KR101113645B1 - Quantitative analysis method of Acrylonitrile and Additive in Acrylonitrile-Butadiene rubber composition - Google Patents
Quantitative analysis method of Acrylonitrile and Additive in Acrylonitrile-Butadiene rubber composition Download PDFInfo
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Abstract
Description
The present invention relates to a method for quantitative analysis of acrylonitrile and additives of an acrylonitrile-butadiene rubber composition, and can be usefully applied to product development and quality maintenance of acrylonitrile-butadiene rubber materials.
Acrylonitrile-butadiene rubber (hereinafter referred to as 'NBR rubber') is a material that is widely applied to automotive parts requiring oil and fuel resistance such as seals, gaskets, diaphragms, hoses, and cave jackets. The rubber composition is prepared by mixing a vulcanizing agent, carbon black, an inorganic filler, a vulcanization accelerator, a softener, an anti-aging agent, a processing aid, and other additives according to desired physical properties in addition to the base polymer, which is a rubber component. NBR rubber is a resin obtained by copolymerizing butadiene and acrylonitrile, and NBR rubber has rubber properties such as fuel resistance, low temperature flexibility, compression shrinkage, heat resistance, and ozone resistance depending on the content of acrylonitrile (ACN). In the industry, four types of NBR rubbers having an acrylonitrile content of 28 wt%, 34 wt%, 41 wt% and rarely 18 wt% are mainly applied.
As such, the physical properties of the NBR rubber composition depend on the additives and the acrylonitrile content of the NBR rubber. Therefore, for product development and quality improvement, an analytical method capable of accurately analyzing the additive and acrylonitrile content is required. Conventionally, an elemental analysis method for analyzing nitrogen content by measuring thermal conductivity of gas generated by burning rubber in order to analyze acrylonitrile content in NBR rubber has been applied to the industry. In addition, the conventional pyrolysis gas chromatography method (Py-GC / MS) is mainly used as a method for qualitatively analyzing the base polymer or additive of the rubber composition, and is not applied to the quantitative analysis of the additive content contained in the vulcanized rubber. have. In order to analyze the additives in the NBR rubber composition, a solvent extraction method is mainly applied. The process is as follows. That is, 50 mg of the sample is pulverized to about 1 to 5 mm, and the rubber composition is mixed with a solvent such as acetone, chloroform and methanol, and the mixed solution is mixed with a stirrer, a shaker, or a sonicator. Stir for time to extract the additive. The extract is then injected into gas chromatography and subjected to a complex step of quantitative analysis. However, since such an experiment takes at least one day, a new analysis method is required to quickly and accurately analyze rubber materials in which various parts such as hoses, seals, gaskets, and diaphragms are applied.
In this regard, the present inventors studied pyrolysis gas chromatography analysis for simple and rapid analysis of acrylonitrile (ACN) content and additives, especially plasticizer content in rubber materials, particularly acrylonitrile-butadiene rubber (NBR rubber) compositions. As a result, a calibration curve for quantifying acrylonitrile was obtained from pyrolysis gas chromatography results of NBR rubber standard samples having acrylonitrile content, and NBR rubber standard samples and additives having acrylonitrile content were formulated. From the pyrolysis gas chromatography results of the sample, a calibration curve from which the additive can be quantified was derived. Then, using the above two calibration curves and pyrolysis gas chromatography results of the unknown NBR rubber composition, it was found that acrylonitrile components and additives in the NBR rubber material, which were not possible in the conventional analytical method, can be quantitatively analyzed. Was completed.
Therefore, an object of the present invention is to provide a method capable of quantitatively analyzing the content of acrylonitrile component and additives contained in the NBR rubber composition with high reliability.
The present invention,
Three or more acrylonitrile-butadiene rubbers having different acrylonitrile contents were analyzed by pyrolysis gas chromatography, and the relative area ratio of acrylonitrile was obtained by the following equation (1), and the acrylonitrile content was corresponded to the acrylonitrile content to obtain acrylonitrile by the least square method. Obtaining a calibration curve equation of ronitrile;
[Equation 1]
In Formula 1, ACN is acrylonitrile.
Pyrolysis gas chromatography analysis of three or more samples in which acrylonitrile-butadiene rubber was mixed with different amounts of additives was carried out, and the relative area ratio of the additives was obtained by the following equation (2), and the additives were added by the least square method. Obtaining a calibration curve equation of; And
[Equation 2]
Pyrolysis gas chromatography analysis of an unknown acrylonitri-butadiene rubber composition was carried out to obtain the relative area ratios of acrylonitrile and additives according to
Characterized by the method of quantitative analysis of acrylonitrile and additives of the acrylonitrile-butadiene rubber composition comprising a.
According to the analytical method according to the present invention, it is possible to quickly and accurately derive the quantitative analysis of polymer components and additives of rubber parts applied to automobile parts such as seals, gaskets, diaphragms, hoses, mount dustproof rubbers, and the like. It can be used to check compliance with standards, respond to quality problems, prevent defects and develop new products, thus preventing product defects and contributing to quality improvement.
Figure 1 shows the position of each composition content peak of acrylonitrile-butadiene rubber as a result of pyrolysis gas chromatography (41% by weight of acrylonitrile).
2 is a calibration curve for quantitative analysis of acrylonitrile in acrylonitrile-butadiene rubber compositions.
Figure 3 shows the position of each composition content peak of the acrylonitrile-butadiene rubber composition (N41R) as a result of pyrolysis gas chromatography.
4 is a calibration curve for quantitative analysis of additives in acrylonitrile-butadiene rubber compositions (DOP quantitative analysis at 41 wt% acrylonitrile).
Hereinafter, the present invention will be described in more detail.
The present invention is subjected to pyrolysis gas chromatography analysis of a rubber standard sample having acrylonitrile content, a rubber standard sample having acrylonitrile content and additives, and a calibration curve obtained from relative area ratios for each ratio. It relates to an analytical method for quantifying acrylonitrile and additives from a calibration curve.
The quantitative analysis method of the present invention can be applied to all rubber material parts and plastic parts, but in order to introduce a specific and accurate test method, an acrylonitrile rubber (NBR rubber) material was targeted. As described above, NBR rubber is a material that is widely applied to automotive parts requiring oil and fuel resistance such as seals, gaskets, diaphragms, and hoses.
Conventionally, rubber additives such as plasticizers, vulcanization accelerators and anti-aging agents have a low molecular weight, a boiling point of 300 ° C. or less, are easily extracted with organic solvents such as acetone and chloroform, and quantitatively analyzed by gas chromatography analysis. . That is, it is quantified using the absolute area value of the peak of each component obtained from the data processing device. For the quantification, the absolute test specified in KS M0031 (the general rule for gas chromatography analysis) with a plurality of standard samples of known content The calibration curve function was obtained by applying the curve method.
However, the method of analyzing an additive sample in powder or liquid form can be carried out as described above, but in order to quantify the polymer component in solid vulcanized rubber, the polymer sample cannot be extracted by an extraction method. Pyrolysis gas chromatography analysis with burned gases should be applied. Therefore, in the present invention, without applying the organic solvent extraction method, a method of pyrolyzing the sample at a high temperature of 500 ℃ or more was applied by gas chromatography analysis method. However, depending on the degree of pyrolysis of vulcanized rubber at high temperature, the sensitivity of the peak is different for each component. Therefore, it cannot be quantified by the absolute calibration curve method, the internal standard material method, the area percentage method, etc., and the influence of the peak sensitivity of the polymer sample and the additive included in the rubber should be considered.
In the present invention, in order to eliminate the quantitative analysis impossible and errors due to the sensitivity difference of each component, the relative area ratio of each ratio was obtained, and approached by a method of inferring through a calibration curve. That is, the relative area calibration curve of each ratio is obtained, and the following steps are performed to quantitatively analyze the NBR rubber composition.
First, in order to determine the acrylonitrile (ACN) content in NBR rubber, the area of butadiene and acrylonitrile peaks was determined by pyrolysis gas chromatography, and three acrylonitrile contents of which acrylonitrile content is known Obtained from the above standard samples. The areas of acrylonitrile and butadiene peaks are obtained from the areas of the peaks at positions b and c, respectively, as shown in FIG. The reason for selecting butadiene dimer position for butadiene content calculation is to reduce error due to overlapping peaks at position a by applying a short column length (eg 30m Agilent HP-5) to reduce analysis time. . After calculating the area of the peaks at positions b and c from three or more standard samples, the relative area ratio of acrylonitrile was calculated by
In the next step, by mixing a standard sample and an additive having a known acrylonitrile content, three or more samples having different amounts of additives are prepared for each standard sample. Generally, the blended rubber composition can be obtained by mixing a planned rubber raw material and additives, kneading with a kneader and an open roll, and quenching at 180 ° C. for 10 minutes by heat press, followed by secondary vulcanization at 150 ° C. for 30 minutes. . However, in order to obtain a calibration curve, a plurality of samples should be made by mixing various additives, and making a sample by the above method is problematic in time and economics.
In the present invention, for the sake of experimental convenience, in order to contain the additive planned in the NBR rubber standard sample to the desired content, the weight of the additive is measured and mixed with the standard sample, so that the sample is homogenized while pulverized and mixed at a low temperature with a freeze mill. It was. The freeze crusher is a device for crushing the sample by reciprocating vertically reciprocating the steel sphere of 2 ~ 3 cm at 1250 rpm in a steel container cooled to low temperature under liquid nitrogen to freeze grinding into particles of 100 ㎛ or less. In the case of a rubber sample, since it is changed to glassy glass below the glass transition temperature, it is easily broken and granulated like plastic. In the embodiment of the present invention, the phthalate-based plasticizer selected as an additive is liquid at room temperature but changes to solid at low temperature, so it is mixed in a homogeneous mixture with rubber as it is powdered in a freezing mill. At this time, the amount of rubber used is 3 g, the additive is within 1 g, the grinding time is 3 to 5 minutes is sufficient.
From the sample thus prepared, data is obtained through pyrolysis gas chromatography, and the peak area for each component is obtained as before. Subsequently, the relative area ratio of the additive is calculated by the following Equation 2, and the additive calibration curve equation is obtained by the least-square method corresponding to the content of the additive.
The two calibration curve equations change little by little in accordance with changes in the analysis environment, such as column replacement, detector cleaning, and replacement of gas lines supplied to the equipment. Therefore, if the analysis environment has changed even after the calibration curve equation is drawn, it is desirable to obtain and use it again whenever an unknown sample analysis is performed for reliable analysis.
In the two linear equations obtained through the above two steps, the relative area ratio of acrylonitrile and the relative area ratio of the additive obtained from the pyrolysis gas chromatography results of the unknown sample are respectively substituted to quantify the content of acrylonitrile and the additive in the rubber composition. You can analyze it. In other words, the content of acrylonitrile and additives can be obtained simultaneously by testing one unknown sample.
According to the quantitative analysis method of the present invention, the content of the polymer constituents and various additives in the rubber composition can be analyzed with simple and excellent reliability from two calibration curves obtained from a sample having a known content ratio and pyrolysis gas chromatography results of an unknown sample. Therefore, it can be usefully applied to check rubber material's compliance with material standards, respond to quality problems, prevent defects and benchmark.
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by the following Examples.
[Example]
Pyrolysis gas chromatography analysis was performed on standard samples containing 18, 28, 34, 41 wt% acrylonitrile based on 100 wt% NBR rubber. For reference, NBR rubbers used in industry almost all have acrylonitrile content of one of the four. Pyrolyzer JCI 22S manufactured by JAI Co., Ltd. was used. In order to pyrolyze at 590 ° C, 0.5-0.8 mg of the sample was taken in 590 ° C pyrofoil and the pyrofoil was sampled and injected into the device. . Gas chromatography of the samples vaporized in the Pyrolyzer was analyzed with Agilent's 6890GC / 5975B MS instrument. At this time, the applied column was Agilent's HP-5, helium was flowed at a rate of 1 mL / min as a mobile phase gas, and the oven temperature was raised at a rate of 10 ° C./min from 40 ° C. to 280 ° C. MSD was used as a detector, and the analysis results are shown in Table 1 and FIGS. 1 and 2.
Linear equation of calibration curve: y = 0.022x + 0.0110
In the linear equation, x is acrylonitrile content (% by weight), and y is relative area ratio ACN .
Next, mix the standard sample and the additive so that the additive content is 5, 15, and 30 parts by weight in 100 parts by weight of the standard sample having 18, 28, 34, and 41 weight% of acrylonitrile, for uniform mixing. The sample was ground in a freeze mill (JFC 300, JAI Co., Ltd.) below the sub-zero temperature to prepare a sample. As the additive, dioctylphthalate (DOP), dioctyl adipate (DOA), and dioctyl sebacate (DOS), which are phthalate-based plasticizers, were selected, and each of three standard plasticizers had three contents for each plasticizer. After preparing two samples, pyrolysis gas chromatography analysis of the samples was performed. The results of pyrolysis gas chromatography analysis of the samples are shown in Tables 2 to 5 and FIGS. 3 to 4.
(ACN 18 wt%)
100 parts by weight
Linear equation of calibration curve: y 1 = 0.0038x + 0.8682, y 2 = 0.0055x + 0.8079, y 3 = 0.0045x + 0.844
In the linear equation, x is the additive content (part by weight), y 1 is the relative area ratio DOP , y 2 is the relative area ratio DOA , and y 3 is the relative area ratio DOS .
(28 wt% of ACN)
100 parts by weight
Linear equation of calibration curve: y 4 = 0.0048x + 0.8256, y 5 = 0.0073x + 0.7377, y 6 = 0.0056x + 0.7951
In the linear equation, x is the additive content (parts by weight), y 4 is the relative area ratio DOP , y 5 is the relative area ratio DOA , and y 6 is the relative area ratio DOS .
(ACN 34% by weight)
100 parts by weight
Linear equation of calibration curve: y 7 = 0.0059x + 0.7878, y 8 = 0.0085x + 0.6938, y 9 = 0.0063x + 0.7658
In the linear equation, x is the additive content (parts by weight), y 7 is the relative area ratio DOP , y 8 is the relative area ratio DOA , and y 9 is the relative area ratio DOS .
(ACN 41 wt%)
100 parts by weight
Linear equation of calibration curve: y 10 = 0.0074x + 0.7375, y 11 = 0.0094x + 0.6598, y 12 = 0.0086x + 0.7026
In the linear equation, x is the additive content (part by weight), y 10 is the relative area ratio DOP , y 11 is the relative area ratio DOA , and y 12 is the relative area ratio DOS .
Next, pyrolysis gas chromatography analysis was carried out on samples of which acrylonitrile content and additive content were known. Samples were selected from three O-ring products made of NBR rubber. N28A (JSR) product contains 28% by weight of acrylonitrile in NBR rubber and 5 parts by weight of DOP based on 100 parts by weight of NBR rubber.N41A (JSR) product contains 41% by weight of acrylonitrile and 5% by weight of DOA. Parts and 5 parts by weight of DOS, N41R (JSR) is a sample of 41% by weight of acrylonitrile and 10, 5, 5 parts by weight of DOP, DOA and DOS, respectively. Pyrolysis gas chromatography analysis results are shown in Table 6 below.
From the results of Table 6, it can be seen that the N28A product should be applied to the equations y and y 4 , the N41A product should be applied to the equations y, y 11 and y 12 , and the N41R product to the equations y, y 10 , y 11 and y 12 , Application results are shown in Table 7 below.
As shown in Table 7, it can be seen that the result of applying the quantitative analysis method of the present invention to three O-ring products shows a quantification error within 2%. Therefore, according to the present invention, it was confirmed that the content of acrylonitrile and the additive in the NBR rubber composition can be quantitatively analyzed with simple and excellent reliability.
In addition, the quantitative analysis method of the present invention is expected to be applicable to the analysis of the content of polymer components and various additives such as other rubber material parts and plastic parts in addition to the NBR rubber composition.
Claims (2)
[Equation 1]
In Formula 1, ACN is acrylonitrile.
Pyrolysis gas chromatography analysis of three or more samples in which acrylonitrile-butadiene rubber was mixed with different amounts of additives was carried out, and the relative area ratio of the additives was obtained by the following equation (2), and the additives were added by the least square method. Obtaining a calibration curve equation of; And
[Equation 2]
Pyrolysis gas chromatography analysis of an unknown acrylonitri-butadiene rubber composition was carried out to obtain the relative area ratios of acrylonitrile and additives according to Equations 1 and 2 above, and substituted into the acrylonitrile calibration curve equation and the additive calibration curve equation. Determining the content of ronitrile and additives;
Method for quantitative analysis of acrylonitrile and additives of acrylonitrile-butadiene rubber composition comprising a.
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| CN102628845A (en) * | 2012-04-10 | 2012-08-08 | 中国烟草总公司郑州烟草研究院 | Method for relatively quantifying thermal cracking flavor compounds of tobacco flavor based on internal standard method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102628845A (en) * | 2012-04-10 | 2012-08-08 | 中国烟草总公司郑州烟草研究院 | Method for relatively quantifying thermal cracking flavor compounds of tobacco flavor based on internal standard method |
| KR101349163B1 (en) | 2012-10-10 | 2014-01-09 | 현대자동차주식회사 | A method for quantitative analysis of polycarbonate/acrylonitrile-butadiene-styrene using an elemental analyzer |
| CN107102068A (en) * | 2016-02-19 | 2017-08-29 | 北京橡胶工业研究设计院 | A kind of assay method of fluorubber kind |
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