CN1321987C - Oligomer with double-azo butter-fly shaped rigid large ring, and its prepn. method - Google Patents
Oligomer with double-azo butter-fly shaped rigid large ring, and its prepn. method Download PDFInfo
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- CN1321987C CN1321987C CNB2005100172795A CN200510017279A CN1321987C CN 1321987 C CN1321987 C CN 1321987C CN B2005100172795 A CNB2005100172795 A CN B2005100172795A CN 200510017279 A CN200510017279 A CN 200510017279A CN 1321987 C CN1321987 C CN 1321987C
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Abstract
The present invention relates to a butterfly-shaped oligomer with a double azo rigid large ring and a preparation method thereof. Furthermore, the present invention belongs to the field of the high molecular material. The method has the proposal that two azo groups are introduced to a chain structure of the large ring oligomer of the traditional polyaryletherketone; the trans-isomer, the cis-isomer, and the rigid influence of a ring framework are produced by the light wave of different length carrying out the irradiation for the two azo groups; the cis-isomer and the trans-isomer of the two azo groups can keep stable by the coordinated variation. Moreover, the hole diameter which is in the nanometer level and is formed by the ring can also be varied because of the variation of the cis-isomers and the trans-isomers of the azo groups so that the package capacity of the materials is influenced by a cavity. Finally, the variation of the cis-isomer and the trans-isomer of the double azo ring can be applied to the aspects of a high density storage material, a molecular switch, etc.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a class " butterfly " shape, contain the preparation method of tetrazo rigid macrocyclic oligopolymer and this oligopolymer.
Background technology
Nitrogen benzide and derivative molecular thereof are the molecules of the photic isomery of a quasi-representative, because its good environmental stability makes advantages such as film with easy and polymer-bound, have caused special concern both domestic and external.As far back as nineteen thirty-seven, Hartley finds that light exerts an influence to the configuration of N=N key in the nitrogen benzide: under the 300nm wavelength light irradiation, nitrogen benzide takes place transly to change to cis, when isomerization takes place the maximum absorption optical wavelength with the substituent difference on the phenyl ring difference.The thermostability of the cis-structure of azobenzene derivatives is not as transconfiguration, be heated or＞cis can take place to trans conversion during the rayed of 380nm, even at room temperature, its stable time is generally several hrs to a couple of days.In order to improve its stability and Drawing abillity, azobenzene derivatives is dissolved in polymer formation main body/object system, or directly it is connected on the macromolecular chain by bonding action.Because of the solubleness of azobenzene derivatives in polymkeric substance limited, so to the back a kind of method research quite a lot of.According to the position difference of azobenzene derivatives in polymkeric substance, this bonding system can be divided into side chain, main chain and the polymerization of end of the chain azo again.Required free volume is bigger during because of side chain azo-group generation isomery, and it is fast that light isomery speed is wanted relatively.In addition, azobenzene derivatives takes place in the cis-trans isomerism under photoinduction, be accompanied by a series of optical property and change as photoinduction phase transition, second-order nonlinear optical property, double-colored or birefringent phenomenon, and variation such as electric conductivity, viscosity, pH value and the mechanical property etc. of other physical and chemical performance.Nineteen eighty-three is proposed first by Todorov etc.: utilize double refraction that azobenzene polymer produces when the light isomery or double-colored performance as optical storage material, the chemical research personnel have synthesized the azobenzene polymer of a large amount of different novel molecular structures subsequently, proposed to adopt electrophilic-donor melecules structure so that the dipolar nature of material itself to be provided, thereby reached the speed of photoresponse of raising azobenzene polymer in the azo-group both sides; Or improve the thermal stability of the second-order transition temperature (as polyimide material) of polymkeric substance with the raising material.Natansohn and Rochon etc. are to the systematic research of photoinduction double refraction of azobenzene polymer, studied polymkeric substance phase (amorphous state, liquid crystal state, half hitch crystalline state), blend or multipolymer, the pushing away of chromophore's size and chromophore-pull-up structure has also been inquired into the photonics device problem of this base polymer simultaneously to the influence of the optical property of material.Be that chemist or physicist's effort all are intended to this material practicability.
Summary of the invention
The purpose of this invention is to provide a kind of novel disazo " butterfly " shape rigid macrocyclic oligopolymer that contains, and the preparation method of this polymkeric substance.This method is introduced two azo groups in the chain-like structure of traditional polyaryletherketone macrocyclic oligomer thing, because the tetrazo group is subjected to the irradiation of different lengths light wave to produce suitable, anti-and ring skeleton inflexible influences, the cis-trans isomery of two azo groups needs collaborative variation could keep stable.Because suitable, the anteiso-structure of azo group change, the nano level aperture that ring itself forms also can change thereupon, will influence the parcel ability of hole to some material with this.Suitable, the anteiso-structure of tetrazo ring self change also can be applied to aspects such as high-density storage medium and molecular switch.
The structural formula that contains disazo " butterfly " shape rigid macrocyclic oligopolymer of the present invention is as follows:
Or
N=1 or 2 wherein.
Symmetricly in the main chain backbone of " butterfly " shape rigid macrocyclic oligopolymer contain two azo groups, illumination along with different wave length, two azo group collaborative variation cause the vary in diameter of encircling self nano level hole, thereby realize the parcel of some small-molecule substance or slough.
The method of the invention comprises following two steps:
(1): 4,4 '-dihydroxyl nitrogen benzide synthetic: p-NP is joined among the KOH that mole number is 10 times of amounts, add the water that mole number is 5 times of amounts again, be warmed up to 120 ℃ gradually, kept 120 ℃ of temperature 2～3 hours; And then progressively being warmed up to 195 ℃～200 ℃, reaction finishes.Cooled product poured into an amount of water of adding makes its dissolving in the beaker, add the concentrated hydrochloric acid neutralization again, regulate pH value to 3, this moment, many precipitations were separated out.Use the extracted with diethyl ether water, used the anhydrous sodium sulfate drying ether again 10 hours, ether is removed in underpressure distillation, and the product that obtains is with dehydrated alcohol/water=1: 1 (volume ratio) recrystallization, obtains yellow crystals and be pure 4, and 4 '-dihydroxyl nitrogen benzide, productive rate are more than 43%.
(2) " butterfly " shape macrocyclic oligomer thing is synthetic: with mole number is 4, the above salt of wormwood of 2.2 times of amounts of 4 '-dihydroxyl nitrogen benzide monomer adds in the organic solvent (content range of salt of wormwood is between 0.011mol/L～0.044mol/L in the organic solvent), stirring heating under the nitrogen protection, add again toluene (with the organic solvent volume ratio be 1/25～4/25), band water refluxed 30～60 minutes; Again with equimolar pair of halogen monomer and 4,4 '-dihydroxyl nitrogen benzide monomer mixes and to be dissolved in organic solvent (every kind of monomeric content is 0.02mol/L～0.06mol/L), the speed of mixed solution with 0.005 milliliters/second～0.02 milliliters/second slowly is added drop-wise in the reaction system that is dissolved with salt of wormwood, dropwises the back and continued stirring and refluxing 2～5 hours; Cold filtration product solution, toluene and a large amount of organic solvent to 3～6% liquor capacity are removed in distillation, it is in 2%～5% the hydrochloric acid that solution is poured into 30 times of volumes, mass concentration, washing, drying is removed linear oligomer with the methylene dichloride extracting, is that moving phase, silica gel are that the stationary phase post separates with methylene dichloride/tetrahydrofuran (THF) (volume ratio 50/1) again, get the macrocyclic oligomer thing, productive rate is more than 50%;
We come as can be seen from the structure of the resulting oligopolymer of the present invention, on the main chain of rigid macrocyclic oligopolymer, two azo groups have been symmetrically distributed, when being subjected to different wave length illumination, two azo groups are collaborative suitable, anteiso-structure takes place to be changed that (two azo groups present cis-cis, trans-as transly to be steady state respectively, presenting cis-trans respectively is unsteady state), change of shape is similar to butterfly and flutters the same.
Organic solvent is N in the above-mentioned reaction, dinethylformamide (DMF), N-Methyl pyrrolidone (NMP) or N,N-dimethylacetamide (DMAc);
Two halogen monomers described in the aforesaid method can be 4; 4 '-difluoro benzophenone, 4; 4 '-two chloro benzophenones, 4; 4 '-dibromo benzophenone, 4,4 '-difluorodiphenyl sulfone, 4,4 '-dichloro diphenyl sulfone, 4; 4 '-dibromo sulfobenzide or 4; 4 '-difluorodiphenyl acyl group benzene, 4,4 '-dichloro dibenzoyl benzene or 4,4 '-dibromo dibenzoyl benzene.
Be 4 below, the structural formula of 4 '-dihydroxyl nitrogen benzide
Be benzophenone (sulfone) structural formula that two halogens replace below:
Or
(Z represents halogen)
Description of drawings (at reaction example 1)
Fig. 1: the infrared spectrum of the prepared butterfly-like tetrazo macrocyclic oligomer thing of the present invention;
Fig. 2: the flight time mass spectrum figure of the prepared butterfly-like tetrazo macrocyclic oligomer thing of the present invention;
Fig. 3: the one dimension proton magnetic chart of the prepared butterfly-like tetrazo macrocyclic oligomer thing of the present invention;
Fig. 4: the ultraviolet lighting variation diagram of the prepared butterfly-like tetrazo macrocyclic oligomer thing of the present invention.
As shown in Figure 1, be by 4, the infrared spectrum of the butterfly-like tetrazo macrocyclic oligomer of 4 '-difluoro benzophenone synthetic thing, corresponding embodiment 1:2923,2849cm
-1Be phenyl ring C-H stretching vibration, 1654cm
-1Be the vibration absorption peak of diaryl ketone carbonyl, 1582,1488cm
-1For the phenyl ring skeletal vibration absorbs, 1276 and 1236 is fragrant ehter bond stretching absorption peak.Prove that from infrared spectrum our institute's synthetic is a target product.
As shown in Figure 2, be by 4, the flight time mass spectrum figure of the butterfly-like tetrazo macrocyclic oligomer of 4 '-difluoro benzophenone synthetic thing: n=1, m/z=786.5.The molecular weight that molecular ion peak 786.5 corresponds to target product adds a H ionic molecular weight (molecular weight of theoretical value is 785), proves that from flight time mass spectrum figure we are resulting for target product.
As shown in Figure 3, be by 4, the one dimension proton magnetic chart of the butterfly-like tetrazo macrocyclic oligomer of 4 '-difluoro benzophenone synthetic thing.Prove from the ownership of one dimension proton magnetic chart hydrogen that we are resulting and be target product.
| 1(D，8H) | 2(D，8H) |
| 7.962 7.945 | 7.187 7.170 |
| 3(D，8H) | 4(D，8H) |
| 7.040 7.022 | 7.771 7.754 |
As shown in Figure 4, be by 4, the butterfly-like tetrazo macrocyclic oligomer of 4 '-difluoro benzophenone synthetic thing is through 366nm wavelength UV-irradiation its UV spectrum variation diagram of Continuous Tracking after 1 minute.Curve 1 is the ultra-violet absorption spectrum without UV-irradiation, and the absorption peak at 345nm place is N=N group π-π
*Transition, the 450nm place is N=N group n-π
*Transition; Curve 2 is the ultra-violet absorption spectrum after wavelength 366nm UV-irradiation, because the irradiation of UV-light, two N=N groups absorb energy, and a part is changed the π-π of cis to cis-trans by cis-cis
*Intensity reduces, trans n-π
*Increase, being embodied on the spectrogram is exactly that the peak at 345nm place reduces gradually, and peak, 450nm place raises gradually: stop illumination, ultra-violet absorption spectrum after 3 minutes is shown in curve 3, because the influence of ring rigid backbone tension force, unsettled cis-trans conformation is to stable trans-trans transformation, the π-π of cis
*Intensity reduces gradually, trans n-π
*Intensity increases gradually, and being embodied on the spectrogram is exactly that the peak at 345nm place reduces gradually, and peak, 450nm place raises gradually.
Above data acknowledgement target oligopolymer synthetic, and along with suitable, anteiso-structure variation can take place the different wave length rayed.
Embodiment
Embodiment 1:
4,4 '-dihydroxyl nitrogen benzide synthetic: the 10g p-NP is joined among the 50g KOH, add 10ml water again, be warmed up to 120 ℃ gradually, kept 120 ℃ of temperature 2 hours; And then progressively heat up up to 195 ℃ of reaction end.Cooled product poured in the beaker add 200ml water and make its dissolving, add the neutralization of 69ml concentrated hydrochloric acid again, regulate pH value to 3, this moment, many precipitations were separated out.Use the extracted with diethyl ether water, used the anhydrous sodium sulfate drying ether again 10 hours, ether is removed in underpressure distillation, and the product that obtains is with dehydrated alcohol/water=1: 1 (volume ratio) recrystallization, obtains 4 gram yellow crystals and be pure 4, and 4 '-dihydroxyl nitrogen benzide, productive rate are 43%.
2000 milliliters of DMF, salt of wormwood 3.04 grams (0.022mol) place the 3L three-necked bottle, and stirring heating under the nitrogen protection adds 80 milliliters of toluene band water again and refluxed 30 minutes.With 4,4 '-dihydroxyl nitrogen benzide, 2.14 grams (0.01mol), 4,2.18 gram (0.01mol) mixing of 4 '-difluoro benzophenone are dissolved among 500 milliliters of DMF, and mixed solution drops in the three-necked bottle with 0.01 milliliters/second.Dropwise the back and continued stirring and refluxing 2 hours.Cold filtration product solution, distillation are removed toluene and a large amount of DMF to surplus about 100 milliliters of solution.Solution is poured in 3% the hydrochloric acid and obtains yellow mercury oxide, washing obtains yellow powder after the drying.Using the methylene dichloride extracting, remove insoluble linear oligomer, is that moving phase, silica gel are that the stationary phase post separates with methylene dichloride/tetrahydrofuran (THF) (50/1) again, gets macrocyclic oligomer thing 1.97g, is the colour generation needle-like crystal, productive rate 50%;
Structural formula is as follows:
This moment n=1.
Embodiment 2:
Method such as embodiment 1, with 4,4 '-difluoro benzophenone changes into 4,4 '-difluorodiphenyl sulfone, other condition is identical, and separating purifies obtains orange needle-like crystal 2.08 grams, and productive rate is 51%.Structural formula is as follows:
This moment n=1.
Embodiment 3:
Method such as embodiment 1, with 4,4 '-difluoro benzophenone changes into 4,4 '-difluorodiphenyl acyl group benzene, separating purifies obtains orange needle-like crystal 2.63 grams, and productive rate is 53%.Structural formula is as follows:
This moment n=2.
Embodiment 4:
Method such as embodiment 1 change DMF into DMAc, and separating purifies obtains orange needle-like crystal, and productive rate is more than 50%.Its structural formula is identical with embodiment 1.
Embodiment 5:
Method such as embodiment 1 change DMF into NMP, and separating purifies obtains orange needle-like crystal, and productive rate is more than 52%.Its structural formula is identical with embodiment 1.
Claims (3)
1, contain disazo " butterfly " shape rigid macrocyclic oligopolymer, its structural formula is as follows:
N=1 or 2 wherein.
2, the described preparation method who contains disazo " butterfly " shape rigid macrocyclic oligopolymer of a kind of claim 1 comprises following two steps:
(1): 4,4 '-dihydroxyl nitrogen benzide synthetic: p-NP is joined among the KOH that mole number is 10 times of amounts, add the water that mole number is 5 times of amounts again, be warmed up to 120 ℃ gradually, kept 120 ℃ of temperature 2～3 hours; And then progressively being warmed up to 195 ℃～200 ℃, reaction finishes; Cooled product poured into add entry in the beaker and make its dissolving, add the concentrated hydrochloric acid neutralization again, regulate pH value to 3, this moment, precipitation was separated out; Use the extracted with diethyl ether water, used the anhydrous sodium sulfate drying ether again 10 hours, ether is removed in underpressure distillation, and the product volume ratio that obtains is dehydrated alcohol/water recrystallization of 1: 1, obtains yellow crystals and be pure 4, and 4 '-dihydroxyl nitrogen benzide, productive rate are more than 43%;
(2) " butterfly " shape macrocyclic oligomer thing is synthetic: with mole number is 4, and the above salt of wormwood of 2.2 times of amounts of 4 '-dihydroxyl nitrogen benzide monomer adds in the organic solvent, and the content of salt of wormwood is in the solvent
0.011mol/L～0.044mol/L, stirring heating under the nitrogen protection, adding and described organic solvent volume ratio are 1: 25～4: 25 toluene again, band water refluxed 30～60 minutes; Again with equimolar 4,4 '-difluoro benzophenone, 4,4 '-two chloro benzophenones, 4,4 '-dibromo benzophenone, 4,4 '-difluorodiphenyl sulfone, 4,4 '-dichloro diphenyl sulfone, 4,4 '-dibromo sulfobenzide or 4,4 '-difluorodiphenyl acyl group benzene, 4,4 '-dichloro dibenzoyl benzene or 4, the two halogen monomers and 4 of 4 '-dibromo dibenzoyl benzene, the mixing of 4 '-dihydroxyl nitrogen benzide monomer is dissolved in described organic solvent, every kind of monomeric content is 0.02mol/L～0.06mol/L, and the speed of mixed solution with 0.005 milliliters/second～0.02 milliliters/second slowly is added drop-wise in the reaction system that is dissolved with salt of wormwood, dropwises the back and continues stirring and refluxing 2～5 hours; Cold filtration product solution, toluene and a large amount of described organic solvent to 3～6% liquor capacity are removed in distillation, again solution is poured into 30 times of volumes, mass concentration and is in 2%～5% the hydrochloric acid, washing, drying is removed linear oligomer with the methylene dichloride extracting, is that methylene dichloride/tetrahydrofuran (THF) of 50: 1 is that moving phase, silica gel are that the stationary phase post separates with volume ratio again, get the macrocyclic oligomer thing, productive rate is more than 50%.
3, the preparation method who contains disazo " butterfly " shape rigid macrocyclic oligopolymer as claimed in claim 2, it is characterized in that: described organic solvent is N, dinethylformamide, N-Methyl pyrrolidone or N,N-dimethylacetamide.
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| CN1321987C true CN1321987C (en) | 2007-06-20 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60260948A (en) * | 1984-06-07 | 1985-12-24 | Toyobo Co Ltd | Photosensitive resin laminate |
| EP0457485A2 (en) * | 1990-05-18 | 1991-11-21 | AT&T Corp. | Nonlinear optical devices and methods for making them |
| JPH03276127A (en) * | 1990-03-27 | 1991-12-06 | Toppan Printing Co Ltd | Photoresponsive film and production thereof |
| JP3276127B2 (en) * | 1993-06-18 | 2002-04-22 | 日立マクセル株式会社 | Organic electrolyte battery |
| CN1431192A (en) * | 2003-01-17 | 2003-07-23 | 吉林大学 | Dumbbell form aniline oligomer and its synthesizing method |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60260948A (en) * | 1984-06-07 | 1985-12-24 | Toyobo Co Ltd | Photosensitive resin laminate |
| JPH03276127A (en) * | 1990-03-27 | 1991-12-06 | Toppan Printing Co Ltd | Photoresponsive film and production thereof |
| EP0457485A2 (en) * | 1990-05-18 | 1991-11-21 | AT&T Corp. | Nonlinear optical devices and methods for making them |
| JP3276127B2 (en) * | 1993-06-18 | 2002-04-22 | 日立マクセル株式会社 | Organic electrolyte battery |
| CN1431192A (en) * | 2003-01-17 | 2003-07-23 | 吉林大学 | Dumbbell form aniline oligomer and its synthesizing method |
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