HDPE氯化原位接枝顺丁烯二酸酐共聚物的合成、性能和应用
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摘要
本论文采用氯化原位接枝共聚(ISCGC)的方法对高密度聚乙烯(HDPE)进行酐基化改性,合成了以HDPE为骨架聚合物,顺丁烯二酸酐(MAH)为接枝支链的接枝共聚物,其名称为聚乙烯氯化接枝顺丁烯二酸酐(PE-cg-MAH)。该反应过程中不需要添加任何的引发剂,以氯气分解的氯自由基引发HDPE进行接枝反应,得到酐基官能化的聚乙烯接枝聚合物。
文中用FT-IR和1H-NMR手段对纯化后的酐基化产物PE-cg-MAH进行结构表征,证明了MAH单体接枝到HDPE的分子主链上,以及氯化原位接枝方法对HDPE进行酐基化改性的可行性。并推测了HDPE氯化原位接枝MAH的反应历程。通过对接枝聚合物PE-cg-MAH的凝胶含量和分子量的测定结果表明,氯化原位接枝过程中没有交联反应的发生和分子量的降解。利用DSC和X-射线对接枝聚合物的结晶行为分析,结果表明MAH单体在HDPE主链上的引入,使HDPE的结晶度下降,但下降的程度不大。还考察了反应时间、反应温度、氯气流量、MAH单体量等因素对接枝聚合物接枝率的影响,以此表明MAH对HDPE氯化原位接枝过程。
此外,用扫描电子显微镜(SEM)对聚合物拉伸断裂面形貌进行观察,表征了相对HDPE,PE-cg-MAH的相容性的提高。同时还研究和比较了接枝聚合物PE-cg-MAH的力学性能、亲水亲油性能、热稳定性能以及动态力学性能。并考察了影响接枝聚合物力学性能变化的因素。
最后研究了接枝聚合物PE-cg-MAH的应用。制备一种不含甲醛的胶合板粘合剂,并对该种粘合剂的结构进行了探索,考察了影响胶合板胶合强度变化的因素。结果表明,用接枝聚合物PE-cg-MAH作为胶合板粘合剂使用时,其胶合强度可达到Ⅰ类胶合板标准。
A new kind of graft copolymerization method , in-situ chlorinating graft copolymerization (ISCGC),was employed to modify high-density polyethylene (HDPE) with malefic anhydride (MAH) in this paper. The product synthesized was named as polyethylene-chlorinate,graft- malefic anhydride (PE-cg-MAH) which was composed of HDPE as backbone and MAH as branched chains. Without any initiators were added into reactive system, chlorine radicals derived from the decomposed chlorine molecule were used as to initiate grafting reaction of HDPE. The graft copolymer of polyethylene can be obtained with functionalized of MAH group.
The structure of PE-cg-MAH was characterized by 1H-NMR, FT-IR. The results of FT-IR, 1H-NMR indicated the existence of PE-cg-MAH, which verified the feasibility to modify HDPE with MAH by ISCGC, A possible reaction mechanism of HDPE reacted with MAH by ISCGC was proposed, The results of gel content and viscosity average molecular weight showed that there was no the reaction of cross-link and the degradation in the structure of PE-cg-MAH prepared by ISCGC, The crystal behavior of PE-cg-MAH was characterized by X-ray and DSC, the results of which showed that the crystallinity of graft polymers dropped due to the branched chain of MAH group compared with HDPE. Furthermore, the effects of reaction condition, including reaction temperature, chlorine flow, reaction time, MAH content etc., on graft degree (GD) of PE-cg-MAH were investigated.
In addition, the morphology of graft copolymer was observed by SEM. The purpose of which was to characterize the compatibility with polar polymer, at the same time, the properties of graft polymer, such as mechanical properties, hydrophilicity, lipophilicity, dynamic mechanical properties and thermal stability, were studied. The factors influencing mechanical properties of the graft polymer were also discussed.
At last, the application of graft copolymer synthesized was studied. The graft polymer can be used to prepare a cementing compound without formaldehyde. The structure of cementing compound was also explored and the factors that influenced the plywood agglutinate strength were also discussed. The results indicated that PE-cg-MAH can be used as a cementing compound and its agglutinate strength can reach National Standards of typeⅠp lywood.
文中用FT-IR和1H-NMR手段对纯化后的酐基化产物PE-cg-MAH进行结构表征,证明了MAH单体接枝到HDPE的分子主链上,以及氯化原位接枝方法对HDPE进行酐基化改性的可行性。并推测了HDPE氯化原位接枝MAH的反应历程。通过对接枝聚合物PE-cg-MAH的凝胶含量和分子量的测定结果表明,氯化原位接枝过程中没有交联反应的发生和分子量的降解。利用DSC和X-射线对接枝聚合物的结晶行为分析,结果表明MAH单体在HDPE主链上的引入,使HDPE的结晶度下降,但下降的程度不大。还考察了反应时间、反应温度、氯气流量、MAH单体量等因素对接枝聚合物接枝率的影响,以此表明MAH对HDPE氯化原位接枝过程。
此外,用扫描电子显微镜(SEM)对聚合物拉伸断裂面形貌进行观察,表征了相对HDPE,PE-cg-MAH的相容性的提高。同时还研究和比较了接枝聚合物PE-cg-MAH的力学性能、亲水亲油性能、热稳定性能以及动态力学性能。并考察了影响接枝聚合物力学性能变化的因素。
最后研究了接枝聚合物PE-cg-MAH的应用。制备一种不含甲醛的胶合板粘合剂,并对该种粘合剂的结构进行了探索,考察了影响胶合板胶合强度变化的因素。结果表明,用接枝聚合物PE-cg-MAH作为胶合板粘合剂使用时,其胶合强度可达到Ⅰ类胶合板标准。
A new kind of graft copolymerization method , in-situ chlorinating graft copolymerization (ISCGC),was employed to modify high-density polyethylene (HDPE) with malefic anhydride (MAH) in this paper. The product synthesized was named as polyethylene-chlorinate,graft- malefic anhydride (PE-cg-MAH) which was composed of HDPE as backbone and MAH as branched chains. Without any initiators were added into reactive system, chlorine radicals derived from the decomposed chlorine molecule were used as to initiate grafting reaction of HDPE. The graft copolymer of polyethylene can be obtained with functionalized of MAH group.
The structure of PE-cg-MAH was characterized by 1H-NMR, FT-IR. The results of FT-IR, 1H-NMR indicated the existence of PE-cg-MAH, which verified the feasibility to modify HDPE with MAH by ISCGC, A possible reaction mechanism of HDPE reacted with MAH by ISCGC was proposed, The results of gel content and viscosity average molecular weight showed that there was no the reaction of cross-link and the degradation in the structure of PE-cg-MAH prepared by ISCGC, The crystal behavior of PE-cg-MAH was characterized by X-ray and DSC, the results of which showed that the crystallinity of graft polymers dropped due to the branched chain of MAH group compared with HDPE. Furthermore, the effects of reaction condition, including reaction temperature, chlorine flow, reaction time, MAH content etc., on graft degree (GD) of PE-cg-MAH were investigated.
In addition, the morphology of graft copolymer was observed by SEM. The purpose of which was to characterize the compatibility with polar polymer, at the same time, the properties of graft polymer, such as mechanical properties, hydrophilicity, lipophilicity, dynamic mechanical properties and thermal stability, were studied. The factors influencing mechanical properties of the graft polymer were also discussed.
At last, the application of graft copolymer synthesized was studied. The graft polymer can be used to prepare a cementing compound without formaldehyde. The structure of cementing compound was also explored and the factors that influenced the plywood agglutinate strength were also discussed. The results indicated that PE-cg-MAH can be used as a cementing compound and its agglutinate strength can reach National Standards of typeⅠp lywood.
引文
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