CA1111409A - Process for preparing olefin oxide polymerization catalysts - Google Patents
Process for preparing olefin oxide polymerization catalystsInfo
- Publication number
- CA1111409A CA1111409A CA290,251A CA290251A CA1111409A CA 1111409 A CA1111409 A CA 1111409A CA 290251 A CA290251 A CA 290251A CA 1111409 A CA1111409 A CA 1111409A
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- CA
- Canada
- Prior art keywords
- catalyst
- ammonia
- aging
- carbon
- modifier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/269—Mixed catalyst systems, i.e. containing more than one reactive component or catalysts formed in-situ
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2651—Alkaline earth metals or compounds thereof
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polyethers (AREA)
Abstract
Abstract of the Disclosure In a process for the preparation of an olefin oxide polymerization catalyst comprising:
(i) admixing calcium, ammonia, an alkylene oxide modifier, and an organic nitrile modifier, the alkylene oxide consisting of carbon, hydrogen, and oxirane oxygen atoms and the organic nitrile consisting of carbon, nitrogen, and hydrogen atoms, at least one hydrogen atom being acidic, to form a slurry of modified calcium hexammine in ammonia; and (ii) evaporating ammonia to provide a soled residue, the improvement comprising:
aging the solid residue at a temperature in the range of about 130°C to about 225°C.
(i) admixing calcium, ammonia, an alkylene oxide modifier, and an organic nitrile modifier, the alkylene oxide consisting of carbon, hydrogen, and oxirane oxygen atoms and the organic nitrile consisting of carbon, nitrogen, and hydrogen atoms, at least one hydrogen atom being acidic, to form a slurry of modified calcium hexammine in ammonia; and (ii) evaporating ammonia to provide a soled residue, the improvement comprising:
aging the solid residue at a temperature in the range of about 130°C to about 225°C.
Description
t 9929 ~ ~ 9 Field of the Invention Ihis invention relates to a process for the - preparation of catalysts and, more particularly to the preparation of catalysts for use in the polymerization of olefin oxides.
Description of the Prior Art .
; The catalytic polymerization of olefin oxides has been practiced for the past several years, one of the ~ commercial processes being the suspension polymerization ; lO of ethylene oxide in 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 livin~ polymer is ~enerated and is eventually terminated by impurities which build u~ in t~e ~edium.
Although this polymerization process has proven ~uccessful, it has a certain negative aspect which detracts ...
from optimization and is found both in the polymerization process itself, the process for preparing the catalyst, and the respective polymer and catalyst prodvcts. Among other things, this deficiency serves to inhibit the production of high molecular weight polymers and polymerization productivity. It apparently stems from an acute sensitivity to impurities and changes in operating conditions, e.g., catalyst components and their ratioS~
polymerization time, and chemical and mechanical degradation of the polymer chain. To overcome this deficiency, these .'' ~
: ..
`~ 114~9 `~ processes have come under careful scrutiny but improvements that avoid sensitization of the polymer or catalyst have been few and far between apparently because of the complex ,.. .
:, .
mechanism of the polymerization and the complex, and ,~ still unknown, structure of the catalyst.
' ~ I
Summary of the Invention An object of this invention, therefore, is to provide an improvement in the molecular weight picture and/or in productivity. To achieve this objective, ,:
the improvement must necessarily avoid sensitization of the polymer or catalyst at least in those areas which ~`~ will counter the productivity increase or depress the molecular weight.
Other objects and advantages will become apparent hereinafter.
According to the present invention high molecular -weights and/or productivities are achieved by using a catalyst prepared first in the conventional manner ;~ comprising:
(i) admixing calcium, ammonia, an alkylene oxide modifier, and an organic nitrile modifier, the alkylene oxide consisting of carbon, hydrogen, and oxirane oxygen .' , .
~ . . i , , i .
.. l .
atoms and the organic nitrile consisting of carbon, nitrogen and hydrogen atoms, at least one hydrogen atom being acidic, to form a slurry of modified calcium - hexammine in ammonia; and (ii) evaporating ammonia to provide a solid residue and, then, carrying out the improvement - which comprises:
aging the solid residue at a temperature in the range of about 150C to about 225~C.
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 analyses difficult. Consequently, it is not surprising that the structure of the catalyst prepared by either the conventional process or the improved process, as heretofore described, is unknown. The improved catalyst will have to be, therefore, defined by the process by which it is made.
:' -Description of the Preferred Embodiment The catalyst, the process for making the catalyst with the nitrile modifier, and the polymerization process as known prior to subject invention are described in United States patent numbered 2,969,402 issued on January 24, 1961 to Hill et al for "Preparation of Catalysts for the Polymerization of Epoxides". The term .'',' .~''.
. ..... .
. , .
99~9 ` 1~114~9 `` .
"hexa~oniate" has been changed in the present specification to --hexammine~
The temperature used in step (i) can be in the range of about minus 50C to about plus 25~C and is preferably in the range of about minus 40C to about -~ minus 20~C or as close as possible to minus 33.5~C. This step is carried out in the liquid phase with ammonia in the liquid state under suitable pressure. An excess of 6~ ' ammonia is desirable, e.g., about 12 to about 125 moles of ~,. . .
0 ammonia per gram atom of calcium. The ammonia is essentially ~- anhydrous. Iwo modifiers are also introduced in step (i).One of the modifiers is an alkylene oxide consisting of carbon, hydrogen, and oxirane oxygen atoms. Although ~ the number of carbon atoms in the alkylene oxide can range .~,,.
from 2 to about 20 or higher, alkylene oxides ha~ing 2 to about 5 carbon atoms are preferred, e.g., ethylene oxide, . .
- propylene oxide, 1, 2-epoxybutane, and 2, 3-epoxybutane.
. i ` The second modifier is an organic nitrile consisting of ` carbon, nitrogen, and hydrogen atoms, at least one O hydrogen atom being acidic. The nitrile is preferably - a saturated aliphatic mononitrile wherein the organic moiety has 2 to about 10 carbon atoms, e.~., acetonitrile, ;
propionitrile, and butyronitrile. Aromatic nitriles such as benzonitrile and ortho-toluenenitrile are also useful.
.~ , I
, .j `
- 111~4~9 ~`
!
The aikylene oxide can be used in a ratio of about 0.3 to about 10 moles of alkylene oxide per gram atom of calcium and the nitrile can be used in a ratio of about 0.2 to about 0.8 mole of nitrile per gram atom of calcium. Preferred ratios are about 0.4 to about 1 mole of alkylene oxide and about 0.3 to about 0.6 mole of nitrile, all per gram atom of calcium. Step:(i) is preferably carried out with agitation, a slurry of ~; modified calcium hexammine in a~monia being formed.
Where an organic diluent is present, a slurry is also formed.
The order of introduction of the calcium, the ammonia, and the modifiers in step (i) can vary. The common procedure is to conduct step (i) in two steps, the first step being to add the calcium to the ammonia to form a solution of calcium hexammine and the second step to add .. , - the modifiers. An alternative mode is to introduce the calcium and modifiers first together with a low boiling . ~and low freezing) organic diluent and then add the ammonia.
,~;. .
The least preferred is to add the calcium to a mixture of ,; -the ammonia and the modifiers.
The next step, step (ii) is the evaporation of - ammonia to provide a solid catalyst residue. This can be ' accomplished by merely permitting the catalyst slurry ` to come to room temperature and pressure, or the slurry may be heated gently, e.g., in a cool water bath, to - , ! ' , .
~-:
9 5~ 2 9 3L1114~9 I
I
b~ing it to room temperature, tl-e latter being the usual way of accomplshing the evaporation where step (i) is run at a temperature of about minus 33.5C, which is a common operating temperature for this process step.
Other conventional evaporation or stripping techniques can be applied here. The evaporation is continued until a dry gray solid is observed where it is desired to age the dry solid. This may be done where no diluent or a low boiling organic diluent is used in step (i). Where O it is desired to age the catalyst in slurry form, an organic diluent is usually added when a gray pasty solid is present, again where no diluent or where a low boiler is used initially. The evaporation step is usually conducted at ambient temperatures where no organic diluent ;
is present, or it can be conducted at, or slightly higher than, the boiling point of the low boiling diluent if one is used. It can be carried out in the temperature range between the boiling point of ammonia (minus 33.5~C) and ab~ut 100C, however. The aging step can be conducted on the dry solid or the slurry with no appreciable difference in result.
It is desirable to carry out at least part of the process, or all of the process, in an inert organic -¦ l li~uid diluent, the most preferable condition being I ¦' when the final catalyst product is in slurry form for transfer to, and direct use, in the olefin oxide poly-merization.
-7- 1 , i 4~ 9 .
The ~lternative ways o~ deploying organic diluents in the subject process are as follows:
~ a) prepare a dry or pasty solid, slurry with a high or internediate b~iler (using medium stirring), and age;
(b) same as (a) except slurry concurrently with evaporation of ammonia;
~- (c) carry out the first step in a low boiling, low freezing, organic diluent; strip off ammonia and low boiler to provide dry solid; and age; and (d) same as (c) except slurry solid during or after stripping with a high boiler, i.e., a diluent which will not boil off d~lring aging, or an intermediate boiler.
...
-~ The organic diluent referred to above is one which - ~s inert to any of the reactants or the catalyst product ~:
and ~ill not be affected by operating conditions except, of course, in cases where it is to be stripped. If 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 ., i ;` conditions. I
:., I
The low boiling diluents are exemplified by the Cs - and C6 hydrocarbons such as isopentane and hexane. They have low freezing points and are readily stripped during the evaporation step. The high b~iling diluents are represented by tbe C~2 to Clg hydr~carbons, e.g., dodecane and hexadecane. Intermediate boiling diluents are the !
t 9~
4~9 C7 to Cg hydrocarbons such as heptane and isooctane.
The intermediate boilers have low freezing points so that they will not freeze during the stripping step (step (ii)). These intermediate boilers are the choice for continuous plant processes where pressure equipment is available, and are utilized throughout ,-the catalyst process and the p~lymerization. One advantage of using the inert diluents is in the realm of safety in ~iew of the pyrophoric ar,d air sensitive nature of the catalyst.
As noted, the invention lies in aging the dry catalyst or catalyst slurry at a temperature in the range of about 150C to about 225C and preferably in the range of about 200C to about 225C. The aging step may be carried out for about l to about,15 or more hrs.
~elow about 200c and preferably for no more than about 5 or even 3 hrs. abo~e about 200C. At the end of the aging period the catalyst is cooled to room temperature by air quenching or any other conventional quenchinq means.
Throughout the preparation of the catalyst, conventional precautions are taken to exclude water, oxygen, and carbon dioxide from the system. This may be accomplished by' I
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.
The finishe~ catalyst in dry or slurry for,m is then used in the conventional polymerization process.
J
~ .
~ 9~29 , ~
4~9 A typical polymerization is describeu in Exampie 1. A
- broad range of olefin oxides and mixtures of olefin oxides can be used, e.g., having 2 to about 20 carbon atoms.
A preferred monomer is ethylene oxide. Polymerization temperatures can be in the range of about minus 30C to I about 150C, a preferred range for ethylene oxide monomer being about 0C to about 60C. It is generally carried out in an inorganic diluent with agitation and in an inert atmosphere such as nitrogen to exclude oxygen and carbon dioxide. A catalyst concentration in the range of ~- about 0.02 to about 10 percent by weight based on the weight of the olefin oxide feed can be used. Polymerization i~ times can be run from minutes to days depending on the conditions used. Preferred times are about 1 to about . 10 hours.
~; The molecular weights of the various polymers produced ..,, ~- by the conventional polymerization process described : .;
in more detail hereafter in the examples are approximated by measuring their solution viscosities using a BrooXfield viscometer. The solution viscosities are ~easured as 1% or 5% solutions of polymer in water and are expressed in units of CPS (centistokes per second). Solu,ion viscosities are correlated with molecular weights via , ~ their intrinsic viscosities using the relationship: , -- leta] z 6.4 x 10-5 Mw 0-82 in water at 35C
wherein Mw is weight average molecular ~eight.
: i g929 14~9 Conventional polymers are available in molecular weights ranging from 100 ,noo to greater than 6 million. With the higher molecular weight resins, viscosity measurements are complicated because of the difficulties encountered in dissolving the resins. During dissolution the mixture .~' i - assumes a mucous-like consistency with a high tendency to gel. In addition, the extremely long chains are quite :
sensitive to shearing forces and must be stirred under .
" very low sheari~g conditions in order to minimize mechanical degradation. The procedure for dissolving these resins may be found in Bulletin numbered F 42993 of May, 1970 published by the Union Carbide Corporation and ~ .
;~ entitled, "How to Dissolve Polyox Water-Soluble Resins."
The following examples illustrate the invention:
Example 1 , .~.
Redistilled calcium turnings are added to liquid anhydrous ammonia in a ~essel which is maintained at atmospheric pressure and about minus 33.5~C. The molar ratio of ammonia to calcium is noted below. The vessel ~ is previously swept with nitrogen and a nitrogen atmosphere maintained. Agitation is used throughout the procedure.
A solution is formed, which takes on a blue color. The ~odifiers; propylene oxide and acetonitrile, are then added and the blue color changes to gray and a slurry is formed. The molar ratio of calcium to modifiely is 1~
." ' . 'I
'.. ', I
~ I ~929 !9 and the molar ratio of propylene oxide to acetonitrile is 3:2. A~onia is stripped off at temperatures up to 96C for about 3 hours and the solid is either unaged, aged in the dry state, or slurried with a high boiler and aged before use in the polymerization.
Aging is accomplished at a certain temperature for a certain number of hours hereinafter noted. :
Tbe polymerization is typical of the conventional polymerizations used for olefin oxides. It is carried out in a stirred reactor by charging the dry catalyst or catalyst slurry. The monomer, ethylene oxide, is fed on demand so as to maintain a 31C reaction temperature.
Heat exchange is controlled by reflux cooling of the diluent and the system is continuously purged with ; nitrogen. The reaction is carried out for a certain length of time, noted below, after which the slurry is centrifuged and the resin product is dried. The polymer is treated with C02 to minimize polymer degradation and with 0.5 percent anhydrous and particulate colloidal silica to inhibit agglomeration. About 8 per-cent by weight concentration of monomer is maintained throughout the polymerization. The productivity is measured by determining the number of parts by weight of polymer product per part by weight of calcium present in the catalyst. The solution viscosity is given in CPS and based on a one percent solution at 25CC as discussed .
'.
above using a Broo~field Viscometer RVF 2/2.
Variables and results in this example l are as follows:
. . .
~ (a) The high boiler is dodecane.
; (b) The molar ratio of ammonia to calcium is 100:1.
(c) Aging temperature: 200C
(d) Slurry used in aging and polymerization.
:, :', ` (e) Polymerization time: 1 hour.
(f) A catalyst is prepared and four samples are ; .:
- 10 used, one in each of four polymerizations. Aging times ..:-.~
- and productivities are as follows:
Sample Aging Time Productivity 1 , unaged 187
Description of the Prior Art .
; The catalytic polymerization of olefin oxides has been practiced for the past several years, one of the ~ commercial processes being the suspension polymerization ; lO of ethylene oxide in 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 livin~ polymer is ~enerated and is eventually terminated by impurities which build u~ in t~e ~edium.
Although this polymerization process has proven ~uccessful, it has a certain negative aspect which detracts ...
from optimization and is found both in the polymerization process itself, the process for preparing the catalyst, and the respective polymer and catalyst prodvcts. Among other things, this deficiency serves to inhibit the production of high molecular weight polymers and polymerization productivity. It apparently stems from an acute sensitivity to impurities and changes in operating conditions, e.g., catalyst components and their ratioS~
polymerization time, and chemical and mechanical degradation of the polymer chain. To overcome this deficiency, these .'' ~
: ..
`~ 114~9 `~ processes have come under careful scrutiny but improvements that avoid sensitization of the polymer or catalyst have been few and far between apparently because of the complex ,.. .
:, .
mechanism of the polymerization and the complex, and ,~ still unknown, structure of the catalyst.
' ~ I
Summary of the Invention An object of this invention, therefore, is to provide an improvement in the molecular weight picture and/or in productivity. To achieve this objective, ,:
the improvement must necessarily avoid sensitization of the polymer or catalyst at least in those areas which ~`~ will counter the productivity increase or depress the molecular weight.
Other objects and advantages will become apparent hereinafter.
According to the present invention high molecular -weights and/or productivities are achieved by using a catalyst prepared first in the conventional manner ;~ comprising:
(i) admixing calcium, ammonia, an alkylene oxide modifier, and an organic nitrile modifier, the alkylene oxide consisting of carbon, hydrogen, and oxirane oxygen .' , .
~ . . i , , i .
.. l .
atoms and the organic nitrile consisting of carbon, nitrogen and hydrogen atoms, at least one hydrogen atom being acidic, to form a slurry of modified calcium - hexammine in ammonia; and (ii) evaporating ammonia to provide a solid residue and, then, carrying out the improvement - which comprises:
aging the solid residue at a temperature in the range of about 150C to about 225~C.
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 analyses difficult. Consequently, it is not surprising that the structure of the catalyst prepared by either the conventional process or the improved process, as heretofore described, is unknown. The improved catalyst will have to be, therefore, defined by the process by which it is made.
:' -Description of the Preferred Embodiment The catalyst, the process for making the catalyst with the nitrile modifier, and the polymerization process as known prior to subject invention are described in United States patent numbered 2,969,402 issued on January 24, 1961 to Hill et al for "Preparation of Catalysts for the Polymerization of Epoxides". The term .'',' .~''.
. ..... .
. , .
99~9 ` 1~114~9 `` .
"hexa~oniate" has been changed in the present specification to --hexammine~
The temperature used in step (i) can be in the range of about minus 50C to about plus 25~C and is preferably in the range of about minus 40C to about -~ minus 20~C or as close as possible to minus 33.5~C. This step is carried out in the liquid phase with ammonia in the liquid state under suitable pressure. An excess of 6~ ' ammonia is desirable, e.g., about 12 to about 125 moles of ~,. . .
0 ammonia per gram atom of calcium. The ammonia is essentially ~- anhydrous. Iwo modifiers are also introduced in step (i).One of the modifiers is an alkylene oxide consisting of carbon, hydrogen, and oxirane oxygen atoms. Although ~ the number of carbon atoms in the alkylene oxide can range .~,,.
from 2 to about 20 or higher, alkylene oxides ha~ing 2 to about 5 carbon atoms are preferred, e.g., ethylene oxide, . .
- propylene oxide, 1, 2-epoxybutane, and 2, 3-epoxybutane.
. i ` The second modifier is an organic nitrile consisting of ` carbon, nitrogen, and hydrogen atoms, at least one O hydrogen atom being acidic. The nitrile is preferably - a saturated aliphatic mononitrile wherein the organic moiety has 2 to about 10 carbon atoms, e.~., acetonitrile, ;
propionitrile, and butyronitrile. Aromatic nitriles such as benzonitrile and ortho-toluenenitrile are also useful.
.~ , I
, .j `
- 111~4~9 ~`
!
The aikylene oxide can be used in a ratio of about 0.3 to about 10 moles of alkylene oxide per gram atom of calcium and the nitrile can be used in a ratio of about 0.2 to about 0.8 mole of nitrile per gram atom of calcium. Preferred ratios are about 0.4 to about 1 mole of alkylene oxide and about 0.3 to about 0.6 mole of nitrile, all per gram atom of calcium. Step:(i) is preferably carried out with agitation, a slurry of ~; modified calcium hexammine in a~monia being formed.
Where an organic diluent is present, a slurry is also formed.
The order of introduction of the calcium, the ammonia, and the modifiers in step (i) can vary. The common procedure is to conduct step (i) in two steps, the first step being to add the calcium to the ammonia to form a solution of calcium hexammine and the second step to add .. , - the modifiers. An alternative mode is to introduce the calcium and modifiers first together with a low boiling . ~and low freezing) organic diluent and then add the ammonia.
,~;. .
The least preferred is to add the calcium to a mixture of ,; -the ammonia and the modifiers.
The next step, step (ii) is the evaporation of - ammonia to provide a solid catalyst residue. This can be ' accomplished by merely permitting the catalyst slurry ` to come to room temperature and pressure, or the slurry may be heated gently, e.g., in a cool water bath, to - , ! ' , .
~-:
9 5~ 2 9 3L1114~9 I
I
b~ing it to room temperature, tl-e latter being the usual way of accomplshing the evaporation where step (i) is run at a temperature of about minus 33.5C, which is a common operating temperature for this process step.
Other conventional evaporation or stripping techniques can be applied here. The evaporation is continued until a dry gray solid is observed where it is desired to age the dry solid. This may be done where no diluent or a low boiling organic diluent is used in step (i). Where O it is desired to age the catalyst in slurry form, an organic diluent is usually added when a gray pasty solid is present, again where no diluent or where a low boiler is used initially. The evaporation step is usually conducted at ambient temperatures where no organic diluent ;
is present, or it can be conducted at, or slightly higher than, the boiling point of the low boiling diluent if one is used. It can be carried out in the temperature range between the boiling point of ammonia (minus 33.5~C) and ab~ut 100C, however. The aging step can be conducted on the dry solid or the slurry with no appreciable difference in result.
It is desirable to carry out at least part of the process, or all of the process, in an inert organic -¦ l li~uid diluent, the most preferable condition being I ¦' when the final catalyst product is in slurry form for transfer to, and direct use, in the olefin oxide poly-merization.
-7- 1 , i 4~ 9 .
The ~lternative ways o~ deploying organic diluents in the subject process are as follows:
~ a) prepare a dry or pasty solid, slurry with a high or internediate b~iler (using medium stirring), and age;
(b) same as (a) except slurry concurrently with evaporation of ammonia;
~- (c) carry out the first step in a low boiling, low freezing, organic diluent; strip off ammonia and low boiler to provide dry solid; and age; and (d) same as (c) except slurry solid during or after stripping with a high boiler, i.e., a diluent which will not boil off d~lring aging, or an intermediate boiler.
...
-~ The organic diluent referred to above is one which - ~s inert to any of the reactants or the catalyst product ~:
and ~ill not be affected by operating conditions except, of course, in cases where it is to be stripped. If 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 ., i ;` conditions. I
:., I
The low boiling diluents are exemplified by the Cs - and C6 hydrocarbons such as isopentane and hexane. They have low freezing points and are readily stripped during the evaporation step. The high b~iling diluents are represented by tbe C~2 to Clg hydr~carbons, e.g., dodecane and hexadecane. Intermediate boiling diluents are the !
t 9~
4~9 C7 to Cg hydrocarbons such as heptane and isooctane.
The intermediate boilers have low freezing points so that they will not freeze during the stripping step (step (ii)). These intermediate boilers are the choice for continuous plant processes where pressure equipment is available, and are utilized throughout ,-the catalyst process and the p~lymerization. One advantage of using the inert diluents is in the realm of safety in ~iew of the pyrophoric ar,d air sensitive nature of the catalyst.
As noted, the invention lies in aging the dry catalyst or catalyst slurry at a temperature in the range of about 150C to about 225C and preferably in the range of about 200C to about 225C. The aging step may be carried out for about l to about,15 or more hrs.
~elow about 200c and preferably for no more than about 5 or even 3 hrs. abo~e about 200C. At the end of the aging period the catalyst is cooled to room temperature by air quenching or any other conventional quenchinq means.
Throughout the preparation of the catalyst, conventional precautions are taken to exclude water, oxygen, and carbon dioxide from the system. This may be accomplished by' I
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.
The finishe~ catalyst in dry or slurry for,m is then used in the conventional polymerization process.
J
~ .
~ 9~29 , ~
4~9 A typical polymerization is describeu in Exampie 1. A
- broad range of olefin oxides and mixtures of olefin oxides can be used, e.g., having 2 to about 20 carbon atoms.
A preferred monomer is ethylene oxide. Polymerization temperatures can be in the range of about minus 30C to I about 150C, a preferred range for ethylene oxide monomer being about 0C to about 60C. It is generally carried out in an inorganic diluent with agitation and in an inert atmosphere such as nitrogen to exclude oxygen and carbon dioxide. A catalyst concentration in the range of ~- about 0.02 to about 10 percent by weight based on the weight of the olefin oxide feed can be used. Polymerization i~ times can be run from minutes to days depending on the conditions used. Preferred times are about 1 to about . 10 hours.
~; The molecular weights of the various polymers produced ..,, ~- by the conventional polymerization process described : .;
in more detail hereafter in the examples are approximated by measuring their solution viscosities using a BrooXfield viscometer. The solution viscosities are ~easured as 1% or 5% solutions of polymer in water and are expressed in units of CPS (centistokes per second). Solu,ion viscosities are correlated with molecular weights via , ~ their intrinsic viscosities using the relationship: , -- leta] z 6.4 x 10-5 Mw 0-82 in water at 35C
wherein Mw is weight average molecular ~eight.
: i g929 14~9 Conventional polymers are available in molecular weights ranging from 100 ,noo to greater than 6 million. With the higher molecular weight resins, viscosity measurements are complicated because of the difficulties encountered in dissolving the resins. During dissolution the mixture .~' i - assumes a mucous-like consistency with a high tendency to gel. In addition, the extremely long chains are quite :
sensitive to shearing forces and must be stirred under .
" very low sheari~g conditions in order to minimize mechanical degradation. The procedure for dissolving these resins may be found in Bulletin numbered F 42993 of May, 1970 published by the Union Carbide Corporation and ~ .
;~ entitled, "How to Dissolve Polyox Water-Soluble Resins."
The following examples illustrate the invention:
Example 1 , .~.
Redistilled calcium turnings are added to liquid anhydrous ammonia in a ~essel which is maintained at atmospheric pressure and about minus 33.5~C. The molar ratio of ammonia to calcium is noted below. The vessel ~ is previously swept with nitrogen and a nitrogen atmosphere maintained. Agitation is used throughout the procedure.
A solution is formed, which takes on a blue color. The ~odifiers; propylene oxide and acetonitrile, are then added and the blue color changes to gray and a slurry is formed. The molar ratio of calcium to modifiely is 1~
." ' . 'I
'.. ', I
~ I ~929 !9 and the molar ratio of propylene oxide to acetonitrile is 3:2. A~onia is stripped off at temperatures up to 96C for about 3 hours and the solid is either unaged, aged in the dry state, or slurried with a high boiler and aged before use in the polymerization.
Aging is accomplished at a certain temperature for a certain number of hours hereinafter noted. :
Tbe polymerization is typical of the conventional polymerizations used for olefin oxides. It is carried out in a stirred reactor by charging the dry catalyst or catalyst slurry. The monomer, ethylene oxide, is fed on demand so as to maintain a 31C reaction temperature.
Heat exchange is controlled by reflux cooling of the diluent and the system is continuously purged with ; nitrogen. The reaction is carried out for a certain length of time, noted below, after which the slurry is centrifuged and the resin product is dried. The polymer is treated with C02 to minimize polymer degradation and with 0.5 percent anhydrous and particulate colloidal silica to inhibit agglomeration. About 8 per-cent by weight concentration of monomer is maintained throughout the polymerization. The productivity is measured by determining the number of parts by weight of polymer product per part by weight of calcium present in the catalyst. The solution viscosity is given in CPS and based on a one percent solution at 25CC as discussed .
'.
above using a Broo~field Viscometer RVF 2/2.
Variables and results in this example l are as follows:
. . .
~ (a) The high boiler is dodecane.
; (b) The molar ratio of ammonia to calcium is 100:1.
(c) Aging temperature: 200C
(d) Slurry used in aging and polymerization.
:, :', ` (e) Polymerization time: 1 hour.
(f) A catalyst is prepared and four samples are ; .:
- 10 used, one in each of four polymerizations. Aging times ..:-.~
- and productivities are as follows:
Sample Aging Time Productivity 1 , unaged 187
2 1 hour 250
3 2 hours 421
4 3 hours 436 Example 2 Example 1 is repeated except as follows:
(a) No organic diluent is used. .
(b) The molar ratio of ammonia to calcium is 50:1.
(c) Aging temperature: see below.
(d) Dry solid used in aging and polymerization.
(f) Two catalysts are prepared to provide three ~
samples each; one sample is ~sed in each of six polymeriza-tions. Aging time is one hour. Aging temperatures and productivities are as ollows.
.
." l . ~
~ ~9929 4~9 First Catalyst ~ Sample Aging Temperature C Productivity .. ;
1 unaged 259 - Second Catalyst 1 unaged 250 . 2 200 432 Example 3 ` Example 2 is repeated except as follows:
(a) The high boiler is dodecane except as noted below.
(d) Slurry is used in aging and polymerization except as noted below.
(f) A catalyst is prepared and five samples are used, one in each of five polymerizations. Aging time is three hours. Aging temperatures and productivities are as follows:
Sam~le Agin~ Temperature C Productivity 1 unaged 303 4 217 ~ 743 250 (dry solid) 44 .
; -14-, ' i, ,'~
~ ~ 999 .:.. .
....
Example 4 F~ample 3 is repeated except as follows:
(c) Aging temperature: 200C.
(f) Four catalysts are prepared to provide two samples each for the first two polymerizations and three ~ samples each for the second two polymerizations. Aging : times and productivities are as follows:
- First Catalyst ~ Sample A~inR TimeProductivity - 1 unaged 259 2 2 hours 44Z
Second Catalyst 1 unaged 250 2 2 hours 432 Third Catalyst 1 unaged 154 2 ~ne hour (dry solid) 221 3 one hour 244 Fourth Catalyst 1 unaged 303 2 ~ne hour 492 3 three hours 558 - Example 5 . . -Example 1 is repeated except as follows:
(e) Polymerization time: see below.
(f) A catalyst is prepared and two samples are -15- .
:` ~
.
~ ! 9929 ' used, one in each of two p~lymerizations. Aging time is 3 hours for both samples. Polymerization times, i . !
productivities and solution vi~cosities follow: l . . .
Sample Polymerization Time Prod-~ctivity Solution Viscosity , .
1 1 532 12,500 2 6 1917 16,360 ,; -, Example 6 Example 2 is repeated except as follows:
(a) Same except as noted below.
(c) Aging temperature: 200C.
(d) Same except as noted below.
(e) Polymerization times noted below.
(f) ~our catalysts are prepared to provide eight samples, one for each polymerization. Aging times, .
~ polymerization times, and solution viscosities are as ~
-; follows:
First Catalyst Solution Sample Aging Time Polymerization Time Viscosity 1 ur.aged ~ hour 3720 6 hours 6000 2 1 hour 1 hour 9540 6 hours^ 17,700 Second Catalyst -; 1 unaged 1 hour 1720 6 hours 3380 : 2 1 hour 1 hour 4880 6 hours 8340 . . .
j -16-' . -' ( ' , 992~ 1 11114~9 .'. . , Third Catalyst*
:
1 unaged 1 hour 4080 ~i 6 hours 7980 .~ .
2 three hours 1 hour 10,120 3 1/2 hours 16,180 Fourth Catalyst*
1 unaged 6 hours 10,700 . ~
~' 2 three hours 6 hours 16,040 *Aging and polymerization conducted with dodecane slurry.
Example 7 Example 3 is repeated except as follows:
' (a) The high boiler is a mixture of C13 and C14 ,~ straight chain saturated hydrocarbons boiling in the range of about 230~C (the C13 - C14 mixture is first dried ' over molecular sieves and purged with nitrogen).
(c) Aging temperature: 215C.
,~ , (f) A catalyst, is prepared and three samples are used, one in ea~h of three polymerizations. Aging times, , polymerization times, productivities, and solution .,.
' '0 viscosities are as follows:
' Solution Sample A~ing Time Polym2riz2.ion Times Prod~ctivity ~ SitY ;
1 unaged 1 hour 225 ~ ,¦
' 6 hours 588 8,930 2 three hours 1 hour 625 _ '~
; 6 hours 1838 16 ,ooa 3 two cycles of 1 hour 275 _ three hours each for a ~,1 , total of six hours 14~9 .'''- ' . I
Example 8 Example 7 is repeated except as follows:
(c) Aging temperature: 200C.
(f) Aging time: 3 hours. A catalyst is prepared and samples used in three polymerizations. The poly-merization time is 6.5 hours. The combined productivity is 13~8 parts by weight of polymer per part by weight of calciu.~ and the solution viscosity is 14,6~0. The screen classification of resin particle sizes is as follows:
Mesh Size Percent Passing through screen 99.OO
95.50 - 60 81.40 77.60 100 9.13 :"
Note: the small particle size over conventional operations is considered an advantage in certain applications.
E~ample 9 Example 7 is repeated except as follows:
~- (f) A catalyst is prepared and used in a poly-merization. Aging time, polymerization times, and solution viscosity are as follows:
Aging Time Polymerization Tlme Productivity Solution Viscosit~
three hours 1 hour 680 6 hours 1755 15,600 .~ ' ' , , .
,., I
'................................................................... I
, , ,~ ;
, J , " "' `` ~11~4~9 .
Example 10 Ex~mple 1 is repeated except as follows:
(f) Three catalysts are prepared substituting for the acetonitrile modifier, the modifier noted below.
Aging time is one hour. Modifiers and productivities are as follows:
Modifier Productivity P~oductivity (unaged) benzonitrile 43 321 - ortho-toluenenitrile 60 394 trimethylacetonitrile 167 193 (no acidic hydrogen) Example 11 Example 3 is repeated except as follows:
(a) Hexadecane is used instead of dodecane.
(f) A catalyst is prepared and six samples are used, one in each of six polymerizations. Aging time is one hour. Aging temperatures, productivitie~s, and solution viscosities are as follows:
Sample Aging Temperature C Productivity Solùtion Viscosity ~ 1 unaged - 3080 ; 2 150 - 4200 217 686 10,060 ., I ' 1.
' :
(a) No organic diluent is used. .
(b) The molar ratio of ammonia to calcium is 50:1.
(c) Aging temperature: see below.
(d) Dry solid used in aging and polymerization.
(f) Two catalysts are prepared to provide three ~
samples each; one sample is ~sed in each of six polymeriza-tions. Aging time is one hour. Aging temperatures and productivities are as ollows.
.
." l . ~
~ ~9929 4~9 First Catalyst ~ Sample Aging Temperature C Productivity .. ;
1 unaged 259 - Second Catalyst 1 unaged 250 . 2 200 432 Example 3 ` Example 2 is repeated except as follows:
(a) The high boiler is dodecane except as noted below.
(d) Slurry is used in aging and polymerization except as noted below.
(f) A catalyst is prepared and five samples are used, one in each of five polymerizations. Aging time is three hours. Aging temperatures and productivities are as follows:
Sam~le Agin~ Temperature C Productivity 1 unaged 303 4 217 ~ 743 250 (dry solid) 44 .
; -14-, ' i, ,'~
~ ~ 999 .:.. .
....
Example 4 F~ample 3 is repeated except as follows:
(c) Aging temperature: 200C.
(f) Four catalysts are prepared to provide two samples each for the first two polymerizations and three ~ samples each for the second two polymerizations. Aging : times and productivities are as follows:
- First Catalyst ~ Sample A~inR TimeProductivity - 1 unaged 259 2 2 hours 44Z
Second Catalyst 1 unaged 250 2 2 hours 432 Third Catalyst 1 unaged 154 2 ~ne hour (dry solid) 221 3 one hour 244 Fourth Catalyst 1 unaged 303 2 ~ne hour 492 3 three hours 558 - Example 5 . . -Example 1 is repeated except as follows:
(e) Polymerization time: see below.
(f) A catalyst is prepared and two samples are -15- .
:` ~
.
~ ! 9929 ' used, one in each of two p~lymerizations. Aging time is 3 hours for both samples. Polymerization times, i . !
productivities and solution vi~cosities follow: l . . .
Sample Polymerization Time Prod-~ctivity Solution Viscosity , .
1 1 532 12,500 2 6 1917 16,360 ,; -, Example 6 Example 2 is repeated except as follows:
(a) Same except as noted below.
(c) Aging temperature: 200C.
(d) Same except as noted below.
(e) Polymerization times noted below.
(f) ~our catalysts are prepared to provide eight samples, one for each polymerization. Aging times, .
~ polymerization times, and solution viscosities are as ~
-; follows:
First Catalyst Solution Sample Aging Time Polymerization Time Viscosity 1 ur.aged ~ hour 3720 6 hours 6000 2 1 hour 1 hour 9540 6 hours^ 17,700 Second Catalyst -; 1 unaged 1 hour 1720 6 hours 3380 : 2 1 hour 1 hour 4880 6 hours 8340 . . .
j -16-' . -' ( ' , 992~ 1 11114~9 .'. . , Third Catalyst*
:
1 unaged 1 hour 4080 ~i 6 hours 7980 .~ .
2 three hours 1 hour 10,120 3 1/2 hours 16,180 Fourth Catalyst*
1 unaged 6 hours 10,700 . ~
~' 2 three hours 6 hours 16,040 *Aging and polymerization conducted with dodecane slurry.
Example 7 Example 3 is repeated except as follows:
' (a) The high boiler is a mixture of C13 and C14 ,~ straight chain saturated hydrocarbons boiling in the range of about 230~C (the C13 - C14 mixture is first dried ' over molecular sieves and purged with nitrogen).
(c) Aging temperature: 215C.
,~ , (f) A catalyst, is prepared and three samples are used, one in ea~h of three polymerizations. Aging times, , polymerization times, productivities, and solution .,.
' '0 viscosities are as follows:
' Solution Sample A~ing Time Polym2riz2.ion Times Prod~ctivity ~ SitY ;
1 unaged 1 hour 225 ~ ,¦
' 6 hours 588 8,930 2 three hours 1 hour 625 _ '~
; 6 hours 1838 16 ,ooa 3 two cycles of 1 hour 275 _ three hours each for a ~,1 , total of six hours 14~9 .'''- ' . I
Example 8 Example 7 is repeated except as follows:
(c) Aging temperature: 200C.
(f) Aging time: 3 hours. A catalyst is prepared and samples used in three polymerizations. The poly-merization time is 6.5 hours. The combined productivity is 13~8 parts by weight of polymer per part by weight of calciu.~ and the solution viscosity is 14,6~0. The screen classification of resin particle sizes is as follows:
Mesh Size Percent Passing through screen 99.OO
95.50 - 60 81.40 77.60 100 9.13 :"
Note: the small particle size over conventional operations is considered an advantage in certain applications.
E~ample 9 Example 7 is repeated except as follows:
~- (f) A catalyst is prepared and used in a poly-merization. Aging time, polymerization times, and solution viscosity are as follows:
Aging Time Polymerization Tlme Productivity Solution Viscosit~
three hours 1 hour 680 6 hours 1755 15,600 .~ ' ' , , .
,., I
'................................................................... I
, , ,~ ;
, J , " "' `` ~11~4~9 .
Example 10 Ex~mple 1 is repeated except as follows:
(f) Three catalysts are prepared substituting for the acetonitrile modifier, the modifier noted below.
Aging time is one hour. Modifiers and productivities are as follows:
Modifier Productivity P~oductivity (unaged) benzonitrile 43 321 - ortho-toluenenitrile 60 394 trimethylacetonitrile 167 193 (no acidic hydrogen) Example 11 Example 3 is repeated except as follows:
(a) Hexadecane is used instead of dodecane.
(f) A catalyst is prepared and six samples are used, one in each of six polymerizations. Aging time is one hour. Aging temperatures, productivitie~s, and solution viscosities are as follows:
Sample Aging Temperature C Productivity Solùtion Viscosity ~ 1 unaged - 3080 ; 2 150 - 4200 217 686 10,060 ., I ' 1.
' :
Claims (11)
1. In a process for the preparation of an olefin oxide polymerization catalyst comprising:
(i) admixing calcium, ammonia, and alkylene oxide modifier and an organic nitrile modifier, the alkylene oxide consisting of carbon, .
hydrogen, and oxirane oxygen atoms and the organic nitrile consisting of carbon, nitrogen, and hydrogen atoms, at least one hydrogen atom being acidic, to form a slurry of modified calcium hexammine in ammonia; and (ii) evaporating ammonia to provide a solid residue, the improvement comprising:
aging the solid residue at a temperature in the range of about 150°C to about 225°C.
(i) admixing calcium, ammonia, and alkylene oxide modifier and an organic nitrile modifier, the alkylene oxide consisting of carbon, .
hydrogen, and oxirane oxygen atoms and the organic nitrile consisting of carbon, nitrogen, and hydrogen atoms, at least one hydrogen atom being acidic, to form a slurry of modified calcium hexammine in ammonia; and (ii) evaporating ammonia to provide a solid residue, the improvement comprising:
aging the solid residue at a temperature in the range of about 150°C to about 225°C.
2. The process of claim 1 wherein an organ-ic diluent is used to provide a slurry of the solid residue and the slurry is aged.
3. The process defined in claim 2 wherein the aging time is about 1 to about 3 hours.
4. A catalyst for the preparation of an olefin oxide polymer wherein said catalyst is prepared by:
(i) admixing calcium, ammonia, an alkylene oxide modifier and an organic nitrile modifier, the alkylene oxide consisting of carbon, hydrogen, and 20.
oxirane oxygen atoms and the organic nitrile consisting of carbon, nitrogen, and hydrogen atoms, at least one hydrogen atom being acidic, to form a slurry of modi-fied calcium hexammine in ammonia;
(ii) evaporating ammonia to provide a solid residue; and (iii) aging the solid residue at a temperature in the range of about 150°C to about 225°C.
(i) admixing calcium, ammonia, an alkylene oxide modifier and an organic nitrile modifier, the alkylene oxide consisting of carbon, hydrogen, and 20.
oxirane oxygen atoms and the organic nitrile consisting of carbon, nitrogen, and hydrogen atoms, at least one hydrogen atom being acidic, to form a slurry of modi-fied calcium hexammine in ammonia;
(ii) evaporating ammonia to provide a solid residue; and (iii) aging the solid residue at a temperature in the range of about 150°C to about 225°C.
5. A catalyst for the preparation of an olefin oxide polymer wherein said catalyst is prepared by:
(i) admixing calcium, ammonia, an alkylene oxide modifier and an organic nitrile modifier, the alkylene oxide consisting of carbon, hydrogen, and oxirane oxygen atoms and the organic nitrile consisting of carbon, nitrogen, and hydrogen atoms, at least one hydrogen atom being acidic, to form a slurry of modified calcium hexammine in ammonia; and (ii) evaporating ammonia to provide a solid residue; and (iii) aging the solid residue at a temper-ature in the range of about 150°C to about 225°C for about 3 hours.
(i) admixing calcium, ammonia, an alkylene oxide modifier and an organic nitrile modifier, the alkylene oxide consisting of carbon, hydrogen, and oxirane oxygen atoms and the organic nitrile consisting of carbon, nitrogen, and hydrogen atoms, at least one hydrogen atom being acidic, to form a slurry of modified calcium hexammine in ammonia; and (ii) evaporating ammonia to provide a solid residue; and (iii) aging the solid residue at a temper-ature in the range of about 150°C to about 225°C for about 3 hours.
6. In a process for the polymerization of olefin oxides, the improvement comprising carrying out the process in the presence of a catalytically active amount of the catalyst defined in claim 4.
21.
21.
7. In a process for the polymerization of olefin oxides, the improvement comprising carrying out the process in the presence of a catalytically active amount of the catalyst defined in claim 5.
8. The process defined in claim 1 wherein the temperature at the lower end of the range is about 200°C,
9. The process defined in claim 3 wherein the temperature at the lower end of the range is about 200°C.
10. A catalyst for the preparation of an olefin oxide polymer wherein said catalyst is prepared by:
(i) admixing calcium, ammonia, an alkylene oxide modifier and an organic nitrile modifier, the alkyl-ene oxide consisting of carbon, hydrogen, and oxirane oxygen atoms and the organic nitrile consisting of carbon, nitrogen, and hydrogen atoms, at least one hydrogen atom being acidic, to form a slurry of modified calcium hex-ammine in ammonia;
(ii) evaporating ammonia to provide a solid residue; and (iii) aging the solid residue at a temper-ature of about 200°C.
(i) admixing calcium, ammonia, an alkylene oxide modifier and an organic nitrile modifier, the alkyl-ene oxide consisting of carbon, hydrogen, and oxirane oxygen atoms and the organic nitrile consisting of carbon, nitrogen, and hydrogen atoms, at least one hydrogen atom being acidic, to form a slurry of modified calcium hex-ammine in ammonia;
(ii) evaporating ammonia to provide a solid residue; and (iii) aging the solid residue at a temper-ature of about 200°C.
11. In a process for the polymerization of olefin oxides, the improvement comprising carrying out the process in the presence of a catalytically active amount of the catalyst defined in claim 10.
22.
22.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US74101376A | 1976-11-11 | 1976-11-11 | |
| US741,013 | 1976-11-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1111409A true CA1111409A (en) | 1981-10-27 |
Family
ID=24979008
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA290,251A Expired CA1111409A (en) | 1976-11-11 | 1977-11-04 | Process for preparing olefin oxide polymerization catalysts |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS5812899B2 (en) |
| BE (1) | BE860694A (en) |
| CA (1) | CA1111409A (en) |
| DE (1) | DE2750208C3 (en) |
| GB (1) | GB1539650A (en) |
| NL (1) | NL7712385A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2861224A1 (en) | 2012-01-30 | 2013-08-08 | Dow Global Technologies Llc | Process for preparing high molecular weight polymers by polymerizing epoxide monomers |
| US20150018514A1 (en) * | 2012-01-30 | 2015-01-15 | Dow Global Technologies Llc | Process for preparing olefin oxide polymerization catalysts |
-
1977
- 1977-11-04 CA CA290,251A patent/CA1111409A/en not_active Expired
- 1977-11-10 DE DE19772750208 patent/DE2750208C3/en not_active Expired
- 1977-11-10 GB GB4686477A patent/GB1539650A/en not_active Expired
- 1977-11-10 BE BE182516A patent/BE860694A/en not_active IP Right Cessation
- 1977-11-10 NL NL7712385A patent/NL7712385A/en not_active Application Discontinuation
- 1977-11-10 JP JP13416677A patent/JPS5812899B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5812899B2 (en) | 1983-03-10 |
| GB1539650A (en) | 1979-01-31 |
| BE860694A (en) | 1978-05-10 |
| DE2750208C3 (en) | 1981-02-26 |
| NL7712385A (en) | 1978-05-16 |
| DE2750208B2 (en) | 1980-06-19 |
| JPS5360998A (en) | 1978-05-31 |
| DE2750208A1 (en) | 1978-05-18 |
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