PETA/St双单体聚丙烯挤出改性及其发泡性能研究

doi:10.19491/j.issn.1001-9278.2020.07.001

中国塑料 ›› 2020, Vol. 34 ›› Issue (7): 1-9.DOI: 10.19491/j.issn.1001-9278.2020.07.001

• 材料与性能 • 下一篇

PETA/St双单体聚丙烯挤出改性及其发泡性能研究

郭天浩¹, 陆奕权¹, 刘涛¹(), 赵玲¹^,²

^1.华东理工大学，上海市多相结构材料化学工程重点实验室，上海 200237
^2.新疆大学化学化工学院，乌鲁木齐 820046

收稿日期:2020-02-20 出版日期:2020-07-26 发布日期:2020-07-26
基金资助:
国家重点研发计划(2016YFB0302200)

Study on Modification and Foaming Properties of PP Through PETA/St Double‑Monomer Reactive Extrusion

Tianhao GUO¹, Yiquan LU¹, Tao LIU¹(), Ling ZHAO¹^,²

^1.State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China
^2.School of Chemistry & Chemical Engineering, Xin Jiang University, Urumqi 830046, China

Received:2020-02-20 Online:2020-07-26 Published:2020-07-26
Contact: Tao LIU E-mail:liutao@ecust.edu.cn

摘要/Abstract

摘要：

以季戊四醇三丙烯酸酯（PETA）和苯乙烯（St）为接枝单体，采用反应挤出改性制备具有长支链结构的聚丙烯（LCBPP）。使用红外光谱、差示扫描量热仪、流变测试等表征材料的可发泡性，并通过扫描电子显微镜观测发泡材料的泡孔形貌。并以CO₂为发泡剂进行了间歇熔融发泡实验以评估聚丙烯（PP）的熔融发泡性。结果表明，在未交联改性PP中，用2 %（质量分数，下同）PETA和3 %St改性的PP各项性能最好；改性PP具有不同程度的应变硬化现象，这归因于不同程度的长链支化结构；改性后具有长链支化结构的PP有较好的发泡效果，PP?g?PETA/St样品的发泡温度窗口为25 ℃，最高发泡倍率达到33倍，此时泡孔平均直径为36 μm，泡孔密度为3.17×10⁸个/cm³。

关键词: 长链支化结构, 改性聚丙烯, 流变性能, 发泡

Abstract:

A series of long?chain branched PP compounds were prepared by double?monomer reactive extrusion of conventional isotactic polypropylene with pentaerythriol triacrylate (PETA) and Styrene (St), their faomability was characterized with FTIR, DSC and rheology tests, and their foam structure was observed with SEM. The results indicated that for the modified PP samples without crosslinking structure, the PP compound with 2 wt% of PETA and 3 wt% of St exhibited the optimum comprehensive performance. Meanwhile, the PP compounds showed a different strain hardening behaviors because of the different branching structure. The batch melt foaming experiment was conducted to evaluate the melt foamability of PP compounds with CO₂ as the foaming agent. It was found that the PP compounds with a long branching structure had a better melt foamability, and the the PP samples showed a foaming window temperature of 25 ℃ after grafted with PETA/St double monomers. The resulting PP foams achieved a maximum expansion ratio of 33, an average diameter of 36 μm, and a cell density of 3.17×10⁸ cells/cm³.

Key words: long branching sturcture, modified polypropylene, rheology property, foaming

中图分类号:

TQ325.1⁺4

郭天浩, 陆奕权, 刘涛, 赵玲. PETA/St双单体聚丙烯挤出改性及其发泡性能研究[J]. 中国塑料, 2020, 34(7): 1-9.

Tianhao GUO, Yiquan LU, Tao LIU, Ling ZHAO. Study on Modification and Foaming Properties of PP Through PETA/St Double‑Monomer Reactive Extrusion[J]. China Plastics, 2020, 34(7): 1-9.

图/表 13

样品编号	原料添加量
样品编号	DCP	PETA	St	抗氧剂1010
PP1	—	—	—	—
PP2	0.2	2	—	0.1
PP3	0.2	—	3	0.1
PP4	0.2	2	3	0.1

表1 改性PP样品配方

Tab.1 Experimental formulation of the modified PP

图1 反应机理图

Fig.1 Possible molecular reaction mechanism

图2 不同PP样品的FTIR谱图

Fig.2 FTIR spectra of the iPP and modified samples

图3 iPP及改性PP样品的分子质量分布

Fig.3 MWD curves of iPP and modified PP samples

样品	MFR/ g·(10 min)^-1	M_w/ kg·mol^-1	M_n/ kg·mol^-1	M_W/M_n	η₀/Pa·s
PP1	3.493	403.75	69.03	5.85	2 800
PP2	3.191	436.12	65.98	6.61	5 040
PP3	2.015	460.63	74.61	6.17	40 509
PP4	1.672	485.42	90.23	5.38	66 812

表2 不同PP样品的物性参数

Tab.2 Physical parameters of iPP and modified PP samples

图4 iPP及改性PP样品的熔融及结晶曲线

Fig.4 Melting and crystallation curves of the iPP and modified PP samples

样品	T_m/℃	T_c,onset/ ℃	T_c/℃	ΔH_f/ J·g^-1	X_c/%	k′	t_1/2/min	n	R²
PP1	167.0	125	112.0	72.12	34.51	0.85	1.38	3.83	0.982 6
PP2	165.5	132	122.0	65.98	31.57	0.93	0.97	3.16	0.995 0
PP3	166.5	130	119.5	64.07	30.66	0.91	0.98	3.50	0.998 2
PP4	166.0	136	128.0	63.29	30.28	0.99	0.88	2.76	0.995 6

表3 不同PP样品的熔融及结晶参数

Tab.3 DSC parameters of iPP and modified PP samples

图5 iPP及改性PP样品的流变测试图

Fig.5 Rheological behavior of the iPP and modified PP samples

图6 iPP及改性PP样品cole?cole图、Han图及松弛时间谱图

Fig.6 Cole?cole plot, Han plot and relaxation time spectra of the iPP and modified PP samples

图7 iPP及改性PP样品的拉伸黏度图

Fig.7 Elongational viscosity of the iPP and modified PP samples

图8 iPP及改性PP样品的间歇发泡泡孔形貌图

Fig.8 SEM images of iPP and modified PP foams at 145 ℃ and CO2 pressure of 15 MPa

图9 PP4样品15 MPa不同温度泡孔形貌图

Fig.9 SEM images of PP?g?PETA/St foams at 15 MPa CO2 and different temperature

图10 15 MPa压力下不同温度时PP4泡沫的数据

Fig.10 Characterization of PP?g?PETA/St foams at 15 MPa CO2 and different temperatures

参考文献 20

1	MANFRED R, MANFRED A, EBERHARD B, et al. Radical Reactions on Polypropylene in the Solid State[J]. Progress in Polymer Science, 2002,27(7):1 195‑1 282.
2	TREADWELL J, MALPHRUS A D, GIARDINO A P. The preparation and Rheology Characterization of Long Chain Branching Polypropylene[J]. Polymer, 2006,47(23):7 962‑7 969.
3	GAO J, LU Y, WEI G, et al. Effect of Radiation on the Crosslinking and Branching of Polypropylene[J]. Journal of Applied Polymer Science, 2010,85(8):1 758‑1 764.
4	HU G H, SUN Y J, LAMBLA M. Devolatilization: A Critical Sequential Operation for Insitu Compatibilization of Immiscible Polymer Blends by One‑step Reactive Extrusion[J]. Polymer Engineering & Science, 2010,36(5):676‑684.
5	WANG D, XIE X M, JOW J, et al. Styrene‑Assisted Melt Free‑Radical Grafting of Pentaerythritol Triacrylate onto Polypropylene and Its Crystallization Behavior[J]. Journal of Applied Polymer Science, 2008,108(3):1 737‑1 743.
6	GRAEBLING D. Synthesis of Branched Polypropylene by a Reactive Extrusion Process[J]. Macromolecules, 2002,35(12):4 602‑4 610.
7	LI S, XIAO M, WEI D, et al. The Melt Grafting Preparation and Rheological Characterization of Long Chain Branching Polypropylene[J]. Polymer, 2009,50(25):6 121‑6 128.
8	ZHANG Z, WAN D, XING H, et al. A New Grafting Monomer for Synthesizing Long Chain Branched Polypropylene Through Melt Radical Reaction[J]. Polymer, 2012,53(1):121‑129.
9	ZHOU S, ZHAO S, XIN Z. Preparation and Foamability of High Melt Strength Polypropylene Based on Grafting Vinyl Polydimethylsiloxane and Styrene[J]. Polymer Engineering and Science, 2014,55(2):251‑259.
10	KEAWKANOKSILP C, Apimonsiri W, Patcharaphun S, et al. Rheological Properties and Melt Strength of LDPE During Coextrusion Process[J]. Journal of Applied Polymer Science, 2012,125(3):2 187‑2 195.
11	MOHAMMADREZA N, KAMLESH M, TAKASHI K, et al. The Foamability of Low‑Melt‑Strength Linear Polypropylene with Nanoclay and Coupling Agent[J]. Journal of Cellular Plastics, 2012,48(3):271‑287.
12	BORSIG E, DUIN M V, GOTSIS A D, et al. Long Chain Branching on Linear Polypropylene by Solid State Reactions[J]. European Polymer Journal, 2008,44(1):200‑212.
13	TIAN J H, YU W, ZHOU C X. The Preparation and Rheology Characterization of Long Chain Branching Polypropylene[J]. Polymer, 2006,47(23):7 962‑7 969.
14	TIAN J, YU W, ZHOU C. Crystallization Kinetics of Linear and Long‐Chain Branched Polypropylene[J]. Journal of Macromolecular Science, Part B: Physics, 2006,45(5):969‑985.
15	WANG L, JING X, CHENG H, et al. Blends of Linear and Long‑Chain Branched Poly(l‑lactide)s with High Melt Strength and Fast Crystallization Rate[J]. Industrial & Engineering Chemistry Research, 2012,51(30):10 088‑10 099.
16	SU F H, HUANG H X. Supercritical Carbon Dioxide‑Assisted Reactive Extrusion for Preparation Long‑Chain Branching Polypropylene and Its Rheology[J]. Journal of Supercritical Fluids The, 2011,56(1):114‑120.
17	SU F H, HUANG H X. Rheology and Melt Strength of Long Chain Branching Polypropylene Prepared by Reactive Extrusion With Various Peroxides[J]. Polymer Engineering and Science, 2010,50(2):342‑351.
18	SUGIMOTO M, SUZUKI Y, HYUN K, et al. Melt Rheology of Long‑Chain‑Branched Polypropylenes[J]. Rheologica Acta, 2006, 46(1):33‑44.
19	JIANG R, YAO S, CHEN Y C, et al. Effect of Chain Topological Structure on the Crystallization, Rheological Behavior and Foamability of TPEE Using Supercritical CO2 as a Blowing Agent[J]. Journal of Supercritical Liquids, 2019,vol(147):48‑58.
20	GE Y K, YAO S, XU M L, et al. Improvement of Poly(ethylene terephthalate) Melt‑Foamability by Long‑Chain Branching with the Combination of Pyromellitic Dianhydride and Triglycidyl Isocyanurate[J]. Industrial & Engineering Chemistry Research, 2019,58(9):3 666‑3 678.

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PETA/St双单体聚丙烯挤出改性及其发泡性能研究

Study on Modification and Foaming Properties of PP Through PETA/St Double‑Monomer Reactive Extrusion

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