US4387208A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Phosphorous containing polymers as carriers for transition metals
Assignee: United States Department of the Navy
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Filing: 1981-12-21
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Granted: 1983-06-07
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Expires: 2001-12-21
Abstract
Abstract Synthesis of new (lithiophenoxy)phosphazene high polymers is described whin polymers such as poly(dichlorophosphazene) are used as the starting material to prepare poly(organophosphazenes) by reaction thereof with sodium para-bromophenoxide. Poly(organophophazenes) thus obtained are used in a metal-halogen exchange reaction with n-butyllithium. The lithio derivatives thus obtained are used as reactive intermediates for the synthesis of polymers of formulas [NP(OC 6 H 4 X-p) x (OC 6 H 4 Br)y] n and [NP(OC 6 H 4 Li-p) x (OPh) y ] n , where X is PPh 2 , PPh 2 C 4 H 9 + Br - , SnPh 3 , AuPPh 3 , or COOH.
Inventors
- 👤 Harry R. Allcock
- 👤 Timothy J. Fuller
- 👤 Thomas L. Evans
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-26 15:14
CPC Classifications
C; C08; C08G; C08G79/00; C08G79/02; C08G79/025
Claims Analysis
Total Claims: 14
Claim 1
Independent Claim
122 words
A process for synthesizing new high polymers using poly(dichlorophosphazene) as the starting material comprising the steps of: preparing high molecular weight poly-phosphazenes by reacting a solution containing 4.0 g (0.035 mol) of poly(dichlorophosphazene) in 200 mL of dioxane at 25° C. with sodium para-bromophenoxide obtained by adding dropwise bromophenol solution containing 33 g (0.35 mol) bromophenol in 100 mL of dioxane to stirred suspension of 17 g of sodium hydride in 100 mL of dioxane and sodium phenoxide; replacing bromine atoms of said high molecular weight polyphosphazenes by reaction thereof with excess amount of n-butyllithium solution in dioxane to obtain (lithiophenoxy)phosphazenes at temperature between -40° to -60° C.; and reacting said lithiophenoxy phosphazenes with an electrophile to obtain said new high polymer.
Claim 2
Dependent Claim
122 words
A process for synthesizing new high polymers using poly(dichlorophosphazene) as the starting material comprising the steps of: preparing high molecular weight poly-phosphazenes by reacting a solution containing 4.0 g (0.035 mol) of poly(dichlorophosphazene) in 200 mL of dioxane at 25° C. with sodium para-bromophenoxide obtained by adding dropwise bromophenol solution containing 33 g (0.35 mol) bromophenol in 100 mL of dioxane to stirred suspension of 17 g of sodium hydride in 100 mL of dioxane and sodium phenoxide; replacing bromine atoms of said high molecular weight polyphosphazenes by reaction thereof with excess amount of n-butyllithium solution in dioxane to obtain (lithiophenoxy)phosphazenes at temperature between -40° to -60° C.; and reacting said lithiophenoxy phosphazenes with an electrophile to obtain said new high polymer.
Claim 3
Dependent Claim
25 words
The process of claim 2 wherein the step of preparing high molecular weight poly-phosphazenes includes reaction poly(dichlorophosphazene) with a stoichiometric deficient amount of sodium para-bromophenoxide.
Claim 4
Dependent Claim
37 words
The process of claim 2 wherein the step of preparing high molecular weight poly-phosphazenes includes treating of poly (dichlorophosphazenes) with an excess amount of sodium phenoxide after treatment thereof with a stoichiometric deficient amount of sodium para-bromophenoxide.
Claim 5
Dependent Claim
25 words
The process of claim 3 wherein the step of interacting said high molecular weight poly-phosphazenes with n-butylithium uses excess amount of n-butyllithium in dioxane solution.
Claim 6
Dependent Claim
33 words
The process of claim 4 wherein the step of interacting said high molecular weight poly-phosphazenes with an excess amount of n-butyllithium is carried out at a temperature between -40° C. and -60° C.
Claim 7
Dependent Claim
22 words
The process of claim 5 wherein the step of reacting said lithiophenoxy phosphazenes includes using a solution of diphenylchlorophosphine as said electrophile.
Claim 8
Dependent Claim
33 words
The process of claim 5 wherein the step of reacting said lithiophenoxy phosphazenes includes using a solution of 6.5 g triphenyltin chloride in 75 mL of tetrahydrofuran at -60° C. as said electrophile.
Claim 9
Dependent Claim
35 words
The process of claim 5 wherein the step of reacting said lithiophenoxy phosphazenes includes using a solution of 0.5 g of (triphenylphosphine) gold(I) chloride in 25 mL of tetrahydrofuran at -60° C. as said electrophile.
Claim 10
Dependent Claim
24 words
The process of claim 5 wherein the step of reacting said lithiophenoxyphosphazenes includes using aqueous solution of HCl and carbon dioxide as said electrophile.
Claim 11
Dependent Claim
33 words
A polymer having the formula: ##STR14## where N, P, O, Br represent nitrogen, phosphorous, oxygen and bromine atoms respectively and Ph designates a phenyl group and n is the number of repetitive units.
Claim 12
Dependent Claim
33 words
A polymer having the formula: ##STR14## where N, P, O, Br represent nitrogen, phosphorous, oxygen and bromine atoms respectively and Ph designates a phenyl group and n is the number of repetitive units.
Claim 13
Dependent Claim
33 words
A polymer having the formula: ##STR15## where X is a member of subgroup consisting of PPh 2 , SnPh 3 , AuPPh 3 and COOH and n is the number of repetitive units.
Claim 14
Dependent Claim
33 words
A polymer having the formula: ##STR15## where X is a member of subgroup consisting of PPh 2 , SnPh 3 , AuPPh 3 and COOH and n is the number of repetitive units.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
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| 3.5 Years (Year 4) | 1986-06-06 | 1986-12-06 | 1987-06-07 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-06-06 | 1990-12-06 | 1991-06-07 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-06-06 | 1994-12-06 | 1995-06-07 | $7700.00 | Window Closed / Lapsed |