TW200905195A - Analysis method and analysis device of inorganic phosphorus in organic material - Google Patents
Analysis method and analysis device of inorganic phosphorus in organic material Download PDFInfo
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- TW200905195A TW200905195A TW097115240A TW97115240A TW200905195A TW 200905195 A TW200905195 A TW 200905195A TW 097115240 A TW097115240 A TW 097115240A TW 97115240 A TW97115240 A TW 97115240A TW 200905195 A TW200905195 A TW 200905195A
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- inorganic phosphorus
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- organic material
- phosphorus
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 94
- 239000011574 phosphorus Substances 0.000 title claims abstract description 94
- 238000004458 analytical method Methods 0.000 title claims abstract description 43
- 239000011368 organic material Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 15
- 229920005989 resin Polymers 0.000 claims description 23
- 239000011347 resin Substances 0.000 claims description 23
- 238000001514 detection method Methods 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 5
- 238000002309 gasification Methods 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 abstract description 7
- 239000000470 constituent Substances 0.000 abstract 3
- 238000004817 gas chromatography Methods 0.000 abstract 2
- 239000007789 gas Substances 0.000 description 21
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 20
- 239000003063 flame retardant Substances 0.000 description 20
- 238000005259 measurement Methods 0.000 description 18
- 238000005979 thermal decomposition reaction Methods 0.000 description 13
- 239000011342 resin composition Substances 0.000 description 10
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- -1 polychloroethylene Polymers 0.000 description 8
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 235000021317 phosphate Nutrition 0.000 description 6
- 238000001819 mass spectrum Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 238000007689 inspection Methods 0.000 description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 4
- 239000000347 magnesium hydroxide Substances 0.000 description 4
- 238000004445 quantitative analysis Methods 0.000 description 4
- 239000003814 drug Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 3
- 238000004451 qualitative analysis Methods 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000005042 ethylene-ethyl acrylate Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000000752 ionisation method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/12—Preparation by evaporation
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- 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
-
- 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
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
-
- 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
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/025—Gas chromatography
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- 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/12—Preparation by evaporation
- G01N2030/125—Preparation by evaporation pyrolising
-
- 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
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
- G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
- G01N2030/884—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds
- G01N2030/885—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds involving polymers
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- 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
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
- G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
- G01N2030/8859—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample inorganic compounds
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- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T436/00—Chemistry: analytical and immunological testing
- Y10T436/16—Phosphorus containing
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Description
200905195 九、發明說明: 【發明所屬之技術領域】 本發明係關於一種有使用熱分解氣相層析儀的機材料 中所含之無機磷之分析方法,尤其關於一種分析難燃性樹 脂中所含之作爲難燃劑的赤磷等無機磷之方法。另外,本 發明也關於一種有機材料中之無機磷之分析裝置,其能夠 進行此有機材料中之無機磷之分析方法。 【先前技術】 針對電子機器中所使用之絕緣電線被覆材料或汽車用 內部裝飾材料等之樹脂材料,基於安定性、防火性之觀點, 正尋求難燃性。因此,迄今大多採用難燃性樹脂之聚氯乙 烧(PVC )。但是’由於燃燒時產生大量之有害氯氣,因 此’近年來非鹵素之難燃性樹脂組成物已逐漸被使用。 非鹵素之難燃性樹脂組成物,可列舉:將難燃劑摻雜於 烯烴系樹脂等之非鹵素樹脂中之物。此處,難燃劑係使用 磷系難燃劑。另外’難燃劑也可以使用如氫氧化鋁或氫氧 化鎂之金屬氫氧化物等’爲了提高其難燃效率,並減少金 屬氫氧化物之摻合量而防止機械特性之降低,因此,磷系 難燃劑也被倂用。 磷系難燃劑可列舉:由磷酸酯系、含鹵素磷酸酯系等之 有機磷系難燃劑、赤磷等之無機磷所構成的無機磷系難燃 劑。其中’根據樹脂之種類,因爲無機磷系難燃劑係具有 磷元素之含率爲高的、以少量添加便能夠賦與難燃性之特 徵,所以爲一種較佳之難燃劑,例如,於專利文獻1中, 已有人提案一種含有赤磷系難燃劑之烯烴系樹脂等的難燃 200905195 性樹脂組成物。 因此,使用一種含有此無機磷系難燃劑之難燃性樹脂組 成物的製品,例如,於將此樹脂組成物作爲絕緣被覆之絕 緣電線的製造時或出貨時,爲了其品質管理’因而製造者 期望能夠分析赤磷等無機磷之分析方法’另外’此製品之 購入者也期望此分析方法作爲領取檢查法。 另一方面,赤磷等無機磷之情形,於燃燒時產生有害膦 的問題、發生因來自廢棄物之磷成分向水系溶出所造成之 湖泊優養化的問題等已被指出,也有不期望其使用之情 形。另外,尤其近年來有機材料中之赤磷含量的限制具有 變得嚴格之傾向。因此,基於此等之觀點,領取檢查法等 正尋求一種能夠分析有機材料中所含之赤磷等無機磷之分 析方法。 專利文獻1 :日本專利特開2 0 0 4 - 1 6 1 9 2 4號公報 【發明內容】 發明所欲解決之枝術問顆 然而,赤磷等之無機磷除了不溶於各種溶劑中,分離回 收爲困難之外,於無機磷本身也無紅外分光裝置中之紅外 吸收。另外,即使使用拉曼分光裝置以分析樹脂等之有機 材料中所摻合的無機磷,以有機材料之資訊爲主體,也無 法識別有關無機磷之資訊。因而,利用此等方法則無法分 析樹脂等有機材料中之無機磷。另外,若根據元素分析, 例如使用能量分散型螢光X線裝置之EDX元素分析,雖然 元素磷之偵檢爲可能的,但是無法識別無機磷與有機磷, 考量磷酸酯系等含有有機磷之情形,則無法進行無機碟之 200905195 分析。 因爲本發明係爲了解決習用技術之該問題所進行的,課 題在於特別提供一種分析方法,其簡便、迅速且確實分析 有機材料中之紅磷、黃磷等之無機磷,尤其是樹脂中作爲 難燃劑所含之無機磷,課題上也一倂提供一種用以實施此 分析方法之分析裝置。 解決問顯之抟術手段 爲了解決該課題,本發明人等鑽硏探討之結果發現:儘 管赤磷、黃磷係固體無機物,藉由專門用於高分子材料等 之有機材料分析的熱分解氣相層析儀,能夠進行其偵檢。 而且發現:若根據使用熱分解氣相層析儀之裝置,將試料 予以氣化之後,進行根據氣相層析儀之測定,能夠簡便、 迅速且確實分析有機材料中所含之無機磷,於是完成了本 發明。本發明人等也發現:更進一步將質譜儀作爲氣相層 析儀之組分偵檢手段使用,更確實進行有機材料中所含之 無機磷之分析,並且也可以得到優越之定量性。 亦即,本發明之申請專利範圍第1項,其係提供一種有 機材料中所含之無機磷之分析方法,其特徵係具有: 熱分解有機材料之試料後而予以氣化的步驟; 利用氣相層析儀以將所熱分解之該試料分離成各組分 的步驟;及 進行相當於無機磷滯留時間之組分偵檢的步驟。 本發明之分析方法所適用試料之有機材料,可列舉:樹 脂(聚合物),再者,溶解有樹脂之溶液、單體等其他之 有機材料,例如磷酸酯也能夠適用本發明之分析方法。另 200905195 外’無機磷可列舉:赤磷及黃磷。 進行試料之熱分解後而予以氣化的步驟係藉由將試料 加熱至試料氣化之溫度以上所進行的。於無機憐中,也因 爲赤磷之昇華溫度高達416。(:以上,爲了確實昇華赤磷而 進行精確度筒的分析,加熱溫度較佳爲500 〇C以上。尤其, 樹脂中之無機磷爲分析對象之情形,必須於樹脂之分解溫 度以上之溫度進行加熱。因此,此情形之較佳加熱溫度約 爲 600 〜800〇C。 { 另外’加熱時間係使試料予以完全氣化所必要的時間以 上’視加熱溫度或試料量等而加以變動,並未予以特別限 定°加熱手段也未予以特別限定,能夠使用通常之熱分解 氣相層析儀所使用之加熱手段。 經熱分解而氣化之試料係被導入氣相層析儀之管柱 中’試料中之各成分係根據與固定相之分配平衡常數的差 異而予以分離,依照各個成分而於不同的時間(滯留時間) 流出。此氣相層析儀的各種條件係與樹脂分析一般所使用 . 之熱分解氣相層析儀的條件相等。 管柱能夠使用塡充管柱、毛細管柱中任一種,針對定性 分析,較宜使用毛細管柱。 從氣相層析儀之管柱流出的試料係被導入偵檢器中,因 應於滯留時間的流出(組分)之有無將被偵檢出。無機磷 之分析係根據相當於無機磷之滯留時間組分之偵檢所進行 的。例如,相當於無機磷之滞留時間,若具有偵檢之波峰 (組分)的話,試料中之無機磷的存在將被確認。另外, 因爲有機磷係於不同的滯留時間具有偵檢之波峰(組分), 200905195 根據此分析,於試料之有機材料中所含之磷,能夠識別是 否爲無機磷(赤磷、黃磷等)。 相當於無機磷之滯留時間係視熱分解氣相層析儀之操 作條件、管柱之種類等而加以變動。因此,在試料測定之 前,使用無機磷’例如赤磷之標準試料以進行相同於上述 之分析,預先得到相當於無機磷之滯留時間。 偵檢器能夠使用一般已用於氣相層析儀之FID (氫燄離 子化偵檢器)、FPD (火焰光度偵檢器)、TCD (熱導率型 ( 偵檢器)、NPD (氮磷偵檢器)等。根據此等偵檢器之情 形,能夠依照有無相當於無機磷之滯留時間的波峰而進行 定性分析。 較宜使用質s普儀(M S )以取代上述之偵檢器而進行偵檢 (專利範圍第2項)。亦即,F ID、F P D、T C D、N P D之情 形,因爲僅基於滞留時間’能夠進行無機磷之鑑定,於試 料中包含具有與無機磷相同滯留時間的成分之情形,將有 鑑定變得困難之情形。另—方面,若根據質量分析,因爲 無機磷係在m/Z=3l、62' 93及124顯示特徵性波峰,根 % 據此等波峰之有無’能夠確實進行無機磷之鑑定。 再者,亦可使用上述之FID、Fp£)、TCD、NPD或質譜 儀’進行定量分析。例如’可製作無機磷含量爲既定之樹 脂組成物’利用上述之方法加以測定,基於所得的波峰面 積或波峰商度等而作成檢量線’其後進行試料之測定,藉 由根據檢惠線與試料之測定所得的波峰面積或波峰高度而 進行定量分析。 若根據本發明’能夠分析有機材料中所含之赤磷、黃磷 200905195 等之無機磷,或是能夠識別有機材料中所含之磷是否爲無 機磷。尤其’本發明之分析方法適用於習知簡便且確實之 分析爲困難的樹脂中之無機磷分析,或溶解有樹脂之溶 液、單體 '磷酸酯等之中的無機磷分析(申請專利範圍第 3項)。 本發明能夠適用之樹脂’可列舉:聚烯烴、聚碳酸酯、 聚碳酸酯/ ABS、聚醯胺、聚酯樹脂等,但是本發明能夠適 用之有機材料並不受此等樹脂所限定。另外,本發明也能 ( 夠適用於溶解有樹脂之溶液、單體、其他有機材料,例如 磷酸酯。 再者,本發明係於申請專利範圍第4項中,提供一種有 機材料中所含之無機磷之分析裝置,其特徵係分析有機材 料中所含之無機磷之分析裝置;其係具有:熱分解試料的 氣化手段:並將所熱分解之該試料分離成各組分的管柱; 及含有從管柱流出之氣體的偵檢器之氣相層析儀。使用本 裝置,藉由進行上述本發明之有機材料中所含之無機磷之 / 分析方法,能夠簡便、迅速且確實分析試料中之無機磷。 此分析裝置係由試料之氣化手段及氣相層析儀所構 成’氣相層析儀係一種具有管柱及偵檢器之物,分別相同 於針對有機材料中所含之無機磷分析方法所說明的裝置。 亦即,能夠使用相同於一般熱分解氣相層析儀之物,另外, 偵檢器也可使用FID、FPD、TCD、NPD或質譜儀。 另外,基於上述之理由,偵檢器之中也較佳爲質譜儀(申 請專利範圍第5項)。質譜儀係由與氣相層析儀之管柱相 結合部分的界面、進行試料離子化之離子源、質量分離部、 -10 - 200905195 偵檢器等所構成。離子源之離子化方法能夠利用EI法、CI 法中任一種方法,質量分離部之分析器也能夠使用磁場 型、四極型等中任一種。另外,作爲偵檢器中之測定模式 也能夠使用SCAN模式、SIM模式中任一種。 發明之效果 若根據本發明之有機材料中所含之無機磷之分析方 法,另外,若使用本發明之有機材料中所含之無機磷之分 析裝置,能夠簡便、迅速且確實地進行有機材料中所含之 無機磷之分析。或是於試料之有機材料中所含之磷,能夠 識別是否爲無機磷(赤磷、黃磷等)。再者,能夠以優越 之精度而進行無機磷之定量分析。 【實施方式】 發明實施最佳形態 其次,根據實施例加以說明用以實施本發明之最佳形 態,但是本發明之範圍並非僅限定於實施例。 實施例 藉由下列所示之熱分解裝置以將試料予以熱分解(氣 化),並藉由下列所示之氣相層析儀/質譜儀(GC/M S裝置) 以測定氣化後之試料。 (熱分解裝置、熱分解條件) 使用FrontiaLab公司製。熱分解條件係600 °Cx0.2分鐘。 (GC/MS 裝置) 使用Agilent公司製之Agilent 6890。以下,顯不本裝 置之操作條件: 管柱:HP-5MS (內徑:〇.25mm、膜厚:0.25μιη、長度: 200905195 3 0m) 管柱流量:He氣體l.〇mi/分鐘 升溫條件:從50°C至32〇°C,以25°C/分鐘進行升溫, 於3 2 0 °C維持5分鐘 MS 溫度:230 °C (MS Source) 、150。(: (MS Quad) 界面溫度:2 8 0 °C 測定模式:SCAN模式 還有’質譜分析(M S )之測定係爲了避免氧之波峰,於 f : m/z=33〜550之範圍進行。 〔標準試料之測定(無機磷滞留時間之測定)〕 標準試料係使用赤磷(匕二】24)(關東化學公司製之 試藥)。稱取此試料O.lmg,於上述之條件下熱分解後而 予以氣化’將氣化後之試料導入該GC/MS裝置中,於上述 之條件下進行測定。將所得的測定結果顯示於第1圖。還 有’於第1圖中’上圖係藉由GC (氣相層析儀)所得的數 據(層析圖),下圖係藉由MS (質譜儀)所得的數據(質 .譜圖)。 k 層析圖(上圖數據)之針對在滯留時間4 · 2分鐘所偵檢 出之波峰’於進行質譜分析所得的質譜(下圖數據)中, 在m/z=62、93及124之位置,已偵檢出赤磷(P4=124) 白勺#徵[波峰。亦即,此例之情形,氣相層析儀之滯留時間 4 · 2分' S的波峰係相當於無機磷之波峰,針對於此滯留時間 之波峰’藉由得到質譜而能夠偵檢出無機磷。 〔根據測定用試料所進行之測定1〕 '測$ 試料係使用含有無機磷(赤磷)之樹脂組成物, -12- 200905195 其係利用1 0 0 : 90 : 1 0 (重量比)之比例而於乙烯-丙烯酸 乙酯共聚物(EEA、商品名:EVAFLEXA701)中,混合氫 氧化鎂(關東化學公司製之試藥)及赤磷(關東化學公司 製之試藥)。稱取此試料〇 · 1 m g,於上述之條件下加以熱 分解後而予以氣化’將氣化後之試料導入該G C /M S裝置 中’於上述之條件下進行測定。將所得的測定結果顯示於 第2圖。還有’於第2圖中,上圖係藉由GC所得的層析 圖,下圖係藉由M S所得的質譜圖。 觀察第2圖之層析圖時,相同於標準試料之情形,在滯 留時間4 _ 2分鐘’波峰已被偵檢出。另外,針對滯留時間 4.2分鐘之波峰的質譜中’也相同於標準試料之情形,在 m/z二62、93及124之位置,已偵檢出波峰,根據此結果, 已明確顯示於測定用試料中含有無機磷(赤磷)。如上所 述’根據本發明之方法,顯示樹脂組成物中之赤碟分析爲 可能的。 〔根據測定用試料所進行之測定2 ] 除了如下所示之方式來變更EEA/氫氧化鎂/赤磷系之混 合比例(重量比)以外’進行相同於〔根據測定用試料所 進行之測定1〕之方式’製作含有無機磷之樹脂組成物的 試料(1 )〜(4 ),針對各試料而進行g C / M S之測定。 ΕΕΑ/氫氧化鎂/赤磷= 試料(1) 100/90/2.2 (赤磷含量:l lwt%) 試料(2 ) 1 00/9 0/4.4 (赤磷含量:2 2wt% ) 試料(3) 100/90/6.3 (赤磷含量:3_2wt%) 試料(4) 100/90/8.4 (赤磷含量:4.2wt%) -13- 200905195 將藉由G C / M S之測定所得的滯留時間4.2分鐘之波峰位 置的波峰強度比(利用測定試料重量除以滯留時間4 · 2分 鐘之波峰面積値的値)與無機磷含量(w t % )之關係圖顯 不於弟3圖。由第3圖可明確得知,針對樹脂中之無機磷 含量與GC/MS中之波峰強度,具有良好之相關性,其相關 係數爲〇 . 9 7 8 1。由此結果’藉由本發明之分析方法,不僅 顯示無機磷之定性分析,也可以進行精度高的定量分析。 還有’於上述之實施例中,已揭示僅使用赤磷作爲試料 之情形,本發明也能夠適用於黃磷等其他之無機磷,並不 僅受赤磷之情形所限定。 產業上之可利用性 於本發明之有機材料中所含之無機磷之分析方法及分 析裝置能夠適用(使用)於:例如,使用含有難燃性絕緣 電線等無機磷之樹脂組成物的製品;或是溶解可能含有無 機磷之某樹脂的溶液、可能含有無機磷之的某單體或其他 有機材料,例如,磷酸酯之製造或出貨中之品質管理、製 品購入之際的領取檢查等。 【圖式簡單說明】 第1圖係利用標準試料之GC/MS所得的層析圖及質譜。 第2圖係利用測定用試料之GC/MS所得的層析圖及質 譜。 第3圖係顯示赤磷含量與G C /M S光譜之波峰強度比的 關係之圖形。 【主要元件符號說明】 姐〇 -14-
Claims (1)
- 200905195 十、申請專利範圍: 1. 一種有機材料中所含之無機磷之分析方法,其特徵係具 有: 熱分解有機材料之試料後而予以氣化的步驟; 利用氣相層析儀以將所熱分解之該試料分離成各組分 的步驟;及 進行相當於無機磷的滯留時間之組分偵檢的步驟。 2. 如申請專利範圍第1項之有機材料中所含之無機磷之分 析方法’其中進行該偵檢的步驟係藉由質譜儀所進行的。 3 ·如申g靑專利範圍第1或2項之有機材料中所含之無機磷 之分析方法’其中該試料爲樹脂、溶解有樹脂之溶液或 單體。 4. 一種有機材料中所含之無機磷之分析裝置,其特徵係分 析有機材料之試料中所含之無機磷之分析裝置;該分析 裝置係具有:熱分解試料的氣化手段;與將所熱分解之 該試料分離成各組分的管柱;及含有從管柱流出之氣體 的偵檢器之氣相層析儀。 5. 如申請專利範圍第4項之有機材料中所含之無機磷之分 析裝置,其中該氣體的偵檢器爲質譜儀。 -15-
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