170 kPa. The reaction system was kept under agitation and ethylene
oxide flow was continued until a total of 190 g was fed into the reactor. The resulting finely divided polymer was recovered
following vacuum evaporation of the hydrocarbon diluent. A white, granular polymer was obtained and prepared for
aqueous dissolution.

20 Dissolution of ethylene oxide polymer

[0070] The resulting granular ethylene oxide polymer was dissolved to form a 0.5 % aqueous solution in water/isopropyl
alcohol to determine the dynamic viscosity in the following manner:
[0071] The polymer was screened through a 20 US Mesh screen prior to dissolution. 3.00 g of polymer were weighed
25 into an 800 mL low-form glass beaker and 125 mL anhydrous isopropyl alcohol were added. The mixture was slurried
by agitating at 300-400 RPM for 30-60 s. The stirrer consisted of a shaft with four propellers spaced equidistant. The
bottom propeller was positioned to just clear the bottom of the beaker, while the top cleared the surface of the solution.
597 g of high purity deionized water were added to the slurry while maintaining the agitator speed at 300-400 RPM. The
water was added quickly in a single addition. Following addition of the water, the agitator speed was maintained at
30 300-400 RPM for approximately 60 s. The speed of the agitator was reduced to 60 RPM and the solution covered, stirring
was continued for 3 h. Upon completion of the dissolution, the stirrer was removed from the solution. The solution was
visually examined for the presence of gels, if present, the solution was discarded and a new solution made. The solution
was covered and placed in a 25 °C water bath for a minimum of 30 minutes, until reaching a temperature of 25 °C and
then the 0.5 % aqueous solution viscosity was determined using a Brookfield® DV-II + digital viscometer as described
35 before in the general part of the description (Spindle #2 @ 2 RPM).
[0072] The 1 % aqueous solution viscosity measurement was performed as above with the exception that the amount
of polymer was increased to 6.00 g and the amount of water decreased to 594 g.
[0073] 0.5 % and 1 % aqueous solutions of several commercial poly(ethylene oxide) products were prepared as above
and their viscosities were determined accordingly.
40
Table 1:
Comparison of 0.5 % and 1 % aqueous solution Brookfield® viscosities of commercially available poly(ethylene
oxide)s and inventive poly(ethylene oxide).

45 Sample # Poly(ethylene oxide) Approximate 1% Solution Viscosity 0.5% Solution Viscosity

MW (mPa·s) (mPa·s)
1* POLYOX® WSR-301 4,000,000 3,940 380
2* POLYOX® WSR-303 7,000,000 7,780 940
50 3* POLYOX® WSR UCARFLOC®
309 8,000,000 10,640 2,130
4* POLYOX® WSR UCARFLOC®
309 8,000,000 14,400 3,910
55 5* POLYOX® WSR UCARFLOC®
309 8,000,000 14,470 3,250

10
 EP 2 809 703 B1

(continued)

Comparison of 0.5 % and 1 % aqueous solution Brookfield® viscosities of commercially available poly(ethylene
oxide)s and inventive poly(ethylene oxide).
5
Sample # Poly(ethylene oxide) Approximate 1% Solution Viscosity 0.5% Solution Viscosity
MW (mPa·s) (mPa·s)
6* POLYOX® WSR UCARFLOC®
310 9,000,000 18,120 4,160
10
7 Inventive poly(ethylene oxide) > 10,000,000 Over range (>20,000) 5,7302
prepared above Extrapolated1: 25,470
* Comparative examples
1 Determined by using the correlation of the above viscosities of 0.5 % and 1 % poly(ethylene oxide) solutions shown

15 in Fig. 2
2 Average of two measurements

[0074] Table 1 lists POLYOX® Water-Soluble Resins from The Dow Chemical Company including the highest molecular
weight UCARFLOW Polymers commercially available. The approximate weight average molecular weights (Mw) indicated
20 are the values as claimed by the manufacturer (see for example Bulletin Form No. 326-00001-0302 AMS, published
March 2002 by the Dow Chemical Company and entitled "POLYOX Water-Soluble Resins"). The individual commercial
grades marketed under the trade names mentioned in the table cover relatively broad viscosity ranges. In Examples 3*,
4* and 5* different lots of POLYOX® WSR UCARFLOC® 309 polymer were used. As the indicated Mw is the Mw of the
whole grade the values in the table do not necessarily correspond to the Mw of the single lot. The inventive poly(ethylene
25 oxide) demonstrated a 38 % higher 0.5 % aqueous solution viscosity than commercially available UCARFLOC® 310.
Viscosity of a 1 % aqueous solution of the inventive poly(ethylene oxide) was off scale (>20,000 mPa·s) of the Brookfield®
viscometer spindle speed combination of RV spindle #2 at 2 RPM. Based upon the correlation of the solution viscosity
of commercial ethylene oxide polymers (Samples 1* to 6*) to molecular weight the estimated molecular weight of the
inventive ethylene oxide polymer is greater than 10,000,000 Dalton.
30

Claims

1. A process for polymerizing an epoxide monomer, preferably ethylene oxide, comprising carrying out the process in
35 the presence of a catalytically active amount of a catalyst obtainable by a preparation process comprising
admixing at least one alkaline earth metal, liquid ammonia, an alkylene oxide, which is optionally substituted by
aromatic radicals, and an organic nitrile having at least one acidic hydrogen atom to prepare a slurry of modified
alkaline earth hexammine in liquid ammonia;
continuously transferring the slurry of modified alkaline earth hexammine in liquid ammonia into a stripper vessel
40 and continuously evaporating ammonia, thereby accumulating the modified catalyst in the stripper vessel; and
upon complete transfer of the slurry of modified alkaline earth hexammine into the stripper vessel, aging the modified
catalyst to obtain the final polymerization catalyst.

2. The process of claim 1 wherein during preparation of the catalyst the accumulation of ammonia in the stripper vessel
45 is avoided.

3. The process of claim 1 or 2 wherein during preparation of the catalyst the stripper vessel is held at a temperature
of at least 30°C, preferably at least 40 °C above the boiling point of ammonia at the system pressure.

50 4. The process of any one of the preceding claims wherein during preparation of the catalyst an inert organic diluent,
preferably an inert organic diluent having a boiling point within the range of from 25 to 330 °C, and more preferably
a C12 to C19 hydrocarbon diluent, is contained in the stripper vessel and a slurry of the modified catalyst in the diluent
is formed and aged which catalyst slurry is directly used in the polymerization process.

55 5. The process of any one of the preceding claims wherein during preparation of the catalyst the preparation of the
slurry of modified alkaline earth hexammine in liquid ammonia is conducted in a continuous manner and comprises
continually feeding alkaline earth metal and liquid ammonia, continuously feeding the alkylene oxide and the organic
nitrile and continuously transferring the slurry of modified alkaline earth hexammine in liquid ammonia to the stripper

11
 EP 2 809 703 B1

vessel.

6. The process of any one of the preceding claims wherein the catalyst is obtainable by a preparation process com-
prising:
5
(1a) continually feeding a predetermined amount of alkaline earth metal into a dissolver vessel comprising liquid
ammonia and
(1b) continually adding liquid ammonia to form alkaline earth hexammine dissolved in liquid ammonia;
(2a) continuously transferring the alkaline earth hexammine solution into a modifier vessel;
10 (2b) continuously feeding the alkylene oxide and the organic nitrile into the modifier vessel to form a slurry of
modified alkaline earth hexammine in liquid ammonia;
(3a) continuously transferring the slurry of modified alkaline earth hexammine in liquid ammonia into the stripper
vessel and
(3b) continuously evaporating ammonia, thereby accumulating the modified catalyst in the stripper vessel;
15 (4b) upon consumption of the alkaline earth metal gradually terminating all feeds and emptying the dissolver
vessel via the modifier vessel into the stripper vessel; and
(4c) aging the modified catalyst in the stripper vessel to obtain the final polymerization catalyst.

7. The process of any one of the preceding claims wherein the alkaline earth metal used in the preparation of the
20 catalyst is calcium.

8. The process of any one of the preceding claims wherein the alkylene oxide used in the preparation of the catalyst
is propylene oxide.

25 9. The process of any one of the preceding claims wherein the organic nitrile used in the preparation of the catalyst is
acetonitrile.

10. The process of any of the preceding claims wherein the catalyst is present in an amount corresponding to 0.0004
to 0.0040 g of alkaline earth metal per g of epoxide monomer, preferably 0.0007 to 0.0021 g of alkaline earth metal
30 per g of epoxide monomer, more preferably 0.0010 to 0.0017 g of alkaline earth metal per g of epoxide monomer,
and most preferably 0.0012 to 0.0015 g of alkaline earth metal per g of epoxide monomer.

11. An ethylene oxide polymer, obtainable by the process according to any of the preceding claims and having an weight
average molecular weight of equal to or greater than 10,000,000 Dalton.
35
12. The ethylene oxide polymer of claim 11 having a 1 % aqueous solution viscosity of greater than 20,000 mPa·s at 25 °C.

13. The ethylene oxide polymer of any of claims 11 or 12 having a 0.5 % aqueous solution viscosity of greater than
5,000 mPa·s at 25 °C.
40
14. Use of the ethylene oxide polymer according to any of claims 11 to 13 as flocculation agent, such as in the tissue
paper production or waste treatment, or in pharmaceutical applications, such as to prepare super swelling tablets
for drug delivery or osmotic dosage forms.

45
Patentansprüche

1. Verfahren zum Polymerisieren eines Epoxidmonomers, vorzugsweise Ethylenoxid, umfassend Durchführen des
Verfahrens in Gegenwart einer katalytisch aktiven Menge eines Katalysators, erhältlich nach einem Herstellungs-
50 verfahren, das umfasst:

Mischen mindestens eines Erdalkalimetalls, flüssigen Ammoniaks, eines Alkylenoxids, das optional mit aroma-
tischen Resten substituiert ist, und eines organischen Nitrils mit mindestens einem sauren Wasserstoffatom,
um eine Aufschlämmung von modifiziertem Erdalkalihexammin in flüssigem Ammoniak herzustellen;
55 kontinuierliches Überführen der Aufschlämmung von modifiziertem Erdalkalihexammin in flüssigem Ammoniak
in ein Strippgefäß und kontinuierliches Verdampfen von Ammoniak, wobei sich der modifizierte Katalysator in
dem Strippgefäß ansammelt, und
nach vollständiger Überführung der Aufschlämmung von modifiziertem Erdalkalihexammin in das Strippgefäß

12
 EP 2 809 703 B1

Altern des modifizierten Katalysators, um den endgültigen Polymerisationskatalysator zu erhalten.

2. Verfahren nach Anspruch 1, wobei während der Herstellung des Katalysators die Anreicherung von Ammoniak in
dem Strippgefäß vermieden wird.
5
3. Verfahren nach Anspruch 1 oder 2, wobei während der Herstellung des Katalysators das Strippgefäß bei einer
Temperatur von mindestens 30°C, vorzugsweise mindestens 40°C oberhalb des Siedepunkts von Ammoniak bei
Systemdruck gehalten wird.

10 4. Verfahren nach einem der vorstehenden Ansprüche, wobei während der Herstellung des Katalysators ein inertes
organisches Verdünnungsmittel, vorzugsweise ein inertes organisches Verdünnungsmittel mit einem Siedepunkt
innerhalb des Bereichs von 25 bis 330°C und bevorzugter ein C12- bis C19-Kohlenwasserstoffverdünnungsmittel,
in dem Strippgefäß enthalten ist und eine Aufschlämmung des modifizierten Katalysators in dem Verdünnungsmittel
gebildet und gealtert wird, wobei die Katalysatoraufschlämmung direkt in dem Polymerisationsverfahren verwendet
15 wird.

5. Verfahren nach einem der vorstehenden Ansprüche, wobei während der Herstellung des Katalysators die Herstellung
der Aufschlämmung von modifiziertem Erdalkalihexammin in flüssigem Ammoniak in einer kontinuierlichen Art und
Weise durchgeführt wird und ständiges Zuführen von Erdalkalimetall und flüssigem Ammoniak, kontinuierliches
20 Zuführen des Alkylenoxids und des organischen Nitrils und kontinuierliche Überführung der Aufschlämmung von
modifiziertem Erdalkalihexammin in flüssigem Ammoniak in das Strippgefäß umfasst.

6. Verfahren nach einem der vorstehenden Ansprüche, wobei der Katalysator nach einem Herstellungsverfahren
erhalten wird, das umfasst:
25
(1a) ständiges Zuführen einer vorbestimmten Menge von Erdalkalimetall in ein Lösegefäß, das flüssigen Am-
moniak enthält, und
(1 b) ständiges Hinzugeben von flüssigem Ammoniak, um Erdalkalihexammin zu bilden, das in flüssigem Am-
moniak gelöst ist;
30 (2a) kontinuierliches Überführen der Erdalkalihexamminlösung in ein Modifiziergefäß;
(2b) kontinuierliches Zuführen des Alkylenoxids und des organischen Nitrils in das Modifiziergefäß, um eine
Aufschlämmung von modifiziertem Erdalkalihexammin in flüssigem Ammoniak zu bilden;
(3a) kontinuierliches Überführen der Aufschlämmung von modifiziertem Erdalkalihexammin in flüssigem Am-
moniak in das Strippgefäß und
35 (3b) kontinuierliches Verdampfen von Ammoniak, wobei sich der modifizierte Katalysator in dem Stripgefäß
anreichert;
(4b) nach Verbrauch des Erdalkalimetalls allmähliches Beenden aller Zufuhrströme und Entleeren des Löse-
gefäß über das Modifiziergefäß in das Strippgefäß und
(4c) Altern des modifizierten Katalysators in dem Strippgefäß, um den endgültigen Polymerisationskatalysator
40 zu erhalten.

7. Verfahren nach einem der vorstehenden Ansprüche, wobei das Erdalkalimetall, das bei der Herstellung des Kata-
lysators verwendet wird, Calcium ist.

45 8. Verfahren nach einem der vorstehenden Ansprüche, wobei das Alkylenoxid, das bei der Herstellung des Katalysators
verwendet wird, Propylenoxid ist.

9. Verfahren nach einem der vorstehenden Ansprüche, wobei das organische Nitril, das bei der Herstellung des Ka-
talysators verwendet wird, Acetonitril ist.
50
10. Verfahren nach einem der vorstehenden Ansprüche, wobei der Katalysator in einer Menge entsprechend 0,0004
bis 0,0040 g Erdalkalimetall pro g Epoxidmonomer, vorzugsweise 0,0007 bis 0,0021 g Erdalkalimetall pro g Epo-
xidmonomer, bevorzugter 0,0010 bis 0,0017 g Erdalkalimetall pro g Epoxidmonomer und am meisten bevorzugt
0,0012 bis 0,0015 g Erdalkalimetall pro g Epoxidmonomer vorhanden ist.
55
11. Ethylenoxidpolymer erhältlich nach dem Verfahren gemäß einem der vorstehenden Ansprüche mit einem gewichts-
mittleren Molekulargewicht von gleich oder größer als 10.000.000 Dalton.

13
 EP 2 809 703 B1

12. Ethylenoxidpolymer nach Anspruch 11 mit einer Viskosität in 1 %iger wässriger Lösung von größer als 20.000 mPa·s
bei 25°C.

13. Ethylenoxidpolymer nach einem der Ansprüche 11 oder 12 mit einer Viskosität in 0,5%iger wässriger Lösung von
5 größer als 5.000 mPa·s bei 25°C.

14. Verwendung des Ethylenoxidpolymers nach einem der Ansprüche 11 bis 13 als Flockungsmittel, wie etwa bei der
Herstellung von Tissuepapier oder Abfallbehandlung, oder in pharmazeutischen Anwendungen, wie etwa um extrem
stark aufquellende Tabletten für die Zufuhr von Arzneimitteln oder osmotische Dosierformen herzustellen.
10

Revendications

1. Un procédé pour polymériser un monomère d’époxyde, de préférence de l’oxyde d’éthylène, comprenant le fait
15 d’effectuer le procédé en présence d’une quantité catalytiquement active d’un catalyseur pouvant être obtenu par
un procédé de préparation comprenant
le fait de mélanger ensemble au moins un métal alcalinoterreux, de l’ammoniaque liquide, un oxyde d’alkylène,
lequel est facultativement substitué par des radicaux aromatiques, et un nitrile organique ayant au moins un atome
d’hydrogène acide afin de préparer une boue d’hexammine alcalinoterreuse modifiée dans de l’ammoniaque liquide ;
20 le fait de transférer en continu la boue d’hexammine alcalinoterreuse modifiée dans de l’ammoniaque liquide dans
un récipient rectificateur et le fait de faire s’évaporer en continu l’ammoniaque, accumulant de ce fait le catalyseur
modifié dans le récipient rectificateur ; et
lors du transfert complet de la boue d’hexammine alcalinoterreuse modifiée dans le récipient rectificateur, le fait de
faire vieillir le catalyseur modifié afin d’obtenir le catalyseur de polymérisation final.
25
2. Le procédé de la revendication 1 dans lequel, durant la préparation du catalyseur, l’accumulation d’ammoniaque
dans le récipient rectificateur est évitée.

3. Le procédé de la revendication 1 ou de la revendication 2 dans lequel, durant la préparation du catalyseur, le

30 récipient rectificateur est maintenu à une température d’au moins 30 °C, de préférence d’au moins 40 °C au-dessus
du point d’ébullition de l’ammoniaque à la pression du système.

4. Le procédé de n’importe laquelle des revendications précédentes dans lequel, durant la préparation du catalyseur,
un diluant organique inerte, de préférence un diluant organique inerte ayant un point d’ébullition compris dans la
35 gamme allant de 25 à 330 °C, et plus préférablement un diluant hydrocarbure en C12 à C19, est contenu dans le
récipient rectificateur et une boue du catalyseur modifié dans le diluant est formée et amenée à vieillir, laquelle boue
de catalyseur est directement utilisée dans le procédé de polymérisation.

5. Le procédé de n’importe laquelle des revendications précédentes dans lequel, durant la préparation du catalyseur,
40 la préparation de la boue d’hexammine alcalinoterreuse modifiée dans de l’ammoniaque liquide est menée d’une
manière continue et comprend le fait d’amener en continu un métal alcalinoterreux et de l’ammoniaque liquide, le
fait d’amener en continu l’oxyde d’alkylène et le nitrile organique et le fait de transférer en continu la boue d’hexammine
alcalinoterreuse modifiée dans de l’ammoniaque liquide jusqu’au récipient rectificateur.

45 6. Le procédé de n’importe laquelle des revendications précédentes dans lequel le catalyseur peut être obtenu par
un procédé de préparation comprenant :

(1 a) le fait d’amener continuellement une quantité prédéterminée de métal alcalinoterreux dans un récipient
dissolveur comprenant de l’ammoniaque liquide et
50 (1 b) le fait d’ajouter continuellement de l’ammoniaque liquide afin de former une hexammine de métal alcali-
noterreux dissoute dans de l’ammoniaque liquide ;
(2a) le fait de transférer en continu la solution d’hexammine alcalinoterreuse dans un récipient modificateur ;
(2b) le fait d’amener en continu l’oxyde d’alkylène et le nitrile organique dans le récipient modificateur afin de
former une boue d’hexammine alcalinoterreuse modifiée dans de l’ammoniaque liquide ;
55 (3a) le fait de transférer en continu la boue d’hexammine alcalinoterreuse modifiée dans de l’ammoniaque
liquide dans le récipient rectificateur et
(3b) le fait de faire s’évaporer en continu l’ammoniaque, accumulant de ce fait le catalyseur modifié dans le
récipient rectificateur ;

14
 EP 2 809 703 B1

(4b) lors de la consommation du métal alcalinoterreux le fait de mettre progressivement fin à toutes les amenées
et le fait de vider le récipient dissolveur par l’intermédiaire du récipient modificateur dans le récipient rectificateur ;
et
(4c) le fait de faire vieillir le catalyseur modifié dans le récipient rectificateur afin d’obtenir le catalyseur de
5 polymérisation final.

7. Le procédé de n’importe laquelle des revendications précédentes dans lequel le métal alcalinoterreux utilisé dans
la préparation du catalyseur est du calcium.

10 8. Le procédé de n’importe laquelle des revendications précédentes dans lequel l’oxyde d’alkylène utilisé dans la
préparation du catalyseur est de l’oxyde de propylène.

9. Le procédé de n’importe laquelle des revendications précédentes dans lequel le nitrile organique utilisé dans la
préparation du catalyseur est de l’acétonitrile.
15
10. Le procédé de n’importe lesquelles des revendications précédentes dans lequel le catalyseur est présent dans une
quantité correspondant à de 0,0004 à 0,0040 g de métal alcalinoterreux par g de monomère d’époxyde, de préférence
de 0,0007 à 0,0021 g de métal alcalinoterreux par g de monomère d’époxyde, plus préférablement de 0,0010 à
0,0017 g de métal alcalinoterreux par g de monomère d’époxyde, et de manière préférée entre toutes de 0,0012 à
20 0,0015 g de métal alcalinoterreux par g de monomère d’époxyde.

11. Un polymère d’oxyde d’éthylène, pouvant être obtenu par le procédé selon n’importe lesquelles des revendications
précédentes et ayant une masse moléculaire moyenne en poids supérieure ou égale à 10 000 000 daltons.

25 12. Le polymère d’oxyde d’éthylène de la revendication 11 ayant une viscosité en solution aqueuse à 1 % supérieure
à 20 000 mPa·s à 25 °C.

13. Le polymère d’oxyde d’éthylène de n’importe lesquelles des revendications 11 ou 12 ayant une viscosité en solution
aqueuse à 0,5 % supérieure à 5 000 mPa·s à 25 °C.
30
14. Utilisation du polymère d’oxyde d’éthylène selon n’importe lesquelles des revendications 11 à 13 en tant qu’agent
de floculation, telle que dans la production de papiers minces ou le traitement des déchets, ou dans des applications
pharmaceutiques, telles que pour préparer des comprimés super gonflants pour l’administration de médicaments
ou des formes posologiques osmotiques.
35

40

45

50

55

15
EP 2 809 703 B1

16
EP 2 809 703 B1

17
 EP 2 809 703 B1

REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European
patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be
excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

• US 2969402 A [0004] [0006] • CN 1740209 A [0007]

• US 3037943 A [0004] [0006] • US 3729441 A [0010]
• US 3627702 A [0005] • US 5186942 A [0011]
• US 4193892 A [0006] [0016] • US 3281312 A [0011]
• US 4267309 A [0006] [0016] • US 20070269491 A [0011]

Non-patent literature cited in the description

• Bulletin Form No. 326-00001-0302 AMS. Dow Chem- • Bulletin Form No. 326-00002-0303 AMS. Dow Chem-
ical Company, March 2002 [0009] [0074] ical Company, March 2003 [0064]

18