Effect of Epoxy Modifiers on Properties of PA6/EVOH Blends

doi:10.19491/j.issn.1001-9278.2021.09.002

Abstract

Abstract:

This work reported an investigation on the effect of different type of epoxy modifiers on the tensile properties， rheological properties， and crystallization properties of PA6/EVOH blends. The reaction mechanism of glycidyl methacrylate （GMA） with blends was also and explored. The blends were characterized with torque test， Fourier?transform infrared spectroscopy （FTIR）， hydrogen nuclear magnetic resonance （NMR）， tensile tests， rotational rheological test and differential scanning calorimetry. The results indicated that the blends showed an increase in blending torque， tensile strength， complex viscosity and storage modulus with an increase in the epoxy value of modifiers increases. Their crystallinity and crystallization temperature was found to present a decrease with the epoxy value， whereas the elongation at break tended to increase at first and then decreased. With polyepoxy groups in the molecules， most of epoxy modifiers can react with amine， carboxyl or hydroxyl groups for chain extension to improve the properties of the blends. Taking into account the fluidity issue in the processing procedure， the GMA?modified blend has the optimal properties with the tensile strength increased by 8.5 % and elongation at break increased by 26.6 %. FTIR and ¹H?NMR characterization results indicated that GMA underwent self?polymerization at high temperatures to form polyepoxy oligomers. These oligomers can react with PA6 and EVOH to improve the properties of their blends.

Key words: polyamide 6, ethylene vinyl alcohol copolymer, epoxy chain extender, property

CLC Number:

TQ323.6

LU Weixin, LU Chong, WANG Bin, HU Jing, WU Jingjing, ZHOU Qinpeng. Effect of Epoxy Modifiers on Properties of PA6/EVOH Blends[J]. China Plastics, 2021, 35(9): 8-14.

Figures/Tables 14

References 27

1	LI L L， WU Z H， JIANG S S， et al. Effect of Halloysite Nanotubes on Thermal and Flame Retardant Properties of Polyamide 6/Melamine Cyanurate Composites［J］. Polymer Composites， 2015， 36 （5）： 892⁃896.
2	O'NEILL A， ARCHER E， MCILHAGGER A， et al. Polymer Nanocomposites：in Situpolymerization of Polyamide 6 in the Presence of Graphene Oxide［J］. Polymer Composites， 2017， 38 （3）： 528⁃537.
3	OU B L， ZHOU Z H， LIU Q Q， et al. Mechanical Pro⁃perties and Nonisothermal Crystallization Kinetics of Polyamide 6/Functionalized TiO2 Nanocomposites［J］. Polymer Composites， 2014， 35 （2）： 294⁃300.
4	ERDOGAN A R， KAYGUSUZ I， KAYNAK C. Influences of Aminosilanization of Halloysite Nanotubes on the Mechanical Properties of Polyamide⁃6 Nanocomposites［J］. Polymer Composites， 2014， 35 （7）： 1 350⁃1 361.
5	SHENG Z， JIA G， YONGYUAN S， et al. Enhancing the Flame Retardancy of Polyamide 6 by Guanidine Sulfamate⁃Modified Carbon Nanoparticles： Carbon Nanotubes versus Graphite Oxide［J］. Polymer Composites， 2018， 40 （S2）： 1 884⁃1 892.
6	TANG G， WANG X， JIANG S， et al. Thermal Degradation and Combustion Behaviors of Flame Retarded Glass Fiber Reinforced Polyamide 6 Composites Based on Cerium Hypophosphite［J］. Polymer Composites， 2016， 37 （10）： 3 073⁃3 082.
7	TIAN C， WANG Y Z， LIU H H， et al. Melt⁃Spinning of Carboxylated Mwnts⁃Reinforced Polyamide 6 Fibers with Solid Mixing Nanocomposites［J］. Polymer Composites， 2017， 39 （12）： 4 298⁃4 309.
8	YU K F， LI Z C， LIANG J， et al. Investigation of the Synergy Influence of Ksicb and POE⁃g⁃MAH on Mechanical Properties of Basalt Fiber⁃Reinforced PA6 Composites［J］. Polymer Composites， 2020， 42 （2）： 739⁃752.
9	KODAL M， ERTURK S， SANLI S， et al. Properties of Talc/Wollastonite/Polyamide 6 Hybrid Composites［J］. Polymer Composites， 2015， 36 （4）： 739⁃746.
10	SHAO H， WU B， GUO J B， et al. High Performance Polyamide 6 Composites Prepared by Reactive Extrusion［J］. Polymer Composites， 2014， 35 （5）： 985⁃992.
11	LIU J， YI H， LIN H， et al. Effects of Functional Group on the Mechanical Properties of PA6/SiO₂ Composites［J］. Polymer Composites， 2014， 35 （3）： 435⁃440.
12	LIU Y， LIU S， YIN C. Synthesis and Structure⁃Property of Polyamide 6/Macrogol/Attapulgite Nanocomposites［J］. Polymer Composites， 2014， 35 （9）： 1 852⁃1 857.
13	KIM D， KWON H， SEO J. EVOH Nanocomposite Films with Enhanced Barrier Properties under High Humidity Conditions［J］. Polymer Composites， 2014， 35 （4）： 644⁃654.
14	ELLINGHAM T， YILMAZ G， DUDDLESTON L， et al. Subcritical Gas⁃Assisted Processing of Ethylene Vinyl Alcohol +Nanoclay Composites［J］. Polymer Compo⁃sites， 2020， 41 （4）： 1 584⁃1 594.
15	LEE E J， YOON J S， PARK E S. Morphology， Resistivity， and Thermal Behavior of EVOH/Carbon Black and EVOH/Graphite Composites Prepared by Simple Saponification Method［J］. Polymer Composites， 2011， 32 （5）： 714⁃726.
16	YU R， LIU Y， GAO Z， et al. Preparation and Properties of Nylon 11/Ethylene⁃Vinyl Alcohol/Montmorillonite Ternary Composites［J］. Polymer Composites， 2020， 41 （12）： 5 343⁃5 354.
17	WANG B， LU C， HU J， et al. Effects of Cross⁃Linking by MgCl₂ as An Initiator on the Properties of EVOH［J］. Journal of Thermoplastic Composite Materials， 2020， 089270572091331.
18	LIN X， LIU Y， CHEN X， et al. Reactive Compatibilization of Polyamide 6/Olefin Block Copolymer Blends： Phase Morphology， Rheological Behavior， Thermal Behavior， and Mechanical Properties［J］. Materials， 2020， 13 （5）： 1 146.
19	ARTZI N， KHATUA B B， TCHOUDAKOV R， et al. Physical and Chemical Interactions in Melt Mixed Nylon‐6/EVOH Blends［J］. Journal of Macromolecular Science， Part B， 2006， 43 （3）： 605⁃624.
20	FOLDES E， PUKANSZKY B. Miscibility⁃Structure⁃Property Correlation in Blends of Ethylene Vinyl Alcohol Copolymer and Polyamide 6/66［J］. Journal of Colloid and Interface Science， 2005， 283 （1）： 79⁃86.
21	YEH J T， CHEN H Y. Blending and Oxygen Permeation Properties of the Blown Films of Blends of Modified Polyamide and Ethylene Vinyl Alcohol Copolymer with Varying Vinyl Alcohol Contents［J］. Journal of Materials Science， 2007， 42 （14）： 5 742⁃5 751.
22	YEH J T， CHEN H Y， TSAI F C. Blending and White Spirit Permeation Properties of the Blends of Modified Polyamide and Ethylene Vinyl Alcohol with Varying Vinyl Alcohol Contents［J］. Journal of Applied Polymer Science， 2006， 102 （2）： 1 224⁃1 233.
23	YEH J T， YAO W H， DU Q， et al. Blending and Barrier Properties of Blends of Modified Polyamide and Ethylene Vinyl Alcohol Copolymer［J］. Journal of Polymer Science Part B： Polymer Physics， 2005， 43 （5）： 511⁃521.
24	CERRUTI P， LAURIENZO P， MALINCONICO M， et al. Thermal Oxidative Stability and Effect of Water on Gas Transport and Mechanical Properties in PA6⁃EVOH Films［J］. Journal of Polymer Science Part B： Polymer Physics， 2007， 45 （7）： 840⁃849.
25	OZMEN S C， OZKOC G， ThermalSERHATLI E， Mechanical and Physical Properties of Chain Extended Recycled Polyamide6via Reactive Extrusion： Effect of Chain Extender Types［J］. Polymer Degradation and Stability， 2019， 162： 76⁃84.
26	XU M， CHEN Y， LIU T， et al. Determination of Modified Polyamide 6's Foaming Windows by Bubble Growth Simulations Based on Rheological Measurements［J］. Journal of Applied Polymer Science， 2019， 136 （42）： 48138.
27	杨海玉，黄春龙，姜鹏，等. 环氧化合物一步法制备醇醚的合成方法： CN 106946663 A［P］. 2017⁃07⁃14.

样品名称	PA6含量	EVOH含量	SOG?02含量	PEGE含量	ADR4468含量	GMA含量	TGIC含量	抗氧剂1010 含量	抗氧剂168 含量
70/30	70	30	0	0	0	0	0	0.2	0.2
70/30+1SOG	70	30	1	0	0	0	0	0.2	0.2
70/30+1PEGE	70	30	0	1	0	0	0	0.2	0.2
70/30+1ADR	70	30	0	0	1	0	0	0.2	0.2
70/30+1GMA	70	30	0	0	0	1	0	0.2	0.2
70/30+1TGIC	70	30	0	0	0	0	1	0.2	0.2

样品名称	PA6含量	EVOH含量	SOG?02含量	PEGE含量	ADR4468含量	GMA含量	TGIC含量	抗氧剂1010 含量	抗氧剂168 含量
70/30	70	30	0	0	0	0	0	0.2	0.2
70/30+1SOG	70	30	1	0	0	0	0	0.2	0.2
70/30+1PEGE	70	30	0	1	0	0	0	0.2	0.2
70/30+1ADR	70	30	0	0	1	0	0	0.2	0.2
70/30+1GMA	70	30	0	0	0	1	0	0.2	0.2
70/30+1TGIC	70	30	0	0	0	0	1	0.2	0.2

样品	改性剂环氧值/ mol·（100 g）^-1	最终转矩/N·m
70/30	—	6.0
70/30+1SOG	0.05	6.2
70/30+1PEGE	0.35	9.9
70/30+1ADR	0.35	10.8
70/30+1GMA	0.70	15.3
70/30+1TGIC	1.01	19.0

样品	改性剂环氧值/ mol·（100 g）^-1	最终转矩/N·m
70/30	—	6.0
70/30+1SOG	0.05	6.2
70/30+1PEGE	0.35	9.9
70/30+1ADR	0.35	10.8
70/30+1GMA	0.70	15.3
70/30+1TGIC	1.01	19.0

特征峰	初始面积		校正面积
特征峰	加热前的GMA	加热后的GMA	加热前的GMA	加热后的GMA
C=O峰（1 719）	10.88	15.85	100	100
C=C峰（1 638）	4.54	4.53	41.7	28.6
C—H峰（3 062）	0.52	0.54	4.78	3.41
C—O峰（1 163）	16.95	24.40	156	154