KR100369712B1 - Analytical method of solution-sbr - Google Patents
Analytical method of solution-sbr Download PDFInfo
- Publication number
- KR100369712B1 KR100369712B1 KR10-1999-0034537A KR19990034537A KR100369712B1 KR 100369712 B1 KR100369712 B1 KR 100369712B1 KR 19990034537 A KR19990034537 A KR 19990034537A KR 100369712 B1 KR100369712 B1 KR 100369712B1
- Authority
- KR
- South Korea
- Prior art keywords
- sbr
- rubber
- analysis
- analysis method
- extracted
- Prior art date
Links
- 238000004458 analytical method Methods 0.000 title claims abstract description 16
- 229920001971 elastomer Polymers 0.000 claims abstract description 16
- 239000005060 rubber Substances 0.000 claims abstract description 16
- 230000009477 glass transition Effects 0.000 claims abstract description 9
- 238000007707 calorimetry Methods 0.000 claims description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000000045 pyrolysis gas chromatography Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000005259 measurement Methods 0.000 claims 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 30
- 239000002174 Styrene-butadiene Substances 0.000 description 26
- 229920000642 polymer Polymers 0.000 description 10
- 229920002857 polybutadiene Polymers 0.000 description 9
- 239000005062 Polybutadiene Substances 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 238000004451 qualitative analysis Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 238000004445 quantitative analysis Methods 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/84—Systems specially adapted for particular applications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/44—Resins; Plastics; Rubber; Leather
- G01N33/445—Rubber
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Immunology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
- Sampling And Sample Adjustment (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating Or Analyzing Materials Using Thermal Means (AREA)
Abstract
본 발명은 S-SBR 분석법에 관한 것으로서, 좀더 상세하게는 시차열량 분석기를 이용하여 고무의 유리전이온도를 측정하는 것을 특징으로 하는 S-SBR의 분석법에 관한 것이다.The present invention relates to an S-SBR analysis method, and more particularly, to an analysis method of S-SBR characterized by measuring the glass transition temperature of a rubber using a differential calorimeter.
Description
본 발명은 용액 중합 스티렌 부타디엔 고무(SOLUTION-SBR: 이하 S-SBR이라 한다) 분석법에 관한 것으로서, 좀더 상세하게는 시차열량 분석기를 이용하여 고무의 유리전이온도를 측정하는 것을 특징으로 하는 S-SBR의 분석법에 관한 것이다.The present invention relates to a solution-polymerized styrene butadiene rubber (SOLUTION-SBR: hereinafter referred to as S-SBR) analysis method, and more particularly S-SBR characterized by measuring the glass transition temperature of the rubber using a differential calorimetry analyzer It is about the method of analysis.
고성능의 스포츠카, 전기 자동차 및 환경친화적 제품의 필요성으로 S-SBR의 트레드 사용량이 날로 증가하고 있다. 현재 사용되고 있는 S-SBR은 약 50 종이 넘는다. S-SBR은 4개의 미세구조로 구성되는데, 그 구성은 트랜스(trans), 시스 (cis), 비닐(vinyl), 스티렌(styrene)이며 촉매에 의해 그 함량을 변화시킬 수 있어 다종의 제품을 만들수 있는 장점이 있다.The demand for high-performance sports cars, electric vehicles and environmentally friendly products is increasing the use of treads in the S-SBR. There are more than 50 S-SBRs in use today. S-SBR is composed of 4 microstructures, which are trans, cis, vinyl, and styrene, and the content can be changed by a catalyst to make a variety of products. There is an advantage.
이와는 달리 유화 중합 스티렌 부타디엔 고무(Emulsion-SBR: 이하 E-SBR이라 한다)는 이들 4개의 미세구조의 함량이 고정되므로 1종류밖에는 만들 수 없다. 따라서 E-SBR이 타이어에서 다른 폴리머인 천연고무와 합성고무인 폴리부타디엔, 부틸고무, 그리고 이피디엠고무와 서로 일정비율로 혼용되어 있을 때 E-SBR의 정성과 정량분석이 쉽다.On the other hand, emulsion-polymerized styrene butadiene rubber (Emulsion-SBR: hereinafter referred to as E-SBR) can only be made of one type because the content of these four microstructures is fixed. Therefore, when E-SBR is mixed with other polymers such as natural rubber, synthetic rubber, polybutadiene, butyl rubber, and EPDM rubber in a certain ratio, it is easy to quantitatively and quantitatively analyze E-SBR.
그러나 S-SBR은 종류가 많고 미세구조함량도 다양하므로 정성과 정량분석이어렵다.However, S-SBR is difficult to qualitatively and quantitatively analyze because it has many kinds and various microstructure contents.
기존의 S-SBR 분석은 열분해 기체크로마토그래피를 이용하여 분석하였는데, 시료를 550℃에서 열분해시키면 폴리머 별 분해물의 구조가 달라 분리관을 통과할 때 머무르는 시간이 다르게 되므로 폴리머의 혼용비와 S-SBR의 정성이 가능하다. 그러나 이 방법은 반드시 표준시료가 있어야 하는 단점이 있기 때문에 S-SBR의 경우 표준시료 갯수가 수천개를 필요로 하므로 분석이 불가능하다. 그리고 이 방법은 부타디엔의 고무와 혼용되었을 때 분석을 할 수 없다는 최대의 단점을 지니고 있다.Conventional S-SBR analysis was performed using pyrolysis gas chromatography. When the sample was pyrolyzed at 550 ° C, the decomposition time of each polymer was different, so that the time to stay when passing through the separation tube was different. Sincerity is possible. However, this method has the disadvantage of having a standard sample, so it is impossible to analyze because S-SBR requires thousands of standard samples. And this method has the biggest disadvantage of being unable to analyze when mixed with rubber of butadiene.
이러한 단점을 보완한 기존의 또 하나의 방법은 적외선 분광계를 이용한 방법이다. 이 방법은 S-SBR의 미세구조인 트랜스, 시스, 비닐, 스티렌이 각각 자기 고유적외선 영역에서 빛 에너지를 흡수하기 때문에 사용 가능한 방법이다. 트랜스는 파수 968, 시스는 910, 비닐은 739, 스티렌은 700에서 흡수하므로 S-SBR의 정성이 가능하며, 이들 각각의 몰흡광 계수는 1.13, 2.50, 1.00, 0.7이다. 이들로부터 이들 4개의 미세구조에 대한 절대함량을 구할 수 있어 정량이 가능하므로 정성과 정량분석이 가능함을 보여준다.Another conventional method that solves these shortcomings is the method using an infrared spectrometer. This method can be used because S-SBR's microstructures, such as trans, sheath, vinyl and styrene, absorb light energy in the region of their own infrared rays. Since the trans is absorbed by wave number 968, sheath 910, vinyl 739, and styrene 700, the S-SBR can be qualitative, and their respective molar absorption coefficients are 1.13, 2.50, 1.00, and 0.7. From these, the absolute contents of these four microstructures can be obtained and quantification is possible, which shows that qualitative and quantitative analysis is possible.
그러나 이 분석법도 S-SBR과 폴리부타디엔고무(BR)와 혼용되거나 서로 다른 두개 이상의 S-SBR이 혼용된 경우는 정확한 분석이 어렵다. 그 이유는 S-SBR/BR 혼용계에서 S-SBR의 미세구조인 시스와 폴리부타디엔의 시스의 적외선 흡수영역이 겹치기 때문이다. 그리고 이종의 S-SBR이 혼용된 경우에도 4개의 미세구조가 같은 파수 영역에서 중첩되기 때문에 정확한 정성분석이 어렵다. 그리고 폴리머의 혼용성도 알 수가 없다.However, this method is also difficult to analyze correctly when S-SBR and polybutadiene rubber (BR) are mixed or when two or more different S-SBRs are mixed. This is because the infrared absorption regions of the sheath of polybutadiene and the sheath of microstructure of S-SBR overlap in the S-SBR / BR mixed system. And even if heterogeneous S-SBR is mixed, it is difficult to accurately analyze qualitatively because the four microstructures overlap in the same wave range. And the compatibility of the polymer is unknown.
본 발명의 목적은 상기와 같은 문제점을 개선하기 위한 것으로서, 정확한 정성과 정량분석이 가능한 S-SBR의 분석법을 제공하는 것이다.An object of the present invention is to improve the above problems, to provide an analysis method of S-SBR capable of accurate qualitative and quantitative analysis.
본 발명의 S-SBR의 분석법은 타이어로부터 채취된 고무시료를 건조시킨 후, 오르소 다이클로로벤젠 중에서 가열하여 추출한 고무를 시차열량분석용 용기에 담아 용매를 완전히 증발시킨 후 급냉시키고, 승온속도 10℃, 측정온도범위 -105~100℃에서 시차열량 분석기를 이용하여 고무의 유리전이온도를 측정하는 것을 특징으로 한다.In the analysis method of S-SBR of the present invention, after drying the rubber sample collected from the tire, the rubber extracted by heating in ortho dichlorobenzene is put in a container for differential calorimetry, the solvent is completely evaporated and then quenched, and the heating rate is 10 It is characterized by measuring the glass transition temperature of the rubber using a differential calorimetry analyzer in the temperature range of -105 ~ 100 ℃ ℃.
폴리머는 자기 고유의 유리전이온도를 가지고 있으므로, 고유의 유리전이온도를 측정하여 고무가 구성하고 있는 폴리머가 몇 종류인지 어떤 종류의 폴리머인지 분석이 가능하다. 따라서 시차열량 분석기를 이용하여 고무의 유리전이온도를 측정하여 폴리머를 확인할 수 있었다.Since the polymer has its own glass transition temperature, it is possible to analyze how many kinds of polymers and what kind of polymer the rubber comprises by measuring its own glass transition temperature. Therefore, the polymer was identified by measuring the glass transition temperature of the rubber using a differential calorimeter.
또한 폴리머가 확인이 되면, 상기 추출한 고무를 일정양 취하여 브롬화칼륨에 일정두께로 바르고 건조시킨 후 분석을 행하는 적외선 분광계와 상기 추출한 고무를 550℃에서 열분해시키는 열분해 기체크로마토그래피에 의해 구해진 미세구조의 절대함량에서 S-SBR의 정성과 정량분석을 할 수 있다.In addition, when the polymer is confirmed, an absolute amount of the microstructure obtained by taking a predetermined amount of the extracted rubber, applying it to potassium bromide to a certain thickness, drying, and analyzing the infrared spectrometer and pyrolysis gas chromatography to thermally decompose the extracted rubber at 550 ° C From the content, the qualitative and quantitative analysis of S-SBR can be performed.
본 발명은 하기 실시예에 의하여 보다 구체적으로 이해될 수 있고, 하기의 실시예는 본 발명을 예시하기 위한 것에 지나지 않으며 본 발명의 보호범위를 제한하고자 하는 것은 아니다.The present invention can be understood in more detail by the following examples, the following examples are only for illustrating the present invention and are not intended to limit the protection scope of the present invention.
실시예Example
고무배합물에 함유된 유기물을 아세톤으로 추출한 후 비등점이 높은 용매를 사용하여 자유로운(free) 폴리머를 추출하고 이 시료를 적외선 분광기에 의한 미세구조 분석과 시차열량 분석기에 의한 유리전이온도를 측정하여 정량 및 정성분석을 실시하였다.After extracting the organic substance contained in the rubber compound with acetone, the free polymer is extracted using a solvent having a high boiling point, and the sample is quantitatively determined by measuring the glass transition temperature by infrared spectroscopy and differential calorimetry. Qualitative analysis was performed.
실시예 1Example 1
부타디엔 고무(BR)와 SL-574가 혼합된 S-SBR 조성물을 정성과 정량분석하여 그 결과를 표 1에 나타내었다.Butadiene rubber (BR) and S-SBR composition mixed with SL-574 qualitatively and quantitatively analyzed the results are shown in Table 1.
표 1Table 1
실시예 2Example 2
SBR1502과 NS116이 혼합된 S-SBR 조성물을 정성과 정량분석하여 그 결과를 표 2에 나타내었다.Qualitative and quantitative analysis of the S-SBR composition mixed with SBR1502 and NS116 is shown in Table 2 the results.
표 2TABLE 2
표 1에서 보이듯이 적외선 분광기에 의한 미세구조의 함량을 측정하고 유리전이온도를 측정한 결과 부타디엔 고무와 S-SBR의 혼용성을 알 수 있었다. 일반적으로 S-SBR 폴리머의 시스(cis) 함량이 20% 미만임으로 이를 근거로 하여 미세구조의 상대적인 함량을 알 수 있었다. 분석결과는 부타디엔 고무와 SL-574가 혼용된 것으로 확인되었다.As shown in Table 1, the content of the microstructure by the infrared spectrometer and the glass transition temperature were measured, and the compatibility between butadiene rubber and S-SBR was found. In general, since the cis content of the S-SBR polymer is less than 20%, the relative content of the microstructure was found. The analysis results showed that butadiene rubber was mixed with SL-574.
또한 표 2에서 보이듯이 미세구조 분석만으로는 혼용 가능성이 SBR1502/NS116 = 70/30 이거나 SBR1502/NS116 = 50/50 으로 볼 수 있으나 유리전이온도 결과치에서 SBR1502/NS116으로 혼용되었다는 것을 알 수 있었다.In addition, as shown in Table 2, the microstructure analysis alone shows the possibility of mixing SBR1502 / NS116 = 70/30 or SBR1502 / NS116 = 50/50.
이상에서 볼 수 있는 바와 같이, 본 발명의 분석법에 의하여 S-SBR의 혼용비와 정성분석이 가능한 효과가 있다.As can be seen from the above, the mixing ratio and qualitative analysis of the S-SBR is possible by the analysis method of the present invention.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-1999-0034537A KR100369712B1 (en) | 1999-08-20 | 1999-08-20 | Analytical method of solution-sbr |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-1999-0034537A KR100369712B1 (en) | 1999-08-20 | 1999-08-20 | Analytical method of solution-sbr |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20010018544A KR20010018544A (en) | 2001-03-05 |
| KR100369712B1 true KR100369712B1 (en) | 2003-01-29 |
Family
ID=19607987
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR10-1999-0034537A KR100369712B1 (en) | 1999-08-20 | 1999-08-20 | Analytical method of solution-sbr |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR100369712B1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4777211A (en) * | 1985-08-21 | 1988-10-11 | Monsanto Company | Rubber-modified nylon composition |
| JPH03148046A (en) * | 1989-11-02 | 1991-06-24 | Toshiba Corp | Method for measuring glass transition temperature |
| JPH06330404A (en) * | 1993-05-24 | 1994-11-29 | Asahi Chem Ind Co Ltd | Production of polyamide fiber |
| JPH10253558A (en) * | 1997-03-07 | 1998-09-25 | Setaram Soc Etud Automat Regulation & Appareils De Mesures | Measuring device for thermal characteristics and/or reaction characteristics |
-
1999
- 1999-08-20 KR KR10-1999-0034537A patent/KR100369712B1/en not_active IP Right Cessation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4777211A (en) * | 1985-08-21 | 1988-10-11 | Monsanto Company | Rubber-modified nylon composition |
| JPH03148046A (en) * | 1989-11-02 | 1991-06-24 | Toshiba Corp | Method for measuring glass transition temperature |
| JPH06330404A (en) * | 1993-05-24 | 1994-11-29 | Asahi Chem Ind Co Ltd | Production of polyamide fiber |
| JPH10253558A (en) * | 1997-03-07 | 1998-09-25 | Setaram Soc Etud Automat Regulation & Appareils De Mesures | Measuring device for thermal characteristics and/or reaction characteristics |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20010018544A (en) | 2001-03-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Rover et al. | Total water-soluble sugars quantification in bio-oil using the phenol–sulfuric acid assay | |
| CN103399105B (en) | Aanalysis method of residual quantities of eighteen photoinitiators in ultra violet (UV) printing ink | |
| Lachenmeier et al. | Application of tandem mass spectrometry combined with gas chromatography and headspace solid‐phase dynamic extraction for the determination of drugs of abuse in hair samples | |
| Tranchida et al. | Untargeted and targeted comprehensive two-dimensional GC analysis using a novel unified high-speed triple quadrupole mass spectrometer | |
| Wang | Polymer analysis by pyrolysis gas chromatography | |
| CN102175785B (en) | Method for detecting VOC (Volatile Organic Compound) matters in toy paint | |
| CN103575828B (en) | Method for measuring anti-scorching agent CTP of rubber | |
| CN111239267B (en) | Method for detecting short-chain fatty acids in serum and lymph tissue based on GC-MS | |
| CN108885195A (en) | The analysis method of the copolymer of conjugated diene compound and aromatic ethenyl compound | |
| CN103399096A (en) | Method for detecting content of malachite green and metabolin thereof in sediment of aquaculture environment | |
| CN104655582B (en) | Infrared spectrometry method for determining content of bound acrylonitrile in nitrile rubber | |
| CN110763644B (en) | Separation method of four components of asphalt | |
| CN104820030A (en) | Method for detecting six phthalates in drinking water through liquid chromatography-mass spectrometry | |
| KR100369712B1 (en) | Analytical method of solution-sbr | |
| CN109870559A (en) | A kind of discrimination method of ABS plastic reworked material | |
| CN102507773B (en) | Method for selectively determining residual vinyl acetate in white latex for cigarette through static headspace gas and chromatography mass spectrometry | |
| CN107727602B (en) | Method for quantitatively analyzing content of sucralose by combining mid-infrared spectrum with vector included angle | |
| Brown et al. | Microbore liquid chromatography with flow cell Fourier transform infrared spectrometric detection | |
| CN109633047B (en) | Method for simultaneously detecting multiple phthalate plasticizers in consumer products | |
| Quinn et al. | Fractionation of phenol-formaldehyde reaction mixtures with gel permeation chromatography | |
| Kuligowski et al. | Application of point-to-point matching algorithms for background correction in on-line liquid chromatography–Fourier transform infrared spectrometry (LC–FTIR) | |
| JP2006329641A (en) | Analyzing method of solvent soluble coloring matter | |
| Lu et al. | Quantitative determination on binary-component polymer bonded explosives: A joint study of ultraviolet spectrophotometry and multivariate calibration methods | |
| Kaiser et al. | Diffuse reflectance infrared spectrometric analysis of ultrathin film Carbowax 20M on Chromosorb W | |
| Klun et al. | Electrospray mass spectrometry determination of linear and cyclic oligomers of polyamide-6 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20080111 Year of fee payment: 6 |
|
| LAPS | Lapse due to unpaid annual fee |