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US4397970A
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US
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Process for epoxy phosphate coating resins
Assignee: Dow Chemical Co
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Filing: 1981-11-13
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Granted: 1983-08-09
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Expires: 2001-11-13
Abstract
Abstract The invention is an improved process for preparing epoxy resin/phosphoric acid reaction products having high enough phosphomonoester contents to be water-dispersible (as base salts) and low enough free acid contents to yield water-resistant cured coatings. The phosphoric acid is provided as an acid source material deriveable by the reaction of a hydroxylic P--OH functionality-limiting agent (blocking agent) with phosphoric anhydride as such or as a reaction product thereof with less than six molecular proportions of water. A resin solvent, which may also function as the P--OH blocking agent but otherwise is inert and acceptable as part of the final coating resin formulation, is employed as the reaction medium. The epoxide/acid reaction is allowed to proceed, effectively in the absence of water, until the content in the reaction mixture of species indistinguishable from H 3 PO 4 by base-titration has dropped to a minimum. Then enough water to hydrolyze the phosphopolyesters present is added and the hydrolysis is carried out, thereby cleaving the ester groups formed from the blocking agent and generating the P--OH groups needed for salification. The disclosed resin compositions are of particular utility for coating the interiors of beverage cans.
Inventors
- 👤 Kent D. Campbell
- 👤 Horst G. Langer
- 👤 Patrick H. Martin
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-31 02:20
CPC Classifications
C; C08; C08G; C08G59/00; C08G59/14; C08G59/1405; C08G59/1422; C08G59/1427; C08G59/18; C08G59/40; C08G59/4007; C08G59/4071; Y; Y10; Y10T; Y10T428/00; Y10T428/13; Y10T428/1352; Y10T428/1355
Claims Analysis
Total Claims: 23
Claim 1
Independent Claim
207 words
In the process of preparing aqueous coating compositions wherein a polyol, polyether epoxide is reacted with a phosphoric acid source material and water in a reaction medium, the reaction mixture is salified with a base and diluted with water and the reaction medium removed from it, the improvement comprising: (1) employing as said acid source material one deriveable by the reaction of a hydroxylic (P--OH)-blocking agent with (a), P 4 O 10 , (b), a reaction product of P 4 O 10 with less than six molecular proportions of water or (c), an adduct of (b) with some of the oxirane groups in said epoxide, (2) employing as said medium a hydrophilic solvent for said epoxide which is acceptable as a component of said coating composition, (3) phosphorylating said epoxide by reacting P--OH groups in the acid source material--effectively in the absence of free water molecules--with oxirane groups in said epoxide until the content in the reaction mixture of species indistinguishable from H 3 PO 4 by titration drops to a preselected level and then (4) subjecting the resultant reaction product to hydrolysis until the content in the reaction mixture of oxirane-derived phosphomonoester groups rises to a preselected value, and (5) omitting removal of the reaction medium.
Claim 2
Dependent Claim
207 words
In the process of preparing aqueous coating compositions wherein a polyol, polyether epoxide is reacted with a phosphoric acid source material and water in a reaction medium, the reaction mixture is salified with a base and diluted with water and the reaction medium removed from it, the improvement comprising: (1) employing as said acid source material one deriveable by the reaction of a hydroxylic (P--OH)-blocking agent with (a), P 4 O 10 , (b), a reaction product of P 4 O 10 with less than six molecular proportions of water or (c), an adduct of (b) with some of the oxirane groups in said epoxide, (2) employing as said medium a hydrophilic solvent for said epoxide which is acceptable as a component of said coating composition, (3) phosphorylating said epoxide by reacting P--OH groups in the acid source material--effectively in the absence of free water molecules--with oxirane groups in said epoxide until the content in the reaction mixture of species indistinguishable from H 3 PO 4 by titration drops to a preselected level and then (4) subjecting the resultant reaction product to hydrolysis until the content in the reaction mixture of oxirane-derived phosphomonoester groups rises to a preselected value, and (5) omitting removal of the reaction medium.
Claim 3
Dependent Claim
24 words
The process of claim 1 in which said preselected level is the minimum attainable level and said preselected value is the maximum attainable value.
Claim 4
Dependent Claim
160 words
The process of claim 1 in which said epoxide can be represented by either of the following formulas I and II: ##STR14## wherein Q, independently, in each occurrence, is ##STR15## n is an integer of from 0 to 40, r is zero, 1 or 2 and, independently in each occurrence; R 1 is H, methyl or ethyl, R 2 is --Br, --Cl or a C 1 to C 4 alkyl or alkenyl group, R 3 is a C 1 -C 4 alkylene or alkenylene group, >C(CF 3 )2, --CO--, --SO 2 --, --S--, --O-- or a valence bond, R 4 is --Br, --Cl or a C 1 to C 4 alkyl or alkenyl group; and R 5 is H or alkyl of 1 to 12 carbons and the amount of said acid source material employed is such as to provide from about 0.1 to about 0.2 gram atoms of phosphorus per gram equivalent weight of oxirane provided by said epoxide.
Claim 5
Dependent Claim
27 words
The process of claim 3 wherein the epoxide is of formula I and n is from about 12 to 14 and Q is a bisphenol A residue.
Claim 6
Dependent Claim
71 words
The process of claim 1 wherein the blocking agent is phenol, n-butanol or a 2-alkoxyethanol which (1) is capable of reacting with P--O--P groups in said acid source material to form phosphoester groups more readily hydrolyzed than the monoester groups deriveable from the reaction of the oxirane groups in said epoxide with the P--OH groups in the acid source material, and (2) is acceptable as a component of said coating composition.
Claim 7
Dependent Claim
11 words
The process of claim 5 wherein said blocking agent is 2-n-butoxyethanol.
Claim 8
Dependent Claim
16 words
The process of claim 1 wherein the blocking agent and the reaction medium are the same.
Claim 9
Dependent Claim
14 words
The process of claim 7 in which said agent and medium are both 2-n-butoxyethanol.
Claim 10
Dependent Claim
19 words
The process of claim 1 in which said acid source material is pre-formed in the absence of said epoxide.
Claim 11
Dependent Claim
46 words
The process of claim 1 in which said acid source material is formed in-situ by the introduction of P 4 O 10 , or a reaction product thereof with less than six molecular proportions of water, to a solution of said epoxide comprising said blocking agent.
Claim 12
Dependent Claim
24 words
The process of claim 1 wherein said acid source material is a reaction product of said blocking agent with super, pyro- or polyphosphoric acid.
Claim 13
Dependent Claim
15 words
The process of claim 10 in which said reaction product with water is polyphosphoric acid.
Claim 14
Dependent Claim
36 words
The process of claim 4 in which R 1 is H, and said acid source material is formed in-situ by reaction of polyphosphoric with 2-n-butoxyethanol comprised in a solution of said epoxide in said reaction medium.
Claim 15
Dependent Claim
12 words
The process of claim 13 in which said reaction medium is 2-n-butoxyethanol.
Claim 16
Dependent Claim
62 words
The process of claim 14 wherein said phosphorylation is carried out over a period of from about 15 minutes to about 60 minutes at a temperature of from about 145° to about 100° C. and said hydrolysis is carried out over a period of from about 1 hour to about 6 hours at a temperature of from about 130° to about 100°.
Claim 17
Dependent Claim
43 words
The process of claim 15 in which the phosphorylation and hydrolysis are both carried out at about the same temperature, which is within the range of from about 124° to about 126° C., for respective periods of about 0.5 and about two hours.
Claim 18
Dependent Claim
54 words
The process of claim 16 in which said epoxide has an epoxide equivalent weight of about 1800, the weight of said polyphosphoric acid is about 0.8% of the weight of the epoxide and the amount of water added to initiate hydrolysis is from about 1 to about 2% of the weight of said epoxide.
Claim 19
Dependent Claim
11 words
The process of claim 17 in which said base is dimethylaminoethanol.
Claim 20
Dependent Claim
22 words
The process of claim 1 in which said epoxide constitutes from about 60 to about 85 weight percent of the phosphorylation mixture.
Claim 21
Dependent Claim
22 words
The process of claim 18 in which said epoxide constitutes from about 72 to about 76 weight percent of the phosphorylation mixture.
Claim 22
Dependent Claim
11 words
The process of claim 1 wherein said reaction medium is cyclohexanone.
Claim 23
Dependent Claim
11 words
The process of claim 21 wherein said blocking agent is 2-n-butoxyethanol.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1986-08-08 | 1987-02-07 | 1987-08-09 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-08-08 | 1991-02-07 | 1991-08-09 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-08-08 | 1995-02-07 | 1995-08-09 | $7700.00 | Window Closed / Lapsed |