橡胶技术网

合成橡胶工业
CHINA SYNTHETIC RUBBER INDUSTRY
2008 Vol.31 No.2 P.113-117

橡胶技术网

核磁共振法表征硫黄用量对天然橡胶交联密度及结构的影响

赵菲  张萍  赵树高  Winfried Kuhn  于建 

摘 要:用核磁共振(NMR)法测定了硫黄用量及硫化温度对天然橡胶(NR)硫化胶交联结构的影响,并与传统的平衡溶胀法进行了对比.结果表明,用NMR法可以测定硫化胶的总交联密度、未硫化胶的物理交联密度和由于交联反应产生的化学交联密度;NR硫化胶的总交联密度和化学交联密度随硫黄用量的增加而呈线性增加;随着硫黄用量的增加.交联密度增加,NR硫化胶的纵向弛豫时间和横向弛豫时间下降;NR硫化胶的交联密度越大,弛豫时间对温度的依赖性越小;NMR法可以清晰展示NR/硫黄/促进剂NS硫化体系的硫化过程中橡胶交联点间的相对分子质量、化学交联密度及橡胶大分子连到橡胶交联网络上的演变过程.
关键词:天然橡胶;核磁共振法;交联密度;弛豫参数;硫化;平衡溶胀法
分类号:TQ332  文献标识码:B

文章编号:1000-1255(2008)02-0113-05

Influence of amount of sulfur on crosslinking density and structure of natural rubber characterized by nuclear magnetic resonance spectroscopy

Zhao Fei  Zhang Ping  Zhao Shugao  Winfried Kuhn  Yu Jian 

基金项目:国家自然科学基金资助项目(20674043).
作者简介:赵菲(1968-),女,副教授,博士研究生.
作者单位:赵菲(青岛科技大学橡塑材料与工程教育部重点实验室,山东,青岛266042;清华大学化学工程系,北京 100084) 
     张萍(青岛科技大学橡塑材料与工程教育部重点实验室,山东,青岛266042) 
     赵树高(青岛科技大学橡塑材料与工程教育部重点实验室,山东,青岛266042) 
     Winfried Kuhn(Innovative Imaging Corp,Blieskastel,Germany,D-66440) 
     于建(清华大学化学工程系,北京 100084) 

参考文献:

[1]Litvinov V M,Dias A A.Analysis of network structure of UV-cured acrylates by1H-NMR relaxation,13 C-NMR spectroscopy and dynamic mechanical experiments[J].Macromolecules,2001,34(12):4051-4059.
[2]Litvinov V M,Pranan P D.Spectroscopy of rubbem and rubbery materiMs[M].Netherlands:Kluwer Academic Publisher,2002:355.
[3]Kuhn W,Theis I,Koeller E.Network dynamics of erosslinked polymers-crosslinking,filler and aging characterized by NMR pa-rameters[J].Mater Res Soc Symp Proc,1991,33(1):217-223.
[4]Kuhn W,Barth P,Hafner S,et aL Materials properties imaging of Cross-linked polymen by NMR[J].Macromolecules,1994,27(20):5773-5779.
[5]Garbaczyk M,Grinberg F,Nestle N,et aL A novel approach to the determination of the erosslink density in rubber materials with the dipolar correlation effect in low magnetic fields[J].J Polym sci:part B.2001,39(18):2207-2214.
[6]Grinberg F,Heidenreich M,Kuhn W.Changes in oxygenation ofintracranial tumors with earbogen[J].J Magn Res,2002,159(5):87-93.
[7]Grinberg F,Garbaczyk M,Kuhn W.Influence of the cross-linkdensity and the filler content on segment dynamics in dry and swollen natural rubber studied by the NMR dipolar-correlation effect[J].J Chem Phys,1999,111(5):1122-1128.
[8]Knorgen M,Heuert U,Schneider H,et aL Spatially resolved and integral NMR investigation of the aging process of carbon black filled natural robber[J].J Polym Bull,1997,38(1):101-109.
[9]de Gennes P G.Reptation of a polymer chain in the presence of fixed obstacles[J].J Chem Phys,1971,55(22):572.
[10]Gronski W,Hasachiril A,Freund B,et aL High resolution solid Btate13C-NMR studies of the erosslink structure in accelerated sulfur vulcanizated natural robber[J].Kautsch und GummiKunststorff,1991.44(2):119-123.
[11]Parker A,Marcinco J,Rinaldi P,et al.A relationship between NMR cross-polarization rates and dynamic storage modulus of polymers[J].J Appl Polym Sci,1993,48(4):677-684.
[12]Kuhn W.NMR microscopy-principles,limits and applications[J].Angew Chem,Int Edn,1990,29(1):1-5.
[13]Kuhn W,Barth P,Denner P,et al.Characterization of elasto-menc materials by NMR-microscopy[J].Solid State Nuclear Magnetic Resonance,1996,6(4):295-301.
[14]赵菲,毕薇娜,张萍,等.用核磁共振法研究促进剂对硫黄硫化天然橡胶结构的影响[J].合成橡胶工业,2007,31(1):50-53.
[15]Gronski W,Hoffmann U,Simon G,et al.Structure and density of crosslinks in natural rubber vulcanizates:A combined analysis by NMR spectroscopy,mechanical measurements and robber-elastic theory[J].Rubb Chem Technol,1992,65(2):63-77.
[16]Simon G,Baumann K,Gronski W.Mc determination and molec-ular dynamics in crosslinked 1,4-cis-polybutadiene:A compari-son of transversal proton and deuterium NMR relaxation[J].Macromolecules,1992,25(14):3624-3632.
[17]张士齐.用现代物理表征技术研究高聚物的力化学反应[J].合成橡胶工业,1995,18(5):257-259.
[18]Ghosh P,Katare S,Patkar P,et al.Sulfur vulcanization of natu-ral rubber for benzothiazole accelerated formulations:From reae-tion mechanisms to a rational kinetic model[J].Rubber Chem-istry and Technology,2003,76(3):592-599.
[19]Ding R,Leonov A L A kinetic model for sulfur accelerated vul-eanization of a natural robber compound[J].J Appl Polym Sei,1996,61(3):455-461.

收稿日期:2007年1月22日

修稿日期:2007年11月30日

出版日期:2008年3月15日

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