β晶成核剂邻苯二甲酸锌的制备及其对聚丙烯性能的影响研究
发布时间：2019-03-18 14:56
【摘要】：(β晶型聚丙烯(β-PP)比α晶聚丙烯(α-PP)具有更优异的韧性和更高的热变形温度,广泛应用于日用品、家居电器、汽车及排水管领域,如何生产稳定的β-PP日益成为人们关注的重点。而添加β晶型成核剂,是目前制备β晶型聚丙烯最有前景且高效可靠的方式,所以开发稳定、高效高选择性的β晶成核剂已经成为β-PP改性领域研究的热点。首先,本文通过溶液法成功合成出邻苯二甲酸锌(PAZn(Solution)),并发现其在聚丙烯中具有β晶成核效果,但是其在聚丙烯中分散不均,团聚明显,导致成核效率较低,基于此我们提出在挤出加工过程中原位制备邻苯二甲酸锌(PAZn(In situ))的思想和方法,并系统研究两种方法制备的邻苯二甲酸锌对等规均聚聚丙烯(iPP)成核效果的影响。结果表明,在添加量为0.2wt%时,PAZn(Insitu)与PAZn(Solution)的抗冲击强度均达到最大值,相比于空白iPP分别提升了 215%和151%。在成核效率和β晶型选择性方面原位制备方法也显示出了其特有的优势,0.05 wt%的PAZn(In situ)诱导的β晶含量(kβ值)可达0.95;而对于PAZn(Solution),在其最优添加浓度下(0.05wt%),kβ仅为0.64。通过透射电子显微镜(TEM)、能谱分析(EDS)得知,原位制备的PAZn(In situ)在聚丙烯体系中具有更好的分散性,颗粒尺径小且均一,解释了 PAZn(In situ)具有更高成核效率的原因。其次,研究了 PAZn(Insitu)及PAZn(Solution)对嵌段共聚聚丙烯(PPB)成核效果的影响。当成核剂的添加浓度为0.2wt%时,PPB/PAZn(Insitu)常温冲击强度和低温冲击强度相比空白PPB分别提高了 359%和107%,而PPB/PAZn(Solution)则分别提高了 302%和101%。PAZn(In situ)对PPB韧性改善效果略优于PAZn(Solution)。在成核效率和β晶选择性方面两种制备方法显示出了明显的差异,当添加浓度为0.1 wt%时,PAZn(In situ)与PAZn(Solution)诱导的β晶含量都基本上达到最大值,kβ分别为0.97和0.80。PAZn(In situ)在 0.05-0.8 wt%浓度范围内,kβ 均保持在 0.96 以上;而 PAZn(Solution)在 0.05-0.8 wt%浓度范围内,kβ逐渐降低直至接近0。表明在PPB体系,PAZn(In situ)是一种高效稳定的β晶型成核剂。利用Mo法研究PPB体系非等温结晶动力学,PPB/PAZn(In situ)的F(T)值小于PPB/PAZn(Solution),也表明PAZn(In situ)在PPB体系中具有更好的成核效果。最后,探索了结晶成核剂对高熔体强度聚丙烯(HMSPP)基体性能及发泡性能的影响。差示扫描量热仪(DSC)测试表明,成核剂均可以消除实验室基于长支链接枝制备的HMSPP的双结晶峰现象,而对商业化的HMSPP品种WB260体系却没有产生明显的影响。力学性能方面,成核剂对HMSPP体系的刚性及韧性都没有明显的影响。发泡性能的测试表明,成核剂的加入可以有效调控HMSPP体系的泡孔直径,泡孔尺寸可达到50μm以上,发泡倍率至少提高2倍以上,均可以得到高发泡倍率的泡沫产品。
[Abstract]:尾-crystalline polypropylene (尾-PP) has better toughness and higher thermal deformation temperature than 伪-crystalline polypropylene (伪-PP), and is widely used in household appliances, automobiles and drain pipes. How to produce stable 尾-PP has become the focus of attention. The addition of 尾-crystalline nucleating agent is the most promising and reliable way to prepare 尾-crystalline polypropylene at present, so the development of stable, high-efficiency and high-selectivity 尾-crystalline nucleating agent has become a hot spot in the field of 尾-PP modification. Firstly, zinc phthalate (PAZn (Solution), was successfully synthesized by solution method and found to have the effect of 尾 crystal nucleation in polypropylene, but it was unevenly dispersed in polypropylene and agglomerated obviously, which led to lower nucleation efficiency. Based on this, we put forward the idea and method of in-situ preparation of zinc phthalate (PAZn (In situ) during extrusion processing, and systematically study the effect of the two methods on the nucleation effect of zinc phthalate isohomopolymer polypropylene (iPP). The results showed that the impact strength of, PAZn (Insitu) and PAZn (Solution) reached the maximum at 0.2 wt%, which was 215% and 151% higher than that of blank iPP, respectively. In the aspects of nucleation efficiency and 尾 crystal form selectivity, the in situ preparation method also shows its unique advantages. The content of 尾 crystals (k 尾 value) induced by PAZn (In situ) of 0.05 wt% is up to 0.95; The optimal concentration of PAZn (Solution), (0.05wt%), k 尾) was 0.64. The transmission electron microscopy (TEM),) analysis of (EDS) showed that the in-situ prepared PAZn (In situ) had better dispersibility, smaller particle size and uniform size in polypropylene system. The reason why PAZn (In situ) has more Gao Cheng nuclear efficiency is explained. Secondly, the effects of PAZn (Insitu) and PAZn (Solution) on the nucleation of block copolymer polypropylene (PPB) were studied. When the addition concentration as nucleating agent was 0.2 wt%, the impact strength of PPB/PAZn (Insitu) at room temperature and low temperature increased by 35.9% and 107%, respectively, compared with blank PPB. On the other hand, PPB/PAZn (Solution) increased 302% and 101%.PAZn (In situ) slightly improved the toughness of PPB than that of PAZn (Solution). There were obvious differences in nucleation efficiency and 尾-crystal selectivity between the two methods. When the concentration was 0.1 wt%, the content of 尾-crystals induced by, PAZn (In situ) and PAZn (Solution) reached the maximum. K 尾 was 0.97 and 0.80.PAZn (In situ) was within 0. 05 渭 0. 8 wt%, and k 尾 was above 0. 96 in the range of 0. 05 and 0. 8 wt%, respectively. In the range of 0. 05 and 0. 8 wt% of PAZn (Solution), k 尾 gradually decreased to close to 0. 0. The results show that, PAZn (In situ) in PPB system is an efficient and stable nucleating agent in 尾 crystal form. The non-isothermal crystallization kinetics of PPB system was studied by Mo method. The F (T) value of PPB/PAZn (In situ) was less than that of PPB/PAZn (Solution), which indicated that PAZn (In situ) had better nucleation effect in PPB system. Finally, the effects of nucleating agent on the matrix properties and foaming properties of high melt strength polypropylene (HMSPP) were investigated. Differential scanning calorimetry (DSC) showed that nucleating agents could eliminate the biphasic peaks of HMSPP based on long branch links in the laboratory, but had no obvious effect on the WB260 system of commercial HMSPP varieties. In terms of mechanical properties, nucleating agent has no obvious effect on the rigidity and toughness of HMSPP system. The test of foaming property shows that the addition of nucleating agent can effectively control the cell diameter of HMSPP system, the cell size can be more than 50 渭 m, and the foaming rate can be increased by at least 2 times. The foam products with high foaming rate can be obtained by the addition of nucleating agent.
【学位授予单位】：华东理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TQ325.14
本文编号：2442965
[Abstract]:尾-crystalline polypropylene (尾-PP) has better toughness and higher thermal deformation temperature than 伪-crystalline polypropylene (伪-PP), and is widely used in household appliances, automobiles and drain pipes. How to produce stable 尾-PP has become the focus of attention. The addition of 尾-crystalline nucleating agent is the most promising and reliable way to prepare 尾-crystalline polypropylene at present, so the development of stable, high-efficiency and high-selectivity 尾-crystalline nucleating agent has become a hot spot in the field of 尾-PP modification. Firstly, zinc phthalate (PAZn (Solution), was successfully synthesized by solution method and found to have the effect of 尾 crystal nucleation in polypropylene, but it was unevenly dispersed in polypropylene and agglomerated obviously, which led to lower nucleation efficiency. Based on this, we put forward the idea and method of in-situ preparation of zinc phthalate (PAZn (In situ) during extrusion processing, and systematically study the effect of the two methods on the nucleation effect of zinc phthalate isohomopolymer polypropylene (iPP). The results showed that the impact strength of, PAZn (Insitu) and PAZn (Solution) reached the maximum at 0.2 wt%, which was 215% and 151% higher than that of blank iPP, respectively. In the aspects of nucleation efficiency and 尾 crystal form selectivity, the in situ preparation method also shows its unique advantages. The content of 尾 crystals (k 尾 value) induced by PAZn (In situ) of 0.05 wt% is up to 0.95; The optimal concentration of PAZn (Solution), (0.05wt%), k 尾) was 0.64. The transmission electron microscopy (TEM),) analysis of (EDS) showed that the in-situ prepared PAZn (In situ) had better dispersibility, smaller particle size and uniform size in polypropylene system. The reason why PAZn (In situ) has more Gao Cheng nuclear efficiency is explained. Secondly, the effects of PAZn (Insitu) and PAZn (Solution) on the nucleation of block copolymer polypropylene (PPB) were studied. When the addition concentration as nucleating agent was 0.2 wt%, the impact strength of PPB/PAZn (Insitu) at room temperature and low temperature increased by 35.9% and 107%, respectively, compared with blank PPB. On the other hand, PPB/PAZn (Solution) increased 302% and 101%.PAZn (In situ) slightly improved the toughness of PPB than that of PAZn (Solution). There were obvious differences in nucleation efficiency and 尾-crystal selectivity between the two methods. When the concentration was 0.1 wt%, the content of 尾-crystals induced by, PAZn (In situ) and PAZn (Solution) reached the maximum. K 尾 was 0.97 and 0.80.PAZn (In situ) was within 0. 05 渭 0. 8 wt%, and k 尾 was above 0. 96 in the range of 0. 05 and 0. 8 wt%, respectively. In the range of 0. 05 and 0. 8 wt% of PAZn (Solution), k 尾 gradually decreased to close to 0. 0. The results show that, PAZn (In situ) in PPB system is an efficient and stable nucleating agent in 尾 crystal form. The non-isothermal crystallization kinetics of PPB system was studied by Mo method. The F (T) value of PPB/PAZn (In situ) was less than that of PPB/PAZn (Solution), which indicated that PAZn (In situ) had better nucleation effect in PPB system. Finally, the effects of nucleating agent on the matrix properties and foaming properties of high melt strength polypropylene (HMSPP) were investigated. Differential scanning calorimetry (DSC) showed that nucleating agents could eliminate the biphasic peaks of HMSPP based on long branch links in the laboratory, but had no obvious effect on the WB260 system of commercial HMSPP varieties. In terms of mechanical properties, nucleating agent has no obvious effect on the rigidity and toughness of HMSPP system. The test of foaming property shows that the addition of nucleating agent can effectively control the cell diameter of HMSPP system, the cell size can be more than 50 渭 m, and the foaming rate can be increased by at least 2 times. The foam products with high foaming rate can be obtained by the addition of nucleating agent.
【学位授予单位】：华东理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TQ325.14
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