PE100管材料的聚集态结构和性能的固体NMR分析.pdf

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1、?22?2?Vol.22 No.22 0 0 8?4?CHINESE JOURNAL OF MATERIALS RESEARCHApril 2 0 0 8?PE100?NMR?1?1?1?1?1Siegfried Stapf2Bernhard Bl umich21.?3100272.Institut f ur Technische Chemie und Makromolekulare Chemie,Rheinisch-Westf alischeTechnische Hochschule,Worringerweg 1,D-52056 Aachen,Germany?PE100?(?10%),?.?

2、,?PE100?.?(?)?,?,?.?,PE100?,?,?,?TB324?1005-3093(2008)02-0157-07Investigations of the structure and property relationship ofPE100 pipe materials by solid state NMR techniquesYAN Xiaowei1LI Wei1REN Xiaohong1WANG Jingdai1YANG Yongrong1Siegfried Stapf2Bernhard Bl umich21.State Key Laboratory of Chemica

3、l Engineering,Department of Chemical and Engineering,Zhejiang University,Hangzhou 3100272.Institute for Technical and Macromolecular Chemistry,RWTH Aachen,Worringerweg 1,52074 Aachen Germany*Supported by National Natural Science Foundation of China Nos.20676114 and 20490205,Natural ScienceFoundation

4、 of Zhejiang Province No.Y406293,and Cooperation Program of CSC-DAAD(PPP,2004).Manuscript received May 10,2007;in revised form October 11,2007.*To whom correspondence should be addressed,Tel:(0571)87951227,E-mail:ABSTRACTThe PE100 materials could be characterized by relatively high amounts of crysta

5、lline-amorphous interface,and the content of the mobile amorphous fraction contributed only a small part ofthe total non-crystalline region.The chain fragments in the non-crystalline region of PE100 materials hada strong tendency to be entangled.The superior long-term mechanical property of the PE10

6、0 materialswas shown to be in close relation to the non-crystalline fraction composition for which the interfacecomponent had the main contribution.The two PE100 materials with unimodal and bimodal molecularweight distribution respectively were investigated by correlating the NMR results.The notable

7、 drop of theminimum required strength of unimodal PE100 material was explained from its relatively low contents ofrigid component.The interplay of the interface fraction and the rigid fraction plays the key role for thelong-term use properties of PE pipe materials.KEY WORDS organic polymer materials

8、,PE100 pipe,solid state1H NMR,phase structure,mechanicalproperties*?20676114?20490205?;?(Y406293),CSC-DAAD(PPP,2004)?.2007?5?10?;2007?10?11?.?:?PE100?20?80?,?50?(MRS)?10 MPa.?(SCG)?(RCP)?,?158?22?158?22?158?22?1.?PE100?,?.?,?28.?,?,?.?,?9.?,?,?.?RCP?10,11,?,RCP?12.Yen?13?,SCG?,?,?.?,?,?:1)?,?(DSC)?X

9、?(XRD)?14,15;2)?.?(NMR)?15.?PE100?,?.1?1.1?PE100?1.CP1?,?ZieglerNatta?Borstar?16.CP2?,?.?ISO/TR9080?,?PE100?.?,?CPA?CPB.?,?HPA.?,?SCG?17.?1?.?DSC7(PerkinElmer Corp.,USA)?,N2?,?20 mL/min.?10 K/min?(?5 mg)?180?,?,?XC=Hm/H0?,?Hm?,H0?100%?,?293 J/g18.?PLGPC220(Polymer LaboratoriesLtd.,UK)?,?150?,?1,3,5-

10、?.?(?)?5 mm?,?Bruker DSX200?1H?,?200.02 MHz,?,?.NMR?:90?3.5 s;?:2 K;?:5 s.?DMFIT?19?,?,?,?.?/?15?,?3540?.?.?4?,?Z?/?20.?Z?,?1PE100?Table 1 Mw,MWD and Physical properties of basic resins for PE100 pipesElongationSampleCo-unit/MWDMwMw/MnDensityStress yieldat breakDurability(kg/mol)(g/cm3)/MPa/%gradeCP

11、1Butene/BM28236.70.95926.2783PE100CP2Hexene/UM24227.10.94321.0860PE100HPAHomopolymer/UM3192.8Notes:BM indicates the bimodal distribution of molecular weight;UM indicates the unimodal distribution ofmolecular weight.2?:PE100?NMR?1592?:PE100?NMR?1592?:PE100?NMR?159?=6 s,?tDQ?5 s.?35SFV655038?ASTM D150

12、5-1998?.?200P?,?180?,?5 min,?15 MPa,?5 min.?ASTM D6381999?Zwick/Roell Z202?,?50 mm/min.2?2.1PE100?NMR?,?(?),?,?2123?24?,?Ivanov?25?PET?.?,?,?.?2?NMR?DSC?.?,NMR?DSC?,?.?NMR?,?,?.?,?,?NMR?DSC?.?NMR?DSC?,?26.?L.Mandelkern?,?DSC?27,?.?NMR?.?1?,?(?2).?1?,CP1A?CP2A?,?HPA?.?2?,CP1A?CP2A?,?1%2%.?HPA?,?CP1A?

13、CP2A?,?.?,NMR?HPA?PE100?CP1A?CP2A?,?,?.?,?.?,?CP1A?CP2A?(SCG)?.?SCG?17.?,?,?.?,?,?,?.?,?,?,?,?.?,NMR?,?.?,?PE?,?,?.?,?26.2.2?2?,?1H?(doublequantum filter)?20,?.?,?2?Table 2 Phase structure of powder PE samples as extracted from the decomposition of widelinespectraDSCPhase compositions/%Linewidth/kHz

14、Sample IdcystallinityRIARIACP1A67%84.214.11.7649.211.82.36CP2A59%82.215.91.8548.012.92.30HPA73%91.14.414.4950.66.961.98*R:rigid phase;I:interphase;A:amorphous phase160?22?160?22?160?22?1CP1A/CP2A/HPA?(?:CP1A;?:CP2A;?:HPA)Fig.1 Comparison between the wideline spectra ofPE100 resins and linear HDPE:bo

15、ld line,CP1A;dashed line,CP2A;dashdotted line,HPA.?,?.?,?;?.?,?28,29.A.Buda?,?20.?,?.?Drigid112?2ln2?r2?v1/2Dmobile16?r2?v1/21/2?30,?v1/2?,?,?r2?,?r2?1/20.22 nm31.?20.?3?,?3?.?1020 nm,?(2?)?410 nm,?(TEM)?DSC?28,29.2.3?PE100?CP1?Bostar?.?,CP2?UCC?2?Fig.2(a)1H spectrum of polyethylene,(b)1H double-qua

16、ntum filtered signal belonging to the crys-talline phase,(c)evolution of the magnetization after 100 s diffusion time.The appearance ofthe signal from the interphase can be seen,(d)evolution of the magnetization after 50 ms diffu-sion time.The signal now contains contributions from all phases and ap

17、proaches the equilibriumsignal.2?:PE100?NMR?1612?:PE100?NMR?1612?:PE100?NMR?161?3?,?,?.?10%Fig.3 Experimental points from spin-diffusion mea-surement and its model fitting?3?PE100?Table 3 Domain sizes of unimodal and bimodalpolyethylene for PE100 pipesDomain sizes/nmSampleRIACP1B131.680.74CP2B101.68

18、0.88The uncertainties are estimated to be lower than 10%.?,?.?P.J.DesLauriers?Cr/AlPO4?PE100?32,?,?PE?.L.Hubert?7,?PE100?(SCB)?,?Cr?SCB?,?SCG?SCB?.?PE100?,?(?35).?,CP2?CP1?,?,?CP2?CP1.?,CP2?,?.?,CP2?,?CP1?.?CP2?(?1?,CP2?CP1?)?.?,?,?.?CP2?,?.?,?4?PE100?Table 4 Phase compositions of unimodal and bimod

19、al polyethylene for PE100 pipesPhase compositions/%Linewidth/kHzSampleRIARIACP1B78.117.84.0850.810.63.38CP2B73.521.45.1247.911.13.21R:rigid phase;I:interphase;A:amorphous phase.The uncertainties are estimated to be lower than 5%.?5?PE100?T1?Table 5 T1results of unimodal and bimodal polyethylene for

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