Preparation and properties of high meltstrength polypropylene
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摘要: 聚丙烯（PP）因其优良性能广泛应用于诸多领域，但同时也有着韧性差，熔体强度低等缺点。而高熔体强度聚丙烯（HMSPP）是一种具有较高熔体强度、较好熔体弹性的聚丙烯树脂，它的发现拓展了聚丙烯在物理发泡、挤出涂布及热成型等领域的应用，多年来一直是聚烯烃研究工作的重点。本文以2,5-二甲基-2,5-双-（叔丁基过氧）己烷（DHBP）为引发剂，采用多官能团单体三羟甲基丙烷三丙烯酸酯（TMPTA）对市售聚丙烯（PP）进行接枝，同时加入支化促进剂二硫化四丁基秋兰姆（TBTDS）以提高接枝效率，成功制备了具有高熔体强度的聚丙烯并进行了配方优化。本文测定了接枝产物的熔体流动速率(MFR)及采用公式法计算熔体强度(MS)。通过红外光谱（IR）对所得高熔体强度聚丙烯的分子结构进行表征，结果表明单体已接枝在PP主链上，通过差示扫描量热法（DSC）、热重分析（TG）方法，对所得高熔体强度聚丙烯的热性能进行分析和表征，结果表明接枝产物的熔融温度没有显著变化，耐热温度有所上升。拉伸强度、弯曲强度、冲击强度等力学性能的测定结果表明接枝产物的力学性能有显著提高。
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关键词:
- 三羟甲基丙烷丙烯酸酯
Abstract: Polypropylene is widely used because of its excellent performance in many fields, but also has some defects such as poor toughness, poor melt strength. The high melt strength polypropylene which has high melt strength, melt elasticity, has been focus of the research on polyolefin over the years. It is found that expand the polypropylene in the physical foaming, extrusion coating and thermoforming, and other fields of application. In this paper, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane as the initiator, a multi-functional monomer trimethylolpropane triacrylate was grafted with commercially polypropylene, while adding a branching accelerators tetrabutyl thiuram disulfide to improve grafting efficiency. The high melt strength polypropylene is successfully prepared and its recipe is optimized. In this paper,The melt flow rate of grafted product are determined and its melt strength is calculated by formula method. By infrared spectroscopy, the molecular structure of the high melt strength polypropyleneare analyzed and characterized，and the result showed the monomer has been grafted onto the main chain of polypropylene. By differential scanning calorimetry, thermal gravimetric analysis method, thermal properties of the high melt strength polypropylene are analyzed and characterized. The results showed that the melting temperature of the grafting products were not significantly change, and heat temperature has increased.The mechanical properties measurement results such as tensile strength, bending strength, impact strength, show that the mechanical properties of grafted products have improved significantly.-
Keywords:
- Trimethylolpropane triacrylate
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Tong X W，Li Y T， Yang L T．Study on the compatibility of PP/ABS and the mechanical properties of its high cotent of CaCO3 filled composites[J]．Journal of South China Normal University：Natural Science Edition，2014，46（6）：75-78
[2] 杨美珠，石光，张力，等．新型无卤阻燃聚丙烯的制备以及性能研究[J]．华南师范大学学报：自然科学版，2009（3）：79-83
Yang M Z， Shi G， Zhang L， et al． Preparation and properties if new intumescent flame retardant polypropylene[J]．Journal of South China Normal University：Natural Science Edition，2009(3)，79-83
[3] Shuzhao Li, Miaomiao Xiao, Anna Zheng, et al. The melt grafting perparation and rheological characterization of long chain branching polypropylene[J]. Polymer,2009,50:6121–6128.DOI:10.1016/j.polymer.2009.10.006
[4] Fenghua Su, Hanxiong Huang. Rheology and Thermal Properties of Polypropylene Modified by Reactive Extrusion with Dicumyl Preoxide and Trimethylol Propane Triacrylate[J].Advances in Polymer Technology,2009,28(1):16–25.DOI:10.1002/adv.20146
[5]D Graebling. Synthesis of Branched Polypropylene by a Reactive Extrusion Process[J].Mscromolecules,2002,35:4602–4610.DOI:10.1021/ma0109469
[6] Yanjie An, Zhenjiang Zhang, Yanhui Wang, et al. Structure and Properties of High Melt Strength Polypropylene Prepared by Combined Method of Blending and Crosslinking[J]. Journal of Applied Polymer Science,2010,116:1739–1746.DOI:10.1002/app.31610
[7] 汪晓鹏，李文磊，贺建梅．高熔体强度聚丙烯的制备及性能研究[J]．塑料工业，2013，41（12）：9—12
Wang X P，Li W L，He J M．Preparation and Properties Study on High Melt Strength Polypropylene[J]．China Plastics Industry，2013，41（12）：9—12
[8] 郭鹏，刘有鹏，吕明福，等．高熔体强度聚丙烯的研究进展[J]．石油化工，2012，41（8）：958—964
Guo P，Liu Y P，Lv M F，et al．Research Progresses in High Melt Strength Polypropylene[J]，Petrochemical Technology，2012，41（8）：958—964
[9] J. E. Guillet, R. L. Combs, D. F. Slonaker, et al. Effects of Molecular Weight Distribution and Branching on Rheological Parameters of Polyethylene Melts[J]. Journal of Applied Polymer Science,1965,8:757–765
[10] 王红英，胡徐腾，董金勇，等．高熔体强度聚丙烯的制备与表征[J]．化学进展，2007，19（6）：932—957
Wang H Y，Hu X T，Dong J Y，et al．Preparation and Characterization of High Melt Strength Polypropylene[J]．Process in Chemistry，2007，19（6）：932—957
[11] 段宝颜．高熔体强度聚丙烯的制备及性能研究[D]．大庆．东北石油大学．2014
Duan B Y．Preparation and properties of high melt strength polypropylene[D]．Daqing．Northeast Petroleum University．2014
[12]李志锋，邓清华，冯凯，等．高熔体强度聚丙烯树脂的结构与性能[J]．合成树脂塑料，2012，29（3）：47—49
Li Z F，Deng Q H，Feng K，et al．Structure and properties of high melt strength polypropylene resin[J]．China Synthetic Resin and Plastics，2012，29（3）：47—49
[13] 林剑英．熔融接枝制备高熔体强度聚丙烯及其性能研究[D]．福州．福建师范大学．2010
Lin J Y．Research on Melt Grafting Preparation and Performance of High Melt Strength Polypropylene[D]．Fuzhou．Fujian Normal University．2010
[14]王姝．长链支化聚丙烯的制备[D]．哈尔滨．哈尔滨工程大学．2006
Wang S．Preparation of long chain branching Polypropylene[D]．Harbin．Harbin Engineering University．2006
[15] 杨淑静．反应挤出法制备发泡用高熔体强度聚丙烯的研究 [D]．北京．北京化工大学．2006
Yang S J．Research on the High melt strength Polypropylene for Foaming Prepared by Reactive Extrusion[D]．Beijing．Beijing University of Chemical Technology
[1] 童绪文，李彦涛，杨丽庭．PP/ABS 相容性及其碳酸钙高填充材料力学性能研究[J]．华南师范大学学报：自然科学版，2014，46（6）：75-78
Tong X W，Li Y T， Yang L T．Study on the compatibility of PP/ABS and the mechanical properties of its high cotent of CaCO3 filled composites[J]．Journal of South China Normal University：Natural Science Edition，2014，46（6）：75-78
[2] 杨美珠，石光，张力，等．新型无卤阻燃聚丙烯的制备以及性能研究[J]．华南师范大学学报：自然科学版，2009（3）：79-83
Yang M Z， Shi G， Zhang L， et al． Preparation and properties if new intumescent flame retardant polypropylene[J]．Journal of South China Normal University：Natural Science Edition，2009(3)，79-83
[3] Shuzhao Li, Miaomiao Xiao, Anna Zheng, et al. The melt grafting perparation and rheological characterization of long chain branching polypropylene[J]. Polymer,2009,50:6121–6128.DOI:10.1016/j.polymer.2009.10.006
[4] Fenghua Su, Hanxiong Huang. Rheology and Thermal Properties of Polypropylene Modified by Reactive Extrusion with Dicumyl Preoxide and Trimethylol Propane Triacrylate[J].Advances in Polymer Technology,2009,28(1):16–25.DOI:10.1002/adv.20146
[5]D Graebling. Synthesis of Branched Polypropylene by a Reactive Extrusion Process[J].Mscromolecules,2002,35:4602–4610.DOI:10.1021/ma0109469
[6] Yanjie An, Zhenjiang Zhang, Yanhui Wang, et al. Structure and Properties of High Melt Strength Polypropylene Prepared by Combined Method of Blending and Crosslinking[J]. Journal of Applied Polymer Science,2010,116:1739–1746.DOI:10.1002/app.31610
[7] 汪晓鹏，李文磊，贺建梅．高熔体强度聚丙烯的制备及性能研究[J]．塑料工业，2013，41（12）：9—12
Wang X P，Li W L，He J M．Preparation and Properties Study on High Melt Strength Polypropylene[J]．China Plastics Industry，2013，41（12）：9—12
[8] 郭鹏，刘有鹏，吕明福，等．高熔体强度聚丙烯的研究进展[J]．石油化工，2012，41（8）：958—964
Guo P，Liu Y P，Lv M F，et al．Research Progresses in High Melt Strength Polypropylene[J]，Petrochemical Technology，2012，41（8）：958—964
[9] J. E. Guillet, R. L. Combs, D. F. Slonaker, et al. Effects of Molecular Weight Distribution and Branching on Rheological Parameters of Polyethylene Melts[J]. Journal of Applied Polymer Science,1965,8:757–765
[10] 王红英，胡徐腾，董金勇，等．高熔体强度聚丙烯的制备与表征[J]．化学进展，2007，19（6）：932—957
Wang H Y，Hu X T，Dong J Y，et al．Preparation and Characterization of High Melt Strength Polypropylene[J]．Process in Chemistry，2007，19（6）：932—957
[11] 段宝颜．高熔体强度聚丙烯的制备及性能研究[D]．大庆．东北石油大学．2014
Duan B Y．Preparation and properties of high melt strength polypropylene[D]．Daqing．Northeast Petroleum University．2014
[12]李志锋，邓清华，冯凯，等．高熔体强度聚丙烯树脂的结构与性能[J]．合成树脂塑料，2012，29（3）：47—49
Li Z F，Deng Q H，Feng K，et al．Structure and properties of high melt strength polypropylene resin[J]．China Synthetic Resin and Plastics，2012，29（3）：47—49
[13] 林剑英．熔融接枝制备高熔体强度聚丙烯及其性能研究[D]．福州．福建师范大学．2010
Lin J Y．Research on Melt Grafting Preparation and Performance of High Melt Strength Polypropylene[D]．Fuzhou．Fujian Normal University．2010
[14]王姝．长链支化聚丙烯的制备[D]．哈尔滨．哈尔滨工程大学．2006
Wang S．Preparation of long chain branching Polypropylene[D]．Harbin．Harbin Engineering University．2006
[15] 杨淑静．反应挤出法制备发泡用高熔体强度聚丙烯的研究 [D]．北京．北京化工大学．2006
Yang S J．Research on the High melt strength Polypropylene for Foaming Prepared by Reactive Extrusion[D]．Beijing．Beijing University of Chemical Technology
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