CN106338568B - A kind of method for detecting automobile and automotive trim odoring substance - Google Patents
A kind of method for detecting automobile and automotive trim odoring substance Download PDFInfo
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- CN106338568B CN106338568B CN201610815615.9A CN201610815615A CN106338568B CN 106338568 B CN106338568 B CN 106338568B CN 201610815615 A CN201610815615 A CN 201610815615A CN 106338568 B CN106338568 B CN 106338568B
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- odoring substance
- automotive trim
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- chitosan
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Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
- G01N30/7206—Mass spectrometers interfaced to gas chromatograph
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
- G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
- G01N33/0036—Specially adapted to detect a particular component
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
- G01N30/7206—Mass spectrometers interfaced to gas chromatograph
- G01N2030/7226—OWTC, short capillaries or transfer line used as column
Abstract
The present invention provides a kind of method for detecting automobile and automotive trim odoring substance, and the step is：S1 collects odoring substance by adsorbate；Odoring substance described in S2 is entered in GC O/MS by way of desorption；Simultaneously qualitative and quantitative detection goes out each component in the odoring substance for S3 GC O/MS separation；Meanwhile, the taste and odour intensity of each component are determined using smell nose, and taste and each component are mapped；Wherein, the adsorbate is the polysiloxanes prepared using chitosan as template.
Description
Technical field
Discriminating conduct is detected the present invention relates to a kind of volatile flavor, is more related to a kind of detection automobile and automotive trim gas
The method of taste material, more particularly to G01N fields.
Background technology
Volatile organic matter (VOC, Volatile Organic Compounds), be under standard state initial boiling point be less than or
Organic compound equal to 250 DEG C.And during the universal use of automobile, because motor space is narrow, often in closed
State, therefore the exceeded extent of injury to human body more exceeded than house indoor pernicious gas of vapour harmful gas in vehicle is bigger.In new car
The toxic gas contained in ornament materials mainly includes benzene, formaldehyde, acetone, dimethylbenzene etc., can make one to occur in headache, weak etc.
Toxication shape；The luxurious car of upholstery is more prone to pollution.
On March 1st, 2008 implements HJ/T400-2007《In-car volatile organic matter and aldoketones material sampling determination side
Method》, while the end of the year 2009, Environmental Protection Department is disclosed《In-car volatile organic matter in air concentration requirement》, should《It is required that》Rule
Determined the concentration requirement of in-car volatile organic matter in air, and determine with benzene,toluene,xylene, styrene, ethylbenzene, formaldehyde,
Acetaldehyde and methacrylaldehyde etc. are used as major control material.
Conventional vehicle is to be required to safe to dispatch from the factory by VOC detection before dispatching from the factory, but in actual use process
In, even if the automobile of purchase still still has going out for related peculiar smell by the testing standard of associated vehicle interior decoration
It is existing.This is because, there is many gaseous matters nontoxic to human body, it will also tend to the presence of very heavy peculiar smell, and these gases
Material is not present in examination criteria.
Regarding to the issue above and situation, a kind of method for detecting automobile and automotive trim odoring substance, institute are needed badly at this stage
Poisonous and hazardous gaseous matter can not only be detected by stating method, can also confirm that the main thing of middle influence gas peculiar smell at this stage
Matter, is included in list to be measured.Smell control to auto vendor and automotive trim manufacturer is of great importance, can not only
Enough improve the satisfaction of consumer, moreover it is possible to promote the renewal of vapour environment inside car appraisement system, set up a set of new automobile air and comment
Valency system, supports the development of Domestic Automotive Industry.
The content of the invention
In view of the above-mentioned problems, first aspect present invention provides a kind of method for detecting automobile and automotive trim odoring substance,
The step is：
S1 collects odoring substance by adsorbate；
Odoring substance described in S2 is entered in GC-O/MS by way of desorption；
Simultaneously qualitative and quantitative detection goes out each component in the odoring substance for S3GC-O/MS separation；Meanwhile, determined using smell nose
The taste and odour intensity of each component, and taste and each component are mapped；
Wherein, the adsorbate is the polysiloxanes prepared using chitosan as template.
As one embodiment of the present invention, the GC test parameters are：Heating schedule：40 DEG C of holding 2-4min, with
20K/min rises to 155-170 DEG C, and 12K/min rises to 285 DEG C, keeps 30min；The flow velocity of He carrier gas is 1.0-2.0mL/min.
As one embodiment of the present invention, the GC test parameters are：Heating schedule：40 DEG C of holding 2min, with
20K/min rises to 165 DEG C, and 12K/min rises to 285 DEG C, keeps 30min；The flow velocity of He carrier gas is 1.6mL/min.
As one embodiment of the present invention, the MS test parameters are：Electron impact ion source；Electron energy is set
For 65eV；Transmission line temperature is 280 DEG C；Ion source temperature is 210 DEG C；Mass scan range m/z is between 20~1050.
As one embodiment of the present invention, the mode of the desorption is thermal desorption.
As one embodiment of the present invention, the mode of the collection odoring substance is SPME.
As one embodiment of the present invention, adsorbate described in the step S1 be using chitosan as template,For main material, prepared with the reaction of one or both of following material：
Wherein, the R1For quaternary ammonium salt group；The R2And R3It is respectively selected from different polar groups；R4For benzo-crown ether
Group；AndMol ratio be 1：(0-0.55)：(0-
0.45) it is, describedMolal quantity it is different when be 0.
As one embodiment of the present invention, the viscosity of the chitosan is 0.45~1Pas.
As one embodiment of the present invention, the viscosity of the chitosan is 0.7~0.95Pas.
As one embodiment of the present invention, the R1For the quaternary ammonium salt group containing aromatic rings and carbon-carbon double bond.
As one embodiment of the present invention, the aromatic rings is one kind in benzene, naphthalene or anthracene.
As one embodiment of the present invention, at least one carbon number is connected with the quaternary ammonium salt group on nitrogen-atoms
For 1-5 alkyl.
It is described as one embodiment of the present inventionFor
As one embodiment of the present invention, the R2、R3Be respectively selected from carboxylic acid group, carboxylic acid derivatives, anhydride group,
One kind in sulfonic group, phosphate, hydroxyl, amino, ester group.
The second aspect of the present invention provides the above-mentioned method for detecting automobile and automotive trim odoring substance, and it is used for quality
Control, environmental judgment field.
Brief description of the drawings
Fig. 1：The gas chromatogram of embodiment 1.
Fig. 2：Work as R2During for hydroxyl,'s1H-NMR schemes.
Embodiment
The participation in the election detailed description of the invention below for being preferable to carry out method and including embodiment this hair can be more easily understood
Bright content.Unless otherwise defined, all technologies used herein and scientific terminology have common with art of the present invention
The identical implication that technical staff is generally understood that.When there is contradiction, the definition in this specification is defined.
As used herein term " by ... prepare " it is synonymous with "comprising".Term "comprising" used herein, " comprising ",
" having ", " containing " or its any other deformation, it is intended that cover including for non-exclusionism.For example, the combination comprising listed elements
Thing, step, method, product or device are not necessarily limited to those key elements, but can include not expressly listed other key elements or
Such a composition, step, method, product or the intrinsic key element of device.
Conjunction " Consists of " excludes any key element do not pointed out, step or component.If be used in claim, this
Phrase will make claim be closed, it is not included the material in addition to materials of those descriptions, but relative normal
Except rule impurity.When being rather than immediately following in the clause that phrase " Consists of " appears in claim main body after theme,
It is only limited to the key element described in the clause；Other key elements are not excluded outside as the overall claim.
Equivalent, concentration or other values or parameter are excellent with scope, preferred scope or a series of upper limit preferred values and lower limit
During the Range Representation that choosing value is limited, this, which is appreciated that, specifically discloses by any range limit or preferred value and any scope
All scopes that any pairing of lower limit or preferred value is formed, regardless of whether whether the scope separately discloses.For example, when open
During scope " 1 to 5 ", described scope should be interpreted as including scope " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When number range is described herein, unless otherwise indicated, otherwise the scope is intended to include its end
Value and all integers and fraction within the range.
Singulative includes plural number and object is discussed, unless the context clearly dictates otherwise." optional " or it is " any
It is a kind of " refer to that the item or event that describe thereafter may or may not occur, and the description include situation that event occurs and
The situation that event does not occur.
Approximate term in specification and claims is used for modifying quantity, represents that the present invention is not limited to this specific
Quantity, includes the part of the amendment of the acceptable change without cause related basic function close to the quantity.Phase
Answer, modify a numerical value with " about ", " about " etc., mean that the invention is not restricted to the exact numerical.In some examples, approximately
Term likely corresponds to the precision of the instrument of measured value.In present specification and claims, scope is limited can be with
Combine and/or exchange, these scopes include all subranges contained therebetween if not stated otherwise.
In addition, the indefinite article " one kind " and " one " before key element of the present invention or component are to key element or the quantitative requirement of component
(i.e. occurrence number) unrestriction.Therefore " one " or " one kind " should be read as including one or at least one, and odd number
The key element or component of form also include plural form, unless the obvious purport of the quantity refers to singulative.
The first aspect of the present invention provides a kind of method for detecting automobile and automotive trim odoring substance, and the step is：
S1 collects odoring substance by adsorbate；
Odoring substance described in S2 is entered in GC-O/MS by way of desorption；
Simultaneously qualitative and quantitative detection goes out each component in the odoring substance for S3GC-O/MS separation；Meanwhile, determined using smell nose
The taste and odour intensity of each component, and taste and each component are mapped；
Wherein, the adsorbate is the polysiloxanes prepared using chitosan as template.
GC-O/MS
Gas-chromatography-smelling-mass spectrum (GC-O/MS) combination is by gas-chromatography (GC), odor detection instrument (O) and mass spectrum
(MS) it is combined.
GC-MS plays greatly effect, but some odoring substance threshold values are extremely low in odoring substance analysis, it is impossible to pass through GC-
MS is detected, so there is significant limitations by GC-MS detections merely.Gas-chromatography-smelling technology (GC-O) is by GC
Separating capacity is combined identification odoring substance with the sensitive smell of odor detection instrument；Wherein, the odor detection instrument can be people
The nose or electronic nose of body.GC-O is combined with MS mutually concurrently to wave greater advantages by tonifying for the deficiency.
GC-O principle is very simple, i.e., install diffluence pass in tendency chromatographic column end, after being separated through GC capillary columns
Obtained outflow component is diverted to detector (such as mass spectrum) and nose.When sample enters GC, after being separated via capillary column, flow out
Component is split valve and is divided into two-way, all the way into chemical detector, and another road enters sniff mouthful by special transmission line.Sniff
Mouth is typically cone, is made up of glass or polytetrafluoroethylene (PTFE).The smell of smelling personnel just at sniff mouth to being smelt
It is described and records.Chemical detector can be qualitative to each component in odoring substance, while being returned to each chromatographic peak using area
One standard measure.
As one embodiment of the present invention, the GC test parameters are：Heating schedule：40 DEG C of holding 2-4min, with
20K/min rises to 155-170 DEG C, and 12K/min rises to 285 DEG C, keeps 30min；The flow velocity of He carrier gas is 1.0-2.0mL/min.
As one embodiment of the present invention, the GC test parameters are：Heating schedule：40 DEG C of holding 2min, with
20K/min rises to 165 DEG C, and 12K/min rises to 285 DEG C, keeps 30min；The flow velocity of He carrier gas is 1.6mL/min.
As one embodiment of the present invention, the MS test parameters are：Electron impact ion source；Electron energy is set
For 65eV；Transmission line temperature is 280 DEG C；Ion source temperature is 210 DEG C；Mass scan range m/z is between 20~1050.
As one embodiment of the present invention, the mode of the desorption is thermal desorption.
As one embodiment of the present invention, the mode of the collection odoring substance is SPME.
Automotive trim
Automotive trim is primarily referred to as the used automobile product of automotive interior repacking, is related to side's aspect of automotive interior
Face, such as automobile steering wheel cover, automobile cushion, automatic foot-mat, automobile perfume, automobile pendant, internal goods of furniture for display rather than for use, containing box etc. are all
Automotive trim product.Because a part of auto parts and components have certain dicoration, so common translation is all named at present in the industry
Do " automotive trim ".
Automotive trim mainly includes following subsystem：Instrument panel syste, auxiliary fasia console system, door inner casing system, ceiling
System, seat system, column guard board system, remaining driver's cabin built-in fitting system, the cabin air circulatory system, luggage case are built-in
Part system, enging cabin built-in fitting system, carpet, safety belt, air bag, steering wheel, and room light, in-car acoustics system
System etc..
The material of conventional automotive trim has many kinds, such as leather, rubber, plastics.Specifically for example：PP (polypropylene), ABS
(acrylonitrile-butadiene-styrene copolymer), PC (makrolon)+ABS, ABS+PC, PP+EPDM (ethylene propylene diene rubber) etc..
Adsorbate
In the present invention, the adsorbate is the polysiloxanes prepared using chitosan as template.
Chitosan：Chitosan, also known as chitosan, are product of the chitin through deacetylated processing, chemical name for (1,
4) -2- amino -2- deoxidations-p-D- glucans, molecular formula is (C6H13NO5) n, its structure is the homogeneous state straight-chain polysaccharide containing amino,
Contain free amine group.In general, N- acetamidos slough more than 55% just referred to as chitosan, N- deacetylations are 55%
~70% is low deacetylation chitosan, 70%~85% is middle deacetylation chitosan, and 85%~95% is high de-
Acetyl degree chitosan, 95%~100% is chitosan with ultrahigh deacetylation degree, and N- takes off the extremely difficult system of chitosan of second phthalein degree 100%
It is standby.Usual viscosity is in l000 × 10-3More than Pas's is decided to be high-viscosity chitosan, (1000-100) × 10-3Pas quilt
It is set to middle viscosity chitosan, 100 × 10-3Below Pas's is decided to be low viscosity chitosan.
As one embodiment of the present invention, the viscosity of the chitosan is 0.45~1Pas.
As one embodiment of the present invention, the viscosity of the chitosan is 0.7~0.95Pas.
Viscosity test：
Instrument and reagent：With Ubbelohde viscometer (capillary inner diameter is 0.57mm), thermometer, stopwatch, thermostat water bath, shell
Glycan, solvent：0.2mol/L NaCl and 0.3mol/L acetic acid.
Experimental method：
The washing of viscosimeter：First viscosimeter is soaked with absolute ethyl alcohol, then, scouring of wool is flowed repeatedly thin with distilled water flushing several times
Tube portion, dry for standby after washing.
Temperature adjustment：Regulating thermostatic bath temperature degree is to 25 ± 0.05 DEG C, the rubber tube on the B pipes and C pipes all sets of viscosimeter, so
It is vertically put into thermostat afterwards, the water surface is totally submerged C balls, and checked whether vertically with sash weight.
The measure of solution delivery time：Take a certain amount of chitosan to be dissolved in solvent, with 3# sand core funnel suction filtrations, discard just
Filtrate about 1mL, subsequent filtrate 15mL is pipetted with pipette, is injected constant temperature 15min in viscosimeter by A pipes, is measured.Assay method
It is as follows：The C effective cycles of sixty years are clamped and are allowed to stuffiness, are evacuated to solution from F ball warp D balls, capillary, E balls with ear washing bulb at B pipes
At C balls 2/3, solution removes C pipe clamps, allows C pipes to ventilate, now the solution in D balls is to back into F balls, hangs liquid more than capillary
It is empty.Liquid more than capillary falls, and when liquid level flows through a scales, starts immediately by table between clocking, when the page is down to b scales
When, then by stopwatch, measure the liquid between scale a, b and flow through capillary required time.This operation at least 3 times is repeated, they
Between be more or less the same in 0.3s, take 3 times average value be t1.Then successively with the time for being measured in the same method every part of solution and flowing through capillary
t2、t3、t4。
The measure of solvent delivery time：Viscosimeter is cleaned with distilled water, is washed 1-2 times with solvent, is then added about by A pipes
15ml solvents.With the time t for being measured in the same method solvent outflow0,
By formula η=1.81 × 105M0.93Calculate mean molecule quantity.
As one embodiment of the present invention, the chitosan is bought in Henan Xin Hongtai bio tech ltd.
As one embodiment of the present invention, the chitosan can also be prepared via a method which：
Shrimp, crab shell are cleaned up, immersion, decalcification in 4%-6% hydrochloric acid remove the shell of inorganic salts, burnt 10%
A period of time is boiled in alkali lye, then in KMnO4And NaHSO4Clean, bleach in solution, dry, obtain chitin；Chitin is existed
A period of time is incubated in high alkali liquid, cleans, dry, obtain chitosan.
Polysiloxanes：The Si-O keys that polysiloxanes is a class to repeat are directly connected to organic group as main chain on silicon atom
Polymer.
In the present invention, the polysiloxanes be withOne or both of for main material, with following material
Reaction is prepared：
Wherein, the R1For quaternary ammonium salt group；The R2And R3It is respectively selected from different polar groups；R4For benzo-crown ether
Group.
Quaternary ammonium salt：Refer generally to quarternary ammonium salt, all replaced the chemical combination generated by alkyl for four hydrogen atoms in ammonium ion
Thing, general formula R4NX, wherein four alkyl R can be with identical, also can be different.X mostly be halogen anion (F, Cl, Br, I) or
Acid group (such as HSO4, RCOO etc.).
As one embodiment of the present invention, heretofore described quaternary ammonium salt group is to contain aromatic rings and carbon-carbon double bond
Quaternary ammonium salt group.
Aromatic rings：Aromatic rings is a class organic aromatic compound.Aromatic rings possess between the planar ring system of conjugation, atom into
Key is not discontinuous single double bond alternating, but is covered by delocalizedπelectron cloud.Simple monocyclic aromatic compounds are usually five
Yuan of rings (such as pyrroles) or hexatomic ring (such as pyridine), mixing aromatic nucleus such as naphthalene and purine are the merging of simple ring, and share them
The key of connection.When having non-carbon element in ring, simple aromatic rings just becomes for heterocycle.For example there are oxygen, nitrogen, sulphur.
As one embodiment of the present invention, the aromatic rings is one kind in benzene, naphthalene or anthracene.
As a kind of preferred embodiment of the present invention, the aromatic rings is benzene or naphthalene, more preferably naphthalene.
Carbon-carbon double bond：Three sp are hybridized to by the 2s subgrade and two 2P subgrades of carbon2Hybridized orbit.These three sp2It is miscellaneous
Change orbit distribution at grade.
In the present invention, the carbon-carbon double bond is olefin group；As one embodiment of the present invention, the olefin group
For vinyl group, propylene group, butylene group and amylene group.
As a kind of preferred embodiment of the present invention, the olefin group is vinyl group and propylene group.
It is used as a kind of preferred embodiment of the present invention, the R2And R3It is respectively selected from different polar groups.
As one embodiment of the present invention, at least one carbon number is connected with the quaternary ammonium salt group on nitrogen-atoms
For 1-5 alkyl；More preferably containing the alkyl that a carbon number is 1.
In the present invention, as long as group of the polar group with the atom beyond carbon atom and hydrogen atom, example
Such as can be carboxylic acid group, carboxylic acid derivatives, anhydride group, isocyanate group, sulfonic group, phosphate, hydroxyl, amino, thiol base, ester
Base, cyano group, silicyl etc..
As one embodiment of the present invention, the R2、R3Be respectively selected from carboxylic acid group, carboxylic acid derivatives, anhydride group,
One kind in sulfonic group, phosphate, hydroxyl, amino, ester group.
It is used as a kind of preferred embodiment of the present invention, the R2、R3It is respectively selected from carboxylic acid group, sulfonic group, phosphate, hydroxyl, ammonia
One kind in base, ester group.
It is used as a kind of preferred embodiment of the present invention, the R2Selected from hydroxyl, the R3Selected from carboxyl.
It is described as a kind of more preferred mode of the present inventionFor
Work as R2It is described during hydroxylPreparation method be：
1st, 1 molar part N- methyl ethylenes amine and the blending of 1 molar part triethylamine, using tetrahydrofuran as solvent, in ice-water bath
Under the conditions of, the trimethoxy chlorosilane of 1-1.5 molar parts is added, is reacted 5-20 minutes, after reaction terminates, is dried, washs,
Obtain product 1；
2nd, 1 molar part product 1 and the blending of 1 molar part triethylamine, using tetrahydrofuran as solvent, under the conditions of ice-water bath, plus
Enter 1- (chloromethyl) -3,5- divinylbenzenes of 1-1.5 molar parts, react 5-20 minutes, after reaction terminates, be dried, wash,
Obtain product 2；
3rd, it is blended, prepares by product 2 and with alkene sulfuric acid reaction
As one embodiment of the present invention, the R4For benzo-crown ether group.
Benzo-crown ether：Crown ether is the artificial synthesized acceptor of a class, and crown ether is classified, be broadly divided into calixarenes crown ether,
Heterocycle crown ether, chiral crown ether.Different substituents are connected on the phenyl ring of benzo-crown ether, the performance of benzo-crown ether can be made to occur necessarily
Change.
Monosubstituted benzo-crown ether：Benzo-crown ether can be introduced easily as a human subject compound on aromatic rings
Different types of substituent.
As one embodiment of the present invention, heretofore described benzo-crown ether is preferably Benzo-18-crown-6, two
Benzo-18-crown-6.
As one embodiment of the present invention, the monosubstituted benzo-crown ether be selected from 4- vinyl benzo -18- crown ethers -
6。
As a kind of preferred embodiment of the present invention, the benzo-crown ether is preferably dibenzo dilating ether and 4- vinyl benzos
18- crown ethers -6.
It is described as one embodiment of the present invention Mol ratio be 1：(0-0.55)：(0-0.45), it is described
Molal quantity it is different when be 0.
It is described as a kind of preferred embodiment of the present invention Mol ratio be 1：(0-0.45)：(0-0.3).
It is described as a kind of preferred embodiment of the present invention Mol ratio be 1：0.4：0.28.
In the present invention, the adsorbate is the polysiloxanes prepared using chitosan as template, the preparation method master
To be prepared using sol-gal process.The step is as follows：
1. by reaction raw materialsIt is blended according to mol ratio,
According to reaction raw materials, ethanol and deionized water according to weight ratio be 1：3：As clear as crystal solution is made in 2 proportioning, obtains mixing molten
Liquid A, it is standby；
2. weighing 0.01mol chitosan, add 10ml ethanol and be stirred, then drained ethanol with Suction filtration device,
So 2-4 times repeatedly, drained with air stream；
3. the mixed solution A in the chitosan and step 1 in step 2 is slowly blended, solution is then warming up to 70 DEG C
Stirring 1-2 hours, then adds proper catalyst in the solution, continues to form different gels after stirring 1 hour, dries.
4. the product that step 3 is obtained carries out proper temperature calcining or ultraviolet light is radiated, you can obtains removal shell and gathers
The adsorbate of sugared template.
As one embodiment of the present invention, the catalyst is that the volume ratio of oxalic acid and ammoniacal liquor is 1.2：1.8 are total to
Mixed thing.
In the present invention, the concrete operations of the GC-O/MS are mainly using Headspace-solid phase microextraction-gas-chromatography-smell inspection
The method for surveying instrument/mass spectrum (HS-SPME-GC-O/MS)：
1. obtaining 5g automobile inner ornaments, crushed, be added in ml headspace bottle, push away the extraction that SPME handles will scribble adsorbate
Take probe to stretch into ml headspace bottle, be subsequently placed in 70-90 DEG C of water-bath and heat, absorb SPME adsorbates and waved in automobile inner ornament
The mixed gas sent.Extraction probe is withdrawn after being kept for 20-40 minutes, SPME handles, insertion gas chromatographic sample introduction mouthful solution is removed
Analysis 8-15 minutes, the gas adsorbed on probe adsorbate is inhaled by the high temperature pyrolysis of injection port, makes to enter in GC-O/MS.
2. isolating each component in mixed gas by gas-chromatography, the component isolated is all the way by MS to various
Material is qualitative, and another road is described and graded to the smell of material by smelling personnel, while to colors by odor detection instrument
Spectral peak uses area normalization standard measure.
As one embodiment of the present invention, in the present invention, the gas phase and mass spectrometric parameter are as follows：
Chromatogram (GC) condition：DB-5 quartz capillary columns (50m × 0.32mm × 0.52 μm)；Heating schedule：40 DEG C of holdings
2min, rises to 165 DEG C with 20K/min, 12K/min rises to 285 DEG C, keeps 30min；The flow velocity of He carrier gas (99.999%) is
1.6mL/min。
Mass spectrum (MS) condition：Electron bombardment (EI, Electron impact) ion gun；Electron energy is set as 65eV；Pass
Defeated line temperature is 280 DEG C；Ion source temperature is 210 DEG C；Mass scan range m/z is between 20~1050.Olfactometry device connects
Mouth temperature is 180 DEG C, and to prevent smelling personnel nostril from drying, wet air is passed through during detection.Capillary end effluent is with 1：1
Split ratio separately flow into MS and smelling detector.
The method that the second aspect of the present invention provides the detection automobile and automotive trim odoring substance, it is used for quality control
System, environmental judgment, field of food detection etc., can be used for setting up national examination criteria.
Mechanism is explained：
Present inventor find by using chitosan be the polysiloxanes for preparing of template as loose structure, have to gas
Body material has very strong adsorptivity, simultaneously because the presence of the quaternary ammonium salt group containing aromatic rings and carbon-carbon double bond, its is special
There is very strong adsorptivity to olefines and the gaseous matter of lipid；Simultaneously the adsorbate for preparing of the present invention its have it is very strong
Heat endurance, the reason for its is possible is that crosslinking has been internally formed when preparing adsorbate, so as to improve heat endurance.
Embodiment 1：The invention provides a kind of method for detecting automobile and automotive trim odoring substance, the step
For：
S1 collects odoring substance by adsorbate；
Odoring substance described in S2 is entered in GC-O/MS by way of desorption；
Simultaneously qualitative and quantitative detection goes out each component in the odoring substance for S3 GC-O/MS separation；Meanwhile, it is true using smell nose
Determine the taste and odour intensity of each component, and taste and each component are mapped；
Wherein, the adsorbate is the polysiloxanes prepared using chitosan as template.
Embodiment 2：The method of detection automobile and automotive trim odoring substance described in embodiment 1, the step S1
Described in adsorbate be using chitosan as template,It is anti-with one or both of following material for main material
It should prepare：
Wherein, the R1For quaternary ammonium salt group；The R2And R3It is respectively selected from different polar groups；R4For benzo-crown ether
Group；AndMol ratio be 1：(0-0.55)：(0-
0.45) it is, describedMolal quantity it is different when be 0.
Embodiment 3：The method of detection automobile and automotive trim odoring substance described in embodiment 1, the chitosan
Viscosity be 0.45~1Pas.
Embodiment 4：The method of detection automobile and automotive trim odoring substance described in embodiment 1, the chitosan
Viscosity be 0.7~0.95Pas.
Embodiment 5：The method of detection automobile and automotive trim odoring substance described in embodiment 1, the R1For containing
There is the quaternary ammonium salt group of aromatic rings and carbon-carbon double bond.
Embodiment 6：The method of detection automobile and automotive trim odoring substance described in embodiment 5, the aromatic rings
For one kind in benzene, naphthalene or anthracene.
Embodiment 7：The method of detection automobile and automotive trim odoring substance described in embodiment 5, the quaternary ammonium salt
The alkyl that at least one carbon number is 1-5 is connected with group on nitrogen-atoms.
Embodiment 8：The method of detection automobile and automotive trim odoring substance described in embodiment 1, it is describedFor
Embodiment 9：The method of detection automobile and automotive trim odoring substance described in embodiment 1, the R2、R3Point
One kind not in carboxylic acid group, carboxylic acid derivatives, anhydride group, sulfonic group, phosphate, hydroxyl, amino, ester group.
Embodiment 10：The method of detection automobile and automotive trim odoring substance described in embodiment 1, it is used for quality
Control, environmental judgment field.
Embodiment 11：The method of detection automobile and automotive trim odoring substance described in embodiment 1, the GC tests
Parameter is：Heating schedule：40 DEG C of holding 2-4min, rise to 155-170 DEG C, 12K/min rises to 285 DEG C, holding with 20K/min
30min；The flow velocity of He carrier gas is 1.0-2.0mL/min.
Embodiment 12：The method of detection automobile and automotive trim odoring substance described in embodiment 1, the GC tests
Parameter is：Heating schedule：40 DEG C of holding 2min, rise to 165 DEG C with 20K/min, 12K/min rises to 285 DEG C, keep 30min；He
The flow velocity of carrier gas is 1.6mL/min.
Embodiment 13：The method of detection automobile and automotive trim odoring substance described in embodiment 1, the MS tests
Parameter is：Electron impact ion source；Electron energy is set as 65eV；Transmission line temperature is 280 DEG C；Ion source temperature is 210 DEG C；
Mass scan range m/z is between 20~1050.
Embodiment 14：The method of detection automobile and automotive trim odoring substance described in embodiment 1, the desorption
Mode is thermal desorption.
Embodiment 15：The method of detection automobile and automotive trim odoring substance described in embodiment 1, the collection gas
The mode of taste material is SPME.
The present invention is specifically described below by embodiment.It is necessarily pointed out that, following examples are only used
In the invention will be further described, it is impossible to be interpreted as limiting the scope of the invention, professional and technical personnel in the field
Some the nonessential modifications and adaptations made according to the content of the invention described above, still fall within protection scope of the present invention.
In addition, if without other explanations, raw materials used is all commercially available, and number used in following material is weight
Part.
Embodiment 1：Embodiment 1 provides a kind of mode for detecting automobile and automotive trim odoring substance, and the step is：S1
Odoring substance is collected by adsorbate；
Odoring substance described in S2 is entered in GC-O/MS by way of desorption；
Simultaneously qualitative and quantitative detection goes out each component in the odoring substance for S3GC-O/MS separation；Meanwhile, determined using smell nose
The taste and odour intensity of each component, and taste and each component are mapped；
The adsorbate is the polysiloxanes prepared using chitosan as template, wherein, the preparation of the polysiloxanes
Raw material is：
Wherein, the viscosity 0.9Pas of chitosan, describedForR2
For hydroxyl.
Wherein, it is describedPreparation method be：
1st, 1 molar part N- methyl ethylenes amine and the blending of 1 molar part triethylamine, using tetrahydrofuran as solvent, in ice-water bath
Under the conditions of, the trimethoxy chlorosilane of 1.2 molar parts is added, is reacted 13 minutes, after reaction terminates, is dried, washs, obtain
Product 1；
2nd, 1 molar part product 1 and the blending of 1 molar part triethylamine, using tetrahydrofuran as solvent, under the conditions of ice-water bath, plus
Enter 1- (chloromethyl) -3,5- divinylbenzenes of 1.2 molar parts, react 15 minutes, after reaction terminates, be dried, wash, obtain
Product 2；
3rd, it is that 2mol/L is dilute sulfuric acid reactive blending by product 2 and concentration, reacts 1 minute, prepare at 35 DEG C
With CD3CN is solvent,'s1H-NMR figures are Fig. 2.Chemical shift δ (ppm) is：
2.9(s,3H),3.55(s,6H),4.50(s,2H),5.0(s,1H),5.18(s,1H),5.34(s,1H),5.44(s,1H),
5.61(s,1H),6.63(s,1H),6.90(s,1H),7.05(s,1H),7.06(d,1H),7.13(d,1H)。
Wherein, R3For carboxyl, R4It is described during for Benzo-18-crown-6 groupPreparation method be：
With 0.1mol trimethoxy carboxylic acids silane (No. CAS：944457-91-4) be preparing raw material, and 0.103mol 4- vinyl benzenes
And -18- crown ethers -6 react, with 0.01mol H2PtCl6For catalyst, using 100ml tetrahydrofurans as reaction dissolvent, under ice-water bath
Reaction 15 minutes；
Wherein, it is describedMol ratio be 1：0.4：
0.28。
The adsorbate is the polysiloxanes prepared using chitosan as template, and the preparation method mainly uses colloidal sol
Gel method is prepared.The step is as follows：
1. by reaction raw materialsIt is blended according to mol ratio,
According to reaction raw materials, ethanol and deionized water according to weight ratio be 1：3：As clear as crystal solution is made in 2 proportioning, obtains mixing molten
Liquid A, it is standby；
2. weighing 0.01mol chitosan, add 10ml ethanol and be stirred, then drained ethanol with Suction filtration device,
So 3 times repeatedly, drained with air stream；
3. the mixed solution A in the chitosan and step 1 in step 2 is slowly blended, solution is then warming up to 70 DEG C
Stirring 1-2 hours, then adds proper catalyst in the solution, continues to form different gels after stirring 1 hour, dries.
4. the product that step 3 is obtained carries out 130 DEG C of temperature calcination 5min, you can obtain removing the absorption of chitosan template
Thing.
Wherein, the catalyst is that the volume ratio of oxalic acid and ammoniacal liquor is 1.2：1.8 blend.
In the present invention, the concrete operations of the GC-O/MS are mainly using Headspace-solid phase microextraction-gas-chromatography-smell inspection
The method for surveying instrument/mass spectrum (HS-SPME-GC-O/MS)：
1. obtaining 5g automobile inner ornaments, crushed, be added in ml headspace bottle, push away the extraction that SPME handles will scribble adsorbate
Take probe to stretch into ml headspace bottle, be subsequently placed in 80 DEG C of water-baths and heat, SPME adsorbates is absorbed in automobile inner ornament and volatilize
The mixed gas gone out.Extraction probe is withdrawn after being kept for 30 minutes, SPME handles, 10 points of insertion gas chromatographic sample introduction mouthful parsing is removed
Clock, the gas adsorbed on probe adsorbate is inhaled by the high temperature pyrolysis of injection port, makes to enter in GC-O/MS.
2. isolating each component in mixed gas by gas-chromatography, the component isolated is all the way by MS to various
Material is qualitative, and another road is described and graded to the smell of material by smelling personnel, while to colors by odor detection instrument
Spectral peak uses area normalization standard measure.
In the present embodiment, the gas phase and mass spectrometric parameter are as follows：
Chromatogram (GC) condition：DB-5 quartz capillary columns (50m × 0.32mm × 0.52 μm)；Heating schedule：40 DEG C of holdings
2min, rises to 165 DEG C with 20K/min, 12K/min rises to 285 DEG C, keeps 30min；The flow velocity of He carrier gas (99.999%) is
1.6mL/min。
Mass spectrum (MS) condition：Electron bombardment (EI, Electron impact) ion gun；Electron energy is set as 65eV；Pass
Defeated line temperature is 280 DEG C；Ion source temperature is 210 DEG C；Mass scan range m/z is between 20~1050.Olfactometry device connects
Mouth temperature is 180 DEG C, and to prevent smelling personnel nostril from drying, wet air is passed through during detection.Capillary end effluent is with 1：1
Split ratio separately flow into MS and smelling detector.
Embodiment 2：It is same as Example 1, except the preparation method of the adsorbate is, not using chitosan as template, directly to adopt
Polysiloxanes is prepared with sol-gal process, its preparation method is：
By reaction raw materialsIt is blended according to mol ratio, according to
Reaction raw materials, ethanol and deionized water are 1 according to weight ratio：2：As clear as crystal solution is made in 2 proportioning, obtains mixed solution A,
Then solution is warming up into 70 DEG C to stir 1.5 hours, proper catalyst is then added in the solution, continue shape after stirring 1 hour
Into different gels, dry, you can.
Embodiment 3：It is same as Example 1, except the preparing raw material of the polysiloxanes only has
Embodiment 4：It is same as Example 1, except the preparing raw material of the polysiloxanes is
Embodiment 5：It is same as Example 1, except the preparing raw material of the polysiloxanes is
Embodiment 6：It is same as Example 1, except described Mol ratio be 1：0.8：0.5.
Embodiment 7：It is same as Example 1, except the viscosity of the chitosan is 0.4Pas.
Embodiment 8：It is same as Example 1, except the R2、R3It is methyl.
Embodiment 9：It is same as Example 1, except the R4For methyl.
Embodiment 10：It is same as Example 1, except the R1For methyl.
Testing standard：
The gas flowed out from the gas outlet of odor detection instrument is heard by trained smelling personnel, the intensity for smell of grading simultaneously is retouched
State odor types.
Evaluation method：
1) dilution method：Smelt the person of distinguishing by the same the smell monomer that the sample for gradually decreasing sample size is isolated is smelt
Distinguish, can smell the odoring substance species distinguished be gradually reduced to it is several；
2) frequency method：Smelt the smell monomer that the person of distinguishing measures to the same terms by several and smell distinguishing, the smell thing distinguished can be smelt
Matter species is gradually reduced to several；
3) odour intensity evaluation criteria：
| Odour intensity | Odor level |
| 1 | Imperceptible smell |
| 2 | The smell easily felt |
| 3 | Strong smell |
| 4 | Smell strong and excitatory |
4) smell species
Table 1：It is usually used in describing the vocabulary of smell：
The escaping gas of certain sample is gathered using SPME methods, smell smell using frequency method to distinguish.
Test result：Embodiment 1-10 test result is respectively in table 2.1-2.10
The test result of 2.1 embodiments 1
The test result of 2.2 embodiments 2
2.3 the test result of embodiment 3
The test result of 2.4 embodiments 4
The test result of 2.5 embodiments 5
The test result of 2.6 embodiments 6
The test result of 2.6 embodiments 7
The test result of 2.8 embodiments 8
The test result of 2.9 embodiments 9
The test result of 2.10 embodiments 10
As can be seen from the table, the composition in the present invention, in the feelings for the adsorbance that can keep conventional gas pollutant
Under condition, there is very strong adsorptivity to olefines and lipid material.
Foregoing example is merely illustrative, some features of the feature for explaining the disclosure.Appended claim
The scope as wide as possible for requiring to be contemplated that is intended to, and embodiments as presented herein is only according to all possible embodiment
Combination selection embodiment explanation.Therefore, the purpose of applicant is appended claim not by the explanation present invention
Feature example selectional restriction.And the progress in science and technology by formed language performance it is inaccurate due to and not
The possible equivalent or son being presently considered are replaced, and these changes should also be interpreted by appended in the conceived case
Claim is covered.
Claims (7)
1. a kind of method for detecting automobile and automotive trim odoring substance, it is characterised in that steps of the method are：
S1 collects odoring substance by adsorbate；
Odoring substance described in S2 is entered in GC-O/MS by way of desorption；
Simultaneously qualitative and quantitative detection goes out each component in the odoring substance for S3GC-O/MS separation；Meanwhile, each group is determined using smell nose
The taste and odour intensity divided, and taste and each component are mapped；
Adsorbate described in the step S1 is that tetramethoxy-silicane is main material using chitosan as template, and in following material
One or two kinds of reactions prepare：
Wherein,Mol ratio be 1：(0-0.55)：(0-
0.45) it is, describedMolal quantity it is different when be 0；
The R1For the quaternary ammonium salt group containing aromatic rings and carbon-carbon double bond；The R2、R3Carboxylic acid group, carboxylic acid group is respectively selected to spread out
One kind in biology, anhydride group, sulfonic group, phosphate, hydroxyl, amino, ester group；R4For benzo-crown ether group；
The preparation process of the adsorbate is as follows：
1) is by reaction raw materialsIt is blended according to mol ratio, will be anti-
It is 1 according to weight ratio to answer raw material, ethanol and deionized water：3：As clear as crystal solution is made in 2 proportioning, obtains mixed solution A, standby
With；
2) 0.01mol chitosan is weighed, 10ml ethanol is added and is stirred, then drained ethanol with Suction filtration device, so
2-4 times repeatedly, drained with air stream；
3) by step 2) in chitosan and step 1 in mixed solution A be slowly blended, solution is then warming up to 70 DEG C of stirrings
1-2 hours, proper catalyst is then added in the solution, is continued to form different gels after stirring 1 hour, is dried；
4) by step 3) obtained product carries out proper temperature calcining or ultraviolet light radiation, that is, obtains removing chitosan template
Adsorbate；
Wherein described catalyst is that the volume ratio of oxalic acid and ammoniacal liquor is 1.2：1.8 blend.
2. the method for the detection automobile and automotive trim odoring substance described in claim 1, it is characterised in that the GC tests ginseng
Number is：Heating schedule：40 DEG C of holding 2-4min, rise to 155-170 DEG C, 12K/min rises to 285 DEG C, holding with 20K/min
30min；The flow velocity of He carrier gas is 1.0-2.0mL/min.
3. the method for the detection automobile and automotive trim odoring substance described in claim 1, it is characterised in that the GC tests ginseng
Number is：Heating schedule：40 DEG C of holding 2min, rise to 165 DEG C with 20K/min, 12K/min rises to 285 DEG C, keep 30min；He is carried
The flow velocity of gas is 1.6mL/min.
4. the method for the detection automobile and automotive trim odoring substance described in claim 1, it is characterised in that the MS tests ginseng
Number is：Electron impact ion source；Electron energy is set as 65eV；Transmission line temperature is 280 DEG C；Ion source temperature is 210 DEG C；Matter
Scanning range m/z is measured between 20~1050.
5. the method for the detection automobile and automotive trim odoring substance described in claim 1, it is characterised in that the side of the desorption
Formula is thermal desorption.
6. the method for the detection automobile and automotive trim odoring substance described in claim 1, it is characterised in that the collection smell
The mode of material is SPME.
7. the method for the detection automobile and automotive trim odoring substance described in claim 1, it is used for quality control, environmental judgment
Field.
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