硅烷接枝交联聚乙烯的结构与性能及其在纳米复合材料中的应用
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摘要
本文采用有限差分法模拟了乙烯基硅烷在聚乙烯中的扩散行为；研究了乙烯基硅烷与聚乙烯的熔融接枝反应，根据聚合物弹性理论，研究了硅烷交联聚乙烯的结构与性能，从结晶结构和结晶动力学两个方面研究了硅烷接枝交联聚乙烯的结晶行为，制备并表征了HDPE／nano-SiO_2复合材料和HDPE／SiO_2有机—无机杂化材料，首次系统地研究了硅烷接枝交联聚乙烯的结构与性能及其在纳米复合材料中的应用。
采用有限差分法建立了数学模型，编制计算机程序模拟了不饱和硅烷在聚乙烯中的扩散行为，得到了硅烷在聚乙烯中传输的扩散系数，并计算出扩散活化能E_D，VTMS在HDPE，LDPE，LLDPE中扩散活化能分别为38.2、24.0和22.0kJ。
采用FTIR、Raman、NMR和ICP表征了硅烷接枝聚乙烯，FTIR谱图上1170cm~(-1)、1110cm~(-1)、1090cm~(-1)和960cm~(-1)等处出现-Si-O-CH_3的特征吸收峰，激光Raman光谱上，硅烷的散射峰出现在1090cm~(-1)，~1H和~(13)C NMR谱图上，-OCH_3的特征峰分别出现在δ为4.25处和68处。采用ICP测得VTMS接枝LLDPE、LDPE和HDPE的接枝率分别为0.671-0.988％、0.349-0.972％和0.254-750％之间。
按照交联网络状态方程和Mooney-Rivlin方程可以测定交联聚乙烯的交联密度，当凝胶含量相同时，硅烷交联聚乙烯的交联密度大于过氧化物交联聚乙烯。在70℃的二甲苯和沸腾的苯中进行交联物的平衡溶胀试验，也可以证明当凝胶含量相同时，硅烷交联聚乙烯的交联密度大于过氧化物交联聚乙烯。同时测得了LDPE／沸腾苯体系的Huggins参数x1=0.30。
DSC、XRD和Raman光谱都可以研究接枝和交联反应引起的聚乙烯结晶结构的变化。对于LLDPE，随着硅烷用量的增加，Raman光谱分析表明，硅烷接枝聚乙烯的晶相由57.58％下降到46.99％，非晶相由11.58％上升到16.52％，中间相也由30.84％上升到36.48％。DSC测定的结晶度由40.73％下降到32.02％，XRD测定的结晶度由39.66％下降到32.87％，且结晶的熔点降低，晶粒变小，晶面间距增大，HDPE和LLDPE也有类似的结果。非等温结晶动力学研究表明接枝处理后聚乙烯Avrami指数n基本不变；结晶速率常数Z_c下降；半结晶期t_(12)延长。交联后Z_c进一步下降，t_(12)进一步延长。
对聚乙烯进行硅烷接枝，对SiO_2进行表面处理，都可以改善HDPE／nano-SiO_2共混体系的相容性，提高复合材料的力学性能。当nano-SiO_2的含量为10％左右时，体系的拉伸强度可提高近30％，并且复合材料的热分解温度提高20℃。
以PEW为模型化合物，研究了HDPE与TEOS的Sol-Gel反应，在小型密炼机上实施了硅烷接枝聚乙烯与TEOS的Sol-Gel过程，当密炼机的转速以60min~(-1)；聚乙烯的接枝单体VTMS的用量应控制在2.0phr以内；水的加入量为前驱体TEOS量的1／5时，可以制得性能较好的HDPE／SiO_2有机-无机杂化材料，当纳米SiO_2含量0.99％时，杂化材料的拉伸强度提高近30％。分解温度由472.17℃提高到476.68℃。FTIR和XPS证实杂化材料中纳米SiO_2与聚乙烯分子链形成了化学键结合。TEM还显示SiO_2粒子以50-100nm的球形分布在杂化材料之中。
The dissertation simulates the diffusion of vinyl-silane in polyethylene employinglimited differentiation and studies the molten graft of the vinyl-silane and polyethylene.The Structure and property of silane grafted and crosslinked polyethylene is also studied interms of the theory of polymer elasticity. The study in the crystallization of silane graftedand crosslinked polyethylene is performed too from the angles of the crystal structure andcrystal dynamics. Both the HDPE/nano-SiO_2 composite and HDPE/nano-SiO_2organic-inorganic hybrid are made and their structures are proved. The structures andproperties of silane grafted and crosslinked polyethylene and its application in polymernanocomposite is studied systematically for the first time in the dissertation.
The mathematical model is constructed in terms of finite differences. Then the specificcomputer program is compiled to simulate the diffusion of unsaturated silane inpolyethylene and diffusion coefficient is obtained to express the transmission of silane inpolyethylene. The activation energy of diffusion (E_D) can also be calculated. The E_D valuesof VTMS in HDPE, LDPE and LLDPE are 38.2、24.0 and 22.0KJ respectively.
The existence of silane grafted polyethylene is characterized by FTIR、Raman、NMRand ICP. The particular absorbance peaks of-Si-O-CH_3 are found in FTIR spectrograph at1170cm~(-1)、1110cm~(-1)、1090cm~(-1) and 960cm~(-1). In Raman spectrograph, the scattering peak ofsilane shows up at 1090cm~(-1). The resonance of -OCH_3 group appears atδ=4.25 andδ=68in ~1H and ~(13)C NMR spectrographs. According to ICP, the percentage of VTMS grated toLLDPE, LDPE and HDPE turns out to be between 0.671-0.988%, 0.349-0.972% and0.254-750% respectively.
The Mooney-Rivlin equation and the network state equation of cross-linked can beapplied to measure the density of cross-linkage of silane cross-linked polyethylene, whichis larger than that of peroxide cross-linked polyethylene when the content of gel is same.The above result can also be proved by the test of equilibrated dissolution and swell ofcross-linked polymer in dimethyl benzene at 70℃and boiled benzene. The parameter ofHuggins x1 in the system of LDPE and boiled benzene can be obtained at the same time,which is 0.31.
DSC, XRD and Raman laser light scattering can be employed to study the structure change of the crystalline resulted from grafted and cross-linked polyethylene. Based onRaman spectrograph, with increasing amount of silane, the crystalline phase of silanegrafted LLDPE decreases from 57.58% to 46.99%, amorphous phase increases from11.58% to 16.52%, and the mesophase increases from 30.84% to 36.48%. The degree ofcrystallization based on DSC decreases from 40.73% to 32.32%, while XRD result showsthe percentage decreases from 39.66% to 32.87%. Furthermore, the melting point and thesize of the crystal decrease, while the distance between the surfaces of the crystalsincreases. Similar results have also been obtained with HDPE and LDPE. Thenon-isothermal crystallization kinetics indicates that the Avrami Index (n) of graftedpolyethylene barely changes, while the velocity constant of the crystallization (Z_c) dropsand the half-time of the crystallization (t_(12)) lengthens. After the cross-linking, Z_c dropsmore and t_(12) lengthens more.
Silane grafting to polyethylene and surface treatment of SiO_2 can both improve thecompatibility of HDPE/nano-SiO_2 composite and enhance the mechanics properties of thecomposites. When the amount of nano-SiO_2 is around 10%, the tension strength of thesystem increases by about 30% and the decomposing temperature increases by 20℃.
PEW is employed as a model compound to study the Sol-Gel reaction of HDPE andTEOS. The Sol-Gel reaction of slane grafted polyethylene and TEOS is performed with asmall banbury mixer. When the amount of grafting monomer VTMS is below 2.0phr andthe added water is 20% of the amount of TEOS, a HDPE/SiO_2 organic-inorganic hybridwith good properties can be made if the banbury mixer runs at 60 min~(-1). The tensionstrength of the hybrid can be improved by 30% and the decomposing temperature isincreased from 472.17℃to 476.68℃when the content of nano-SiO_2 is 0.99%. Both FTIRand XPS results can proved that a chemical bond is formed between nano-SiO_2 and themolecular chain of PE in the hybrid. TEM data also indicates that the SiO_2 particles aredispersed in the hybrid as 50-100 nm spheres.
采用有限差分法建立了数学模型，编制计算机程序模拟了不饱和硅烷在聚乙烯中的扩散行为，得到了硅烷在聚乙烯中传输的扩散系数，并计算出扩散活化能E_D，VTMS在HDPE，LDPE，LLDPE中扩散活化能分别为38.2、24.0和22.0kJ。
采用FTIR、Raman、NMR和ICP表征了硅烷接枝聚乙烯，FTIR谱图上1170cm~(-1)、1110cm~(-1)、1090cm~(-1)和960cm~(-1)等处出现-Si-O-CH_3的特征吸收峰，激光Raman光谱上，硅烷的散射峰出现在1090cm~(-1)，~1H和~(13)C NMR谱图上，-OCH_3的特征峰分别出现在δ为4.25处和68处。采用ICP测得VTMS接枝LLDPE、LDPE和HDPE的接枝率分别为0.671-0.988％、0.349-0.972％和0.254-750％之间。
按照交联网络状态方程和Mooney-Rivlin方程可以测定交联聚乙烯的交联密度，当凝胶含量相同时，硅烷交联聚乙烯的交联密度大于过氧化物交联聚乙烯。在70℃的二甲苯和沸腾的苯中进行交联物的平衡溶胀试验，也可以证明当凝胶含量相同时，硅烷交联聚乙烯的交联密度大于过氧化物交联聚乙烯。同时测得了LDPE／沸腾苯体系的Huggins参数x1=0.30。
DSC、XRD和Raman光谱都可以研究接枝和交联反应引起的聚乙烯结晶结构的变化。对于LLDPE，随着硅烷用量的增加，Raman光谱分析表明，硅烷接枝聚乙烯的晶相由57.58％下降到46.99％，非晶相由11.58％上升到16.52％，中间相也由30.84％上升到36.48％。DSC测定的结晶度由40.73％下降到32.02％，XRD测定的结晶度由39.66％下降到32.87％，且结晶的熔点降低，晶粒变小，晶面间距增大，HDPE和LLDPE也有类似的结果。非等温结晶动力学研究表明接枝处理后聚乙烯Avrami指数n基本不变；结晶速率常数Z_c下降；半结晶期t_(12)延长。交联后Z_c进一步下降，t_(12)进一步延长。
对聚乙烯进行硅烷接枝，对SiO_2进行表面处理，都可以改善HDPE／nano-SiO_2共混体系的相容性，提高复合材料的力学性能。当nano-SiO_2的含量为10％左右时，体系的拉伸强度可提高近30％，并且复合材料的热分解温度提高20℃。
以PEW为模型化合物，研究了HDPE与TEOS的Sol-Gel反应，在小型密炼机上实施了硅烷接枝聚乙烯与TEOS的Sol-Gel过程，当密炼机的转速以60min~(-1)；聚乙烯的接枝单体VTMS的用量应控制在2.0phr以内；水的加入量为前驱体TEOS量的1／5时，可以制得性能较好的HDPE／SiO_2有机-无机杂化材料，当纳米SiO_2含量0.99％时，杂化材料的拉伸强度提高近30％。分解温度由472.17℃提高到476.68℃。FTIR和XPS证实杂化材料中纳米SiO_2与聚乙烯分子链形成了化学键结合。TEM还显示SiO_2粒子以50-100nm的球形分布在杂化材料之中。
The dissertation simulates the diffusion of vinyl-silane in polyethylene employinglimited differentiation and studies the molten graft of the vinyl-silane and polyethylene.The Structure and property of silane grafted and crosslinked polyethylene is also studied interms of the theory of polymer elasticity. The study in the crystallization of silane graftedand crosslinked polyethylene is performed too from the angles of the crystal structure andcrystal dynamics. Both the HDPE/nano-SiO_2 composite and HDPE/nano-SiO_2organic-inorganic hybrid are made and their structures are proved. The structures andproperties of silane grafted and crosslinked polyethylene and its application in polymernanocomposite is studied systematically for the first time in the dissertation.
The mathematical model is constructed in terms of finite differences. Then the specificcomputer program is compiled to simulate the diffusion of unsaturated silane inpolyethylene and diffusion coefficient is obtained to express the transmission of silane inpolyethylene. The activation energy of diffusion (E_D) can also be calculated. The E_D valuesof VTMS in HDPE, LDPE and LLDPE are 38.2、24.0 and 22.0KJ respectively.
The existence of silane grafted polyethylene is characterized by FTIR、Raman、NMRand ICP. The particular absorbance peaks of-Si-O-CH_3 are found in FTIR spectrograph at1170cm~(-1)、1110cm~(-1)、1090cm~(-1) and 960cm~(-1). In Raman spectrograph, the scattering peak ofsilane shows up at 1090cm~(-1). The resonance of -OCH_3 group appears atδ=4.25 andδ=68in ~1H and ~(13)C NMR spectrographs. According to ICP, the percentage of VTMS grated toLLDPE, LDPE and HDPE turns out to be between 0.671-0.988%, 0.349-0.972% and0.254-750% respectively.
The Mooney-Rivlin equation and the network state equation of cross-linked can beapplied to measure the density of cross-linkage of silane cross-linked polyethylene, whichis larger than that of peroxide cross-linked polyethylene when the content of gel is same.The above result can also be proved by the test of equilibrated dissolution and swell ofcross-linked polymer in dimethyl benzene at 70℃and boiled benzene. The parameter ofHuggins x1 in the system of LDPE and boiled benzene can be obtained at the same time,which is 0.31.
DSC, XRD and Raman laser light scattering can be employed to study the structure change of the crystalline resulted from grafted and cross-linked polyethylene. Based onRaman spectrograph, with increasing amount of silane, the crystalline phase of silanegrafted LLDPE decreases from 57.58% to 46.99%, amorphous phase increases from11.58% to 16.52%, and the mesophase increases from 30.84% to 36.48%. The degree ofcrystallization based on DSC decreases from 40.73% to 32.32%, while XRD result showsthe percentage decreases from 39.66% to 32.87%. Furthermore, the melting point and thesize of the crystal decrease, while the distance between the surfaces of the crystalsincreases. Similar results have also been obtained with HDPE and LDPE. Thenon-isothermal crystallization kinetics indicates that the Avrami Index (n) of graftedpolyethylene barely changes, while the velocity constant of the crystallization (Z_c) dropsand the half-time of the crystallization (t_(12)) lengthens. After the cross-linking, Z_c dropsmore and t_(12) lengthens more.
Silane grafting to polyethylene and surface treatment of SiO_2 can both improve thecompatibility of HDPE/nano-SiO_2 composite and enhance the mechanics properties of thecomposites. When the amount of nano-SiO_2 is around 10%, the tension strength of thesystem increases by about 30% and the decomposing temperature increases by 20℃.
PEW is employed as a model compound to study the Sol-Gel reaction of HDPE andTEOS. The Sol-Gel reaction of slane grafted polyethylene and TEOS is performed with asmall banbury mixer. When the amount of grafting monomer VTMS is below 2.0phr andthe added water is 20% of the amount of TEOS, a HDPE/SiO_2 organic-inorganic hybridwith good properties can be made if the banbury mixer runs at 60 min~(-1). The tensionstrength of the hybrid can be improved by 30% and the decomposing temperature isincreased from 472.17℃to 476.68℃when the content of nano-SiO_2 is 0.99%. Both FTIRand XPS results can proved that a chemical bond is formed between nano-SiO_2 and themolecular chain of PE in the hybrid. TEM data also indicates that the SiO_2 particles aredispersed in the hybrid as 50-100 nm spheres.
引文
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