冰片烯和冰片二烯聚砜树脂的合成与表征
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摘要
本文以冰片烯(Be)、冰片二烯(Bd)、二氧化硫(SO_2)等单体为原料,采用自由基聚合方式,常温下使用聚合催化剂(引发剂),低温下不使用聚合催化剂(引发剂),使冰片烯(Be)、二氧化硫(SO_2),冰片烯(Be)、二氧化硫(SO_2)和马来酸酐(Ma),冰片烯(Be)、二氧化硫(SO_2)和苯乙烯(St),冰片二烯(Bd)、二氧化硫(SO_2),冰片二烯(Bd)、二氧化硫(SO_2)和马来酸酐(Ma),冰片二烯(Bd)、二氧化硫(SO_2)和苯乙烯(St)等单体组合的共聚合反应,探讨了Be和Bd与SO_2等单体共聚合的可行性和适宜的聚合工艺条件,并对聚合物进行了表征。
主要研究结果如下:
1)采取多种方法和技术提高Be和Bd单体的纯度,单体纯度由原来的92.1 %和98.3 %提高到95.3 %和98.5 %。从根本上提高单体的聚合“浓度”,为聚合反应提供了较高纯度的单体原料。
2)采取自由基聚合反应方式,制备了Be-SO_2、Be-SO_2-Ma、Be-SO_2-St等三种共聚物。经GPC检测,共聚物Be-SO_2、Be-SO_2-Ma、Be-SO_2-St的重均分子量分别达到1069、1576、33054。
3)参照上述研究方法和技术,制备了Bd-SO_2、Bd-SO_2-Ma、Bd-SO_2-St等三种共聚物。经GPC检测,共聚物Bd-SO_2、Bd-SO_2-Ma、Bd-SO_2-St的重均分子量分别达到1034、1896、37864。
4)提出了合成上述共聚物的方法、技术和适宜的工艺条件。
5)以蒎烯衍生物为原料与SO_2进行聚合反应制备聚砜类功能性新材料,对我国资源优势产品的高值化利用及对大气污染气体SO_2的资源化利用提供了一种新的思路、途径和方法。
In this article, bornylene(Be), bornadiene (Bd) and SO_2 were used as the raw material to synthesis polysulfone resins, through free radical polymerization with different catalysts. The main copolymerization reactions including Be-SO_2, Be-SO_2-maleic anhydride (Ma), Be-SO_2- styrene(St), Bd-SO_2, Bd-SO_2- Ma, Bd-SO_2- St. The practicability and optimal experimental conditions of the copolymerization reaction of Be, Bd and SO_2 were investigated in our reasearch. Then the characterization work of the copolymers were carried out. The main results of this paper are as follows:
(1) The Be, Bd monomers purity were enhenced from 92.1% and 98.3% to 95.3% and 98.5% respectively using different technologies and pathways. This step supplied high purity raw materials for the polymerization reactions.
(2) The copolymers: Be-SO_2、Be-SO_2-Ma、Be-SO_2-St were prepared through free radical polymerization reactions. The molecular weight of the copolymers were 1069、1576、33054 respectively detected by GPC.
(3) According to the pathways above, coplymers: Bd-SO_2, Bd-SO_2-Ma, Bd-SO_2-St were prepared, and the molecular weight of the copolymers were 1034、1896、37864 respectively detected by GPC.
(4) The pathways, technologies and the optimal experimental conditions were put forward in this paper.
(5) The preparation of new material polysulfone resin using pinene derivatives and SO_2 as raw material offers new directions and approaches for the resources application and atmospheric pollutant SO_2 in China .
主要研究结果如下:
1)采取多种方法和技术提高Be和Bd单体的纯度,单体纯度由原来的92.1 %和98.3 %提高到95.3 %和98.5 %。从根本上提高单体的聚合“浓度”,为聚合反应提供了较高纯度的单体原料。
2)采取自由基聚合反应方式,制备了Be-SO_2、Be-SO_2-Ma、Be-SO_2-St等三种共聚物。经GPC检测,共聚物Be-SO_2、Be-SO_2-Ma、Be-SO_2-St的重均分子量分别达到1069、1576、33054。
3)参照上述研究方法和技术,制备了Bd-SO_2、Bd-SO_2-Ma、Bd-SO_2-St等三种共聚物。经GPC检测,共聚物Bd-SO_2、Bd-SO_2-Ma、Bd-SO_2-St的重均分子量分别达到1034、1896、37864。
4)提出了合成上述共聚物的方法、技术和适宜的工艺条件。
5)以蒎烯衍生物为原料与SO_2进行聚合反应制备聚砜类功能性新材料,对我国资源优势产品的高值化利用及对大气污染气体SO_2的资源化利用提供了一种新的思路、途径和方法。
In this article, bornylene(Be), bornadiene (Bd) and SO_2 were used as the raw material to synthesis polysulfone resins, through free radical polymerization with different catalysts. The main copolymerization reactions including Be-SO_2, Be-SO_2-maleic anhydride (Ma), Be-SO_2- styrene(St), Bd-SO_2, Bd-SO_2- Ma, Bd-SO_2- St. The practicability and optimal experimental conditions of the copolymerization reaction of Be, Bd and SO_2 were investigated in our reasearch. Then the characterization work of the copolymers were carried out. The main results of this paper are as follows:
(1) The Be, Bd monomers purity were enhenced from 92.1% and 98.3% to 95.3% and 98.5% respectively using different technologies and pathways. This step supplied high purity raw materials for the polymerization reactions.
(2) The copolymers: Be-SO_2、Be-SO_2-Ma、Be-SO_2-St were prepared through free radical polymerization reactions. The molecular weight of the copolymers were 1069、1576、33054 respectively detected by GPC.
(3) According to the pathways above, coplymers: Bd-SO_2, Bd-SO_2-Ma, Bd-SO_2-St were prepared, and the molecular weight of the copolymers were 1034、1896、37864 respectively detected by GPC.
(4) The pathways, technologies and the optimal experimental conditions were put forward in this paper.
(5) The preparation of new material polysulfone resin using pinene derivatives and SO_2 as raw material offers new directions and approaches for the resources application and atmospheric pollutant SO_2 in China .
引文
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[4] Retolaza A,Eguiazabal J I, Nazabal J. Structure and mechanical properties of poly(sulfone of bisphenol A) /poly (butylene terephthalate) blends [J].Polym Int,2004,53(12): 2107–2114.
[5] Linares A, Acosta J L. Structural characterization of polymer blends based on polysulfones [ J]. J Appl Polym Sc,i 2004, 87 (1): 3030–3039.
[6] Garciam, Eguiazabal J I, Nazabal J. Processability,morphology and mechanical properties of glass fiber reinforced poly (ether sulfone) modified by a liquid crystalline copolyes-ter [J]. Polym Compos, 2003, 24 (6): 686–696.
[7]马海松.聚醚砜材料的性能及其在汽车上的应用[ J].汽车工艺与材料, 2005 (11): 35–37.
[8]钱伯章.特种工程塑料发展现状和进展[J].化工新型材料, 2005, 33 (1): 1–5.
[9] Masahiro Yamazaki. Industrialization and application development of cyclo-olefin polymer[J].Journal of Molecular Catalysis A: Chemical 2004,213:81–87.
[10] Hsin Her Yu,Shug-June Hwang,Ming-Chun Tseng, Chien-Chang Tseng .The effect of ITO films thickness on the properties of flexible organic light emitting diode[J].Optics Communications . 2006, 259:187–193.
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[12] Liang-sun Lee , Hsin-jung Ou, Hsiu-ling Hsu. The experiments and correlations of the solubility of ethylene in toluene solvent[J].Fluid Phase Equilibria 2005,231:221–230.
[13] Chenyang Liu, Jian YuXinghua Sun, Jun Zhang, Jiasong He.Thermal degradation studies of cyclic olefin copolymers[J].Polymer Degradation and Stability 2003,81:197–205.
[14] Julian M. Lippmann, Emil J. Geiger, Albert P. Pisano. Polymer investment molding: Method for fabricating hollow ,microscale parts. Sensors and Actuators A physical[J].2007, Article in press.
[15] W. Kaminsky. Polymerization catalysis[J].Catalysis Today 2000, 62 :23–34.
[16] Shan-Chun Chang, Ming-Jer Lee , Ho-Mu Lin. Nanoparticles formation for metallocene catalyzed cyclic olefin copolymer via a continuous supercritical anti-solvent process[J].J.of Supercritical Fluids. 2007,Artical in press.
[17] V. Seydewitza, M. Krumov, G.H. Michler, J.Y. Park, S.C. Kim.Morphology and micromechanical behaviour of ethylene cycloolefincopolymers (COC) [J]. Polymer. 2005, 46:5608–5614.
[18] Mario Casta?o-álvarez, M. Teresa Fernández-Abedul, Agustín Costa-García. Amperometric detectordesigns for capillary electrophoresis microchips[J]. Journal of Chromatography A.2006,1109:291–299.
[19]徐军.新型功能高分子材料的研究与应用[J].纺织高校基础科学学报. 2002,15(3):258-263.
[20] Mu-Jen Young , Wen-Sheng Chang , Chen-Chi M.Ma . Polymerization kinetics and modeling of a metallocene cyclic olefin copolymer system[J]. European Polymer Journal .2003,39:165-171.
[21] J.C. Mol. Industrial applications of olefin metathesis[J].Journal of Molecular Catalysis A: Chemical 2004,213:39–45.
[22] Wu-Jang Huang, Feng-Chih Chang, Peter Po-Jen Chu.Functionalization and chemical modification of cyclo olefin copolymers (COC) [J]. Polymer . 2000,41:6095–6101.
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