EP0000790A1 - Process for the production of phosphazene polymers - Google Patents
Process for the production of phosphazene polymers Download PDFInfo
- Publication number
- EP0000790A1 EP0000790A1 EP7878100652A EP78100652A EP0000790A1 EP 0000790 A1 EP0000790 A1 EP 0000790A1 EP 7878100652 A EP7878100652 A EP 7878100652A EP 78100652 A EP78100652 A EP 78100652A EP 0000790 A1 EP0000790 A1 EP 0000790A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- solution
- process according
- hal
- group
- dihalophosphazene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/025—Polyphosphazenes
Definitions
- This invention relates to an improved process for the production of polyphosphazenes in which the substituents on the phosphorus atoms are those described in any of the following United States Patents: and others of a similar nature in which products having the general formula wherein R and R t are each selected from the group consisting of alkyl, alkylaryl, aryl any of which may be either substituted or unsubstituted as shown in the above noted patents, and need not be the same and n is an integer between about 7 and about 50,000 or more, and in which some of the R or R' groups may contain some unsaturation to facilitate curing the products.
- a principal object of this invention is to improve the process in which the halogen atoms in the polydihalophosphazene starting material are replaced by alkoxy and/or aryloxy groups, in the derivatization reaction described in any of the above noted patents.
- a further object of the invention is to effect said improvement by the provision of a single solvent for both the polydihalophosphazene reactant and the alkoxide or aryloxide reactant and which is also a solvent for the desired ester product and which is a non-solvent for the inorganic halide by-product, i.e. the alkali metal halide or alkaline earth halide formed as the other reaction product.
- a further object of this invention is to provide a stabilized solution of the polydihalophosphazene in the solvent of choice, suitable for carrying out such a reaction.
- a further object is to provide a procedure for the preparation of phosphazene polymers in which the rate of reaction is faster than in prior art heterogeneous derivatizations and in which complete substitution of the halogen atoms is more readily achieved than in such prior art processes.
- a further object of the invention is to simplify the separation of the inorganic halide from the solution of the polyphosphazene derivative formed during said reaction.
- THF tetrahydrofuran
- THF THF
- separation and recovery of a plurality of solvents is eliminated, and in which separate recovery of the polyphosphazene derivative and the inorganic halide is simplified.
- solutions of the poly(dihalophosphazene) in THF are unstable since as reported in United States Patent 3,260,684 the polydihalophosphazene may catalyze polymerization of the THF. In accordance with the present invention this is avoided by the addition of certain amines to the THF.
- Amines which were found to inhibit the formation of poly-THF in solutions of polydihalophosphazenes in THF included diphenylamine, N-methyldiphenylamine, N-methylpyrrole, pyrrole and 6-dodecyl-1,2-dihydro-2,2,4-trimethyl- quinoline.
- the amount of amine is between 0.25 and 5.0 parts by weight for each part by weight of poly(dihalophosphazene ).
Abstract
Description
- This invention relates to an improved process for the production of polyphosphazenes in which the substituents on the phosphorus atoms are those described in any of the following United States Patents:
- In prior art descriptions of the process in which linear polydihalophosphazenes are derivatized by reaction with an alkali or alkaline earth compound represented by the general formula M(OR)x in which M represents lithium, sodium, potassium, magnesium or calcium; x is equal to the valence of M; and R represents an alkyl radical either of which may be substituted, e.g. as described in United States Patent 3,370,020 issued February 20, 1968 to Allcock et al, the esterification step (see column 3 of the patent) has usually been conducted by bringing a solution of the polydihalophosphazene dissolved in an aromatic solvent into contact with a solution of the alkoxide or aryloxide dissolved in an entirely different solvent.
- Solvents for the polydihalophosphazene reactant have usually been benzene, toluene, xylene or other similar aromatic hydrocarbons which are commercially readily available and are relatively inexpensive (see Rose United States Patent 3,515,688 issued June 2, 1970 and the other above noted patents, for example).
- A variety of solvents have been utilized for the alkoxide or aryloxide including: methanol disclosed in Example 2 of the Allcock et al patent; tetrahydrofuran disclosed in the Rose patent, and ethers disclosed in Reynard et al United States Patent 3,883,541 noted above, but in every such reported synthesis in which the two reactants were brought together as solutions, two distinct and different solvents were utilized and the resulting derivatized product precipitates from the solutions being reacted, usually with entrapment of the metal halide by-product formed in the reaction. This results in a heterogeneous system in which the reacting solutes are in.contact with each other for only limited times, with consequent adverse effect on yields of the desired esters. In addition, it has been found that complete substitution of P-Hal bonds is very difficult to achieve in a heterogeneous system, and is relatively simple to achieve in a homogeneous system.
- A principal object of this invention is to improve the process in which the halogen atoms in the polydihalophosphazene starting material are replaced by alkoxy and/or aryloxy groups, in the derivatization reaction described in any of the above noted patents.
- A further object of the invention is to effect said improvement by the provision of a single solvent for both the polydihalophosphazene reactant and the alkoxide or aryloxide reactant and which is also a solvent for the desired ester product and which is a non-solvent for the inorganic halide by-product, i.e. the alkali metal halide or alkaline earth halide formed as the other reaction product.
- A further object of this invention is to provide a stabilized solution of the polydihalophosphazene in the solvent of choice, suitable for carrying out such a reaction.
- A further object is to provide a procedure for the preparation of phosphazene polymers in which the rate of reaction is faster than in prior art heterogeneous derivatizations and in which complete substitution of the halogen atoms is more readily achieved than in such prior art processes.
- A further object of the invention is to simplify the separation of the inorganic halide from the solution of the polyphosphazene derivative formed during said reaction.
- These and other objects of the invention are accomplished by selecting a solvent in which all of the following are soluble:
- (1) the (NPHal2)n linear polydihalophosphazene 'starting material, in which Hal is either Cl or Br and n is an integer greater than 7;
- (2) the M(OR)x alkoxide or aryloxide starting material with which the polydihalophosphazene reacts;
- (3) the polyphosphazene derivative formed by the reaction of (1) and (2) and represented by the formula
- (4) the inorganic (alkali or alkaline earth) halide which is also produced in the reaction between (1) and (2) is insoluble.
- The solvent which has been found to best satisfy all of the above requirements is tetrahydrofuran (THF).
- By use of THF as the solvent a homogeneous system is provided in which longer contact times are available for the reactants (1) and (2) to react, and in which separation and recovery of a plurality of solvents (necessary to the economics of the process if it is to be commercially viable) is eliminated, and in which separate recovery of the polyphosphazene derivative and the inorganic halide is simplified. However solutions of the poly(dihalophosphazene) in THF are unstable since as reported in United States Patent 3,260,684 the polydihalophosphazene may catalyze polymerization of the THF. In accordance with the present invention this is avoided by the addition of certain amines to the THF. Amines which were found to inhibit the formation of poly-THF in solutions of polydihalophosphazenes in THF included diphenylamine, N-methyldiphenylamine, N-methylpyrrole, pyrrole and 6-dodecyl-1,2-dihydro-2,2,4-trimethyl- quinoline. Preferably the amount of amine is between 0.25 and 5.0 parts by weight for each part by weight of poly(dihalophosphazene ).
- The following examples are illustrative of the preferred practice of this invention and are not intended to limit the same.
- A solution of linear polydichlorophosphazene (NPCl2)n (n> 7) in THF [5-10% (NPCl2)n by weight] was prepared after the lower molecular weight cyclic oligomers had been removed from the linear polydichlorophosphazene by known purification procedures such as solvent extraction or sublimation, as described in the open literature. A small amount of an amine, e.g. diphenylamine was added to inhibit the formation of poly-tetrahydrofuran in the solution of linear polydihalophosphazene.
- Sixty grams (1.03 mol) of polydichlorophosphazene in 590 g (a 9.2% solution) of tetrahydrofuran (distilled from sodium) was pressurized into a 3 liter glass reactor under nitrogen into which a solution of 584 g of 2.00 mm sodium fluoroalkoxides per gram of solution (1.17 m sodium fluoroalkoxide) had previously been charged. The contents of the reactor were stirred for three hours at 60-65°C and then cooled to 25-30°C. Excess sodium fluoroalkoxides present in the reaction mixture were then neutralized. The sodium chloride was then filtered or removed by centrifugation. The volatile tetrahydrofuran was then removed by a solvent evaporator, for reuse. Traces of fluoroalcohol were then removed at a higher temperature (100-1100C) for 20 hours at 5 mm Hg giving 130 g of a dry elastomeric poly(fluoroalkoxyphosphazene) with the following typical analysis: Dilute Solution Viscosity--2.61; % Gel--0.0: Weight Percent Sodium 0.11; Weight Percent Chloride 0.06.
- Similar reactions were effected between poly- dibromophosphazene (NPBr2)n and alkali metal or alkaline earth metal alkoxides, including methoxides, ethoxides, propoxides and butoxides, and/or aryloxides including alkali metal phenoxides including sodium, potassium and lithium phenoxides, both unsubstituted (e.g. NaOC6H5) and substituted (e.g. as described in Allcock et al 3,370,020) and other aryloxides as described in said patent; in which tetrahydrofuran was the solvent for both the reactants and the desired derivatized polyphosphazene product.
- Accordingly it is not intended that this invention be limited except as may be required by the appended claims.
Claims (8)
wherein a solution of a linear dihalophosphazene represented by the formula (NPHal2)n wherein Hal represents a halogen selected from the group consisting of Cl and Br and n is an integer greater thaw about 7; is reacted with a solution of an alkoxide or aryloxide represented by the formula M(OR)x in which M represents a metal selected from the group consisting of the alkali and alkaline earth metals and x is the valence of M;
and a solution of the desired ester is produced along with M(Hal)x as a by-product of the reaction;
the improvement which comprises providing a single common solvent for (1) the solution of said linear dihalophosphazene; (2) the solution of said alkoxide or aryloxide; and (3) the solution of said polyphosphazene ester; whereby the reaction is carried out in a homogeneous system and complete replacement of the P-Hal atoms is more readily effected than in a heterogeneous system in which a plurality of different solvents are utilized in said solutions.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US05/824,004 US4129529A (en) | 1977-08-12 | 1977-08-12 | Process for the production of phosphazene polymers |
US824004 | 1977-08-12 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0000790A1 true EP0000790A1 (en) | 1979-02-21 |
EP0000790B1 EP0000790B1 (en) | 1984-01-04 |
Family
ID=25240354
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP78100652A Expired EP0000790B1 (en) | 1977-08-12 | 1978-08-12 | Process for the production of phosphazene polymers |
Country Status (4)
Country | Link |
---|---|
US (1) | US4129529A (en) |
EP (1) | EP0000790B1 (en) |
CA (1) | CA1098534A (en) |
DE (1) | DE2862358D1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0312435A1 (en) * | 1987-10-14 | 1989-04-19 | Elf Atochem S.A. | Method for cleaning polyorganophosphazines obtained by co-substitution of polydichlorophosphazines |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU530988B2 (en) * | 1978-09-08 | 1983-08-04 | Firestone Tire And Rubber Co., The | Polyphosphazenes |
US4609724A (en) * | 1985-04-29 | 1986-09-02 | The Firestone Tire & Rubber Company | Process for preparing and purifying alkoxyphosphazene polymer |
US4665152A (en) * | 1985-09-09 | 1987-05-12 | The Firestone Tire & Rubber Company | Curable poly(aryloxyphosphazene) copolymers |
US4663420A (en) * | 1986-01-21 | 1987-05-05 | Ethyl Corporation | Polyetheroxy-substituted polyphosphazene purification |
US4870113A (en) * | 1988-12-23 | 1989-09-26 | Ethyl Corporation | Rigid polyphosphazene foam and process for making same |
US5286469A (en) * | 1991-12-17 | 1994-02-15 | Northeastern University | Metal-phosphorus-nitrogen polymers, metal-phosphorus compounds and methods of preparation thereof |
JP4184158B2 (en) * | 2003-06-05 | 2008-11-19 | 旭化成ケミカルズ株式会社 | Method for producing phosphonitrile ester |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB991201A (en) * | 1962-03-27 | 1965-05-05 | Albright & Wilson Mfg Ltd | Polymeric phosphonitrilic derivatives |
FR1473887A (en) * | 1964-09-29 | 1967-03-24 | American Cyanamid Co | Polymers and process for the production of such phosphonitrile polymers |
US3344087A (en) * | 1960-04-01 | 1967-09-26 | Olin Mathieson | Polymeric phosphorus-nitrogen compounds and the production thereof |
FR2074147A5 (en) * | 1969-12-24 | 1971-10-01 | Sandoz Sa | |
FR2156306A1 (en) * | 1971-10-13 | 1973-05-25 | Horizons Research Inc | |
DE2708319A1 (en) * | 1976-02-27 | 1977-09-08 | Armstrong Cork Co | ELASTOMERES COPOLYMERES BY POLY (ARYLOXYPHOSPHAZEN) |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3271330A (en) * | 1962-01-29 | 1966-09-06 | Minnesota Mining & Mfg | High molecular weight phosphonitrile fluoroesters |
US3443913A (en) * | 1967-10-12 | 1969-05-13 | Grace W R & Co | Process for preparing high molecular weight linear phosphonitrilic polymers |
-
1977
- 1977-08-12 US US05/824,004 patent/US4129529A/en not_active Expired - Lifetime
-
1978
- 1978-08-12 DE DE7878100652T patent/DE2862358D1/en not_active Expired
- 1978-08-12 EP EP78100652A patent/EP0000790B1/en not_active Expired
- 1978-08-14 CA CA309,273A patent/CA1098534A/en not_active Expired
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3344087A (en) * | 1960-04-01 | 1967-09-26 | Olin Mathieson | Polymeric phosphorus-nitrogen compounds and the production thereof |
GB991201A (en) * | 1962-03-27 | 1965-05-05 | Albright & Wilson Mfg Ltd | Polymeric phosphonitrilic derivatives |
FR1473887A (en) * | 1964-09-29 | 1967-03-24 | American Cyanamid Co | Polymers and process for the production of such phosphonitrile polymers |
FR2074147A5 (en) * | 1969-12-24 | 1971-10-01 | Sandoz Sa | |
FR2156306A1 (en) * | 1971-10-13 | 1973-05-25 | Horizons Research Inc | |
DE2708319A1 (en) * | 1976-02-27 | 1977-09-08 | Armstrong Cork Co | ELASTOMERES COPOLYMERES BY POLY (ARYLOXYPHOSPHAZEN) |
Non-Patent Citations (1)
Title |
---|
CHEMICAL ABSTRACTS, vol. 84, 1976, 136925x * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0312435A1 (en) * | 1987-10-14 | 1989-04-19 | Elf Atochem S.A. | Method for cleaning polyorganophosphazines obtained by co-substitution of polydichlorophosphazines |
Also Published As
Publication number | Publication date |
---|---|
DE2862358D1 (en) | 1984-02-09 |
EP0000790B1 (en) | 1984-01-04 |
US4129529A (en) | 1978-12-12 |
CA1098534A (en) | 1981-03-31 |
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