CN102564988A - Method for measuring unsaturation degree of sticky solid matter by infrared spectrometer and sample support for same - Google Patents
Method for measuring unsaturation degree of sticky solid matter by infrared spectrometer and sample support for same Download PDFInfo
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- CN102564988A CN102564988A CN2010106204555A CN201010620455A CN102564988A CN 102564988 A CN102564988 A CN 102564988A CN 2010106204555 A CN2010106204555 A CN 2010106204555A CN 201010620455 A CN201010620455 A CN 201010620455A CN 102564988 A CN102564988 A CN 102564988A
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Abstract
The invention provides a method for measuring the unsaturation degree of sticky solid matter by an infrared spectrometer, comprising the following steps of: putting a sticky solid matter with a certain quantity into a hole of a single-hole sample preparation plate, tabletting in a tabletting machine to prepare a sample, and putting the sample preparation plate carried with the sample on a special sample support, so that the infrared measurement can be carried out on the infrared spectrometer. According to an obtained spectrum chart, and a standard curve obtained according to a standard sample with a known saturation degree, the unsaturation degree of the sticky solid matter to be detected can be directly obtained. The invention further relates to a sample support which can be used in the infrared measurement method.
Description
Technical field
The present invention relates to a kind of infrared spectrometer that utilizes and come the particularly method of the degree of unsaturation of rubber polymer of quantitative test viscous solid material.The present invention be particularly suitable for low-unsaturation-degree rubber for example the degree of unsaturation of butyl rubber and ethylene-propylene-diene rubber measure.The invention still further relates to the used sample holder of said method.
Background technology
In China Synthetic Rubber Industry, the degree of unsaturation of some rubber is lower, like butyl rubber and ethylene-propylene-diene rubber.For the low-unsaturation-degree butyl rubber, its degree of unsaturation is merely between 0.5%～3.3% (mol); For the low-unsaturation-degree ethylene-propylene-diene rubber, its degree of unsaturation is usually below 10% (mol).The method of disclosed mensuration degree of unsaturation comprises online predicted method, iodine index method, epoxy titrimetry, nuclear magnetic resonance spectroscopy in the document, gel permeation chromatography-ultraviolet coupling method and infrared method.
Wherein, The on-line prediction method need be set up flow model according to the reactor used type of low-unsaturation-degree rubber production; And the composition through gas chromatography on-line determination feed composition and unreacted monomer; Set up experimental mathematical model according to the parameters such as reactivity ratio of monomer under polymerization reaction mechanism and the concrete polymerizing condition again and calculate, in time feed back the information of product degree of unsaturation.Because this method need be set up experimental mathematical model, and relates to the mensuration of some parameters, be difficult to simply apply mechanically for the different production device, therefore have certain limitation.
Iodine index method and epoxy titration are owned by France in the chemical titration analysis method, also are the methods of generally using in the commercial production, and the iodine index method is to utilize I
2Oxidisability and I
-The reductibility analytical approach of carrying out titration.The source that the iodine index method possibly produce error has two:
I
2Has volatility, easily volatilization loss;
I
-In acid solution, be prone to be oxygen institute oxidation in the air:
4I
-+4H
++O
2＝2I
2+2H
2O
This be reflected at carry out in the neutral solution slower, but with I in the solution
-Concentration increases and accelerates, if receive direct solar radiation, the reaction rate increase is faster.So the iodine index method is generally carried out titration, I in neutrality or weakly acidic solution and under the low temperature (＜25 ℃)
2Solution should be stored in the brown airtight reagent bottle.In the iodine index method, the I that oxidation is separated out
2Must after reaction finishes, carry out titration immediately, titration is preferably in the iodine flask to be carried out, in order to reduce I
-With air contact titration the time do not answer overshoot oscillation.
The terminal point of iodine index method starch indicator commonly used is confirmed.A small amount of I is being arranged
-There is down I
2Form blue adsorbate with starch reaction, come directing terminal according to blueness appearance or disappearance.At room temperature and a small amount of I
2Under the situation about existing, the sensitivity of this reaction is [I
2]=1-2 * 10
-5MolL
-1No I
-The time, the sensitivity of reaction reduces; I
-Concentration is too big, and the terminal point variable color is insensitive, and the sensitivity of reaction also raises with solution temperature and reduces.So the iodine index method has certain shortcoming, one is the use of iodine solution, has increased the source of an error, and in addition, organomercurial use exists environment pollutes.
The principles of chemistry of epoxy titrimetry are to make the double bond epoxidation among the IIR with 3-chlorine benzylhydroperoxide.Epoxidation is a second order reaction, and the rate constant under its 25 ℃ is k=287L/mols.The activation enthalpy that between 25-40 ℃, carries out the epoxidation reaction that speed measurement obtains is Δ H=32KJ/mol (7.66kcal/mol)
[3]Temperature and time is excessive or too smallly all can influence result of experiment, makes the result of degree of unsaturation that very big error arranged.And this analytical approach relates to the use of multiple poisonous chemical reagent, and complex operation step, and analysis time is long, and source of error is many, also can bring environmental pollution problems.
It is accurate that the spectral analysis of the nuclear magnetic resonance method is measured the result, but still have the problem that feedback time is long, cost is high.Because industrial installation needs quick feedback analysis result to carry out next step production, so this method can not satisfy the requirement of quick feedback.
Since China has begun since the external introduction FTIS seventies in 20th century; In 30 years; The development of Fourier transform infrared spectroscopy technology (FTIR) is very fast, and along with the Fourier transform infrared spectroscopy technology rapid development, its application more and more widely.It can be used for qualitative analysis, also can be used for quantitative test, can also resolve unknown material.To solid, liquid, gas, can use infrared spectroscopic determination to the pure substance of one-component and the potpourri of various ingredients.Infrared spectrum can be used for the analysis of organism, inorganics, polymkeric substance, coordination compound, also can be used for the analysis of compound substance, timber grain, jewelry, soil, rock, various mineral, inclusion etc.
At document " several kinds of spectrographic technique (FTIR; FT-Raman; NMR) application in RUBBER ANALYSIS " (Yin Xiaoling, Lu Dayong, Tu Xueyan, the 29th the 3rd phase of volume of " Yunnan chemical " June in 2002) and " Spectroscopy Studies of the structures of Butyl and Bromobutyl Rubber [J] " (Cheng D M, Gadner IJ; Wang H C.Rubb Chem Technol; 1990,63 (2): simply mentioned 265) with spectral analysis of the nuclear magnetic resonance method combination infrared spectrum technology and measured the degree of unsaturation of rubber, but do not related to the preparation of sample.
Yet, expect high-quality infrared spectrum, except that the good instrument of needs, suitable operating conditions, the technology of preparing of sample is also very important, and the quality of infrared spectrum depends on the method for making sample of sample to a great extent.The position of infrared absorption band, intensity and the shape physical state and the method for making sample of sample when measuring changes, for example with a kind of gaseous state infrared spectrum of sample and liquid state, solid-state different; With a kind of solid sample, the grain size difference has different spectrum shapes.In addition, blocked up and thin, the unevenness of sample, existence, residual solvent and the interference fringe of impurity all possibly lose considerable spectral information with excessivelying, even the bands of a spectrum that lead to errors are discerned and judgement.Therefore need to choose concrete sample preparation methods like sample state, analysis purpose etc. as the case may be.
Solid sample is with various multi-form existence, and test purpose has nothing in common with each other, thereby various solid sample preparation methods are arranged.The most frequently used is pressed halide disk technique, paste method and membrane process.As far as pressed halide disk technique, the most frequently used halogenide compressing tablet matrix is potassium bromide, and it is transparent fully at middle infrared, under high pressure can be changed into transparent compressing tablet.The small pieces of the sample that general infrared analysis uses about as diameter 13mm, the about 1mm of thickness.Get about 1-2mg sample and after agate mortar or vibrations are levigate in the bowl mill, add the dry levigate potassium bromide powder of 100-200mg, fully mix and grind, making average particle size particle size is to get final product about 2 μ m.Ground potpourri is put into equably between the backform and bed die of mould, put into sheeter to mould then, at 10T/cm
2About pressure under can obtain transparent or semitransparent sample in 1-2 minute, pressure should not be too high, otherwise can mold damage.From mould, take out sample and want extreme care in order to avoid sample is broken.Best compacting when compressing tablet while vacuumizing, so that extract the air between powder particle out, otherwise the sample that is pressed into suction and become opaque easily, and be prone to break.Potassium bromide is very big to the corrosivity on steel die surface.Mould is kept in the dry environment with must in time cleaning up later then.A shortcoming of the method is a compressing tablet process very complicated; Operation must be carried out in the room of low humidity, and the potassium bromide powder is easy to suction, and the metal surface is easy to adhere to the potassium bromide powder; Need water to remove the potassium bromide on specimen holder, compressing tablet frame and the filtrator, use acetone drying then.Especially specimen holder, pressing potassium bromide troche mould and compressing tablet frame need be kept in the exsiccator.
It is to be noted especially, for the viscous solid material, because its viscosity is big; Yielding characteristics; When with above-mentioned pressed disc method sample preparation, because its viscosity is difficult to from mould, take out greatly, this on the other hand taking-up is operated also can cause the very big distortion of sample generation on the one hand; Thereby influence the result of infrared analysis, cause analysis result inaccurate.In addition; Above-mentioned pressed disc method can not guarantee the thickness of sample compressing tablet, and must carry out the mensuration of thickness of sample, but because the viscosity of viscous solid material is big; Yielding; Its Determination of thickness is difficulty very, and therefore above-mentioned pressed disc method can not guarantee the accuracy of thickness of sample, and this also can have influence on infrared analysis result's accuracy.
In addition; In above-mentioned pressed disc method, use potassium bromide that sample to be tested is diluted; This is perhaps feasible for analyzing higher component concentration, but for low component concentration, for example is low to moderate the butyl rubber degree of unsaturation of 0.5%～3.3% (mol); It is difficult to draw measurement result accurately through infrared analysis after further being diluted by potassium bromide.
Summary of the invention
The object of the present invention is to provide the method for a kind of simple and direct express-analysis viscous solid material, for example butyl rubber degree of unsaturation; This method is accurate, quick, simple to operation and pollution-free; Can be used to replace the method for above prior art, the information feedback of in time carrying out industrial installation is to instruct next step production.
For realizing above-mentioned purpose, the present invention provides a kind of method with infrared gear measurement viscous solid material degree of unsaturation, and this method comprises:
1) step of using degree of unsaturation viscous solid material to be measured to carry out sample preparation, this sample preparation step comprises:
A) a certain amount of said viscous solid material is put into the single through hole of a single hole sample preparation plate; And at the both sides of said single hole sample preparation plate covering spacer assembly; Wherein said single hole sample preparation plate has the thickness identical with sample to be processed, and said single hole sample preparation plate and said spacer assembly are formed single hole sample preparation mould jointly;
The single hole sample preparation mould that b) will be loaded with said viscous solid material is put into sheeter and is carried out compressing tablet;
C) after compressing tablet is accomplished, cool off, remove said spacer assembly then, thereby obtain being loaded in the sample of the said viscous solid material on the said single hole sample preparation plate,
2) sample that makes is carried out the step of IR survey, this measuring process comprises:
D) use infrared spectrometer that the sample that is loaded in the said single hole sample preparation plate is carried out IR survey, thereby obtain spectrogram;
E) peak height of characteristic absorption peak of on spectrogram, getting carbon-carbon double bond is as absorbance; The reflection absorbance that contrast has been made and the typical curve of the corresponding relation between the degree of unsaturation directly draw the degree of unsaturation of said viscous solid material, and wherein said typical curve is to use the known standard model of degree of unsaturation under sample preparation condition identical with above-mentioned testing sample and IR survey condition, to carry out sample preparation and IR survey is set up.
Preferably, at above-mentioned steps d) before, the single hole sample preparation plate that loads said sample is placed on the special sample holder, so that in infrared spectrometer, keep the position of said single hole sample preparation plate.Certainly, suspension method is for example adopted in the position of sample preparation plate in infrared spectrometer that also can use the alternate manner except that sample holder to keep said load sample, as long as make light beam can see through sample so that measure just passable.
Preferably, the foundation of the related typical curve of measuring method of the present invention is based on Lambert-Beer's law A=ε cl.According to Lambert-Beer's law, at thickness of sample one regularly, the absorbance of component is directly proportional with concentration of component in the sample.Therefore, for example can adopt the peak height of the characteristic absorption peak of carbon-carbon double bond to set up the typical curve of degree of unsaturation as absorbance.Like this, to viscous solid material to be measured after carrying out sample preparation and IR survey under the identical condition,, the contrast typical curve of having made can directly draw the degree of unsaturation of viscous solid material to be measured.
Preferably, get 1658.7cm on the spectrogram
-1Place's peak height (for example for butyl rubber) or 1687.6cm
-1Place's peak height (for example for ethylene-propylene-diene rubber) is set up the typical curve of degree of unsaturation as absorbance.Certainly, drift also possibly appear in the characteristic absorption peak of carbon-carbon double bond on spectrogram.
Should point out that the time that in air, exposes behind the viscous solid material compressing tablet is long more, influence the quality of sample more, it is uneven that sample surfaces is produced, and then the intensity of the absorption peak of infrared spectrogram is changed, and influences test accuracy.Therefore, for the test condition of infrared spectrogram, the resolution of the preferred infrared spectrometer of the present invention is 4.0cm
-1, scanning times is 20 times, sweep limit 400-4000cm
-1
Viscous solid material involved in the present invention can be a unsaturated polymer, especially the low-unsaturation-degree polymkeric substance.Preferably, it can be a low-unsaturation-degree rubber, for example butyl rubber or ethylene-propylene-diene rubber.。
For the spacer assembly that covers said single hole sample preparation plate both sides, for example, it can be a for example polytetrafluoroethylene film of one deck barrier film; Perhaps, it can be one deck barrier film for example polytetrafluoroethylene film be positioned at one deck dividing plate on the said barrier film.Said dividing plate can be a sheet metal, and for example steel plate, copper coin, cast iron plate, sheet tin, aluminium sheet etc. are preferably corrosion resistant plate.
Preferably, the single hole sample preparation plate that uses in the measuring method of the present invention is processed by metal material, for example stainless steel, cast iron, tin, aluminium etc.Thickness for said single hole sample preparation plate is generally 0.1mm-1cm, and when said single hole sample preparation plate was used for infrared analysis, in general, the sample preparation plate was thick more, and the absorption peak on the infrared spectrogram is strong more, but then, also makes the spectrogram degradation; And the sample preparation plate thickness is too thin, make absorption peak strength too again a little less than, the result that influence is measured.Therefore, the thickness of said single hole sample preparation plate for example can be 0.1-1mm, preferably 0.5-0.8mm when being used for infrared analysis.
Single through hole on the said single hole sample preparation plate can have arbitrary shape, for example circle, polygon etc.Preferably, said single through hole is circular.
The temperature of the employed sheeter of measuring method of the present invention can change in very wide scope; Temperature is high more; The compressing tablet effect is good more; But the heat decomposition temperature that can not surpass the viscous solid material, hot pressing temperature are crossed low smooth inadequately or surperficial the growing dim of sample surfaces that make of possibly causing, and influence measurement result.The preferred hot pressing temperature of the present invention is 120-180 ℃.
The pressure limit of the employed sheeter of measuring method of the present invention also can be very big, but for making general sample, pressure needn't be excessive; Temperature, pressure is excessive or the pressurization overlong time; All possibly cause the thermal decomposition of sample, pressure is not enough, also influences the quality of the sample that makes.The preferred compressing tablet pressure of the present invention is the 4-10 ton, and hot pressing time is 3-10 minute.
Preferably, the cooling procedure behind compressing tablet that is comprised in the measuring method of the present invention can prevent the thermal deformation of sample in temperature-fall period so better for the cooling of pressure is arranged.For example, can adopt two for example thickness be that the steel plate of 2cm is as cooling device, in sheeter after the compressing tablet; The single hole sample preparation mould that is loaded with sample is taken out from sheeter; Be placed between said two blocks of steel plates, the cooling certain hour is so that cool to room temperature for example.Certainly, also can adopt other cooling means, for example water-cooled or air cooling.
Certainly; Have in use under the situation of sheeter of cooling device;, compressing tablet can directly in sheeter, carry out cooling after accomplishing; And then the single hole sample preparation mould that will be loaded with sample takes out from sheeter, removes spacer assembly, thereby obtains being arranged in the sample of the viscous solid material of single hole sample preparation plate.
Should point out that the sample preparation step that measuring method of the present invention adopted has is easy, characteristics fast.This sample preparation step mainly comprises following 3 points with respect to the important difference and the beneficial effect of method for making sample of the prior art:
1) the sample preparation step that adopts among the present invention is directly carried out compressing tablet with a certain amount of viscous solid material to be measured, need not use KBr as dispersion medium.That is to say that the sample that this sample preparation step makes is the pure sample article.This not only can simplify technological process, saves time and expense, and also significant for the low component concentration of measuring in the viscous solid material with infrared method.As mentioned above, in the time need analyzing the low component concentration in the viscous solid material, if use KBr to carry out sample preparation as dispersion medium, then wherein low component concentration is by further dilution, thereby is difficult to guarantee the accuracy of measurement result.On the contrary, use the pure sample article then to prevent low component concentration in the present invention, thereby improved the accuracy of measurement result by further dilution.
2) the single hole sample preparation plate that the sample preparation step that adopts among the present invention is used has identical thickness with sample to be made.Like this, can make the certain sample of thickness exactly, avoid thickness of sample is measured.Therefore As mentioned above, for the viscous solid material, Determination of thickness is difficulty very, can not guarantee the accuracy of thickness measurement, this so that have influence on infrared analysis result's accuracy.In the present invention, because the thickness of single hole sample preparation plate is sample thickness, therefore can guarantees the accuracy of thickness of sample, thereby improve infrared analysis result's accuracy.
3) the sample preparation step that adopts among the present invention need not taken out the sample that makes from single hole sample preparation plate after sample is processed, but the single hole sample preparation plate of load sample is directly placed on the special sample holder, on infrared spectrometer, carries out assay determination then.As mentioned above, the viscous solid material is because easy bonding, so its sample can not separate with mould well, is easy to generate distortion.Therefore; After making sample, sample is retained in the present invention and not only omitted sample in the single hole sample preparation plate and take out operation; Significantly practiced thrift the running time, and prior meaning also is to have avoided the sample distortion, thereby improved infrared analysis result's accuracy.
According to IR survey method of the present invention;, do not take out by sample after processing from single hole sample preparation plate; Measure but take on the infrared gear together with single hole sample preparation plate; Therefore the holder device that carries on the infrared gear for example sample cell becomes unavailable, needs to adopt new mode to keep the position of sample preparation plate in spectrometer, makes light beam can see through sample.For example, can be the special a kind of sample holder of single hole sample preparation plate.Therefore; Except above-mentioned IR survey method; The present invention also provides a kind of special sample holder that can be used in the above-mentioned IR survey method, and said sample holder is used to support the single hole sample preparation plate of the specimen preparation that is used for the viscous solid material, and said single hole sample preparation plate has the thickness identical with sample to be processed; And the single through hole of said single hole sample preparation plate is used to hold the sample of only being made up of said viscous solid material; Wherein, said sample holder has holding device to keep the accommodating single hole sample preparation plate of said viscous solid material sample, so that on analytical instrument, said viscous solid material sample is carried out assay determination.
Preferably, the holding device of said sample holder comprises body, has groove at the top of said body, and said single hole sample preparation plate can be maintained in the said groove and can in said groove, slide.
The holding device that it is also contemplated that said sample holder comprises a pair of jaw, and said single hole sample preparation plate can be by said jaw clamping.
The not special restriction of the size and dimension of said sample holder is as long as can play in effect that stably keeps said single hole sample preparation plate and the test cabinet that can be placed on analytical instrument suitably just passable.For example, the body of said sample holder can be rectangular shape.
Preferably, said sample holder has at least one leg, on said leg, has roller.Like this, can be when measuring along any direction mobile example support easily, thereby find best measuring position to measure rapidly.
The also not special restriction of the material of said sample holder for example can be processed by stainless steel, copper, cast iron, aluminium, plastics etc.
What need particularly point out is, is illustrated although be used for the IR survey method with above-mentioned sample holder in this manual, and the purposes of obvious said sample holder is not limited to this.In fact, said sample holder also can be used at other analytical instrument supporting sample preparation plate.
Description of drawings
Fig. 1 is the decomposing schematic representation of the single hole sample preparation mould that in the preferred embodiment of IR survey method of the present invention, uses, and viscous solid material wherein to be measured also is not placed in the single through hole of single hole sample preparation plate;
Fig. 2 is the synoptic diagram that is loaded with the single hole sample preparation plate of the viscous solid material sample that completes;
Fig. 3 is the synoptic diagram of the sample holder that in the preferred embodiment of IR survey method of the present invention, uses;
Fig. 4 is the infared spectrum of the butyl rubber sample to be measured that in the preferred embodiment 1 of IR survey method of the present invention, obtains through IR survey;
Fig. 5 is the typical curve that in the preferred embodiment 1 of IR survey method of the present invention, uses the butyl rubber degree of unsaturation of standard butyl rubber sample foundation; And
Fig. 6 is the infared spectrum of the ethylene-propylene-diene rubber sample to be measured that in the preferred embodiment 2 of IR survey method of the present invention, obtains through IR survey.
Embodiment
With reference to Fig. 1, wherein show the decomposing schematic representation of the single hole sample preparation mould that uses in the preferred embodiment of IR survey method of the present invention.Said single hole sample preparation mould representes with reference number 1 that totally it comprises single hole sample preparation plate 2, will cover the polytetrafluoroethylene film 3 and the steel plate 4 of single hole sample preparation plate 2 both sides successively.Said single hole sample preparation plate 2 comprises the single through hole 5 that holds viscous solid material 6, and has the thickness identical with sample to be made.
Fig. 2 shows the synoptic diagram of the single hole sample preparation plate 2 that is loaded with the viscous solid material sample that completes.After sample making is accomplished, need not from single hole sample preparation plate 2, to take out, carry out IR survey but be retained in the single hole sample preparation plate 2.
Fig. 3 shows the synoptic diagram of the sample holder that in a preferred embodiment of IR survey method of the present invention, uses.This sample holder is processed by stainless steel and is totally represented with reference number 7; It comprises body 8; Have groove 9 at the top of this body 8; Single hole sample preparation plate 2 can stably be placed in this groove 9 and can in this groove 9, be slided, thereby can adjust the measuring position through the slip of single hole sample preparation plate 2 when on infrared gear, measuring.
This sample holder 7 also comprises the legs 10 of two band rollers, like this, can be when carrying out IR survey along any direction mobile example support easily, thereby find best measuring position to measure rapidly.
In the present embodiment, used hot sheeter is the CARVER-3800 hot press, (U.S. laboratory equipment company), and used balance is METTLER AL-204, precision 0.1mg.Used chromatograph is day island proper Tianjin FTIR-8201PC Fourier transformation infrared spectrometer.
Take by weighing 0.1850g butyl rubber sample to be measured, put into the single hole sample preparation plate 2 of aperture 13mm, thickness 0.6mm, both sides cover polytetrafluoroethylene film 3, and then press from both sides two steel plates 4, put into sheeter and carry out compressing tablet.The compressing tablet condition is: 7 tons of pressure, 150 ℃ of temperature, 5 minutes compressing tablet time.Randomly, can add 1 ton of pressure before the compressing tablet, put pressure then, repeatedly twice, to eliminate bubble.In addition, the plasticity inorganics of chemical change not taking place for thermoplastic polymer or near softening point, can before compressing tablet, sample be placed on the preheating regular hour in the sheeter.After compressing tablet is accomplished; From sheeter, take out by polytetrafluoroethylene film 3 and the single hole sample preparation plate 2 that steel plate 4 keeps, place it in addition two for example thickness be in the steel plate of 2cm cooling 10 minutes so that the butyl rubber sample cooling and shaping in the through hole 5 of single hole sample preparation plate 2.After cooling; Take out the single hole sample preparation plate 2 that is kept by polytetrafluoroethylene film 3 and steel plate 4 two blocks of steel plates in addition from said; Remove steel plate 4 then, take polytetrafluoroethylene film 3 off, thereby obtain being retained in the butyl rubber sample in the single through hole 5 of single hole sample preparation plate 2.The single hole sample preparation plate 2 that will have sample inserts in the groove 9 of sample holder 7, on said infrared spectrometer, carries out infrared analysis.In the mensuration process; Single hole sample preparation plate 2 can slide in groove 9, and two legs 10 of sample holder 7 can move along any direction, thereby can find best locating very soon; Make IR just in time can pass the center of through hole 5, carry out sample determination fast.The infrared analysis condition is: resolution 4cm
-1, scanning times 20 times, wave number 400-4000cm
-1Fig. 4 illustrates the infrared spectrogram of acquisition.Get 1658.7cm from the infrared spectrogram that obtains
-1The place is as degree of unsaturation quantitative characteristic peak; Scope according to the manual selected characteristic spectrum of actual conditions district; Obtain proofreading and correct peak height as absorbance; The correction equation (as shown in table 1) of the reflection butyl rubber degree of unsaturation as shown in Figure 5 that its substitution has been set up and the typical curve of the corresponding relation between the absorbance, thus the degree of unsaturation that draws butyl rubber to be measured is 1.70mol%.
Wherein, said typical curve is to set up like this: the butyl rubber that uses synthetic different degrees of unsaturation is as standard model, and its degree of unsaturation is confirmed through nuclear magnetic resonance spectroscopy.Under sample preparation same as described above and measuring condition, carry out sample preparation and measurement, to obtain infrared spectrogram.Get 1658.7cm from these infrared spectrograms
-1The place is as degree of unsaturation quantitative characteristic peak, thus many groups numerical value of degree of unsaturation that gets standard samples and corresponding absorbance.12 groups of numerical value that obtain have like this been listed in the table 1 below; According to these numerical value; With the degree of unsaturation is ordinate, and the absorbance analog value is a horizontal ordinate, can make the reflection butyl rubber degree of unsaturation as shown in Figure 5 and the typical curve of the corresponding relation between the absorbance; And obtain correction equation corresponding to typical curve, as shown in table 1.
Table 1 is by the correction equation of the typical curve of manual correction peak height match
The typical curve that obtains so just can be used for commercial production afterwards and in the laboratory butyl rubber of degree of unsaturation the unknown carried out infrared analysis.Can find out that measuring method of the present invention is quick, simple and pollution-free, thereby therefore the information feedback that can in time carry out industrial installation has the better industrial practicality to instruct next step production.
In the present embodiment, equipment such as used hot sheeter, balance, chromatograph is identical with above embodiment 1.
Take by weighing 0.1850g ethylene-propylene-diene rubber sample to be measured, put into the single hole sample preparation plate 2 of aperture 13mm, thickness 0.6mm, both sides cover polytetrafluoroethylene film 3, and then press from both sides two steel plates 4, put into sheeter and carry out compressing tablet.The compressing tablet condition is: 7 tons of pressure, 160 ℃ of temperature, 5 minutes compressing tablet time.Corresponding steps about butyl rubber in ensuing cooling step, infrared analysis step etc. and the foregoing description 1 is identical, thereby obtains the infrared spectrogram of ethylene-propylene-diene rubber to be measured as shown in Figure 6.On infrared spectrogram, get 1687.6cm
-1The place is as degree of unsaturation quantitative characteristic peak; Scope according to the manual selected characteristic spectrum of actual conditions district; Obtain proofreading and correct peak height as absorbance; With the correction equation (not shown) of the typical curve of the corresponding relation of its substitution between reflection ethylene-propylene-diene rubber degree of unsaturation of setting up under identical sample preparation and the test condition and absorbance, thereby the degree of unsaturation that draws ethylene-propylene-diene rubber to be measured is 5.63mol%.
Claims (16)
1. method with determination of infrared spectroscopy viscous solid material degree of unsaturation, this method comprises:
1) step of using degree of unsaturation viscous solid material to be measured to carry out sample preparation, this sample preparation step comprises:
A) a certain amount of said viscous solid material is put into the single through hole of a single hole sample preparation plate; And at the both sides of said single hole sample preparation plate covering spacer assembly; Wherein said single hole sample preparation plate has the thickness identical with sample to be processed, and said single hole sample preparation plate and said spacer assembly are formed single hole sample preparation mould jointly;
The single hole sample preparation mould that b) will be loaded with said viscous solid material is put into sheeter and is carried out compressing tablet;
C) after compressing tablet is accomplished, cool off, remove said spacer assembly then, thereby obtain being loaded in the sample of the said viscous solid material on the said single hole sample preparation plate,
2) sample that makes is carried out the step of IR survey, this measuring process comprises:
D) use infrared spectrometer that the sample that is loaded in the said single hole sample preparation plate is carried out IR survey, thereby obtain spectrogram;
E) peak height of characteristic absorption peak of on spectrogram, getting carbon-carbon double bond is as absorbance; The reflection absorbance that contrast has been made and the typical curve of the corresponding relation between the degree of unsaturation directly draw the degree of unsaturation of said viscous solid material, and wherein said typical curve is to use the known standard model of degree of unsaturation under sample preparation condition identical with above-mentioned testing sample and IR survey condition, to carry out sample preparation and IR survey is set up.
2. according to claims 1 described method, it is characterized in that, before said step d), also comprise the single hole sample preparation plate that loads said sample is placed on the sample support, so that in infrared spectrometer, keep the position of said single hole sample preparation plate.
3. according to claims 1 described method, it is characterized in that said viscous solid material is a unsaturated polymer, is preferably the low-unsaturation-degree polymkeric substance, more preferably low-unsaturation-degree rubber.
4. according to claims 3 described methods, it is characterized in that said low-unsaturation-degree rubber is butyl rubber.
5. according to claims 3 described methods, it is characterized in that said low-unsaturation-degree rubber is ethylene-propylene-diene rubber.
6. according to claims 4 described methods, it is characterized in that, in said step e), get the 1658.7cm on the spectrogram
-1The peak height at place is as absorbance.
7. according to claims 5 described methods, it is characterized in that, in said step e), get the 1687.6cm on the spectrogram
-1The peak height at place is as absorbance.
8. according to claims 1 described method, it is characterized in that the thickness of said single hole sample preparation plate is 0.1-1mm, is preferably 0.5-0.8mm.
9. according to claims 1 described method, it is characterized in that in said step b), hot pressing temperature is 120-180 ℃, compressing tablet pressure is the 4-10 ton, and hot pressing time is 3-10 minute.
10. one kind can require among the 1-9 sample holder that uses in each the method at aforesaid right; Said sample holder is used to support the single hole sample preparation plate of the specimen preparation that is used for the viscous solid material; Said single hole sample preparation plate has the thickness identical with sample to be processed; And the single through hole of said single hole sample preparation plate is used to hold the sample of only being made up of said viscous solid material; Wherein, said sample holder has holding device to keep the accommodating single hole sample preparation plate of said viscous solid material sample, so that on analytical instrument, said viscous solid material sample is carried out assay determination.
11., it is characterized in that the holding device of said sample holder comprises body according to claims 10 described sample holders, have groove at the top of said body, said single hole sample preparation plate can be maintained in the said groove and can in said groove, slide.
12. according to claims 10 described sample holders, it is characterized in that the holding device of said sample holder comprises a pair of jaw, said single hole sample preparation plate can be by said jaw clamping.
13., it is characterized in that the body of said sample holder is a rectangular shape according to claims 11 described sample holders.
14., it is characterized in that said sample holder has at least one leg according to claims 10 described sample holders.
15. according to claims 14 described sample holders, it is characterized in that, on said at least one leg, have roller.
16., it is characterized in that the material of said sample holder is selected from stainless steel, copper, cast iron, aluminium, plastics according to claims 10 described sample holders.
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| CN102721661A (en) * | 2011-03-30 | 2012-10-10 | 中国石油化工股份有限公司 | Method for determining unsaturated degree of viscous solid substance by infrared spectrum and specimen rack used in method |
| CN102944531A (en) * | 2012-12-01 | 2013-02-27 | 上海微谱化工技术服务有限公司 | Method for determining trace substances on surface of solid |
| CN109025924A (en) * | 2018-05-08 | 2018-12-18 | 中国海洋石油集团有限公司 | Oil saturation dynamic monitoring platform based on microcosmic petrographic thin section |
| CN110579380A (en) * | 2018-06-07 | 2019-12-17 | 贝内克-长顺汽车内饰材料（张家港）有限公司 | preparation method of test sample and method for testing light transmittance of material |
| CN111077101A (en) * | 2019-12-12 | 2020-04-28 | 湖北航天化学技术研究所 | Preparation method of film sample for infrared spectrum quantitative analysis |
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| CN110579380B (en) * | 2018-06-07 | 2022-08-16 | 贝内克-长顺汽车内饰材料（张家港）有限公司 | Preparation method of test sample and method for testing light transmittance of material |
| CN111077101A (en) * | 2019-12-12 | 2020-04-28 | 湖北航天化学技术研究所 | Preparation method of film sample for infrared spectrum quantitative analysis |
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