US3867353A
Expired / Lapsed
US
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Polymerization of oxiranes and lactones
Assignee: Phillips Petroleum Co
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Filing: 1973-01-17
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Granted: 1975-02-18
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Expires: 1993-01-17
Abstract
Abstract Monitored addition of lactone, or of lactone with oxirane or oxetane, to a polymerization mixture containing catalyst and a monohalooxirane, such as epihalohydrin, results in a copolymer of higher ultimate conversion than otherwise obtainable. Preferably, the monitored addition is commenced after the epihalohydrin has polymerized at least to some extent.
Inventors
- 👤 Henry L Hsieh
- 👤 Ollie G Buck
- 👤 Floyd E Naylor
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-29 21:53
CPC Classifications
C; C08; C08G; C08G65/00; C08G65/02; C08G65/26; C08G65/2603; C08G65/2615; C08G63/00; C08G63/78; C08G63/82; C08G63/823; C08G65/04; C08G65/06; C08G65/08; C08G65/10; C08G65/12; C08G65/2642; C08G65/269
Claims Analysis
Total Claims: 18
Claim 1
Independent Claim
187 words
A COPOLYMERIZATION PROCESS WHICH COMPRISES THE STEPS: A. ADMIXING AT LEAST ONE MONOHALOOXIRANE MONOMER OR MONOHALOOXIRANE MONOMER AND A LACTONE AND AN INITIATOR SYSTEM CONSISTING ESSENTIALLY OF (A) (1) AN ORGANOALUMINUM COMPOUND AND (II) WATER OR LOWER ALCOHOL, OR (B) (I) AN ORGANOALUMINUM COMPOUND, (II) WATER OR LOWER ALCOHOL, AND (III) A BETA-KIKETPNE OR METAL SALT OF A BETADIKETONE, B. COMMENCING POLYMERIZATION OF THE ADMIXTURE OF SAID STEP A) UNDER POLYMERIZATION CONDITIONS, C. ADDING THERETO DURING AT LEAST A PORTION OF THE POLYMERIZATIO TION OF SAID STEP (B) A FURTHER MONOMER COMPRISING A LACTONE, A LACTONE AND AN OXIRANE, A LACTONE AND AN OXETANE, OR A LACTONE AND OXIRANE AND OXETANE WHEREIN THE ADDITION OF SAID FURTHER MONOMER IS DELAYED AFTER THE INITIATION OF SAID POLYMERIZATION FOR A TIME OF ABOUT 0.5 TO 120 MINUTES, THEREBY COPOLYMERIZING SAID MONOHALOOXIRANE MONOMER AND SAID FURTHER MONOMER, WHEREIN SAID (1) ORGANOALUMINUM COMPOUND IS REPRESENTED BY RA''ALXB'' WHEREIN A IS AN INTEGER OF 1-3, B IS AN INTEGER AND IS 1 OR 2, SUCH THAT A + B = 3, X'' IS HYDROGEN OR HALOGEN, AND R'' IS A HYDROCARBON RADICAL.
Claim 2
Dependent Claim
187 words
A COPOLYMERIZATION PROCESS WHICH COMPRISES THE STEPS: A. ADMIXING AT LEAST ONE MONOHALOOXIRANE MONOMER OR MONOHALOOXIRANE MONOMER AND A LACTONE AND AN INITIATOR SYSTEM CONSISTING ESSENTIALLY OF (A) (1) AN ORGANOALUMINUM COMPOUND AND (II) WATER OR LOWER ALCOHOL, OR (B) (I) AN ORGANOALUMINUM COMPOUND, (II) WATER OR LOWER ALCOHOL, AND (III) A BETA-KIKETPNE OR METAL SALT OF A BETADIKETONE, B. COMMENCING POLYMERIZATION OF THE ADMIXTURE OF SAID STEP A) UNDER POLYMERIZATION CONDITIONS, C. ADDING THERETO DURING AT LEAST A PORTION OF THE POLYMERIZATIO TION OF SAID STEP (B) A FURTHER MONOMER COMPRISING A LACTONE, A LACTONE AND AN OXIRANE, A LACTONE AND AN OXETANE, OR A LACTONE AND OXIRANE AND OXETANE WHEREIN THE ADDITION OF SAID FURTHER MONOMER IS DELAYED AFTER THE INITIATION OF SAID POLYMERIZATION FOR A TIME OF ABOUT 0.5 TO 120 MINUTES, THEREBY COPOLYMERIZING SAID MONOHALOOXIRANE MONOMER AND SAID FURTHER MONOMER, WHEREIN SAID (1) ORGANOALUMINUM COMPOUND IS REPRESENTED BY RA''ALXB'' WHEREIN A IS AN INTEGER OF 1-3, B IS AN INTEGER AND IS 1 OR 2, SUCH THAT A + B = 3, X'' IS HYDROGEN OR HALOGEN, AND R'' IS A HYDROCARBON RADICAL.
Claim 3
Dependent Claim
15 words
The process according to claim 1 wherein said oxirane and said oxetane are represented by:
Claim 4
Dependent Claim
12 words
The process according to claim 1 wherein said monohalooxirane is represented by:
Claim 5
Dependent Claim
12 words
The process according to claim 1 wherein said lactone is represented by:
Claim 6
Dependent Claim
34 words
The process according to claim 1 wherein said admixture of said initiator system and said monohalooxirane monomer further contains an oxirane or oxetane, and said lactone monomer is added thereto in said step (c).
Claim 7
Dependent Claim
34 words
The process according to claim 1 wherein in said step (c) said lactone monomer is added during the polymerization of said monohalooxirane by monitored addition which is in discrete periodic addItions, or substantially continuously.
Claim 8
Dependent Claim
50 words
The process according to claim 6 wherein the lactone portion of the monomers employed represents 0.5 to 95 parts, and the oxirane and monohalooxirane together correspondingly represent 95.5 to 5 parts, and wherein of the total of 100 parts oxirane and halooxirane, the halooxirane represents from 25 to 75 parts.
Claim 9
Dependent Claim
13 words
The process according to claim 7 wherein said catalyst system is said (B).
Claim 10
Dependent Claim
36 words
The process of claim 8 wherein said (III) is said metal salt of a beta-diketone wherein the metal employed therein is a metal of Group IIA, IIIA, IVA, IB, IIB, IVB, VA, VIB, VIIB, or VIII.
Claim 11
Dependent Claim
17 words
The process according to claim 9 wherein said metal salt of a beta-diketone can be represented by:
Claim 12
Dependent Claim
48 words
The process according to claim 9 wherein said metal is beryllium, magnesium, calcium, strontium, barium; boron, aluminum, gallium, indium, thallium; silicon, germanium, tin, lead; copper, silver; zinc, cadmium, mercury; titanium, zirconium, vanadium, niobium, tantalum; chromium, molybdenum, tungsten; manganese; iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum.
Claim 13
Dependent Claim
72 words
The process according to claim 8 wherein said catalyst is employed in an amount sufficient to provide about 1 to 100 gram millimoles of organoaluminum compound per 100 grams of total monomer employed, and wherein the amount of beta-diketone:organoaluminum compound is in the range of from 0.01:1 to 0.5:1, and the amount of water or lower alcohol is in the range of about 0.02 to 1.6 moles per mole of organoaluminum compound.
Claim 14
Dependent Claim
52 words
The process according to claim 12 wherein said copolymerization is conducted at temperatures in the range of about 5* C. to 150* C., the polymerization pressure is sufficient to maintain reactants substantially in the liquid phase, and said copolymerization is conducted in a hydrocarbon or halogenated hydrocarbon or ether or mixture diluent.
Claim 15
Dependent Claim
12 words
The process according to claim 13 wherein said monohalooxirane is an epihalohydrin.
Claim 16
Dependent Claim
25 words
The process according to claim 14 wherein said lactone is epsilon-caprolactone, said halooxirane is epichlorohydrin, and said catalyst system comprises triisobutylaluminum, zinc acetylacetonate, and water.
Claim 17
Dependent Claim
33 words
The process according to claim 14 wherein said halooxirane is epichlorohydrin, said lactone is epsilon-caprolactone, and said oxirane is propylene oxide or 2,2-di(chloromethyl)oxetane, and said catalyst system comprises triisobutylaluminum, zinc acetylacetonate, and water.
Claim 18
Dependent Claim
20 words
The process according to claim 8 wherein in said copolymerization process further employs a catalyst activator which is an ether.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1978-02-17 | 1978-08-19 | 1979-02-18 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1982-02-17 | 1982-08-19 | 1983-02-18 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1986-02-17 | 1986-08-19 | 1987-02-18 | $7700.00 | Window Closed / Lapsed |