单环氧化合物接枝改性PA6材料的制备及其性能研究
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摘要
利用反应挤出法制备了聚酰胺6(PA6)接枝新癸酸缩水甘油酯(GND)改性材料,通过红外光谱分析对改性产物的分子结构进行了测试,并对改性材料的结晶性能、流变性能和力学性能等进行了研究。结果表明,单环氧化合物能够在挤出过程中与PA6发生接枝反应,生成支化PA6产物;接枝链降低了PA6的结晶速率和结晶度,在宏观上相应地表现出材料力学性能的变化;GND最佳用量范围为1～3份,当其用量为1份时,相对于纯PA6,支化PA6的拉伸强度降低了8%,断裂伸长率和缺口冲击强度分别提高了161%和35%。
Polyamide 6(PA6) was grafted with a monoepoxy compound, glycidyl neodecanoate(GND), through reactive extrusion. The molecular structure of grafted PA6 was characterized by infrared spectroscopy, and its crystalline, rheological and mechanical properties were also investigated. The results indicated that GND could well react with PA6 to form branched PA6 copolymers. The branched chains reduced the crystallization rate and crystallinity degree of PA6, resulting in a change in the mechanical properties of grafted PA6 accordingly. The optimum dosage of GND was found to be in the range of 1～3 phr. There was a decrease in tensile strength by 8 % when 1 phr of GND was grafted into PA6. On the other hand, the elongation at break and notched impact strength increased by 161 % and 35 % compared to those of pure PA6, respectively.
Polyamide 6(PA6) was grafted with a monoepoxy compound, glycidyl neodecanoate(GND), through reactive extrusion. The molecular structure of grafted PA6 was characterized by infrared spectroscopy, and its crystalline, rheological and mechanical properties were also investigated. The results indicated that GND could well react with PA6 to form branched PA6 copolymers. The branched chains reduced the crystallization rate and crystallinity degree of PA6, resulting in a change in the mechanical properties of grafted PA6 accordingly. The optimum dosage of GND was found to be in the range of 1～3 phr. There was a decrease in tensile strength by 8 % when 1 phr of GND was grafted into PA6. On the other hand, the elongation at break and notched impact strength increased by 161 % and 35 % compared to those of pure PA6, respectively.
引文
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[3] DING X,RONG J,XU R,et al.Effect of a Chain Extender on the Crystallization Behavior of Nylon 66[J].Journal of Applied Polymer Science,2010,91(1):68-71.
[4] 郭宝华,徐军,钱震宇,等.高柔韧性尼龙1010材料的制备[J].橡塑技术与装备,2008(1):32-36.GUO B H,XU J,QIAN Z Y,et al.The Preparation of High Flexibility Nylon 1010 Materials[J].China Rubber/Plastics Technology and Equipment,2008,34(1):32-36.
[5] 钱震宇,郭宝华,史建中,等.双■唑啉扩链尼龙1010[J].高分子学报,2004(4):506-510.QIAN Z Y,GUO B H,SHI J Z,et al.Chain Extension of PA1010 by Bisoxazolines[J].Acta Polymerica Sinica,2004(4):506-510.
[6] 赵育和,栾娜.双■唑啉对尼龙 - 11扩链增粘作用的研究[J].化工新型材料,2001,29(9):51-53.ZHAO Y H,LUAN N.Study on the Viscosity-Increasing and Chain Extension Effect of Dioxazoline on Nylon 11[J].New Chemical Materials,2001,29(9):51-53.
[7] SHIRAHAMA H,KAWAGUCHI Y,ALUDIN M S,et al.Synthesis and Enzymatic Degradation of High Molecular Weight Aliphatic Polyesters[J].Journal of Applied Polymer Science,2015,80(3):340-347.
[8] STOREY R F,KENT R H,DOUGLAS C H.Hydroxy-terminated Poly(ε-caprolactone-co-δ-valerolactone) Oligomers:Synthesis,Characterization,and Polyurethane Network Formation[J].Journal of Polymer Science Part A:Polymer Chemistry,1991,29(12):1 759-1 777.
[9] 伍威,彭军,王文志,等.PA6-b-PPG嵌段共聚物的合成与表征[J].工程塑料应用,2015,43(4):17-21.WU W,PENG J,WANG W Z,et al.Synthesis and Characterization of PA6-b-PPG Block Copolymers[J].Engineering Plastics Application,2015(4):17-21.
[10] ZHANG Y,FAN H,LI B.Synthesis and Characterization of Advance PA6-b-PDMS Multiblock Copolymers[J].Journal of Applied Polymer Science,2014,131(22):17-24.
[11] WANG C,HU F,YANG K,et al.Synthesis and Pro-perties of Star-branched Nylon 6 with Hexafunctional Cyclotriphosphazene Core[J].RSC Advances,2015,5(107):88 382-88 391.
[12] BANERJEE S S,JANKE A,GOHS U,et al.Some Nanomechanical Properties and Degree of Branching of Electron Beam Modified Polyamide 6[J].European Polymer Journal,2017,88:221-230.
[13] 宗胜男,胡国胜,张静婷,等.环氧类扩链剂制备高黏度尼龙6及其性能表征[J].工程塑料应用,2014(7):30-33.ZONG S N,HU G S,ZHANG J T,et al.Preparation and Characteri-zation of High Viscosity PA6 via Melting Epoxy Chain Extender[J].Engineering Plastics Application,2014(7):30-33.
[14] 张永,周华龙,王丰,等.尼龙66与尼龙6及其共混物的熔融与结晶行为[J].工程塑料应用,2015,43(6):86-89.ZHANG Y,ZHOU H L,WANG F,et al.Melting and Crystallization Behaviors of Nylon 66 and Nylon 6 and Their Blends[J].Engineering Plastics Application,2015(6):86-89.
[15] ARIMOTO H.α-γ Transition of Nylon 6[J].Journal of Polymer Science Part A:General Papers,1964,2(5):2 283-2 295.
[16] BRELA M Z,WóJCIK M J,BOCZAR M,et al.Study of Hydrogen Bond Dynamics in Nylon 6 Crystals Using IR Spectroscopy and Molecular Dynamics Focusing on the Differences Between α and γ Crystal Forms[J].International Journal of Quantum Chemistry,2018:e25595.
[17] NAKASON C,NARATHICHAT M,KUMMERL?WE C,et al.Thermoplastic Natural Rubber Based on Polyamide-12 Blended with Various Types of Natural Rubber[J].Journal of Elastomers & Plastics,2012,45(1):47-75.
[18] 周持兴.聚合物流变实验与应用[M].上海交通大学出版社,2003:57-68.
[19] 娄立娟,刘建叶,俞炜,等.聚合物长支链的流变学表征方法[J].高分子通报,2009(10):15-23.LOU L J,LIU J Y,YU W,et al.Rheological Characterization of Long Chain Branching[J],Chinese Polymer Bulletin,2009(10):15-23.
[20] 田敬华.长支链聚丙烯及聚丙烯反应共混材料的制备、结构与性能的研究[D].上海:上海交通大学,2007.
[21] TIAN J,YU W,ZHOU C.The Preparation and Rheo-logy Characterization of Long Chain Branching Polypropylene[J].Polymer,2006,47(23):7 962-7 969.