在相同条件下,分别以4,4'-双马来酰亚胺二苯基甲烷(BM)与二乙烯基苯(DVB)的摩尔配比1∶4、1∶1、4∶1,采用悬浮共聚法合成了BM-DVB珠状多孔共聚体.炭化前,对所制BM-DVB共聚体用二种方法进行预处理:(1)热空气稳定化(产物标名PO-C 800);(2)H3PO4浸渍(产物标名P 800).而后,将两种预处理所获产物在Ar气中800℃进行炭化.采用热重(TG)和热差(DSC)法表征了BM-DVB多孔共聚体及其炭化物的热性征.结果表明:单体配比的差异导致了初始聚合体的不同交链程度.共聚体及其炭化物的热稳定性与其组成存在一定的相关性.在BM:DVB摩尔比为4∶1时,BM-DVB共聚体的耐热性最高;其因在于共聚体中含有的氮原子浓度最高.在BM:DVB摩尔比为1∶4时,BM-DVB共聚体具有高的交链度,但热性能最差;这可能由其微孔性能和较少的含氮量所致.而它们炭化物的热性能却非常相似,几乎不受BM-DVB共聚体的影响.可以认为,影响BM-DVB炭化物热性能更重要因素是BM-DVB共聚体在预处理过程中形成的孔隙率和表面化学性能.
Thermogravimetry and differential scanning calorimetry were used for characterization of the thermal properties of new 4,4'-bismaleimidodiphenylmethane (BM) and divinylbenzene (DVB) porous copolymers and their carbonization products. Bead-shaped porous copolymers BM-DVB with the following monomer ratios 1:4, 1:1,4:1 were synthesized using suspension copolymerization under the same conditions. Differences in the monomer ratio caused a different degree of cross-linking of the starting polymers. Before carbonization, the BM-DVB copolymers were pretreated using two methods. In one method, the starting material was stabilized in hot air ( product was labeled PO-C800). In the other method, the copolymer was soaked in H3PO4 (product was named P800). Then, materials obtained by both methods were carbonized at 800 ℃ in an argon atmosphere. To characterize the heat resistance of the BM-DVB copolymers and their carbonized derivatives, their thermostabilities were evaluated. The data suggest the existence of a relationship between the composition and thermal stability of the copolymers and their carbonized derivatives. The most thermally resistant copolymer was that obtained with a 4:1 molar ratio of BM to DVB. Its thermal stability is caused by the high concentration of nitrogen atoms in the polymeric structure. 1:4 BM-DVB copolymer with a high degree of cross-linking was the least thermally stable, which might be caused by its microporous nature and small fraction of nitrogen. The derived carbons have very similar thermal properties, and an insignificant influence of the nature of the polymer precursor was observed. More important factors affecting thermal stability were the porosity and surface chemistry, which were created in the thermal pretreatment processes.
参考文献
| [1] | Ozawa T. .Thermal analysis - review and prospect[J].Thermochimica Acta: An International Journal Concerned with the Broader Aspects of Thermochemistry and Its Applications to Chemical Problems,2000(1/2):35-42. |
| [2] | Howell BA .Utilization of thermogravimetry in the study of reaction mechanism[J].Journal of thermal analysis and calorimetry,2008(1):27-34. |
| [3] | H.-S. Kim;H.-J. Kim;D. Choi .THERMAL ANALYSIS OF HYDROLYSIS AND DEGRADATION OFBIODEGRADABLE POLYMER AND BIO-COMPOSITES[J].Journal of thermal analysis and calorimetry,2009(1):111-118. |
| [4] | Chrissafis, K .Kinetics of thermal degradation of polymers[J].Journal of thermal analysis and calorimetry,2009(1):273-283. |
| [5] | Minkina M;Mianowski A .Thermokinetics of the combustion of carbon containing materials.practical aspects of the investigations[J].Journal of Thermal Analysis and Calorimetry,2000,60(01):85-90. |
| [6] | Illekova E;Csomorova K .Kinetics of oxidation in various forms of carbon[J].Journal of thermal analysis and calorimetry,2005(1):103-108. |
| [7] | Hatori H.;Shiraishi M.;Yoshihara M.;Kimura T.;Yamada Y. .THE MECHANISM OF POLYIMIDE PYROLYSIS IN THE EARLY STAGE[J].Carbon: An International Journal Sponsored by the American Carbon Society,1996(2):201-208. |
| [8] | Marianne Blazso .Recent trends in analytical and applied pyrolysis of polymers[J].Journal of analytical & applied pyrolysis,1997(1):1-25. |
| [9] | Szocik H;Jantas R .Multimonomer and cross-linked polymers formed by its copolymerization:Thermal studies[J].Journal of Thermal Analysis and Calorimetry,2004,76(01):307-312. |
| [10] | Bolbukh Y N;Tertykh V A;Gawdzik B .TG and DSC studies of filled porous copolymers[J].Journal of Thermal Analysis and Calorimetry,2006,86(01):125-132. |
| [11] | B. A. Howell;K. Chaiwong .THERMAL STABILITY OF POLY(STYRENE) CONTAINING NOHEAD-TO-HEAD UNITS[J].Journal of thermal analysis and calorimetry,2009(1):219-223. |
| [12] | Li Y;Fan Y;Ma J .The thermal properties of porous polyvinylbenzene beads[J].Reactive and Functional Polymers,2001,50(01):57-65. |
| [13] | Seidel A.Characterization and Analysis of Polymers[M].John Wiley and Sons,Inc,Hoboken,New Jersey,2008:805-837. |
| [14] | Gribanov A V;Sazanov Y N;Mokeev M V .Role of structural characteristics of aromatic polyimides in carbonization[J].Russian Journal of Applied Chemistry,2002,75(04):606-610. |
| [15] | Yu. N. Sazanov;A. V. Gribanov .Cocarbonization of Polymers as a New Concept for Synthesis of Carbon Composites[J].Russian journal of applied chemistry,2006(3):433-438. |
| [16] | Gawdzik B.;Sobiesiak M. .Chemical composition of plasma treated polyimide microspheres[J].Applied Surface Science: A Journal Devoted to the Properties of Interfaces in Relation to the Synthesis and Behaviour of Materials,2003(1/4):52-57. |
| [17] | Takeichi T.;Kaburagi Y.;Hishiyama Y.;Inagaki M.;Endo Y. .Carbonization and graphitization of polyimide films: Effect of size of leaving group at imidization[J].Journal of Applied Polymer Science,1998(10):1613-1620. |
| [18] | Sazanov Y N .Applied significance of polyimides[J].Russian Journal of Applied Chemistry,2001,74(08):1253-1259. |
| [19] | Butt MS;Akhtar Z;Zafar-uz-Zaman M;Munir A .Synthesis and characterization of some novel aromatic polyimides[J].European Polymer Journal,2005(7):1638-1646. |
| [20] | Volksen W;Cha H J;Sanchez M I et al.Polyimides derived from nonaromatic monomers:synthesis,characterization and potential applications[J].Reactive and Functional Polymers,1996,30(1-3):61-69. |
| [21] | Im JK.;Jung JC. .Synthesis and properties of polyimides derived from N-[4-(4-aminophenyloxy)phenyl]-4-aminophthalimide[J].Polymer: The International Journal for the Science and Technology of Polymers,2000(24):8709-8716. |
| [22] | Tang, HY;Li, WW;Fan, XH;Chen, XF;Shen, ZH;Zhou, QF .Synthesis, preparation and properties of novel high-performance allyl-maleimide resins[J].Polymer,2009(6):1414-1422. |
| [23] | Roberto Aguado;Martin Olazar;Beatriz Gaisan;Ruben Prieto;Javier Bilbao .Kinetics of polystyrene pyrolysis in a conical spouted bed reactor[J].Chemical Engineering Journal,2003(1/3):91-99. |
| [24] | Yu. N. Sazanov;A. V. Gribanov;V. A. Lysenko .THE ROLE OF NITROGEN ATOMS IN FORMING THE CARBON STRUCTURE IN THE CARBONIZATION OF POLYMER COMPOSITES[J].Fibre Chemistry,2008(4):355-364. |
| [25] | Michio Inagaki;Mayuka Omura;Osamu Tanaike .Reversible water adsorption into carbonized polyimide films in ambient atmsphere[J].Carbon: An International Journal Sponsored by the American Carbon Society,2002(13):2502-2505. |
| [26] | Brennan JK.;Thomson KT.;Gubbins KE.;Bandosz TJ. .Water in porous carbons[J].Colloids and Surfaces, A. Physicochemical and Engineering Aspects,2001(0):539-568. |
| [27] | Analysis of structure and properties of active carbons and their copolymeric precursors[J].Applied Surface Science: A Journal Devoted to the Properties of Interfaces in Relation to the Synthesis and Behaviour of Materials,2010(17):5355. |
- 下载量()
- 访问量()
- 您的评分：
-
10%
-
20%
-
30%
-
40%
-
50%