CN107384376A - A kind of alkane sensing material, preparation method and application method - Google Patents

A kind of alkane sensing material, preparation method and application method Download PDF

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CN107384376A
CN107384376A CN201710606290.8A CN201710606290A CN107384376A CN 107384376 A CN107384376 A CN 107384376A CN 201710606290 A CN201710606290 A CN 201710606290A CN 107384376 A CN107384376 A CN 107384376A
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alkane
sensing material
sensing
sepectrophotofluorometer
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王珊
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Xianyang Normal University
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Abstract

The invention provides a kind of alkane sensing material, preparation method and application method, the alkane sensing material is inlayed to be formed by amino with the hybridization of FeS nano-particles, and the general structure of described alkane sensing material is：Wherein, R1、R2And R3For containingGroup；N is the positive integer not less than 40.Shown by a series of experiments result, alkane sensing material provided by the invention has feature sensitivities to alkane.

Description

A kind of alkane sensing material, preparation method and application method
Technical field
The present invention relates to technical field of chemistry, more particularly to a kind of alkane sensing material, preparation method and application method.
Background technology
For alkane as common are solvent, volatility is very high, because the mode absorbed often through suction or skin is entered Enter human body, cause the acute or chronic poisoning of human body, therefore, the toxicity damage of alkane it is accumulative stronger.In addition, some alkane Inflammable, running into high temperature heat source and naked light just has the danger of blast；Also some alkane mix when volatilization reaches a certain amount of with air Closing just can form a kind of explosive mixture.So that alkane arouses widespread concern.Therefore, the inspection for alkane is established Survey method is to realize the important content that effectively control, management and early warning are carried out to alkane.
At present, the instruments such as chromatogram, high performance liquid chromatography mainly are used in conjunction by makings to be detected, but using it is existing this When kind detection mode is detected, it is easy to disturbed by other organic matters.Therefore, spy can be had to alkane by finding one kind The material of sign sensitivities then seems particularly significant.
The content of the invention
The embodiments of the invention provide a kind of alkane sensing material, preparation method and application method, there is feature to alkane Sensitivities.
The embodiments of the invention provide a kind of alkane sensing material, amino is inlayed to form alkane with the hybridization of FeS nano-particles Sensing material, the general structure of described alkane sensing material are：
Wherein, R1、R2And R3For containingGroup；N is the positive integer not less than 40.
Show by test experience result, the fluorescence intensity of alkane sensing material provided by the invention can be by the shadow of alkane Ring, this is probably because the Fe in the FeS nano-particles in alkane sensing material is more sensitive to alkane.In addition, by entering one Walk test experience to find, Fe3+, Pb2+, K+, Hg+, Cu2+, Cd2+, Al3+, Cu2+, Mg2+, Na+, Mn2+, Hg2+, Ba2+, Ca2+, Hg+, SO4 2-, NO3 -, Ac-, CO3 2-, Cl-Deng inorganic solvent and methanol, ethylene glycol, DMF, ether, formaldehyde, second The organic solvents such as aldehyde, carbon tetrachloride, acetone, benzene, dimethylbenzene, para-nitrotoluene, ethyl acetate do not interfere with alkane sensing material The fluorescence intensity of material, therefore, alkane sensing material provided by the invention have feature sensitivities to alkane.
Preferably, the R1、R2And R3Structure is：
The amine ester structure can effectively strengthen feature sensitivities of the alkane sensing material to alkane.
Preferably, above-mentioned alkane sensing material is applied to C2~C8The detection of linear paraffin.By using different alkane solutions Alkane sensing material is soaked, to detect under the influence of different alkane, the change of the fluorescence intensity of alkane sensing material, testing result Show, C2~C8Linear paraffin can influence the fluorescence intensity of alkane sensing material, therefore, alkane sensing material provided by the invention It may be used primarily for C2~C8The detection of linear paraffin.
The present invention provides a kind of preparation method of alkane sensing material, including：
Prepare hexamethylene diamine methyl formate：Mol ratio is 1:1:1 1,6- hexamethylene diamines, liquid carbonic acid dimethyl ester and ferrous salt It is dissolved in the sodium alkoxide solvent below a certain amount of four carbon atom, and under the conditions of reaction temperature is 60-70 DEG C, is stirred anti- Should, control stirring reaction duration is not less than 8h；
Preparation contains Fe2+Polyurethane：Hexamethylene diamine methyl formate obtained above is dissolved in a certain amount of four carbon atom In following alcohols solvent, in AlCl3·6H2Under the catalytic action of O and epoxy resin, in N2Or under inert gas atmosphere protection, Stirring heating, and controlling reaction temperature is not less than 160 DEG C, reaction duration is not less than 1.5h；
Prepare alkane sensing material：Fe will be contained2+Polyurethane be dissolved in a certain amount of organic dispersion solvent, obtain PU Solution；And be mixed into after thioacetamide to be dissolved in pH=10 sodium hydroxide solution in the PU solution, shaken by ultrasound Swinging stirring makes its dissolving be uniformly dispersed, and reacts more than 4 hours at room temperature, wherein, contain Fe2+Polyurethane and thioacetamide Mass ratio is 2:1.1~1.5.
The preparation method of above-mentioned alkane sensing material provided by the invention uses raw material simple and easy to get, in addition, whole system Standby process reaction bar is gentle, has certain practicality.
Preferably, the ferrous salt, including：Ferrous sulfate or frerrous chloride.
Preferably, the sodium alkoxide solvent below the four carbon atom, including：Sodium methoxide, wherein, the dosage of the sodium methoxide For 0.4~1.1 times of ferrous salt dosage.
Preferably, the alcohols solvent below the four carbon atom, including：Ethylene glycol.
Preferably, organic dispersion solvent, including：Ethanol, methanol, chloroform, glacial acetic acid, N, N- dimethyl formyls Any one in amine, tetrahydrofuran and acetone.Alkane sensing material provided by the invention can be dissolved in above-mentioned organic scattered molten In agent, in addition, being shown experimentally that, FeS nano-particles dispersive property in DMF is more preferable, therefore, N, N- Dimethylformamide can more preferably selecting as organic dispersion solvent.
The present invention provides a kind of application method of alkane sensing material, by alkane sensing material solution cast film formation, and 0.5h is dried at a temperature of 45~60 DEG C, alkane sensing composite membrane is made, in addition to：
The deionized water for sensing composite membrane in sample cell immersed with the alkane is scanned by sepectrophotofluorometer, 385nm excites the blank fluorescence spectrum at place；
The solution to be measured for sensing composite membrane in sample cell immersed with the alkane is scanned by sepectrophotofluorometer, 385nm excites the fluorescent spectrum at place；
When the position of spectral line of the fluorescent spectrum deviates the position of spectral line of the blank fluorescence spectrum, it is determined that described Contain alkane in solution to be measured.
Preferably, when it is described scanned by sepectrophotofluorometer when, alkane sensing composite membrane is held on sample cell Front surface reflection specimen holder on, to ensure that it is multiple that fluorescence caused by the sepectrophotofluorometer passes perpendicularly through alkane sensing Close film.
Preferably, the application method of above-mentioned alkane sensing material is applied to C2~C8The detection of linear paraffin.
Preferably, when above-mentioned alkane composite is used to detect normal heptane, what the sepectrophotofluorometer detected Meet following linear equations between fluorescence intensity and normal heptane concentration：
I=538.05+4.9749C
Wherein, I characterizes fluorescence intensity at the 385nm that the sepectrophotofluorometer detects, C characterizes normal heptane in solution Concentration.
The invention provides a kind of alkane sensing material, preparation method and application method, the fluorescence of the alkane sensing material Intensity can be influenceed by alkane, and this is probably because the Fe in the FeS nano-particles in alkane sensing material is quicker to alkane Sense.In addition, found by further test experience, Fe3+, Pb2+, K+, Hg+,Cu2+, Cd2+, Al3+, Cu2+, Mg2+, Na+, Mn2+, Hg2+, Ba2+, Ca2+, Hg+, SO4 2-, NO3 -, Ac-, CO3 2-, Cl-Deng inorganic solvent and methanol, ethylene glycol, N, N- dimethyl formyls The organic solvents such as amine, ether, formaldehyde, acetaldehyde, carbon tetrachloride, acetone, benzene, dimethylbenzene, para-nitrotoluene, ethyl acetate will not The fluorescence intensity of alkane sensing material is influenceed, therefore, alkane sensing material provided by the invention has feature sensitivities to alkane.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are the present invention Some embodiments, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis These accompanying drawings obtain other accompanying drawings.
Fig. 1 is the infrared contrast spectrogram of the alkane sensing material that one embodiment of the invention provides and polyurethane；
Fig. 2 is the result for the alkane sensing material differential scanning instrument measure that one embodiment of the invention provides；
Fig. 3 is corresponding to the various concentrations normal heptane immersed with alkane sensing composite membrane that one embodiment of the invention provides Fluorescence spectrum；
Fig. 4 is normal heptane concentration-fluorescence intensity linear relation figure that one embodiment of the invention provides.
Embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention In accompanying drawing, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is Part of the embodiment of the present invention, rather than whole embodiments, based on the embodiment in the present invention, those of ordinary skill in the art The every other embodiment obtained on the premise of creative work is not made, belongs to the scope of protection of the invention.
Experimental method used in following embodiments is conventional method unless otherwise specified.In following embodiments, institute Various kinds of equipment, reagent and the material used is that conventional commercial can obtain unless otherwise noted.
The preparation process of alkane sensing material mainly comprises the following steps：
Step A：Prepare hexamethylene diamine methyl formate：Mol ratio is 1:1:1 1,6- hexamethylene diamines, liquid carbonic acid dimethyl ester and Ferrous salt is dissolved in the sodium alkoxide solvent below a certain amount of four carbon atom, and under the conditions of reaction temperature is 60-70 DEG C, is carried out Stirring reaction, control stirring reaction duration are not less than 8h；
Step B：Preparation contains Fe2+Polyurethane：Hexamethylene diamine methyl formate obtained above is dissolved in a certain amount of four In alcohols solvent below carbon atom, in AlCl3·6H2Under the catalytic action of O and epoxy resin, in N2Or inert gas atmosphere Under protection, stirring heating, and controlling reaction temperature is not less than 160 DEG C, reaction duration is not less than 1.5h；
Step C：Prepare alkane sensing material：Fe will be contained2+Polyurethane be dissolved in a certain amount of organic dispersion solvent, Obtain PU solution；And be mixed into after thioacetamide to be dissolved in pH=10 sodium hydroxide solution in the PU solution, pass through Ultrasonic vibration stirring makes its dissolving be uniformly dispersed, and reacts more than 4 hours at room temperature, wherein, contain Fe2+Polyurethane and thio second The mass ratio of acid amides is 2:1.1~1.5.
The reaction mechanism of above-mentioned preparation process institute foundation is as follows：
Wherein, TAA characterizes thioacetamideCharacterize Fes nano-particles
It can be seen from above-mentioned reaction mechanism, polymerizate is that polyurethane is inlayed to be formed with the hybridization of FeS nano-particles.
In order to verify the accuracy of the reaction mechanism of above-mentioned preparation process and preparation process institute foundation, below with specific real Apply example 1 and prepare alkane sensing material, and the product prepared to embodiment 1 characterizes.
Embodiment 1：
Step O：Prepare sodium methoxide：After sodium is taken out from kerosene, kerosene is cleaned, is put into methanol solution, makes sodium mistake Amount, makes reaction complete until bubble-free is emerged.
Step A1：Prepare hexamethylene diamine methyl formate：11.6g 1,6- hexamethylene diamines are placed in three-neck flask, added 41.3mL liquid carbonic acid dimethyl esters, 0.7g sodium methoxides, 0.9343gFeSO4, 60-70 DEG C is kept the temperature at, after stirring 8 hours Obtained white liquid will be reacted, through cooling, filtering, after drying, obtain the solid powdery thing of white.
Step B1：Preparation contains Fe2+Polyurethane：The obtained products of above-mentioned steps A1 are weighed into 9.003g to be put into In 250mL three-neck flasks, 2.89mL ethylene glycol is added, in 0.7488g AlCl3·6H2The catalysis of O and 3.31g epoxy resin Under effect, N is passed through2Heating is stirred simultaneously, and temperature is maintained at 160 DEG C or so, is completed after reacting 1.5h, reaction is obtained yellowish green Color viscous liquid is poured out while hot, is dark-brown glassy solids after cooling.
Step C1：Prepare alkane sensing material：The product that 1.0043g above-mentioned steps B1 is obtained is weighed, uses 3.0049gDMF (DMF) solution is dissolved in small beaker.0.579g thioacetamides are dissolved in pH=10 hydroxide again It is mixed into after in sodium solution (0.5-1.0mL) in above-mentioned DMF solution, solution produces yellow green floccule, ultrasonic vibration immediately Stirring makes its dissolving be uniformly dispersed, and reacts more than 4 hours at room temperature, it is sufficiently formed FeS nano particles.
It is consistent with the reaction mechanism of the preparation process of alkane sensing material in order to characterize the product that embodiment 1 obtains, The product that the embodiment of the present invention further obtains to embodiment 1 carries out pressing potassium bromide troche, with IRPrestige-21 type infrared spectrums Instrument determines the infrared spectrogram of the product that embodiment 1 obtains and the polyurethane containing ferrous salt respectively.As shown in figure 1, in reality Applying in the infrared spectrogram for the product that example 1 obtains clearly to find out：1690cm-1Left and right is C=O stretching vibration peaks, 1250cm-1Left and right is C-O-C symmetrical stretching vibrations, 1540cm-1Left and right be N-H flexural vibrations peak, 3330cm-1Left and right is N-H Stretching vibration peak.These peaks are the eigen vibration peaks of the carbamate in polyurethane.In 2940cm-1Locate as polyurethane In-CH2Stretching vibration peak.It can thus be appreciated that this polymer is polyurethane.By the infrared spectrogram and reality of the polyurethane of ferrous salt The infrared spectrogram for applying the product that example 1 obtains is made comparisons, it can be seen that the carbonyl of polyurethane and the characteristic peak of ehter bond are still deposited , but there is new absworption peak to occur：1690cm-1Left and right, 1490cm-1Left and right and 1210cm-1Left and right, thus illustrate polyurethane It polymerize with FeS crystal.
The product result actually obtained according to the reaction mechanism of above-mentioned alkane sensing material institute foundation and embodiment 1, can The general structure for knowing alkane sensing material is：
Wherein, R1、R2And R3For containingGroup；N is the positive integer not less than 40.It is preferred that Ground, R1、R2And R3Structure is：
In order to further clearly show position of the FeS nano-particles in alkane sensing material and be sensed with alkane The relation of polyurethane portion in material, alkane sensing material is further analyzed below by differential scanning instrument.Wherein, scheme 2 be the result of alkane sensing material differential scanning instrument measure, and with differential scanning instrument continuous mode, test temperature is 10 DEG C and arrived 330 DEG C, heating rate is 20 DEG C/min.
As shown in Fig. 2 this alkane sensing material is dehydration peak at 149 DEG C, Tg is 242.46 DEG C, and polyurethane Tg about exists Near 284 DEG C.Illustrate that the embedded FeS nano-particles of hybridization make the performance of alkane sensing material change.This alkane sensing material There is heat endurance below 256 DEG C.The Tg and crystallization peak temperature of the polyurethane of the embedded FeS nano-particles of hybridization all on Rise.FeS nano-particles play a part of crosslinking points and are mainly manifested in two aspects in the base：On the one hand, its surface is advantageous to chain The entanglement of section, form physical crosslinking；On the other hand, FeS ties as good interface is formed between particle filled composite and polymeric matrix Close.
In addition, the process that above-mentioned steps O prepares sodium methoxide can be omitted, and directly can also be completed using the sodium methoxide of purchase Step A1 preparation process.In addition, the purpose of sodium methoxide is to make inorganic matter FeSO4With organic solvent 1,6- hexamethylene diamines and liquid carbon Dimethyl phthalate is miscible, and this purpose can be achieved in the sodium alkoxide below four carbon, therefore, also can use other alcohol below four carbon Sodium substitutes sodium methoxide and reaches same purpose.And it is because sodium methoxide prepares simple and easy to get, and first from sodium methoxide in embodiment 1 Ferrous salt amount ranges of the dosage control of sodium alkoxide at 0.4~1.1 times.
Ethylene glycol used in above-mentioned steps B1 primarily to dissolving hexamethylene diamine methyl formate, can also select four carbon with Under other alcohols solvents substitute ethylene glycol and achieve the goal.In addition, the N used in step B12Mainly avoid hexamethylene diamine formic acid Methyl esters generates other accessory substances, therefore, N with air contact2It also can use other gas such as inert gas institutes for being not involved in reaction Substitute.
For DMF used in above-mentioned steps C1 as organic dispersion solvent, main purpose is to dissolve Contain Fe2+Polyurethane, and promote the formation of FeS nano-particles, while hinder growing up for FeS nano-particles.By under detection Various organic solvents are stated in table 1 to containing Fe2+Polyurethane and alkane sensing material dissolubility, it is known that, above-mentioned steps C1 institutes The DMF used also can use ethanol, methanol, chloroform, glacial acetic acid, DMF, tetrahydrochysene furan Mutter and acetone substituted, still, formation of the DMF to FeS nanocrystals advantageously, and can further Hinder growing up for FeS nano crystal particles.Therefore, more preferably selected with reference to the characteristic of these organic solvents, organic dispersion solvent For N,N-dimethylformamide.
Table 1 contains Fe2+Polyurethane and alkane sensing material in some dissolving situations in common are solvent
In addition, reaction temperature involved in the preparation process of above-described embodiment 1, reaction duration are to select lowest bid Standard, to ensure the security of experiment.And to a certain extent, reaction temperature is raised, shadow will not be produced to product by extending reaction duration Ring.
Find that alkane sensing material has response to fluorescence by fluorometric investigation, and the presence of a part of alkane will influence it is this The intensity of fluorescence response.In the presence of detecting different alkane, using 385nm as excitation wavelength, obtained alkane sensing material is determined The fluorescence intensity of material.Testing result shows, C2~C8The presence of linear paraffin can cause laminated film fluorescent emission to strengthen.Thus Illustrate, alkane sensing material provided in an embodiment of the present invention can be applied to C2~C8The detection of linear paraffin.
The application method of alkane sensing material, i.e. alkane sensing material detect C2~C8The process of linear paraffin can include such as Lower step：
Step a：By alkane sensing material solution cast film formation, and 0.5h is dried at a temperature of 45~60 DEG C, alkane is made Sense composite membrane；
Step a can complete as last step in the preparation method of above-mentioned alkane sensing material, also may be used Completed as first step in the application method of alkane sensing material., should when little to alkane sensing material demand Step a can realize that detailed process may include by casting film-forming on a glass substrate：By substrate in the chromic acid lotion newly prepared Middle immersion 24h, take out and be then sonicated 10min with after a large amount of distillation water washings, fully washed with deionized water, drying is standby With；The alkane sensing material solution prepared is placed on horizontal positioned glass substrate, casting film-forming.Film is put together with substrate Enter standing and drying 0.5h in 45~60 DEG C of baking ovens.
Step b：The non-hydrocarbons for sensing composite membrane in sample cell immersed with the alkane are scanned by sepectrophotofluorometer Organic solvent, the blank fluorescence spectrum at place is excited in 385nm；
Non-hydrocarbons organic solvent in the step can be ethanol, acetone and other organic solvent.
Step c：Scanned by sepectrophotofluorometer in sample cell and sense the to be measured molten of composite membrane immersed with the alkane Liquid, the fluorescent spectrum at place is excited in 385nm；
Step d：When the position of spectral line of the fluorescent spectrum deviates the position of spectral line of the blank fluorescence spectrum, then really Contain alkane in the fixed solution to be measured.
In above-mentioned steps b and step c, when being scanned by sepectrophotofluorometer, alkane sensing composite membrane is held on On the front surface reflection specimen holder of sample cell, to ensure that fluorescence caused by the sepectrophotofluorometer passes perpendicularly through the alkane Composite membrane is sensed, meanwhile, avoid alkane from sensing error caused by the difference of compound film location.
In order to clearly illustrate that the process of alkane sensing material detection alkane, and the presence of alkane sense to alkane The influence of material fluorescence intensity, deploy narration so that embodiment 2 detects normal heptane as an example below.
Embodiment 2：Normal heptane is detected using alkane sensing material：
Step a2：The alkane sensing material that above-described embodiment 1 is prepared is placed in horizontal positioned cleaned glass On substrate, casting film-forming, and film is put into standing and drying 0.5h in 45 DEG C of baking ovens together with glass substrate, it is compound that alkane sensing is made Film；
Step b2：The ethanol for sensing composite membrane in sample cell immersed with the alkane is scanned by sepectrophotofluorometer, Blank fluorescence spectrum corresponding to acquisition；
Step c2：Scanned by sepectrophotofluorometer in sample cell and sense the different dense of composite membrane immersed with the alkane The n-heptane solution of degree, obtain each self-corresponding fluorescent spectrum of n-heptane solution of concentration；
Step d2：The fluorescent spectrogram obtained by the blank fluorescence spectrogram and step c2 that contrast step b2 acquisitions can Know, normal heptane will sense fluorescence intensity of the composite membrane at 385nm to alkane and have an impact.
The fluorescence spectrum that above-mentioned steps b2 and step c2 is obtained is as shown in figure 3, Fig. 3 indicates normal heptane corresponding to 1 to 15 Concentration (mg/L) is followed successively by：0,2,3.98,5.96,7.95,9.92,11.86,13.81,15.75,17.68,19.61,21.53, 23.44,25.34,27.24, i.e., normal heptane concentration is 0 corresponding to 1, and what as step b2 was obtained senses composite membrane immersed with alkane Deionized water corresponding to fluorescence spectrum.Can significantly it find out from Fig. 3, normal heptane has strong to alkane sensing composite membrane Sensitization.Place is excited in 385nm in figure, with being continuously increased for normal heptane concentration, alkane sensing composite membrane fluorescent emission increases By force, and the shape of fluorescence spectrum is little with Strength Changes.
It is in addition, strong by fluorescence at 385nm in further self-corresponding fluorescence spectrum each to various concentrations n-heptane solution The analysis of degree, normal heptane concentration-fluorescence intensity linear relation figure as shown in Figure 4 can be obtained.From fig. 4, it can be seen that fluorescence intensity Meet following linear equations between normal heptane concentration：
I=538.05+4.9749C
Wherein, I characterizes fluorescence intensity at the 385nm that the sepectrophotofluorometer detects, C characterizes normal heptane in solution Concentration.
By a series of experiment of other alkane similar to above-described embodiment 2, it is believed that sensed when immersed with alkane The position of spectral line of 385nm fluorescence spectrums corresponding to the solution to be detected of composite membrane deviates senses composite membrane immersed with the alkane The position of spectral line of fluorescence spectrum corresponding to deionized water, it is determined that contain C in solution to be measured2~C8Linear paraffin.
According to such scheme, the present invention at least has the advantages that：
1. the fluorescence intensity of alkane sensing material provided in an embodiment of the present invention can be influenceed by alkane, this be probably due to The Fe in FeS nano-particles in alkane sensing material is more sensitive to alkane.In addition, found by further test experience, Fe3+, Pb2+, K+, Hg+, Cu2+, Cd2+, Al3+, Cu2+, Mg2+, Na+, Mn2+, Hg2+, Ba2+, Ca2+, Hg+, SO4 2-, NO3 -, Ac-, CO3 2-, Cl-Deng inorganic solvent and methanol, ethylene glycol, DMF, ether, formaldehyde, acetaldehyde, carbon tetrachloride, third The organic solvents such as ketone, benzene, dimethylbenzene, para-nitrotoluene, ethyl acetate do not interfere with the fluorescence intensity of alkane sensing material, because This, alkane sensing material provided by the invention has feature sensitivities to alkane.
2. the amine ester structure that alkane sensing material prepared by the embodiment of the present invention is included can effectively strengthen alkane biography Feature sensitivities of the material to alkane are felt, in addition, alkane sensing material is soaked by using different alkane solutions, to detect not Under the influence of alkane, the change of the fluorescence intensity of alkane sensing material, testing result shows, C2~C8Linear paraffin can influence alkane The fluorescence intensity of hydrocarbon sensing material, therefore, alkane sensing material provided in an embodiment of the present invention may be used primarily for C2~C8Straight chain The detection of alkane.
3. the preparation method of alkane sensing material provided in an embodiment of the present invention uses raw material simple and easy to get, in addition, whole Individual preparation process reaction bar is gentle, has certain practicality.
It should be noted that herein, such as first and second etc relational terms are used merely to an entity Or operation makes a distinction with another entity or operation, and not necessarily require or imply and exist between these entities or operation Any this actual relation or order.Moreover, term " comprising ", "comprising" or its any other variant be intended to it is non- It is exclusive to include, so that process, method, article or equipment including a series of elements not only include those key elements, But also the other element including being not expressly set out, or also include solid by this process, method, article or equipment Some key elements.In the absence of more restrictions, the key element limited by sentence " including one ", is not arranged Except other identical factor in the process including the key element, method, article or equipment being also present.
It is last it should be noted that：Presently preferred embodiments of the present invention is the foregoing is only, is merely to illustrate the skill of the present invention Art scheme, is not intended to limit the scope of the present invention.Any modification for being made within the spirit and principles of the invention, Equivalent substitution, improvement etc., are all contained in protection scope of the present invention.

Claims (10)

  1. A kind of 1. alkane sensing material, it is characterised in that amino is inlayed to form alkane sensing material with the hybridization of FeS nano-particles, The general structure of described alkane sensing material is：
    Wherein, R1、R2And R3For containingGroup；N is the positive integer not less than 40.
  2. 2. alkane sensing material according to claim 1, it is characterised in that the R1、R2And R3Structure is：
  3. 3. alkane sensing material according to claim 1 or 2, it is characterised in that applied to C2~C8The inspection of linear paraffin Survey.
  4. 4. the preparation method of any described alkane sensing material of claims 1 to 3, it is characterised in that including：
    Prepare hexamethylene diamine methyl formate：Mol ratio is 1:1:1 1,6- hexamethylene diamines, liquid carbonic acid dimethyl ester and ferrous salt is dissolved in In sodium alkoxide solvent below a certain amount of four carbon atom, and under the conditions of reaction temperature is 60-70 DEG C, reaction is stirred, Control stirring reaction duration is not less than 8h；
    Preparation contains Fe2+Polyurethane：Hexamethylene diamine methyl formate obtained above is dissolved in below a certain amount of four carbon atom Alcohols solvent in, in AlCl3·6H2Under the catalytic action of O and epoxy resin, in N2Or under inert gas atmosphere protection, stirring Heating, and controlling reaction temperature is not less than 160 DEG C, reaction duration is not less than 1.5h；
    Prepare alkane sensing material：Fe will be contained2+Polyurethane be dissolved in a certain amount of organic dispersion solvent, it is molten to obtain PU Liquid；And be mixed into after thioacetamide to be dissolved in pH=10 sodium hydroxide solution in the PU solution, pass through ultrasonic vibration Stirring makes its dissolving be uniformly dispersed, and reacts more than 4 hours at room temperature, wherein, contain Fe2+Polyurethane and thioacetamide matter Amount is than being 2:1.1~1.5.
  5. 5. preparation method according to claim 4, it is characterised in that
    The ferrous salt, including：Ferrous sulfate or frerrous chloride；
    And/or
    Sodium alkoxide solvent below the four carbon atom, including：Sodium methoxide, wherein, the dosage of the sodium methoxide is 0.4~1.1 Ferrous salt dosage again；
    And/or
    Alcohols solvent below the four carbon atom, including：Ethylene glycol.
  6. 6. preparation method according to claim 4, it is characterised in that organic dispersion solvent, including：
    Any one in ethanol, methanol, chloroform, glacial acetic acid, DMF, tetrahydrofuran and acetone.
  7. 7. the application method of any described alkane sensing material of claims 1 to 3, it is characterised in that by alkane sensing material Solution cast film formation, and 0.5h is dried at a temperature of 45~60 DEG C, alkane sensing composite membrane is made, in addition to：
    The non-hydrocarbons organic solvent for sensing composite membrane in sample cell immersed with the alkane is scanned by sepectrophotofluorometer, 385nm excites the blank fluorescence spectrum at place；
    The solution to be measured for sensing composite membrane in sample cell immersed with the alkane is scanned by sepectrophotofluorometer, in 385nm Excite the fluorescent spectrum at place；
    When the position of spectral line of the fluorescent spectrum deviates the position of spectral line of the blank fluorescence spectrum, it is determined that described to be measured Contain alkane in solution.
  8. 8. the application method of alkane sensing material according to claim 7, it is characterised in that
    When it is described scanned by sepectrophotofluorometer when, alkane sensing composite membrane is held on the front surface reflection of sample cell On specimen holder, to ensure that fluorescence caused by the sepectrophotofluorometer passes perpendicularly through the alkane sensing composite membrane.
  9. 9. the application method of the alkane sensing material according to claim 7 or 8, it is characterised in that applied to C2~C8Straight chain The detection of alkane.
  10. 10. the application method of alkane sensing material according to claim 9, it is characterised in that
    When for detecting normal heptane, meet between fluorescence intensity and normal heptane concentration that the sepectrophotofluorometer detects Following linear equations：
    I=538.05+4.9749C
    Wherein, I characterizes the 385nm places fluorescence intensity that the sepectrophotofluorometer detects, normal heptane is dense in C sign solution Degree.
CN201710606290.8A 2017-07-24 2017-07-24 A kind of alkane sensing material, preparation method and application method Pending CN107384376A (en)

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Publication number Priority date Publication date Assignee Title
CN109085145A (en) * 2018-07-02 2018-12-25 深圳砺剑防卫技术有限公司 A kind of fluorescence sense film and preparation method thereof and explosive detection instrument
CN110196241A (en) * 2019-05-21 2019-09-03 哈尔滨工程大学 A kind of selective enumeration method iron ion test paper and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
付铁岩等，: ""纳米催化剂FeS的制备及其在气相生长碳纤维中的应用"", 《材料科学与工程学报》 *
王珊等，: ""绿色合成法制备聚氨酯/ TiO2杂化材料"", 《食品与生物技术学报》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109085145A (en) * 2018-07-02 2018-12-25 深圳砺剑防卫技术有限公司 A kind of fluorescence sense film and preparation method thereof and explosive detection instrument
CN110196241A (en) * 2019-05-21 2019-09-03 哈尔滨工程大学 A kind of selective enumeration method iron ion test paper and preparation method thereof
CN110196241B (en) * 2019-05-21 2022-02-22 哈尔滨工程大学 Test paper for selectively detecting iron ions and preparation method thereof

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Application publication date: 20171124