EP0000790B1 - Process for the production of phosphazene polymers - Google Patents
Process for the production of phosphazene polymers Download PDFInfo
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- EP0000790B1 EP0000790B1 EP78100652A EP78100652A EP0000790B1 EP 0000790 B1 EP0000790 B1 EP 0000790B1 EP 78100652 A EP78100652 A EP 78100652A EP 78100652 A EP78100652 A EP 78100652A EP 0000790 B1 EP0000790 B1 EP 0000790B1
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- EP
- European Patent Office
- Prior art keywords
- solution
- dihalophosphazene
- reaction
- thf
- linear
- Prior art date
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- Expired
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- 238000000034 method Methods 0.000 title claims description 18
- 229920000642 polymer Polymers 0.000 title description 3
- 238000004519 manufacturing process Methods 0.000 title description 2
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 title description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 50
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 8
- 229920002627 poly(phosphazenes) Polymers 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 150000004703 alkoxides Chemical class 0.000 claims description 7
- -1 poly(THF) Polymers 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical group C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 3
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 claims description 2
- DOFLWDGGNKBGSL-UHFFFAOYSA-N 6-dodecyl-2,2,4-trimethyl-1h-quinoline Chemical compound N1C(C)(C)C=C(C)C2=CC(CCCCCCCCCCCC)=CC=C21 DOFLWDGGNKBGSL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- DYFFAVRFJWYYQO-UHFFFAOYSA-N n-methyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(C)C1=CC=CC=C1 DYFFAVRFJWYYQO-UHFFFAOYSA-N 0.000 claims 1
- 239000000376 reactant Substances 0.000 description 5
- 239000007858 starting material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000001212 derivatisation Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 150000002897 organic nitrogen compounds Chemical class 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Chemical group 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- NYQDCVLCJXRDSK-UHFFFAOYSA-N Bromofos Chemical compound COP(=S)(OC)OC1=CC(Cl)=C(Br)C=C1Cl NYQDCVLCJXRDSK-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052791 calcium Chemical group 0.000 description 1
- 239000011575 calcium Chemical group 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- AQYSYJUIMQTRMV-UHFFFAOYSA-N hypofluorous acid Chemical compound FO AQYSYJUIMQTRMV-UHFFFAOYSA-N 0.000 description 1
- 229910001502 inorganic halide Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- XAVQZBGEXVFCJI-UHFFFAOYSA-M lithium;phenoxide Chemical class [Li+].[O-]C1=CC=CC=C1 XAVQZBGEXVFCJI-UHFFFAOYSA-M 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000004704 methoxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical class CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical compound [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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 a process for producing alkoxy and/or aryloxy polyphosphazene esters represented by the general formula wherein R and R' are each selected from alkyl, alkylaryl, aryl, any of which may be either substituted or unsubstituted and need not be the same, and n is an integer between 7 and 50,000 and in which some of the R or R' groups may contain some unsaturation to facilitate curing the products;
- Phosphazene polymers of this kind are described, e.g., in US-A 3,370,020; 3,515,688; 3,700,629; 3,702,833; 3,856,712; 3,856,713; 3,853,794; 3,883,451; and 3,970,533.
- 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 (US-A 3,515,688 and the other above noted patents, for example).
- the object of this invention is to improve the process in which the halogen atoms in certain polydihalophosphaphene starting materials are replaced by alkoxy and/or aryloxy groups in the derivatization reaction as described in any of the above noted patents 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 while the specific solvent used in this process should be stabilized against polymerization.
- THF tetrahydrofuran
- the solution of said linear dihalophosphazene (2) the solution of said alkoxide or. aryloxide; and (3) the solution of said polyphosphazene; (4) the inorganic (alkali or alkaline earth) halide which is also produced in the reaction between (1) and (2) being insoluble; 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; and adding an organic amine to the solution of the linear dihalophosphazene to inhibit the formation of poly (THF).
- THF tetrahydrofuran
- tetrahydrofuran is used as single common solvent in which all of the following are soluble:
- 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 US-A 3,260,684 the polydihalophosphazene may catalyze polymerization of the THF, any polymerization 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-trimethylquinoline.
- the amount of amine is between 0.25 and 5.0 parts by weight for each part by weight of poly(dihalophosphazene).
- a solution of linear polydichlorophos- phazene (NPCl 2 ) n (n>7) in THF (5-10% (NPC1 2 ) n by weight) was prepared after the lower molecular weight cyclic oligomers had been removed from the linear polydichloro- phosphazene 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.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Description
- This invention relates to a process for producing alkoxy and/or aryloxy polyphosphazene esters represented by the general formula
- wherein a solution of a linear dihalophosphazene represented by the formula (NPHaI2)n wherein Hal represents a halogen selected from CI and Br and n is an integer between 7 and 50,000; is reacted under homogeneous condition, with a solution of an alkoxide or aryloxide represented by the formula M(OR)x in which M represents a metal selected from
- 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). as a by-product of the reaction, and tetrahydrofuran is used as solvent.
- Phosphazene polymers of this kind are described, e.g., in US-A 3,370,020; 3,515,688; 3,700,629; 3,702,833; 3,856,712; 3,856,713; 3,853,794; 3,883,451; and 3,970,533.
- 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 US-A 3,370,020, 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 (US-A 3,515,688 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 US-A 3,370,020; tetrahydrofuran disclosed in US-A 3,515,688, and ethers disclosed in US-A 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.
- From GB-A 991,201 it is known that the use of different solvents may give soluble products (Example 1 of this patent). Chemical Abstract vol. 84, 1976, 136925x describes a reaction in which polydichlorophosphazenes and sodium butoxide are reacted in THF, dioxane, BuOH, dioxane-BuOH or THF-BuOH mixtures. Although this article comprises the case that THF is used as a common solvent for the reactions, any general teaching as to the use of THF as common solvent for reactions as described above cannot be taken from this prior art reference. The use of THF as a common solvent in a ligand exchange procedure in the course of a process for the production of polyphosphazene polymers is described in FR-A 2,156,306. However, the reaction of this prior art reference is different from the reaction according to the present invention because the prior art reaction comprises a ligand exchange procedure. US-A 3,344,087 describes the preparation of polymeric phosphorous nitrogen compounds by a reaction of phosphonitrile halides with organic nitrogen compounds. In view of the use of different starting materials than in the present process, different end-products are obtained. Further, in the prior art process the organic nitrogen compound is used as a reactant and not in order to inhibit the formation of poly(THF). The addition of tertiary amines to tetrahydrofuran solutions of phosphonitrilic halide materials is known from FR-A 2,074,147 albeit for a different purpose as hydrohalide acceptors.
- The object of this invention is to improve the process in which the halogen atoms in certain polydihalophosphaphene starting materials are replaced by alkoxy and/or aryloxy groups in the derivatization reaction as described in any of the above noted patents 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 while the specific solvent used in this process should be stabilized against polymerization.
- This object is accomplished by the invention by providing tetrahydrofuran (THF) as 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; (4) the inorganic (alkali or alkaline earth) halide which is also produced in the reaction between (1) and (2) being insoluble; 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; and adding an organic amine to the solution of the linear dihalophosphazene to inhibit the formation of poly (THF).
- Thus, according to the present invention tetrahydrofuran is used as single common solvent in which all of the following are soluble:
- (1) the (NPHaI2)n linear polydihalophosphazene starting material, in which Hal is either Cl or Br and n is an integer between 7 and 50,000;
- (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.
- 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. Since solutions of the poly(dihalophosphazene) in THF are unstable, since as reported in US-A 3,260,684 the polydihalophosphazene may catalyze polymerization of the THF, any polymerization 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-trimethylquinoline. 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 polydichlorophos- phazene (NPCl2)n (n>7) in THF (5-10% (NPC12)n by weight) was prepared after the lower molecular weight cyclic oligomers had been removed from the linear polydichloro- phosphazene 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 polydichlorophos- phazene 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 fluoro- alcohol were then removed at. a higher temperature (100-110°C) 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 polydibromophosphazene (NPBr2)n and alkali metal or alkaline earth metal alkoxides, including methoxides, ethoxides, propoxides and but- oxides, and/or aryloxides including alkali metal phenoxides including sodium, potassium and lithium phenoxides, both unsubstituted (e.g. NaOCeH5) and substituted (e.g. as described in US-A 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.
Claims (6)
1. A process for producing alkoxy and/or aryloxy polyphosphazene esters represented by the general formula
wherein R and R' are each selected from alkyl, alkylaryl, aryl, any of which may be either substituted or unsubstituted and need not be the same, and n is an integer between 7 and 50,000 and in which some of the R or R' groups may contain some unsaturation to facilitate curing the products; wherein a solution of a linear dihalophosphazene represented by the formula (NPHaI2)ri wherein HAI represents a halogen selected from CI and Br and n is an integer between 7 and 50,000 is reacted under homogeneous conditions with a solution of an alkoxide or aryloxide represented by the formula M(OR)x in which M represents a metal selected from alkali and alkaline earth metals and x is the valence of M; a solution of the desired ester is produced along with M(Hal)x as a by-product of the reaction; and tetrahydrofuran is used as solvent; characterized by providing tetrahydrofuran (THF) as 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; (4) the inorganic (alkali or alkaline earth) halide which is also produced in the reaction between (1) and (2) being insoluble; 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; and adding an organic amine to the solution of the linear dihalophosphazene to inhibit the formation of poly(THF).
2. A process according to Claim 1 wherein the amine is selected from diphenylamine, N-methyldiphenylamine, N-methylpyrrole, pyrrole; and 6-dodecyl-1,2-dihydro-2,2,4-tri- methylquinoline.
3. A process according to Claim 1 wherein the amine is added in an amount between 0.25 and 5.0 parts by weight for each part by weight of poly(dihalophosphazene).
4. A process according to Claim 1 wherein M is an alkali metal.
5. A process of Claim 1 wherein M is sodium.
6. A process according to Claim 1 wherein Hal is chlorine.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US824004 | 1977-08-12 | ||
| US05/824,004 US4129529A (en) | 1977-08-12 | 1977-08-12 | Process for the production of phosphazene polymers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0000790A1 EP0000790A1 (en) | 1979-02-21 |
| EP0000790B1 true 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) |
Families Citing this family (8)
| 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 |
| JPH01123833A (en) * | 1987-10-14 | 1989-05-16 | Soc Atochem | Purification of crude polyorganophosphazene obtained by co-substitution of polydichlorophosphazene |
| 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 |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1143027B (en) * | 1960-04-01 | 1963-01-31 | Olin Mathieson | Process for the production of polymeric phosphorus-nitrogen compounds |
| US3271330A (en) * | 1962-01-29 | 1966-09-06 | Minnesota Mining & Mfg | High molecular weight phosphonitrile fluoroesters |
| 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 |
| US3443913A (en) * | 1967-10-12 | 1969-05-13 | Grace W R & Co | Process for preparing high molecular weight linear phosphonitrilic polymers |
| CH1923569A4 (en) * | 1969-12-24 | 1972-08-31 | ||
| BE790016A (en) * | 1971-10-13 | 1973-04-12 | Horizons Research Inc | PREPARATION OF POLYPHOSPHAZENES |
| US4053456A (en) * | 1976-02-27 | 1977-10-11 | Armstrong Cork Company | Poly(aryloxyphosphazene) copolymers |
-
1977
- 1977-08-12 US US05/824,004 patent/US4129529A/en not_active Expired - Lifetime
-
1978
- 1978-08-12 EP EP78100652A patent/EP0000790B1/en not_active Expired
- 1978-08-12 DE DE7878100652T patent/DE2862358D1/en not_active Expired
- 1978-08-14 CA CA309,273A patent/CA1098534A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CA1098534A (en) | 1981-03-31 |
| US4129529A (en) | 1978-12-12 |
| EP0000790A1 (en) | 1979-02-21 |
| DE2862358D1 (en) | 1984-02-09 |
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