# US 2019/0315786 A1 · Phosphazene compound, preparation method and use thereof

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- Number: US 2019/0315786 A1
- Document ID: US20190315786A1
- Status: Published application
- Kind: A1
- Application number: 16/446,466
- Filed: 2019-06-19
- Published: 2019-10-17
- Earliest claimed: 2016-12-26
- Assignees: Qingdao University of Science and Technology
- Applicants: Qingdao University of Science and Technology
- Inventors: Zhibo LI; Na ZHAO; Chuanli REN; Xiaohui FU; Shaofeng LIU
- Web page: https://patentgrep.com/patent/US20190315786A1

## CPC

- C07F 9/65817: {n = 4}
- B01J 31/0265: {Phosphazenes, oligomers thereof or the corresponding phosphazenium salts (polyphosphazenes per se C07F9/067)}
- C07F 9/65815: {n = 3}
- C08G 63/08: Lactones or lactides
- C08G 63/664: derived from hydroxy carboxylic acids
- C08G 63/87: Non-metals or inter-compounds thereof (boron C08G63/84)
- C08G 65/06: Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G 77/04: Polysiloxanes
- C08G 77/08: characterised by the catalysts used
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS

## Abstract

Provided are a phosphazene compound, a method for preparing a phosphazene compound and a method for producing a polymer with a phosphazene compound as a catalyst. The compound of formula (I) or a solvate thereof, where A is a six- or eight-membered ring consisting of repeated P═N, and B is at least one of unsubstituted or substituted C1-6 alkylamino, unsubstituted or substituted C1-6 cycloalkylamino, unsubstituted or substituted arylamino, or halogen, and B is attached to A at phosphorus in P═N, where R is unsubstituted or substituted C1-6 alkyl, unsubstituted or substituted C1-6 cycloalkyl, unsubstituted or substituted aryl, or unsubstituted or substituted benzyl, or R forms C1-6 heterocycloalkyl together with N attached thereto.

## Claims

### Claim 1

A compound of formula (I),
wherein A is a six- or eight-membered ring consisting of repeated P═N, and
B is at least one of unsubstituted or substituted C1-6 alkylamino, unsubstituted or substituted C1-6 cycloalkylamino, unsubstituted or substituted arylamino,
or halogen, and B is attached to A at phosphorus in P═N, wherein
R is unsubstituted or substituted C1-6 alkyl, unsubstituted or substituted C1-6 cycloalkyl, unsubstituted or substituted aryl, or unsubstituted or substituted benzyl,
or
R forms C1-6 heterocycloalkyl together with N attached thereto;
or a solvate thereof.

### Claim 2 (depends on 1)

The compound according to claim 1, wherein
B is at least one selected from the group consisting of
and Cl, wherein R is methyl, ethyl, isopropyl, n-butyl, cyclohexyl, phenyl or benzyl, or R forms
together with nitrogen attached thereto.

### Claim 3 (depends on 1)

The compound according to claim 1, wherein the compound is a compound of any one of formulas:
or a solvate thereof.

### Claim 4

A method for preparing a compound of formula (I),
where A is a six- or eight-membered ring consisting of repeated P═N, and
B is at least one of unsubstituted or substituted C1-6 alkylamino, unsubstituted or substituted C1-6 cycloalkylamino, unsubstituted or substituted arylamino,
or halogen, and B is attached to A at phosphorus in P═N,
wherein the method comprising:
(a) allowing phosphorus pentachloride to be in contact with a compound of formula X and ammonia gas, thereby obtaining a compound of formula 1;
(b) allowing the compound of formula 1 to be in contact with a base, thereby obtaining a compound of formula 2; and
(c) allowing the compound of formula X or the compound of formula 2 to be in contact with hexachloro-cyclotriphosphazene or octachloro-cyclotetraphosphazene, thereby obtaining the compound of formula (I),
wherein the formula X is NHR2, the formula 1 is
and the formula 2 is
wherein
R is unsubstituted or substituted C1-6 alkyl, unsubstituted or substituted C1-6 cycloalkyl, unsubstituted or substituted aryl, or unsubstituted or substituted benzyl,
or
R forms C1-6 heterocycloalkyl together with N attached thereto.

### Claim 5 (depends on 4)

The method according to claim 4, wherein in step (a), the contact is performed in a first anhydrous solvent.

### Claim 6 (depends on 5)

The method according to claim 5, wherein the step (a) comprises:
allowing phosphorus pentachloride in the first anhydrous solvent to be in contact with the compound of formula X in a nitrogen atmosphere for 1-6 hours thereby obtaining an intermediate, and
allowing the intermediate to be in contact with ammonia gas for another 1 to 6 hours, thereby obtaining the compound of formula 1 after filtration and solvent distillation.

### Claim 7 (depends on 5)

The method according to claim 5, wherein the first anhydrous solvent comprises at least one selected from the group consisting of benzene, toluene, xylene, dichloromethane and tetrahydrofuran.

### Claim 8 (depends on 4)

The method according to claim 4, wherein in step (a), a molar ratio of the phosphorus pentachloride to the compound of the formula X is 1: (3 to 10).

### Claim 9 (depends on 4)

The method according to claim 4, wherein the base is sodium hydroxide or an aqueous solution thereof.

### Claim 10 (depends on 4)

The method according to claim 4, wherein the step (c) comprises:
allowing hexachloro-cyclotriphosphazene or octachloro-cyclotetraphosphazene to be in contact with the compound of formula X or the compound of formula 2, in a second anhydrous solvent in the presence of an acid scavenger.

### Claim 11 (depends on 10)

The method according to claim 10, wherein the second anhydrous solvent comprises at least one selected from the group consisting of benzene, toluene, xylene, chlorobenzene and tetrahydrofuran.

### Claim 12 (depends on 10)

The method according to claim 10, wherein hexachloro-cyclotriphosphazene or octachloro-cyclotetraphosphazene, the compound of formula 2 and the acid scavenger are provided at a molar ratio ranging from 1:(1 to 8):(1 to 8).

### Claim 13 (depends on 10)

The method according to claim 10, wherein the acid scavenger comprises at least one selected from the group consisting of triethylamine, sodium carbonate, sodium hydrogen carbonate, sodium hydroxide and potassium hydroxide.

### Claim 14 (depends on 4)

The method according to claim 4, wherein in step (c), the contact is performed at 40 to 150° C. for 3 to 18 hours.

### Claim 15 (depends on 4)

The method according to claim 4, comprising:
placing phosphorus pentachloride in anhydrous dichloromethane and adding the compound of formula X in anhydrous dichloromethane at a temperature of −80 to 0° C. in a nitrogen atmosphere for 1 to 6 hours, thereby obtaining an intermediate,
continuously introducing an ammonia gas into the intermediate at a temperature of −80 to 0° C. for another 1 to 6 hours, performing a filtration treatment to obtain a first filtrate, and removing solvent remained in the first filtrate by distillation, thereby obtaining a compound of formula 1,
mixing the compound of formula 1 with a 50 wt % aqueous sodium hydroxide solution for 1 to 5 hours, performing a filtration treatment to obtain a second filtrate, and removing solvent remained in the second filtrate by distillation, thereby obtaining the compound of formula 2,
mixing hexachloro-cyclotriphosphazene or octachloro-cyclotetraphosphazene, the compound of formula X or the compound of formula 2, and triethylamine in a nitrogen atmosphere in anhydrous toluene to obtain a mixture, refluxing the mixture for 3 to 18 hours, performing a filtration treatment to obtain a third filtrate, and removing solvent remained in the third filtrate by distillation, thereby obtaining the compound.

### Claim 16

A method for producing a polymer with a compound of formula (I),
wherein A is a six- or eight-membered ring consisting of repeated P═N, and
B is at least one of unsubstituted or substituted C1-6 alkylamino, unsubstituted or substituted C1-6 cycloalkylamino, unsubstituted or substituted arylamino,
or halogen, and B is attached to A at phosphorus in P═N, wherein
R is unsubstituted or substituted C1-6 alkyl, unsubstituted or substituted C1-6 cycloalkyl, unsubstituted or substituted aryl, or unsubstituted or substituted benzyl,
or
R forms C1-6 heterocycloalkyl together with N attached thereto;
or a solvate thereof as a catalyst,
the method comprising:
allowing the catalyst to be in contact with at least one monomer, thereby obtaining the polymer.

### Claim 17 (depends on 16)

The method according to claim 16, wherein the monomer comprises at least one selected from the group consisting of epoxy ethane, epoxy propane, epoxy chloropropane, 1,2-epoxy butane, glycolide, lactide, γ-butyrolactone, δ-valerolactone, ε-caprolactone, β-lactam, methyl-substituted β-lactam, butyrolactam, caprolactam, trimethylene carbonate, 2,2-dimethyltrimethylene carbonate, 1,3-dioxan-2-one, trioxane, five-membered cyclic phosphate, six-membered cyclic phosphate, octamethyl-cyclotetrasiloxane, hexamethyl-cyclotrisiloxane, acrylamide, methyl-substituted acrylamide, methyl acrylate, methyl methacrylate and N-carboxy-α-amino-anhydride.

### Claim 18 (depends on 16)

The method according to claim 16, wherein the contact is performed in an anhydrous solvent in the presence of an initiator.

### Claim 19 (depends on 18)

The method according to claim 18, wherein the initiator comprises at least one selected from methanol, ethanol, isopropanol, n-butanol, tert-butanol, glycol, glycerol, cholesterol, phenol, benzyl alcohol, n-butyric acid, n-pentanoic acid, n-hexanoic acid, n-heptanoic acid, n-octanoic acid, n-decanoic acid, dodecanoic acid, tetradecanoic acid, palmitic acid, triethylamine, tri-n-butylamine, trihexylamine, benzamide, polyethylene glycol, polyoxypropylene glycol and polytetramethylene ether glycol.

### Claim 20 (depends on 18)

The method according to claim 18, wherein the catalyst, the initiator and the monomer are provided at a molar ratio of 1:(0 to 200):(50 to 100000).