CN106855509A - infrared spectrum ATR (attenuated reflectance) determination method for microstructure content of solution polymerized styrene butadiene rubber - Google Patents
infrared spectrum ATR (attenuated reflectance) determination method for microstructure content of solution polymerized styrene butadiene rubber Download PDFInfo
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- 238000002329 infrared spectrum Methods 0.000 title claims abstract description 56
- 229920003048 styrene butadiene rubber Polymers 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 36
- 230000002238 attenuated effect Effects 0.000 title abstract 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 43
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 41
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims abstract description 35
- 239000000126 substance Substances 0.000 claims abstract description 24
- 238000002835 absorbance Methods 0.000 claims abstract description 10
- -1 Vinyl Chemical group 0.000 claims description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- 238000003556 assay Methods 0.000 claims description 26
- 230000003595 spectral effect Effects 0.000 claims description 26
- 238000010521 absorption reaction Methods 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000012046 mixed solvent Substances 0.000 claims description 11
- 239000003963 antioxidant agent Substances 0.000 claims description 10
- 230000003078 antioxidant effect Effects 0.000 claims description 10
- 150000001298 alcohols Chemical class 0.000 claims description 9
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 238000006467 substitution reaction Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 230000008033 biological extinction Effects 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 238000000638 solvent extraction Methods 0.000 claims description 2
- 238000005102 attenuated total reflection Methods 0.000 abstract 2
- 238000004566 IR spectroscopy Methods 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 85
- 238000012360 testing method Methods 0.000 description 58
- 239000000243 solution Substances 0.000 description 27
- 230000010076 replication Effects 0.000 description 19
- 238000005259 measurement Methods 0.000 description 14
- 238000000576 coating method Methods 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 11
- 238000011017 operating method Methods 0.000 description 9
- 238000012956 testing procedure Methods 0.000 description 9
- 239000005562 Glyphosate Substances 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000003292 glue Substances 0.000 description 6
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 6
- 229940097068 glyphosate Drugs 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- YASYVMFAVPKPKE-UHFFFAOYSA-N acephate Chemical compound COP(=O)(SC)NC(C)=O YASYVMFAVPKPKE-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000002203 pretreatment Methods 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000003905 agrochemical Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 230000009931 harmful effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 2
- 238000004451 qualitative analysis Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 238000004483 ATR-FTIR spectroscopy Methods 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- PDYXIVPKOMYDOK-UHFFFAOYSA-N Glyphosate-monoammonium Chemical compound [NH4+].OC(=O)CNCP(O)([O-])=O PDYXIVPKOMYDOK-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000012356 Product development Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- QLULGSLAHXLKSR-UHFFFAOYSA-N azane;phosphane Chemical compound N.P QLULGSLAHXLKSR-UHFFFAOYSA-N 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3563—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing solids; Preparation of samples therefor
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to an infrared spectrum ATR (attenuated reflectance) measuring method for microstructure content of solution polymerization styrene butadiene rubber, which comprises the steps of firstly obtaining the content of styrene, 1, 4-trans-polybutadiene, 1, 2-vinyl-polybutadiene and 1, 4-cis-polybutadiene; then measuring the absorbance of 4 microstructures of the standard substance by using an infrared spectroscopy ATR (attenuated total reflectance) measuring method to obtain a constant coefficient a1-a4、k1-k4(ii) a Then establishing quantitative formulas (I) - (IV), and calculating the content of 4 microstructures;
Description
Technical field
The present invention relates to a kind of infrared spectrum ATR assay methods of solution polymerization styrene-butadiene rubber microstructure content, solution
4 kinds of microstructures of polymerized sbr are styrene, Isosorbide-5-Nitrae-trans-polybutadiene, 1,2- vinyl-polybutadiene, Isosorbide-5-Nitrae-suitable
Formula-polybutadiene.
Background technology
Solution polymerization styrene-butadiene rubber (SSBR) be it is a kind of by butadiene with styrene synthesizing as obtained by anionic polymerisation
Rubber.SSBR has the various excellent properties for being suitable for tire purposes.Its rolling resistance is than emulsion polymerization polymerized sbr
ESBR reduces 20%~30%, and wet-sliding resistant performance is better than butadiene rubber, and anti-wear performance is excellent, used as tire tread glue, performance
It is substantially better than ESBR and butadiene rubber.As China's highway, high-performing car, the development of high-performance tire and society are right
The reinforcement of environment and power conservation requirement, SSBR as environment-friendly type tire primary raw material, the consumption ratio in butadiene-styrene rubber in recent years
Example constantly increases, and production capacity amplification is also very rapid.
The microstructure content of SSBR directly affects anti-slippery, rolling resistance, impact strength, softening temperature and vulcanization
The important performances such as characteristic, thus SSBR microstructure contents control in the research of SSBR technologies, new product development, product matter
It is significant in the work such as amount control, it is necessary to be measured.
At present, the method for determining SSBR microstructure contents has nuclear magnetic resonance method and infra-red sepectrometry.Nuclear magnetic resonance method is needed
NMR is equipped with, because the instrument price is expensive, maintenance, operating cost are very high, are not universal instruments, with wideless
It is general, conventional detection is rarely used in, it is used for standard substance definite value.Infra-red sepectrometry is the general of measure SSBR microstructure contents
Method.The infra-red sepectrometry for determining SSBR microstructures includes infrared spectrum solution coating method and infrared spectrum ATR methods.
GB/T 28728-2012 is defined using infrared spectrum solution coating process, and microstructure content in SSBR is carried out
The analysis method of quantitative determination.The method is that the SSBR rubbery samples that will be extracted on a small quantity are dissolved in hexamethylene, and in bromination
Film on potassium piece, determines the infrared spectrum of SSBR rubbery samples on KBr smear.According to 4 absorbances of certain wave strong point,
Using Hampton method, the content of Isosorbide-5-Nitrae-trans key, Isosorbide-5-Nitrae-cis key, 1,2- vinyl and styrene monomer is calculated.
Although infrared spectrometer is universal instrument, but the method is needed sample dissolving film again, and course of dissolution needs 5
More than individual hour, and experimental result is easily influenceed by analysis human users' level, the completeness of dissolving and smooth, the planarization of diaphragm
Large effect will be produced to measurement result, the repeatability of laboratory monitoring is not fine.Also, the method needs sample is molten
Solve, not only time-intensive, expensive, and have certain harmful effect to environment and experimenter's health.
Patent 201210229795.4) disclose combinated styrene content content in a kind of emulsion polymerized styrene butadiene rubber infrared spectrum survey
Determine method, one has 15 constant factors in its quantitative equation, is obtained by following two approach：(1) industry mark is directly quoted
9 constant factor a in quasi- SH/T1727-20041-a3、k1-k6, (2) carry out infrared spectrum survey using 2 kinds of substitute standard glue
It is fixed, obtain other 6 constant factor a4、k7-k11.In second approach, substitute standard glue is according to polybutadiene and polyphenyl
The mass ratio 2 of ethene:1~5:1 ratio, the mixed solution of preparation.The method is also to use solution coating process, it is necessary to by sample
It is coated in after being completely dissolved on KBr chip and is measured.The method is only used for determining SBR of emulsion polymerization, it is impossible to use
In measure SSBR.
ATR (decay total reflection) technology obtains the structure of sample top layer organic principle by the optical signal that sample surfaces reflect
Information, its principle is that infrared light is refracted to sample surfaces through too high refracting crystal, and light beam occurs when the angle of incidence is larger than a critical angle
Reflection.But infrared light is not to be all reflected, but during by sample, part light after certain depth is absorbed again
From sample surfaces reflection, the Spectral Signal of generation is similar to transmission absorption spectrogram, thus is referred to as " decay total reflection ", need to be
Device ATR annexes are to be capable of achieving test on original infrared spectrum instrument.In order to increase absorption peak strength, test signal to noise ratio is improved,
Modern ATR annexes all strengthen absorption intensity using total reflection number of times (can typically reach tens times) is increased.Infrared ATR (declines
Subtracting total reflection) technology is due to without sample dissolution, it is not required that prepare sample salt piece and transmission pond is set, easily and fast, have no
Sample surfaces are damaged, therefore is widely used in the qualitative and quantitative analysis of material composition.
Infrared ATR technologies are mainly used in determining can not carry out the sample of pre-treatment, i.e., the insoluble structural information for not melting sample,
It is used for qualitative analysis.But because the technology dissolves or melts completely without by sample, it is not required that other sample tests
Device, it is only necessary to which sample is placed on ATR annexes the structural information that can obtain sample, it is also increasing to be used to quantitatively divide
Analysis.
" ATR-FTIR quantitative analysis methods research of acephate pesticide ", Liu Wenfeng,《Guangzhou University's journal》, the 4th
Phase, page 17~page 20,2013.The method is made to concentration respectively with the peak height and peak area of orthene characteristic absorption peak
Standard curve, as a result shows, is linearly integrally slightly better than with peak area with the standard curve that orthene peak height is mapped to concentration
Standard curve to concentration mapping is linear, and orthene is linear in 1.0~8.0 μ g/mL.
" content of infrared spectroscopic determination ammonium glyphosate ", Dai Yujing,《Agricultural chemicals》, the tenth phase, page 732~page 733,
2011.The method directly determines agricultural chemicals glyphosate content using ATR annexes.Glyphosate standard items and glyphosate sample it is infrared
Spectral comparison experiment shows：Glyphosate is in 1321cm-1The absworption peak at place is not disturbed by other compositions in agricultural chemicals, can select this
Peak is the absworption peak of quantitative analysis.Glyphosate infrared spectrum is in 1295~1348cm-1The peak area at place meets linear with its content
Relation, correlation coefficient r is 0.9997.Standard curve is made to content with the peak area of glyphosate standard items, grass can be determined sweet
The content of phosphine ammonium salt.
At present, the infrared spectrum ATR methods of solution polymerization styrene-butadiene rubber microstructure are not determined also.
The content of the invention
It is an object of the invention to provide a kind of infrared spectrum ATR measure sides of solution polymerization styrene-butadiene rubber microstructure content
Method, 4 kinds of microstructures of solution polymerization styrene-butadiene rubber are styrene, Isosorbide-5-Nitrae-trans-polybutadiene, 1,2- vinyl-polybutadiene
Alkene, Isosorbide-5-Nitrae-cis-polybutadine.
The infrared spectrum ATR assay methods that the present invention is provided are mainly used to replace infrared spectrum solution coating process.With it is infrared
Spectrum solution coating process is compared, and solution polymerization styrene-butadiene rubber microstructure content is determined using infrared spectrum ATR assay methods,
It is environmental protection, convenience, economical, quick without sample dissolution, it is not required that prepare sample salt piece, and lossless sample surfaces, be it is a kind of more
It is suitable method.
The infrared spectrum ATR assay methods that the present invention is provided are firstly the need of 4 standards of solution polymerization styrene-butadiene rubber of collection
Material.This 4 the 4 of standard substance kinds of microstructure contents are styrene, Isosorbide-5-Nitrae-trans-polybutadiene, 1,2- vinyl-poly- fourth
The content of diene, Isosorbide-5-Nitrae-cis-polybutadine, according to standard GB/T/T 28728-2012, is applied using infrared spectrum solution
Embrane method is determined and drawn.
Using infrared spectrum ATR assay methods measure standard substance 4 kinds of microstructures i.e. styrene,
Isosorbide-5-Nitrae-trans-polybutadiene, 1,2- vinyl-polybutadiene, the absorbance of Isosorbide-5-Nitrae-cis-polybutadine, respectively
It is expressed as AStyrene、AIt is trans、AVinyl、AIt is cis, 4 kinds of microstructure contents and the corresponding extinction number of degrees measured according to known to standard substance
Value, by mathematical computations, specific calculating process is shown in embodiment 1, it is possible to obtain constant factor a1-a4、k1-k4。
Obtain constant factor a1-a4、k1-k4After, you can quantitative equation (I)-(IV) is set up, because quantitative equation (I)-
(IV) all coefficients are all constant factors in, and the microstructure for determining solution polymerization styrene-butadiene rubber testing sample every time later contains
Amount, need to only measure 4 kinds of absorbance As of microstructure of the testing sample using infrared spectrum ATR assay methodsStyrene、AIt is trans、
AVinyl、AIt is cis, can just calculate 4 kinds of contents of microstructure in substitution quantitative equation (I)-(IV) respectively.
Wherein：
CIt is trans=a1×AIt is trans-k1×AVinyl
CVinyl=a2×AVinyl-k2×AIt is trans
CIt is cis=a3×AIt is cis-k3×AStyrene
CStyrene=a4×AStyrene-k4×AIt is cis。
C in quantitative equation (I)-(IV) of the present inventionIt is trans、CVinyl、CIt is cis、CStyreneIt is respectively Isosorbide-5-Nitrae-trans-polybutadiene
Alkene, 1,2- vinyl-polybutadiene, Isosorbide-5-Nitrae-cis-polybutadine, the mass concentration of styrene；AIt is trans、AVinyl、AIt is cis、AStyrenePoint
It is not Isosorbide-5-Nitrae-trans-polybutadiene, 1,2- vinyl-polybutadiene, Isosorbide-5-Nitrae-cis-polybutadine, the extinction number of degrees of styrene
Value.
Application infrared spectrum ATR assay methods of the present invention measure 4 kinds of microstructures i.e. styrene, Isosorbide-5-Nitrae-trans-
Polybutadiene, 1,2- vinyl-polybutadiene, the absorbance A of Isosorbide-5-Nitrae-cis-polybutadineStyrene、AIt is trans、AVinyl、AIt is cis, mainly
Including sample preparation, the acquisition of the infrared spectrogram of testing sample and 4 kinds of readings of microstructure absorption values.It is specifically walked
Suddenly it is：
1) preparation of sample
1. with the addition oil and antioxygen in alcohols and aromatic hydrocarbons MIXED SOLVENT EXTRACTION solution polymerization styrene-butadiene rubber testing sample
Agent, the solution polymerization styrene-butadiene rubber testing sample after then drying extracting in 50-65 DEG C of vacuum drying oven；
2. about 1 gram of a fritter is cut from the testing sample for extracting, holding surface is smooth, is positioned over the crystalline substance of ATR annexes
On piece.
Step of the present invention one kind 1. in the preferred methyl alcohol of middle alcohols solvent, ethanol and normal propyl alcohol, the preferred first of aromatic hydrocarbon solvent
One kind in benzene, dimethylbenzene.
Step of the present invention 1. middle alcohols and aromatic hydrocarbons mixed solvent, alcohols and aromatic hydrocarbons press volume proportion 3:1 to 1:3 it
Between.Alcohols and aromatic hydrocarbons press volume proportion preferably 2:1、1:1、1:One kind in 2.
2) acquisition of the infrared spectrogram of testing sample
1. in 400cm-1~3000cm-1In the range of, determine the infrared spectrum of air；It is preferred that 400cm-1~2000cm-1, more
It is preferred that 600cm-1~1600cm-1。
2. in 400cm-1~3000cm-1In the range of, determine the infrared spectrum of testing sample；It is preferred that 400cm-1~2000cm-1, more preferably 600cm-1~1600cm-1。
3. the infrared spectrum of air is subtracted with the infrared spectrum of testing sample, the infrared spectrogram of testing sample is obtained.Should
Infrared spectrogram eliminates the interference of air.
3) 4 kinds of readings of microstructure absorption values
In the infrared spectrogram of the testing sample for obtaining, 4 kinds of infrared spectral peaks of microstructure are determined：
1. with 695cm-1-705cm-1Inside most strong absworption peak is the infrared spectral peak of styrene；
2. with 960cm-1-970cm-1Inside most strong absworption peak is the infrared spectral peak of Isosorbide-5-Nitrae-trans-polybutadiene；
3. with 905cm-1-915cm-1Inside most strong absworption peak is the infrared spectral peak of 1,2- vinyl-polybutadiene；
4. with 718cm-1-726cm-1Inside most strong absworption peak is the infrared spectral peak of Isosorbide-5-Nitrae-cis-polybutadine.
With 1200cm-1The horizontal line at place is accordingly as baseline, the peak height for determining 4 kinds of infrared spectral peaks of microstructure
Absorption values AStyrene、AIt is trans、AVinyl、AIt is cis。
Measure 4 kinds of microstructures i.e. styrene, Isosorbide-5-Nitrae-trans-polybutadiene, 1,2- vinyl-polybutadiene, Isosorbide-5-Nitrae-suitable
The absorption values A of formula-polybutadieneStyrene、AIt is trans、AVinyl、AIt is cis, 4 can be calculated in substitution quantitative equation (I)-(IV)
Plant the content of microstructure.
Quantitative equation (I)-(IV) of the present invention has 8 constant factors, including 4 absorption coefficient a1-a4With 4 influence because
Sub- k1-k4。
The inventive method needs to use standard substance to determine this 4 absorption coefficients and 4 factors of influence.Standard substance 4
The content for planting microstructure is drawn according to standard GB/T/T 28728-2012 using infrared spectrum solution coating process measure.
The specific reckoning process of absorption coefficient and factor of influence is as follows：
According to formula
Wherein：
CIt is trans=a1×AIt is trans-k1×AVinyl
CVinyl=a2×AVinyl-k2×AIt is trans
Converted in the following manner：
Isosorbide-5-Nitrae-trans-polybutadiene content/1,
There was only a in this equation1、a2、k1、k2Four unknowm coefficients, are 4 yuan of 1 equation of n th order n, select 4 standards of known microstructure content
Material, measures 4 groups of corresponding AIt is trans、AVinyl, in substituting into this 4 yuan of 1 equation of n th order n, you can 44 yuan of 1 equation of n th order n are obtained, so as to ask
Go out a1、a2、k1、k2Four unknowm coefficients.
Similarly, a can be obtained3、a4、k3、k4Four unknowm coefficients.
The resolution ratio of infrared spectrometer of the present invention is not more than 0.2cm-1。
The inventive method is not limited for the model of infrared spectrometer, it is adaptable to the infrared spectrum of various models
Instrument.
The inventive method is only used for the measure of combinated styrene content content in solution polymerization styrene-butadiene rubber, is not suitable for emulsion
The measure of microstructure content in polymerized sbr, styrene-butadiene latex.
This method is directly measured using ripe commercialization ATR annexes to sample.
Because all coefficients are all constant factors in quantitative equation (I)-(IV), polymerisation in solution butylbenzene rubber is determined every time later
The microstructure content of glue testing sample, need to only measure 4 kinds of microcosmic knots of the testing sample using infrared spectrum ATR assay methods
The absorbance A of structureStyrene、AIt is trans、AVinyl、AIt is cis, can just calculate 4 kinds of testing sample in substitution quantitative equation (I)-(IV) respectively micro-
See the content of structure.
Using ATR methods, testing sample does not need organic solvent hexamethylene to be dissolved, and volatility will not be produced to have poison gas
Body, does not pollute to laboratory environment, and to the healthy without harmful effect of experimenter, the environment with height is friendly
Property.
The testing sample of this method does not need pre-treatment, can directly determine, it is entirely avoided sample pre-treatment it is organic
The consumption of the experimental articles such as solvent, KBr chip, glassware, reduces experimental cost, with good economic benefit.
Meanwhile, because testing sample does not need pre-treatment, the scope of application being have also been enlarged, some can not dissolve or cannot dissolve completely
Full experimental sample can also be measured by this method.
This method sample testing time is very short, and 1 sample only needs just can complete once to test for 2 minutes, and other experiment sides
Method at least needs half an hour to complete 1 test of sample, drastically increases analysis efficiency.
Brief description of the drawings
Fig. 1 is the spectrogram that solution polymerization styrene-butadiene rubber microstructure content is determined using infrared spectrum ATR assay methods；
Wherein, the infrared spectral peak of 1.1,4- trans-polybutadienes；The infrared spectral peak of 2.1,2- vinyl-polybutadiene；
The infrared spectral peak of 3.1,4- cis-polybutadines, the 4. infrared spectral peak of styrene.
The peak height for measuring this 4 kinds of infrared spectral peaks of microstructure is corresponding absorption values AIt is trans、AVinyl、AIt is cis、AStyrene。
Specific embodiment
The present invention is further illustrated by the following examples, but the present invention is not limited to these embodiments.
This method is not more than 0.2cm suitable for resolution ratio-1Various models infrared spectrometer, this method be applied to differentiate
Rate is not more than 0.2cm-1Various models infrared spectrometer, the present invention used by instrument be：Nicolet companies of the U.S. produce
Nexus670 Fourier transformation infrared spectrometers, spectral region：12000–350cm-1, resolution ratio：0.09cm-1.ATR annexes are
The commercialization annex of Nicolet companies of U.S. production.
Embodiment 1
For 4 solution polymerization styrene-butadiene rubber standard substances, with volume proportion 2:1 absolute ethyl alcohol/toluene Mixed Solvent
Addition oil and antioxidant in extracted solution polymerized sbr standard substance, then dry extracting in 60 DEG C of vacuum drying oven
Solution polymerization styrene-butadiene rubber standard substance afterwards.
Standard substance is dissolved using organic solvent hexamethylene, dissolution time is 6 hours.After 6 hours, standard substance is complete
Dissolving, obtains the solution of solution polymerization styrene-butadiene rubber standard substance.According to the operating procedure of GB/T 28728-2012, using red
External spectrum solution coating process has altogether carries out 6 replications, and repeated experiment data are shown in Table 1, table 2.6 measurement results altogether
Maximum relative standard deviation is 0.19%, and maximum extreme difference is 0.5, and repeatability is preferably.
The 1,2- vinyl of 14 standard substances of table, the repeated data of styrene-content
The 1,4- of 24 standard substances of table is trans, 1,4- cis-contents repeated data
For 4 standard substances, 4 kinds of contents of microstructure use infrared according to standard GB/T/T 28728-2012
Spectrum solution coating process is determined and drawn.4 the 4 of standard substance kinds of microstructure contents are shown in Table 3.
34 data of the 4 of standard substance kinds of microstructure contents of table
The relational expression of each microstructure content and corresponding absorption values is obtained according to Lambert-Beer's law:
CIt is trans=a1×AIt is trans-k1×AVinyl, CVinyl=a2×AVinyl-k2×AIt is trans, CIt is cis=a3×AIt is cis-k3×AStyrene, CStyrene
=a4×AStyrene-k4×AIt is cis。
The specific reckoning process of absorption coefficient and factor of influence is as follows：
According to formula
Wherein：
CIt is trans=a1×AIt is trans-k1×AVinyl
CVinyl=a2×AVinyl-k2×AIt is trans
Converted in the following manner：
Isosorbide-5-Nitrae-trans-polybutadiene content/1,
There was only a in this equation1、a2、k1、k2Four unknowm coefficients, are 4 yuan of 1 equation of n th order n, 4 known microstructure contents of selection it is alternative
Standard rubber, measures 4 groups of corresponding AIt is trans、AVinyl, in substituting into this 4 yuan of 1 equation of n th order n, you can obtain 44 yuan of 1 equation of n th order n:
49.4/6.5=(a1×0.312-k1×0.055)/(a2×0.055-k2×0.312)
46.3/7.3=(a1×0.345-k1×0.071)/(a2×0.071-k2×0.345)
43.4/7.5=(a1×0.412-k1×0.086)/(a2×0.086-k2×0.412)
42.6/7.6=(a1×0.408-k1×0.088)/(a2×0.088-k2×0.408)
So as to obtain a1、a2、k1、k2Four unknowm coefficients are respectively 0.385,0.318,0.0069,0.0052.
Similarly, a can be obtained3、a4、k3、k4Four unknowm coefficients are respectively 1.359,0.367,0.0075,0.0081.
By 8 constant factor a1-a4、k1-k4Numerical value substitute into quantitative equation (I)-(IV) in CIt is trans、CVinyl、CIt is cis、
CStyrene, following equation can be expressed as.
CIt is trans=0.385 × AIt is trans-0.0069×AVinyl
CVinyl=0.308 × AVinyl-0.0052×AIt is trans
CIt is cis=1.359 × AIt is cis-0.0075×AStyrene
CStyrene=0.367 × AStyrene-0.0081×AIt is cis。
For testing sample, styrene, Isosorbide-5-Nitrae-trans-polybutadiene, 1,2- vinyl-polybutadiene, Isosorbide-5-Nitrae-suitable are measured
The absorbance A of formula-polybutadieneStyrene、AIt is trans、AVinyl、AIt is cis.Substitute into quantitative equation (I)-(IV) in can calculate 4 kinds it is micro-
See the content of structure.
Embodiment 2
1 testing procedure
(1) preparation of sample
1. volume proportion 2 is used:In 1 absolute ethyl alcohol/toluene Mixed Solvent extracted solution polymerized sbr testing sample
Addition oil and antioxidant, the solution polymerization styrene-butadiene rubber testing sample after extracting is then dried in 60 DEG C of the vacuum drying oven；
2. about 1 gram of a fritter is cut from the testing sample for extracting, holding surface is smooth, is positioned over the crystalline substance of ATR annexes
On piece.
(2) acquisition of the infrared spectrogram of testing sample
1. in 600cm-1~1600cm-1In the range of, determine the infrared spectrum of air；
2. in 600cm-1~1600cm-1In the range of, determine the infrared spectrum of testing sample；
3. the infrared spectrum of air is subtracted with the infrared spectrum of testing sample, the infrared spectrogram of testing sample is obtained.Should
Infrared spectrogram eliminates the interference of air.
(3) 4 kinds of readings of microstructure absorption values
In the infrared spectrogram of the testing sample for obtaining, 4 kinds of infrared spectral peaks of microstructure are determined：
1. with 695cm-1-705cm-1Inside most strong absworption peak is the infrared spectral peak of styrene；
2. with 960cm-1-970cm-1Inside most strong absworption peak is the infrared spectral peak of Isosorbide-5-Nitrae-trans-polybutadiene；
3. with 905cm-1-915cm-1Inside most strong absworption peak is the infrared spectral peak of 1,2- vinyl-polybutadiene；
4. with 718cm-1-726cm-1Inside most strong absworption peak is the infrared spectral peak of Isosorbide-5-Nitrae-cis-polybutadine.
With 1200cm-1The horizontal line at place is accordingly as baseline, the peak height for determining 4 kinds of infrared spectral peaks of microstructure
Absorption values AStyrene、AIt is trans、AVinyl、AIt is cis。
Measure 4 kinds of microstructures i.e. styrene, Isosorbide-5-Nitrae-trans-polybutadiene, 1,2- vinyl-polybutadiene, Isosorbide-5-Nitrae-suitable
The absorption values A of formula-polybutadieneStyrene、AIt is trans、AVinyl、AIt is cis, 4 can be calculated in substitution quantitative equation (I)-(IV)
Plant the content of microstructure.
24 kinds of measure of microstructure content
5 replications, replication are carried out again to this solution polymerized butadiene styrene rubber testing sample by identical operating procedure
The results are shown in Table 4.6 maximum relative standard deviations of measurement result are 0.22% altogether, and maximum extreme difference is 0.5, and repeatability is preferably.
The repeated experiment data of 44 kinds of microstructure contents of table
Embodiment 3
From volume proportion 2:In 1 absolute methanol/toluene Mixed Solvent extracted solution polymerized sbr testing sample
Addition oil and antioxidant.Other testing procedures are same as Example 1.
This solution polymerized butadiene styrene rubber testing sample is had altogether by identical operating procedure carry out 6 replications, repeats to survey
Determine result replication and the results are shown in Table 5.6 maximum relative standard deviations of measurement result are 0.20% altogether, and maximum extreme difference is
0.5, repeatability is preferably.
The repeated experiment data of 54 kinds of microstructure contents of table
Embodiment 4
From volume proportion 2:In 1 normal propyl alcohol/xylene mixture solvent extracted solution polymerized sbr testing sample
Addition oil and antioxidant.Other testing procedures are same as Example 1.
This solution polymerization styrene-butadiene rubber testing sample is had altogether by identical operating procedure carry out 6 replications, weight
Multiple measurement result replication the results are shown in Table 6.6 maximum relative standard deviations of measurement result are 0.16%, maximum pole altogether
Difference is 0.4, and repeatability is preferably.
The repeated experiment data of 64 kinds of microstructure contents of table
Embodiment 5
From volume proportion 1:In 1 absolute ethyl alcohol/toluene Mixed Solvent extracted solution polymerized sbr testing sample
Addition oil and antioxidant.Other testing procedures are same as Example 1.
This solution polymerization styrene-butadiene rubber testing sample is had altogether by identical operating procedure carry out 6 replications, weight
Multiple measurement result replication the results are shown in Table 7.6 maximum relative standard deviations of measurement result are 0.16%, maximum pole altogether
Difference is 0.4, and repeatability is preferably.
The repeated experiment data of 74 kinds of microstructure contents of table
Embodiment 6
From volume proportion 1:In 2 absolute ethyl alcohol/toluene Mixed Solvent extracted solution polymerized sbr testing sample
Addition oil and antioxidant.Other testing procedures are same as Example 1.
This solution polymerization styrene-butadiene rubber testing sample is had altogether by identical operating procedure carry out 6 replications, weight
Multiple measurement result replication the results are shown in Table 8.6 maximum relative standard deviations of measurement result are 0.20%, maximum pole altogether
Difference is 0.4, and repeatability is preferably.
The repeated experiment data of 84 kinds of microstructure contents of table
Embodiment 7
The scope of infrared spectrogram is selected in 400cm-1~2000cm-1.Other testing procedures are same as Example 1, to molten
Liquid polymerized sbr testing sample is measured.
This solution polymerization styrene-butadiene rubber testing sample is had altogether by identical operating procedure carry out 6 replications, weight
Multiple measurement result replication the results are shown in Table 9.6 maximum relative standard deviations of measurement result are 0.15%, maximum pole altogether
Difference is 0.4, and repeatability is preferably.
The repeated experiment data of 94 kinds of microstructure contents of table
Embodiment 8~10
From volume proportion 2:In 1 absolute ethyl alcohol/toluene Mixed Solvent extracted solution polymerized sbr testing sample
Addition oil and antioxidant.Other testing procedures are same as Example 1.Using infrared spectrum ATR assay methods respectively to three
Solution polymerization styrene-butadiene rubber testing sample 1~3 carries out 1,2- vinyl-polybutadiene, the measure of styrene-content, repeated number
According to being shown in Table 10.
The vinyl of table 10, styrene repeated experiment data
Comparative example 1
For solution polymerization styrene-butadiene rubber testing sample, with volume proportion 2:1 absolute ethyl alcohol/toluene Mixed Solvent extracting
Addition oil and antioxidant in solution polymerization styrene-butadiene rubber testing sample, after then drying extracting in 60 DEG C of vacuum drying oven
Solution polymerization styrene-butadiene rubber testing sample.
Using organic solvent hexamethylene dissolved samples, dissolution time is 6 hours.After 6 hours, sample is almost totally insoluble,
The sample solution of solution polymerization styrene-butadiene rubber testing sample cannot be obtained, it is impossible to surveyed using infrared spectrum solution coating process
It is fixed.
Using infrared spectrum ATR assay methods, according to the testing procedure in embodiment 1, to this polymerisation in solution butylbenzene rubber
Glue testing sample has altogether carries out 6 replications, and 6 maximum relative standard deviations of measurement result are 0.22% altogether, maximum
Extreme difference is 0.4, and repeatability is preferably.
Comparative example 2
For solution polymerization styrene-butadiene rubber testing sample, with volume proportion 2:1 absolute ethyl alcohol/toluene Mixed Solvent extracting
Addition oil and antioxidant in solution polymerization styrene-butadiene rubber testing sample, after then drying extracting in 60 DEG C of vacuum drying oven
Solution polymerization styrene-butadiene rubber testing sample.
Using organic solvent hexamethylene dissolved samples, dissolution time is 6 hours.After 6 hours, sample is completely dissolved, and obtains
To the sample solution of solution polymerization styrene-butadiene rubber testing sample.According to the operating procedure of GB/T 28728-2012, using infrared
Spectrum solution coating process has altogether carries out 6 replications, and each replication spends 10 minutes, and 1 hour is needed altogether.Sample from
Start to be dissolved into 6 replications of completion, 7 hours are needed altogether.
Using infrared spectrum ATR assay methods, according to the testing procedure in embodiment 1, to this polymerisation in solution butylbenzene rubber
Glue testing sample has altogether carries out 6 replications, it is not necessary to dissolve sample, and each replication spends 2 minutes, needs altogether
12 minutes, the testing time greatly shortened.
Comparative example 3~5
According to the operating procedure of GB/T 28728-2012, using infrared spectrum solution coating process respectively to embodiment 7-9
In three solution polymerization styrene-butadiene rubber testing samples 1~3 carry out 1,2- vinyl-polybutadiene, the measure of styrene quality,
Repeated data are shown in Table 11.
The vinyl of table 11, styrene repeated experiment data
Find out from embodiment 8~10 and comparative example 3~5, to same sample, using infrared spectrum ATR assay methods with
1,2- vinyl-polybutadiene that infrared spectrum solution coating process is obtained, styrene weight/mass percentage composition are sufficiently close to, and 6 times
The standard deviation of measurement result is with extreme difference also very close to its repeatability is all preferable.Therefore, two methods can be used in measure and contain intermingle with
The microstructure content of butadiene-styrene rubber, but infrared spectrum ATR assay methods do not use chemical solvent to dissolve, and sample prepares very simple
The single, testing time is very short, is the analysis method higher to more environment-friendly, detection efficiency.
Certainly, the present invention can also have other various embodiments, ripe in the case of without departing substantially from spirit of the invention and its essence
Knowing those skilled in the art can make various corresponding changes and deformation, but these corresponding changes and deformation according to the present invention
Protection scope of the present invention should all be belonged to.
Claims (9)
1. infrared spectrum ATR assay methods of a kind of solution polymerization styrene-butadiene rubber microstructure content, it is characterised in that including such as
Lower step：4 the 4 of standard substance kinds of microstructure content, i.e. styrene, Isosorbide-5-Nitrae-trans-polybutadiene, 1,2- second are obtained first
The content of alkenyl-polybutadiene, Isosorbide-5-Nitrae-cis-polybutadine；Then standard substance is measured using infrared spectrum ATR assay methods
4 kinds of absorbances of microstructure, be expressed as AStyrene、AIt is trans、AVinyl、AIt is cis, 4 kinds of microcosmic knots according to known to standard substance
Structure content and the corresponding absorption values measured, by mathematical computations, obtain constant factor a1-a4、k1-k4；Then set up quantitative
Formula (I)-(IV), reuses 4 kinds of absorbance As of microstructure that infrared spectrum ATR assay methods measure sample to be testedStyrene、
AIt is trans、AVinyl、AIt is cis, calculate 4 kinds of contents of microstructure in substitution quantitative equation (I)-(IV) respectively；
Wherein：CIt is trans=a1×AIt is trans-k1×AVinyl, CVinyl=a2×AVinyl-k2×AIt is trans, CIt is cis=a3×AIt is cis-k3×AStyrene,
CStyrene=a4×AStyrene-k4×AIt is cis。
2. assay method according to claim 1, it is characterised in that measure sample to be tested using infrared spectrum ATR methods
4 kinds of absorbance As of microstructureStyrene、AIt is trans、AVinyl、AIt is cisComprise the following steps：Sample preparation, the infrared light of sample to be tested
The acquisition of spectrogram and 4 kinds of readings of microstructure absorption values：
1) preparation of sample
1. with volume proportion 3:1~1:Alcohols and aromatic hydrocarbons MIXED SOLVENT EXTRACTION solution polymerization styrene-butadiene rubber between 3 is to be measured
Addition oil and antioxidant in sample, the solution polymerization styrene-butadiene rubber after then drying extracting in 50-65 DEG C of vacuum drying oven
Sample to be tested；
2. about 1 gram of a fritter is cut from the sample to be tested for extracting, holding surface is smooth, is positioned on the chip of ATR annexes；
2) acquisition of the infrared spectrogram of sample to be tested
1. in 400cm-1~3000cm-1In the range of, determine the infrared spectrum of air；
2. in 400cm-1~3000cm-1In the range of, determine the infrared spectrum of sample to be tested；
3. the infrared spectrum of air is subtracted with the infrared spectrum of sample to be tested, the infrared spectrogram of sample to be tested is obtained；
3) 4 kinds of readings of microstructure absorption values
In the infrared spectrogram of the sample to be tested for obtaining, 4 kinds of infrared spectral peaks of microstructure are determined：
1. with 695cm-1-705cm-1Inside most strong absworption peak is the infrared spectral peak of styrene；
2. with 960cm-1-970cm-1Inside most strong absworption peak is the infrared spectral peak of Isosorbide-5-Nitrae-trans-polybutadiene；
3. with 905cm-1-915cm-1Inside most strong absworption peak is the infrared spectral peak of 1,2- vinyl-polybutadiene；
4. with 718cm-1-726cm-1Inside most strong absworption peak is the infrared spectral peak of Isosorbide-5-Nitrae-cis-polybutadine；
With 1200cm-1The horizontal line at place is corresponding extinction as baseline, the peak height for determining 4 kinds of infrared spectral peaks of microstructure
Number of degrees value AStyrene、AIt is trans、AVinyl、AIt is cis。
3. assay method according to claim 2, it is characterised in that 1) 1. middle alcohols solvent is first to the preparation process of sample
One kind in alcohol, ethanol and normal propyl alcohol.
4. assay method according to claim 2, it is characterised in that the 1) preparation process of sample 1. middle aromatic hydrocarbon solvent choosing
One kind from toluene, dimethylbenzene.
5. assay method according to claim 2, it is characterised in that 1) 1. middle alcohols and aromatic hydrocarbons are mixed for the preparation process of sample
The volume proportion of bonding solvent, alcohols and aromatic hydrocarbons is 2:1、1:1 or 1:2.
6. assay method according to claim 2, it is characterised in that 2) the acquisition step of the infrared spectrogram of sample to be tested
1. in 400cm-1~2000cm-1In the range of, determine the infrared spectrum of air.
7. assay method according to claim 2, it is characterised in that 2) the acquisition step of the infrared spectrogram of sample to be tested
2. in 400cm-1~2000cm-1In the range of, determine the infrared spectrum of sample to be tested.
8. assay method according to claim 2, it is characterised in that 2) the acquisition step of the infrared spectrogram of sample to be tested
1. in 600cm-1~1600cm-1In the range of, determine the infrared spectrum of air.
9. assay method according to claim 2, it is characterised in that 2) the acquisition step of the infrared spectrogram of sample to be tested
2. in 600cm-1~1600cm-1In the range of, determine the infrared spectrum of sample to be tested.
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