KR20050120258A - Apparatus for analysing vocalization accelerator contained in vulcanized natural and synthetic rubber product - Google Patents
Apparatus for analysing vocalization accelerator contained in vulcanized natural and synthetic rubber product Download PDFInfo
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- KR20050120258A KR20050120258A KR1020040045541A KR20040045541A KR20050120258A KR 20050120258 A KR20050120258 A KR 20050120258A KR 1020040045541 A KR1020040045541 A KR 1020040045541A KR 20040045541 A KR20040045541 A KR 20040045541A KR 20050120258 A KR20050120258 A KR 20050120258A
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- 229920003052 natural elastomer Polymers 0.000 title claims abstract description 18
- 229920001194 natural rubber Polymers 0.000 title claims abstract description 18
- 229920003051 synthetic elastomer Polymers 0.000 title claims abstract description 18
- 239000005061 synthetic rubber Substances 0.000 title claims abstract description 18
- 238000004073 vulcanization Methods 0.000 claims abstract description 42
- 150000001412 amines Chemical class 0.000 claims abstract description 26
- 229920001971 elastomer Polymers 0.000 claims abstract description 24
- 239000005060 rubber Substances 0.000 claims abstract description 24
- 238000001179 sorption measurement Methods 0.000 claims abstract description 23
- 238000004458 analytical method Methods 0.000 claims abstract description 17
- 238000003795 desorption Methods 0.000 claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims abstract description 10
- 239000011521 glass Substances 0.000 claims abstract description 8
- 238000000605 extraction Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 5
- 239000010935 stainless steel Substances 0.000 claims abstract description 5
- 239000012141 concentrate Substances 0.000 claims abstract description 4
- 238000010257 thawing Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 5
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 2
- 238000009472 formulation Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 8
- 238000004949 mass spectrometry Methods 0.000 description 5
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000010058 rubber compounding Methods 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- 229940054266 2-mercaptobenzothiazole Drugs 0.000 description 1
- XTDMOBIAHSICBE-UHFFFAOYSA-N 3h-1,3-benzothiazole-2-thione;cyclohexanamine Chemical compound NC1CCCCC1.C1=CC=C2SC(S)=NC2=C1 XTDMOBIAHSICBE-UHFFFAOYSA-N 0.000 description 1
- VVZQSQQMQGBSPB-UHFFFAOYSA-N 3h-1,3-benzothiazole-2-thione;morpholine Chemical compound C1COCCN1.C1=CC=C2SC(=S)NC2=C1 VVZQSQQMQGBSPB-UHFFFAOYSA-N 0.000 description 1
- MHKLKWCYGIBEQF-UHFFFAOYSA-N 4-(1,3-benzothiazol-2-ylsulfanyl)morpholine Chemical compound C1COCCN1SC1=NC2=CC=CC=C2S1 MHKLKWCYGIBEQF-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 229940032017 n-oxydiethylene-2-benzothiazole sulfenamide Drugs 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical class [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
- G01N30/7206—Mass spectrometers interfaced to gas chromatograph
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
본 발명은 가황된 천연 또는 합성 고무 중에 원래의 배합 시 사용된 가황촉진제를 효율적으로 분석해낼 수 있는 장치를 제공하기 위한 것이다. The present invention is to provide a device capable of efficiently analyzing the vulcanization accelerator used in the original formulation in vulcanized natural or synthetic rubber.
본 발명의 분석장치는 가황된 천연 또는 합성고무에 배합된 가황촉진제를 분석하기 위해 세단한 고무시료로부터 휘발되어 나오는 아민성분을 충진 흡착관으로 이송하기 위한 연속 추출장치; 내경이 0.1 내지 1.0cm이고, 길이가 5 내지 15cm의 크기를 갖는 스테인레스 스틸 또는 유리 재질로 된 원형관으로 이루어진 상기 아민성분을 흡착하기 위한 충진 흡착관; 상기 흡착된 아민 성분을 분석이 가능한 농도 이상으로 농축하기 위하여 상기 충진 흡착관의 주변을 원형 코일형태로 둘러싸고 있는 액체 질소도관의 저온농축장치; 상기 충진 흡착관을 해동하여 흡착된 아민성분을 열탈착시키기 위한 열탈착 장치; 상기 열탈착된 성분을 분리·분석하게 되는 가스크로마토그래프 및 아민의 분자량을 확인하여 가황촉진제의 종류를 분석하게 되는 질량분석기로 구성되어 있다.The analysis device of the present invention comprises a continuous extraction device for transferring the amine component volatilized from the fine rubber sample to the packed adsorption tube to analyze the vulcanization accelerator blended in vulcanized natural or synthetic rubber; A packed adsorption tube for adsorbing the amine component made of a stainless steel or glass circular tube having an inner diameter of 0.1 to 1.0 cm and a length of 5 to 15 cm; A low temperature concentrating device of a liquid nitrogen conduit surrounding the periphery of the packed adsorption tube in the form of a circular coil in order to concentrate the adsorbed amine component above a concentration that can be analyzed; A heat desorption apparatus for desorption of the adsorbed amine component by thawing the packed adsorption tube; It consists of a gas chromatograph to separate and analyze the thermally desorbed components and a mass spectrometer to analyze the type of vulcanization accelerator by checking the molecular weight of the amine.
Description
본 발명은 가황된 천연 또는 합성고무 제품의 가황촉진제 분석장치에 관한 것이다. 가황된 천연 또는 합성 고무 중에 원래의 배합 시 사용된 가황촉진제를 분석해낼 수 있는 장치에 관한 것이다. The present invention relates to a vulcanization accelerator analyzer for vulcanized natural or synthetic rubber products. The present invention relates to a device capable of analyzing the vulcanization accelerator used in the original formulation in vulcanized natural or synthetic rubber.
고무 제품은 점탄성체일 때 공업적 용도에 적합하게 된다. 이와 같은 소량의 점성과 많은 탄성을 갖는 고무제품을 만들기 위해 고무 배합에는 통상적으로 유황(S), 아연화(ZnO), 스테아린산 및 가황촉진제와 기타 배합제가 사용된다. Rubber products are suitable for industrial use when they are viscoelastic. In order to make a rubber product having such a small amount of viscosity and a lot of elasticity, rubber (S), zinc (ZnO), stearic acid and vulcanization accelerators and other compounding agents are commonly used in rubber compounding.
가황촉진제는 고무와 점탄성체로서의 성질을 갖도록 하기 위한 가황반응이 매우 느리기 때문에 그 반응 속도를 증진시키기 위한 목적으로 사용되는 화학성분으로 설펜아마이드계, 구아니딘계 등 여러 가지 종류가 있다. 가황촉진제를 배합에 처방함으로써 공업적 생산성의 이익을 얻을 수 있게 된다. Since vulcanization accelerators have very slow vulcanization reactions for rubber and viscoelastic properties, there are various kinds of chemical components used for the purpose of enhancing the reaction rate, such as sulfenamide series and guanidine series. By prescribing a vulcanization accelerator in the formulation, it is possible to benefit from industrial productivity.
이와 같은 가황촉진제는 고무 배합표 전체의 내용에 따라 달라지는 목표 물성에 따라 그 사용량(통상적으로는 0.1 내지 수 PHR)과 촉진제 종류가 달라지며, 따라서, 적절한 가황촉진제의 사용은 고무배합제 설계 기술에서 매우 중요한 요소 중 하나이며, 이와 같은 촉진제의 분석은 리버스엔지니어링 관점에서 매우 중요하다.Such vulcanization accelerators have different amounts (typically 0.1 to several PHR) and types of accelerators depending on the target physical properties, which depend on the contents of the entire rubber compounding table. Therefore, the use of a suitable vulcanization accelerator is very important in the rubber compound design technology. This is one of the most important factors, and the analysis of such accelerators is very important from a reverse engineering perspective.
종래의 고무 분석기술에 의하면, 가황촉진제는 가황반응 중에 분해되므로 분석이 불가능하다. 예를들어, 티아졸계 촉진제로 CZ(N-시클로헥실-2-벤조티아질 설펜아미드), MOR(N-옥시디에틸렌-2-벤조티아졸 설펜아미드)의 경우 가황 공정 중 분해가 일어나면 다음 반응식과 같이 CZ의 경우는 2-머캅토 벤조티아졸과 아민의 일종인 시클로헥실아민으로 MOR의 경우는 머캅토 벤조티아졸과 역시 아민의 일종인 모르폴린으로 분해된다. According to the conventional rubber analysis technology, the vulcanization accelerator is decomposed during the vulcanization reaction and thus cannot be analyzed. For example, in the case of CZ (N-cyclohexyl-2-benzothiazyl sulfenamide) and MOR (N-oxydiethylene-2-benzothiazole sulfenamide) as thiazole-based accelerators, when decomposition occurs during the vulcanization process, As for CZ, cyclohexylamine, which is a kind of 2-mercapto benzothiazole and amine, is decomposed into mercapto benzothiazole and morpholine, which is also a kind of amine.
[반응식][Scheme]
CZCZ
머캅토벤조티아졸 시클로헥실아민Mercaptobenzothiazole cyclohexylamine
MORMOR
머캅토벤조티아졸 모르폴린Mercaptobenzothiazole morpholine
이때, 분해 생성물로 생성된 머캅토 벤조티아졸은 증발력이 약해 고무 중에 대부분 잔존하게 되나 아민류들은 휘발성이 강하여 대부분 증발하여 고무 중에 극소량만 남게 된다. 가황반응 후 주로 잔존하는 머캅토 벤조티아졸(이하 "M"이라 칭함)은 서로 다른 촉진제에서 공통적으로 생성되므로 실제적으로 촉진제를 구별하는데 도움이 되지 못하며, 아민은 극소량이라 역시 분석하는 것이 곤란하였다. 또한, 분리분석이나 화학분석법으로도 분석이 어려워 지금까지 고무 중 가황촉진제의 분석은 거의 불가능한 실정이었다.At this time, the mercapto benzothiazole produced as a decomposition product is weak in evaporation power and remain mostly in the rubber, but amines are mostly volatile and evaporate, leaving only a very small amount in the rubber. The mercapto benzothiazole (hereinafter referred to as "M"), which remains predominantly after vulcanization, is commonly produced by different promoters and thus does not really help to distinguish between promoters, and amines are also very difficult to analyze. In addition, the analysis of the vulcanization accelerator in rubber is almost impossible until the analysis is difficult even by separation analysis or chemical analysis.
이에 본 발명은 상기와 같은 종래 문제점을 해결하기 위해 발명된 것으로, 본 발명자들은 가황된 천연 고무 또는 합성 고무 제품에서 원래 배합되어 있는 가황촉진제를 분석해 낼 수 있는 분석장치를 개발하여 본 발명을 완성하게 되었다. Accordingly, the present invention has been invented to solve the conventional problems as described above, the present inventors have developed an analysis device capable of analyzing the vulcanization accelerator originally blended in vulcanized natural rubber or synthetic rubber products to complete the present invention It became.
이에 본 발명은 가황된 천연 또는 합성고무 제품 중에서 가황촉진제를 효율적으로 분석해 낼 수 있는 분석장치를 제공하는데 그 목적이 있다.Accordingly, an object of the present invention is to provide an analysis apparatus capable of efficiently analyzing vulcanization accelerators in vulcanized natural or synthetic rubber products.
본 발명의 가황된 천연 또는 합성고무 제품의 가황촉진제 분석장치는 Vulcanization accelerator analysis device of the vulcanized natural or synthetic rubber products of the present invention
가황된 천연 또는 합성 고무에 배합된 가황촉진제를 분석하기 위해 세단한 고무시료를 담을 10 내지 20㎖ 크기의 석영제 외통 원형튜브와 내통 유리제 튜브, 상기 시료를 가열하기 위한 가열장치 및 가열에 의해 고무로부터 휘발되어 나오는 아민성분을 충진 흡착관으로 이송하기 위한 고순도 헬륨가스 연결튜브로 이루어진 연속 추출장치; 내경이 0.1 내지 1.0cm이고, 길이가 5 내지 15cm의 크기를 갖는 스테인레스스틸 또는 유리 재질로 된 원형관으로서 평균 기공크기가 150 나노미터이고, 비표면적인 25 ㎡/g이며 최고 사용온도가 350℃인 충진제로서 2,6-디페닐렌-옥사이드 폴리머 또는 활성탄이 충진되어 있는 흡착관; 상기 가황촉진제로부터 분해된 아민 성분을 흡착하여 분석이 가능한 농도 이상으로 농축하기 위하여 상기 충진 흡착관의 주변을 원형 코일형태로 둘러싸고 있는 액체 질소도관의 저온농축장치; 상기 충진 흡착관을 해동하여 흡착된 아민성분을 열탈착시키기 위한 열탈착 장치; 및 상기 열탈착된 성분을 분리 분석하게 되는 가스크로마토그래프 및 아민의 분자량을 확인하여 가황촉진제의 종류를 분석하게 되는 질량분석기로 구성되어 있는 것을 특징으로 한다. In order to analyze the vulcanization accelerator blended with vulcanized natural or synthetic rubber, a cylindrical outer tube and inner tube made of quartz having a size of 10 to 20 ml containing a thin rubber sample, a glass tube for heating the sample and rubber by heating Continuous extraction device consisting of a high purity helium gas connecting tube for transferring the amine component volatilized from the packed adsorption tube; Round tube made of stainless steel or glass with an inner diameter of 0.1 to 1.0 cm and a length of 5 to 15 cm, with an average pore size of 150 nanometers, a specific surface area of 25 m2 / g, and a maximum operating temperature of 350 ° C. Adsorption tubes filled with 2,6-diphenylene-oxide polymer or activated carbon as phosphorus fillers; A low temperature concentrating device of a liquid nitrogen conduit surrounding the periphery of the packed adsorption tube in the form of a circular coil in order to adsorb the amine component decomposed from the vulcanization accelerator and concentrate above a concentration that can be analyzed; A heat desorption apparatus for desorption of the adsorbed amine component by thawing the packed adsorption tube; And a mass spectrometer configured to analyze the type of the vulcanization accelerator by checking the molecular weight of the gas chromatograph and the amine to separate and analyze the thermally desorbed components.
이와 같은 본 발명을 더욱 상세하게 설명하면 다음과 같다. The present invention will be described in more detail as follows.
본 발명의 가황된 천연 또는 합성고무 제품의 가황촉진제 분석장치는 첨부 도면 중 도 1에 나타낸 바와 같이, 연속 추출장치(11), 충진 흡착관(12), 저온농축(Cryo-focusing : 13) 장치, 열탈착 장치(14) 및 가스크로마토그래프(15), 질량분석기(16)로 구성되어 있다.Vulcanization accelerator analysis device of the vulcanized natural or synthetic rubber product of the present invention, as shown in Figure 1 of the accompanying drawings, continuous extraction device 11, packed adsorption tube 12, cryo-focusing device (13) And a heat desorption apparatus 14, a gas chromatograph 15, and a mass spectrometer 16.
도 1에서 부호 11로 나타낸 연속 추출장치는 분석하고자 하는 세단한 고무시료를 담을 10 내지 20㎖ 크기의 석영제 외통 원형 튜브(111)와 내통 유리제 튜브(112), 상기 시료 튜브를 가열할 수 있는 가열장치(113) 및 가열에 의해 고무로부터 휘발되어 나오는 아민성분을 충진 흡착관(12)으로 이송하는데 필요한 운반 가스인 불활성의 일종인 고순도 헬륨가스 연결튜브(114)로 구성되어 있다.The continuous extraction device indicated by reference numeral 11 in Fig. 1 is capable of heating the outer tube round tube 111 and the inner tube glass 112 made of quartz having a size of 10 to 20 ml to hold the fine rubber sample to be analyzed, and the sample tube. It consists of a heating device 113 and a high purity helium gas connecting tube 114 which is a kind of inert gas which is a carrier gas necessary for transferring the amine component volatilized from the rubber by heating to the packed adsorption tube 12.
도 1에서 부호 12로 나타낸 충진 흡착관은 내경이 0.1 내지 1.0cm이고, 길이가 5 내지 15cm의 크기의 스테인레스스틸 또는 유리 재질로 된 원형관으로, 상기 연결튜브(114)로부터의 아민성분을 흡착하기 위한 충진제로서 2,6-디페닐렌-옥사이드 폴리머 또는 활성탄이 충진되어 있고, 평균 기공크기(Average pore size)가 150 나노미터 이상이며, 비표면적은 25 ㎡/g 이상이고, 최고 사용온도는 350℃ 이다.Filled adsorption tube, denoted by reference numeral 12 in FIG. 1, is a round tube made of stainless steel or glass of 0.1 to 1.0 cm in diameter and 5 to 15 cm in length, adsorbing the amine component from the connecting tube 114. As a filler to be filled with 2,6-diphenylene-oxide polymer or activated carbon, the average pore size (Average pore size) is more than 150 nanometers, the specific surface area is more than 25 m2 / g, the maximum operating temperature is 350 ° C.
휘발성이 강한 가황촉진제로부터 분해된 아민성분을 연속적으로 흡착하여 분석이 가능한 농도이상으로 농축하기 위해서는 저온장치가 필요하게 되는 바, 이를 위해 본 발명에서는 상기 충진 흡착관(12) 주변을 둘러싸서 액체 질소가 흐를 수 있도록 내경이 1/4인치인 원형 코일형태의 액체 질소도관의 저온농축장치(13)가 설치되어 있다.In order to continuously adsorb the amine component decomposed from the highly volatile vulcanization accelerator and concentrate it above the concentration that can be analyzed, a low temperature device is necessary. For this purpose, in the present invention, a liquid nitrogen is wrapped around the packed adsorption tube 12. The low temperature concentrating device 13 of the liquid nitrogen conduit in the form of a circular coil having an internal diameter of 1/4 inch is installed to allow flow.
도 1에서 부호 14로 나타낸 열탈작 장치는 상기 저온농축장치(13)와 연결 설치되어 있는 바, 상기 저온 농축에 의해 흡착제 고분자가 충진 흡착관(12)에서 일정시간 동안 연속적으로 아민류를 모은 후 상기 충진 흡착관(12)을 해동하게 되면, 헬륨가스의 불활성 분위기 하에서 순간적으로 고온으로 상승하여 흡착된 가황촉진제로의 아민 성분이 짧게는 수밀리초 길게는 수초에 걸쳐 열탈착하게 된다. In FIG. 1, the thermal denitrification device indicated by reference numeral 14 is installed in connection with the low temperature concentration device 13, and the sorbent polymer is continuously collected in the adsorption tube 12 filled with the adsorbent by the low temperature concentration for a predetermined time. When the packed adsorption tube 12 is thawed, the amine component to the adsorbed vulcanization accelerator instantly rises to a high temperature under an inert atmosphere of helium gas, and desorptions for several milliseconds for several seconds.
도 1에서 부호 15로 나타낸 가스크로마토그래피는 상기 열탈착 장치(14)와 연결되어 있으며, 열탈착된 성분을 분리 분석하게 되고, 부호 16으로 나타낸 질량분석기는 아민의 분자량을 확인하여 가황촉진제의 종류를 분석해내는 역할을 하게 된다. The gas chromatography shown in FIG. 1 is connected to the thermal desorption apparatus 14, and the thermal desorption component is separated and analyzed, and the mass spectrometer indicated by the code 16 analyzes the type of vulcanization accelerator by checking the molecular weight of the amine. I play a role.
본 발명에 따른 가황된 천연 또는 합성고무 제품의 가황촉진제 분석장치는 가황된 고무 제품 중 가황촉진제의 분해 잔류물 중 아민 성분을 고무로부터 열탈착하여 액체질소로 냉각된 고분자 흡착제 중에 흡착 농축한 것을 다시 순간 열탈착하고, 해당 열탈착 성분을 가스크로마토그래프-질량분석기로 주입하여 고무 중에 배합 설계 시 사용한 가황촉진제의 종류를 분석해내게 된다. The vulcanization accelerator analyzing apparatus of the vulcanized natural or synthetic rubber product according to the present invention is the instantaneous concentration of the amine component in the decomposition residue of the vulcanization accelerator in the vulcanized rubber product by adsorption and concentration in the polymer adsorbent cooled by liquid nitrogen. Thermal desorption is performed, and the thermal desorption component is injected into a gas chromatograph-mass spectrometer to analyze the type of vulcanization accelerator used in the formulation design in rubber.
도 2에 나타낸 바와 같이 저온농축장치(13)와 열탈착장치(14)는 가스크로마토그래피(15)와 같은 블록 내에 위치할 수 있고, 충진 흡착관(12)의 상부에 위치할 수도 있다. As shown in FIG. 2, the low temperature concentration device 13 and the heat desorption device 14 may be located in the same block as the gas chromatography 15, or may be located above the filling adsorption tube 12.
첨부 도면 중 도 2는 고무 중 가황촉진제인 CZ(N-시클로헥실-2-벤조티아질 설펜아미드)를 본 발명의 분석장치를 이용하여 분석한 결과를 나타낸 도면으로서, CZ의 열탈착 생성물인 시클로헥실아민과 벤조티아졸의 피크를 분석하는 것이 가능함을 알 수 있었다.FIG. 2 is a diagram showing the results of analyzing CZ (N-cyclohexyl-2-benzothiazyl sulfenamide), a vulcanization accelerator in rubber, using an analytical device of the present invention, and cyclohexyl, a thermal desorption product of CZ. It was found that it is possible to analyze the peaks of amines and benzothiazoles.
첨부 도면 중 도 3은 고무 중 가황촉진제를 분석한 질량분석 스펙트럼을 나타낸 도면으로서, 가스크로마토그래피와 연결된 질량분석기를 통해 도 2의 각각의 피크에 해당하는 성분의 질량분석스펙트럼을 확인하여 가황고무 중에 사용된 촉진제 종류를 분석한 것으로, 즉, 질량대 하전비값(m/z)이 99, 70, 56인 질량분석 스펙트럼으로 이는 시클로아민의 특성 질량스펙트럼에 해당한다. 즉, 고무 제품으로부터 열추출과 저온농축 및 열탈착 과정을 통해 얻어진 성분이 가황촉진제 CZ로부터 기인함을 알 수 있었다.3 is a diagram showing a mass spectrometry spectrum of a vulcanization accelerator in rubber. The mass spectrometry spectrum of each component peak of FIG. 2 is identified through a mass spectrometer connected to gas chromatography in vulcanized rubber. The type of accelerator used was analyzed, i.e., mass spectrometry with mass-to-charge ratios (m / z) of 99, 70 and 56, which corresponds to the characteristic mass spectrum of cycloamines. That is, it can be seen that the components obtained through heat extraction, low temperature concentration, and heat desorption from rubber products originated from the vulcanization accelerator CZ.
도 3에서 상단 스펙트럼은 분석한 스펙트럼이고, 하단의 화학구조가 있는 스펙트럼은 질량분석 스펙트럼 라이브러리와 대조한 예를 나타낸 것으로 상단의 질량분석 스펙트럼이 시클로헥실아민임을 알 수 있었다.In FIG. 3, the upper spectrum is the analyzed spectrum, and the spectrum with the chemical structure at the bottom shows an example contrasted with the mass spectrometric library, and it can be seen that the mass spectrometry at the top is cyclohexylamine.
이상에서 설명한 바와 같이, 본 발명의 가황된 천연 또는 합성고무 제품의 가황촉진제 분석장치는 종래의 고무 분석 기술로는 불가능하였던 가황된 천연 또는 합성 고무 제품 중에서 가황촉진제의 성분을 효율적으로 분석할 수 있다는데 그 효과가 있다.As described above, the vulcanization accelerator analyzer of the vulcanized natural or synthetic rubber product of the present invention can efficiently analyze the components of the vulcanization accelerator in vulcanized natural or synthetic rubber products that were not possible with conventional rubber analysis techniques. It works.
도 1은 본 발명에 따른 가황된 천연 또는 합성고무 제품의 가황촉진제 분석장치의 전체 구성을 보여주기 위한 개략도이다.Figure 1 is a schematic diagram showing the overall configuration of the vulcanization accelerator analysis apparatus of vulcanized natural or synthetic rubber products according to the present invention.
도 2는 고무 중 가황촉진제 CZ를 본 발명에 따른 분석장치를 이용하여 분석한 결과를 보여주기 위한 그래프이다.Figure 2 is a graph showing the results of analyzing the vulcanization accelerator CZ in the rubber using the analysis device according to the present invention.
도 3은 고무 중 가황촉진제 CZ를 본 발명에 따른 분석장치를 이용하여 질량분석 스펙트럼의 결과를 보여주기 위한 그래프이다.Figure 3 is a graph showing the results of the mass spectrometry of the vulcanization accelerator CZ in the rubber using the analysis apparatus according to the present invention.
<도면의 주요부분에 대한 부호의 설명><Description of the symbols for the main parts of the drawings>
11 ---- 연속 추출장치 12 ---- 충진 흡착관11 ---- continuous extractor 12 ---- packed adsorption tube
13 ---- 저온농축장치 14 ---- 열탈착장치13 ---- Low Temperature Concentrator 14 ---- Thermal Desorption Unit
15 ---- 가스크로마토그래프 16 ---- 질량분석기15 ---- Gas Chromatograph 16 ---- Mass Spectrometer
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| KR100933194B1 (en) * | 2007-09-04 | 2009-12-22 | 건국대학교 산학협력단 | Adsorption tube unit capable of temperature control by section and thermal desorption method using the same |
| KR101872356B1 (en) * | 2017-03-16 | 2018-06-28 | (주)에코리사이클링 | Mercury treatment apparatus from Waste |
| CN111912733A (en) * | 2020-08-12 | 2020-11-10 | 威海拓展纤维有限公司 | Method for testing mass fraction of fibers in carbon fiber reinforced nylon plastic |
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| KR100933194B1 (en) * | 2007-09-04 | 2009-12-22 | 건국대학교 산학협력단 | Adsorption tube unit capable of temperature control by section and thermal desorption method using the same |
| KR101872356B1 (en) * | 2017-03-16 | 2018-06-28 | (주)에코리사이클링 | Mercury treatment apparatus from Waste |
| CN111912733A (en) * | 2020-08-12 | 2020-11-10 | 威海拓展纤维有限公司 | Method for testing mass fraction of fibers in carbon fiber reinforced nylon plastic |
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