CN102515121A - Preparation method of linear polyhalophosphazene with high relative molecular mass - Google Patents
Preparation method of linear polyhalophosphazene with high relative molecular mass Download PDFInfo
- Publication number
- CN102515121A CN102515121A CN2011103621842A CN201110362184A CN102515121A CN 102515121 A CN102515121 A CN 102515121A CN 2011103621842 A CN2011103621842 A CN 2011103621842A CN 201110362184 A CN201110362184 A CN 201110362184A CN 102515121 A CN102515121 A CN 102515121A
- Authority
- CN
- China
- Prior art keywords
- linear
- preparation
- molecular weight
- molecular sieve
- reaction
- 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.)
- Granted
Links
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention discloses a preparation method of linear polyhalophosphazene with high relative molecular mass. The method comprises the following steps of: dissolving phosphorus pentachloride and ammonium chloride into a chlorinated solvent with a high boiling point, then, adding a catalyst, a corrosion and scale inhibiting protective agent and a non-powdery carbon molecular sieve adsorption decoloring agent, raising the temperature to 170-180 DEG C under the protection of inert gases, and carrying out heat insulation reaction for 3-7h; and after the reaction is ended, reducing the temperature, carrying out solid-liquid separation on the materials, removing solids, and then carrying out purification treatment on liquid obtained through the separation. The synthesis method is short in reaction time, low in reaction temperature not higher than 200 DEG C, lower in production cost as comparison with that of other common methods, easy to control in synthesis reaction and suitable for large-scale industrial production; and the linear polyhalophosphazene as a product obtained by using the method has the yield of 38-50% and the molecular weight distribution coefficient of 1.3-1.4 when the relative molecular mass (weight-average molecular weight) is up to over 100000.
Description
Technical field
The present invention relates to a kind of preparation method of linear phosphazene nitrile polymer, especially a kind of preparation method of linear polydichlorophosphazenes of high molecular weight.
Background technology
The linear phosphazene nitrile polymer is one type of inorganic main chain functional polymer, has the skeleton main chain of alternately being made up of P, N atom, is connected with two side group R, R ' (molecular formula is as follows) on each P atom.
Polyphosphonitrile is owing to have water-fast, anti-solvent, oil resistant class and a chemical, and high temperature resistant again, low temperature and premium properties such as do not burn can be processed specialty elastomer, low temperature elasticity body, flame-resistant electronic material, biomedical material etc.The phosphorus of phosphazene compound, nitrogen content height constitute fire-retardant collaboration system certainly, have highly effective flame-retardant property, low cigarette, washing fastness, excellent biological compatibility and degradability.Phosphazene compound can be made into various forms such as liquid, solid, is convenient to blend make an addition in the various materials, processes good self-extinguishing applied fireproofing.
Linear polydichlorophosphazenes PDCP is a kind of important polyphosphonitrile, and it is an important intermediate synthetic and other polymer polyphosphonitrile of preparation, and the synthetic of most of linear polyphosphonitrile is to realize through the nucleophilic substitution reaction of PDCP.Therefore compound method and the technology of studying linear PDCP are significant.
The compound method of present linear PDCP mainly comprises ring-opening polymerization (melt polymerization and solution polymerization), small molecule monomer direct polymerization and the room temperature controlled polymerization etc. of hexachlorocyclotriphosphazene.Synthesis material adopts the higher monomers of price such as hexachlorocyclotriphosphazene more.Hexachlorocyclotriphosphazene fusion ring-opening polymerization generally is in the vacuum polymerization pipe of secluding air and moisture, to carry out, and temperature is about 250 ℃, and this method needs highly purified raw material, and temperature of reaction is high, and the time is also long, and PDCP can be partial cross-linked simultaneously.Hexachlorocyclotriphosphazene solution ring-opening polymerization is to be catalyzer with the boron trichloride, in high boiling solvent (chlorinated benzene or α-Lv Dainai etc.), carries out, and the molecular weight of the PDCP that this method obtains is relatively low, strict to polymerization temperature control.Compare with melt polymerization; Solution polymerization has advantages such as the gel polydichlorophosphazenes that polymerization velocity is fast, the reaction times is short, polymerization temperature is low, form is less, molecular weight of product narrow distribution; But molecular weight of product is relatively low, and is also strict to the requirement of polymerization temperature control.
Small molecule monomer direct polymerization method, concrete grammar are to be that raw material is processed the single phosphonitrile monomer of N-dichlor-phosphoryl-P-trichlorine earlier with the reaction of ammonium sulfate and phosphorus pentachloride, prepare PDCP through mass polymerization or solution polymerization process then.This method is more loaded down with trivial details, and the molecular weight of product that its mass polymerization obtains is lower.
Summary of the invention
The deficiency that the present invention has overcome that ubiquitous production cost is high among the polydichlorophosphazenes preparation method in the past, temperature of reaction is too high, long reaction time and product decompose easily provides a kind of preparation method of linear polydichlorophosphazenes of high molecular weight.
Technical scheme of the present invention is: a kind of preparation method of linear polydichlorophosphazenes of high molecular weight may further comprise the steps:
(1) in anhydrous dry reaction container, adds boiling point greater than 220 ℃ high boiling point chloro thing solvent; With phosphorus pentachloride and chloride leach in above-mentioned solvent; Add catalyzer, corrosion-mitigation scale-inhibition protective material and non-powder formed carbon molecular sieve adsorption discoloring agent again; Under protection of inert gas, be warming up to 170～180 ℃, insulation reaction 3～7 hours; Wherein, the mol ratio of phosphorus pentachloride and ammonium chloride is 1: 1～1.3: 1; With ammonium chloride is datum quantity, and catalyst consumption is 1.2～2.0% (mass percents); The protectant consumption of corrosion-mitigation scale-inhibition is 1.2～1.5% (mass percents); The consumption of non-powder formed carbon molecular sieve adsorption discoloring agent is 0.02～0.05%; The mass ratio of the add-on of high boiling point chloro thing and reactant feed (ammonium chloride and phosphorus pentachloride total mass) is 1: 2～1: 1.
(2) after reaction finished, temperature was reduced to 60～70 ℃, and above-mentioned material is carried out solid-liquid separation, removes solid;
(3) liquid that above-mentioned separation is obtained carries out purification processes; Preferred purification method is following: with non-polar solvent (as; Sherwood oil etc.) carry out recrystallization; Remove solvent in the above-mentioned reaction mixture, small molecule by-product etc., obtain the linear polydichlorophosphazenes light yellow solid thing of high molecular weight.With the linear polydichlorophosphazenes vacuum drying treatment of product, (THF etc.) are preserved in appropriate organic solvent.
Said high boiling point chloro thing is meant the chloro thing more than boiling point＞220 ℃, like trichlorotoluene zotrichloride, chlorinated benzene equal solvent.
Described catalyzer is magnesium chloride, NSC 51149 or amino acid (as: polyglutamic acid etc.).
Said corrosion-mitigation scale-inhibition protective material is a sulfonic acid copolymer, as: sulfonated phenylethylene/maleic acid, vinylformic acid/3-allyl alcohol radical-2-hydroxypropyl sulfonic acid copolymer etc.
Said non-powder formed carbon molecular sieve adsorption discoloring agent is cylindrical gac molecular sieve, granule activated carbon molecular sieve, spherical activated carbon molecular sieve, bar-shaped gac molecular sieve etc.
The molecular characterization of the linear polydichlorophosphazenes that the present invention is prepared is:
The building-up reactions of the linear polydichlorophosphazenes of the present invention is:
The invention has the beneficial effects as follows:
(1) need not carry out refinement treatment before use to reactant feed ammonium chloride and phosphorus pentachloride; And reactant feed adopts the solution mode to feed intake in this method, has avoided that solid materials dissolve slow, caking in the solid feeding mode in reaction kettle, the deficiency that rate of heat release is too high, so simplified operation steps and more convenient operation;
(2) this compound method reaction times weak point, temperature of reaction is no more than 200 ℃, and production cost is lower than other domestic method; This building-up reactions is controlled easily, is suitable for commercial scale prodn;
(3) the linear polydichlorophosphazenes productive rate of the product that obtains of this method is 38%～50%, and relative molecular mass (weight-average molecular weight) is reached for 100,000 when above, and the MWD coefficient is 1.3～1.4;
(4) in addition, the linear polydichlorophosphazenes of the high molecular weight that this preparation method obtains can react with other nucleophilic reagent, obtains having concurrently the multiple polyphosphazene polymer phosphonitrile and the polyphosphonitrile functional materials thereof of inorganic functional and organic functions.All have great importance for synthesizing preparation and developing other functional polyalkylene phosphonitrile material.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to following embodiment, embodiment should not regard the qualification to protection domain of the present invention as.
Embodiment 1:
In the anhydrous dry four-hole reactor drum that whisking appliance, TM, spherical condensation tube and hydrogen chloride absorption device are housed, at first add naphthalene chloride solvent 80ml, then phosphorus pentachloride 90.12g and ammonium chloride 21.57g are dissolved in the above-mentioned solvent, add sulfonated phenylethylene/maleic acid 0.30g again; Magnesium chloride 0.30g, bar-shaped gac molecular sieve 5mg stirs nitrogen protection; Behind the heat temperature raising to 90 ℃, the temperature rise rate with 1～2 ℃/min slowly rises to 180 ℃ again, reacts 3.5 hours, then reaction solution is cooled to 70 ℃; Remove by filter remaining solid formation, above-mentioned filtrating is moved in the sherwood oil of 40ml, stir; Supernatant liquid is removed in the solution layering, uses a small amount of petroleum ether 3 times again; Liquid is that achromaticity and clarification is transparent to the upper strata, and after the whole separated and dissolved of naphthalene chloride, the linear polydichlorophosphazenes PDCP of product stays in solid phase; With vacuum-drying under the linear PDCP normal temperature of solid product 6 hours, the 18.62g that weighs, productive rate 39.8%.Molecular weight 7～110,000: MWD coefficient: 1.34, linear PDCP is dissolved in the THF preserves at last.
Embodiment 2:
In the anhydrous dry four-hole reactor drum that whisking appliance, TM, spherical condensation tube and hydrogen chloride absorption device are housed; At first add naphthalene chloride solvent 100ml; Then phosphorus pentachloride 100.45g and ammonium chloride 21.57g are dissolved in the above-mentioned solvent; And then adding polyglutamic acid 0.36g, granular active carbon molecular sieve 6mg, vinylformic acid/3-allyl alcohol radical-2-hydroxypropyl sulfonic acid copolymer 0.30g; Stir, behind the controlled atmosphere, heat temperature raising to 90 ℃, the temperature rise rate with 1～2 ℃/min slowly rises to 180 ℃ again; Reacted 4.0 hours, and then reaction solution was cooled to 60 ℃, remove by filter remaining solid formation, above-mentioned filtrating is moved in the 50ml sherwood oil; Stir, supernatant liquid is removed in the solution layering, uses a small amount of petroleum ether 3 times again; Liquid is that achromaticity and clarification is transparent to the upper strata, and after the whole separated and dissolved of naphthalene chloride, the linear polydichlorophosphazenes PDCP of product stays in solid phase; With vacuum-drying under the linear PDCP normal temperature of solid product 6 hours, the 21.04g that weighs, productive rate 45%.Molecular weight: 8～110,000, MWD: 1.32.At last linear PDCP is dissolved in the THF and preserves.
Embodiment 3:
In the anhydrous dry four-hole reactor drum that whisking appliance, TM, spherical condensation tube and hydrogen chloride absorption device are housed; At first add naphthalene chloride solvent 70ml; Then phosphorus pentachloride 96.26g and ammonium chloride 21.57g are dissolved in the above-mentioned solvent; And then adding magnesium chloride 0.40g, granular active carbon molecular sieve 6mg, sulfonated phenylethylene/maleic acid 0.32g; Stir, behind the controlled atmosphere, heat temperature raising to 90 ℃, the temperature rise rate with 1～2 ℃/min slowly rises to 175 ℃ again; Reacted 3.0 hours, and then reaction solution was cooled to about 65 ℃, remove by filter remaining solid formation, above-mentioned filtrating is moved in the 35ml sherwood oil; Stir, supernatant liquid is removed in the solution layering, uses a small amount of petroleum ether 3 times again; Liquid is that achromaticity and clarification is transparent to the upper strata, and after the whole separated and dissolved of trichlorobenzene, the linear polydichlorophosphazenes PDCP of product stays in solid phase; With vacuum-drying under the linear PDCP normal temperature of solid product 6 hours, the 17.77g that weighs, productive rate 38%.Molecular weight: 6～90,000, MWD: 1.41.At last linear PDCP is dissolved in the THF and preserves.
Claims (5)
1. the preparation method of the linear polydichlorophosphazenes of a high molecular weight is characterized in that, may further comprise the steps:
(1) in anhydrous dry reaction container, adds boiling point greater than 220 ℃ high boiling point chloro thing solvent; With phosphorus pentachloride and chloride leach in high boiling point chloro thing solvent; Add catalyzer, corrosion-mitigation scale-inhibition protective material and non-powder formed carbon molecular sieve adsorption discoloring agent again; Under protection of inert gas, be warming up to 170～180 ℃, insulation reaction 3～7 hours; Wherein, the mol ratio of phosphorus pentachloride and ammonium chloride is 1: 1～1.3: 1; With ammonium chloride is datum quantity, and catalyst consumption is 1.2～2.0wt%; The protectant consumption of corrosion-mitigation scale-inhibition is 1.2～1.5wt%; The consumption of non-powder formed carbon molecular sieve adsorption discoloring agent is 0.02～0.05wt%; Said catalyzer is magnesium chloride, NSC 51149 or amino acid, and said corrosion-mitigation scale-inhibition protective material is a sulfonic acid copolymer;
(2) after reaction finished, temperature was reduced to 60～70 ℃, and above-mentioned material is carried out solid-liquid separation, removes solid; The liquid that then separation is obtained carries out purification processes.
2. the preparation method of the linear polydichlorophosphazenes of high molecular weight as claimed in claim 1 is characterized in that, said sulfonic acid copolymer is sulfonated phenylethylene/maleic acid or vinylformic acid/3-allyl alcohol radical-2-hydroxypropyl sulfonic acid copolymer.
3. the preparation method of the linear polydichlorophosphazenes of high molecular weight as claimed in claim 1; It is characterized in that said non-powder formed carbon molecular sieve adsorption discoloring agent is cylindrical gac molecular sieve, granule activated carbon molecular sieve, spherical activated carbon molecular sieve or bar-shaped gac molecular sieve.
4. like the preparation method of the linear polydichlorophosphazenes of any described high molecular weight among the claim 1-3, it is characterized in that the mass ratio of the add-on of said high boiling point chloro thing and reactant feed ammonium chloride and phosphorus pentachloride total amount is 1: 2～1: 1.
5. the preparation method of the linear polydichlorophosphazenes of high molecular weight as claimed in claim 4 is characterized in that, said high boiling point chloro thing is trichlorotoluene zotrichloride or chlorinated benzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110362184 CN102515121B (en) | 2011-11-15 | 2011-11-15 | Preparation method of linear polyhalophosphazene with high relative molecular mass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110362184 CN102515121B (en) | 2011-11-15 | 2011-11-15 | Preparation method of linear polyhalophosphazene with high relative molecular mass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102515121A true CN102515121A (en) | 2012-06-27 |
| CN102515121B CN102515121B (en) | 2013-07-10 |
Family
ID=46286275
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110362184 Active CN102515121B (en) | 2011-11-15 | 2011-11-15 | Preparation method of linear polyhalophosphazene with high relative molecular mass |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102515121B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108217613A (en) * | 2018-02-11 | 2018-06-29 | 北京化工大学 | It is a kind of to catalyze and synthesize the method for preparing linear polydichlorophosphazenes |
| CN108439357A (en) * | 2018-05-22 | 2018-08-24 | 济南泰星精细化工有限公司 | A kind of preparation method of linear chlorine for phosphonitrile |
| CN114044904A (en) * | 2021-11-02 | 2022-02-15 | 湖北兴瑞硅材料有限公司 | Synthesis method of load type linear phosphonitrile chloride catalyst |
-
2011
- 2011-11-15 CN CN 201110362184 patent/CN102515121B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| 宋青等: "线型聚二氯磷腈衍生物用于提高聚丙烯、尼龙6的阻燃性能", 《塑料工业》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108217613A (en) * | 2018-02-11 | 2018-06-29 | 北京化工大学 | It is a kind of to catalyze and synthesize the method for preparing linear polydichlorophosphazenes |
| CN108217613B (en) * | 2018-02-11 | 2019-08-13 | 北京化工大学 | A method of it catalyzes and synthesizes and prepares linear polydichlorophosphazenes |
| CN108439357A (en) * | 2018-05-22 | 2018-08-24 | 济南泰星精细化工有限公司 | A kind of preparation method of linear chlorine for phosphonitrile |
| CN114044904A (en) * | 2021-11-02 | 2022-02-15 | 湖北兴瑞硅材料有限公司 | Synthesis method of load type linear phosphonitrile chloride catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102515121B (en) | 2013-07-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104262398A (en) | Phosphorus-nitrogen type flame retardant containing active double bond as well as preparation method and application thereof | |
| CN103044286A (en) | Synthetic method of malononitrile | |
| CN102515121B (en) | Preparation method of linear polyhalophosphazene with high relative molecular mass | |
| CN107721854A (en) | The manufacture method of α fluoro acrylic esters | |
| CN108794525A (en) | A kind of preparation method of phosphonium flame retardant | |
| CN107353438A (en) | A kind of phosphorous, nitrogen combustion inhibitor and preparation method thereof | |
| CA2724066C (en) | Method for producing bicyclic guanidines by use of a cyclic thiourea | |
| CN102268043B (en) | Sulfur-containing organic phosphine double-cage cyclic ester compound and preparation method thereof | |
| CN111454286A (en) | Synthetic method of difluoroalkenyl boron compound | |
| CN106565866B (en) | Schiff base ligand ruthenium metal catalyst, and preparation and application thereof | |
| CN101967162A (en) | Synergetic flame retardant compound containing four elements of P, N, S and Br and preparation method thereof | |
| CN102532601A (en) | Novel halogen-free fire retardant ethanediamine diphenyl diphosphate and preparation method thereof | |
| CN108084438A (en) | A kind of phenyl T10 cage-type silsesquioxanes and its synthetic method and application | |
| AU2017239770B9 (en) | New polymer having aldaric acid as structural unit, and method for producing same | |
| CN108276439B (en) | Brominated phosphate flame retardant and preparation method thereof | |
| CN101817846A (en) | Thio-phenyl phosphonic piperazine polymer and preparation method thereof | |
| CN113861242B (en) | Synthetic method of caged phosphonate | |
| CN102276653A (en) | Novel sulphur-containing organic phosphine flame retardant compound and preparation method thereof | |
| CN104926879B (en) | The preparation method of trihydroxy methyl phosphine oxide caged phosphorothioate compound | |
| CN113788950B (en) | Polyphosphazene and preparation method and application thereof | |
| KR20140029603A (en) | Production method for flame-retardant polyethyleneterephthalate having high char yield | |
| CN117603156A (en) | Synthesis method of pinoxaden intermediate N-acetyl- [1,4,5] -oxydiazepam | |
| CN105566386A (en) | Phenylthiophosphonic bi-(tribromophenyl) ester compound and preparation method thereof | |
| CN105753770A (en) | Protein kinase inhibitor preparation method, protein kinase inhibitor intermediate, intermediate preparation method and application | |
| CN101284788B (en) | Preparation method of 2,3-di(2,4-dinitro phenoxy)naphthalin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 100029, No. 15 East Third Ring Road, Chaoyang District, Beijing Co-patentee after: Shandong Taixing New Materials Co., Ltd. Patentee after: Beijing University of Chemical Technology Address before: 100029, No. 15 East Third Ring Road, Chaoyang District, Beijing Co-patentee before: Jinan TaiXing Fine Chemical Co., Ltd. Patentee before: Beijing University of Chemical Technology |