US4714731A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Metal container coating compositions comprising stable emulsions of water resistant polyvinyl alcohol-stabilized vinyl chloride-ethylene copolymers
Assignee: Air Products and Chemicals Inc
•
Filing: 1987-03-13
•
Granted: 1987-12-22
•
Expires: 2007-03-13
Abstract
Abstract A metal container coating composition comprising a crosslinking resin and an aqueous polyvinyl alcohol/vinyl chloride-ethylene copolymer emulsion, the copolymer having a Tg from 0° to 50° C., about 65 to 90 wt % vinyl chloride, about 5 to 35 wt % ethylene, 0 to 10 wt % olefinically unsaturated copolymerizable monomer and prepared by emulsion polymerization of vinyl chloride, ethylene and, optionally, an olefinically unsaturated comonomer in the presence of 3 to 15 wt % polyvinyl alcohol as the dispersing agent. Also a method for preparing such stable vinyl chloride based resin emulsions comprising (a) forming an aqueous emulsion reaction mixture containing substantially all the polyvinyl alcohol and a portion, preferably at least 5%, of the total vinyl chloride monomer, (b) pressurizing the reaction mixture with an ethylene pressure sufficient to provide the copolymer with a 5 to 35 wt % ethylene content, (c) initiating the reaction mixture by the addition of a free radical generating source and continuing polymerization until the rate of polymerization begins to decrease to provide a prepolymer emulsion, and (d) adding the remaining vinyl chloride at a substantially uniform rate and continuing polymerization until the polymerization reaction is no longer self-sustaining, ethylene being neither withdrawn nor added during the polymerization in one embodiment.
Inventors
- 👤 John G. Iacoviello
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-07 20:57
CPC Classifications
C; C08; C08F; C08F214/00; C08F214/02; C08F214/04; C08F214/06; C09; C09D; C09D127/00; C09D127/02; C09D127/04; C09D127/06
Claims Analysis
Total Claims: 20
Claim 1
Independent Claim
259 words
A metal container coating composition comprising (a) about 45 to 95 wt % of a stable aqueous vinyl chlorideethylene copolymer emulsion, the copolymer having a T g from 0° to 50° C., consisting essentially of about 65 to 90 wt % vinyl chloride, about 5 to 35 wt % ethylene, and up to about 10 wt % C 3 -C 10 alkenoic acid or nitrogen-containing comonomer, provided that when the nitrogen-containing comonomer is acrylamide up to about 1 wt % is present, and prepared by the emulsion polymerization of the monomers in the presence of an an emulsifying system consisting essentially of about 3 to 15 wt % polyvinyl alcohol which is 70 to 91 mole % hydrolyzed, which emulsion polmerization process comprises forming an aqueous emulsion reaction mixture containing substantially all the polyvinyl alcohol and a portion of the total vinyl chloride monomer, pressurizing the reaction mixture with an ethylene pressure sufficient to provide the copolymer with a 5 to 35 wt % ethylene content, initiating the reaction mixture by the addition of a free radical generating source and continuing polymerization until the rate of polymerization begins to decrease, adding the remaining vinyl chloride over a period of time while continuing polymerization until the reaction is no longer self-sustaining, and removing the unreacted ethylene and reducing the vinyl chloride free monomer content of the emulsion, (b) about 5 to 40 wt % of a crosslinking resin, based on emulsion solids, (c) up to about 10 wt % organic solvent, and (d) 0 to 5 wt % acid catalyst.
Claim 2
Dependent Claim
259 words
A metal container coating composition comprising (a) about 45 to 95 wt % of a stable aqueous vinyl chlorideethylene copolymer emulsion, the copolymer having a T g from 0° to 50° C., consisting essentially of about 65 to 90 wt % vinyl chloride, about 5 to 35 wt % ethylene, and up to about 10 wt % C 3 -C 10 alkenoic acid or nitrogen-containing comonomer, provided that when the nitrogen-containing comonomer is acrylamide up to about 1 wt % is present, and prepared by the emulsion polymerization of the monomers in the presence of an an emulsifying system consisting essentially of about 3 to 15 wt % polyvinyl alcohol which is 70 to 91 mole % hydrolyzed, which emulsion polmerization process comprises forming an aqueous emulsion reaction mixture containing substantially all the polyvinyl alcohol and a portion of the total vinyl chloride monomer, pressurizing the reaction mixture with an ethylene pressure sufficient to provide the copolymer with a 5 to 35 wt % ethylene content, initiating the reaction mixture by the addition of a free radical generating source and continuing polymerization until the rate of polymerization begins to decrease, adding the remaining vinyl chloride over a period of time while continuing polymerization until the reaction is no longer self-sustaining, and removing the unreacted ethylene and reducing the vinyl chloride free monomer content of the emulsion, (b) about 5 to 40 wt % of a crosslinking resin, based on emulsion solids, (c) up to about 10 wt % organic solvent, and (d) 0 to 5 wt % acid catalyst.
Claim 3
Dependent Claim
22 words
The metal container coating composition of claim 1 in which the copolymer is about 1 to 5 wt % alkenoic acid comonomer.
Claim 4
Dependent Claim
37 words
The metal container coating composition of claim 2 in which the copolymer is prepared by emulison polymerization in the presence of about 4 to 10 wt % polyvinyl alcohol which is 85 to 89 mole % hydrolyzed.
Claim 5
Dependent Claim
16 words
The metal container coating composition of claim 3 in which the alkenoic acid is acrylic acid.
Claim 6
Dependent Claim
32 words
The metal container coating composition of claim 4 in which the copolymer is about 75 to 80 wt % vinyl chloride and has a T g of about 20° to 35° C.
Claim 7
Dependent Claim
21 words
The metal container coating composition of claim 1 in which the copolymer is about 1 to 5 wt % nitrogen-containing comonomer.
Claim 8
Dependent Claim
37 words
The metal container coating composition of claim 6 in which the copolymer is prepared by emulsion polymerization in the presence of about 4 to 10 wt % polyvinyl alcohol which is 85 to 89 mole % hydrolyzed.
Claim 9
Dependent Claim
18 words
The metal container coating composition of claim 7 in which the nitrogen-containing monomer is acrylamide or N-isobutoxymethyl acrylamide.
Claim 10
Dependent Claim
32 words
The metal container coating composition of claim 8 in which the copolymer is about 75 to 80 wt % vinyl chloride and has a T g of about 20° to 35° C.
Claim 11
Dependent Claim
256 words
A metal container coating composition comprising: (a) about 45 to 95 wt % of a stable aqueous vinyl chlorideethylene copolymer emulsion, the copolymer having a T g from 0° to 50° C., about 65 to 90 wt % vinyl chloride, about 5 to 35 wt % ethylene, about 1 to less than about 5 wt % olefinically unsaturated copolymerizable monomer, provided that when the copolymerizable monomer is acrylamide about 1 wt % is present, and prepared by emulsion polymerization of vinyl chloride monomer, ethylene and the olefinically unsaturated comonomer, in the presence of an emulsifying system consisting essentially of about 3 to 15 wt % polyvinyl alcohol which is 70 to 91 mole % hydrolyzed, the emulsion polymerization process comprising forming an aqueuos emulsion reaction mixture containing substantially all the polyvinyl alcohol and a portion of the total vinyl chloride monomer, pressurizing the reaction mixture with an ethylene pressure sufficient to provide the copolymer with a 5 to 35 wt % ethylene content, initiating the reaction mixture by the addition of a free radical generating source and continuing polymerization until the rate of polymerization begins to decrease, adding the remaining vinyl chloride over a period of time while continuing polymerization until the reaction is no longer self-sustaining, and removing the unreacted ethylene and reducing the vinyl chloride free monomer content of the emulsion, (b) about 5 to 40 wt %, based on emulsion solids, of a crosslinking resin, (c) up to about 10 wt % organic cosolvent, and (d) 0 to 5 wt % acid catlyst.
Claim 12
Dependent Claim
256 words
A metal container coating composition comprising: (a) about 45 to 95 wt % of a stable aqueous vinyl chlorideethylene copolymer emulsion, the copolymer having a T g from 0° to 50° C., about 65 to 90 wt % vinyl chloride, about 5 to 35 wt % ethylene, about 1 to less than about 5 wt % olefinically unsaturated copolymerizable monomer, provided that when the copolymerizable monomer is acrylamide about 1 wt % is present, and prepared by emulsion polymerization of vinyl chloride monomer, ethylene and the olefinically unsaturated comonomer, in the presence of an emulsifying system consisting essentially of about 3 to 15 wt % polyvinyl alcohol which is 70 to 91 mole % hydrolyzed, the emulsion polymerization process comprising forming an aqueuos emulsion reaction mixture containing substantially all the polyvinyl alcohol and a portion of the total vinyl chloride monomer, pressurizing the reaction mixture with an ethylene pressure sufficient to provide the copolymer with a 5 to 35 wt % ethylene content, initiating the reaction mixture by the addition of a free radical generating source and continuing polymerization until the rate of polymerization begins to decrease, adding the remaining vinyl chloride over a period of time while continuing polymerization until the reaction is no longer self-sustaining, and removing the unreacted ethylene and reducing the vinyl chloride free monomer content of the emulsion, (b) about 5 to 40 wt %, based on emulsion solids, of a crosslinking resin, (c) up to about 10 wt % organic cosolvent, and (d) 0 to 5 wt % acid catlyst.
Claim 13
Dependent Claim
30 words
The metal container coating composition of claim 10 in which the emulsion polymerization is performed in the presence of a polyvinyl alcohol which is 85 to 89 mole % hydrolyzed.
Claim 14
Dependent Claim
17 words
The metal container coating composition of claim 11 in which the olefinically unsaturated comonomer is vinyl acetate.
Claim 15
Dependent Claim
34 words
The metal container coating composition of claim 1 in which the emulsion polymeriztion is performed using a free radical generating source comprising hydrogen peroxide and ascorbic acid or erythorbic acid as the redox system.
Claim 16
Dependent Claim
34 words
The metal container coating composition of claim 10 in which the emulsion polymerization is performed using a free radical generating source comprising hydrogen peroxide and ascorbic acid or erythorbic acid as the redox system.
Claim 17
Dependent Claim
28 words
The metal container coating composition of claim 1 in which the copolymer is prepared by emulsion polymerization in the presence of an 87-89 mole % hydrolyzed polyvinyl alcohol.
Claim 18
Dependent Claim
28 words
The metal container coating composition of claim 5 in which the copolymer is prepared by emulsion polymerization in the presence of an 87-89 mole % hydrolyzed polyvinyl alcohol.
Claim 19
Dependent Claim
28 words
The metal container coating composition of claim 9 in which the copolymer is prepared by emulsion polyerization in the presence of an 87-89 mole % hydrolyzed polyvinyl alcohol.
Claim 20
Dependent Claim
28 words
The metal container coating composition of claim 10 in which the copolymer is prepared by emulsion polymerization in the presence of an 87-89 mole % hydrolyzed polyvinyl alcohol.
References Cited (Backward Citations)
US2771457A
Cited
US2843562A
Cited
US3403137A
Cited
US3399157A
Cited
US3501440A
Cited
US3642740A
Cited
US3736303A
Cited
US3725367A
Cited
US3875130A
Cited
US3689447A
Cited
US3830761A
Cited
US3895167A
Cited
US4133791A
Cited
US4189415A
Cited
US4150210A
Cited
US4331577A
Cited
EP0076511A2
Cited
US4528315A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1990-12-21 | 1991-06-22 | 1991-12-22 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1994-12-21 | 1995-06-22 | 1995-12-22 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1998-12-21 | 1999-06-22 | 1999-12-22 | $7700.00 | Window Closed / Lapsed |