Flame‐retarded polyethylene terephthalate with carbon microspheres/magnesium hydroxide compound flame retardant

A novel compound flame retardant (carbon microspheres/magnesium hydroxide, abbreviated as CMSs/MH) was used to improve the fire performance of polyethylene terephthalate (PET). LOI, UL94, and Cone test results showed that CMSs/MH/PET composites obtained the best fire performance at the mass ratio of CMSs to MH, which was 5:5, where the CMSs/MH content was 1.0 wt. % of PET. The Py‐CS‐MS, TGA‐DSC results, and morphology of char residue revealed the flame‐retardant mechanism. CMSs/MH increased the thermal stability of PET by increasing the activation energy at the initial combustion stage. At the second stage of combustion, CMSs/MH increased the chance of recombination of free radicals and slowed the combustion. Additionally, CMSs/MH promoted the cross‐linking of pyrolysis products and further improved the continuity of the char layer. Thus, a dense and continuous char layer of CMSs/MH/PET composites was produced; this char layer reduced the heat release rate and increased the amount of char residue.     

Action of alkali on polybutylene terephthalate and polyethylene terephthalate polyesters

The two polyesters (polybutylene terephthalate and polyethylene terephthalate) were treated with aqueous as well as alcoholic solutions of sodium hydroxide at varying temperatures for different durations of time. The results were evaluated in terms of the loss in weight of the samples. The fabric samples of polyethylene terephthalate showed a greater degree of weight loss as compared to those of polybutylene terephthalate. The mechanism for the differences in the action of alkali on these two polyesters is explained. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1097–1102, 2000     

PET／PC原位复合纤维的微纤形态和力学性能研究

采用“熔融挤出-热拉伸-淬冷”法制取了聚对苯二甲酸乙二酯（PET）／聚碳酸酯（PC）原位复合纤维,研究了PET的质量含量（Cm）对PET成纤性和原位复合纤维拉伸性能的影响。结果表明：PET和PC是热力学不相容的,但这种不相容性却有利于微纤的形成;随着Cm的增加,PET微纤的数量增多,当Cm30％时,PET微纤数量呈现最大值,微纤直径分布最窄,而后随着Cm的增加,微纤数量减少,微纤直径分布变宽。力学性能测试结果表明,原位复合纤维的断裂强度以Cm=30％为界,先增大而后减小。     

Toughening of polyethylene terephthalate/amorphous copolyester blends with a maleated thermoplastic elastomer

The toughening of polyethylene terephthalate (PET)/amorphous copolyester (PETG) blends using a maleic anhydride grafted mixture (TPEg) of polyethylene‐octene elastomer and a semicrystalline polyolefin plastic (60/40 by weight) was examined. The TPEg was more effective in toughening PETG than PET, although the dispersion qualities of the TPEg particles in PET and PETG matrices were very similar. At the fixed TPEg content of 15 wt %, replacing partial PET by PETG resulted in a sharp brittle‐ductile transition when the PETG content exceeded the PET content. Before the transition, PET/PETG blends were not toughened with the TPEg of 15 wt %, whereas after the transition, the PET/PETG blends with 15 wt % of TPEg, similar to the PETG/TPEg (85/15) binary blend, maintained a super‐tough level. The impact‐fractured surfaces of the PET/PETG/TPEg blends were also evaluated. When PETG content was lower than PET content, the ternary blend showed a brittle feature in its impact‐fractured surface, similar to the PET/TPEg (85/15) binary blend. While PETG content exceeded PET content, however, the impact‐fractured surface of the ternary blend was very similar to that of PETG/TPEg (85/15) binary blend, exhibiting intensive cavitation and massive matrix shear yielding, which were believed to be responsible for the super‐tough level of the blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 797–805, 2003     

Deformation mechanisms in rubber toughened semicrystalline polyethylene terephthalate

The deformation mechanisms of rubber toughened polyethylene terephthalate (PET) are studied with fractography of impact fractured samples and tensile dilatometry. The dispersed phase consists of a mixture of an ethylene-co-propylene rubber (EPR) and a compatibilising agent (E-GMA8: copolymer of ethylene and 8 wt% of glycidyl methacrylate). It is found that the ductile fracture behaviour, above the brittle-ductile transition temperature (T_bd), consists of a high degree of rubber cavitation and extensive matrix shear yielding, both in the fracture plane and the stress whitened zone surrounding the crack. A steep increase in the volume strain upon tensile loading confirms the presence of the rubber voiding mechanism in the PET/(EPR/E-GMA8) blend system. It is seen that the stress whitened zone below the impact fracture surface consists of different zones, depending on the test temperature. Below T_bd, a layer of a highly deformed structure is followed by a cavitation layer containing only a limited number of cavitaties. Increasing the temperature, causes the deformation layer to be replaced by a zone lacking structure. It is believed that part of the fracture energy has been dissipated in the form of heat inducing a relaxation in the structure. Dynamical mechanical analysis under superimposed axial stresses reveals that the dispersed rubber particles internally cavitate in the presence of volume strain. At increased volume strains, the biaxial stress state in the cavitated particle is disturbed, resulting in the rupture of the rubber chains closest to the void by a tearing mechanism; revealing that the rubber particle is damaged upon cavitation.     

Cycloolefin copolymer/fumed silica nanocomposites

We prepared cycloolefin copolymer (COC)/fumed silica nanocomposites by melt compounding to study the effect of the filler dimensions (filler surface area) on the physical properties, with particular attention to their thermal, mechanical, and optical behaviors. Thermogravimetric analysis revealed a positive contribution of silica nanoparticles to the thermal degradation resistance of COC, as the decomposition temperature of the nanofilled samples increased by 40°C with respect to that of the unfilled matrix. Dynamic mechanical thermal analysis and quasi‐static tensile tests of the nanocomposites evidenced a slight stiffening effect, proportional to the nanofiller surface area, without any reduction in the fracture toughness. Creep resistance of the nanocomposites was increased by the addition of silica nanoparticles, especially when high‐surface‐area nanoparticles were used. The positive effect of the nanoparticles on the viscoelastic and fracture behavior was related to the uniform dispersion of silica aggregates in the matrix. Ultraviolet–visible spectrometry measurements evidenced that the original transparency of neat COC was practically maintained after the addition of silica nanoparticles. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

聚对苯二甲酸乙二醇酯的改性及其发泡材料的最新进展

综述了聚对苯二甲酸乙二醇酯(PET)的改性方法及其发泡工艺的研究进展,其中改性方法主要包括固相缩聚、原位共聚和扩链改性,发泡工艺主要有釜压法、模压法、挤出法等.最后,简要介绍了我国PET发泡材料的工业化现状,并指出未来研究和发展的方向.     

PET熔融挤出后的特性黏数变化

分别使用单螺杆挤出机、双螺杆挤出机、反应型挤出机挤出聚对苯二甲酸乙二酯(PET),研究其在不同挤出温度、不同螺杆转速下熔融挤出后PET的特性黏数变化情况。使用双螺杆挤出机时,PET降解最严重,特性黏数平均降低23.5%。使用单螺杆挤出机:在较低挤出温度时挤出产物基本不降解;在高温时挤出产物降解明显,挤出温度每提高10℃,产物特性黏数平均降低5.8%;较高的螺杆转速有利于防止PET的降解;原料含水量越低,PET分子越不易降解。使用反应型挤出机时,PET热降解程度大于使用单螺杆挤出机。PET最适合使用单螺杆挤出机,在较低挤出温度、较高螺杆转速、物料经过烘干的情况下进行熔融挤出加工。     

Light scattering studies on crystallization in polyethylene terephthalate

The light scattering from the spherulites of polyethylene terephthalate grown near the glass transition temperature has been investigated. The Hv scattering profiles can be reproduced by the sum of the ideal spherulite scattering with the distribution of spherulite radius and the isotropic scattering from randomly oriented crystallites. The ratio of optical anisotropies in the isotropic scattering to the ideal spherulite scattering is obtained by the method established to eliminate the effects of the number density of spherulites and the coefficient depending on the experimental conditions. It is found that the anisotropy ratio is almost independent of the crystallization time and of temperature above 106 °C, while it is larger at a crystallization temperature of 103 °C. The spherulitic structure is discussed in terms of the anisotropy ratio.     

Synthesis and characterization of polyimide–silica nanocomposites using novel fluorine‐modified silica nanoparticles

Polyimide–silica nanocomposites were synthesized with 4,4′‐oxydianiline, 4,4′‐(4,4′‐isopropylidenediphenoxy)bis(phthalic anhydride), and fluorine‐modified silica nanoparticles. Fluorinated precursors such as 4″,4?‐(hexafluoroisopropylidene)bis(4‐phenoxyaniline) (6FBPA) and 4,4′‐(hexafluoroisopropylindene)diphenol (BISAF) were employed to modify the surface of the silica nanoparticles. The microstructures and thermal, mechanical, and dielectric properties of the polyimide–silica nanocomposites were investigated. An improvement in the thermal stability and storage modulus of the polyimide nanocomposites due to the addition of the modified silica nanoparticles was observed. The microstructures of the polyimide–silica nanocomposites containing 6FBPA‐modified silica exhibited more uniformity than those of the nanocomposites containing BISAF‐modified silica. The dielectric constants of the polyimide were considerably reduced by the incorporation of pristine silica or 6FBPA‐modified silica but not BISAF‐modified silica. The addition of a modifier with higher fluorine contents did not ensure a lower dielectric constant. The uniformity of the silica distribution, manipulated by the reactivity of the modifier, played an important role in the reduction of the dielectric constant. Using 6FBPA‐modified silica nanoparticles demonstrated an effective way of synthesizing low‐dielectric‐constant polyimide–silica nanocomposites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 882–890, 2007     

Preparation and properties of polyimide/silica hybrid composites based on polymer‐modified colloidal silica

A new type of polyimide/silica (PI/SiO₂) hybrid composite films was prepared by blending polymer‐modified colloidal silica with the semiflexible polyimide. Polyimide was solution‐imidized at higher temperature than the glass transition temperature (T_g) using 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA) and 4,4′‐diaminodiphenyl ether (ODA). The morphological observation on the prepared hybrid films by scanning electron microscopy (SEM) pointed to the existence of miscible organic–inorganic phase, which resulted in improved mechanical properties compared with pure PI. The incorporation of the silica structures in the PI matrix also increased both T_g and thermal stability of the resulting films. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2053–2061, 2006     

Use of silica from rice husk ash as an antiblocking agent in low‐density polyethylene film

In packaging applications, blocking is always found in low‐density polyethylene (LDPE) films. Practically, such problems can be solved by incorporation of antiblocking agents, for example, silica and talc. The objective of this research was to explore the possibility of using silica from rice husk ash (RHA silica) as an antiblocking agent in LDPE film. Properties of RHA silica were compared with commercial silica, Sylo‐1. The appropriate amount of silica to be used as an antiblocking agent in LDPE film was also investigated. The results indicate that RHA silica has a smaller particle size and a higher specific surface area but a higher bulk density than those of Sylo‐1 silica. In the plastic film industry, 500–1000 ppm of silica is added in LDPE films as an antiblocking agent. It was also found that LDPE film with 2000–3000 ppm RHA silica showed similar properties to LDPE film filled with commercial silica in terms of its blocking behavior, mechanical strength, and film clarity. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 848–852, 2003     

有色废弃PET材料化学回收新工艺

为了解决有色废弃PET材料回收难的问题,促进资源循环利用,研究了有色PET以超临界甲醇技术进行解聚,并脱色提纯得到对苯二甲酸二甲酯的工艺流程。探讨了有色PET在超临界甲醇中的降解规律,并对脱色方案进行了筛选。探索了不同级别的PET材料解聚条件的差异。结果表明：纤维级材料在265 ℃,11 MPa下,超临界甲醇解聚30 min后,用溶解-热过滤-沉析的方法脱色提纯,对苯二甲酸二甲酯的产率可达到85%,纯度达到99.9%以上,白度达到87.5%;瓶片级材料呈现的解聚规律与纤维级变化趋势相同,但达到相同的解聚率,明显需要更长的反应时间。     

新型钛系聚酯催化剂的催化性能研究

合成了一种应用型钛系聚酯(PET)催化剂TY,考察了在PET合成中催化剂TY对酯化时间、缩聚时间、产品性能等的影响;并与传统锑系催化剂三氧化二锑(Sb2O3)的性能进行了对比。结果表明:钛系催化剂TY不仅能缩短酯化时间和聚合时间,而且催化剂用量少、催化活性高;钛系催化剂TY用量为20~25μg/g时,催化活性最佳,催化剂TY 20~25μg/g的催化活性相当于Sb2O3350~400μg/g的催化活性;钛系催化剂合成的PET切片的特性黏数达0.683 d L/g,与锑系PET相比,色相L值提高达71.68,b值相差不大,端羧基含量及二甘醇含量降低,结晶行为及热性能相当;钛系催化剂TY适合无重金属聚酯的工业生产,工业应用性强。     

Thermal expansion of fumed silica/cyanate ester nanocomposites

The thermal expansion behavior of a cyanate ester matrix reinforced by fumed silica nanoparticles with average primary particle diameters of 12 and 40 nm was investigated with thermomechanical analysis. All nanocomposites showed decreased coefficients of thermal expansion (CTEs) in comparison with the neat bisphenol E cyanate ester resin, but the 12-nm fumed silica nanocomposites had lower CTEs than the 40-nm nanocomposites for equal volume fractions. The largest decrease in CTE was 27.0% for 20.7 vol % 40-nm fumed silica. When the data were compared to applicable theory, the best fit of the data was given by Schapery's upper limit and Shi's model. Estimates of the interphase volume fraction and effective thickness surrounding the nanoparticles were made with the results of Shi's model, and the results showed that the interphase volume fraction was larger for the 12-nm fumed silica nanocomposites, given an equal fraction of silica. The glass-transition temperature of the nanocomposites from thermomechanical analysis varied only slightly with the volume fraction. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Mechanical and thermal properties of polypropylene/recycled polyethylene terephthalate/chopped rice husk composites

The various ratios of recycled polyethylene terephthalate (rPET) into polypropylene (PP) filled with 40 parts chopped rice husk per hundred part of polymer have been studied. Composites were prepared using a corotating twin screw extruder at temperature zones of 165–215, well below 250°C (rPET mp temperature) and characterized by mechanical and thermal properties. To improve the compatibility between different components, PP grafted with maleic anhydride was added as a coupling agent in all the compositions studied. The results showed that the addition of rPET improved the tensile and flexural modulus and impact strength of the composite while reducing its tensile and flexural strength. The scanning electron microscopy micrographs of samples in the injection direction showed that some particle shaped rPET inside the composites appear as drawn fibrils and some appear as plates. Differential scanning calorimetric studies showed that the addition of rPET particles to the composites decrease the PP crystallization temperatures. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Visualization study and analysis on preform growth in polyethylene terephthalate stretch blow molding

In stretch blow molding (SBM) process, the preform growth during the stretching and blowing is critical to the thickness distribution and properties of the final bottle. Whereas the thickness distribution is one of the most important criteria in the production of bottles. So this work focused on the polyethylene terephthalate (PET) preform growth using a transparent mold, through which the instantaneous images of the preform in the stretching and blowing stage were captured. By changing the delay time of the preblow, the three preform growth types, referred to as dolphin, sandpile, and two‐bubble, were observed. The longitudinal and hoop stresses acting on the preform segment during the stretching and blowing were analyzed. Two parameters, on which the longitudinal and hoop stresses depend, respectively, were defined. Then combining the geometry and sizes of the preform, the stresses and temperature distribution on it, and the stress–strain curves of the PET material used, the cause for different preform growth types was systematically analyzed. On the basis of preform growth types, the thickness distributions of the bottles obtained under different delay times of the preblow were explained. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 564–573, 2007     

Synthesis of epoxy resin–silica nanocomposites provided from perhydropolysilazane as a curing reagent and the precursor of silica domain

Epoxy resin–silica nanocomposites with spherical silica domains with 29.0 nm in diameter in an epoxy resin matrix were synthesized from Bisphenol‐A type epoxide monomer, 2,2‐bis(4‐glycidyloxyphenyl)propane (DGEBA), and perhydropolysilazane (PHPS, ? [Si₂? NH]_n? ). The volume fraction of silica domain in the composite varied from 5.4 to 37.8 vol % by varying the feed ratio of PHPS to the epoxide monomer. The reaction mechanism of epoxy group and PHPS was investigated by using glycidyl methacrylate as a model compound of the epoxy monomer by ¹H‐nucular magnetic resonance and Fourier transform infrared spectrometry. Ammonia gas provided by the decomposition of PHPS with moisture converted PHPS to silica and cured the epoxy monomer. The curing of epoxy monomer preferably proceeded than the conversion of silica. The addition of 1,4‐diaminobutane drastically accelerated the rate of curing; white and hard epoxy resin–silica nanocomposites were obtained. The good thermal stability of the composite prepared with DGEBA/PHPS/1,4‐diaminobutane was observed by thermogravimetric analysis. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

裂解气相色谱-质谱法研究芳香族聚酯类纤维热分解

采用裂解气相色谱质谱法研究了600℃时聚对苯二甲酸丁二酯纤维(PBT)、聚对苯二甲酸丙二酯纤维(PTT)和聚对苯二甲酸乙二酯纤维(PET)的热裂解反应,分别鉴别到22种、25种和25种主要裂解产物。PBT的特征性裂解产物是苯甲酸丁烯酯、苯甲酸丁酯、1,4-苯二甲酸-3-丁烯酯、1,4-苯二甲酸-双-3-丁烯酯和二苯甲酸-1,4-丁二醇酯;PTT的特征性裂解产物为苯甲酸丙烯酯、苯甲酸丙酯、对苯二甲酸单丙烯酯、1,4-苯二甲酸-双-2-丙烯基酯、二苯甲酸-1,3-丙二醇酯;PET的特征性裂解产物为苯甲酸乙烯酯、苯甲酸乙酯、苯二甲酸双乙烯酯、二苯甲酸-1,2-乙二醇酯。