CN107290446B - A kind of molecular weight or molecular weight distribution detection method of alkaline polymer - Google Patents
A kind of molecular weight or molecular weight distribution detection method of alkaline polymer Download PDFInfo
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Abstract
The present invention relates to high molecular material detection technique fields, in particular to the molecular weight or molecular weight distribution detection method of a kind of alkaline polymer prepare acetate methanol solution, and acetate methanol solution is added in alkaline polymer sample, tetrahydrofuran is added after dissolution, even rear filtering sample introduction is shaken in dissolution.Technical solution of the present invention pre-processes detection with sample, subsequent detection is used for after being completely dissolved alkaline polymer, and, sample pretreating method will not all generate too big negative effect to stability, the accuracy of testing result of sample itself, provide a technology place mat for alkaline polymerization analyte detection.
Description
Technical field
The present invention relates to high molecular material detection technique field, in particular to the molecular weight or molecule of a kind of alkaline polymer
Amount distribution detection method.
Background technique
In high molecular material detection technique field, molecular weight distribution is measured, usually uses gel permeation chromatograph, ultraviolet
The case where detector, differential refraction detector, Organic chromatography column etc. are detected, and carry out qualitative molecular weight distribution from the variation at peak.
Chromatography detection.In these detection methods, sample is usually first dissolved using tetrahydrofuran, make the concentration of sample introduction solution between
0.1mg/ml is between 5mg/ml.But there are many high molecular polymers, be in apparent acid-base property, this results in these in apparent
The high molecular polymer of acid-base property cannot be dissolved in tetrahydrofuran well, led to detection inaccuracy or be unable to complete inspection
It surveys.
In the prior art, in view of the above-mentioned problems, the measure taken is a certain amount of acid to be added into sample to adjust sample
PH value stirs evenly, and then washes, and sample after treatment becomes solid and can be dissolved completely in gel permeation chromatography
In mobile phase tetrahydrofuran.And by the detection of a period of time discovery treated sample and unstable, increase at any time, molecule
Amount has the tendency that becoming larger.As recorded in CN105510508A.And it is found by high performance liquid chromatography detection, treated sample
Product structure is changed, and most of small molecule is washed with water in water-washing process.The method of direct acid adding washing is unable to table
Levy the true molecular amount and molecular weight distribution of polymer.
Demonstrating that treated by the spectrogram of liquid phase analysis, sample is implicitly present in problem, many in treated sample
Small molecule part has been washed with water, and finding the processing method of sample, there are Railway Project (1): by small point in liquid phase verification sample
Subdivision may be washed off in water-washing process, so weight average molecular weight result measured by treated sample is bigger than normal.And
Treated, and molecular weight analyte is distributed in that sample true molecular amount differing distribution is very remote, and treated, and sample cannot reflect sample
True structure.(2): treated, and molecular weight analyte is unstable, it is multiple batches of between it is not comparable due to detection time etc.
Property.And treated cannot really embody molecular weight analyte and molecular weight distribution.
Summary of the invention
In order to solve the above alkaline polymer in the prior art molecular weight and molecular weight distribution detection present in small point
The unstable problem of molecular weight analyte that subdivision may be washed off in water-washing process, treated, this application discloses one kind
More acurrate, the higher alkaline polymer of stability molecular weight or molecular weight distribution detection method.
What the present invention was obtained through the following steps:
A kind of molecular weight or molecular weight distribution detection method of alkaline polymer, before detection to alkaline polymer sample into
Row pretreatment, prepares acetate methanol solution, and alkaline polymer sample is added in acetate methanol solution, and tetrahydro furan is added after dissolution
It mutters, filters sample introduction after being uniformly dissolved.
The molecular weight or molecular weight distribution detection method, preferably the volume content of acetic acid is in acetate methanol solution
0.5-1.5%。
The molecular weight or molecular weight distribution detection method, preferably the volume content of acetic acid is in acetate methanol solution
1%。
The molecular weight or molecular weight distribution detection method, preferably alkaline polymer pH are 11.0-13.95.
Preferably 1mL acetic acid is added in 10mg alkaline polymer sample by the molecular weight or molecular weight distribution detection method
It is dissolved in methanol solution.
The molecular weight or molecular weight distribution detection method, the preferably molecular weight or molecular weight distribution detection method
For gel permeation chromatography, the sample pre-treatments of high performance liquid chromatography.
The molecular weight or molecular weight distribution detection method, preferably gel permeation chromatography testing conditions are as follows: mobile phase:
Tetrahydrofuran, column oven: 40 DEG C, sample volume: 200 μ L, ultraviolet wavelength: 270nm, flow velocity: 1mL/min.
Beneficial effects of the present invention:
Technical solution of the present invention pre-processes alkaline polymer sample, uses after being completely dissolved alkaline polymer
It is detected in subsequent molecular weight or molecular weight distribution, also, stability, testing result of the sample pretreating method to sample itself
Accuracy will not all generate too big negative effect, provide a technology place mat for alkaline polymerization analyte detection.
Detailed description of the invention
Fig. 1 is direct sample detection and detection gel permeation chromatography spectrogram after 48 hours in embodiment 1,
Fig. 2 is alkalescent phenol resin liquid phase spectrogram after acid processing in embodiment 1,
Fig. 3 is that sample carries out treated liquid phase spectrogram in embodiment 2.
Fig. 4 is that sample carries out treated gel permeation chromatography spectrogram in embodiment 2.
Specific embodiment
Invention is further explained combined with specific embodiments below:
Embodiment 1
It adds an acid in alkalescent phenol resin, adjusts pH value, then wash.Make alkalescent phenol resin sample at neutrality, so
It is added in tetrahydrofuran afterwards, is completely dissolved, is detected using gel permeation chromatography.It is directly detection and 48H after sample presentation in Fig. 1
Testing result afterwards, wherein peak to the left in two peaks is testing result after 48H.
It can be seen that sample all has occurred obviously through placement after a period of time, molecular weight and molecular weight distribution from spectrogram
Variation.
Detection is excessively criticized, finally determines that sample changes over time, molecular weight increases.It is several Comparative results in following table:
| Model | Same day sampling result | The next day sampling result |
| JF-SY151112 | 1207/2568 | 1255/3474 |
| JF-SY151112-1 | 1022/1911 | 1325/3216 |
| JF-SY151205-1 | 1371/2388 | 1482/2862 |
| JF-SY151205 | 1295/2208 | 1397/2626 |
| JF-SY151203 | 1185/1947 | 1310/2385 |
| JF-SY151203-1 | 1209/1965 | 1335/2530 |
There are some problems for sample of tentatively suspecting that treated by above-mentioned experiment, therefore do to the sample after sour neutralisation treatment
Liquid phase analysis, is shown in Fig. 2.Demonstrating that treated by the spectrogram of liquid phase analysis, sample is implicitly present in problem, treated sample
Many small molecule parts have been washed with water in product, by linking up with research and development department, it is found that the processing method of sample is asked there are several
Topic (1): it may be washed off in water-washing process by liquid phase verification sample small molecular part, so treated, sample is surveyed
The weight average molecular weight result obtained is bigger than normal.And treated that molecular weight analyte is distributed in sample true molecular amount differing distribution very
Far, treated, and sample cannot reflect the true structure of sample.(2): treated, and molecular weight analyte is unstable, it is multiple batches of it
Between there is no comparativity due to detection time etc..And treated cannot really embody molecular weight analyte and molecular weight
Distribution.
Embodiment 2
Alkali phenol resin belongs to the stronger resin of alkalinity, and dissolubility is very poor in tetrahydrofuran.By multi-solvents to sample
The dissolubility of product is developed with methanol sample dissolution, a certain amount of acetic acid is added into methanol.It is last true by test of many times
Fixed centesimal acetate methanol solution is the most suitable, and sample can be made to be completely dissolved and tetrahydrofuran can be added will not be again
Insoluble matter is precipitated.
It is legal by test rear are as follows: it weighs 10mg sample (pH 12.18) and 1mL acetate methanol solution is added, it is complete to sample
1mL tetrahydrofuran is added after fully dissolved, filters sample introduction after abundant dissolution rolling is even.It can directly be dissolved by this method sample,
Fig. 3 is the liquid phase spectrogram detected using efficient liquid phase, and Fig. 4 is alkali phenol resin molecular weight distribution detected.It can from spectrogram
To find out that sample increased significantly and liquid phase spectrogram relatively coincide compared with treated for small molecule part.
By the data accumulation of a period of time, result stability detected by improved method is higher, is in following table
The reperformance test of sample:
| Model | Testing result | The next day repetition measurement result |
| JF-3D-2 | 219/314 | 217/309 |
| External alkali phenol | 467/1363 | 464/1316 |
| JF-108-161114-1 | 535/1640 | 532/1720 |
| JF-108-161122 | 519/1574 | 521/1536 |
| JF-3D-1 | 205/277 | 208/312 |
The method more can satisfy needs close to theoretical value, separating effect.
Embodiment 3
Taking three groups of sample pH values is respectively 12.18,12.7,13.95, respectively weighs 10mg sample and 1mL ethanol acetate solution is added,
Sample is not completely dissolved, and has a little floccule, rear that 1mL tetrahydrofuran is added, the whole dissolutions of discovery, mistake after abundant dissolution rolling is even
Filter sample introduction.Following table is two groups of Comparative results of ethanol acetate solution Yu acetate methanol solution:
| JF-810-170303(pH=12.8) | Acetate ethanol solution Mn/Mw | Methanol acetum Mn/Mw |
| 1 | 494/895 | 493/977 |
| 2 | 495/923 | 492/969 |
| 3 | 492/882 | 493/972 |
| 4 | 491/881 | 494/978 |
| 5 | 495/926 | 493/985 |
Acetate methanol solution compares, and ethanol acetate solution is more stable, and as a result repeatability is higher.
Embodiment 4
Taking three groups of sample pH values is respectively 12.18,12.7,13.95, respectively weighs 10mg sample and 1mL acetate acetonitrile solution is added,
Sample is not completely dissolved, and floccule occurs, and rear that 1mL tetrahydrofuran is added, sample dissolubility is poor, so not considering.
Embodiment 5
Taking three groups of sample pH values is respectively 12.18,12.7,13.95, respectively weighs 10mg sample and 1mL acetic acid acetone acetic acid is added
Solution, sample are not completely dissolved, and floccule occur, and rear that 1mL tetrahydrofuran is added, sample dissolubility is poor, so not considering.
Embodiment 6
Taking three groups of sample pH values is respectively 12.18,12.7,13.95, respectively weigh 10mg sample be separately added into 1mL0.5%,
1.0%, 1ml tetrahydrofuran is added in 1.5% acetate methanol solution after sample dissolution, as a result as follows:
| Sample pH value | 0.5% methanol acetum | 1% methanol acetum | 1.5% methanol acetum |
| 12.18 | 581/1428 | 593/1377 | 600/1306 |
| 12.7 | 578/1148 | 576/1119 | 577/1100 |
| 13.95 | 558/1204 | 557/1177 | 565/1141 |
When sample pH >=14.4, acetic acid content proportion need to be improved.
By the comparison of several similar solvents, acetonitrile, acetone are poor to sample dissolubility, and dissolubility is more compared with ethyl alcohol for methanol
Better, as a result more stable, so determining methanol is as solvent, test sample, 1% acetate methanol solution is closer neutral, sample
What product examine was surveyed is relative molecular weight, in view of making sample result have more comparativity, so finally determining 1% acetate methanol solution.
Embodiment 7
Wood adhesive resinoid, resin pH directly make solvent in 11.0-13.8, with tetrahydrofuran, and sample cannot be complete
Dissolution, is added 1% acetate methanol solution, sample can be made to be completely dissolved and tetrahydrofuran can be added will not be precipitated again not
Molten object.By repeated detection sample repeatability within 2%.The resin for taking one group of pH=13.0 weighs 6mg sample, and 1ml vinegar is added
1ml tetrahydrofuran is added in sour methanol solution after dissolution, be made into the sample that concentration is 3mg/ml, filter after mixing dissolution, sample introduction.
It is the reperformance test of same batch of sample in the following figure:
| Sample number into spectrum | Testing result | The next day repetition measurement |
| 1 | 464/1104 | 457/1098 |
| 2 | 458/1089 | 465/1105 |
| 3 | 450/1066 | 463/1101 |
| 4 | 466/1098 | 465/1089 |
| 5 | 459/1091 | 458/1080 |
Data are shown in upper table, using the method for this method, detect wood adhesive resinoid, testing result stability
It is high.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by the limit of embodiment
System, other any changes made without departing from the spirit and principles of the present invention, modification, combination, substitution, simplification should be
Equivalence replacement mode, is included within the scope of the present invention.
Claims (8)
1. the molecular weight or molecular weight distribution detection method of a kind of alkaline polymer, it is characterised in that alkaline polymerization before detection
Object sample is pre-processed, and acetate methanol solution is prepared, and acetate methanol solution is added in alkaline polymer sample, is added after dissolution
Enter tetrahydrofuran, filters sample introduction after being uniformly dissolved；
The volume content of acetic acid is 0 .5-1 .5% in the acetate methanol solution.
2. according to molecular weight described in claim 1 or molecular weight distribution detection method, it is characterised in that vinegar in acetate methanol solution
The volume content of acid is 1%.
3. according to molecular weight described in claim 1 or molecular weight distribution detection method, it is characterised in that alkaline polymer pH is 11
.0-13 .95。
4. molecular weight according to claim 1 or molecular weight distribution detection method, it is characterised in that by 10mg alkaline polymerization
Object sample, which is added in 1mL acetate methanol solution, to be dissolved.
5. according to molecular weight described in claim 1 or molecular weight distribution detection method, it is characterised in that the molecular weight divides
Son amount distribution detection method is suitable for gel permeation chromatography and high performance liquid chromatography.
6. molecular weight or molecular weight distribution detection method that claim 5 is stated, it is characterised in that gel permeation chromatography testing conditions
It is as follows: mobile phase: tetrahydrofuran, column oven: 40 DEG C, sample volume: 200 μ L, ultraviolet wavelength: 270nm, flow velocity: 1mL/min.
7. according to molecular weight described in any one of claims 1-6 or molecular weight distribution detection method, it is characterised in that the alkalinity
Polymer is alkalescent phenol resin, and pH is 12 .18-13 .95.
8. the molecular weight or molecular weight distribution detection method stated according to claim 7, it is characterised in that detection method is gel infiltration
Chromatographic detection method.
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| CN105001385A (en) * | 2014-04-25 | 2015-10-28 | 株式会社国都化学 | Narrowly-dispersed phenol-phenolic varnish resin preparation method and narrowly-dispersed phenol-phenolic varnish resin obtained by means of the preparation method |
| CN105510508A (en) * | 2016-02-15 | 2016-04-20 | 北京泛博科技有限责任公司 | Method for detecting content of small-molecule residues in phenolic resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105001385A (en) * | 2014-04-25 | 2015-10-28 | 株式会社国都化学 | Narrowly-dispersed phenol-phenolic varnish resin preparation method and narrowly-dispersed phenol-phenolic varnish resin obtained by means of the preparation method |
| CN105510508A (en) * | 2016-02-15 | 2016-04-20 | 北京泛博科技有限责任公司 | Method for detecting content of small-molecule residues in phenolic resin |
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