JP5406069B2 - 劣化評価方法 - Google Patents
劣化評価方法 Download PDFInfo
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- JP5406069B2 JP5406069B2 JP2010028861A JP2010028861A JP5406069B2 JP 5406069 B2 JP5406069 B2 JP 5406069B2 JP 2010028861 A JP2010028861 A JP 2010028861A JP 2010028861 A JP2010028861 A JP 2010028861A JP 5406069 B2 JP5406069 B2 JP 5406069B2
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- 229920006324 polyoxymethylene Polymers 0.000 claims description 64
- 239000004215 Carbon black (E152) Substances 0.000 claims description 57
- 229930195733 hydrocarbon Natural products 0.000 claims description 57
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- 238000000465 moulding Methods 0.000 description 4
- 125000006353 oxyethylene group Chemical group 0.000 description 4
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 4
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical class FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
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- 238000011002 quantification Methods 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000005702 oxyalkylene group Chemical group 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- LMRJHNFECNKDKH-UHFFFAOYSA-N 4-(trifluoromethyl)nicotinic acid Chemical compound OC(=O)C1=CN=CC=C1C(F)(F)F LMRJHNFECNKDKH-UHFFFAOYSA-N 0.000 description 1
- 229920005177 Duracon® POM Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920012196 Polyoxymethylene Copolymer Polymers 0.000 description 1
- 229920009382 Polyoxymethylene Homopolymer Polymers 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000012854 evaluation process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010101 extrusion blow moulding Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001542 size-exclusion chromatography Methods 0.000 description 1
- UYCAUPASBSROMS-AWQJXPNKSA-M sodium;2,2,2-trifluoroacetate Chemical compound [Na+].[O-][13C](=O)[13C](F)(F)F UYCAUPASBSROMS-AWQJXPNKSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000009757 thermoplastic moulding Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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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
- G01N33/442—Resins; Plastics
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/30—Staining; Impregnating ; Fixation; Dehydration; Multistep processes for preparing samples of tissue, cell or nucleic acid material and the like for analysis
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N24/00—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects
- G01N24/08—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects by using nuclear magnetic resonance
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- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Pathology (AREA)
- Immunology (AREA)
- General Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Biomedical Technology (AREA)
- Molecular Biology (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Testing Resistance To Weather, Investigating Materials By Mechanical Methods (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Description
評価準備工程は、評価対象となる樹脂成形品を用意する。炭化水素系液体に浸漬した際の浸漬時間が異なる複数のポリアセタール共重合体を含む樹脂組成物のそれぞれを1H−NMR測定するために樹脂成形品を準備する。なお、樹脂組成物は樹脂成形品から採取する1H−NMR測定用のサンプルである。
定量工程は、上記樹脂組成物サンプルに含まれるポリアセタール共重合体の−CH2CH2OCHO末端基の含有量の定量を行う工程である。上記末端基の含有量の定量は、1H−NMRスペクトルの測定により行う。
本発明の劣化評価方法においては、例えば、炭化水素系液体への浸漬前後での樹脂組成物に含まれる−CH2CH2OCHO末端基の含有量の変化量を1H−NMR測定で定量することによって、炭化水素系液体浸漬前後での分子量の変化を評価し、樹脂組成物の劣化を評価する。上記末端基の含有量の変化と分子量の変化との関係を導出しておくことでより正確に劣化評価を行うことができる。分子量がどの程度減少するかを具体的に評価できるからである。
ポリアセタール系樹脂(ジュラコンM90−44、ポリプラスチックス株式会社製)からなる試験片を用意した。
NMR装置:AC400P型(ブルカー社製)
パルスフィリップアングル:30♯
積算繰り返し時間:10sec
積算回数:128回
装置:HLC−8220GPC(東ソー社製)
カラム:TSK−Gel Super HM−H(日本)
溶媒:HFIP/5mM TFNa(トリフルオロ酢酸ナトリウム)
流速:0.3ml/min
検出器:RI
温度:40℃
標準試料:PoLymer Laboratories EasiCal PM−1 PMMA Standards(Mw:1944000〜1020)
市販の軽油に試験片を(燃料中90℃×100時間+空気中90℃×48時間)×10サイクルの条件で浸漬させた。その後、試験片表面から200μm以内の領域から採取したサンプルと試験片表面を300μm切削した部分から採取した試験片内部のサンプルとについて、重量平均分子量、数平均分子量の測定を行った。測定結果を表3に示した。表3から明らかなように、劣化の程度は成形品表面付近で大きいことが確認された。なお、試験片及び分子量の測定条件は実施例1の条件と同様である。
Claims (7)
- 炭化水素系液体に浸漬した際の浸漬時間が異なる複数のポリアセタール共重合体を含む樹脂組成物のそれぞれを1H−NMR測定した時に、それぞれの測定結果の8.04ppmから8.07ppmにピークトップを有するピークの合計面積から前記ポリアセタール共重合体の分子量の変化を評価することによって、前記樹脂組成物の劣化を評価する劣化評価方法。
- 炭化水素系液体に浸漬した際の浸漬時間が異なる複数のポリアセタール共重合体を含む樹脂組成物のそれぞれを1H−NMR測定した時に、前記ポリアセタール共重合体に含まれる8.05ppm近傍をピークトップとする−CH2CH2OCHO末端基のアルデヒドの水素原子に由来するピークの面積から前記ポリアセタール共重合体の分子量の変化を評価することによって、前記樹脂組成物の劣化を評価する劣化評価方法。
- 前記炭化水素系液体が燃料である請求項1又は2に記載の劣化評価方法。
- 前記樹脂組成物が、樹脂成形品の表面から300μm以内の領域から採取した樹脂組成物である請求項1から3のいずれかに記載の劣化評価方法。
- 前記浸漬時間は、5000時間以内である請求項1から4のいずれかに記載の劣化評価方法。
- 前記炭化水素系液体が軽油である請求項1から5のいずれかに記載の劣化評価方法。
- 前記樹脂組成物が自動車の燃料系部品から採取される樹脂組成物である請求項1から6のいずれかに記載の劣化評価方法。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010028861A JP5406069B2 (ja) | 2010-02-12 | 2010-02-12 | 劣化評価方法 |
KR1020110007704A KR20110093628A (ko) | 2010-02-12 | 2011-01-26 | 열화 평가방법 |
CN201110035695.3A CN102192920B (zh) | 2010-02-12 | 2011-02-10 | 劣化评价方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010028861A JP5406069B2 (ja) | 2010-02-12 | 2010-02-12 | 劣化評価方法 |
Publications (2)
Publication Number | Publication Date |
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JP2011162707A JP2011162707A (ja) | 2011-08-25 |
JP5406069B2 true JP5406069B2 (ja) | 2014-02-05 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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JP2010028861A Expired - Fee Related JP5406069B2 (ja) | 2010-02-12 | 2010-02-12 | 劣化評価方法 |
Country Status (3)
Country | Link |
---|---|
JP (1) | JP5406069B2 (ja) |
KR (1) | KR20110093628A (ja) |
CN (1) | CN102192920B (ja) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6592405B2 (ja) * | 2016-06-10 | 2019-10-16 | 日本電信電話株式会社 | 熱可塑性ポリエステルの延性低下による寿命の推定方法 |
JP6560641B2 (ja) * | 2016-06-10 | 2019-08-14 | 日本電信電話株式会社 | 熱可塑性ポリエステルの数平均分子量及び最大応力の推定方法 |
CN113325025B (zh) * | 2021-05-11 | 2023-06-16 | 宁波海关技术中心 | 一种聚甲醛的鉴定方法 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH0662830B2 (ja) * | 1985-04-11 | 1994-08-17 | 住友化学工業株式会社 | ポリアセタ−ル樹脂組成物 |
US6376605B1 (en) * | 1998-02-09 | 2002-04-23 | Mitsui Chemicals, Inc. | Styrene resin and resin composition comprising the same |
US20050131124A1 (en) * | 2003-12-15 | 2005-06-16 | Jean-Michel Philippoz | High temperature diesel-resistant polyacetal molded articles |
JP2006337126A (ja) * | 2005-06-01 | 2006-12-14 | Nagaoka Univ Of Technology | 固体高分子電解質膜の劣化計測方法及びその装置 |
-
2010
- 2010-02-12 JP JP2010028861A patent/JP5406069B2/ja not_active Expired - Fee Related
-
2011
- 2011-01-26 KR KR1020110007704A patent/KR20110093628A/ko not_active Application Discontinuation
- 2011-02-10 CN CN201110035695.3A patent/CN102192920B/zh not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
CN102192920B (zh) | 2015-06-10 |
CN102192920A (zh) | 2011-09-21 |
KR20110093628A (ko) | 2011-08-18 |
JP2011162707A (ja) | 2011-08-25 |
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