Summary of the invention
In order to improve the various performances of polyarylether, the present invention adopts a kind of simple, easy method to synthesize the polymkeric substance of the polyarylether of series of new.
Technical scheme of the present invention is for raw material with dichloro monomer and diphenol monomer, use N,N-DIMETHYLACETAMIDE (DMAc) or N-Methyl pyrrolidone (NMP) respectively as solvent, be catalyzer with salt of wormwood, react complete and treatedly obtain polyarylether polymer.
Wherein diphenol monomer is dihydroxyphenyl propane (BPA), hexafluoro bisphenol-a (6FBPA), sulfur-bearing diphenol (TDP) or containing oxygen diphenol (ODP), its structural formula is as follows:
R is:---O---,---S---
Dichloro monomer is 2-phenyl-4,6-dichloro pyrimidine or 4,6-dichloro pyrimidine, and its structural formula is as follows:
The preparation method of novel polyarylether polymer of the present invention, concrete steps are as follows:
(1) under normal pressure, logical nitrogen, 20 ~ 30 DEG C of conditions, in solvent, dichloro monomer and diphenol monomer is added; Wherein, dichloro monomer and diphenol monomer molar consumption and be 1mmol:1 ~ 2mL with the volume ratio of solvent;
(2) under 30 ~ 40 DEG C of agitation conditions, salt of wormwood (K is dripped to above-mentioned system
2cO
3), then at 120 ~ 140 DEG C, stirring reaction 1 ~ 2h; Wherein, the mol ratio of dichloro monomer and salt of wormwood is 1:2 ~ 3, filters after completion of the reaction and obtains polyarylether crude product;
(3) the polyarylether crude product obtained is poured in distilled water, repeatedly boil solvent contained in rear removal product and inorganic salt;
(4) will boil after product and dry 20 ~ 24h at 100 ~ 120 DEG C, the product with methylalcohol after oven dry is purified precipitation again;
(5) product of separating out 50 ~ 60 DEG C, dry 5 ~ 8h under vacuum condition, thus obtain the polymkeric substance of the polyarylether class of white powder of the present invention.
Its preparation process and product structure formula as follows:
The structural formula of the polymkeric substance of the polyarylether class of synthesis is as follows:
Wherein, R is:---O---,---S---,
Ar is
N is positive integer, represents the quantity of repeating unit;
Advantage of the present invention:
The synthesis of novel polyarylether polymer is that make catalyzer by adding salt of wormwood, final high temperature polymerization obtains by dichloro monomer and diphenol monomer in DMAc or nmp solvent.This polymerization process has an enormous advantage.First, when selecting solvent as polyreaction of DMAC and nmp solvent, N,N-DIMETHYLACETAMIDE (DMAc) boiling point at 166 DEG C and N-Methyl pyrrolidone (NMP) boiling point at 200 DEG C, because the boiling point of two kinds of solvents is not high so when polyreaction, need not also can realization response under too high temperature condition, so we react under adopting certain moderate moisture also can obtain higher molecular weight.And N,N-DIMETHYLACETAMIDE (DMAc) and N-Methyl pyrrolidone (NMP) at 120 DEG C as a kind of stable solvent, the decomposition of other solvents when high temperature can be eliminated on the impact of polymerisate.Secondly, this polyreaction need not use solvent bank water, just can reach good polymerization when being with water, makes the molecular weight that product reaches very high.Some band water reactions can introduce another kind of solvent, thus can affect the purity of product, also will consider how solvent will remove.This reaction need not be with water, decreases the step of reaction, and the impact of other solvents reduced.Moreover this reaction times is short, when water need not be with, and moderate temperature, just can complete without comparatively high temps, so shorten the overall time of reaction, obtain good polymkeric substance.
Novel polyarylether polymer prepared by the present invention has higher second-order transition temperature (Fig. 1), illustrates to have very high thermostability; It has good solvability, can be dissolved in N,N-DIMETHYLACETAMIDE (DMAc), trichloromethane, N-Methyl pyrrolidone (NMP) equal solvent.
Embodiment
Embodiment 1
Normal pressure (1.01x10
5pa) under, being equipped with agitator, thermometer, gas passes in the 50mL there-necked flask of mouth nitrogen (always nitrogen terminate to pass into experiment from experiment), the dihydroxyphenyl propane of 1.0mmoL2-phenyl-4,6-dichloro pyrimidine and 1.0mmoL is added, 1.3gN at 25 DEG C, N-dimethyl second phthalein amine (DMAc), under 35 DEG C of agitation conditions, add the Anhydrous potassium carbonate of 2.2mmoL, then start slow heating, maintain 140 DEG C of reaction 2h, now system is sorrel.After having reacted, under constantly stirring, pour distilled water into separate out white strip product, then 6 times are boiled with distilled water, wash away residual solvent and inorganic salt, finally will the solid that obtain in an oven 120 DEG C dry 24h, and be dissolved in methyl alcohol and separate out, 60 DEG C of oven dry 4h in vacuum drying oven again, obtain white solid, output is 0.39g (product, title: polyarylether).
Embodiment 2
Normal pressure (1.01x10
5pa) under, being equipped with agitator, thermometer, gas passes in the 50mL there-necked flask of mouth nitrogen (always nitrogen terminate to pass into experiment from experiment), 2.0mmoL2-phenyl-4 is added at 25 DEG C, the hexafluoro bisphenol-a of 6-dichloro pyrimidine and 2.0mmoL, 2.8gN, N-dimethyl second phthalein amine (DMAc), under 35 DEG C of agitation conditions, add the Anhydrous potassium carbonate of 4.4mmoL, stir under normal temperature, then start slow heating, maintain 140 DEG C of reaction 2h, now system is sorrel.After having reacted, under constantly stirring, pour distilled water into separate out white strip product, then 6 times are boiled with distilled water, wash away residual solvent and inorganic salt, finally by the solid obtained in a conventional oven 110 DEG C dry 24h and obtain white solid, and be dissolved in methyl alcohol and separate out, then in vacuum drying oven 60 DEG C dry 4h, output is 0.39g (product, title: polyarylether).
Embodiment 3
Normal pressure (1.01x10
5pa) under, being equipped with agitator, thermometer, gas passes in the 50mL there-necked flask of mouth nitrogen (always nitrogen terminate to pass into experiment from experiment), 1.2mmoL2-phenyl-4 is added at 25 DEG C, the sulfur-bearing diphenol of 6-dichloro pyrimidine and 1.2mmoL, 1.56gN, N-dimethyl second phthalein amine (DMAc), under 35 DEG C of agitation conditions, add the Anhydrous potassium carbonate of 2.64mmoL, stir under normal temperature, then start slow heating, maintain 140 DEG C of reaction 2h, now system is sorrel.After having reacted, under constantly stirring, pour distilled water into separate out white strip product, then 6 times are boiled with distilled water, wash away residual solvent and inorganic salt, finally by the solid obtained in a conventional oven 120 DEG C dry 24h and obtain white solid, and be dissolved in methyl alcohol and separate out, then in vacuum drying oven 60 DEG C dry 4h, output is 0.36g (product, title: polyarylether).
Embodiment 4
Normal pressure (1.01x10
5pa) under, being equipped with agitator, thermometer, gas passes in the 50mL there-necked flask of mouth nitrogen (always nitrogen terminate to pass into experiment from experiment), add at 25 DEG C 1.0mmoL2-phenyl-4,6-dichloro pyrimidine and 1.0mmoL containing oxygen diphenol, 1.3gN, N-dimethyl second phthalein amine (DMAc), under 35 DEG C of agitation conditions, adds the Anhydrous potassium carbonate of 2.2mmoL, stir under normal temperature, then start slow heating, maintain 140 DEG C of reaction 2h, now system is sorrel.After having reacted, under constantly stirring, pour distilled water into separate out white strip product, then 6 times are boiled with distilled water, wash away residual solvent and inorganic salt, finally by the solid obtained in a conventional oven 120 DEG C dry 24h and obtain white solid, and be dissolved in methyl alcohol and separate out, then in vacuum drying oven 60 DEG C dry 4h, output is 0.39g (product, title: polyarylether).
Embodiment 5
Normal pressure (1.01x10
5pa) under, being equipped with agitator, thermometer, gas passes in the 50mL there-necked flask of mouth nitrogen (always nitrogen terminate to pass into experiment from experiment), adds the bisphenol fluorene of 2.0mmoL2-phenyl-4,6-dichloro pyrimidine and 2.0mmoL at 25 DEG C, 2.8gN, N-dimethyl second phthalein amine (DMAc), under 35 DEG C of agitation conditions, adds the Anhydrous potassium carbonate of 4.4mmoL, stir under normal temperature, then start slow heating, maintain 140 DEG C of reaction 2h, now system is sorrel.After having reacted, under constantly stirring, pour distilled water into separate out white strip product, then 6 times are boiled with distilled water, wash away residual solvent and inorganic salt, finally by the solid obtained in a conventional oven 120 DEG C dry 24h and obtain white solid, and be dissolved in methyl alcohol and separate out, then in vacuum drying oven 60 DEG C dry 4h, output is 0.38g (product, title: polyarylether).
Embodiment 6
Normal pressure (1.01x10
5pa) under, being equipped with agitator, thermometer, gas passes in the 50mL there-necked flask of mouth nitrogen (always nitrogen terminate to pass into experiment from experiment), adds the sulfobenzide of 1.0mmoL2-phenyl-4,6-dichloro pyrimidine and 1.0mmoL at 25 DEG C, 1.3gN, N-dimethyl second phthalein amine (DMAc), under 35 DEG C of agitation conditions, adds the Anhydrous potassium carbonate of 2.2mmoL, stir under normal temperature, then start slow heating, maintain 140 DEG C of reaction 2h, now system is sorrel.After having reacted, under constantly stirring, pour distilled water into separate out white strip product, then 6 times are boiled with distilled water, wash away residual solvent and inorganic salt, finally by the solid obtained in a conventional oven 120 DEG C dry 24h and obtain white solid, and be dissolved in methyl alcohol and separate out, then in vacuum drying oven 60 DEG C dry 4h, output is 0.39g (product, title: polyarylether).
Embodiment 7
Normal pressure (1.01x10
5pa) under, being equipped with agitator, thermometer, gas passes in the 50mL there-necked flask of mouth nitrogen (always nitrogen terminate to pass into experiment from experiment), 1.0mmoL4 is added, the dihydroxyphenyl propane of 6-dichloro pyrimidine and 1.0mmoL, 1.3gN-methyl-2-pyrrolidone (NMP) at 25 DEG C, under 35 DEG C of agitation conditions, add the Anhydrous potassium carbonate of 2.2mmoL, stir under normal temperature, then start slow heating, maintain 140 DEG C of reaction 2h, now system is sorrel.After having reacted, under constantly stirring, pour distilled water into separate out white strip product, then 6 times are boiled with distilled water, wash away residual solvent and inorganic salt, finally by the solid obtained in a conventional oven 120 DEG C dry 24h and obtain white solid, and be dissolved in methyl alcohol and separate out, then in vacuum drying oven 60 DEG C dry 4h, output is 0.32g (product, title: polyarylether).
Embodiment 8
Normal pressure (1.01x10
5pa) under, being equipped with agitator, thermometer, gas passes in the 50mL there-necked flask of mouth nitrogen (always nitrogen terminate to pass into experiment from experiment), 2.0mmoL4 is added, the hexafluoro bisphenol-a of 6-dichloro pyrimidine and 2.0mmoL, 2.8gN-methyl-2-pyrrolidone (NMP) at 25 DEG C, under 35 DEG C of agitation conditions, add the Anhydrous potassium carbonate of 4.4mmoL, stir under normal temperature, then start slow heating, maintain 140 DEG C of reaction 2h, now system is sorrel.After having reacted, under constantly stirring, pour distilled water into separate out white strip product, then 6 times are boiled with distilled water, wash away residual solvent and inorganic salt, finally by the solid obtained in a conventional oven 110 DEG C dry 12h and obtain white solid, and be dissolved in methyl alcohol and separate out, then in vacuum drying oven 60 DEG C dry 4h, output is 0.32g (product, title: polyarylether).
Embodiment 9
Normal pressure (1.01x10
5pa) under, being equipped with agitator, thermometer, gas passes in the 50mL there-necked flask of mouth nitrogen (always nitrogen terminate to pass into experiment from experiment), 1.2mmoL4 is added, the sulfur-bearing diphenol of 6-dichloro pyrimidine and 1.2mmoL, 1.56gN-methyl-2-pyrrolidone (NMP) at 25 DEG C, under 35 DEG C of agitation conditions, add the Anhydrous potassium carbonate of 2.64mmoL, stir under normal temperature, then start slow heating, maintain 140 DEG C of reaction 2h, now system is sorrel.After having reacted, under constantly stirring, pour distilled water into separate out white strip product, then 6 times are boiled with distilled water, wash away residual solvent and inorganic salt, finally by the solid obtained in a conventional oven 120 DEG C dry 24h and obtain white solid, and be dissolved in methyl alcohol and separate out, then in vacuum drying oven 60 DEG C dry 4h, output is 0.31g (product, title: polyarylether).
Embodiment 10
Normal pressure (1.01x10
5pa) under, being equipped with agitator, thermometer, gas passes in the 50mL there-necked flask of mouth nitrogen (always nitrogen terminate to pass into experiment from experiment), at 25 DEG C, add 1.2mmoL4,6-dichloro pyrimidine and 1.2mmoL containing oxygen diphenol, 1.56gN-methyl-2-pyrrolidone (NMP), under 35 DEG C of agitation conditions, add the Anhydrous potassium carbonate of 2.64mmoL, stir under normal temperature, then start slow heating, maintain 140 DEG C of reaction 2h, now system is sorrel.After having reacted, under constantly stirring, pour distilled water into separate out white strip product, then 6 times are boiled with distilled water, wash away residual solvent and inorganic salt, finally by the solid obtained in a conventional oven 120 DEG C dry 24h and obtain white solid, and be dissolved in methyl alcohol and separate out, then in vacuum drying oven 60 DEG C dry 4h, output is 0.31g (product, title: polyarylether).
Embodiment 11
Normal pressure (1.01x10
5pa) under, being equipped with agitator, thermometer, gas passes in the 50mL there-necked flask of mouth nitrogen (always nitrogen terminate to pass into experiment from experiment), 1.0mmoL4 is added, the bisphenol fluorene of 6-dichloro pyrimidine and 1.0mmoL, 1.3gN-methyl-2-pyrrolidone (NMP) at 25 DEG C, under 35 DEG C of agitation conditions, add the Anhydrous potassium carbonate of 2.2mmoL, stir under normal temperature, then start slow heating, maintain 140 DEG C of reaction 2h, now system is sorrel.After having reacted, under constantly stirring, pour distilled water into separate out white strip product, then 6 times are boiled with distilled water, wash away residual solvent and inorganic salt, finally by the solid obtained in a conventional oven 120 DEG C dry 24h and obtain white solid, and be dissolved in methyl alcohol and separate out, then in vacuum drying oven 60 DEG C dry 4h, output is 0.32g (product, title: polyarylether).
Embodiment 12
Normal pressure (1.01x10
5pa) under, being equipped with agitator, thermometer, gas passes in the 50mL there-necked flask of mouth nitrogen (always nitrogen terminate to pass into experiment from experiment), 1.0mmoL4 is added, the sulfobenzide of 6-dichloro pyrimidine and 1.0mmoL, 1.3gN-methyl-2-pyrrolidone (NMP) at 25 DEG C, under 35 DEG C of agitation conditions, add the Anhydrous potassium carbonate of 2.2mmoL, stir under normal temperature, then start slow heating, maintain 140 DEG C of reaction 2h, now system is sorrel.After having reacted, under constantly stirring, pour distilled water into separate out white strip product, then 6 times are boiled with distilled water, wash away residual solvent and inorganic salt, finally by the solid obtained in a conventional oven 120 DEG C dry 24h and obtain white solid, and be dissolved in methyl alcohol and separate out, then in vacuum drying oven 60 DEG C dry 4h, output is 0.32g (product, title: polyarylether).