CN102585220A - Hyperbranched polytriazole formate as well as preparation method and application thereof - Google Patents
Hyperbranched polytriazole formate as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses hyperbranched polytriazole formate as well as a preparation method and application thereof. The preparation method of hyperbranched polytriazole formate comprises the following steps: firstly, synthesizing binary azide containing a tetraphenyl ethylene unit; then synthesizing a ternary ester compound containing alkynyl based on ternary alcohol and propiolic acid as raw materials; and finally, carrying out non-metal-catalytic 'click' polymerization reaction under the heating condition in a polar solvent by utilizing the azide and the alkynyl-containing ester compound so as to obtain a target polymer in high yield. The hyperbranched polytriazole formate prepared by using the method is high in 1,4-stereoregularity, good in workability and high in thermal stability, degradability, illumination patterning and aggregation-induced emission property. The invention also discloses application of hyperbranched polytriazole formate in detection of a polynitroarene explosive.
Description
Technical field
The present invention relates to polymer chemistry and material science, be specifically related to a kind of novel hyperbranched poly triazole manthanoate.
Background technology
The sixties in 20th century, Germanization scholar Rolf Huisgen has at first studied and has utilized 1 of organic nitrine and alkynyl compounds preparation ring triazole class compounds, 3-Dipolar Cycloaddition (Chem.Ber.1967,100,2494).But, make this reaction not be used widely because speed of reaction is slow and product does not have stereoselectivity.2002, Meldal and Sharpless seminar independently reported the cycloaddition reaction of the catalytic nitrine-alkynyl of cuprous salt respectively, and the discovery speed of reaction is accelerated greatly, and product has stereoselectivity; Only generate 1, the dibasic 1,2,3-triazoles compound of 4-(J.Org.Chem.2002; 67,3057, Angew.Chem.; Int.Ed.2011,40,2004).Immediately, Sharpless etc. should react called after " click chemistry " reaction.
The characteristics of " click " reaction are that reaction conditions is simple, and raw material is easy to get, and reaction has very strong stereoselectivity and meets Atom economy etc.Cycloaddition reaction conduct typical " click " reaction of the catalytic nitrine-alkynyl of cuprous salt, it is synthetic to be widely used in functional polymer, finishing, a plurality of fields such as preparation of biology and chemical sensor.
Aspect polymkeric substance synthetic, the cycloaddition reaction of the catalytic nitrine-alkynyl of monovalence copper is used for the back functional modification of polymkeric substance morely.Should react as a kind of polyreaction and prepare polymkeric substance, especially the research of hyperbranched polymer aspect is less.2004, people such as Voit attempted utilizing AB
2The type monomer prepares hyperbranched polymer under the catalysis of copper sulfate and sodium ascorbate, but has had to insoluble polymkeric substance (Macromol.Rapid Commun.2004,25,1175).2008, Katritzky seminar utilized A through changing monomer type
2+ B
3The type monomer is the preparation hyperbranched polymer under the catalysis of copper sulfate and sodium ascorbate or thermal polymerization condition, and the solvability of the polymkeric substance that obtains is relatively poor, and the reaction times is grown (J. Polym.Sci., PartA:Polym.Chem.2008,46,238).Seminar of the present invention is through utilizing A
2+ B
3The type monomer under organic solvent soluble monovalence copper and divalent ruthenium catalysis, prepared respectively soluble 1,4-and 1; The stereoregulated hyperbranched polymer of 5-; And attempted the heat polymerization of no metal catalytic, obtained soluble upright structure random hyperbranched polymer (Macromolecules, 2008; 41,3808).Li Zhen seminar of Wuhan University utilizes A through changing reaction solvent, temperature and end capping
2+ B
3The type monomer has prepared soluble hyperbranched polymer (Macromolecules 2009,42,1589, J.Polym.Sci., PartA:Polym.Chem.2011,49,1977) under the catalysis of copper sulfate and sodium ascorbate.
The catalytic click polyreaction of monovalence copper prepares hyperbranched polymer, often causes the solvability of polymkeric substance relatively poor, and residual copper catalyst is difficult to remove clean in the polymkeric substance.If this base polymer is used for biomedicine and photoelectric field; Will produce the photophysical property of cytotoxicity and destruction polymkeric substance; Thereby limited the application of the catalytic click polyreaction of monovalence copper, the click polyreaction that therefore develops no metal catalytic prepares hyperbranched polymer and has very important science and using value.
In addition, most of luminous organic materials can present luminous efficiency usually to be reduced even non-luminous phenomenon in state of aggregation or when solid-state, promptly assembles fluorescent quenching, and this has just limited the range of application of luminous organic material greatly.
Calendar year 2001; This loyal seminar of Tang finds that silole is not luminous when solution; And when solid-state, present (Chem.Commun.2001,1740) after the very strong characteristics of luminescence, with luminous (the Aggregation-induced emission of this phenomenon called after aggregation inducing; AIE): i.e. emitting fluorescence not under solution state, and fluorescence strengthens under state of aggregation.Since finding the AIE phenomenon; A series of small molecules with AIE performance and linear, a chain polymkeric substance are synthesized out; And be widely used in a plurality of fields (Chem.Commun.2009,4332) such as analyzing and testing, bio-sensing and electroluminescent device as fluorescent probe and electroluminescent material.Polymkeric substance than other type; Hyperbranched polymer is owing to have highly branched three-dimensional ball-like structure and many functionality end groups; And show numerous excellent specific properties, like LV, no chain entanglement and good consistency, and its compound method is simple; Cost is low, so hyperbranched polymer has important use value in fields such as coating, processing aid, biological medicine carrier, photoelectric functional material, Journal of Molecular Catalysis and reactor drums.But it is less that up to the present, preparation has the report of the active hyperbranched polymer of AIE.Our seminar adopts A recently
2+ B
3The type monomer under the catalysis of monovalence copper, prepared polymkeric substance with AIE performance (Chinese patent, application number: 201010590712.5, J.Mater.Chem.2011; 21; 4056) but in the polymkeric substance residual copper catalyst be difficult to remove clean, tend to the biology and the photoelectric properties of impact polymer.Therefore, adopt the click polyreaction of no metal catalytic to prepare hyperbranched polymer, have important scientific meaning and using value with aggregation inducing luminescent properties.
Summary of the invention
The invention provides a kind of hyperbranched poly triazole manthanoate, and the preparation method of this hyperbranched poly triazole manthanoate is provided and under state of aggregation, has been used for the application of the detection of many nitro arene explosive substances.
For realizing above-mentioned purpose, the technical scheme that the present invention taked is: a kind of hyperbranched poly triazole manthanoate has suc as formula the structure shown in (I):
R is in the formula:
The preparation method of hyperbranched poly triazole manthanoate of the present invention is: binary triazo-compound and the ternary ester compound that contains alkynyl are not had " click " polyreaction of metal catalytic under the heating condition in polar solvent, obtain said hyperbranched poly triazole manthanoate.Its preparation process is:
(1) preparation binary triazo-compound
Through the McMurry linked reaction of 4-methyldiphenyl ketone, again with the NBS bromination, last and sodiumazide carries out nucleophilic substitution reaction, synthetic binary triazo-compound, and its preparation process divides three-step reaction to carry out:
The first step with the reaction under the nitrogen protection in THF of 4-methyldiphenyl ketone, zinc powder and titanium tetrachloride, obtains first midbody.
In second step, with first midbody, N-bromo-succinimide (NBS) and BPO (BPO) be reaction under the nitrogen protection in tetracol phenixin, obtains second midbody.
The 3rd step, second monomer and sodiumazide are reacted in methyl-sulphoxide (DMSO), generate the binary triazo-compound, its structural formula is:
(2) preparation contains the ternary ester compound of alkynyl
With trivalent alcohol and propynoic acid is raw material, contains the ternary ester compound of alkynyl through esterification preparation, and its preparation process is: in solution, contain ternary ester compound synthetic of alkynyl, solvent is selected benzene or toluene for use; Add the tosic acid (TsOH) of catalytic amount, temperature of reaction is 90～140 ℃, and the reaction times is 24～72h, and its structural formula is:
Wherein R is:
(3) preparation hyperbranched poly triazole manthanoate
In polar aprotic solvent, carry out 1 under the heating condition, 3-dipole cycloaddition polyreaction (" click " polyreaction of promptly not having metal catalytic) with binary triazo-compound of producing and the ternary ester compound that contains alkynyl.
Described polyreaction is: is to join in polymerizing pipe at 1～1.5: 1 binary triazo-compound and the ternary ester compound that contains alkynyl with the ratio of amount of substance, adds polar aprotic solvent, and being mixed with the ternary ester compound amount of substance concentration that contains alkynyl is the mixed solution of 0.1～0.2mol/L; Be preferably 0.12～0.17mol/L, fully after the dissolving, be warming up to 50～80 ℃; Be preferably 60～70 ℃, stirring reaction 2～12 hours is preferably 4-8 hour; Obtain polymers soln,, polymers soln is added drop-wise in an amount of normal hexane through a spot of chloroform dilution; Obtain white precipitate, leave standstill, filter; Obtain hyperbranched poly triazole manthanoate after the drying, its reaction formula is:
Wherein: R is:
Described polar aprotic solvent can be selected conventional polar aprotic solvent for use, is preferably: N, dinethylformamide, DMAC N,N, methyl-sulphoxide or N-Methyl pyrrolidone.
It is higher 1 that the hyperbranched poly triazole manthanoate of the present invention preparation has, and dissolves in common organic solvent under the 4-taxis, room temperature; Like methylene dichloride, chloroform, THF, acetone, N; Dinethylformamide and methyl-sulphoxide etc., higher thermostability, property capable of being fast degraded; Under illumination crosslinked patterning can take place, and have the aggregation inducing luminescent properties.
Hyperbranched poly triazole manthanoate of the present invention has good workability, higher thermostability, property capable of being fast degraded, but illumination patterning and aggregation inducing luminescent properties.
The click polyreaction that utilization of the present invention does not have a metal catalytic prepares the method for functional hyperbranched polytriazoles manthanoate, and reaction raw materials is easy to get, and can directly buy or through simple prepared in reaction; Polymeric reaction condition is gentle, and is insensitive to empty G&W, need not protection of inert gas; This polyreaction has higher upright structure selection type (1, the 4-content of isomer is up to 90%); No coupling product generates in the polymerization process, meets Atom economy; It is compatible that this polyreaction has good functional group, can introduce multiple functional groups easily; This polyreaction is not used metal catalyst, can eliminate cytotoxicity that catalyst residue produces and to the influence of material photoelectric properties.
Hyperbranched poly triazole manthanoate of the present invention has the aggregation inducing luminescent properties, can detect nitro arene explosive substance in high sensitivity, makes it prevent to have important application prospects aspect the explosive attack.
Description of drawings
Fig. 1 be hyperbranched poly triazole manthanoate (wherein
) monomer corresponding with it be at DMSO-d
6In proton nmr spectra comparison diagram (* represents solvent peak);
Fig. 2 is hyperbranched poly triazole manthanoate
three-dimensional fluorescence pattern;
Fig. 3 is the AIE curve of hyperbranched poly triazole manthanoate
;
Fig. 4 is hyperbranched poly triazole manthanoate
detects TNP (PA) under state of aggregation a fluorescent quenching curve;
Fig. 5 is hyperbranched poly triazole manthanoate
detects TNP (PA) under state of aggregation a Stem-Volmer curve.
Embodiment
To combine embodiment that the present invention is described particularly below, but protection scope of the present invention is not limited to following examples.
(1) contains the first monomeric synthetic of binary azido group
In 250mL twoport flask, add 4-methyldiphenyl ketone 9.81g (50mmol), zinc powder 6.54g (100mmol) vacuumizes logical nitrogen three times; Add the 100mL THF, ice bath drips titanium tetrachloride 5.56mL (50mmol) down, after reaction system returns to room temperature; Reflux 12h cools off, filters, revolves dried, and the gained crude product carries out separation and purification with chromatography column; Vacuum-drying obtains white solid 8.59g (productive rate is 95.3%), is first midbody.
1H?NMR(400MHz，CDCl
3)，δ(TMS，ppm)：7.81(d，2H)，7.74(d，2H)，7.54(t，1H)，7.08(m，10H)，6.98(m，8H)，2.23(d，6H).
Get the first midbody 7.21g (20mmol), NBS 7.48g (40mmol), BPO 0.05g (0.2mmol) and put into 250mL twoport flask, vacuumize logical nitrogen three times, add the dissolving of 125mL tetracol phenixin, reflux is spent the night; Reacted the back suction filtration, revolved driedly,, washed three times with methylene dichloride dissolving; Organic phase is revolved dried, and vacuum-drying obtains yellow solid (11.13g); Be second midbody, be not further purified, directly do next step reaction.This yellow solid is dissolved among the 100mL DMSO, adds NaN
3(3.10g), stirring at room, reaction is spent the night, and adds the water termination reaction, uses extracted with diethyl ether, and dry organic phase is revolved driedly, and the gained crude product is used the chromatography column separation and purification, obtains white solid 4.70g (two-step reaction overall yield 53.1%), is first monomer.
IR(KBr)，v(cm
-1)：2094，1597，1508，1248，1491，1443，1246，752，699.
1H?NMR(400MHz，DMSO-d
6)，δ(TMS，ppm)：7.12(m，10H)，6.98(m，8H)，4.36(s，4H).
13C?NMR(100MHz，DMSO-d
6)，δ(ppm)：143.6，143.5，141.2，134.5，131.6，131.3，128.6，128.5，127.3，53.8.
(2) it is monomeric synthetic to contain the ternary ester
second of alkynyl
In the 250mL twoport flask of water trap, spherical condensation tube is housed, add season penta triol 2.47g (20mmol), tosic acid 1.16g (6mmol), propynoic acid 5.69g (80mmol) and toluene 100mL, reflux steamed toluene after 36 hours; With the methylene dichloride dissolving, wash dry organic phase three times; Revolve driedly, use the chromatography column separation and purification, vacuum-drying; Getting white solid 4.14g (productive rate is 75.0%), is second monomer.
IR(KBr)，v(cm
-1)：3274，2936，2122，1748，1594，1472，1382，1228，995，752，698.
1H?NMR(400MHz，DMSO-d
6)，δ(TMS，ppm)：4.59(s，3H)，4.12(s，6H)，0.98(s，3H).
13C?NMR(100MHz，DMSO-d
6)，δ(ppm)：152.3，80.0，74.7，67.2，38.4，16.6.
(3) " click " polymerization of no metal catalytic prepares hyperbranched poly triazole manthanoate
In the 10mL polymerizing pipe, add the first monomer 66.3mg (0.15mmol), second monomer 27.6mg (0.10mmol) and the 0.6mL N, dinethylformamide, treat that monomer dissolves fully after, be warming up to 60 ℃ and reacted 5 hours.Reaction solution is added drop-wise in the quick normal hexane that stirs of 200mL after the dilution of 5mL chloroform, obtains white flocks.Hold over night is filtered, and drying obtains polymkeric substance 82.8mg (productive rate 88.2%).
Gel permeation chromatography (GPC) result shows: weight-average molecular weight (M
w) be 7200, MWD (PDI) is 2.65.IR (KBr), v (cm
-1): 3275,2970,2867,2113,1725; 1545,1460,1391,1357; 1219,1039,768,698. these polymkeric substance with it corresponding monomeric proton nmr spectra comparison diagram see accompanying drawing 1; From figure, can confirm that this polymkeric substance is a hyperbranched poly triazole manthanoate, chemical shift 8.92ppm and 8.65ppm place respectively to emergencing copolymer in 1,4-and 1, the characteristic peak of Wasserstoffatoms on the 5-isomer triazole ring; Calculate integral area, draw 1, the 4-content of isomer is 89.2%, explains that this polymkeric substance has higher taxis.
(4) performance characterization of hyperbranched poly triazole manthanoate
This hyperbranched poly triazole manthanoate at room temperature is soluble in methylene dichloride, chloroform, THF, acetone, N, and common organic solvent such as dinethylformamide and methyl-sulphoxide show to have good workability; This polymkeric substance 5% thermal weight loss temperature is 375 ℃, shows to have higher thermostability; This polymkeric substance can be degraded in Pottasium Hydroxide effect following half a hour of catalytic amount fully, shows to have property capable of being fast degraded; Crosslinked patterning takes place in this polymkeric substance under UV-irradiation, see accompanying drawing 2; The tetrahydrofuran solution of this polymkeric substance is not luminous, and strong luminescence behind the adding poor solvent shows to have the aggregation inducing luminescent properties, sees accompanying drawing 3.
(5) hyperbranched poly triazole manthanoate is to the detection of nitro arene explosive substance
Detect the process of TNP (PA): at first formulation content is 10
-5The tetrahydrofuran solution (water cut volume(tric)fraction 90%) of the hyperbranched poly triazole manthanoate of M adds the detected material PA of different content successively as detecting thing, tests fluorescence spectrum respectively fast.The result finds: when not adding PA, the fluorescence that detects thing is very strong; When adding PA, fluorescent weakening, and along with the increase successively that adds PA content, fluorescence weakens successively, sees accompanying drawing 4.To the fluorescent weakening multiple of detection thing and the add-on mapping of PA is that Stem-Volmer curve (accompanying drawing 5) is found, when detected material PA content was low, this curve was a straight line; When PA content was higher, this curve off-straight was bent upwards, and the change in fluorescence that promptly detects thing strengthens, and shows that this hyperbranched poly triazole manthanoate can detect nitro arene explosive substance in high sensitivity.
Embodiment 2
(1) first is monomeric synthetic with embodiment 1.
Synthesizing of (2) second monomers
with embodiment 1.
(3) preparation of hyperbranched poly triazole manthanoate
In the 10mL polymerizing pipe, add the first monomer 66.3mg (0.15mmol), second monomer 27.6mg (0.10mmol) and the 1mL N, dinethylformamide, treat that monomer dissolves fully after, be warming up to 60 ℃ and reacted 5 hours.Reaction solution is added drop-wise in the quick normal hexane that stirs of 200mL after the dilution of 5mL chloroform, obtains white flocks.Hold over night is filtered, and drying obtains polymkeric substance 73.0mg (productive rate 77.7%).GPC result shows: M
w=5100, PDI=2.63.Other characterization result is with embodiment 1.
Embodiment 3
(1) first is monomeric synthetic with embodiment 1.
Synthesizing of (2) second monomers
with embodiment 1
(3) preparation of hyperbranched poly triazole manthanoate
In the 10mL polymerizing pipe, add the first monomer 66.3mg (0.15mmol), second monomer 33.2mg (0.12mmol) and the 0.5mL N, dinethylformamide, treat that monomer dissolves fully after, be warming up to 60 ℃ and reacted 12 hours.Reaction solution is added drop-wise in the quick normal hexane that stirs of 200mL after the dilution of 5mL chloroform, obtains white flocks.Hold over night is filtered, and drying obtains polymkeric substance 82.4mg (productive rate 84.7%).GPC result shows: M
w=13000, PDI=5.27.Other characterization result is with embodiment 1.
Embodiment 4
(1) first is monomeric synthetic with embodiment 1.
Synthesizing of (2) second monomers
with embodiment 1.
(3) preparation of hyperbranched poly triazole manthanoate
In the 10mL polymerizing pipe, add the first monomer 66.3mg (0.15mmol), second monomer 27.6mg (0.10mmol) and the 0.6mL N, dinethylformamide, treat that monomer dissolves fully after, be warming up to 60 ℃ and reacted 5 hours.Reaction solution is added drop-wise in the quick normal hexane that stirs of 200mL after the dilution of 5mL chloroform, obtains white flocks.Hold over night is filtered, and drying obtains polymkeric substance 78.3mg (productive rate 83.4%).GPC result shows: M
w=6800, PDI=2.90.Other characterization result is with embodiment 1.
(1) first is monomeric synthetic with embodiment 1.
Synthesizing of (2) second monomers
with embodiment 1.
(3) preparation of hyperbranched poly triazole manthanoate
In the 10mL polymerizing pipe, add the first monomer 66.3mg (0.15mmol), the second monomer 27.6mg (0.10mmol), vacuumize logical nitrogen three times, add 0.6mL N, dinethylformamide, treat that monomer dissolves fully after, be warming up to 60 ℃ of reactions 5 hours.Reaction solution is added drop-wise in the quick normal hexane that stirs of 200mL after the dilution of 5mL chloroform, obtains white flocks.Hold over night is filtered, and drying obtains polymkeric substance 80.6mg (productive rate 85.8%).GPC result shows: M
w=6100, PDI=2.44.In this polymkeric substance proton nmr spectra, chemical shift 8.90ppm and 8.62ppm place respectively to emergencing copolymer in 1,4-and 1, the characteristic peak of Wasserstoffatoms on the 5-isomer triazole ring calculates integral area, draws 1, the 4-content of isomer is 90.1%.Other characterization result is with embodiment 1.
Embodiment 6
(1) first is monomeric synthetic with embodiment 1.
Synthesizing of (2) second monomers
with embodiment 1.
(3) preparation of hyperbranched poly triazole manthanoate
In the 10mL polymerizing pipe, add the first monomer 66.3mg (0.15mmol), second monomer 27.6mg (0.1mmol) and the 0.6mL N, dinethylformamide, treat that monomer dissolves fully after, be warming up to 70 ℃ and reacted 4 hours.Reaction solution is added drop-wise in the quick normal hexane that stirs of 200mL after the dilution of 5mL chloroform, obtains white flocks.Hold over night is filtered, and drying obtains polymkeric substance 76.8mg (productive rate 81.8%).GPC result shows: M
w=20600, PDI=6.06.Other characterization result is with embodiment 1.
Embodiment 7
(1) first is monomeric synthetic with embodiment 1.
Synthesizing of (2) second monomers
with embodiment 1.
(3) preparation of hyperbranched poly triazole manthanoate
In the 10mL polymerizing pipe, add the first monomer 66.3mg (0.15mmol), second monomer 27.6mg (0.10mmol) and the 0.6mL N, dinethylformamide, treat that monomer dissolves fully after, be warming up to 80 ℃ and reacted 4 hours.Reaction solution is added drop-wise in the quick normal hexane that stirs of 200mL after the dilution of 5mL chloroform, obtains white flocks.Hold over night is filtered, and drying obtains polymkeric substance 80.7mg (productive rate 85.9%).GPC result shows: M
w=52700, PDI=7.08.Other characterization result is with embodiment 1.
Embodiment 8
(1) contains the first monomeric synthetic of binary azido group with embodiment 1.
(2) contain the ternary ester second monomer (R=CH of alkynyl
2-CH-CH
2) synthetic
In the 250mL twoport flask of water trap, spherical condensation tube is housed, add USP Kosher 1.84g (20mmol), tosic acid 1.16g (6mmol), propynoic acid 5.60g (80mmol) and toluene 100mL, behind the heating reflux reaction 48h, steam toluene; With the methylene dichloride dissolving, wash dry organic phase three times; Revolve driedly, use the chromatography column separation and purification, vacuum-drying; Get light yellow oily liquid 1.51g (productive rate is 28.8%), be R=CH
2-CH-CH
2Second monomer.
1H?NMR(400MHz，DMSO-d
6)，δ(TMS，ppm)：5.40(m，1H)，4.66(d，3H)，4.44(m，4H).
13C?NMR(100MHz，DMSO-d
6)，δ(ppm)：152.0，151.7，80.9，80.4，74.5，74.4，70.6，63.8.HRMS(MALDI-TOF)，m/z?calculated?for?C
12H
8O
6Na[M+Na]
+＝271.0219，found＝271.0223.
(3) " click " polymerization of no metal catalytic prepares hyperbranched poly triazole manthanoate
In the 10mL polymerizing pipe, add the first monomer 132.8mg (0.30mmol), second monomer 49.6mg (0.20mmol) and the 1.2mL N, dinethylformamide, treat that monomer dissolves fully after, be warming up to 60 ℃ and reacted 5 hours.Reaction solution is added drop-wise in the quick normal hexane that stirs of 300mL after the dilution of 10mL chloroform, obtains white flocks.Hold over night is filtered, and drying obtains polymkeric substance 167.1mg (productive rate 91.6%).
Gel permeation chromatography (GPC) result shows: GPC result shows: M
w=4400, PDI=2.21.In the hydrogen nuclear magnetic resonance spectrogram of this hyperbranched poly triazole manthanoate; Chemical shift 8.82ppm and 8.68ppm place respectively to emergencing copolymer in 1,4-and 1, the characteristic peak of Wasserstoffatoms on the 5-isomer triazole ring; Calculate integral area; Draw 1, the 4-content of isomer is 82.6%, explains that this polymkeric substance has higher taxis.
(4) performance characterization of hyperbranched poly triazole manthanoate
This hyperbranched poly triazole manthanoate at room temperature is soluble in methylene dichloride, chloroform, THF, acetone, N, and common organic solvent such as dinethylformamide and methyl-sulphoxide show to have good workability; This polymkeric substance 5% thermal weight loss temperature is 333 ℃, shows to have higher thermostability; This polymkeric substance is capable of being fast degraded in Pottasium Hydroxide effect following half a hour of catalytic amount; Crosslinked patterning can take place in this polymkeric substance under UV-irradiation; This polymkeric substance is not luminous at solution state, and strong luminescence behind state of aggregation or solid state shows to have the aggregation inducing luminescent properties.
(5) hyperbranched poly triazole manthanoate is to the detection of nitro arene explosive substance
Detect the process of TNP (PA): at first formulation content is 10
-5The tetrahydrofuran solution (water cut volume(tric)fraction 90%) of the hyperbranched poly triazole manthanoate of M adds the detected material PA of different content successively as detecting thing, tests fluorescence spectrum respectively fast.The result finds: when not adding PA, the fluorescence that detects thing is very strong; When adding PA, fluorescent weakening, and along with the increase successively that adds PA content, fluorescence weakens successively, sees accompanying drawing 4.The fluorescent weakening multiple of detection thing and the add-on of PA are made graph discovery, and when detected material PA content was low, this curve was a straight line; When PA content was higher, this curve off-straight was bent upwards, and the change in fluorescence that promptly detects thing strengthens, and shows that this hyperbranched poly triazole manthanoate can detect nitro arene explosive substance in high sensitivity.
Claims (8)
1. hyperbranched poly triazole manthanoate is characterized in that: have suc as formula the structure shown in (I):
Wherein: R is:
Or CH
2-CH-CH
2
2. the preparation method of a hyperbranched poly triazole manthanoate according to claim 1; It is characterized in that: structural formula is carried out polyreaction suc as formula first monomer shown in (II) and structural formula suc as formula second monomer shown in (III) under the heating condition in polar aprotic solvent, obtain described hyperbranched poly triazole manthanoate.
In the formula (III): R is:
Or CH
2-CH CH
2
3. the preparation method of hyperbranched poly triazole manthanoate according to claim 2 is characterized in that: the ratio of said first monomer and the second monomeric amount of substance is 1～1.5: 1, and the second monomeric amount of substance concentration is 0.1～0.2mol/L.
4. the preparation method of hyperbranched poly triazole manthanoate according to claim 2 is characterized in that: the temperature of reaction of said polyreaction is 50～80 ℃.
5. the preparation method of hyperbranched poly triazole manthanoate according to claim 2 is characterized in that: the reaction times of said polyreaction is 2～12 hours.
6. the preparation method of hyperbranched poly triazole manthanoate according to claim 2 is characterized in that: described polar aprotic solvent is: N, dinethylformamide, DMAC N,N, methyl-sulphoxide or N-Methyl pyrrolidone.
7. the purposes of hyperbranched poly triazole manthanoate according to claim 1 is characterized in that: said hyperbranched poly triazole manthanoate is used for the detection of many nitro arene explosive substances under state of aggregation.
8. the purposes of hyperbranched poly triazole manthanoate according to claim 7 is characterized in that: said state of aggregation is meant that said hyperbranched poly triazole manthanoate is dispersed in the mixed solvent that volume ratio is 1: 1～9 THF and water.
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Cited By (12)
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| CN104109176A (en) * | 2014-06-06 | 2014-10-22 | 浙江工业大学 | A compound and an alkaline phosphatase activity fluorescence detection method adopting the compound |
| CN104403103A (en) * | 2014-10-27 | 2015-03-11 | 华东师范大学 | Hyperbranched polytriazole hb-PTA-OEG, and preparation method and application thereof |
| CN106632102A (en) * | 2016-09-14 | 2017-05-10 | 华南理工大学 | Application of hyper branched polytriazole in detection of diarylamines antioxidant |
| CN107132207A (en) * | 2017-05-22 | 2017-09-05 | 中国烟草总公司郑州烟草研究院 | It is a kind of for fluorescent optical sensor of quick detection explosive and preparation method thereof, the method for quick detection explosive |
| CN107325284A (en) * | 2017-07-02 | 2017-11-07 | 苏州大学 | A kind of hyperbranched poly phenyl triazole formic acid esters and preparation method and application |
| CN109400894A (en) * | 2018-06-18 | 2019-03-01 | 上海大学 | Hyperbranched poly triazole functional polymer material and preparation method thereof |
| CN112390948A (en) * | 2020-10-27 | 2021-02-23 | 华南理工大学 | Hyperbranched poly (1, 4, 5-substituted triazole), and preparation method and application thereof |
| WO2021042494A1 (en) * | 2019-09-05 | 2021-03-11 | 深圳市华星光电半导体显示技术有限公司 | Perovskite film additive, method for preparing perovskite film and use thereof |
| CN113667132A (en) * | 2021-07-31 | 2021-11-19 | 华南理工大学 | Hyperbranched polyallylamine compound, preparation method thereof, post-functionalization method and application |
| US11322687B2 (en) | 2012-09-07 | 2022-05-03 | Novaled Gmbh | Charge transporting semi-conducting material and semi-conducting device |
| WO2022266820A1 (en) * | 2021-06-21 | 2022-12-29 | 苏州大学 | Hyperbranched polybenzoate, and preparation method therefor and use thereof |
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| US11322687B2 (en) | 2012-09-07 | 2022-05-03 | Novaled Gmbh | Charge transporting semi-conducting material and semi-conducting device |
| CN104109176A (en) * | 2014-06-06 | 2014-10-22 | 浙江工业大学 | A compound and an alkaline phosphatase activity fluorescence detection method adopting the compound |
| CN104109176B (en) * | 2014-06-06 | 2016-07-06 | 浙江工业大学 | A kind of compound and be applied to the fluorescence detection method of alkaline phosphatase activities |
| CN104403103A (en) * | 2014-10-27 | 2015-03-11 | 华东师范大学 | Hyperbranched polytriazole hb-PTA-OEG, and preparation method and application thereof |
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| CN106632102B (en) * | 2016-09-14 | 2019-06-18 | 华南理工大学 | A kind of application of hyperbranched poly triazole in detection diarylamines anti-aging agent |
| CN106632102A (en) * | 2016-09-14 | 2017-05-10 | 华南理工大学 | Application of hyper branched polytriazole in detection of diarylamines antioxidant |
| CN107132207A (en) * | 2017-05-22 | 2017-09-05 | 中国烟草总公司郑州烟草研究院 | It is a kind of for fluorescent optical sensor of quick detection explosive and preparation method thereof, the method for quick detection explosive |
| CN107132207B (en) * | 2017-05-22 | 2019-10-22 | 中国烟草总公司郑州烟草研究院 | It is a kind of for quickly detecting the fluorescent optical sensor and preparation method thereof of explosive, quickly detect explosive method |
| CN107325284A (en) * | 2017-07-02 | 2017-11-07 | 苏州大学 | A kind of hyperbranched poly phenyl triazole formic acid esters and preparation method and application |
| CN107325284B (en) * | 2017-07-02 | 2020-01-14 | 苏州大学 | Hyperbranched polyphenyl triazole formate as well as preparation method and application thereof |
| CN109400894A (en) * | 2018-06-18 | 2019-03-01 | 上海大学 | Hyperbranched poly triazole functional polymer material and preparation method thereof |
| WO2021042494A1 (en) * | 2019-09-05 | 2021-03-11 | 深圳市华星光电半导体显示技术有限公司 | Perovskite film additive, method for preparing perovskite film and use thereof |
| CN112390948A (en) * | 2020-10-27 | 2021-02-23 | 华南理工大学 | Hyperbranched poly (1, 4, 5-substituted triazole), and preparation method and application thereof |
| WO2022266820A1 (en) * | 2021-06-21 | 2022-12-29 | 苏州大学 | Hyperbranched polybenzoate, and preparation method therefor and use thereof |
| CN113667132A (en) * | 2021-07-31 | 2021-11-19 | 华南理工大学 | Hyperbranched polyallylamine compound, preparation method thereof, post-functionalization method and application |
| CN116515105A (en) * | 2023-03-31 | 2023-08-01 | 东华大学 | Poly (diphenyl ether) high molecular compound and preparation method and application thereof |
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