CN105424743A - Method for rapidly determining purity of raw materials in process of producing polyglycolic acid - Google Patents
Method for rapidly determining purity of raw materials in process of producing polyglycolic acid Download PDFInfo
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- CN105424743A CN105424743A CN201510870693.4A CN201510870693A CN105424743A CN 105424743 A CN105424743 A CN 105424743A CN 201510870693 A CN201510870693 A CN 201510870693A CN 105424743 A CN105424743 A CN 105424743A
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Abstract
The invention relates to a differential scanning calorimetry (DSC) method for determining the purity of glycollic acid, glycolide and a catalyst. In order to synthesize polyglycolic acid with a high molecular weight, the purity of glycollic acid needs to be higher than 98%, the purity of the glycolide needs to be higher than 99.5% and the purity of the catalyst needs to be higher than 99%. The invention provides a simple and rapid method for determining the purity of glycollic acid and the glycolide in a process of producing polyglycolic acid. The DSC detection method of the purity of glycollic acid comprises the following steps: taking a proper amount (0.5mg-1.0mg) of a glycollic acid sample and raising the temperature to be 85 DEG C from 65 DEG C at a temperature rising speed of 1 DEG C/min, so as to obtain a DSC curve. The purity of glycollic acid is calculated by using a temperature interval of a melting point. Purity determination methods of the glycolide and the catalyst are similar to the method. The method provided by the invention has a simple process and short time, and the production efficiency can be easily improved.
Description
Technical field
The invention belongs to macromolecule analysis field, disclose a kind of method of DSC working sample purity, especially a kind of analytical approach measuring synthesis polyglycolic acid process Raw purity.
Background technology
Polyglycolic acid (PGA) is structure the simplest linear aliphatic adoption ester, is a business-like kind the earliest in human body Absorbable rod macromolecule.It has very excellent mechanical property, has a extensive future at medical fields such as operation suture thread, medicament slow release and artificial skins.
The primary synthetic methods of PGA is ring-opening polymerization method, as follows:
In order to synthesize the polyglycolic acid of high molecular, glycollic acid purity need higher than 98%, and glycolide purity need higher than 99.5%, and the purity of catalyzer need higher than 99%.
Document 1 provides a kind of method using liquid chromatogram measuring sample purity.Compared with chromatography, DSC method measures purity and has easy and simple to handle, and finding speed is fast, and amount of samples is few, does not need the advantage of standard specimen.
Inventive principle
It is determine the content of impurity according to the decline of fusing point that DSC method measures purity, and it is based on the theory of Van't Hoff fusing point decline.The fusing point decline rule caused by the impurity that molecular size is close meets Van ˊ tHoff equation:
In formula: T
sfor the sample temperature corrected through thermal resistance; T
0for the fusing point of pure sample product; R is gas law constant; X is the concentration (mole fraction) of impurity in sample; Δ H
ffor the ablation heat in pure sample product; F is that sample is at temperature T
stime fusing mark.
The melting absorption peak area of sample is melting heat Δ H
f.By on sample melting peak, certain a bit makes vertical line, and melting peak is divided into two parts, and the area of left-hand component is F divided by the total area.Make the slope straight line equal with indium standard substance melting peak decline side flex point slope by this point, the temperature corresponding with the intersection point of baseline is T
s(thermal resistance correction).By T
sright
mapping, after fritting corrects, obtain straight line, the intercept of straight line is the theoretical fusing point T of unlimited pure sample product
0, the impurity concentration x in sample can be obtained by the slope of straight line, and then calculate the purity (mole fraction) (document 2) of sample.
Summary of the invention
1. one kind combines with thermal analyses theoretical formula method based on differential scanning calorimeter technology, and Accurate Determining produces the purity of polyglycolic acid process Raw, it is characterized in that the concrete steps of the method are as follows:
(1) appropriate sample is taken out for dsc measurement.DSC experiment is carried out on the PerkinElmer8500DSC instrument being equipped with cooling system.The nitrogen flow passing into DSC sample cell is 20mLmin
-1.Take appropriate sample, load in sealed crucible.Obtain the experimental datas such as DSC curve;
(2) according to the DSC spectrogram (see Fig. 1 and Fig. 2) obtained, the relation between polymerization system thermal discharge and time in cyclic esters ring-opening polymerization process, temperature is analyzed;
(3) use dynamics software to analyze the purity of raw material, whether accurate evaluation raw material meets the requirement of production high molecular polyglycolic acid.
2. wherein said raw material, cyclic ester comprises glycollic acid, glycolide and catalyzer etc.The structure of glycollic acid is shown in formula 1:
The structure of glycolide is shown in formula 2:
3. wherein said building-up process, catalyzer comprises the carboxylic acid compound of Bi and the halogenide of Sn.
4. wherein said building-up process, the carboxylic acid compound of Bi comprises (see formulas 3) such as bismuth acetate, caproic acid bismuth, Bismuth Octoate and basic bismuth salicylates.
5. wherein said building-up process, the halogenide of Sn comprises stannous chloride, two hydration stannous chloride, butter of tin, tin bibromide and tin diiodide etc.
6. wherein said building-up process, the sampling amount mass range of sample is 0.1 ~ 10mg, preferably 0.5 ~ 1mg.
7. wherein said DSC measures process, and wherein measuring tempeature scope is 30 ~ 300 DEG C, is preferably 100 ~ 250 DEG C.
8. wherein said DSC measures process, and the temperature measuring scope of glycollic acid is 20 ~ 200 DEG C, is preferably 70 ~ 90 DEG C.
9. wherein said DSC measures process, and the temperature measuring scope of glycolide is 20 ~ 200 DEG C, is preferably 75 ~ 95 DEG C.
10. wherein said DSC measures process, and the temperature measuring scope of Bi carboxylic acid compound is 20 ~ 300 DEG C.
11. wherein said DSC mensuration processes, the halid temperature measuring scope of Sn is 20 ~ 300 DEG C.
12. wherein said DSC mensuration processes, the heating rate scope of DSC is 0.1 ~ 10 DEG C/min, is preferably 1 ~ 5 DEG C/min.
The Accurate Determining of the present invention purity of glycollic acid, glycolide and catalyzer, guarantees the polyglycolic acid synthesizing high molecular.
Accompanying drawing explanation
Fig. 1 is the melting absorption peak DSC spectrogram of glycollic acid
Fig. 2 is the melting absorption peak DSC spectrogram of glycolide
List of references
Document 1: Sun Guiying. method [P] .CN102435685, the 2012-5-2. of 2-mercaptobenzothiazole purity is measured with high performance liquid chromatograph
Document 2: Hu Shaoqiang, Liu Hongyu, Li Jie, etc. the differential scanning calorimetry of resorcinol dihydroxyethyl ether purity measures [J]. chemical propellant and macromolecular material, 2006,4 (4): 59-61.
Embodiment
Instrument
Differential calorimetric scan instrument, PE8500;
Embodiment 1
Precision takes glycollic acid sample, with acid-resistant stainless steel crucible press seal.Utilize differential scanning calorimeter (DSC) to detect its purity, from 70 DEG C, be warmed up to 90 DEG C with 1 DEG C/min.For avoiding sample oxidized in experimentation, adopt high pure nitrogen as purified gas, adjustment flow velocity is 20mL/min.Relevant DSC spectrogram purity software process, the mean value of glycollic acid purity detecting result is 98.12%.
Embodiment 2
Accurately take glycollic acid sample, with acid-resistant stainless steel crucible press seal.Utilize differential scanning calorimeter (DSC) to detect its purity, from 70 DEG C, be warmed up to 90 DEG C with 3 DEG C/min.For avoiding sample oxidized in experimentation, adopt high pure nitrogen as purified gas, adjustment flow velocity is 20mL/min.Relevant DSC spectrogram purity software process, the mean value of glycollic acid purity detecting result is 97.78%.
Embodiment 3
Precision takes glycollic acid sample, with acid-resistant stainless steel crucible press seal.Utilize differential scanning calorimeter (DSC) to detect its purity, from 70 DEG C, be warmed up to 90 DEG C with 1 DEG C/min.For avoiding sample oxidized in experimentation, adopt high pure nitrogen as purified gas, adjustment flow velocity is 20mL/min.Relevant DSC spectrogram purity software process, the mean value of glycollic acid purity detecting result is 98.56%.
Embodiment 4
Accurately take glycolide sample, with aluminum liquid crucible press seal.Utilize differential scanning calorimeter (DSC) to detect its purity, from 75 DEG C, be warmed up to 95 DEG C with 1 DEG C/min.For avoiding sample oxidized in experimentation, adopt high pure nitrogen as purified gas, adjustment flow velocity is 20mL/min.Relevant DSC spectrogram purity software process, the mean value of glycolide purity detecting result is 99.54%.
Embodiment 5
Precision takes glycolide sample, with aluminum liquid crucible press seal.Utilize differential scanning calorimeter (DSC) to detect its purity, from 75 DEG C, be warmed up to 95 DEG C with 3 DEG C/min.For avoiding sample oxidized in experimentation, adopt high pure nitrogen as purified gas, adjustment flow velocity is 20mL/min.Relevant DSC spectrogram purity software process, the mean value of glycolide purity detecting result is 99.78%.
Embodiment 6
Accurately take glycolide sample, with aluminum liquid crucible press seal.Utilize differential scanning calorimeter (DSC) to detect its purity, from 75 DEG C, be warmed up to 95 DEG C with 5 DEG C/min.For avoiding sample oxidized in experimentation, adopt high pure nitrogen as purified gas, adjustment flow velocity is 20mL/min.Relevant DSC spectrogram purity software process, the mean value of glycolide purity detecting result is 99.89%.
Embodiment 7
Precision takes proper catalyst Bi (OAc)
3, with acid-resistant stainless steel crucible press seal.Utilize differential scanning calorimeter (DSC) to Bi (OAc)
3purity detects, and from 200 DEG C, is warmed up to 300 DEG C with 1 DEG C/min.For avoiding sample oxidized in experimentation, adopt high pure nitrogen as purified gas, adjustment flow velocity is 20mL/min.Relevant DSC spectrogram purity software process, Bi (OAc)
3the mean value of purity detecting result is 99.08%.
Embodiment 8
Accurately take proper catalyst Bi (OAc)
3, with acid-resistant stainless steel crucible press seal.Utilize differential scanning calorimeter (DSC) to Bi (OAc)
3purity detects, and from 200 DEG C, is warmed up to 300 DEG C with 3 DEG C/min.For avoiding sample oxidized in experimentation, adopt high pure nitrogen as purified gas, adjustment flow velocity is 20mL/min.Relevant DSC spectrogram purity software process, Bi (OAc)
3the mean value of purity detecting result is 99.12%.
Embodiment 9
Precision takes proper catalyst Bi (OAc)
3, with acid-resistant stainless steel crucible press seal.Utilize differential scanning calorimeter (DSC) to Bi (OAc)
3purity detects, and from 200 DEG C, is warmed up to 300 DEG C with 5 DEG C/min.For avoiding sample oxidized in experimentation, adopt high pure nitrogen as purified gas, adjustment flow velocity is 20mL/min.Relevant DSC spectrogram purity software process, Bi (OAc)
3the mean value of purity detecting result is 99.19%.
Embodiment 10
Accurately take proper catalyst SnCl
22H
2o, with acid-resistant stainless steel crucible press seal.Utilize differential scanning calorimeter (DSC) to detect its purity, from 30 DEG C, be warmed up to 250 DEG C with 1 DEG C/min.For avoiding sample oxidized in experimentation, adopt high pure nitrogen as purified gas, adjustment flow velocity is 20mL/min.Relevant DSC spectrogram purity software process, SnCl
22H
2the mean value of O purity detecting result is 99.06%.
Embodiment 11
Precision takes proper catalyst SnCl
22H
2o, with acid-resistant stainless steel crucible press seal.Utilize differential scanning calorimeter (DSC) to detect its purity, from 30 DEG C, be warmed up to 150 DEG C with 3 DEG C/min.For avoiding sample oxidized in experimentation, adopt high pure nitrogen as purified gas, adjustment flow velocity is 20mL/min.Relevant DSC spectrogram purity software process, SnCl
22H
2the mean value of O purity detecting result is 99.15%.
Embodiment 12
Accurately take proper catalyst SnCl
22H
2o, with acid-resistant stainless steel crucible press seal.Utilize differential scanning calorimeter (DSC) to detect its purity, from 30 DEG C, be warmed up to 150 DEG C with 5 DEG C/min.For avoiding sample oxidized in experimentation, adopt high pure nitrogen as purified gas, adjustment flow velocity is 20mL/min.Relevant DSC spectrogram purity software process, SnCl
22H
2the mean value of O purity detecting result is 99.20%.
Claims (10)
1. one kind combines with thermal analyses theoretical formula method based on differential scanning calorimeter technology, and Accurate Determining produces the purity of polyglycolic acid process Raw, it is characterized in that the concrete steps of the method are as follows:
(1) appropriate sample is taken out for dsc measurement.DSC experiment is carried out on the PerkinElmer8500DSC instrument being equipped with cooling system.The nitrogen flow passing into DSC sample cell is 20mLmin
-1.Take appropriate sample, load in sealed crucible, obtain the experimental datas such as DSC curve;
(2) according to the DSC spectrogram obtained, the relation between polymerization system thermal discharge and time in cyclic esters ring-opening polymerization process, temperature is analyzed;
(3) use dynamics software to analyze the purity of glycollic acid and glycolide, whether accurate evaluation glycollic acid and glycolide meet the requirement of production high molecular polyglycolic acid.
2. raw material according to claim 1, wherein raw material comprises glycollic acid, glycolide and catalyzer etc.
3. building-up process according to claim 1, wherein catalyzer comprises the carboxylic acid compound of Bi and the halogenide of Sn.
4. building-up process according to claim 1, the sampling amount mass range of sample is 0.1 ~ 10mg, preferably 0.5 ~ 1mg.
5. DSC according to claim 1 measures process, and wherein measuring tempeature scope is 30 ~ 300 DEG C, is preferably 100 ~ 250 DEG C.
6. DSC according to claim 4 measures process, and the temperature measuring scope of glycollic acid is 20 ~ 200 DEG C, is preferably 70 ~ 90 DEG C.
7. DSC according to claim 4 measures process, and the temperature measuring scope of glycolide is 20 ~ 200 DEG C, is preferably 75 ~ 95 DEG C.
8. DSC according to claim 4 measures process, and the temperature measuring scope of Bi carboxylic acid compound is 20 ~ 300 DEG C.
9. DSC according to claim 4 measures process, and the halid temperature measuring scope of Sn is 20 ~ 300 DEG C.
10. DSC according to claim 1 measures process, and the heating rate scope of DSC is 0.1 ~ 10 DEG C/min, is preferably 1 ~ 5 DEG C/min.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105784762A (en) * | 2016-04-29 | 2016-07-20 | 山东大学 | Quick purity testing and analyzing method for low-melting-point materials |
| CN105842279A (en) * | 2016-06-20 | 2016-08-10 | 重庆食品工业研究所 | Method for identifying alcohol-washed amorphophallus konjac micro powder doped with glucose |
| CN105928971A (en) * | 2016-04-22 | 2016-09-07 | 北京彤程创展科技有限公司 | Determination method for polyacrylate vulcanizing agent |
| CN108387605A (en) * | 2018-05-07 | 2018-08-10 | 国网电力科学研究院武汉南瑞有限责任公司 | One kind being based on Thermal Conductivity perfluor isobutyronitrile moderate purity detection method of content |
| CN110174437A (en) * | 2019-07-04 | 2019-08-27 | 云南中烟工业有限责任公司 | A method of nicotine content in tobacco juice for electronic smoke is quickly measured according to differential scanning calorimetry heat enthalpy value |
| CN110174436A (en) * | 2019-07-04 | 2019-08-27 | 云南中烟工业有限责任公司 | A kind of method of glycerol in quick measurement tobacco juice for electronic smoke, content of propylene glycol |
| CN111189877A (en) * | 2018-11-15 | 2020-05-22 | 中国科学院大连化学物理研究所 | Sample purity measuring and calculating method based on adiabatic calorimetry |
| CN113008720A (en) * | 2021-02-19 | 2021-06-22 | 广东省计量科学研究院（华南国家计量测试中心） | Method for determining purity of 4-bromodiphenyl ether |
| CN113075253A (en) * | 2021-03-08 | 2021-07-06 | 江苏斯尔邦石化有限公司 | Method for detecting residual peroxide in polyolefin |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105928971A (en) * | 2016-04-22 | 2016-09-07 | 北京彤程创展科技有限公司 | Determination method for polyacrylate vulcanizing agent |
| CN105784762A (en) * | 2016-04-29 | 2016-07-20 | 山东大学 | Quick purity testing and analyzing method for low-melting-point materials |
| CN105842279A (en) * | 2016-06-20 | 2016-08-10 | 重庆食品工业研究所 | Method for identifying alcohol-washed amorphophallus konjac micro powder doped with glucose |
| CN108387605A (en) * | 2018-05-07 | 2018-08-10 | 国网电力科学研究院武汉南瑞有限责任公司 | One kind being based on Thermal Conductivity perfluor isobutyronitrile moderate purity detection method of content |
| CN111189877A (en) * | 2018-11-15 | 2020-05-22 | 中国科学院大连化学物理研究所 | Sample purity measuring and calculating method based on adiabatic calorimetry |
| CN110174437A (en) * | 2019-07-04 | 2019-08-27 | 云南中烟工业有限责任公司 | A method of nicotine content in tobacco juice for electronic smoke is quickly measured according to differential scanning calorimetry heat enthalpy value |
| CN110174436A (en) * | 2019-07-04 | 2019-08-27 | 云南中烟工业有限责任公司 | A kind of method of glycerol in quick measurement tobacco juice for electronic smoke, content of propylene glycol |
| CN113008720A (en) * | 2021-02-19 | 2021-06-22 | 广东省计量科学研究院（华南国家计量测试中心） | Method for determining purity of 4-bromodiphenyl ether |
| CN113008720B (en) * | 2021-02-19 | 2022-05-10 | 广东省计量科学研究院（华南国家计量测试中心） | Method for determining purity of 4-bromodiphenyl ether |
| CN113075253A (en) * | 2021-03-08 | 2021-07-06 | 江苏斯尔邦石化有限公司 | Method for detecting residual peroxide in polyolefin |
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