CN102286149A - Polyphosphazene-semi-aromatic amide material and preparation method thereof - Google Patents
Polyphosphazene-semi-aromatic amide material and preparation method thereof Download PDFInfo
- Publication number
- CN102286149A CN102286149A CN 201110178029 CN201110178029A CN102286149A CN 102286149 A CN102286149 A CN 102286149A CN 201110178029 CN201110178029 CN 201110178029 CN 201110178029 A CN201110178029 A CN 201110178029A CN 102286149 A CN102286149 A CN 102286149A
- Authority
- CN
- China
- Prior art keywords
- hours
- semi
- polyphosphazene
- acid amides
- dissolved
- 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
Images
Abstract
The invention relates to a novel polyphosphazene-semi-aromatic amide material and a preparation method thereof. The polyphosphazene-semi-aromatic amide has the following structural formula. The polyphosphazene-semi-aromatic amide is easily dissolved in a high polar organic solvent on the premise of keeping excellent thermal stability of full aromatic polyamide, so the machining performance of the polyphosphazene-semi-aromatic amide is enhanced; and the polyphosphazene-semi-aromatic amide material has relatively high carbon residue rate at the temperature of 600 DEG C, is mainly applied to automobile engine components, mechanical components and aerospace equipment components, and provides a new choice for mechanical high-temperature solid lubricating materials.
Description
Technical field
The present invention relates to fragrant acid amides material of a kind of poly phosphazene-half and preparation method thereof.
Background technology
The special construction of poly phosphazene (HCCP) and high-performance have determined it in the much extensive studies and application in fields.Mainly concentrate on nonlinear optical material, specialty elastomer and resilient material, separatory membrane, fire retardant material, solid electrolyte and medicine and biomedical material etc. at present.Chemical structural formula:
Poly-terephthaldehyde's phthalein Ursol D (PPTA) fiber, be called as Fanglun l414 in China, resistance toheat is near inorganic fibre, dimensional stability height under the high temperature, and very high flame retardant resistance is arranged, can not shrink when contacting with flame, can there be the long time to keep the physicals of fiber, and its maximum characteristics are that density is low, so specific tenacity and specific modulus will be higher than several times of steel fibers,, be applied to automobile as metallic substance such as the structured material replacement iron and steel and the alloys of admiring, aircraft, during the vehicles such as vehicle and boats and ships, lightweight is obvious especially, this gives fuel saving, miniaturization, high speed has brought a lot of favourable conditions, simultaneously because Fanglun l414 still has the flexibility of general fibre, can not fracture because of crooked, can not become fragile yet, thereby can spin cotton and weave cloth because of being heated.Chemical structural formula:
For simple PPTA fiber, its processing and preparing technology harshness, the solvability of material is single.And the novel poly phosphazene of synthetic-Fang acid amides has solvability preferably to polar solvent, excellent flame, and the heat decomposition temperature height has the excellent comprehensive performance again, thereby can be applied to fields such as weaving, automobile, aerospace widely.
Summary of the invention
One of purpose of the present invention is to provide a kind of poly phosphazene-half fragrant acid amides material.Characteristics such as this material has that solubility property is good, heat decomposition temperature is high, flame retardant properties good, high temperature high residue and other excellent combination property, be mainly used in automotive engine component, mechanical part and air equipment parts, and provide new selection for mechanical high-temperature solid lubrication material.
Two of purpose of the present invention is to provide this preparation methods.
For achieving the above object, the reaction mechanism that the present invention adopts is:
For achieving the above object, the present invention takes following technical scheme:
The preparation of a kind of poly phosphazene-half fragrant acid amides material is characterized in that the structural formula of this material is:
A kind of preparation method according to above-mentioned poly phosphazene-half fragrant acid amides is characterized in that the concrete steps of this method are:
A. will encircle the triphosphine nitrile and be dissolved in the solvents tetrahydrofurane (THF), drip the THF solution of sodium phenylate, under inert atmosphere protection, 20～50 ℃ of reactions 12～24 hours, remove and desolvate, deionized water wash, drying obtain 1,1,3,5-four phenoxy group ring triphosphine nitriles; The mol ratio of wherein encircling triphosphine nitrile and sodium phenylate is 1: (3.9～4.1);
B. 1,1,3,5-four phenoxy group ring triphosphine nitriles with step a gained are dissolved in the THF solvent, drip the THF solution of quadrol (EDA), under inert atmosphere, react 12～24 hours under 20～60 ℃ of temperature.Remove desolvate, deionized water and ethanol repetitive scrubbing, vacuum-drying 12～24 hours, faint yellow colloid have end group and is amino ring triphosphine nitrile oligopolymer N
3P
3(OC
6H
5)
4(NHCH
2CH
2NH
2)
2The mol ratio of described 1,1,3,5-four phenoxy group ring triphosphine nitriles and EDA is 1: (2～3);
C. step b gained ring three phosphonitrile oligopolymers and pyridine or triethylamine are dissolved in LiCl and N-Methyl pyrrolidone or N, in the double solvents of N-N,N-DIMETHYLACETAMIDE, under inert atmosphere protection, gradation adds p-phthaloyl chloride under condition of ice bath, react after 30 minutes, at room temperature react until rod climbing phenomenon occurring, termination reaction; The deionized water wash product, 80～120 ℃ of slakings 6～12 hours, vacuum-drying got the fragrant acid amides of poly phosphazene-half; The mol ratio of described ring three phosphonitrile oligopolymers, pyridine or triethylamine, LiCl and p-phthaloyl chloride is 1: (1.96～2.94): (0.2～0.5): (1～1.01).
The semiaromatic polyamide material of the present invention's preparation has good polar solvent solubility property, good flame retardancy, and thermal stability and other excellent properties similar to the PPTA polymeric amide have a good application prospect preferably.
Description of drawings
Fig. 1 is the infrared spectrum of polyphosphonitrile of the present invention-half fragrant acid amides material;
Fig. 2 is the phosphorus spectrum spectrogram of the fragrant acid amides material of polyphosphonitrile of the present invention-half;
Fig. 3 is the XRD spectra of polyphosphonitrile of the present invention-half fragrant acid amides material;
The TGA spectrogram of Fig. 4 polyphosphonitrile-half fragrant acid amides 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 the following examples.
Embodiment 1:
Synthesizing of the fragrant acid amides material of polyphosphonitrile-half, realize by following step:
(1) in the 500mL there-necked flask of magnet rotor stirring, prolong, thermometer is housed; repeatedly the hexachlorocyclotriphosphazene of sublimation production (17.4g 0.05mol) is dissolved in 50mL tetrahydrofuran (THF) (THF) solvent; the sodium phenylate that drips (the 2.32g 0.2mol) that prepare is (under nitrogen protection; (4.6g 0.2mol) sodium Metal 99.5 made with the 25 ℃ of reactions in 50mL THF solution of (18.822g 0.2mol) phenol in 2 hours) THF solution; nitrogen protection, 40 ℃ were reacted 12 hours.Rotary distillation remove THF, again with deionized water repeatedly wash, 50 ℃ of vacuum-drying 24 hours, obtain the oyster white colloid.
(2) in the 500mL there-necked flask that magnet rotor stirring, prolong, HCl absorption unit are housed; (10.37g 0.018mol) oyster white colloid of step (1) gained is dissolved in the 50mL THF solvent; dropping is dissolved with the quadrol (EDA) of (2.4g 0.04mol) and the 50mL THF solution of (5.56 mL 0.04mol) triethylamine; nitrogen protection, 40 ℃ were reacted 24 hours down.Rotary distillation remove THF, deionized water and ethanol repetitive scrubbing repeatedly, 50 ℃ of vacuum-drying 24 hours, faint yellow colloid.
(3) in the 150mL there-necked flask that mechanical stirrer, HCl absorption unit are housed; the faint yellow colloid of step (2) gained (6.25g 0.01mol), room temperature are dissolved in the double solvents of (0.1g 0.0023mol) LiCl and 20mL N-Methyl pyrrolidone (NMP); add (2.78mL 0.02mol) triethylamine; mechanical stirring; under nitrogen protection; 0 ° of C joins the p-phthaloyl chloride (TPC) of (2.04g 0.01mol) in the reaction system down at twice, and filler is spaced apart 5 minutes.React after 30 minutes, withdraw ice bath, room temperature reaction is to rod climbing phenomenon occurring, termination reaction.With deionized water washed product repeatedly, 120 ℃ of slakings 8 hours, 50 ℃ of vacuum-dryings 12 hours the white object product, yield 72%.
Embodiment 2:
Synthesizing of the fragrant acid amides material of polyphosphonitrile-half, realize by following step:
(1) in the 500mL there-necked flask of magnet rotor stirring, prolong, thermometer is housed; repeatedly the hexachlorocyclotriphosphazene of sublimation production (13.9g 0.04mol) is dissolved in 50mL tetrahydrofuran (THF) (THF) solvent; the sodium phenylate that drips (the 1.856g 0.16mol) that prepare is (under nitrogen protection; (3.68g 0.16mol) sodium Metal 99.5 made with the 25 ℃ of reactions in 50mL THF solution of (15.06g 0.16mol) phenol in 2 hours) THF solution; nitrogen protection, 40 ℃ were reacted 12 hours.Rotary distillation remove THF, again with deionized water repeatedly wash, 50 ℃ of vacuum-drying 24 hours, obtain the oyster white colloid.
(2) in the 500mL there-necked flask that magnet rotor stirring, prolong, HCl absorption unit are housed; (11.52g 0.02mol) oyster white colloid of step (1) gained is dissolved in the 50mL THF solvent; dropping is dissolved with the quadrol (EDA) of (2.4g 0.04mol) and the 50mL THF solution of (3.32mL 0.04mol) pyridine; nitrogen protection, 40 ℃ were reacted 24 hours down.Rotary distillation remove THF, deionized water and ethanol repetitive scrubbing repeatedly, 50 ℃ of vacuum-drying 24 hours, faint yellow colloid.
(3) in the 150mL there-necked flask that mechanical stirrer, HCl absorption unit are housed; the faint yellow colloid of step (2) gained (12.50g 0.02mol), room temperature are dissolved in the double solvents of (0.20g 0.0046mol) LiCl and 20mL N-Methyl pyrrolidone (NMP); add (3.32mL 0.04mol) pyridine; mechanical stirring; under nitrogen protection; 0 ° of C joins the p-phthaloyl chloride (TPC) of (4.08g 0.02mol) in the reaction system down at twice, and filler is spaced apart 5 minutes.React after 30 minutes, withdraw ice bath, room temperature reaction is to rod climbing phenomenon occurring, termination reaction.With deionized water washed product repeatedly, 120 ℃ of slakings 8 hours, 50 ℃ of vacuum-dryings 12 hours the white object product, yield 79.9%.
Embodiment 3:
Synthesizing of the fragrant acid amides material of polyphosphonitrile-half, realize by following step:
(1) in the 500mL there-necked flask of magnet rotor stirring, prolong, thermometer is housed; repeatedly the hexachlorocyclotriphosphazene of sublimation production (34.8g 0.1mol) is dissolved in 100mL tetrahydrofuran (THF) (THF) solvent; the sodium phenylate that drips (the 9.28g 0.4mol) that prepare is (under nitrogen protection; (9.2g 0.4mol) sodium Metal 99.5 made with the 25 ℃ of reactions in 100mL THF solution of (37.64g 0.4mol) phenol in 2 hours) THF solution; nitrogen protection, 40 ℃ were reacted 24 hours.Rotary distillation remove THF, again with deionized water repeatedly wash, 50 ℃ of vacuum-drying 24 hours, obtain the oyster white colloid.
(2) in the 500mL there-necked flask that magnet rotor stirring, prolong, HCl absorption unit are housed; (28.81g 0.05mol) oyster white colloid of step (1) gained is dissolved in the 100mL THF solvent; dropping is dissolved with the 100mL THF solution of the quadrol (EDA) of (6g 0.1mol); nitrogen protection, 40 ℃ were reacted 24 hours down.Rotary distillation remove THF, deionized water and ethanol repetitive scrubbing repeatedly, 50 ℃ of vacuum-drying 24 hours, faint yellow colloid.
(3) in the 150mL there-necked flask that mechanical stirrer, HCl absorption unit are housed; the faint yellow colloid of step (2) gained (31.25g 0.05mol), room temperature are dissolved in (0.1g 0.0023mol) LiCl and 20mL N; in the double solvents of N-N,N-DIMETHYLACETAMIDE (DMAc); add (8.3mL 0.1mol) pyridine; mechanical stirring; under nitrogen protection; 0 ° of C joins the p-phthaloyl chloride (TPC) of (10.2g 0.05mol) in the reaction system down at twice, and filler is spaced apart 5 minutes.React after 30 minutes, withdraw ice bath, room temperature reaction is to rod climbing phenomenon occurring, termination reaction.With deionized water washed product repeatedly, 120 ℃ of slakings 8 hours, 50 ℃ of vacuum-dryings 12 hours the white object product, yield is 78.4%.
Characterize by the structure and the performance of means such as infrared, nuclear-magnetism, thermal characteristics to poly phosphazene of the present invention-half fragrant acid amides, test result sees also Fig. 1, Fig. 2, Fig. 3 and Fig. 4, and the solubility property test result sees also following table 1:
The solubility property test of the fragrant acid amides material of table 1 polyphosphonitrile-half
| Solvent | CHCl 3 | DCM | THF | DMF | DMAc | NMP | Py | DMSO | DOV |
| Solvability | + | ± | ± | ± | + | + | ± | + | + |
Remarks :+expression room temperature solubilized; – represents that room temperature do not dissolve; ± expression heating for dissolving
Verified that from Fig. 1,2 infrared and phosphorus spectrum nuclear magnetic spectrogram the structure of synthetic complete fragrant polymeric amide is consistent with the new material structures of design; Fig. 3 utilizes the x x ray diffractometer x that the crystal property of material is tested, and the result shows the introducing owing to the phosphonitrile inorganic group, and the novel material crystal property reduces, and peak crystallization weakens; Fig. 4 shows that then the fragrant acid amides material of polyphosphonitrile-half has excellent thermostability and higher charcoal residual rate, thereby infers that this material also has good flame retardancy; Data in the table 1 have proved that fully novel material has the solubility property of good polar solvent, for the formulations prepared from solutions of polymeric amide Industrial materials provides more choices.
Claims (2)
1. the preparation of poly phosphazene-half fragrant acid amides material is characterized in that the structural formula of this material is:
2. the preparation method of a poly phosphazene according to claim 1-half fragrant acid amides is characterized in that the concrete steps of this method are:
A. will encircle the triphosphine nitrile and be dissolved in the solvents tetrahydrofurane, drip the tetrahydrofuran solution of sodium phenylate, under inert atmosphere protection, 20～50 ℃ of reactions 12～24 hours, remove and desolvate, deionized water wash, drying obtain 1,1,3,5-four phenoxy group ring triphosphine nitriles; The mol ratio of wherein encircling triphosphine nitrile and sodium phenylate is 1: (3.9～4.1);
B. 1,1,3,5-four phenoxy group ring triphosphine nitriles with step a gained are dissolved in the tetrahydrofuran solvent, drip the tetrahydrofuran solution of quadrol, under inert atmosphere, react 12～24 hours under 20～60 ℃ of temperature; Remove desolvate, deionized water and ethanol repetitive scrubbing, vacuum-drying 12～24 hours, faint yellow colloid be to have end group to be amino ring triphosphine nitrile oligopolymer N
3P
3(OC
6H
5)
4(NHCH
2CH
2NH
2)
2The mol ratio of described 1,1,3,5-four phenoxy group ring triphosphine nitriles and quadrol is 1: (2～3);
C. step b gained ring three phosphonitrile oligopolymers and pyridine or triethylamine are dissolved in LiCl and N-Methyl pyrrolidone or N, in the double solvents of N-N,N-DIMETHYLACETAMIDE, under inert atmosphere protection, gradation adds p-phthaloyl chloride under condition of ice bath, react after 30 minutes, at room temperature reaction until rod climbing phenomenon occurring, termination reaction; The deionized water wash product, 80～120 ℃ of slakings 6～12 hours, vacuum-drying got the fragrant acid amides of poly phosphazene-half; The mol ratio of described ring three phosphonitrile oligopolymers, pyridine or triethylamine, LiCl and p-phthaloyl chloride is 1: (1.96～2.94): (0.2～0.5): (1～1.01).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110178029 CN102286149B (en) | 2011-06-29 | 2011-06-29 | Polyphosphazene-semi-aromatic amide material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110178029 CN102286149B (en) | 2011-06-29 | 2011-06-29 | Polyphosphazene-semi-aromatic amide material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102286149A true CN102286149A (en) | 2011-12-21 |
| CN102286149B CN102286149B (en) | 2013-01-09 |
Family
ID=45332919
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110178029 Expired - Fee Related CN102286149B (en) | 2011-06-29 | 2011-06-29 | Polyphosphazene-semi-aromatic amide material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102286149B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554460A (en) * | 2013-10-18 | 2014-02-05 | 浙江工业大学之江学院工业研究院 | Polycyclotriphosphazene-semi aryl ester and preparation method thereof |
| CN107936245A (en) * | 2017-11-29 | 2018-04-20 | 广东聚航新材料研究院有限公司 | A kind of permanent halogen-free flameproof PA10T polyamides and its synthetic method |
| CN107955162A (en) * | 2017-11-29 | 2018-04-24 | 广东聚航新材料研究院有限公司 | A kind of halogen-free flameproof, high working property PA6T polyamides and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1284508A (en) * | 2000-09-07 | 2001-02-21 | 中国科学院兰州化学物理研究所 | Synthesis process of aryloxy cyclotrinitrile phosphide |
| CN1916051A (en) * | 2005-08-15 | 2007-02-21 | 中国科学院化学研究所 | Substituent polyphosphonitrile, prepartion method and application |
| US7419504B2 (en) * | 2004-12-27 | 2008-09-02 | Advanced Cardiovascular Systems, Inc. | Poly(ester amide) block copolymers |
-
2011
- 2011-06-29 CN CN 201110178029 patent/CN102286149B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1284508A (en) * | 2000-09-07 | 2001-02-21 | 中国科学院兰州化学物理研究所 | Synthesis process of aryloxy cyclotrinitrile phosphide |
| US7419504B2 (en) * | 2004-12-27 | 2008-09-02 | Advanced Cardiovascular Systems, Inc. | Poly(ester amide) block copolymers |
| CN1916051A (en) * | 2005-08-15 | 2007-02-21 | 中国科学院化学研究所 | Substituent polyphosphonitrile, prepartion method and application |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554460A (en) * | 2013-10-18 | 2014-02-05 | 浙江工业大学之江学院工业研究院 | Polycyclotriphosphazene-semi aryl ester and preparation method thereof |
| CN107936245A (en) * | 2017-11-29 | 2018-04-20 | 广东聚航新材料研究院有限公司 | A kind of permanent halogen-free flameproof PA10T polyamides and its synthetic method |
| CN107955162A (en) * | 2017-11-29 | 2018-04-24 | 广东聚航新材料研究院有限公司 | A kind of halogen-free flameproof, high working property PA6T polyamides and preparation method thereof |
| CN107936245B (en) * | 2017-11-29 | 2020-12-11 | 广东聚航新材料研究院有限公司 | Permanent halogen-free flame-retardant PA10T polyamide resin and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102286149B (en) | 2013-01-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102321241B (en) | Polyphosphazene-sulfone amide material and preparation method thereof | |
| WO2020182111A1 (en) | Molybdenum disulfide hybrid flame retardant coated with phosphorus-nitrogen-zinc two-dimensional supramolecule and application thereof | |
| CN102286149B (en) | Polyphosphazene-semi-aromatic amide material and preparation method thereof | |
| CN111303434B (en) | Preparation method of high-flame-retardant cross-linked polyphosphazene elastomer | |
| CN101885824B (en) | Fluorine-containing phosphoric polyurethane elastomer and preparation method thereof | |
| CN110982121B (en) | Triazinyl phosphorus-nitrogen flame retardant, and preparation method and application thereof | |
| CN103509167A (en) | Anti-droplet and high temperature resistant polyimide type polyurethane and preparation method thereof | |
| CN107501493A (en) | Phosphorus nitrogen expansion type combustion inhibitor and its production and use | |
| CN102731778B (en) | Self-flowing meta-aramid and preparation method thereof | |
| CN102382298B (en) | Polyphosphazene-ether amide material and preparation method thereof | |
| CN103570929B (en) | A kind of polycyclic three phosphonitriles-sulfone phenyl ester and preparation method thereof | |
| CN102702521B (en) | Macromolecule triazine charring agent with main chain containing piperazidine structure, and preparation method thereof | |
| EP3378976B1 (en) | Polyimide fiber and preparation method therefor | |
| CN104817686A (en) | Reactive epoxy resin flame retardant and preparation method thereof | |
| CN102382299B (en) | Polyphosphazene-alkylamide material and preparation method thereof | |
| CN102702522B (en) | Macromolecule triazine charring agent and preparation method thereof | |
| CN105463621A (en) | Method for preparing organic modification nano-montmorillonite enhanced polyimide fiber | |
| CN105714411B (en) | A kind of preparation method of poly- pyrrole throat/polyether sulfone/carbon nanometer pipe ternary composite material | |
| CN102702513A (en) | Self-flowing para-phenylene terephthalamide and preparation method thereof | |
| CN106045992B (en) | Synthesis of diazo fluorenyl aromatic diacid monomer and polybenzimidazole polymer thereof | |
| CN111825696B (en) | Benzoxazole ion compound, PBO fiber emulsion sizing agent containing benzoxazole ion compound and preparation method of PBO fiber emulsion sizing agent | |
| CN103554460A (en) | Polycyclotriphosphazene-semi aryl ester and preparation method thereof | |
| CN112500561B (en) | High-strength meta-aramid polymer and preparation method thereof | |
| CN104031090A (en) | Preparation method of cyclic phosphorus-nitrogen synergistic halogen-free flame retardant | |
| CN112341619A (en) | High-elongation meta-aramid polymer and preparation method thereof |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130109 Termination date: 20180629 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |