CN110068617A - With the extraordinary fluoropolymer-containing method of gel osmoticing chromatogram analysis - Google Patents
With the extraordinary fluoropolymer-containing method of gel osmoticing chromatogram analysis Download PDFInfo
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- CN110068617A CN110068617A CN201810059662.4A CN201810059662A CN110068617A CN 110068617 A CN110068617 A CN 110068617A CN 201810059662 A CN201810059662 A CN 201810059662A CN 110068617 A CN110068617 A CN 110068617A
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- fluoropolymer
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
Abstract
The invention belongs to technical field of chromatography, it is proposed a kind of extraordinary fluoropolymer-containing method of gel osmoticing chromatogram analysis, comprising steps of the preparation of (one) standard sample solution, (2) production of standard curve, the standard sample solution of preparation is analyzed one by one with 35 DEG C of chromatographic condition of column temperature using high performance liquid chromatograph, standard curve is produced, determines calibration curve equation；(3) analysis of actual sample relative molecular weight and its distribution.Method proposed by the present invention, it can be used for weight average molecular weight in the analysis of the extraordinary fluoropolymer relative molecular weight and its distribution of 200-2000000, the reference method of science is provided for the control and improvement of extraordinary fluoropolymer manufacture technique, also it can be used as the enterprise-quality examination criteria of article, and its mechanism of polymerization can be studied.
Description
Technical field
The invention belongs to technical field of chromatography, and in particular to one kind is directed to fluoropolymer-containing detection method.
Background technique
Extraordinary fluoropolymer refers mainly to be obtained by vinylidene and chlorotrifluoroethylene by free radical polymerization fluorine-containing total
Polymer.It is member more special in high molecular material family because its strand has fluorine atom substitution.Due to the key of C-F key
485kJmol can be up to-1, it is that bond energy is maximum in all covalent bonds, therefore be one of most stable of chemical bond.A large amount of C-F
The presence of key make polymer have excellent heat resistance, corrosion resistance, weatherability, solvent resistance, resistance to acid and alkali, anti-flammability,
Insulating properties and low-surface-energy are widely used the fields such as automobile, space flight, defence and military, petrochemical industry.Extraordinary fluoropolymer
The molecular chain conformation of object is one of the basic parameter for measuring high molecular material, mechanical property, the flowing of it and high molecular material
Many critical natures such as performance, solubility property are all closely related.
In the prior art, still without for extraordinary fluoropolymer-containing suitable assay, can obtain simultaneously molecular weight and
The data of relative molecular mass distribution.
Summary of the invention
For the shortcomings in the field, it is fluorine-containing with gel osmoticing chromatogram analysis special type that the purpose of the present invention is to propose to a kind of
The method of polymer.
Realize above-mentioned purpose technical solution of the present invention are as follows:
A kind of extraordinary fluoropolymer-containing method of gel osmoticing chromatogram analysis, comprising steps of
(1) preparation of standard sample solution
4~8 polystyrene standard samples of weight-average molar mass Mw from 3000 to 4000000 are successively accurately weighed, are used
Tetrahydrofuran is dissolved as the series standard solution that concentration is 0.2~1.0mg/mL；
(2) production of standard curve
Using Shimadzu high performance liquid chromatograph, with 35 DEG C of chromatographic condition of column temperature, to the standard sample solution of above-mentioned preparation
It is analyzed one by one, produces standard curve, determine calibration curve equation；
(3) analysis of actual sample relative molecular weight and its distribution:
By extraordinary fluoropolymer samples, it is dissolved in tetrahydrofuran, is configured to the sample solution that concentration is 8~20mg/mL, with
The chromatographic condition directly carries out analysis measurement, obtains the molecular chain conformation of extraordinary fluoropolymer samples.
Preferably, in step (1), successively accurately weigh weight-average molar mass Mw be 3850000 respectively, 956000,
189000,52400,13000,3790 polystyrene standard sample, being dissolved as concentration with tetrahydrofuran is 0.2~1.0mg/mL
Series standard solution.
Wherein, in step (2), chromatographic column is silica gel chromatographic column, and column length 300mm, internal diameter 7.5mm, mobile phase is chromatographically pure
Tetrahydrofuran, flow velocity 1.0mL/min.
Further, the filler partial size of the silica gel chromatographic column is 5 μm.
Wherein, in step (2), the standard curve of logMw- elution time is drawn, wherein Mw is weight average molecular weight.
Preferably, in step (3), it is to be measured special type fluoropolymer samples be dissolved in tetrahydrofuran, be kept in dark place 48 hours with
On with dissolve completely, after stable system use six-way valve quantitative loop 20uL sample introduction.
Wherein, in step (3) chromatographic determination, the symmetrical chromatographic peak that elution time is 4~7min is extraordinary fluoropolymer
Sample peak, 9~11min are solvent peak.
The beneficial effects of the present invention are:
1, it is opposite in the extraordinary fluoropolymer of 200-2000000 to can be used for weight average molecular weight for method proposed by the present invention
The analysis of molecular weight and distribution provides the reference side of science for the control and improvement of extraordinary fluoropolymer manufacture technique
Method, also can be used as the enterprise-quality examination criteria of article, and can study its mechanism of polymerization.
2, the present invention convenient for operation, reproducible, precision is high.
Detailed description of the invention
Fig. 1 is that the chromatography of polystyrene standards flows out figure.
Fig. 2 is the canonical plotting of polystyrene standards.
Fig. 3 is the GPC spectrogram of gel osmoticing chromatogram analysis special type fluoropolymer samples.
Fig. 4 is extraordinary fluoropolymer samples chromatogram and standard curve comparison diagram.
Fig. 5 is extraordinary fluoropolymer relative molecular mass differential distribution curve and integral distribution curve.
Specific embodiment
With reference to the accompanying drawings and examples, specific embodiments of the present invention will be described in further detail.
If not otherwise specified, means employed in specific embodiment are this field conventional technology.
Embodiment 1
(1) preparation of standard sample solution
According to test substance molecular weight feature, choose weight-average molar mass Mw be 3850000 respectively, 956000,189000,
52400, each 0.005g of 13000,3790 polystyrene standard sample, and being dissolved to concentration with 10mL tetrahydrofuran is 0.5mg/
The series standard solution of mL.
(2) selection of chromatographiccondition
1, chromatographiccondition
Agilent Plgel using organic solvent is applicable in and usually to measure medium and relatively large molecular mass sample
5 μm of MIXED-C, partial size chromatographic columns are tested.The result shows that the polystyrene standards of 6 kinds of different relative molecular masses are in this color
It can be efficiently separated on spectrum column, and peak shape is narrow, column effect is high.Extraordinary fluoropolymer samples retention time in spectrogram is moderate,
Peak shape is good, therefore selects the chromatographic column.
Mobile phase: chromatography pure tetrahydrofuran (U.S. TEDIA)
Guard column: Shimadzu Shim-pack GPC-800P
Column temperature: 35 DEG C
Flow velocity: 1.0mL/min
2, instrument equipment
Shimadzu high performance liquid chromatograph SHIMADZ LC-10A, configuration LC-10AD pump, CTO-10A column oven, RID-10A
Differential refraction detector.
3, specifications of raw materials
Polystyrene standards matter (PS standard specimen)
Tetrahydrofuran: HPLC grades (moisture content < 0.5%)
(3) production of standard curve
After chromatography detection architecture is stablized, using above-mentioned chromatographic condition SHIMADZ LC-10A, differential refraction detector
RID-10A, chromatographic column Agilent Plgel MIXED-C, column length 300mm, internal diameter 7.5mm, mobile phase chromatography pure tetrahydrofuran
(THF), flow velocity 1.0mL/min, analyzes the standard sample solution of above-mentioned preparation one by one by 35 DEG C of column temperature.With elution time
Logarithm for abscissa, weight average molecular weight is ordinate, produces standard curve, obtains linear equation, obtains linear correlation
Coefficient.
Fig. 1 is that the chromatography of concentration 0.5mg/mL polystyrene mixed sample flows out figure.The ordinate on the left side Fig. 1 is voltage letter
Number value V, the ordinate on the right are voltage signal values V, and abscissa is time (min)；Standard curve is shown in that Fig. 2, abscissa are to retain
Time (min), ordinate are logMw(weight average molecular weight)；Setting-out line related coefficient is 0.996.
Calibration curve equation are as follows:
LogMw=-0.96066X+10.70339
Wherein Mw--- weight average molecular weight
X --- elution time
As shown in Figure 2, weight-average molar mass MwAt 3790-3850000, logarithm logMwWith retention time in good
Linear relationship.
(4) analysis of relative molecular weight and its distribution
It weighs extraordinary fluoropolymer samples to be measured and is dissolved in THF, being configured to concentration is appointing within the scope of 8~20mg/mL
Meaning concentration value is ok, and optimum concentration value is 10mg/mL；Testing sample solution is placed in conical flask, is sealed with port grinding bottle lid
Firmly bottleneck is kept in dark place 48 hours and dissolves completely to sample, uses six-way valve quantitative loop 20uL sample introduction, after stable system with step
(2), (three) same chromatographic condition directly carries out analysis measurement.The ordinate on the left side Fig. 3 is voltage signal values V, and the right is indulged
Coordinate is voltage signal values V, and abscissa is time (min).
The symmetrical chromatographic peak that elution time is 4~7min as shown in Figure 3 is extraordinary fluoropolymer samples peak, 9~11min
It is solvent peak, and 13min can elute completely a collection of sample from chromatographic column.The baseline stability of map, does not drift about, and
In symmetrical Gaussian peak, show that this method is suitable for extraordinary fluoropolymer.By Class-VP workstation software through data processing point
The average weight-molecular mass Mw for analysing derived sample is 519527g/mol, and number-average molecular weight Mn is 213709g/mol, opposite point
It is 2.43 that protonatomic mass, which is distributed Mw/Mn, shows that the relative molecular mass distribution of sample is relatively narrow, relative molecular mass uniformity is preferable.
The extraordinary fluoropolymer samples chromatogram and standard curve comparison diagram of Fig. 4 shows Mw between standards calibration curve.Fig. 5's
Extraordinary fluoropolymer relative molecular mass differential distribution curve and integral distribution curve show to be located in relative molecular mass
Part between logMw=5.1~5.7, integral distribution curve tangent slope is maximum, i.e. point of the relative molecular mass in this section
Cloth is most, accounts for about the 60% of entire relative molecular mass, and accumulation of the relative molecular mass less than logMw=5.7 reaches 80%.
(5) reproducibility is tested
It weighs appropriate extraordinary fluoropolymer samples and is dissolved in tetrahydrofuran (sample as step 4), be configured to concentration
For the sample solution of 10mg/mL, the six-way valve quantitative loop after sample dissolves complete stable system is respectively placed in three sample bottles
20uL sample introduction after chromatograph stable system, carries out analysis measurement with above-mentioned chromatographic condition.Specific determination data is shown in Table 1.
The extraordinary fluoropolymer reproducibility experimental data of table 1
| Sample number into spectrum | Mw/(g.mol-1) | Mn/(g.mol-1) | Mw/Mn |
| 1 | 519527 | 213709 | 2.43 |
| 2 | 536851 | 223687 | 2.40 |
| 3 | 506899 | 210331 | 2.41 |
The relative standard deviation RSD that sample is measured it can be seen from the data that table 1 measures, which is far smaller than in GPC specification, to be wanted
5% asked illustrates that the analysis method is reproducible, precision is high.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, several improvement and replacement can also be made, these are improved and replacement
Also it should be regarded as protection scope of the present invention.
Claims (7)
1. a kind of extraordinary fluoropolymer-containing method of gel osmoticing chromatogram analysis, which is characterized in that comprising steps of
(1) preparation of standard sample solution
4~8 polystyrene standard samples for successively accurately weighing weight-average molar mass Mw from 3000 to 4000000, use tetrahydro
Furans is dissolved as the series standard solution that concentration is 0.2~1.0mg/mL；
(2) production of standard curve
The standard sample solution of preparation is analyzed one by one with 35 DEG C of chromatographic condition of column temperature using high performance liquid chromatograph,
Standard curve is produced, determines calibration curve equation；
(3) analysis of actual sample relative molecular weight and its distribution:
Extraordinary fluoropolymer samples to be measured are dissolved in tetrahydrofuran, are configured to the sample solution that concentration is 8~20mg/mL, with
The chromatographic condition of step (2) carries out analysis measurement, obtains the molecular chain conformation of extraordinary fluoropolymer samples.
2. the method according to claim 1, wherein successively accurately weighing weight-average molar mass in step (1)
Mw is 3850000,956000,189000,52400,13000,3790 polystyrene standard sample respectively, molten with tetrahydrofuran
Solution is the series standard solution that concentration is 0.5mg/mL.
3. the method according to claim 1, wherein chromatographic column is silica gel chromatographic column, column length in step (2)
300mm, internal diameter 7.5mm, mobile phase are chromatography pure tetrahydrofuran, flow velocity 1.0mL/min.
4. according to the method described in claim 3, it is characterized in that, the filler partial size of the silica gel chromatographic column is 5 μm.
5. method according to any one of claims 1 to 4, which is characterized in that in step (2), when drawing logMw- elution
Between standard curve, wherein Mw be weight average molecular weight.
6. method according to any one of claims 1 to 4, which is characterized in that in step (3), special type fluoropolymer to be measured
Object sample is dissolved in tetrahydrofuran, is kept in dark place 48 hours or more to dissolve completely, six-way valve quantitative loop is used after stable system
20uL sample introduction.
7. method according to any one of claims 1 to 4, which is characterized in that in step (3) chromatographic determination, elution time
Symmetrical chromatographic peak for 4~7min is extraordinary fluoropolymer samples peak, and 9~11min is solvent peak.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114235992A (en) * | 2021-11-30 | 2022-03-25 | 湖北航天化学技术研究所 | Method for measuring contents of different types of PET (polyethylene terephthalate) |
Citations (2)
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| CN101281176A (en) * | 2008-05-16 | 2008-10-08 | 中国石油兰州石油化工公司 | Method for analyzing C5 hydrogenation hydrocarbon resin relative molecular weight and distribution with jelly glue pervasion chromatogram |
| CN106198799A (en) * | 2016-07-04 | 2016-12-07 | 巨化集团技术中心 | A kind of analysis method of PFPE relative molecular weight and its distribution |
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2018
- 2018-01-22 CN CN201810059662.4A patent/CN110068617A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101281176A (en) * | 2008-05-16 | 2008-10-08 | 中国石油兰州石油化工公司 | Method for analyzing C5 hydrogenation hydrocarbon resin relative molecular weight and distribution with jelly glue pervasion chromatogram |
| CN106198799A (en) * | 2016-07-04 | 2016-12-07 | 巨化集团技术中心 | A kind of analysis method of PFPE relative molecular weight and its distribution |
Non-Patent Citations (2)
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| 陶蕙芬 等: "凝胶渗透色谱法测定偏氟乙烯-六氟乙烯共聚物的分子量及其分布", 《色谱》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114235992A (en) * | 2021-11-30 | 2022-03-25 | 湖北航天化学技术研究所 | Method for measuring contents of different types of PET (polyethylene terephthalate) |
| CN114235992B (en) * | 2021-11-30 | 2023-12-12 | 湖北航天化学技术研究所 | Method for measuring content of PET of different types |
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