共聚酰胺生产及应用

介绍二元、三元、四元共聚酰胺的共聚反应机理、生产工艺,产品特性和应用,指出共聚酰胺的发展方向。     

聚酰胺类TPV的研究进展

以聚酰胺为基体采用动态硫化工艺制备的热塑性动态硫化弹性体（TPV）是一类颇具发展潜力的热塑性弹性体（TPE）。目前很多高性能橡胶材料都可以采用聚酰胺类的TPV代替,特别是我国汽车工业的高速发展,为这种TPV的发展提供了巨大的空间。本文重点介绍了这类TPV的研究进展。     

聚酰胺/溴化丁基橡胶动态硫化热塑性弹性体研究进展

介绍了聚酰胺/溴化丁基橡胶动态硫化热塑性弹性体(PA/BIIR TPV)的制备及应用研究进展。概述了国外使用溴化对甲基苯乙烯-异丁烯共聚物(BIMS)与尼龙进行动态硫化制备TPV的工艺优缺点和制备的TPV特性。描述了国内用PA/BIIR体系制备TPV的特点及不足,阐明了用改性BIIR和尼龙制备TPV的工艺优点及制备的TPV优良性能。     

聚酰胺类热塑性弹性体的研究进展

简介聚酰胺(PA)类热塑性弹性体(TPAE)的种类及其性能,重点介绍共混型TPAE的研究进展。TPAE主要包括PA/丁腈橡胶热塑性动态硫化橡胶(TPV)、PA/丁基橡胶TPV、PA/三元乙丙橡胶TPV和PA/丙烯酸酯橡胶TPV,现阶段被广泛应用于汽车工业、电线电缆和密封制品等方面,但该种材料形态结构控制困难,物理性能波动大、重复性差。目前多采用熔点低、价格贵的PA12作为连续相基体材料制备TPV,导致TPV价格较高,不利于发展。开发新型高温硫化体系和加工工艺,采用熔点较高、价格便宜的PA6制备PA类TPV具有更高的实用价值。     

影响三元聚酰胺酰亚胺合成的因素分析

聚酰胺酰亚胺(PAI)是一种分子链中含有酰胺键和酰亚胺键的高分子聚合物,其涂层具有优良的耐高温性、绝缘性和防紫外线性,在微电子、航空航天、消防等领域具有广泛的应用。传统的二元PAI在特殊环境中应用时,其耐热性有待进一步提高,吸水性能有待改善。通过三元缩聚反应,合成了一种新型的三元PAI。利用傅里叶变换红外光谱仪(FTIR)测试了所合成的PAI的结构;探讨了反应时间、反应温度、单体配比、单体添加顺序、带水剂及凝固浴种类等对所合成PAI比浓黏度的影响,得到了新型三元PAI的最佳合成工艺。     

三元聚酰胺酰亚胺涂膜性能的研究

聚酰胺酰亚胺(PAI)因其分子链中酰胺键和酰亚胺键的存在,具有一定的柔性和优良的耐高温性、介电性、绝缘性,常作为耐高温绝缘涂层应用于国防、民生、消防等领域,但传统二元PAI涂膜在特定条件下使用时,其热稳定性有待改善。通过在反应体系中添加新单体均苯四甲酸二酐,得到一种新型三元PAI,利用傅里叶变换红外光谱仪(FTIR)对其结构进行了表征,并对其涂膜性能进行了测试。结果表明:三元PAI保持了良好的溶解性,拥有出众的耐酸碱性、绝缘性和热稳定性,进一步拓宽了PAI的应用领域。     

新型聚酰胺酰亚胺的合成及其涂膜性能的研究

传统二元聚酰胺酰亚胺的软化点和热变形温度较低,耐热性欠佳。本研究以N-甲基吡咯烷酮为溶剂,以偏苯三酸酐(TMA)、均苯四甲酸二酐(PMDA)、4,4’-二苯基甲烷二异氰酸酯(MDI)为单体,进行三元共聚反应,制得一种新型的聚酰胺酰亚胺(PAI)。利用傅里叶转换红外光谱(FT-IR)对合成的PAI结构进行了表征,利用热重分析(TGA)、差示扫描量热(DSC)、紫外-可见光谱、宽频介电阻抗谱等对PAI涂层性能进行了测试。结果表明:与传统二元共聚所得的PAI相比,三元共聚型PAI的硬度、热稳定性显著提高,此外,还具有优良的光学性能和电学性能,拓宽了PAI的应用范围。     

满足汽车发动机罩下橡胶制品苛刻使用条件的新型热塑性硫化胶

热塑性硫化胶可通过设计、加工方法和成本提供许多优势。由于受到耐温和耐油的限制，所以目前研制出的热塑性硫化胶(TPV)[包括那些以三元乙丙橡胶(EPDM)和聚丙烯(PP)为基料的热塑性硫化胶]和共聚多酯只限制在电车密封件、热风管和防尘套上应用。本文介绍了新型耐热、耐油的TPv品种Zeotherm。用具有代表性的新品种——以聚丙烯酸酯(ACM)／聚酰胺为基料的TPV与现生产的普通TPV、典型的热固性橡胶进行了对比，经(150℃)l500多个小时的测试表明，以ACM／聚酰胺为基料的TPV样品的拉伸强度和扯断伸长率的损失小于50％。     

溴化丁基橡胶/聚酰胺动态硫化热塑性弹性体的性能与应用研究

采用溴化丁基(BIIR)和聚酰胺(PA)为主要原材料,通过动态硫化技术制备了BIIR/ PA热塑性弹性体(TPV),TEM和AFM测试结果显示TPV分散相BIIR的粒径在0.5至5μm之间。采取挤出吹膜方法试制成功了TPV薄膜,测定分析了TPV薄膜的阻隔性能、拉伸性能、伸张疲劳性能及耐热空气老化性能,结果表明其各项性能优良,阻隔性能突出,特别适合用于轮胎气密层和要求高阻隔性的软管等的生产。。进行了薄膜用于轮胎气密层的应用研究,制备了TPV薄膜与过渡层的复合胶片,利用该复合胶片作为气密层部件进行轮胎试制,解决了TPV薄膜与胎体复合时存气、皱褶的工艺难题。试制的轮胎通过GB/T 4502-2016标准中的高速性能、耐久性和低气压性能等,轮胎减重5%以上。     

聚酰胺类热塑性弹性体含量对PLLA/三元聚酰胺共混物形态和性能的影响

以聚酰胺类热塑性弹性体（TPAE）为增容剂增容左旋聚乳酸（PLLA）与三元聚酰胺共混物,采用扫描电子显微镜（SEM）、差热扫描量热仪（DSC）、X射线衍射仪（XRD）等研究了TPAE含量对PLLA/三元聚酰胺（70/30,质量比,下同）共混物的形态、力学性能和热性能的影响。力学性能研究结果表明,添加TPAE后,PLLA/三元聚酰胺共混物的拉伸强度、断裂伸长率、缺口冲击强度显著提高,TPAE含量为5份时,共混物的断裂伸长率为370 %,缺口冲击强度为90 J/m,拉伸强度为39 MPa;SEM分析表明,添加TPAE后,共混物中三元聚酰胺相的粒径显著变小;DSC与XRD分析结果表明,TPAE含量对PLLA/三元聚酰胺共混物的熔融行为和结晶行为无明显影响,而共混物拉伸后,其结晶度显著提高。     

Effect of Polyamide 66 on the Mechanical and Thermal Properties of Post-Industrial Waste Polyamide 6

Post-industrial waste (PIW) polyamide 6 is successfully used in lieu of commercial virgin polyamide 6, in several automotive applications. The presence of polyamide 66 in the final formulation may affect the mechanical and thermal properties of the PIW polyamide 6 materials. Using unreinforced polyamide 6 from PIW and commercial sources, it was found that the addition of polyamide 66 (below 10 wt.%) lowered the crystallization rate and crystallinity level of all polyamide 6 materials. The thermal and mechanical properties of glass fiber (GF) reinforced PIW polyamide 6 compounds with and without polyamide 66 were also studied. Differential scanning calorimetry (DSC) showed that reinforced materials without polyamide 66 had a higher level of crystallinity. Furthermore, dynamic mechanical analysis (DMA) showed that reinforced compounds without polyamide 66 also had a faster storage modulus buildup immediately after injection molding. Reinforced PIW polyamide 6 compounds without polyamide 66 also exhibited higher tensile and higher vibration weld strengths as well as a thicker heat affected zone (HAZ) than those with polyamide 66, leading to the conclusion that polyamide 66 had a detrimental effect on crystallinity level and consequently on the mechanical properties of GF-reinforced PIW polyamide 6 materials.     

Amine-terminated nylon 6/66/1010 (AM-6/66/1010) used for hot melt adhesives: synthesis and properties

A new amine-terminated nylon 6/66/1010 (AM-6/66/1010) copolyamide hot melt adhesive with the molecular weight of 21,000–96,000 Da was synthesized and blocked with 1-hexadecylamine. The AM-6/66/1010 samples were characterized by ¹H-NMR spectroscopy, differential scanning calorimetry (DSC), thermal gravimetric analysis, and gel permeation chromatography. The ¹H-NMR spectroscopy demonstrated that 1-hexadecylamine functions as blocking agent in this polymerization. The DSC thermograms showed that the extra peak (peak (II)) and the melting peak (peak (I)) of AM-6/66/1010 are moving left and the glass transition temperature of AM-6/66/1010 decreases as the mole ratio α_H/C (1-hexadecylamine/total carboxyl) increases. The thermal gravimetric analysis indicated that AM-6/66/1010 hot melt adhesive has a high thermal stability. The peel strength of the test specimen obtained by hot melt glutinous lining of AM-6/66/1010 or AC-6/66/1010 and fabric 6535 (65% PET, 35% cotton) was studied using T-peel tests, and the results showed that the washable and dry-cleaning resistant of AM-6/66/1010 copolyamide hot melt adhesive is better than that of carboxyl-terminated nylon 6/66/1010 (AC-6/66/1010) copolyamide hot melt adhesive.     

Polyamide 6 and polyamide 66 blends with functionalized polyolefins: Effect of phenomenal increase in viscosity and melt strength of polyamide 66-based materials

The effect of adding blends of linear low-density polyethylene (LLDPE) and ethylene-octene copolymer (EOC) functionalized by grafting (in the course of reactive extrusion) of trans-ethylene-1,2-dicarboxylic acid (TEDA) onto polyamide 6 (PA6) and polyamide 66 (PA66) on rheological and elastic properties of their melts, structural morphology, and mechanical properties has been studied. It is shown that PA66/functionalized polyolefins (fPO) blends are characterized by more significant changes in the characteristics being analyzed as compared to PA6/fPO blends. A phenomenally sharp increase (by more than two decimal orders of magnitudes) in the melt viscosity of PA66/fPO blend as compared to the initial PA66 was established. At the same time, the melt strength may increase more than 50-fold. The degree of TEDA grafting (β) onto PO macromolecules is the most important parameter determining the level of the values of property indices, as well as the structural features of PA/fPO blends. Only when particular β values (varying in a relatively narrow range) are reached, a quasi-homogeneous morphology is formed in PA/fPO blends and their deformation capacity as well as the impact strength of materials increase dramatically. The observed effects are caused by the influence of TEDA grafting on interphase interactions in PA/fPO and PA66/fPO blends.     

PA1010/羟基磷灰石复合材料的制备与性能

利用熔融共混法制备了聚酰胺1010(PA1010)/羟基磷灰石(HA)复合材料,采用傅立叶变换红外光谱、热重分析仪和差示扫描量热仪测试了PA1010/HA复合材料的结构特征和热稳定性,利用电子万能试验机测试了PA1010/HA复合材料的力学性能。结果表明:复合材料中PA1010与HA之间通过氢键作用结合,而氢键作用的主要发生位置在PA1010酰胺键的氨基与HA的羟基之间;PA1010/HA复合材料具有良好的热稳定性,HA的加入对PA1010/HA复合材料的熔点基本没有影响,随着HA含量的增加,其熔融焓和结晶焓都降低。HA的加入,增强了PA1010/HA复合材料的拉伸性能和弯曲性能,与纯PA1010相比,分别提高了33.4%,98.3%。     

尼龙66改性研究

用三元乙丙胶(EPDM)和三元乙丙胶接枝马来酸酐(MA)的共聚物(EPDM-g-MA)作为增韧增容材料,研究了PA66与EPDM-g-MA组成的二元共混体系(PA66/EPDM-g-MA)及PA66、EPDM和FPDM-g-MA组成的三元共混体系(PA66/EPDM/EPDM-g-MA)的各种力学性能。结果表明:随着EPDM-g-MA含量的增加,PA66/EPDM-g-MA二元共混体系的耐冲击性能明显提高,当EPDM-g-MA含量为20％(质量)时、Izod缺口冲击强度为纯PA66的7倍,但拉伸强度、模量等随之下降;对于PA66/EPDM/EPDM-g-MA三元共混体系,其力学性能介于PA66/EPDM和PA66/EPDM-g-MA两种二元共混体系之间。此外,本文还对EPDM与MA接枝物及EPDM与马来酸二丁酯(DBM)接枝物的制备作了初步探讨。     

PET/聚酰胺类共混体系相容性的研究

将聚对苯二甲酸乙二醇酯(PET)分别与聚酰胺类(PA1010、PA6和PA66)熔融共混,通过热力学分析、示差扫描量热法、扫描电镜和红外光谱等手段,对PET/PA类共混体系进行了研究.热力学分析结果与实验结果不同,表明热力学分析不适用于PET/PA共混体系;DSC分析结果表明:不同的PET/PA共混体系对PET相玻璃化温度向低温区移动程度有影响;SEM分析表明:PET/PA共混体系断面形态不同,相容性关系为PET/PA66>PET/PA6>PET/PA1010;红外光谱分析表明:共混体系中PET的羟基和PA分子的-NH-之间产生了氢键,导致PET的C=0拉伸震动吸收峰移向低波数.     

In situ fibrillar reinforced PET/PA‐6/PA‐66 blend

Ternary fibrillar reinforced blends are obtained by melt‐blending of poly(ethylene terephthalate) (PET), polyamide 6 (PA‐6) and polyamide 66 (PA‐66) (20/60/20 by weight) in the presence of a catalyst, followed by cold drawing of the extruded bristles to a draw ratio of about 3.4 and additional annealing of the drawn blend at 220 or 240°C for 4 or 8 h. The blend samples are studied by DSC, X‐ray diffraction, SEM, and static and dynamic mechanical testing (DMA). SEM and DMA show that PA‐6 and PA‐66 form a homogeneous, continuous matrix in which PET regions are dispersed. X‐ray and DSC measurements of the drawn and annealed at 220°C samples suggest mixed crystallization (solid solubility) of PA‐6 and PA‐66, and cooperative crystallization of PET with the two polyamides. After annealing at 240°C (above the melting point of PA‐6 and below that of PET), the polyamide matrix becomes partially disoriented, while the oriented, fibrillar PET is preserved and plays the role of a reinforcing element. The DSC results for the same samples suggest in situ generation of an additional amount of copolymer. This additional copolymerization, together with that generated during blend mixing in the extruder, improves the compatibility of the blend components (mostly at the PET‐polyamide interface) and alters the chemical composition of the blend.     

聚酰胺66热交联行为的研究

对高温交联行为进行了研究,将聚酰胺66放入300℃的管式炉中热处理不同时间(2、4、6、8 h),使用甲酸作溶剂测量了凝胶含量随热处理时间的变化,分析了凝胶含量变化的原因。使用差示扫描量热法对热处理不同时间的聚酰胺66样品进行测试,发现结晶峰温度和熔融峰温度随着热处理时间的延长逐渐向低温方向移动。使用裂解色谱对未热处理和热处理6 h后的聚酰胺66样品进行测试,确定了聚酰胺66在300℃热降解过程中生成了有环戊酮基团的物质,并分析凝胶产生的原因。     

不同增容剂对聚酰胺1010/聚丙烯共混物的增容作用研究

采用熔体共混的方法制备了三种增容剂增容的聚酰胺1010/聚丙烯（PA1010/PP）共混物,通过傅里叶变换红外光谱（FTIR）、力学性能和差示扫描量热（DSC）测试,对马来酸酐接枝乙烯-辛烯共聚物（POE-g-MAH）、马来酸酐接枝聚丙烯（PP-g-MAH）和乙烯-丙烯酸丁酯-甲基丙烯酸缩水甘油酯共聚物（PTW）对PA1010/PP共混物的增容作用进行了比较研究。结果表明,和非增容体系相比,PP-g-MAH、POE-g-MAH和PTW的拉伸强度分别是非增容体系的125 %、89 %和94 %,冲击强度分别是非增容体系的140 %、200 %和200 %,PTW具有较好的增容效果。     

Sliding Wear Performance of TiO2/Short Carbon Fiber/Polyamide 66 Hybrid Composites

In the present work, polyamide 66 (PA66) based composites filled with hybrid TiO₂ particles and short pitch based carbon fiber were prepared. By evaluating sliding wear properties of the composites as a function of the components concentrations. Both wear rate and friction coefficient of the hybrid composites were significantly lower than those of the pure polyamide 66. The composite with 4 wt.% TiO₂ and 6 wt.% carbon fiber offered the greatest improvement of the tribological performance.