CN102375043B - Detection method for volatile substances in rubber plug - Google Patents
Detection method for volatile substances in rubber plug Download PDFInfo
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- CN102375043B CN102375043B CN201010263615.5A CN201010263615A CN102375043B CN 102375043 B CN102375043 B CN 102375043B CN 201010263615 A CN201010263615 A CN 201010263615A CN 102375043 B CN102375043 B CN 102375043B
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Abstract
The invention provides a detection method for volatile substances in a rubber plug, which comprises the following steps of: 1) constructing a database for volatile substances in the rubber plug; and 2) determining the volatile substances in the rubber plug to be detected. The detection method for the volatile substances in the rubber plug has the advantages that two groups of data can be obtained at the same time when one specimen is detected in one experiment, the test time of qualitative screening is greatly saved and the interference of co-shown peaks can be effectively eliminated; by constructing the database for the volatile substances in the rubber plug, the volatile substances in the rubber plug can be screened rapidly and comprehensively, the database is not limited to specific varieties and the database is a universal database; and moreover, the method provided by the invention is easy to popularize.
Description
Technical field
The present invention relates to the detection method of Medical Packing Materials composition, specifically, relate to the detection method of volatile substances in rubber plug.
Background technology
Volatile matter in plug refers to some compositions that add in the production run of plug in order to improve the usability of plug and the durability of plug itself.Above-mentioned volatile matter (as: BHT, tygon fat, stearic acid, silicone oil etc.) can evaporate in the use procedure of plug, and particularly the volatile matter in medical rubber plug can pollute medicine.When if contained above-mentioned volatile matter level is higher than safety value in medicine, will affects the quality of medicine and human body is produced to harm.
The difficult point that volatile substances in rubber plug is controlled is, the volatile matter in the plug of same breed has uncertainty.This is can adopt the plug of different formulas and production technology production same breed due to different manufacturing enterprises, and the production technology of plug is also constantly changing and is improving, volatile matter in plug is constantly changed, and therefore setting up comprehensively detection system is fast the trend that plug volatile matter is measured.
At present, the domestic detection method there is no for plug volatile matter, pharmacopeia is commonly used vapor-phase chromatography (GC) and the residual solvent in medicine is detected to (residual solvent is also volatile, but be different from the volatile matter in plug), if the detection method of 2010 editions recommendations of < < Chinese Pharmacopoeia > > is head space capillary gas chromatography.Qualitative analysis in vapor-phase chromatography is mainly according to retention time, and this needs and the retention time of known standard substance is compared, and still for unknown peak, is difficult to carry out qualitative analysis.
In addition, while detecting by conventional vapor-phase chromatography the volatile matter containing in plug, because the volatile species in plug is more, the retention time of different volatile matter on a root chromatogram column may be identical or close, and this has all brought difficulty to the qualitative and quantitative test of volatile matter.
Summary of the invention
The object of the present invention is to provide a kind of method that detects efficiently, accurately volatile substances in rubber plug.
To achieve these goals, the detection method of volatile substances in rubber plug of the present invention, it comprises the steps:
1) foundation of database
A, by opposite polarity two chromatographic columns, the volatile matter of building in the sample of storehouse is carried out to gas chromatographic analysis, the BHT (BHT) of then take is reference material, calculates respectively the relative retention time of each chromatographic peak;
B and then the described volatile matter of building in the sample of storehouse is carried out to Gc-ms by described opposite polarity two chromatographic columns, carries out qualitative analysis to the described volatile matter of building in the sample of storehouse respectively, determines kind under it;
C, described, add internal standard compound in building storehouse sample, repeating step a, b, then by gas chromatography detector via described opposite polarity two chromatographic peaks that chromatographic column obtains, carry out similarity with the peak obtaining on mass detector respectively and mate;
D, according to the similarity matching result of step c, set up the peak-to-peak corresponding relation of chromatogram of described opposite polarity two chromatographic columns, and and mass spectrogram between corresponding relation, and sort out according to mass spectrum, thus building database;
2) mensuration of volatile substances in rubber plug to be measured
E, by described opposite polarity two chromatographic columns, the volatile matter in plug to be measured is carried out to gas chromatographic analysis, and according to step a method, calculate the relative retention time of each chromatographic peak of two chromatographic columns;
F, relative retention time and step 1 that step e is obtained) database compare, thereby determine the kind of the volatile matter containing in plug to be measured.
Wherein, described in, build storehouse sample and comprise the known various plugs such as butyl rubber plug, brominated butyl rubber plug and chlorinated butyl plug; Can also comprise tygon fat, phenolics, stearic acid, brominated butyl rubber plug virgin rubber, the various supplementary materials of the existing plugs such as chlorinated butyl plug virgin rubber and Russian glue.
Described internal standard compound is benzene, toluene, butyl acetate, tetralin, normal butyl alcohol, n-amyl alcohol or BHT etc.
Described opposite polarity two chromatographic columns refer to two opposite polarity chromatographic columns in parallel in gas chromatography, are preferably nonpolar chromatographic column and polarity chromatographic column.Wherein, it is the chromatographic column of polyoxy silane or poly dimethyl silane mutually that described nonpolar chromatographic column comprises fixing, as the nonpolar chromatographic column of SPB-1 type of Supelco company production; Described polarity chromatographic column comprises fixing chromatographic column of modifying for polyglycol-nitro terephthalic acid (TPA) mutually, as the HP-FFAP type polarity chromatographic column of Agilent company production.
In step a, the chromatographic condition of gas chromatography is:
Temperature programme: 40 ℃ keep 10min, then rises to 170 ℃ and keep 10min with the speed of 10 ℃/min; Injector temperature: 200 ℃; Constant flow rate: 2.0mL/min; Carrier gas: helium; Split ratio: 5: 1; Detector temperature: 250 ℃; Head space temperature: 150 ℃; The head space time: 30min.
In step b, gas chromatography mass spectrometry chromatographic condition is:
Temperature programme: 40 ℃ keep 10min, then rises to 170 ℃ and keep 10min with the speed of 10 ℃/min; Injector temperature: 200 ℃; Constant flow rate: 1.0mL/min; Do not shunt; Detector temperature: 250 ℃; Head space temperature: 150 ℃; The head space time: 30min.
Similarity coupling of the present invention is to use similarity evaluation (2004A version, Chinese Pharmacopoeia Commission) carry out similarity analysis, similarity is at the peak that more than 800 can think to match, and the Computing Principle of described similarity analysis is included angle cosine.
In addition,, in order to verify the repeatability of the inventive method, can also after building database, increase the step of the time window of determining every kind of volatile matter.
The inventive method has increased a binary channels or three-channel isocon after the sampling system of gas chromatography, each passage has independently switch to control its circulation, after isocon, connect at least side by side two opposite polarity chromatographic columns, thereby realized the object of two opposite polarity chromatographic columns of use in parallel, it can, guaranteeing sample introduction sample and conforming while of sampling condition, make the volatile matter that retention time is identical or close on a root chromatogram column in opposite polarity chromatographic column, have the retention time that differs larger.
Specifically, the gas chromatography of using in the inventive method, when using twin-channel isocon, what connect side by side with it is two opposite polarity chromatographic columns; When using three-channel isocon, connect side by side with it except above-mentioned opposite polarity chromatographic column, also have mass spectrometry system, make mass spectrometry system and gas chromatography form the analytic system operating side by side.
Described isocon can be the isocon that in the existing chromatographic apparatuss such as glass tube, stainless-steel tube prepared by operable material, and its shape, size etc. are not particularly limited, and can select according to the instrument of different model.Described isocon can be applied in gas chromatography removably; Also can be fixed in gas chromatograph or gas chromatography mass spectrometry instrument, now by controlling the switch of each passage, select different detection systems, for example, be single chromatographic column, two chromatographic column or gas phase and mass spectrum use detection system.
Detection method of the present invention, for the deficiencies in the prior art, by the use in parallel of opposite polarity two chromatographic columns, guaranteeing sample introduction sample and conforming while of sampling condition, make the volatile matter that retention time is identical or close on a root chromatogram column in opposite polarity chromatographic column, have the retention time that differs larger.By retention time and database after two root chromatogram columns are measured, compare, result can be carried out qualitative analysis in the situation that there is no standard items, tentatively determines the kind of volatile matter in medical rubber plug, thereby has avoided unknown peak to carry out blindness screening.While occurring that in measuring process unknown chromatographic peak needs are further determined, can use the mass spectrometry system in parallel with chromatogram column system to detect, comprehensive income result is determined simultaneously.
In addition, because the retention time of same volatile matter in the different chromatographic column of polarity is different, relative retention time is also different, therefore by coupling mass spectrum, determine the retention time of same volatile matter in two kinds of chromatographic columns, and these two retention times are connected, form a system of evidence each other, and the structural formula providing by mass spectrographic NIST database, and name by nomenclature of organic compound method, thereby volatile matter is sorted out, thereby set up the database of plug volatile matter.
The invention has the advantages that, the inventive method can make same sample once obtain two groups of data in experiment simultaneously, has greatly saved the test period of qualitative screening, and can effectively get rid of the interference that goes out altogether peak; By setting up the database of plug volatile matter, can to plug volatile matter, screen all sidedly fast, be not limited to concrete kind, be universal database; In addition, the inventive method is easy to promote.
Accompanying drawing explanation
Fig. 1 is binary channels chromatogram column system mode chart in parallel;
Fig. 2 is plug volatile matter polarity chromatographic system matching collection of illustrative plates;
Fig. 3 is the nonpolar chromatographic system matching of plug volatile matter collection of illustrative plates.
Embodiment
By specific embodiment, further illustrate the present invention below, but be not used for limiting the scope of the invention.
The foundation of embodiment 1 plug volatile matter database
Instrument and software 1:(gas phase)
Trace GC Ultra (power & light company); Headspace system (power & light company); Data analysis software is Xcalibur data handling system (power & light company); Chromatographic column: the nonpolar chromatographic column of SPB-1 type (30m * 0.32mm * 1um, supelco), HP-FFAP type polarity chromatographic column (30m * 0.32mm * 0.52um, Agilent company), each parts connection diagram is as shown in Figure 1.
Chromatographic condition 1:(gas phase)
Temperature programme: 40 ℃ keep 10min, then rises to 170 ℃ and keep 10min with the speed of 10 ℃/min; Injector temperature: 200 ℃; Constant flow rate: 2.0mL/min; Carrier gas: helium; Split ratio: 5: 1; Detector temperature: 250 ℃; Head space temperature: 150 ℃; The head space time: 30min.
Instrument and software 2:(gas chromatography mass spectrometry)
Trace GC Ultra-Polaris Q (power & light company); Headspace system (power & light company); Data analysis software is Xcalibur data handling system (power & light company); Chromatographic column: the nonpolar chromatographic column of SPB-1 type (30m * 0.25mm * 0.25um, supelco), HP-FFAP type polarity chromatographic column (30m * 0.25mm * 0.25um, Agilent company).
Chromatographic condition 2:(gas chromatography mass spectrometry)
Temperature programme: 40 ℃ keep 10min, then rises to 170 ℃ and keep 10min with the speed of 10 ℃/min; Injector temperature: 200 ℃; Constant flow rate: 1.0ml/min; Do not shunt; Detector temperature: 250 ℃; Head space temperature: 150 ℃; The head space time: 30min.
The configuration of BHT reference material: precision takes 5mgBHT, analyzes pure sodium chloride with 50g and in mortar, mixes and develop evenly, makes the reference substance of concentration 0.1 μ g/mg.
Build storehouse sample: chlorinated butyl rubber bung (Jiangyin Lan Ling, Shandong medicine glass), chlorinated butyl rubber bung (Jiangsu Bo Sheng medical material incorporated company, Anhui Hua Feng, south, Chengdu ring), butyl rubber bung (Chongqing San Hai Lan Ling company).
Internal standard compound: benzene, toluene, butyl acetate, tetralin, normal butyl alcohol, n-amyl alcohol and BHT.
Step:
(1), above-mentioned given chromatographic condition 1 time, with the Methane determination dead time, measure respectively the volatile matter built in the sample of the storehouse retention time in polarity and nonpolar chromatographic column (two chromatographic systems); Using the adjustment retention time of BHT as reference, calculate the adjustment relative retention time of every kind of volatile matter, the results are shown in Table 1, wherein T
r(min) be retention time, RART is for adjusting relative retention time;
(2) above-mentioned given chromatographic condition 2 times, with mass detector, the volatile matter in above-mentioned standard model is detected, the results are shown in Table 2;
(3) in standard model, add multiple different internal standard compound, repeating step (1), (2), the peak of the volatile matter then respectively polarity in parallel and nonpolar chromatogram column system being obtained on fid detector mates with the peak of the volatile matter obtaining on mass detector, the results are shown in Table 3～4;
Described coupling is to carry out similarity analysis with similarity evaluation (2004A version, Chinese Pharmacopoeia Commission), and similarity is at the peak that more than 800 can think to match;
(4) then according to matching result, the volatile matter of Criterion sample is at the peak-to-peak corresponding relation (as shown in table 5) of opposite polarity two chromatographic columns, and and mass spectrogram between corresponding relation, and according to mass spectrum, volatile matter is sorted out, thereby set up volatile substances in rubber plug database, result is as shown in table 6;
(5) determine every kind of volatile matter time window, to verify the repeatability of the inventive method, the results are shown in Table 7.
In table 1 gas phase plug volatile matter retention time and relative retention time
In table 2 gas chromatography mass spectrometry plug volatile matter retention time
The nonpolar system matches result of table 3
Table 4 polar system matching result
The nonpolar system of table 5 and polar system corresponding relation
Classes of compounds under the nonpolar system of table 6 volatile matter corresponding to polar system peak
Table 7 time window
As mentioned above, table 6 is the plug volatile matter database in the present invention.On this basis, we only need to carry out gas chromatographic detection by opposite polarity two chromatographic columns in parallel to plug to be measured, then the relative retention time of opposite polarity two chromatographic columns that obtain and above-mentioned database are compared, just standard items can there is no, do not need to carry out in the situation of Mass Spectrometer Method the kind of the volatile matter in qualitative analysis plug yet.
In addition, after having known the kind of these volatile matter, just can be by the analysis to the auxiliary material of using in plug production run, know the possible source of volatile matter, such as straight or branched alkane major part comes from auxiliary material tygon fat, and straight or branched ketone compounds major part comes from auxiliary material stearic acid etc., then by corroborating each other of two chromatogram column systems, just can affirm the existence of certain compound, thereby control the formula of plug, grasp the quality of plug.
The mensuration of volatile constituent in embodiment 2 chlorinated butyl rubber bungs
The source of test sample: the rich raw lot number in 1 Jiangsu: 09051314
2 Anhui Hua Feng lot number: S090502573
3 south, Chengdu ring lot numbers: 090506
The preparation of test sample: appropriate chlorinated butyl rubber bung is shredded, be placed in 20ml headspace gas bottle, and seal and gland packing with plug to be measured.
The configuration of BHT reference material: precision takes 5mg BHT, analyzes pure sodium chloride with 50g and in mortar, mixes and develop evenly, makes the reference substance of concentration 0.1 μ g/mg.
Head space condition and chromatographic condition be with embodiment 1, measures respectively the retention time of volatile constituent in the retention time of BHT and need testing solution, then compares with the database of embodiment 1 gained.Measurement result is in Table 8～9; With database comparative result in Table 10～12.
Table 8SPB-1 chromatographic system result
Note: the retention time of methane is that the retention time of 1.623min BHT is 27.741min
Table 9HP-FFAP chromatographic system result
Note: the retention time of methane is that the retention time of 1.220min BHT is 23.217min
The result that table 10 is compared with the database of embodiment 1 gained
The result that table 11 is compared with the database of embodiment 1 gained
The result that table 12 is compared with the database of embodiment 1 gained
By table 8～12, can be found out, the rich raw chlorinated butyl rubber bung of producing in Jiangsu, its volatile matter is straight or branched ketone compounds, straight or branched alkane and alkane substituting group phenol; And the chlorinated butyl rubber bung that Anhui Hua Feng produces, its volatile matter is straight or branched ketone compounds, alkane substituting group benzene, straight or branched alkane and silica compounds; And the chlorinated butyl rubber bung that south, Chengdu ring is produced, its volatile matter is straight or branched ketone compounds, straight or branched alkane and enols used.
Therefore, although can find out and be all a large class plug, also may be because difference or the difference on synthesis technique on formula cause containing different volatile matter, but the database of setting up by the inventive method can find certain rule in various volatile matter, and making becomes possibility to the refinement of plug quality control.
Although above, by general explanation and embodiment, the present invention is described in detail, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements, all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (4)
1. the detection method of volatile substances in rubber plug, it comprises the steps:
1) foundation of database
A, by opposite polarity two chromatographic columns, the volatile matter of building in the sample of storehouse is carried out to gas chromatographic analysis, then take BHT as reference material, calculate respectively the relative retention time of each chromatographic peak;
B and then the described volatile matter of building in the sample of storehouse is carried out to Gc-ms by described opposite polarity two chromatographic columns, carries out qualitative analysis to the described volatile matter of building in the sample of storehouse respectively, determines kind under it;
C, described, add internal standard compound in building storehouse sample, repeating step a, b, then by gas chromatography detector via described opposite polarity two chromatographic peaks that chromatographic column obtains, carry out similarity with the peak obtaining on mass detector respectively and mate;
D, according to the similarity matching result of step c, set up the peak-to-peak corresponding relation of chromatogram of described opposite polarity two chromatographic columns, and and mass spectrogram between corresponding relation, and sort out according to mass spectrum result, thus building database;
2) mensuration of volatile substances in rubber plug to be measured
E, by described opposite polarity two chromatographic columns, the volatile matter in plug to be measured is carried out to gas chromatographic analysis, and according to step a method, calculate the relative retention time of each chromatographic peak of two chromatographic columns;
F, the relative retention time that step e is obtained are compared with the database of step 1), thereby determine the kind of the volatile matter containing in plug to be measured;
The wherein said storehouse sample of building comprises butyl rubber plug, brominated butyl rubber plug and chlorinated butyl plug; Also comprise tygon fat, phenolics, stearic acid, brominated butyl rubber plug virgin rubber, chlorinated butyl plug virgin rubber and Russian glue;
Described opposite polarity two chromatographic columns refer to nonpolar chromatographic column and polarity chromatographic column; Described nonpolar chromatographic column comprises that fixing is the chromatographic column of polyoxy silane or poly dimethyl silane mutually; Described polarity chromatographic column comprises fixing chromatographic column of modifying for polyglycol-nitro terephthalic acid (TPA) mutually.
2. detection method according to claim 1, is characterized in that, described internal standard compound is benzene, toluene, butyl acetate, tetralin, normal butyl alcohol, n-amyl alcohol or BHT.
3. detection method according to claim 1, is characterized in that, the chromatographic condition of gas chromatography described in step a is:
Temperature programme: 40 ℃ keep 10min, then rises to 170 ℃ and keep 10min with the speed of 10 ℃/min; Injector temperature: 200 ℃; Constant flow rate: 2.0mL/min; Carrier gas: helium; Split ratio: 5:1; Detector temperature: 250 ℃; Head space temperature: 150 ℃; The head space time: 30min.
4. detection method according to claim 1, is characterized in that, the chromatographic condition of gas chromatography mass spectrometry described in step b is:
Temperature programme: 40 ℃ keep 10min, then rises to 170 ℃ and keep 10min with the speed of 10 ℃/min; Injector temperature: 200 ℃; Constant flow rate: 1.0mL/min; Do not shunt; Detector temperature: 250 ℃; Head space temperature: 150 ℃; The head space time: 30min.
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| CN108828123B (en) * | 2018-06-26 | 2020-06-02 | 安徽皖维高新材料股份有限公司 | Method for measuring content of butyraldehyde and paraldehyde in polyvinyl butyral resin |
| CN111077237B (en) * | 2018-10-22 | 2022-12-30 | 山东省医疗器械产品质量检验中心 | Gas chromatography-mass spectrometry detection method for medicine compatibility of medicinal butyl rubber plug |
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