CN1004003B - Synthesis for phenolphthalein type polyarylether sulfone copolymer - Google Patents

Abstract

The present invention is principal monomer with phenolphthalein, and introduces other bis-phenol by suitable proportion ground, improves the synthesis condition of different structure polyether sulphone, and the thermotolerance of telomerized polymer improves its toughness, and improves the heat flow performance.The structure of four kinds of novel polyarylether sulfone copolymers is as follows

Wherein A is

B is

In each series copolymer, contain the A chain link, correspondingly contain the B chain link at 90～10mol% at 10～90mol%.

Description

Synthesizing of phenolphthalein type polyarylether sulfone copolymer

The invention belongs to the synthetic of polyether sulphone.

Because the excellent properties of polyether sulphone, in recent years, with it as functional materials (as gas separation membrane, ultra-filtration membrane and reverse osmosis membrane) in the application of aspects such as chemical industry, environmental protection, caused people's very big interest.For this reason, the various countries scholar also strives to find new polyarylsulphone kind except the performance of the existing several structure polyether sulphones of positive improvement.

In these work, be worth should be mentioned that Soviet Union Korshak(USSR495,336) once attempted the phenolphthalein chain link is incorporated in the bisphenol A-type polyether sulphone molecule quantitatively, to improve its heat-resisting and other performance, aspect in addition, also imagination improves the molecular weight of phenolphthalein polyether sulphone by the introducing of the 3rd monomer (dihydroxyphenyl propane).It seems from its result, though the thermotolerance of multipolymer obtains some improvement, but, they can not quantitatively participate in polyreaction because still continuing to use " two step method " (promptly preparing phenates with the KOH or the NaOH aqueous solution) phenolphthalein under this reaction conditions, cause the molecular weight of multipolymer to be difficult to improve, so work is not further developed.Chinese patent is announced among the CN85101721, has proposed the novel method of synthetic macromolecule amount phenolphthalein type polyarylether sulfone, promptly with K ₂CO ₃Or Na ₂COv replaces the KOH or the NaOH aqueous solution, and we are referred to as " single stage method " to carry out the salify condensation reaction simultaneously.This method is compared with traditional nucleophilic method, and it is low that it has temperature of reaction, and the time is short, and products obtained therefrom viscosity is than advantages such as height, but the toughness of its resulting polymers and thermal fluidity are not ideal enough, bring difficulty to processing.

No matter be " single stage method " or " two step method ", in synthetic non-phenolphthalein type polyarylether sulfone, all there is certain shortcoming, as bisphenol synthesis Type B polyether sulphone (SS) (I), Resorcinol type polyether sulphone (HS) (II), bisphenol A-type polyether sulphone (AS), bisphenol-c type polyether sulphone (CS) (IV).

Because the monomer of (I) is a bisphenol S, the solubleness in dimethyl sulfoxide (DMSO) or tetramethylene sulfone equal solvent is very little, is difficult to obtain high molecular weight product, and because its heat decomposition temperature and processing temperature are very approaching, it is used also very big difficulty.(II) is though have radiation hardness, chemical resistance preferably, but because in the polymerization process, the easy oxidation of Resorcinol, and because the regularity of structure, make its easily from system crystallization separate out, influence the growth of molecular chain, have only raising temperature of reaction (being higher than 300 ℃), the material that just can obtain having Practical significance.The heat flow performance of (III) is outstanding, but heat-resisting and radiation resistance is all relatively poor, and (IV) is because the existence of carbonyl the toughness of this material is increased, but the heat flow performance is undesirable.

Characteristics according to above-mentioned these different structure polyether sulphone polymerization processes and product property, consider the particular reactive that phenolphthalein has in " single stage method " polymerization process, the present invention is incorporated into the phenolphthalein type polyarylether sulfone molecular backbone chain in right amount to the bis-phenol of different structure (as follows)

On, in the hope of thermotolerance and the processing characteristics of improving product, polyreaction because phenolphthalein is incorporated in these polyether sulphone structures, can finely be improved in the aspect in addition, and its temperature of reaction is reduced, and the reaction times shortens, and the high molecular weight product that is easy to get.

The present invention is based on above imagination, synthesized the polyether sulphone terpolymer of various different structures, its general formula is:

The content of A chain link is at 10～90mol%, and B chain link content is at 90～10mol%.

Synthetic multipolymer of the present invention, owing to introduced the phenolphthalein chain link, its thermotolerance all has in various degree raising (Tg can improve 20～40 ℃) than the B series polymer, and its solubility property also is greatly improved, this is very useful for the application as mould material.In addition, the different structure bis-phenol is introduced on the phenolphthalein polyether sulphone chain quantitatively, increased its toughness again and improved its thermal fluidity.With regard to polyreaction itself in fact, because the monomeric existence of phenolphthalein, synthetic synthetic easy to control than the B series polymer that makes multipolymer, and speed of response strengthens (can find out in the example) significantly.

Synthetic multipolymer of the present invention be by different structure bis-phenol (as phenolphthalein and dihydroxyphenyl propane) and equivalent 4,4 '-dichloro diphenyl sulfone excessive 10～30% mol (to bis-phenol than) K ₂CO ₃Exist down, make medium (tetramethylene sulfone, dimethyl sulfoxide (DMSO) with polar aprotic solvent, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone or sulfobenzide), the band aqua is benzene, toluene or dimethylbenzene, temperature of reaction is controlled between 150～320 ℃, and the reaction times is 4～10 hours.

Embodiment

Example 1:(example 1～5th, comparative example)

Agitator is being housed, logical nitrogen pipe, the Dean-sfark water trap in three mouthfuls of reaction flasks of prolong and temperature regulator, adds phenolphthalein 0.02mol, 4,4 '-dichloro diphenyl sulfone (hereinafter to be referred as DCDPS) 0.02mol, anhydrous K ₂CO ₃0.022mol tetramethylene sulfone 16.5ml and dimethylbenzene 20ml were warmed up to 140～150 ℃ in 2 hours, and make the widely different stream of dimethylbenzene, up to the greatest extent, continue to heat up with water base band, remaining dimethylbenzene is all steamed, be warmed up to 220 ℃ at last, and under this temperature, reacted 4 hours, cooling then, when temperature drops to 100 ℃, add the dilution of 20ml dimethyl formamide, solution is poured out, left standstill 12 hours, upper solution is settled out in ethanol.Throw out is dried with distillation washing 3-4 time.Get white thread polymkeric substance (PS).R·V＝0.92（25℃，CHCL ₃）

Example 2:

Replace phenolphthalein with dihydroxyphenyl propane; As the 0.02mol dihydroxyphenyl propane, 0.02mol DCDPS, anhydrous K ₂CO ₃0.026mol, tetramethylene sulfone 15ml, dimethylbenzene 20ml, other 220 ℃ of reactions 10 hours, can get white powdery polymer (AS) then as example 1, and RV=0.34(25 ℃, CHCL ₃).

Example 3: replace phenolphthalein with bisphenol S; As the 0.015mol bisphenol S, 0.015mol DCDPS, anhydrous K ₂CO ₃0.0225mol, tetramethylene sulfone 12ml, dimethylbenzene 20ml with example 2 methods, is reflected at 220 ℃ and carried out 10 hours, can get white powdery polymer (SS).Product is insoluble to CHCL ₃In.

Example 4: replace phenolphthalein with bisphenol-c; As the 0.02mol bisphenol-c, 0.02mol DCDPS, anhydrous K ₂CO ₃0.026mol, tetramethylene sulfone 15 milli ml, dimethylbenzene 25ml with example 1 method, is reflected at 220 ℃ and carried out 8 hours, can get faint yellow polymkeric substance (CS), RV=0.78(CHCL ₃, 25 ℃)

Example 5:

Replace phenolphthalein with Resorcinol, as the 0.02mol Resorcinol, 0.02mol DCDPS, anhydrous K ₂CO ₃0.022mol, tetramethylene sulfone 12ml, dimethylbenzene 25ml, band water process such as example 1 220 ℃ of reactions 2 hours, because the pre-crystallization of oligopolymer, and influence the growth of its molecular chain, can not get high molecular weight product with this understanding.Product is a white (HS).But can not be dissolved in CHCL ₃, in the strong polar agent such as dimethyl formamide and N-Methyl pyrrolidone.

Example 6:

With example 1 method, as the 0.018mol Resorcinol, phenolphthalein 0.002mol, 0.02mol DCDPS, anhydrous K ₂CO ₃0.026mol, tetramethylene sulfone 12.5ml, dimethylbenzene 20ml; Reacted 6.5 hours down at 220 ℃, can get white polymer (HPS).RV=0.95(25 ℃, CHCL ₃) compare with example 5, clearly,, just can make reaction be easy to control owing to introduce a spot of phenolphthalein chain link, the crystallization of destruction polymkeric substance obtains macromolecule product.And can be dissolved in the general polar solvent.

HS and HPS performance are relatively

^*S represents solvable, and IS represents soluble.(down together)

Example 7:

With example 1 method, as the 0.012mol dihydroxyphenyl propane, 0.008mol phenolphthalein, 0.02mol DCDPS, 0.022molK ₂CO ₃, tetramethylene sulfone 17ml, dimethylbenzene 20ml, band water such as example 2 were reacted 10 hours down at 220 ℃, got white polymer (APS), RV=0.50(CHCL ₃, 25 ℃), compare with example 2 product properties, thermotolerance obviously improves.

AS and APS performance are relatively

Example 8:

With example 2 methods, as the 0.006mol bisphenol S, 0.014mol phenolphthalein 0.02mol DCDPS, 0.026mol anhydrous K ₂CO ₃, the 17ml tetramethylene sulfone, 20ml dimethylbenzene reacted 10 hours down at 220 ℃, can get white polymer (supS), RV=0.64(CHCL ₃, 25 ℃), compare with example 3 product properties, thermotolerance, solvability and molecular weight all have raising.

Example 9:

With example 1 method, as 0.01mol bis-phenol 0.01mol phenolphthalein, 0.02mol2C2ps, 0.026mol anhydrous K ₂CO ₃, 16.5ml tetramethylene sulfone, 20ml dimethylbenzene; Reacted 10 hours down at 220 ℃, get slightly yellow polymer (CPS), RV=0.63(25 ℃, CHCL ₃), thermotolerance increases than example 4 products.

CS and CPS performance are relatively

Claims (3)

1, with the synthetic polyether sulphone of single stage method, it is characterized in that Resorcinol with different structure, 4,4 '-dihydroxy diphenylsulphone, 4,4 '-dihydroxy benzophenone, 2,2-two (4,4 '-dihydroxyl hexichol) propane, with two halogen sulfones and phenolphthalein at solid alkali K ₂CO ₃Or Na ₂Co ₃Exist down, in dimethyl sulfoxide (DMSO), tetramethylene sulfone, N,N-DIMETHYLACETAMIDE, direct reaction in N-Methyl pyrrolidone or sulfobenzide (the band aqua is a benzene, toluene or the dimethylbenzene) solvent synthesizes the polyether sulphone terpolymer of following reaction structure

The content of this phenolphthalein chain link is 10-〈 ﹠﹠ 〉, corresponding B chain link is 90-10mol%.