Preparation and properties of wear-resistant and flame-retardant polyphenylsulfoneurea/monomer casting nylon copolymers

A poly(phenylsulfone)-urea (PPSUU) macro-activator is synthesized by in situ anionic polymerization of 4,4′-diaminodiphenylsulfone and hexamethylene diisocyanate. The PPSUU segment is embedded into the nylon molecular chain through copolymerization to improve the wear resistance and flame retardancy of monomer cast nylon 6 (MC PA6) materials. The mechanical properties, thermal stability, friction and wear properties and combustion heat release rate of copolymers with different macro-activator contents are tested. Results indicate that a small amount of PPSUU can improve the wear resistance and impact properties of nylon materials. The wear loss of MC nylon is 54.8% less than pure MC nylon from 1.049 × 10⁻⁸ to 0.474 × 10⁻⁸ g/Nm with 6 wt% PPSUU. Moreover, better flame retardancy is verified. The peak of HRR reduced 36.8% from 654 to 413 kw/m² with 4 wt% PPSUU, accompanied by advanced ignition time and flame extinction time, thus reducing the risk of fire.     

共聚改性MC尼龙的制备和DSC分析

以氢氧化钠为催化剂,N 乙酰基己内酰胺为活化剂,催化剂和活化剂物质的量与反应单体物质的量之比均为1∶400,聚合起始温度为130℃,在绝热条件下,通过活化阴离子共聚制得了增韧MC尼龙共聚体。通过示差扫描量热分析测定共聚物熔点和结晶相含量,吸热熔融峰表明改性MC尼龙是无规共聚物,共聚导致了制品结晶度下降,结晶的特点是熔点的宽分布、不规则生长以及高浓度无定形区域对结晶存在干扰。     

Preparation of polyimide/nylon 6 graft copolymers from polyimides containing ester moieties: Synthesis and characterization

Polyimide‐g‐nylon 6 copolymers were prepared by the polymerization of phenyl 3,5‐diaminobenzoate with several diamines and dianhydrides with a one‐step method. The polyimides containing pendant ester moieties were then used as activators for the anionic polymerization of molten ?‐caprolactam. In the graft copolymer syntheses, the phenyl ester groups reacted quickly with caprolactam anions at 120°C to generate N‐acyllactam moieties, which activated the anionic polymerization. The thermal stability and chemical resistance were dramatically increased by the incorporation of only 5 wt % polyimide in the graft copolymers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 309–318, 2006     

Preparation and characterization of polyimide‐g‐nylon 6 copolymers from nonfunctionalized polyimides

In this research, the anionic polymerization of ?‐caprolactam was carried out in the presence of small amounts of several different polyimides to generate polyimide‐g‐nylon 6 copolymers. The polyimides, which were prepared from 2,2′‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]propane dianhydride and commercially available diamines with a one‐step method, were first dissolved in molten ?‐caprolactam. Phenylmagnesium bromide was then added at 120°C. Under these conditions, caprolactam anions were formed that attacked the five‐membered imide rings to form N‐acyllactam moieties, which activated the anionic polymerization of caprolactam. In essence, nylon 6 chains grew from the polyimide backbones. Probably because of a high activation energy, the process was relatively slow, requiring 1 h at 120°C. The introduction of 5 wt % polyimide into the graft copolymers produced significant increases in the tensile modulus and tensile strength in comparison with those of low‐ and high‐molecular‐weight nylon 6. The elongation to break, however, was reduced. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 292–299, 2006     

Prediction of isothermal crystallization parameters in monomer cast nylon 6

A three-dimensional cellular automaton (CA) model is applied to simulate isothermal crystallization of monomer casting (MC) nylon 6. The kinetics is formulated based on the Kim and Kim's rate theory for spherulite expansion. The probability of distribution of crystalline nuclei and impinging were determined by Monte Carlo method. The spherulite impinging was considered in the simulation through the deduction of overlay of spherulite volume. The number of spherulite nuclei and bulk density of MC nylon 6 after completing crystallization, easily obtained from experiment, were used as input data, allowing one to make predictions on a real time and space scale. Finally, the model was verified by quantitative comparison between the simulation results in this work and experimental data in literatures.     

PA11/白炭黑纳米复合材料的制备及性能研究

以11-氨基十一酸和湿态白炭黑为原料,通过原位聚合的方法制备了尼龙11/白炭黑纳米复合材料,并用红外光谱仪和扫描电子显微镜等研究了纳米复合材料的形态结构、力学性能和阻隔性能。结果显示,当白炭黑含量增加时,拉伸强度和弯曲强度先显增大趋势;当白炭黑质量分数达到8%时,拉伸、弯曲强度达到最大值;之后,拉伸、弯曲强度开始减小。断裂伸长率则一直减小,无明显变化。尼龙11及其纳米复合材料的常温冲击强度也随着白炭黑含量的增加逐渐降低。此外,白炭黑的加入极大地提高了复合材料的阻隔性能。     

Morphology and thermal properties of nylon copolymers containing dimer acid,adipic acid,and hexamethylenediamine

The effects of the molar ratio of adipic acid to total diacid on the phase morphology and thermal properties of nylon copolymers containing dimer acid, adipic acid, and hexamethylenediamine were investigated. A significant structural transition from the γ form to α and β mixture forms occurred with increasing molar ratio. Meanwhile, the content of the crystals increased markedly. A σ–π* hyper conjugation effect was present in all of the as‐prepared samples. A strong σ–π* hyper conjugation effect could decrease the average distance between interchain amide groups and suppress the scission of the C? N bond through the formation of highly combining aza double‐bond C?N groups, which would, consequently, make the nylon copolymer much more stable. Differential scanning calorimetry–thermogravimetric analysis results indicate that the low thermal stability of the nylon copolymers with higher molar ratios of adipic acid to total diacid was simply due to the formation of cyclopentanone and caprolactam at 350–420°C, whereas for the nylon copolymers with lower molar ratios, the scission of the C? C bond at 430–500°C directed the pyrolysis of the main chain. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Polydimethylsiloxane containing isocyanate group-modified epoxy resin: Curing,characterization, and properties

A synthesized polydimethylsiloxane containing an isocyanate group was used to improve the flexibility and to reduce the internal stress of epoxy resin cured with MDA (4,4′-methylene dianiline). The effect of polysiloxane content on the curing kinetics of a novolac-type epoxy modified with an isocyanate group was investigated. It was found that the modified epoxy resin showed significant improvement in impact strength. The polysiloxane containing isocyanate groups effectively depressed the internal stress of cured epoxy resins by reducing the flexural modulus and the coefficient of thermal expansion, while the glass transition temperature was increased. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2739–2747, 1999     

Polyether-segmented nylon hemodialysis membranes. III. Preparation and properties of new polyether-segmented nylon

In order to apply a blood-compatible polymer to hemodialysis membrane, a new polyether-segmented nylon which dissolved in common organic solvents was designed. The basic polyether-segmented nylon was synthesized by melt polycondensation from sebacic acid, m-xylenediamine, and α,ω-bisaminopropyl-poly(ethylene oxide). To improve the solubility, azelaic acid and hexamethylenediamine were copolycondensed with the basic copolymer. The solubility was correlated with the heat of fusion (ΔH_m) of the copolymer. When ΔH_m is < 30 mJ/mg, the polymer is soluble in dimethylsulfoxide and makes a stable solution. The nonthrombogenicity was investigated in the viewpoint of adhesion of platelet onto the copolymer surface. It is made clear that the surface of the block copolymer, having > 10 wt % of poly(ethylene oxide), suppresses the adhesion of platelet, and the composition of the nylon block has no effect on the adhesion of platelet. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1723–1729, 1997     

Preparation and properties of environmental friendly nonhalogen flame retardant melamine cyanurate/nylon 66 composites

Melamine cyanurate (MCA) was utilized as an environmental friendly additive to prepare the nonhalogen flame retardant MCA/Nylon 66 composites by melt blending technique. Because of the strong hydrogen bond interactions and fine interfacial compatibility between MCA and Nylon 66, the resultant even dispersion of MCA filler in polymer matrix leads to the better toughness and strength of MCA/Nylon 66 composites than those of neat Nylon 66. Both Nylon 66 and MCA/Nylon 66 composites exhibit similar α‐crystalline structure, but the presence of MCA influences the distribution of α1 and α2 crystalline phases in Nylon 66 by inducing its hydrogen‐bonded sheet separation. Moreover, the blending of MCA and Nylon 66 increases the crystallization temperature and exothermicity but decreases the thermal stability of Nylon 66 and accelerates the degradation of MCA. The MCA/Nylon 66 composites show better flame retardancy at intermediate MCA contents of 10 and 15 wt %. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation,characterization, and properties of cellulose–polyacrylamide graft copolymers

Graft copolymers of acrylamide on cellulose materials (α‐cellulose 55.8%, DP 287.3) obtained from Terminalia superba wood meal and its carboxymethylated derivative (DS 0.438) were prepared using a ceric ion initiator and batch polymerization and modified batch polymerization processes. The extent of graft polymer formation was measured in graft level, grafting efficiency, molecular weight of grafted polymer chains, frequency of grafting as a function of the polymerization medium, and initiator and monomer concentrations. It was found that the modified batch polymerization process yielded greater graft polymer formation and that graft copolymerization in aqueous alcohol medium resulted in enhanced levels of grafting and formation of many short grafted polymer chains. Viscosity measurements in aqueous solutions of carboxymethyl cellulose‐g‐polyacrylamide copolymer samples showed that interpositioning of polyacrylamide chains markedly increased the specific viscosity and resistance to biodegradation of the graft copolymers. The flocculation characteristics of the graft copolymers were determined with kaolin suspension. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 913–923, 2003     

Preparation and properties of silver‐containing nylon 6 nanofibers formed by electrospinning

Nylon 6 nanofibers containing silver nanoparticles (nylon 6/silver) were successfully prepared by electrospinning. The structure and properties of the electrospun fibers were studied with the aid of scanning electron microscopy, transmission electron microscopy, energy‐dispersive spectroscopy, and X‐ray diffraction. The structural analysis indicated that the fibers electrospun at maximum conditions were straight and that silver nanoparticles were distributed in the fibers. Finally, the antibacterial activities of the nylon 6/silver nanofiber mats were investigated in a broth dilution test against Staphylococcus aureus (Gram‐positive) and Klebsiella pneumoniae (Gram‐negative) bacteria. It was revealed that nylon 6/silver possessed excellent antibacterial properties and an inhibitory effect on the growth of S. aureus and K. pneumoniae. On the contrary, nylon 6 fibers without silver nanoparticles did not show any such antibacterial activity. Therefore, electrospun nylon 6/silver nanocomposites could be used in water filters, wound dressings, or antiadhesion membranes. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and properties of nylon 6/carboxylic silica nanocomposites via in situ polymerization

Nylon 6/carboxylic acid‐functionalized silica nanoparticles (SiO₂‐COOH) nanocomposites were prepared by in situ polymerization of caprolactam in the presence of SiO₂‐COOH. The aim of this work was to study the effect of carboxylic silica on the properties of the nylon 6 through the interfacial interactions between the SiO₂‐COOH nanoparticles and the nylon 6 matrix. For comparison, pure nylon 6, nylon 6/SiO₂ (unmodified) and nylon 6/amino‐functionalized SiO₂ (SiO₂‐NH₂) were also prepared via the same method. Fourier transform infrared spectrometer (FTIR) spectroscopy was used to evaluate the structure of SiO₂‐COOH and nylon 6/SiO₂‐COOH. The results from thermal gravimetric analysis (TGA) indicated that decomposition temperatures of nylon 6/SiO₂‐COOH nanocomposites at the 5 wt % of the total weight loss were higher than the pure nylon 6. Differential scanning calorimeter (DSC) studies showed that the melting point (T_m) and degree of crystallinity (X_c) of nylon 6/SiO₂‐COOH were lower than the pure nylon 6. Mechanical properties results of the nanocomposites showed that nylon 6 with incorporation of SiO₂‐COOH had better mechanical properties than that of pure nylon 6, nylon 6/SiO₂, and nylon 6/SiO₂‐NH₂. The morphology of SiO₂, SiO₂‐NH₂, and SiO₂‐COOH nanoparticles in nylon 6 matrix was observed using SEM measurements. The results revealed that the dispersion of SiO₂‐COOH nanoparticles in nylon 6 matrix was better than SiO₂ and SiO₂‐NH₂ nanoparticles. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Structure and properties of polyimide‐g‐nylon 6 and nylon 6‐b‐polyimide‐b‐nylon 6 copolymers

Polyimide‐g‐nylon 6 copolymers were prepared by the polymerization of phenyl 3,5‐diaminobenzoate with several diamines and dianhydrides with a one‐step method. The polyimides containing pendant ester moieties were then used as activators for the anionic polymerization of molten ε‐caprolactam. Nylon 6‐b‐polyimide‐b‐nylon 6 copolymers were prepared by the use of phenyl 4‐aminobenzoate as an end‐capping agent in the preparation of a series of imide oligomers. The oligomers were then used to activate the anionic polymerization of ε‐caprolactam. In both the graft and copolymer syntheses, the phenyl ester groups reacted quickly with caprolactam anions at 120°C to generate N‐acyllactam moieties, which activated the anionic polymerization. All the block copolymers had higher moduli and tensile strengths than those of nylon 6. However, their elongations at break were much lower. The graft copolymers based on 2,2′‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]propane dianhydride and 2,2′‐bis[4‐(4‐aminophenoxy)phenyl]propane displayed elongations comparable to that of nylon 6 and the highest moduli and tensile strengths of all the copolymers. The thermal stability, moisture resistance, and impact strength were dramatically increased by the incorporation of only 5 wt % polyimide into both the graft and block copolymers. The graft and block copolymers also exhibited improved melt processability. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 300–308, 2006     

Effect of dynamic vulcanization on properties and morphology of nylon/SAN/NBR blends: A new compatibilization method of nylon/ABS blends

Dynamically vulcanized blends of nylon, styrene–acrylonitrile copolymer (SAN), and nitrile–butadiene rubber (NBR) were examined for mechanical properties, Shore D hardness, Vicat softening temperature, impact process, and phase morphology. The effect of a curing system such as phenolic formaldehyde resins (PF), dicumylperoxide (DCP), and a sulfur system on the mechanical properties of the nylon/SAN/NBR blends was studied, and dynamic vulcanization with a PF system was found to lead to outstanding toughness of the blends. The effect of PF content on the mechanical properties, Shore D hardness, and heat resistance of the nylon/SAN/NBR blends was also investigated. With increasing PF content the notched‐impact strength and Vicat softening temperature (VST) of the nylon/SAN/NBR (50/25/25) blends evidently improved, but tensile strength and Shore D hardness of the blends changed slightly. It can be concluded that the nylon/SAN/NBR (50/25/25) blends dynamically vulcanized by high‐content PF can attain excellent comprehensive mechanical properties, especially supertoughness, at room temperature. SEM was used to investigate the effect of dynamic vulcanization on disperse‐phase particle size, particle size distribution, and phase morphology. It was obvious that disperse‐phase particle size decreased with an increasing PF content. Thermal behavior and miscibility of dynamically vulcanized nylon/SAN/NBR with PF were investigated by DMTA. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2057–2062, 2003     

MC尼龙6/纳米SiO_2复合材料的合成

用原位聚合法制备MC尼龙6/纳米SiO2复合材料。当纳米SiO2的加入量为1%时,力学综合性能最优。与纯MC尼龙相比,拉伸强度提高21%,弯曲模量提高40.3%,简支梁冲击强度提高69.1%,断裂伸长率降低43%。随着纳米SiO2含量的增加,复合材料的力学性能呈现减小趋势。采用SEM、XRD对产物进行了表征,表明采用修饰后的纳米SiO2加入到产物中,粒子分布均匀,粒径分布窄,粒子的粒径在30 nm左右。随着纳米SiO2加入量的增加,MC尼龙6/纳米SiO2复合材料的结晶度下降。     

有机硅接枝三聚氰胺树脂的合成与表面性能

以三聚氰胺和多聚甲醛为原料、羟基封端聚二甲基硅氧烷（PDMS-OH）为改性剂，制得一系列改性三聚氰胺树脂（MF-PDMS）。研究了反应介质、PDMS-OH用量对MF-PDMS树脂性能的影响，以及与树脂固化后的MF-PDMS材料性能的关系。采用红外光谱（FT-IR）、固体核磁共振氢谱（1H NMR）、X射线光电子能谱（XPS）、扫描电镜-能谱（SEM-EDS）表征了MF-PDMS材料的结构、表面化学组成，采用接触角测定仪、浸泡法分别测试了材料的接触角、吸水性，采用热重（TG）测试了对材料的热稳定性。结果表明：在二甲基乙酰胺（DMAc）反应介质中，PDMS-OH与三聚氰胺、甲醛可一步合成MF-PDMS树脂，接枝共聚的PDMS-OH可高效的提高MF-PDMS材料的疏水性能和热稳定性，当PDMS-OH的摩尔分数为1.0%（以三聚氰胺物质的量计）时材料的水接触角为91.81°、表面自由能降至28.1 mN/m、吸水质量分数降至2.83%、400 ℃时的残留率为58.03%、700 ℃时的残留率为16.60%。     

凯芙拉纤维/尼龙6热塑性复合材料的研制

研究了凯芙拉纤维与尼龙 6单体通过阴离子原位聚合制备热塑性复合材料的方法。以氢氧化钠为引发剂 ,甲苯二异氰酸酯 (TDI)为活化剂 ,确定体系的聚合温度为 160℃ ,引发剂、活化剂用量为6.42 m ol/L ,聚合时间 60 min,在此条件下聚合速度较快 ,单体转化率 1h后达 95 %以上。研究发现 ,凯芙拉纤维经酰化处理后 ,基本上不会对己内酰胺阴离子聚合体系产生阻聚作用     

动态硫化丁腈橡胶/尼龙6热塑性弹性体的制备及性能

采用动态硫化法制备了丁腈橡胶/尼龙6热塑性弹性体(NBR/PA 6 TPV),考察了硫化体系、羧基丁腈橡胶(XNBR)以及增塑剂高密度氧化聚乙烯蜡(AC-316 A)和正丁基苯磺酰胺(BBSA)对TPV硫化特性、力学性能和微观形貌的影响。结果表明,以促进剂HVA-2/促进剂DM为硫化体系,动态硫化过程体系黏度的变化比以酚醛树脂/SnCl2为硫化体系时更平稳;但用后者制备TPV,其撕裂强度和扯断伸长率等力学性能更优,PA 6的结晶度更低。XNBR能对NBR和PA 6起到增容作用,当XNBR与NBR的质量比为10/90时,TPV的力学性能最好,NBR在PA 6中分散得最均匀。AC-316 A和BBSA都能对TPV起到增塑作用,随其用量的增加,体系黏度降低。     

Preparation and characterization of nylon610/functionalized multiwalled carbon nanotubes composites

Nylon610 nanocomposites containing functionalized multiwalled carbon nanotubes (MWCNTs) were prepared using wet melt blending method, which is a novel preparation technique. In comparison with the pure nylon610, the elastic modulus, tensile strength, bending modulus, and bending strength of the composites increase significantly with the increase of MWCNTs content, and the mechanical properties of the composites are also improved significantly by adding a small amount of MWCNTs (0.1 wt %). The crystallization peak of the composites shifts to higher temperature with the addition of MWCNTs, and among the two melting peaks, the intensity of melting peak at low temperature decreases with increasing MWCNTs content. The composites are more stable than pure PA610 and decompose at higher temperature, suggesting that the accession of MWCNTs can improve the composites' thermal stability. The storage modulus of the composites decreases with the temperature increasing, but under lower temperature it increases significantly with the addition of MWCNTs–COOH except for PANT‐0.1 sample. Transmission electron microscope (TEM) images of composites exhibit that the wet melt blending technique can avoid the excess agglomeration of MWCNTs under vacuum dryness, which benefits MWCNTs to disperse uniformly in matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009