IP Library Granted Patent US 9,598,536
Granted Patent B2
US 9,598,536 · App. 14/371,184 · Granted Mar 21, 2017

Process for preparing high molecular weight polymers by polymerizing epoxide monomers

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Quick Facts
Patent No.
US 9,598,536
App. No.
14/371,184
Granted
Mar 21, 2017
Kind
B2
Abstract

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 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; and a polymer obtainable by this process.

Claims (23)

1. A process for polymerizing ethylene oxide comprising carrying out the process in the presence of a catalytically active amount of a catalyst, wherein the catalyst is obtained 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 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, and

wherein an ethylene oxide polymer having a 1% aqueous solution viscosity of greater than 20,000 mPa·s at 25° C. is produced.

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

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

4. The process of claim 1 wherein during preparation of the catalyst a C 12 to C 19 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.

5. The process of claim 1 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 vessel.

6. The process of claim 1 wherein the catalyst is obtained by a preparation process comprising:

(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 metal hexammine dissolved in liquid ammonia;

(2a) continuously transferring the alkaline earth metal 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 metal hexammine in liquid ammonia;

(3a) continuously transferring the slurry of modified alkaline earth metal hexammine in liquid ammonia into the stripper vessel and

(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 polymerization catalyst.

7. The process of claim 1 wherein the alkaline earth metal used in the preparation of the catalyst is calcium.

8. The process of claim 1 wherein the alkylene oxide used in the preparation of the catalyst is propylene oxide.

9. The process of claim 1 wherein the organic nitrile used in the preparation of the catalyst is acetonitrile.

10. The process of claim 1 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.

11. The process of claim 1 wherein the catalyst is present in an amount corresponding to 0.0010 to 0.0017 g of alkaline earth metal per g of epoxide monomer.

Assignments (7)
CHANGE OF LEGAL ENTITY Recorded Nov 28, 2020
From: DDP SPECIALTY ELECTRONIC MATERIALS US, INC.
To: DDP SPECIALTY ELECTRONIC MATERIALS US, LLC.
Reel/Frame 054530/0384 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 28, 2020
From: DOW GLOBAL TECHNOLOGIES LLC
To: THE DOW CHEMICAL COMPANY
Reel/Frame 054531/0001 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 28, 2020
From: THE DOW CHEMICAL COMPANY
To: DDP SPECIALTY ELECTRONIC MATERIALS US, INC.
Reel/Frame 054533/0001 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 28, 2020
From: DDP SPECIALTY ELECTRONIC MATERIALS US, LLC.
To: NUTRITION & BIOSCIENCES USA 1, LLC
Reel/Frame 054533/0575 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 26, 2017
From: UNION CARBIDE CHEMICALS & PLASTICS TECHNOLOGY LLC
To: DOW GLOBAL TECHNOLOGIES LLC
Reel/Frame 041095/0380 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 26, 2017
From: SIMMS, JOHN R
To: DOW GLOBAL TECHNOLOGIES LLC
Reel/Frame 041095/0573 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 26, 2017
From: KENNEY, JOHN M; LANDON, ROBERT S; HIPPLER, JEFFREY G
To: UNION CARBIDE CHEMICALS & PLASTICS TECHNOLOGY LLC
Reel/Frame 041095/0107 →