CN1226330C - Chiral polyether ketone (sulphone) seres polymer and preparation - Google Patents
Chiral polyether ketone (sulphone) seres polymer and preparation Download PDFInfo
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- CN1226330C CN1226330C CN 200310116015 CN200310116015A CN1226330C CN 1226330 C CN1226330 C CN 1226330C CN 200310116015 CN200310116015 CN 200310116015 CN 200310116015 A CN200310116015 A CN 200310116015A CN 1226330 C CN1226330 C CN 1226330C
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Abstract
The present invention relates to a novel chiral polyaryletherketone (sulfone) series polymer and a preparation technique thereof. The preparation technique comprises: an active tripolymer in a chiral binaphthalene structure is prepared from chiral 1, 1'-bi-2-naphthol as a raw material reacting with double-halogen substituted diphenylketone (sulfone), and further, a nucleophilic substitution reaction occurs between the active tripolymer and bisphenol to synthesize the polyaryletherketone (sulfone) series polymer in a chiral binaphthalene structure. The polyaryletherketone (sulfone) series polymer in a chiral binaphthalene structure, which is prepared by the present invention, has the advantages of obvious chirality characteristic, favorable solvent resistance and favorable temperature resistance, and therefore, the polyaryletherketone (sulfone) series polymer can be applied to the operation of the preparation of a solvent resisting and temperature resisting chiral stationary phase through the two characteristics.
Description
Technical field
The invention belongs to field of polymer technology, be specifically related to the technology of preparing of a kind of chirality polyaryletherketone (sulfone) series polymer and this polymkeric substance.
Background technology
After Cramer has found that at first cyclodextrin has good chiral recognition effect to optical isomer, the fractionation work of chiral racemic body has more and more caused people's attention, and its research has spread all over fields such as synthetic chemistry, biological medicine chemistry, agrochemistry.Wherein particularly outstanding in its degree of concern of pharmaceutical chemistry field, though this is that it is often showing very big difference aspect drug effect and the pharmacokinetics because two enantiomorphs of chiral drug are identical mostly on physics and chemical property.To the more deep understanding of chiral recognition, all have very important significance for the stereochemistry problem in the pharmacology of understanding chiral drug, medicinal design and the life chemistry.
Because the physicochemical property of chirality enantiomorph are extremely similar, therefore the difficulty of its fractionation is very big, the method of enantiomer separation mainly contains two classes at present: non-chromatography and chromatography, non-chromatography commonly used mainly is crystallization, also comprise the digestion of microorganism or enzyme, but it is consuming time longer, and the complicated while of process can not prepare purer enantiomorph, therefore be difficult to generally be accepted by modernization industry institute.And most important means are exactly high performance liquid chromatography in the chromatography, and this kind method has obtained in fields such as modern synthetic chemistry, biologic pharmacological science and agrochemistry using widely to the chirality separation of racemates.And most important factor is selected a kind of chiral stationary phase efficiently exactly in this method, at present still there is not general chiral stationary phase to be used for the fractionation work of racemic modification, in order to solve this important problem, a lot of scientists just are being devoted to the research work of this respect, starch, Mierocrystalline cellulose with and the chiral stationary phase of preparation such as derivative be with fastest developing speed in the present chromatographic separation research, the chromatographic separation chiral stationary phase that application surface is the widest, but consider this type of chiral stationary phase mostly be natural product with and derivative, its derivative reaction is difficult relatively from the molecular designing angle, because also there is certain limitation in it aspect temperature and the solvent, therefore limited its application to a certain extent simultaneously.
The polyaryletherketone series polymer has characteristics such as excellent solvent resistance, heatproof, if therefore the chirality primitive is incorporated in the polyaryletherketone main chain, can attempt being used for as heatproof, solvent-proof chiral stationary phase the work of chiral separation.
Summary of the invention
The purpose of this invention is to provide a kind of chirality polyaryletherketone (sulfone) series polymer, and the preparation method of this polymkeric substance, this method utilizes the di-naphthyl as the chirality primitive, be introduced in the main chain of polyaryletherketone (sulfone) series polymer, be used for chiral separation work thereby prepare chiral stationary phase.
The structural formula of chirality polyaryletherketone of the present invention (sulfone) series polymer is as follows:
Or
Or
The method of the invention comprises following two steps:
(1) active tripolymer is synthetic: [mole number can be chirality 1 with excessive greatly, 10～15 times of 1 '-union-2-naphthol mole number] benzophenone (sulfone) that replaces of two halogens is raw material, add organic solvent (N-Methyl pyrrolidone, tetramethylene sulfone or N, dinethylformamide) 500mL, 80mL toluene, catalyzer adopts salt of wormwood, and (mole number can be chirality 1,1.003～2.2 times of 1 '-union-2-naphthol mole number), stirring is warming up to 145 ℃, drip 200mL and be dissolved with S configuration 1, the DMF solution of 1 '-union-2-naphthol, the dropping time is no less than 1 hour, temperature of reaction is controlled at 145～150 ℃, continue reaction 4～6 hours, after reaction finishes reaction product is poured in 3% the dilute hydrochloric acid, the benzophenone (sulfone) of most of excessive two halogens replacements is removed in underpressure distillation, uses ethanol and distilled water wash product respectively, final product was 60 ℃ of dryings 12 hours, and productive rate reaches more than 80%.
(2) polymkeric substance is synthetic: with mol ratio is that 1.003: 1 active tripolymer and biphenol monomer is raw material, be raw material, add organic polar solvent, N for example, dinethylformamide (DMF), N-Methyl pyrrolidone (NMP) or tetramethylene sulfone, catalyzer adopts salt of wormwood (mole number can be 1.003～2.2 times of biphenol monomer mole number), temperature of reaction is controlled at 145 ℃-240 ℃, reaction times is 5-6 hour, after reaction finishes reaction product is poured in 3% the dilute hydrochloric acid, use acetone and distilled water wash product respectively, final product was 120 ℃ of dryings 12 hours, and productive rate reaches more than 95%.
Its above chirality 1,1 '-union-2-naphthol can be S configuration 1,1 '-union-2-naphthol or R configuration 1,1 '-union-2-naphthol; The benzophenone (sulfone) that two halogens replace can be 4,4 '-difluoro benzophenone, 4,4 '-difluorodiphenyl sulfone or 4,4 '-difluorodiphenyl acyl group benzene; Biphenol monomer can be dihydroxyphenyl propane, Resorcinol or 4, and 4 '-dihydroxyl is to diphenyl sulfide.
Be respectively S configuration 1 below, 1 '-union-2-naphthol or R configuration 1, the structural formula of 1 '-union-2-naphthol:
Be benzophenone (sulfone) structural formula that two halogens replace below:
Be the biphenol monomer structural formula below:
Description of drawings
Fig. 1: the infrared spectrum of the prepared polymkeric substance of the present invention and VCD spectrogram
As shown in Figure 1, being the polymer characterization data, is S configuration 1,1 '-union-2-naphthol and 4, and the polymkeric substance of the active tripolymer of 4 '-difluoro benzophenone and dihydroxyphenyl propane preparation: in infrared spectra, 3055cm
-1Be C-H stretching vibration absorption peak on the phenyl ring, 2965cm
-1For-CH
3The stretching vibration absorption peak, 1654cm
-1Be C=O stretching vibration absorption peak, 1499cm
-1And 1591cm
-1Be phenyl ring breathing vibration absorption peak, 1237cm
-1For-O-stretching vibration absorption peak.GPC: weight-average molecular weight (Mw) is 5404, and number-average molecular weight (Mn) is 3803, and dispersion index (Pl) is 1.42.
1H?NMR(CDCl
3)：δ7.91(m，4H)，δ7.76(t，2H)，δ7.65(m，2H)，δ7.56(m，4H)，δ7.45(m，2H)，δ7.29(m，4H)，δ7.23(m，4H)，δ7.03(m，2H)，δ6.96(m，8H)，δ6.81(m，4H)，δ1.68(m，6H)。By dsc analysis, polymkeric substance is unformed sample, Tg=162 ℃.
Therefrom we can see in the VCD spectrogram of chiral polymer and show tangible positive and negative Cotton effect, be that polymkeric substance itself has the chirality feature, and each vibration absorption peak of infrared spectrum (carbonyl, naphthalene nucleus and ehter bond) all has its feature correspondence basically in the VCD spectrogram, the feature peak position of carbonyl is 1656cm in the VCD spectrogram
-1, the feature peak position of naphthalene nucleus is 1530-1402cm
-1, the feature peak position of ehter bond is 1266-1206cm
-1The polymkeric substance of the present invention's preparation has tangible chirality feature, and has the good solvent resistance and the characteristics of heatproof.
Embodiment
Embodiment 1:
With 218.20g (1mol) 4; 4 '-difluoro benzophenone joins in the there-necked flask that mechanical stirring, thermometer, dropping funnel, water-and-oil separator and nitrogen protection are housed; add 500mL DMF; 80mL toluene (removing the water that dereaction generates); 13.86g (0.1003mol) Anhydrous potassium carbonate; stirring is warming up to 145 ℃; dropping is dissolved with 28.63g (0.1mol) S configuration 1; the 200mL DMF solution of 1 '-union-2-naphthol; the dropping time is no less than 1 hour; continuation is poured reaction product in 3% dilute hydrochloric acid into after reaction finishes 145 ℃ of reactions 5 hours.Underpressure distillation removes most of excessive 4,4 '-difluoro benzophenone, use ethanol and distilled water wash product six times respectively, to remove a spot of 4,4 '-difluoro benzophenone, organic solvent and inorganic salt, final product obtains the active tripolymer sample of yellow powder 60 ℃ of dryings 12 hours, and productive rate is 86%.
Embodiment 2:
In the there-necked flask that mechanical stirring, thermometer, water-and-oil separator and nitrogen protection are housed, add 6.85 gram (0.01003mol) S configurations 1; 1 '-union-2-naphthol and 4; the active tripolymer of 4 '-difluoro benzophenone synthetic; 2.28 gram (0.01mol) dihydroxyphenyl propane and 1.39 gram (0.01003mol) Anhydrous potassium carbonates; add 60mL DMF and 10mL toluene (removing the water that dereaction generates); stir and heat up,, after reaction finishes reaction product is poured in 3% dilute hydrochloric acid 145 ℃ of reactions 5 hours.Use acetone and distilled water wash product six times respectively, removing organic solvent and inorganic salt, final product obtains the white polymer powdered sample 120 ℃ of dryings 12 hours.Productive rate is 97%.
Embodiment 3:
Method such as embodiment 2, with S configuration 1,1 '-union-2-naphthol is changed into R configuration 1,1 '-union-2-naphthol, separating purifies obtains the white powder sample, and productive rate is 97%.
Embodiment 4:
Method such as embodiment 2, with 4,4 '-difluoro benzophenone changes into 4,4 '-difluorodiphenyl sulfone, separating purifies obtains the white powder sample, and productive rate is 96%.
Embodiment 5:
Method such as embodiment 2, with 4,4 '-difluoro benzophenone changes into 4,4 '-difluorodiphenyl acyl group benzene, separating purifies obtains the white powder sample, and productive rate is 95%.
Embodiment 6:
Method such as embodiment 2 change into Resorcinol with dihydroxyphenyl propane, and separating purifies obtains the white powder sample, and productive rate is 95%.
Embodiment 7:
Method such as embodiment 2 change into 4 with dihydroxyphenyl propane, and 4 '-dihydroxyl is to diphenyl sulfide, and separating purifies obtains the white powder sample, and productive rate is 96%.
Embodiment 8:
Method such as embodiment 2 change into NMP with DMF, and separating purifies obtains the white powder sample, and productive rate is 96%.
Embodiment 9:
Method such as embodiment 2 change into tetramethylene sulfone with DMF, and separating purifies obtains the white powder sample, and productive rate is 95%.
Embodiment 10:
Method such as embodiment 2 will change into 6 hours from 5 hours in the reaction times, and separating purifies obtains the white powder sample, and productive rate is 97%.
Claims (6)
1, class chirality polyaryletherketone (sulfone) polymkeric substance, its structural formula is as follows:
2, a kind of method for preparing the described chirality polyaryletherketone of claim 1 (sulfone) polymkeric substance, its step is as follows:
(1) active tripolymer is synthetic: with the mole ratio is 10-15: the benzophenone (sulfone) that two halogens of 1 replace, 1,1 '-union-2-naphthol is a raw material, add organic solvent, with toluene is the band aqua, salt of wormwood is catalyzer, its consumption is a chirality 1,1.003～2.2 times of 1 '-union-2-naphthol mole number, stirring is warming up to 145 ℃, drips to be dissolved with S configuration 1, the DMF solution of 1 '-union-2-naphthol, the dropping time is no less than 1 hour, temperature of reaction is controlled at 145～150 ℃, continues reaction 4～6 hours, after reaction finishes reaction product is poured in 3% the dilute hydrochloric acid, the benzophenone (sulfone) that most of excessive two halogens replace is removed in underpressure distillation, use ethanol and distilled water wash product respectively, final product was 60 ℃ of dryings 12 hours, and productive rate reaches more than 80%;
(2) polymkeric substance is synthetic: with mol ratio is that 1.003: 1 active tripolymer and biphenol monomer is raw material, add organic polar solvent, salt of wormwood is catalyzer, its consumption is 1.003～2.2 times of biphenol monomer mole number, temperature of reaction is controlled at 145 ℃-240 ℃, reaction times is 5-6 hour, after reaction finishes reaction product is poured in 3% the dilute hydrochloric acid, use acetone and distilled water wash product respectively, final product was 120 ℃ of dryings 12 hours, get chirality polyaryletherketone (sulfone) polymkeric substance, productive rate reaches more than 95%.
3, the preparation method of chirality polyaryletherketone as claimed in claim 2 (sulfone) polymkeric substance is characterized in that:
Described organic solvent is N, dinethylformamide, N-Methyl pyrrolidone or tetramethylene sulfone.
4, the preparation method of chirality polyaryletherketone as claimed in claim 2 (sulfone) polymkeric substance is characterized in that:
The benzophenone (sulfone) that two halogens replace is 4,4 '-difluoro benzophenone, 4,4 '-difluorodiphenyl sulfone or 4,4 '-difluorodiphenyl acyl group benzene.
5, the preparation method of chirality polyaryletherketone as claimed in claim 2 (sulfone) polymkeric substance is characterized in that:
In the active tripolymer preparation 1,1 '-union-2-naphthol can be a S configuration 1,1 '-union-2-naphthol or R configuration 1,1 '-union-2-naphthol.
6, the preparation method of chirality polyaryletherketone as claimed in claim 2 (sulfone) polymkeric substance is characterized in that:
Biphenol monomer can be dihydroxyphenyl propane, Resorcinol or 4, and 4 '-dihydroxyl is to diphenyl sulfide.
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| CN1226330C true CN1226330C (en) | 2005-11-09 |
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| CN100374482C (en) * | 2006-03-29 | 2008-03-12 | 长春吉大高科技股份有限公司 | Process for preparing copolymer containing biphenyl polyether ether-sulfone and poly(ether sulfone) |
| CN100374483C (en) * | 2006-03-29 | 2008-03-12 | 长春吉大高科技股份有限公司 | Process for preparing terpolymer of polyether ethersulfone and polyether etherketone |
| CN106939059B (en) * | 2017-03-08 | 2019-03-01 | 浙江大学 | The poromeric method of homochiral molecule construction based on 1,1 '-union -2-naphthols |
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