CN109725082A - A kind of detection method of ethyl orthosilicate purity - Google Patents
A kind of detection method of ethyl orthosilicate purity Download PDFInfo
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- CN109725082A CN109725082A CN201910052485.1A CN201910052485A CN109725082A CN 109725082 A CN109725082 A CN 109725082A CN 201910052485 A CN201910052485 A CN 201910052485A CN 109725082 A CN109725082 A CN 109725082A
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Abstract
The present invention provides a kind of detection methods of ethyl orthosilicate purity, comprising: by ethyl orthosilicate sample to be tested through gas chromatographic detection, obtains gas-chromatography spectrogram；The gas chromatogram is handled using area normalization method, obtains the content of each component in ethyl orthosilicate.Chromatography heating degree in the gas chromatographic detection are as follows: 60 DEG C~80 DEG C of initial temperature, keep 1~3min, be warming up to 170 DEG C~190 DEG C with 8~12 DEG C/min, keep 5~8min.Compared with prior art, the present invention using the boiling point of impurity composition in ethyl orthosilicate, molecular weight, polarity power difference, separation signal is obtained by gas-chromatography, certain ion signal is formed after gas chromatography detector ionizes, it is shown in above spectrogram after amplification conversion again, the content of these tested components is directly proportional to the peak area of its appearance, each component content can be obtained by non-stationary, using area normalization method, detection method is quickly, accurately, simply.
Description
Technical field
The invention belongs to technical field of analysis and detection more particularly to a kind of detection methods of ethyl orthosilicate purity.
Background technique
The purity analysis of ethyl orthosilicate is considerably less in the industry, this is because ethyl orthosilicate is main on the market at present
Applied to manufacture chemicals-resistant coating and heat-resisting paint, organic silicon solvent and hot investment casting binder, as ethyl orthosilicate is complete
After all-hydrolytic, superfine silica powder is generated, for manufacturing fluorescent powder, the performance and manufacture silicon of other resins can also be improved
The raw material of high-molecular compound, these fields are not high to purity requirement, and ethyl orthosilicate there is no country and industry mark at home
Standard leads to many companies and is not concerned with the purity of ethyl orthosilicate.
With the expansion of market application field, ethyl orthosilicate is increasingly extensive in the application of semicon industry.When positive silicic acid
When ethyl ester (TEOS) is used for LPCVD, TEOS flashes to gaseous state from liquid, decomposes under 700 DEG C~750 DEG C, 300mTOR pressure
Silicon chip surface deposit generates silica membrane, and the rate of silica membrane deposition can achieve 50 à/min, the thickness of film
For uniformity less than 3%, these excellent operational characteristiies and its distinguishing feature in terms of safety in utilization make ethyl orthosilicate method
LPCVD has gradually become the prevailing technology of cvd silicon dioxide film, and then constantly narrowing with integrated circuit line width, to just
The product purity of silester requires also to be increasingly stringenter.
Currently, ethyl orthosilicate mainly determines its purity to detect its dioxide-containing silica, but this technology pair
In subsequent applications by technical restriction in terms of accuracy, and for the measurement blank out of specific impurity content.This is because
Ethyl orthosilicate impurity is complicated, and the impurity of isomer and similitude is more, and physical parameter is similar, leads to the knot of analysis
Fruit deviation is big, when carrying out quantitative analysis especially with external standard method, can there is two difficult points, one be without legal, it is another
A is quantitative inaccuracy, because standard substance is not present on the market, causes analysis method complicated.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that provide a kind of detection method of ethyl orthosilicate purity,
Fast and accurately property is higher for the detection method.
The present invention provides a kind of detection methods of ethyl orthosilicate purity, comprising:
By ethyl orthosilicate sample to be tested through gas chromatographic detection, gas-chromatography spectrogram is obtained；
The gas chromatogram is handled using area normalization method, obtains the content of each component in ethyl orthosilicate；
Chromatography heats up degree in the gas chromatographic detection are as follows: 60 DEG C~80 DEG C of initial temperature, 1~3min is kept, with 8~
12 DEG C/min is warming up to 170 DEG C~190 DEG C, keeps 5~8min.
Preferably, the chromatography heating degree are as follows: 75 DEG C of initial temperature, keep 2min, be warming up to 185 with 10 DEG C/min
DEG C, keep 6min.
Preferably, chromatographic column is 5%- diphenyl 95%- dimethyl polysiloxane capillary in the gas chromatographic detection
Chromatographic column.
Preferably, the split ratio of sample volume is 1:100~1:120 in the gas chromatographic detection.
Preferably, the temperature of detector is 240 DEG C~260 DEG C in the gas chromatographic detection.
Preferably, the temperature of sample injector is 190 DEG C~210 DEG C in the gas chromatographic detection.
Preferably, the detector of the gas chromatographic detection is FID hydrogen flame detector.
Preferably, the flow of hydrogen is 40~45ml/min when the FID hydrogen flame detector is lighted a fire；The flow of air is
400ml/min。
Preferably, the column flow of the gas chromatographic detection is 0.8~1.2ml/min.
Preferably, the sample volume of the gas chromatographic detection is 0.2~0.4 μ l.
The present invention provides a kind of detection methods of ethyl orthosilicate purity, comprising: passes through ethyl orthosilicate sample to be tested
Gas chromatographic detection obtains gas-chromatography spectrogram；The gas chromatogram is handled using area normalization method, obtains positive silicic acid second
Chromatography heating degree in gas chromatographic detection described in the content of each component in ester are as follows: 60 DEG C~80 DEG C of initial temperature, holding 1~
3min is warming up to 170 DEG C~190 DEG C with 8~12 DEG C/min, keeps 5~8min.Compared with prior art, the present invention is using just
The boiling point of impurity composition in silester, molecular weight, polarity power difference, separation signal is obtained by gas-chromatography, these
Separation signal forms certain ion signal after gas chromatography detector ionizes, then is shown on spectrogram after amplification conversion
The content in face, these tested components is directly proportional to the peak area of its appearance, can be obtained by non-stationary, using area normalization method
The content of each component, detection method is quickly, accurately, simply.
Detailed description of the invention
Fig. 1 is the gas chromatogram and quantitative analysis results that the embodiment of the present invention 1 obtains；
Fig. 2 is the gas chromatogram and quantitative analysis results that comparative example 1 of the present invention obtains；
Fig. 3 is the gas chromatogram and quantitative analysis results that comparative example 2 of the present invention obtains.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
The present invention provides a kind of detection methods of ethyl orthosilicate purity, comprising: passes through ethyl orthosilicate sample to be tested
Gas chromatographic detection obtains gas-chromatography spectrogram；The gas chromatogram is handled using area normalization method, obtains positive silicic acid second
The content of each component in ester；Chromatography heating degree in the gas chromatographic detection are as follows: 60 DEG C~80 DEG C of initial temperature, holding 1~
3min is warming up to 170 DEG C~190 DEG C with 8~12 DEG C/min, keeps 5~8min.
The present invention using the boiling point of impurity composition in ethyl orthosilicate, molecular weight, polarity power difference, pass through gas phase color
Spectrum obtains separation signal, these separation signals form certain ion signal after gas chromatography detector ionizes, then through amplifying
It is shown in above spectrogram after conversion, the content of these tested components is directly proportional to the peak area of its appearance, by non-stationary, uses
The content of each component can be obtained in area normalization method, and detection method is quickly, accurately, simply.
Wherein, the ethyl orthosilicate sample to be tested is the ethyl orthosilicate well known to those skilled in the art for needing to detect
Sample has no special limitation, can be the raw material, the substance in preparation process and preparation for preparing high-purity ethyl orthosilicate
Obtained high-purity ethyl orthosilicate etc..
By ethyl orthosilicate sample to be tested through gas chromatographic detection, gas-chromatography spectrogram is obtained.
Equipment used in the gas chromatographic detection is gas chromatograph well known to those skilled in the art, has no spy
Different limitation, the detector of heretofore described gas chromatographic detection are preferably FID hydrogen flame detector.
Before detection, carrier gas nitrogen preferably will be first passed through in gas chromatograph (purity is at least 99.999%)；Carrier gas stream
Amount is preferably 20~40ml/min, more preferably 30ml/min；When temperature rises to 120 DEG C, air door and hydrogen are opened simultaneously
Feed channel valve, the flow of air are preferably 400ml/min, and the flow of hydrogen (purity is at least 99.999%) is 35ml/
Min lights FID；When igniting, the flow of hydrogen is preferably 40~45ml/min, more preferably 40ml/min；The flow of air is excellent
It is selected as 400ml/min；Together according to temperature programming setting, sample introduction is waited after polar curve is steady.The chromatography heating degree is preferred
Are as follows: 65 DEG C~75 DEG C of initial temperature, 1~3min is kept, is warming up to 175 DEG C~185 DEG C with 8~12 DEG C/min, keep 5~
8min；More preferably 75 DEG C of initial temperature keeps 1~3min, is warming up to 185 DEG C with 8~12 DEG C/min, keeps 5~8min；Again
Preferably 75 DEG C of initial temperature keeps 2min, is warming up to 185 DEG C with 10 DEG C/min, keeps 6min；The chromatography of the gas-chromatography
Column is preferably low pole capillary chromatographic column, more preferably 5%- diphenyl 95%- dimethyl polysiloxane capillary chromatographic column；
The length of the chromatographic column is preferably 30m；Internal diameter is preferably 0.25 μm；Film thickness is preferably 250 μm.
It in the present invention, is deviation caused by elimination manually sample injection, it is preferred to use automatic sampling；The positive silicon
The sample volume of acetoacetic ester sample to be tested is preferably 0.2~0.4 μ l, more preferably 0.2 μ l；The split ratio of sample volume is preferably 1:
100~1:120；Column flow is preferably 0.8~1.2ml/min, more preferably 0.9~1.1ml/min, is further preferably 1ml/min.
The temperature of sample injector is preferably 190 DEG C~210 DEG C, more preferably 195 DEG C~205 in the gas chromatographic detection
DEG C, it is further preferably 200 DEG C；The temperature of detector is preferably 240 DEG C~260 DEG C, more preferably 245 DEG C~255 DEG C, further preferably for
250℃。
The present invention is strong and weak different using the boiling point, molecular weight, polarity of the impurity composition in ethyl orthosilicate, small-bore
Hp-5 is that separation signal, (5%)-hexichol are obtained on (5%)-diphenyl (95%)-dimethyl polysiloxane capillary chromatographic column
Base (95%)-dimethyl polysiloxane capillary chromatographic column category weak polarity capillary column, and the signal of these separation is by hydrogen flame
Certain ion signal is formed after detector, that is, fid detector ionization, is shown in above spectrogram after amplifier is converted, these quilts
The content of component and the peak area direct proportionality of its appearance are surveyed, every component is accounted for according to the subitem peak area of every component
The gas chromatogram is handled using area normalization method, obtains containing for each component in ethyl orthosilicate by the ratio of the gross area
Amount, specific calculating process are as follows:
Wherein V is volume fraction (%) of the component to be detected in ethyl orthosilicate；
A1+A2+A3+A4+ ... is the peak area (pA.s) of all components in ethyl orthosilicate；
The peak area (pA.s) of component to be detected in Ai-ethyl orthosilicate.
By the conversion of this area and content, calculates A1, A2, A3 ... in ethyl orthosilicate and wait containing for every impurity
Amount, while can also calculate the content of ethyl orthosilicate.
Detection method provided by the invention is easy to operate, low in cost, does not need the analytical equipment of increase and complexity；Analysis
Speed is fast, and detection accuracy is high, using area normalization method, does not need to be quantified with standard sample, carries out without standard substance
It is qualitative；Analytical cycle is short, and analysis detection limit is also low, can continuously recycle sample introduction, does not have to hand sampling, reduces manually-operated inclined
Difference so the detection limit of fractions tested is also low, and can make the impurity of low content because the detection limit of instrument is low.
In order to further illustrate the present invention, with reference to embodiments to a kind of ethyl orthosilicate purity provided by the invention
Detection method is described in detail.
Reagent used in following embodiment is commercially available.
Embodiment 1
1, instrument prepares:
Analytical equipment GC2014C gas chromatograph: Shimadzu Instrument Ltd. has hydrogen flame detector FID.
Hp-5 fills (5%)-diphenyl (95%)-dimethyl polysiloxane capillary chromatographic column: long 30m, 0.25 μ of internal diameter
M, 250 μm of film thickness.
Nitrogen, hydrogen and air, purity is at least 99.999%.
Head-space sampler is furnished with automatic sample handling system.
Temperature setting, column temperature: 75 DEG C of 2min, 10 DEG C/min, 185 DEG C of 6min, detector: 250 DEG C, sample injector: 200 DEG C.
Split ratio: 1:120.0.
Column flow: 1ml/min.
Sample volume: 0.2 μ l.
2, be switched on work, first carrier gas nitrogen will be passed through in gas chromatograph, and the flow that its carrier gas is arranged is 30mL/min, so
After start gas chromatograph；When temperature rises to 120 DEG C, air door and Hydrogen Line valve, the flow of air are opened simultaneously
For 400mL/min, the flow of hydrogen is 35mL/min, lights FID, and when igniting, the flow of hydrogen is 40mL/min；According to program
Heating is to be arranged instrument；Sample introduction is waited after baseline is steady.
3, it samples
Sample collection is come in by 1ml capacity, when there are multiple samples, needs to prepare multiple volumetric flasks and carries out sample receipts
Collection, while waste liquid bottle is got out, to be used when sample introduction flushing.
4, sample introduction
After autosampler installation peace, opens power supply and be configured.
(1) sample clean time 2 times, frequency injection 3 times, 0.2 μ l of sample injection rate.
(2) solvent cleans 1 time, extracts number 5 times, residence time 0.2s, and sample introduction speed is high speed sample introduction.
Sample is successively put into below autosampler, sample introduction is actuated for inside system.The number of sample introduction is at least 3
It is secondary, finally seek the average value of sample gas constituent content；It is to be noted that gap between the area and average value of same component
It is subjected within 5%, the gap between different samples can receive within 5%, otherwise sample introduction again, until condition meets
It can.
5, analysis detection
(1) processing software inside chromatographic work station is clicked, setting area normalizing method is integrated by selecting, color can be passed through
Spectrum work station directly reads out the volume fraction V of various components；The calculating of volume fraction is exactly to occupy percentage by area
What calculating was got.
(2) furnace temperature of instrument is risen into 200 DEG C of aging pillars, while tail is blown and is set as 12mL/min, it will be in pillar
Other impurities, which are driven out of, to be come, and otherwise can be polluted pillar and be influenced next testing result, and prolonged accumulation can cause pillar to block
Deng；The activation of pillar will be carried out after each sample introduction, to be analyzed next time.
200 DEG C after aging pillar 2~3 hours, long-time aging pillar can reduce column effect function, be cooled to 40 DEG C and just close
Chromatograph finally closes gas source；
6, numerical value calculates
The volume fraction (V) of each component in ethyl orthosilicate can be calculated to obtain according to instrument formula (1).
Wherein V: volume fraction (%) of the component to be detected in ethyl orthosilicate；
The peak area (pA.s) of all components in A1+A2+A3+A4+ ... ethyl orthosilicate；
The peak area (pA.s) of component to be detected in Ai-ethyl orthosilicate
By the conversion of this area and content, A1, A2, A3 ... in ethyl orthosilicate can be calculated using this formula and waited respectively
The content of item impurity, while can also calculate the content of ethyl orthosilicate.
The gas chromatogram and quantitative analysis results that embodiment 1 obtains are shown in Fig. 1.
Comparative example 1
1, instrument prepares:
(1) analytical equipment GC2014C gas chromatograph: Shimadzu Instrument Ltd. has hydrogen flame detector FID；
(2) hp-5 fills (5%)-diphenyl (95%)-dimethyl polysiloxane capillary chromatographic column: long 30m, internal diameter
0.25 μm, 250 μm of film thickness.
(3) nitrogen, hydrogen and air, purity is at least 99.999%.
(4) head-space sampler is furnished with automatic sample handling system.
(5) temperature setting, column temperature: 70 DEG C of 2min, 10 DEG C/min, 180 DEG C of 6min, detector: 250 DEG C, sample injector: 200
℃。
(6) split ratio: 1:200.0.
(7) column flow: 1ml/min.
(8) sample volume: 1.0 μ l.
2, be switched on work, first carrier gas nitrogen will be passed through in gas-chromatography, and the flow that its carrier gas is arranged is 30mL/min, then
Start gas chromatograph；When temperature rises to 120 DEG C, air door and Hydrogen Line valve are opened simultaneously, the flow of air is
400mL/min, the flow of hydrogen are 35mL/min, light FID, and when igniting, the flow of hydrogen is 40mL/min；According to program liter
Temperature is arranged instrument；Sample introduction is waited after baseline is steady.
Sampling, sample introduction and other operations are the same as embodiment 1.
The gas chromatogram and quantitative analysis results that comparative example 1 obtains are shown in Fig. 2.As shown in Figure 2, the shunting measured into school is changed
Than appearance effect is unobvious, and many components do not come out.Only have main peak.
Comparative example 2
1, instrument prepares:
Analytical equipment GC2014C gas chromatograph: Shimadzu Instrument Ltd. has hydrogen flame detector FID；
DB-5 capillary chromatographic column: long 30m, 0.25 μm of internal diameter, 250 μm of film thickness.
Nitrogen, hydrogen and air, purity is at least 99.999%.
Head-space sampler is furnished with automatic sample handling system.
Temperature setting, column temperature: 70 DEG C of 2min, 10 DEG C/min, 180 DEG C of 6min, detector: 250 DEG C, sample injector: 200 DEG C.
Split ratio: 1:100.0.
Column flow: 1ml/min.
Sample volume: 0.2 μ l.
2, be switched on work, first carrier gas nitrogen will be passed through in gas-chromatography, and the flow that its carrier gas is arranged is 30mL/min, then
Start gas chromatograph；When temperature rises to 120 DEG C, air door and Hydrogen Line valve are opened simultaneously, the flow of air is
400mL/min, the flow of hydrogen are 35mL/min, light FID, and when igniting, the flow of hydrogen is 40mL/min；According to program liter
Temperature is arranged instrument；Sample introduction is waited after baseline is steady.
Sampling, sample introduction and other operations are the same as embodiment 1.
The gas chromatogram and quantitative analysis results that comparative example 2 obtains are shown in Fig. 3.From the figure 3, it may be seen that selecting equivalent chromatography
When column DB-5, appearance effect is unobvious, and many components do not come out, only has main peak and time main peak, impurity peaks separation not yet in effect.
Claims (10)
1. a kind of detection method of ethyl orthosilicate purity characterized by comprising
By ethyl orthosilicate sample to be tested through gas chromatographic detection, gas-chromatography spectrogram is obtained；
The gas chromatogram is handled using area normalization method, obtains the content of each component in ethyl orthosilicate；
Chromatography heating degree in the gas chromatographic detection are as follows: 60 DEG C~80 DEG C of initial temperature, 1~3min is kept, with 8~12
DEG C/min is warming up to 170 DEG C~190 DEG C, keep 5~8min.
2. detection method according to claim 1, which is characterized in that the chromatography heating degree are as follows: 75 DEG C of initial temperature,
2min is kept, 185 DEG C is warming up to 10 DEG C/min, keeps 6min.
3. detection method according to claim 1, which is characterized in that chromatographic column is 5%- bis- in the gas chromatographic detection
Phenyl 95%- dimethyl polysiloxane capillary chromatographic column.
4. detection method according to claim 1, which is characterized in that the split ratio of sample volume in the gas chromatographic detection
For 1:100~1:120.
5. detection method according to claim 1, which is characterized in that the temperature of detector is in the gas chromatographic detection
240 DEG C~260 DEG C.
6. detection method according to claim 1, which is characterized in that the temperature of sample injector is in the gas chromatographic detection
190 DEG C~210 DEG C.
7. detection method according to claim 1, which is characterized in that the detector of the gas chromatographic detection is FID hydrogen
Flame detector.
8. detection method according to claim 6, which is characterized in that hydrogen when the FID hydrogen flame detector is lighted a fire
Flow is 40~45ml/min；The flow of air is 400ml/min.
9. detection method according to claim 1, which is characterized in that the column flow of the gas chromatographic detection be 0.8~
1.2ml/min。
10. detection method according to claim 1, which is characterized in that the sample volume of the gas chromatographic detection be 0.2~
0.4μl。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111929369A (en) * | 2019-05-13 | 2020-11-13 | 定远县云森科技有限公司 | Method for measuring sulfur content in high-pressure sulfurized isobutylene by gas chromatography |
-
2019
- 2019-01-21 CN CN201910052485.1A patent/CN109725082A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111929369A (en) * | 2019-05-13 | 2020-11-13 | 定远县云森科技有限公司 | Method for measuring sulfur content in high-pressure sulfurized isobutylene by gas chromatography |
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Application publication date: 20190507 |