CN102295743A - Fluorescent conjugated polymer containing polyhedral oligomeric silsesquioxane (POSS), its preparation method and application - Google Patents
Fluorescent conjugated polymer containing polyhedral oligomeric silsesquioxane (POSS), its preparation method and application Download PDFInfo
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Abstract
The invention relates to a fluorescent conjugated polymer containing polyhedral oligomeric silsesquioxane (POSS), its preparation method and application. By introducing polyhedral oligomeric silsesquioxane (POSS) with nanoscale to further improve the properties of luminescence, dissolving, heat resistance, light aging resistance and the like of PPE, a new method of preparing PPE fluorescent conjugated polymers for the detection of TNT and other nitro explosives is provided. The fluorescent conjugated polymer is a fluorescent sensing material with high sensitivity, shows strong fluorescence quenching sensitivity to the TNT explosives. Simultaneously, the prepared PPE can be used in the fields of electroluminescence, photovoltaic cell, chemical and biological sensor.
Description
Technical field
The invention belongs to the fluorescence sense technical field, relate to fluorescent conjugated polymer, preparation method and application, be specifically related to a class to contain alkoxyl group, POSS group substituted benzene monomer and to contain the preparation that contains POSS fluorescent conjugated polymer PPE novel fluorescence conjugated polymers that five butterfly alkene rigid structure monomer copolymerizations form, reach of the application of this polymkeric substance in nitro explosive context of detection such as TNT.
Background technology
As everyone knows, most explosive substances all contain the nitro-aromatic compound, and 2 (TNT) is the main component of most of explosives, and therefore, the detection technique of research TNT is very important, is the emphasis of researching and developing both at home and abroad always.
The detection technique that has multiple explosive substance at present, wherein film fluorescent optical sensor method detect that nitro explosive substance such as TNT has highly sensitive, highly selective, volume is little, the life-span is long, do not pollute system to be measured, easy to use, be easy to outstanding advantage such as device and developed into the important trace explosive detection method of a class.The core sensing member of film fluorescent optical sensor is to grip the fluorescent polymer film altogether.Be different from traditional small molecules fluorescent chemicals, fluorescence polymer shows unique " molecular wire effect ", realizes the multiplication of polymer fluorescent signal, and single quencher molecule just is enough to cause the super quencher of whole polymer fluorescent.
A series of PPE[Yang J S that contain rigidity five butterfly alkene structures that the Swager research group that present more representational achievement is a masschusetts, u.s.a Polytechnics is reported, Swager T M.Porous shape persistent fluorescent polymer films:An approach to TNT sensory materials, J Am Chem Soc, 1998,120:5321-5322.Yang J S, Swager T M.Fluorescent porous polymer films as TNT chemosensors:electronic and structural effects, J Am Chem Soc, 1998,120:11864-11873.].This is one of the highest fluorescence sense polymkeric substance of the present sensitivity of being reported, its characteristics: at first, rigidity five butterfly alkene structures have been avoided the electronics accumulation, improve the fluorescence stability of film; Secondly, there is the hole between polymer molecule, helps explosive substance molecule such as TNT and in film, spread, improve sensitivity.The 3rd, the solvability of PPE in organic solvent is improved.Yet this class material is not high in performances such as fast light thermal ageing, dissolvings, and optical property also needs further improvement.
Summary of the invention
The present invention is on the basis that contains five butterfly alkene PPE of Swager preparation, introducing has the cage modle polyhedral oligomeric silsesquioxane (hereinafter to be referred as POSS) of nanoscale, preparation contains the fluorescence conjugated polyhenylene acetylene support of POSS novel texture (hereinafter to be referred as PPE), purpose is further to improve performances such as luminous, the dissolving of PPE, heat-resisting, light aging resisting, the preparation that detects with PPE class conjugation fluorescent polymer for nitro explosives such as TNT provides new approaches, simultaneously, this material can also be applied to electroluminescent, photovoltaic cell, chemistry and field of biosensors.
The objective of the invention is to be achieved by the following technical programs:
A kind of fluorescent conjugated polymer that contains cage modle POSS is by containing alkoxyl group, POSS group substituted benzene monomer and containing the fluorescent conjugated polymer PPE that the monomer copolymerizable of five butterfly alkene rigid structures forms;
Described fluorescent conjugated polymer is a line style PPE derivative, and its general structure is as follows:
Wherein:
y∶z＝1∶0.1～0.1∶1
R
1Be selected from alkane substituting group or POSS substituting group;
R
2Be the POSS substituting group;
Described alkane substituting group general formula: C
nH
2n+1, C
nH
2n-1, n is 1～20 integer;
Described cage modle POSS general structure is as follows:
Wherein:
R is alkane substituting group or phenyl substituent;
X is halogenic substituent, halogenated alkane substituting group, halogenated aryl hydrocarbon substituting group, aliphatic amide substituting group; The preferred alkane iodide substituting group of X;
Described alkane substituting group general formula: C
nH
2n+1, C
nH
2n-1, n is the integer from 1～16;
Described halogenated alkane substituting group general formula: C
nH
2n+1X, C
nH
2n-1X, n are the integer from 2～16;
Described halogenated aryl hydrocarbon substituting group general formula: C
6H
4-C
nH
2n+1X, n are the integer from 0～10;
Described aliphatic amide substituting group general formula: C
nH
2n+1NH
2, C
nH
2n-1NH
2, (C
nH
2n+1) (C
nH
2n) NH, (C
nH
2n-1) (C
nH
2n-2) NH, n is the integer from 2～16;
The above-mentioned preparation method who contains the fluorescent conjugated polymer of cage modle POSS:
(1) works as R
1Be alkane substituting group, R
2During for the POSS substituting group, the preparation method of this fluorescent conjugated polymer comprises the steps:
1. contain the monomeric preparation of five butterfly alkene rigid structures:
Benzoquinone, anthracene and tetrachlorobenzoquinone are dissolved in the acetate 100 ℃ of reflux preparation in 4 hours, five butterfly alkene benzoquinones; Above-mentioned five butterfly alkene benzoquinones are joined in the tetrahydrofuran solution that contains n-Butyl Lithium and three silyl acetylene, room temperature reaction 4 hours, product is dissolved in it in acetone through extraction, washing, filtration, the dry white solid powder that gets, and drips SnCl
22H
2The acetic acid solution of O, room temperature reaction 2 hours, product after filtration, washing, drying, obtain 1,4-diacetylene-2,3,5,6-is two-(9, the 10-anthracene) benzene;
The mol ratio of described benzoquinone, anthracene and tetrachlorobenzoquinone is 1: 2: 2;
The mol ratio of described five butterfly alkene benzoquinones, n-butyllithium and three silyl acetylene is 1: 4: 4;
Described white solid powder and SnCl
22H
2The mol ratio of O is 1: 2;
2. 2, the preparation of 5-two bromo-monoalkoxy POSS substituted benzenes:
At N
2Protection joins chloropropyl seven isobutyl-POSS (POSS-Cl) and NaI among the mixed solvent a down, reflux preparation in 4 hours POSS-I; Liquid bromine and Resorcinol are added in the HAc solution, got 2,5-two bromo-Resorcinol in 1 hour at room temperature reaction; Then it is joined in the ethanolic soln that contains NaOH and bromo alkane, room temperature reaction 1 hour obtains 2,5-two bromo-1-alkoxyl group-Pyrogentisinic Acids; With 2,5-two bromo-1-alkoxyl group-Pyrogentisinic Acids, POSS-I and K
2CO
3Join among the mixed solvent a, back flow reaction obtained 2 in 5 hours, 5-two bromo-monoalkoxy POSS substituted benzenes;
The mol ratio of described POSS-Cl and NaI is 1: 10;
Described mixed solvent a is that volume ratio is that 3: 1 tetrahydrofuran (THF) and acetone mixes;
The mol ratio of described liquid bromine and Resorcinol is 5: 1;
Described 2, the mol ratio of 5-two bromo-Resorcinol, NaOH and bromo alkane is 1: 1: 1;
Described 2,5-two bromo-1-alkoxyl group-Pyrogentisinic Acids, POSS-I and K
2CO
3Mol ratio be 1: 1: 1;
3. contain the preparation of POSS fluorescent conjugated polymer:
Adopt the Heck-Sonogashira coupled reaction, at N
2Protection down, with step 1. prepared 1,4-diacetylene-2,3,5,6-is two-(9, the 10-anthracene) benzene and 2. prepared 2,5-two bromo-monoalkoxy POSS substituted benzenes place the Schlenk bottle, with Pd (PPh
3)
4With CuI be catalyzer, Diisopropylamine and toluene are solvent, 65～70 ℃ the reaction 48 hours; Reaction through cooling, extraction, washing, filtration, drying, obtains containing the fluorescent conjugated polymer of cage modle POSS after finishing;
Described step 1. prepare 1,4-diacetylene-2,3,5,6-is two-(9, the 10-anthracene) benzene and step 2. prepare 2, the mol ratio of 5-two bromo-monoalkoxy POSS substituted benzenes is 1: 1;
The volume ratio of described Diisopropylamine and toluene is 2: 3.
(2) work as R
1And R
2When all being the POSS substituting group, the preparation method of this fluorescent conjugated polymer comprises the steps:
1. contain the monomeric preparation of five butterfly alkene rigid structures:
Benzoquinone, anthracene and tetrachlorobenzoquinone are dissolved in the acetate 100 ℃ of reflux preparation in 4 hours, five butterfly alkene benzoquinones; Above-mentioned five butterfly alkene benzoquinones are joined in the tetrahydrofuran solution that contains n-Butyl Lithium and three silyl acetylene, room temperature reaction 4 hours, product is dissolved in it in acetone through extraction, washing, filtration, the dry white solid powder that gets, and drips SnCl
22H
2The acetic acid solution of O, room temperature reaction 2 hours, product after filtration, washing, drying, obtain 1,4-diacetylene-2,3,5,6-is two-(9, the 10-anthracene) benzene;
The mol ratio of described benzoquinone, anthracene and tetrachlorobenzoquinone is 1: 2: 2;
The mol ratio of described five butterfly alkene benzoquinone compounds, n-Butyl Lithium and three silyl acetylene is 1: 4: 4;
Described white solid powder and SnCl
22H
2The mol ratio of O is 1: 2;
2. 2, the preparation of 5-two bromo-bis-alkoxy POSS substituted benzenes::
At N
2Protection joins POSS-Cl and NaI among the mixed solvent a down, reflux preparation in 4 hours POSS-I; Liquid bromine and Resorcinol are added in the HAc solution, got 2,5-two bromo-Resorcinol in 1 hour at room temperature reaction; With 2,5-two bromo-Resorcinol, POSS-I and K
2CO
3Join among the mixed solvent a, back flow reaction obtained 2 in 5 hours, 5-two bromo-bis-alkoxy POSS substituted benzenes;
The mol ratio of described POSS-Cl and NaI is 1: 10;
Described mixed solvent a is to be that 3: 1 tetrahydrofuran (THF) and acetone mixes by volume ratio;
The mol ratio of described liquid bromine and Resorcinol is 5: 1;
Described 2,5-two bromo-Resorcinol, POSS-I and K
2CO
3Mol ratio be 1: 2: 1;
3. contain the preparation of POSS fluorescent conjugated polymer:
Adopt the Heck-Sonogashira coupled reaction, at N
2Protection down, with step 1. and 2. prepared 2,5-two bromo-bis-alkoxy POSS substituted benzenes place the Schlenk bottle, with Pd (PPh
3)
4With CuI be catalyzer, Diisopropylamine and toluene are solvent, 65～70 ℃ the reaction 48 hours; Reaction through cooling, extraction, washing, filtration, drying, obtains containing the fluorescent conjugated polymer of cage modle POSS after finishing;
Described step 1. prepare 1,4-diacetylene-2,3,5,6-is two-(9, the 10-anthracene) benzene and 2. prepared 2, the mol ratio of 5-two bromo-bis-alkoxy POSS substituted benzenes is 1: 1;
The volume ratio of described Diisopropylamine and toluene solvant is 2: 3.
The raw materials used chloropropyl seven isobutyl-POSS of the present invention (being called for short POSS-Cl) are available from U.S. hybrid plastics company, article No. HA0635.
Described fluorescent conjugated polymer, wherein five butterfly alkene rigid structure groups comprise the derivative of five butterfly alkene, are included on the aromatic ring of five butterfly alkene to contain substituting groups such as alkyl, alkoxyl group, aryl, amido, fatty amido, butterfly alkene.Substituting group quantity can be single, double, three and four replacements.
Described fluorescent conjugated polymer, both can be directly by spin coating, drip and be coated with, lift, can also pass through solvent, as ink printed system film; Can also be by the method system film polymer blended with other inertia, the polymer that is adopted comprises polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyacrylonitrile, polymeric amide, Polyurethane, poly-methyl methacrylate vinegar, polyarylether etc.
Described fluorescent conjugated polymer has sensing function to aromatic series explosive substance, pannonit class explosive substance or the nitrose explosive substance that TNT, DNT etc. contains nitro; Fluorescent conjugated polymer can form film or be dissolved in and be prepared into transmitter in the solvent on the solid surface, so that nitro explosive is detected.Wherein said solid support comprises sheet glass, quartz plate, silicon chip and solid organic polymer carrier, can also be micro-powder, nano particle, nano wire, nanofiber and nanotube etc. that organic polymer and other material are made.
Fluorescent conjugated polymer of the present invention has following characteristics: the molecular side chain at polymkeric substance is introduced suitable alkoxyl group and POSS, the existence of rigidity POSS molecule, can hinder interaction and gathering between the macromolecular chain, further improve the PPE luminescent properties; Itself has porous nanometer structure POSS, can produce more hole, helps the diffusion of explosive substance molecules such as TNT, improves sensitivity; The inorganic materials character of POSS own can improve the heat-resisting and light stability of PPE; Also has good solubility simultaneously.
Description of drawings
16 in the total accompanying drawing of the present invention, wherein:
Fig. 1: 2,3,5, the synthetic synoptic diagram of 6-pair-(9, the 10-anthracene)-para benzoquinone;
Fig. 2: 1,4-diacetylene-2,3,5, the synthetic synoptic diagram of 6-pair-(9, the 10-anthracene) benzene;
Fig. 3: the synthetic synoptic diagram of iodo sec.-propyl silsesquioxane (POSS-I);
Fig. 4: 2, the synthetic synoptic diagram of the single propyl group POSS of 5-two bromo-1-n-Hexadecane oxygen bases-4-substituted benzene;
Fig. 5: 2,5-two bromo-1, the synthetic synoptic diagram of 4-bis propane oxygen base POSS substituted benzene;
Fig. 6: the synthetic synoptic diagram of PPE A;
Fig. 7: the synthetic synoptic diagram of PPE B;
Fig. 8: 1,4-two iodo-2, the synthetic synoptic diagram of 5-two (n-Hexadecane oxygen base) benzene;
Fig. 9: the synthetic synoptic diagram of PPE C;
Figure 10: the relation curve of PPEA quencher efficient and TNT concentration, a, b, c, the TNT concentration of d correspondence is respectively 0.5ppm, 2.2ppm, 8.8ppm and 36ppm;
Figure 11: the relation curve of PPE B quencher efficient and TNT concentration, a, b, c, the TNT concentration of d correspondence is respectively 0.5ppm, 2.2ppm, 8.8ppm and 36ppm;
Figure 12: the relation curve of PPE C quencher efficient and TNT concentration, a, b, c, the TNT concentration of d correspondence is respectively 0.5ppm, 2.2ppm, 8.8ppm and 36ppm;
Figure 13: PPE A quenching of fluorescence cross-reference figure;
Figure 14: PPE B quenching of fluorescence cross-reference figure;
Figure 15: PPE C quenching of fluorescence cross-reference figure;
Figure 16: the DSC curve contrast figure of PPE A, B and C.
Embodiment
Below in conjunction with the drawings and specific embodiments technical scheme of the present invention is described further, will helps the understanding of the present invention.But the present invention is not limited to following embodiment.
Embodiment 1: contain the synthetic of POSS novel fluorescence conjugation PPE
(1) 2,3,5,6-is two-(9, the 10-anthracene)-para benzoquinone synthetic
Take by weighing benzoquinone 1.92g, anthracene 6.56g and tetrachlorobenzoquinone 8.76g are dissolved in the 250mLHAc solution, 100 ℃ of reflux 4h.Reactant filters, and uses the anhydrous diethyl ether flush cake, and vacuum-drying gets yellow powder, productive rate 87%.Reaction formula as shown in Figure 1.
1H?NMR(400MHz，CDCl
3)δ：5.75(s，4H)，6.97(dd，J
1＝3.2，J
2＝5.3Hz，8H)，7.6(dd，J
1＝3.2，J
2＝5.34Hz，8H)。
(2) 1,4-diacetylenes-2,3,5,6-is two-(9, the 10-anthracene) benzene synthetic
N
2Protection is added drop-wise to the n-BuLi of equivalent in the tetrahydrofuran solution that contains three silyl acetylene down, keeps stirring at room 3h.Take by weighing the middle synthetic para benzoquinone of 1.92g (1) and be dissolved in the tetrahydrofuran solution, and slowly be added drop-wise in the above-mentioned reaction solution stirring at room 4h.With the HCl solution termination reaction of 1ml10%, extract organic phase with the chloroform/water phase-splitting, remove and desolvate.Add the normal hexane flushing in the residuum, filter, vacuum-drying gets the white solid powder.Productive rate 90%.
Above-mentioned white powder is dissolved in the 10ml acetone, takes by weighing 1.96gSnCl
22H
2O is dissolved in the HAc solution of 10ml50%, and it slowly is added drop-wise in the above-mentioned acetone soln, and stirring at room 2h filters.Filter cake is dissolved in the chloroformic solution, respectively the NaHCO of water and 0.3mol/L
3Anhydrous magnesium sulfate drying is used in the solution flushing then, filters, and rotary evaporation desolvates, and uses the normal hexane flush cake, gets the white solid powder.Be dissolved in again in tetrahydrofuran (THF)/methyl alcohol (volume ratio 2: 1) mixing solutions, recrystallization, product filters, the water flushing, vacuum-drying gets the white solid powder, productive rate 76%.Reaction formula as shown in Figure 2.
1HNMR(400MHz，CDCl
3)δ：3.75(s，2H)，5.82(s，4H)，6.95(dd，J
1＝3.2，J
2＝5.3Hz，8H)，7.36(dd，J
1＝3.2，J
2＝5.34Hz，8H)。
(3) iodo sec.-propyl silsesquioxane (POSS-I) is synthetic
N
2Protection takes by weighing 1.986gPOSS-Cl and 14.4gNaI respectively down, joins in tetrahydrofuran (THF)/acetone (volume ratio 3: 1) mixing solutions of 100mL reflux 4h.After reaction finished, cooling was filtered, and rotary evaporation is removed solvent, obtain faint yellow solid, then the gained solid is dissolved in the dichloromethane solution, filter, filtrate rotary evaporation is once more desolvated, vacuum-drying obtains yellow powder, and productive rate 78%, reaction formula are as shown in Figure 3.
1HNMR(400MHz，CDCl
3)δ：3.22(t，2H)，1.89(m，2H)，0.84-1.26(m，49H)，0.71(t，2H)，0.62(m，14H)。
Synthesizing of the single propyl group POSS of (4) 2,5-two bromo-1-n-Hexadecane oxygen bases-4-substituted benzene
Take by weighing 11g liquid bromine and be dissolved in the 20mL acetate, it is added drop-wise in the acetic acid solution that contains the 6.4g Resorcinol, keep stirring at room 1h.Reaction is poured reaction solution in the 200mL water into after finishing, and has brown solid to separate out, filter, and filter cake water recrystallization, vacuum-drying gets white powder 2,5-two bromo-Resorcinol, productive rate 70%.
1HNMR(400MHz，CDCl
3)δ：7.62(s，2H)，6.88(s，2H)。
Take by weighing above-mentioned white powder of 3.68g and 0.75gNaOH and join in the 60mL dehydrated alcohol, stirring at room 1h adds 5.05g5C then
16H
33Br continues to stir 1h.Cooling is filtered, and rotary evaporation is removed solvent.Residuum is poured in the 90mL deionized water, used hcl acidifying, filter, washing, vacuum-drying gets brown solid.Column chromatography for separation (methylene dichloride: normal hexane=4: 6, volume ratio) gets white solid, productive rate 62%.
1HNMR(400MHz，CDCl
3)δ：7.24(s，1H)，6.97(s，1H)，5.14(s，1H)，3.92(t，J＝6Hz，2H)，1.80(q，2H)，1.4(m，26H)，0.86(t，J＝6Hz，3H)。
Take by weighing the above-mentioned brown solid product of 187mg, 230mgPOSS-I, 50mgK
2CO
3Join in 80mL tetrahydrofuran (THF)/acetone (volume ratio 3: 1) mixing solutions back flow reaction 5h.Filter, rotary evaporation is removed solvent, and residuum is poured in the deionized water, uses chloroform extraction, organic phase water extraction respectively, anhydrous MgSO
4Drying is filtered, and rotary evaporation desolvates, and gets thick product.Column chromatography for separation (chloroform: normal hexane=1: 15, volume ratio) gets white powder, productive rate 78%.Reaction formula as shown in Figure 4.
1HNMR(400MHz，CDCl
3)δ：7.08(s，1H)，7.07(s，1H)，3.94(m，4H)，1.91(m，2H)，1.26-1.49(m，28H)，0.97(m，49H)，0.88(t，3H)，0.77(t，2H)，0.62(m，14H)。
(5) 2,5-two bromo-1,4-bis propane oxygen base POSS substituted benzene synthetic
Take by weighing 187mg2,5-two bromo-Resorcinol, 460mgPOSS-I, 50mgK
2CO
3Join in 80mL tetrahydrofuran (THF)/acetone (volume ratio 3: 1) mixing solutions back flow reaction 5h.Filter, rotary evaporation is removed solvent, and residuum is poured in the deionized water, uses chloroform extraction, organic phase water extraction respectively, anhydrous MgSO
4Drying is filtered, and rotary evaporation desolvates, and gets thick product.Column chromatography for separation (CHCl
3: hexane=1: 15, volume ratio), get white powder, productive rate 79%.Reaction formula as shown in Figure 5.
1HNMR(400MHz，CDCl
3)δ：7.07(s，2H)，3.94(m，4H)，1.91(m，4H)，0.99(m，98H)，0.77(t，4H)，0.62(m，28H)。
(6) PPE A's is synthetic
N
2Protection takes by weighing 144mg2 respectively down, 5-two bromo-list n-Hexadecane oxygen base POSS, 80mg1,4-diacetylene-2,3,5,6-couple-(9, the 10-anthracene) benzene, 30mg Pd (PPh
3)
4With 10mgCuI in the Schlenk of 25ml bottle, add the mixing solutions of 10ml Diisopropylamine/toluene (volume ratio 2: 3) then, keep 65～70 ℃ the reaction 72 hours.After reaction finishes, cool off, extract organic phase, separate layer oily matter matter and collection, use anhydrous MgSO with chloroform/water (volume ratio 1: 1)
4Drying, rotary evaporation desolvates, and the residuum methanol extraction filters, and vacuum-drying gets brown ceramic powder, productive rate 76.2%.Reaction formula as shown in Figure 6.
(7) PPE B's is synthetic
N
2Protection takes by weighing 169mg2 respectively down, the two n-Hexadecane oxygen base POSS of 5-two bromo-, and 70mg 1,4-diacetylene-2,3,5,6-couple-(9, the 10-anthracene) benzene, 30mg Pd (PPh
3)
4With 10mgCuI in the Schlenk of 25ml bottle, add the mixing solutions of 10ml Diisopropylamine/toluene (volume ratio 2: 3) then, keep 65～70 ℃ the reaction 72 hours.After reaction finishes, cool off, extract organic phase, separate layer oily matter matter and collection, use anhydrous MgSO with chloroform/water (volume ratio 1: 1)
4Drying, rotary evaporation desolvates, and the residuum methanol extraction filters, and vacuum-drying gets brown ceramic powder, productive rate 76.7%.Reaction formula as shown in Figure 7.
Embodiment 2: do not contain the synthetic of the fluorescence conjugated PPE of POSS
(1) 1,4-two iodo-2,5-two (n-Hexadecane oxygen base) benzene synthetic
The N2 protection takes by weighing 2.00g Resorcinol and 2.30gKOH respectively to join among the anhydrous DMSO down, adds 6gC then
16H
33Br, room temperature reaction 1h.Reaction is poured above-mentioned reaction solution in the 200mL cold water into after finishing, and the adularescent solid is separated out, and filters, and vacuum-drying gets the white solid powder.Productive rate 83%.
Take by weighing the above-mentioned product of 5.00g, 5.00g iodine and 2.00g KIO
3, join dense H
2SO
4, H
2In the mixing solutions of O and acetate, reflux 1h drips Na
2S
2O
4Solution filters, and vacuum-drying gets white solid product, and productive rate 86%, reaction formula are as shown in Figure 8.
1H?NMR(400MHz，CDCl
3)δ：0.88(t，6H)，1.26(br?s，48H)，1.79(m，4H)，1.48(br?m，4H)，3.92(t，4H)，7.17(s，2H)。
(2) PPE C's is synthetic
N
2Protection takes by weighing 122mg 1 respectively down, 4-diacetylene-2,3,5,6-pair-(9, the 10-anthracene) benzene and the above-mentioned product of 60mg, 20mg Pd (PPh
3)
4With 10mgCuI in the Schlenk of 25ml bottle, add the mixing solutions of 10ml Diisopropylamine/toluene (volume ratio 2: 3) then, keep 65～70 ℃ of reactions three round the clock.After reaction finishes, cool off, with chloroform/water (1: 1) extraction organic phase, separate layer oily matter matter and collection, with anhydrous MgSO4 drying, rotary evaporation desolvates, and the residuum methanol extraction filters, and vacuum-drying gets pale yellow powder, productive rate 72.3%.Reaction formula as shown in Figure 9.
Embodiment 3:
(1) contains the luminosity of POSS novel fluorescence sensing material
PPE A, B are mixed with chloroformic solution, and after tested as can be known, PPE A, B have a maximal ultraviolet absorption peak at 410nm and 426nm place respectively.The maximum emission wavelength of PPE A, B is respectively at 451nm and 450nm place, and at 491nm and 482nm place an acromion arranged respectively, shown in the ultra-violet absorption spectrum and fluorescence emission spectrum data sheet (table 1) of PPE A, B and C.
(2) do not contain the luminosity of the fluorescence conjugated PPE of POSS
With the test of (1) method, PPE C has a maximal ultraviolet absorption peak at the 444nm place, there is a maximum emission wavelength respectively at the 455nm place, an acromion arranged, at 484 places shown in the ultra-violet absorption spectrum and fluorescence emission spectrum data sheet (table 1) of PPE A, B and C.
Contrast PPE A, B and C as seen, PPE A, B all have to a certain degree blue shift with respect to PPE C ultraviolet maximum absorption band and fluorescence emission maximum peak position.This is because the adding of macro-radical POSS has strengthened the polymkeric substance chain rigidity, has reduced intermolecular gathering, thereby has caused blue shift.
Table 1
Embodiment 4: contain the fluorescence response character of POSS novel fluorescence sensing material to the TNT explosive substance
PPE A, B are mixed with chloroformic solution, the TNT chloroformic solution of cofabrication 0.5ppm～36ppm.3: 1 by volume ratio of polymkeric substance and TNT is carried out the quenching of fluorescence experiment then.Find that its minimum detectability is 0.5ppm, and TNT concentration is when being 36ppm, the quencher efficient of PPE A, B reaches 57.86% and 55.32% respectively, shown in Figure 10,11.Illustrate that PPE A of the present invention, B have good quenching of fluorescence susceptibility to TNT.TNT mixed with PPE A, B moments later observe its fluorescence spectrum again, find that fluorescence spectrum almost no longer changes, and has verified further that also product of the present invention has good quenching of fluorescence susceptibility to TNT.
Embodiment 5: the fluorescence response character to the TNT explosive substance that does not contain the fluorescence conjugated PPE of POSS
With the test of embodiment 4 methods, when TNT concentration reached 36ppm, the quencher efficient of PPE C reached 52.92%, was lower than the PPE A and the B that contain POSS, as shown in figure 12.
Embodiment 6: contain POSS novel fluorescence sensing material quenching of fluorescence front and back colour contrast
With PPE A, B preparation chloroformic solution, under the exciting of ultraviolet source, observe its quenching of fluorescence front and back colour-change situation, shown in Figure 13,14.As seen from the figure, obvious variation had taken place in the color of PPE A, B solution before and after TNT added.Illustrate that PPEA of the present invention, B have tangible quenching of fluorescence susceptibility to TNT.
Embodiment 7: the quenching of fluorescence front and back colour contrast that does not contain the fluorescence conjugated PPE of POSS
With the test of embodiment 4 methods, as shown in figure 15.As seen from the figure, obvious variation had taken place in the color of PPE C solution before and after TNT added, and also demonstrated good quenching of fluorescence susceptibility.
Embodiment 8: contain POSS novel fluorescence sensing material DSC test
The DSC curve of PPE A and B as shown in figure 16.As seen from the figure, Tg does not appear on the DSC of PPE A, B curve, obviously, because the rigid radical POSS of large volume is incorporated in the macromolecular chain, hinder the motion of macromolecular chain, improved the rigidity of polymer molecular chain greatly, caused having lost motor capacity, because POSS itself has silica cage modle skeleton, can improve the thermostability of PPE simultaneously.
Embodiment 9: do not contain the DSC test of the fluorescence conjugated PPE of POSS
Do not contain POSS PPE C the DSC curve as shown in figure 16.As seen from the figure, the DSC curve of PPE C Tg occurs about 110 ℃.Show that macromolecular chain has certain flexibility, its thermotolerance is starkly lower than PPE A and B among the embodiment.
Claims (5)
1. fluorescent conjugated polymer that contains cage modle POSS has following general structure:
Wherein:
y∶z＝1∶0.1～0.1∶1
R
1Be selected from alkane substituting group or POSS substituting group;
R
2Be the POSS substituting group;
Described alkane substituting group general formula: C
nH
2n+1, C
nH
2n-1, n is 1～20 integer;
Described POSS substituting group has following general structure:
Wherein:
R is alkane substituting group or phenyl substituent;
X is halogenic substituent, halogenated alkane substituting group, halogenated aryl hydrocarbon substituting group or aliphatic amide substituting group;
Described alkane substituting group general formula: C
nH
2n+1, C
nH
2n-1, n is the integer from 1～16;
Described halogenated alkane substituting group general formula: C
nH
2n+1X, C
nH
2n-1X, n are the integer from 2～16;
Described halogenated aryl hydrocarbon substituting group general formula: C
6H
4-C
nH
2n+1X, n are the integer from 0～10;
Described aliphatic amide substituting group general formula: C
nH
2n+1NH
2, C
nH
2n-1NH
2, (C
nH
2n+1) (C
nH
2n) NH, (C
nH
2n-1) (C
nH
2n-2) NH, n is the integer from 2～16.
2. a kind of fluorescent conjugated polymer that contains cage modle POSS according to claim 1 is characterized in that described X is the alkane iodide substituting group.
3. a preparation method who contains the fluorescent conjugated polymer of cage modle POSS as claimed in claim 1 or 2 is characterized in that working as R
1Be alkane substituting group, R
2During for the POSS substituting group, the preparation method of this fluorescent conjugated polymer comprises the steps:
1. contain the monomeric preparation of five butterfly alkene rigid structures:
Benzoquinone, anthracene and tetrachlorobenzoquinone are dissolved in the acetate 100 ℃ of reflux preparation in 4 hours, five butterfly alkene benzoquinones; Above-mentioned five butterfly alkene benzoquinones are joined in the tetrahydrofuran solution that contains n-Butyl Lithium and three silyl acetylene, room temperature reaction 4 hours, product is dissolved in it in acetone through extraction, washing, filtration, the dry white solid powder that gets, and drips SnCl
22H
2The acetic acid solution of O, room temperature reaction 2 hours, product after filtration, washing, drying, obtain 1,4-diacetylene-2,3,5,6-is two-(9, the 10-anthracene) benzene;
The mol ratio of described benzoquinone, anthracene and tetrachlorobenzoquinone is 1: 2: 2;
Described five butterfly alkene benzoquinones, just-mol ratio of butyllithium and three silyl acetylene is 1: 4: 4;
Described white solid powder and SnCl
22H
2The mol ratio of O is 1: 2;
2. 2, the preparation of 5-two bromo-monoalkoxy POSS substituted benzenes:
At N
2Protection joins POSS-Cl and NaI among the mixed solvent a down, reflux preparation in 4 hours POSS-I; Liquid bromine and Resorcinol are added in the HAc solution, got 2,5-two bromo-Resorcinol in 1 hour at room temperature reaction; Then it is joined in the ethanolic soln that contains NaOH and bromo alkane, room temperature reaction 1 hour obtains 2,5-two bromo-1-alkoxyl group-Pyrogentisinic Acids; With 2,5-two bromo-1-alkoxyl group-Pyrogentisinic Acids, POSS-I and K
2CO
3Join among the mixed solvent a, back flow reaction obtained 2 in 5 hours, 5-two bromo-monoalkoxy POSS substituted benzenes;
The mol ratio of described POSS-Cl and NaI is 1: 10;
Described mixed solvent a is that volume ratio is that 3: 1 tetrahydrofuran (THF) and acetone mixes;
The mol ratio of described liquid bromine and Resorcinol is 5: 1;
Described 2, the mol ratio of 5-two bromo-Resorcinol, NaOH and bromo alkane is 1: 1: 1;
Described 2,5-two bromo-1-alkoxyl group-Pyrogentisinic Acids, POSS-I and K
2CO
3Mol ratio be 1: 1: 1;
3. contain the preparation of POSS fluorescent conjugated polymer:
Adopt the Heck-Sonogashira coupled reaction, at N
2Protection down, with step 1. prepared 1,4-diacetylene-2,3,5,6-is two-(9, the 10-anthracene) benzene and 2. prepared 2,5-two bromo-monoalkoxy POSS substituted benzenes place the Schlenk bottle, with Pd (PPh
3)
4With CuI be catalyzer, Diisopropylamine and toluene are solvent, 65～70 ℃ the reaction 48 hours; Reaction through cooling, extraction, washing, filtration, drying, obtains containing the fluorescent conjugated polymer of cage modle POSS after finishing;
Described step 1. prepare 1,4-diacetylene-2,3,5,6-is two-(9, the 10-anthracene) benzene and step 2. prepare 2,5-two bromo-monoalkoxy POSS substituted benzene mol ratios are 1: 1;
Described step 1. prepare 1,4-diacetylene-2,3,5,6-is two-(9, the 10-anthracene) benzene, Pd (PPh
3)
4With the CuI mol ratio be 10: 0.5: 5;
The volume ratio of described Diisopropylamine and toluene is 2: 3.
4. the preparation method who contains the fluorescent conjugated polymer of cage modle POSS as claimed in claim 1 or 2 is characterized in that working as R
1And R
2When all being the POSS substituting group, the preparation method of this fluorescent conjugated polymer comprises the steps:
1. contain the monomeric preparation of five butterfly alkene rigid structures:
Benzoquinone, anthracene and tetrachlorobenzoquinone are dissolved in the acetate 100 ℃ of reflux preparation in 4 hours, five butterfly alkene benzoquinones; Above-mentioned five butterfly alkene benzoquinones are joined in the tetrahydrofuran solution that contains n-Butyl Lithium and three silyl acetylene, room temperature reaction 4 hours, product is dissolved in it in acetone through extraction, washing, filtration, the dry white solid powder that gets, and drips SnCl
22H
2The acetic acid solution of O, room temperature reaction 2 hours, product after filtration, washing, drying, obtain 1,4-diacetylene-2,3,5,6-is two-(9, the 10-anthracene) benzene;
The mol ratio of described benzoquinone, anthracene and tetrachlorobenzoquinone is 1: 2: 2;
The mol ratio of described five butterfly alkene benzoquinone compounds, n-Butyl Lithium and three silyl acetylene is 1: 4: 4;
Described white solid powder and SnCl
22H
2The mol ratio of O is 1: 2;
2. 2, the preparation of 5-two bromo-bis-alkoxy POSS substituted benzenes::
At N
2Protection joins POSS-Cl and NaI among the mixed solvent a down, reflux preparation in 4 hours POSS-I; Liquid bromine and Resorcinol are added in the HAc solution, got 2,5-two bromo-Resorcinol in 1 hour at room temperature reaction; With 2,5-two bromo-Resorcinol, POSS-I and K
2CO
3Join among the mixed solvent a, back flow reaction obtained 2 in 5 hours, 5-two bromo-bis-alkoxy POSS substituted benzenes;
The mol ratio of described POSS-Cl and NaI is 1: 10;
Described mixed solvent a is to be that 3: 1 tetrahydrofuran (THF) and acetone mixes by volume ratio;
The mol ratio of described liquid bromine and Resorcinol is 5: 1;
Described 2,5-two bromo-Resorcinol, POSS-I and K
2CO
3Mol ratio be 1: 2: 1;
3. contain the preparation of POSS fluorescent conjugated polymer:
Adopt the Heck-Sonogashira coupled reaction, at N
2Protection down, with step 1. prepare 1,4-diacetylene-2,3,5,6-is two-(9, the 10-anthracene) benzene and 2. prepared 2,5-two bromo-bis-alkoxy POSS substituted benzenes place the Schlenk bottle, with Pd (PPh
3)
4With CuI be catalyzer, Diisopropylamine and toluene are solvent, 65～70 ℃ the reaction 48 hours; Reaction through cooling, extraction, washing, filtration, drying, obtains containing the fluorescent conjugated polymer of cage modle POSS after finishing;
Described step 1. prepare 1,4-diacetylene-2,3,5,6-is two-(9, the 10-anthracene) benzene and 2. prepared 2, the mol ratio of 5-two bromo-bis-alkoxy POSS substituted benzenes is 1: 1;
Described step 1. prepare 1,4-diacetylene-2,3,5,6-is two-(9, the 10-anthracene) benzene, Pd (PPh
3)
4, the CuI mol ratio is 10: 0.5: 5;
The volume ratio of described Diisopropylamine and toluene solvant is 2: 3.
5. contain the application of the fluorescent conjugated polymer of cage modle POSS according to claim 1, it is characterized in that described fluorescent conjugated polymer is used for the detection of TNT.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106596493A (en) * | 2016-12-29 | 2017-04-26 | 吉林大学 | Test paper for nitrobenzene explosives and preparation method and applications thereof |
| CN107022082A (en) * | 2017-04-18 | 2017-08-08 | 齐鲁工业大学 | A kind of application of silicon substrate hyperbranched conjugated polymer in Nitro-aromatic Compounds in Different detection |
| CN107022083A (en) * | 2017-04-18 | 2017-08-08 | 齐鲁工业大学 | A kind of silicon substrate hyperbranched conjugated polymer and preparation method thereof |
| CN107167462A (en) * | 2017-07-28 | 2017-09-15 | 山东大学 | A kind of fluorescence detection test of quick detection Nitroaromatic explosive and preparation method and application |
| CN108610635A (en) * | 2018-05-08 | 2018-10-02 | 山东大学 | A kind of organic luminescence from silicon method for producing elastomers |
| CN112143178A (en) * | 2020-09-24 | 2020-12-29 | 中国药科大学 | Electrostatic compound fluorescent array sensor and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101501144A (en) * | 2006-08-07 | 2009-08-05 | 西巴控股有限公司 | Novel polyhedral oligomeric silsesquioxane (POSS) based fluorescent colorants |
-
2011
- 2011-06-24 CN CN 201110172167 patent/CN102295743A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101501144A (en) * | 2006-08-07 | 2009-08-05 | 西巴控股有限公司 | Novel polyhedral oligomeric silsesquioxane (POSS) based fluorescent colorants |
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|---|---|---|---|---|
| CN106596493A (en) * | 2016-12-29 | 2017-04-26 | 吉林大学 | Test paper for nitrobenzene explosives and preparation method and applications thereof |
| CN107022082A (en) * | 2017-04-18 | 2017-08-08 | 齐鲁工业大学 | A kind of application of silicon substrate hyperbranched conjugated polymer in Nitro-aromatic Compounds in Different detection |
| CN107022083A (en) * | 2017-04-18 | 2017-08-08 | 齐鲁工业大学 | A kind of silicon substrate hyperbranched conjugated polymer and preparation method thereof |
| CN107022082B (en) * | 2017-04-18 | 2020-11-13 | 齐鲁工业大学 | Application of silicon-based hyperbranched conjugated polymer in detection of nitroaromatic compound |
| CN107022083B (en) * | 2017-04-18 | 2020-11-13 | 齐鲁工业大学 | Silicon-based hyperbranched conjugated polymer and preparation method thereof |
| CN107167462A (en) * | 2017-07-28 | 2017-09-15 | 山东大学 | A kind of fluorescence detection test of quick detection Nitroaromatic explosive and preparation method and application |
| CN108610635A (en) * | 2018-05-08 | 2018-10-02 | 山东大学 | A kind of organic luminescence from silicon method for producing elastomers |
| CN112143178A (en) * | 2020-09-24 | 2020-12-29 | 中国药科大学 | Electrostatic compound fluorescent array sensor and application |
| CN112143178B (en) * | 2020-09-24 | 2022-06-28 | 中国药科大学 | Electrostatic composite fluorescent array sensor and application |
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