CN102382298A - Polyphosphazene-ether amide material and preparation method thereof - Google Patents

Abstract

The invention relates to a novel polyphosphazene-ether amide material and a preparation method thereof. The structural formula of the polyphosphazene-ether amide is disclosed in the specification. The polyphosphazene-ether amide provided by the invention can be easily dissolved in a high-polarity organic solvent on the premise of keeping the excellent thermal stability of the polyamide, thereby enhancing the machining properties; the polyphosphazene-ether amide has high carbon residue rate at 600 DEG C; and the polyphosphazene-ether amide is mainly applicable to automobile engine components, mechanical components and aviation equipment components, and provides a new option for mechanical high-temperature solid lubricating materials.

Description

Poly phosphazene-ether acid amides material and preparation method thereof

Technical field

The present invention relates to a kind of poly phosphazene-ether acid amides material 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:

Gather terephthaldehyde's phthalein Ursol D (PPTA) fiber, be called as Fanglun l414 in China, resistance toheat is near inorganic fibre; Dimensional stability under the high temperature is high, and very high flame retardant resistance is arranged, and can not shrink when contacting with flame; The physicals that long time reservation fiber can be arranged, and its maximum characteristics are that density is low, so specific tenacity and specific modulus will be higher than quite a few times of steel fibers; Replace iron and steel and metallic substance such as the alloy of admiring as structured material, when being applied to the vehicles such as automobile, aircraft, vehicle and boats and ships, lightweight is obvious especially; This has brought a lot of favourable conditions for fuel saving, miniaturized, high speed, 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 is harsh, and the solvability of material is single, only is dissolved in the vitriol oil.And the novel poly phosphazene of synthetic-Fang acid amides has solvability preferably to polar solvent, excellent flame, and heat decomposition temperature is high, has the excellent comprehensive performance again, thereby can be applied to fields such as weaving, automobile, aerospace widely.

Summary of the invention

One of the object of the invention is to provide a kind of poly phosphazene-ether 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 new selection is provided for mechanical high-temperature solid lubrication material.

Two of the object of the invention is to provide this poly phosphazene-ether acid amides preparation methods.

For realizing above-mentioned purpose, the present invention takes following reaction mechanism:

According to above-mentioned mechanism, the present invention adopts following technical scheme:

A kind of poly phosphazene-ether acid amides material is characterized in that the structural formula of this material is:

。

A kind of method for preparing above-mentioned poly phosphazene-ether acid amides material is characterized in that the concrete steps of this method are:

A. hexachlorocyclotriphosphazene is dissolved in the solvents tetrahydrofurane (THF), drips 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 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 ring triphosphine nitriles with step a gained are dissolved in the THF solvent, drip 4, and the THF solution of 4 '-diaminodiphenyl oxide (ODA) under inert atmosphere, reacted 12～24 hours under 20～60 ℃ of temperature.Remove desolvate, deionized water and washing with alcohol, vacuum-drying 12～24 hours, the red solid powder be to have end group to be amino ring triphosphine nitrile oligopolymer N ₃P ₃(OC ₆H ₅) ₄(NHC ₆H ₄OC ₆H ₄NH ₂) ₂The mol ratio of described 1,1,3,5-four phenoxy ring triphosphine nitriles and ODA 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, reacts 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 poly phosphazene-ether acid amides; 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 complete fragrant polymeric amide of the present invention's preparation has good polar solvent solubility property, good flame retardancy, thermal stability and other excellent properties similar with the PPTA polymeric amide preferably.

Description of drawings

Fig. 1 is the infrared spectrum of polyphosphonitrile of the present invention-ether acid amides material;

Fig. 2 is the phosphorus spectrum spectrogram of polyphosphonitrile of the present invention-ether acid amides material;

Fig. 3 is the XRD spectra of polyphosphonitrile of the present invention-ether acid amides material;

Fig. 4 is the TGA spectrogram of polyphosphonitrile of the present invention-ether 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 following embodiment.

Embodiment 1:

Synthesizing of polyphosphonitrile-ether acid amides material, realize through following step:

(1) in the 500mL there-necked flask of magnet rotor stirring, prolong, TM is housed; Repeatedly the hexachlorocyclotriphosphazene of sublimation production (17.4g 0.05mol) is dissolved in 50mL 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 100mL THF solvent; Dropping be dissolved with (8g 0.04mol) 4; The 100mL THF solution of 4 '-diaminodiphenyl oxide (ODA) and (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, the red solid powder.

(3) in the 150mL there-necked flask that mechanical stirrer, HCl absorption unit are housed; Step (2) gained (9.05g 0.01mol) red solid powder, room temperature are dissolved in the double solvents of (0.13g 0.0031mol) 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 red title product, yield 79%.

Embodiment 2:

Synthesizing of polyphosphonitrile-ether acid amides material, realize through following step:

(1) in the 500mL there-necked flask of magnet rotor stirring, prolong, TM is housed; Repeatedly the hexachlorocyclotriphosphazene of sublimation production (13.9g 0.04mol) is dissolved in 50mL 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 be dissolved with (8g 0.04mol) 4; The 50mL THF solution of 4 '-diaminodiphenyl oxide (ODA) and (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, the incarnadine pressed powder.

(3) in the 150mL there-necked flask that mechanical stirrer, HCl absorption unit are housed; Step (2) gained (18.1g 0.02mol) red solid powder, room temperature are dissolved in the double solvents of (0.27g 0.0063mol) 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 red title product, yield 83.1%.

Embodiment 3:

Synthesizing of polyphosphonitrile-ether acid amides material, realize through following step:

(1) in the 500mL there-necked flask of magnet rotor stirring, prolong, TM is housed; Repeatedly the hexachlorocyclotriphosphazene of sublimation production (34.8g 0.1mol) is dissolved in 100mL 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 be dissolved with (20g 0.1mol) 4; The 100mL THF solution of 4 '-diaminodiphenyl oxide (ODA), 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, the red solid powder.

(3) in the 150mL there-necked flask that mechanical stirrer, HCl absorption unit are housed; With step (2) gained (45.25g 0.05mol) red solid powder; Room temperature is dissolved in the double solvents of (0.67g 0.0157mol) LiCl and 20mL DMAC N,N (DMAc), adds (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 red title product, yield is 82%.

Test characterizes through the structure and the performance of means such as infrared, nuclear-magnetism, thermal property to synthetic product, and test result is referring to Fig. 1, Fig. 2, Fig. 3, Fig. 4 and table 1.

 

The solubility property test of table 1 polyphosphonitrile-ether acid amides material

Solvent

CHCl 3

DCM

THF

DMF

DMAc

NMP

Py

DMSO

DOV

Solvability

–

–

–

±

±

+

–

+

+

Remarks :+expression room temperature solubilized; – representes 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 polyphosphonitrile-ether acid amides material 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. poly phosphazene-ether acid amides material is characterized in that the structural formula of this material is:

。

2. poly phosphazene according to claim 1-ether acid amides preparation methods is characterized in that the concrete steps of this method are:

A. hexachlorocyclotriphosphazene is dissolved in the solvents tetrahydrofurane (THF), drips 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 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 ring triphosphine nitriles with step a gained are dissolved in the THF solvent, drip 4, and the THF solution of 4 '-diaminodiphenyl oxide (ODA) under inert atmosphere, reacted 12～24 hours under 20～60 ℃ of temperature; Remove desolvate, deionized water and washing with alcohol, vacuum-drying 12～24 hours, the red solid powder be to have end group to be amino ring triphosphine nitrile oligopolymer N ₃P ₃(OC ₆H ₅) ₄(NHC ₆H ₄OC ₆H ₄NH ₂) ₂The mol ratio of described 1,1,3,5-four phenoxy ring triphosphine nitriles and ODA 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, reacts 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 poly phosphazene-ether acid amides; 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).

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