聚碳酸酯的生产工艺及市场

介绍了聚碳酸酯(PC)生产工艺、产品性能特点,对国内外主要PC生产商的产能进行了统计。2007年全球PC的总产能为3 980 kt,消费量为3 532 kt,而国内PC总产能仅为216 kt,消费量为902 kt。重点介绍了PC产品应用、国内外市场供需状况及市场结构,对PC下游各主要行业市场与发展状况进行了分析。在此基础上,对国内PC的发展趋势进行了预测与展望。     

聚碳酸酯纺丝及其纺织品研究进展

为促进聚碳酸酯(PC)纺织产品的开发与应用，阐述了聚碳酸酯的分类及性能、PC静电纺丝、熔融纺丝以及PC非织造布的研究进展，分析了PC纺丝及其纺织品研究现状，并结合我国对高性价比、功能型和绿色可循环利用纺织品的发展需求，对PC未来的发展方向进行了展望。     

一种新型含硅阻燃剂的制备及在聚碳酸酯中的应用研究

利用低含氢硅油对纳米二氧化硅(NS)进行表面处理,制备了一种新型含硅阻燃剂(STNS),并将其用于聚碳酸酯(PC)的阻燃。采用傅里叶变换红外光谱(FTIR)、极限氧指数(LOI)、垂直燃烧(UL 94)、力学性能测试以及扫描电镜(SEM)、热重分析(TG)等手段研究了阻燃剂STNS的结构及其对PC阻燃性能和热稳定性的影响,同时分析了STNS对PC的作用机理,并考察了STNS在PC中的分散性及其对PC力学性能的影响。结果表明:阻燃剂STNS在高温下能促进PC交联,从而有效提高PC的阻燃性能和热稳定性。另外,适量STNS的添加能够有效改善阻燃PC的韧性,其中当STNS用量为7%时,阻燃PC的冲击强度和断裂伸长率分别提高了89.9%和108.7%,但其弯曲强度和拉伸强度则分别下降了2.7%和0.7%。     

薄壁阻燃聚碳酸酯的研究

采用全氟丁基磺酸钾阻燃剂(PPFBS)与高岭土复配,成功制备了具有0.8 mm V-0阻燃等级的聚碳酸酯(PC),研究了PPFBS和高岭土对PC热稳定性、燃烧特性和力学性能的影响。结果表明,PPFBS对PC的阻燃效果主要取决于促进PC交联成炭和引发PC降解之间的平衡,而高岭土提高了PC燃烧炭层的稳定性,使其热释放速率更加平缓。除此之外,高岭土对PPFBS阻燃PC的力学性能也有一定的改善作用。     

PC多孔膜的制备及其性能研究

采用Breath Figure法成功制备了聚碳酸酯(PC)多孔膜。考察了PC溶液浓度、环境温度和后处理对所成多孔膜结构和形貌的影响,同时进一步研究了多孔结构对PC多孔膜亲水性、热稳定性与透光率的影响。结果表明:在适当的PC溶液浓度、环境温度以及后处理工艺条件下,采用Breath Figure法能够得到具有规整有序多孔结构的PC薄膜。通过控制PC溶液浓度可有效调整多孔膜的孔径与孔隙率,当PC溶液浓度由0.02 g/ml增至0.06 g/ml时,多孔膜孔径尺寸由2.3μm减小至0.5μm。此外,PC薄膜的多孔结构使其亲水性、热稳定性与透光率得到明显提高,为其进一步应用奠定了基础。     

阻燃剂类型对聚碳酸酯阻燃性能的影响

分别选用溴化齐聚物、磺酸盐、聚硅氧烷混合物和磷酸酯阻燃剂对聚碳酸酯(PC)进行阻燃改性,研究了阻燃剂类型对PC阻燃性能的影响,同时探讨了试样厚度对阻燃性能测试结果的影响。结果表明,溴化齐聚物提升了PC的灼热丝起燃温度(GWIT),磺酸盐、聚硅氧烷混合物和磷酸酯降低了PC的GWIT;成炭对起燃的影响远小于热分解,决定GWIT高低的因素是热分解温度,热分解温度越高,GWIT越高。磺酸盐分解的SO2促使PC交联形成的产物为层碳或石墨化结构,不仅隔热、隔氧、阻止气体流通,还具有导电性,是真炭层,磺酸盐阻燃改性PC的相比电痕化指数由纯PC的175 V降低至150 V;聚硅氧烷混合物、磷酸酯及其分解物形成的“炭层”仅具有类似炭层的作用,无导电性,对PC的电痕化性能无影响。添加四种阻燃剂后PC的灼热丝可燃性指数、垂直燃烧等级均有不同程度的提升,针焰试验结果变好。随着试样厚度增加,溴化齐聚物阻燃PC的GWIT升高,磺酸盐和磷酸酯阻燃PC的GWIT降低,聚硅氧烷混合物阻燃PC的GWIT无明显变化。随着试样厚度增加,四种阻燃剂阻燃PC的其它阻燃性能整体变好,但磷酸酯阻燃PC的垂直燃烧等级仍为V–1级。     

腰果酚醛铁聚合物的合成及其表征

本文制备了腰果酚醛铁聚合物 (PC -Fe) ,并对其结构特征和性能进行了研究。结果表明 ,腰果酚醛缩聚物 (PC)分子中的羟基与Fe3 + 发生了配位作用 ,使得PC分子链间进一步交联 ,从而改善了PC的硬度、耐热性能等 ,同时降低了PC在有机溶剂的溶解性     

羧酸类助剂对滑石粉填充PC性能的影响

通过熔融共混法制备了滑石粉填充聚碳酸酯(PC)材料,考察了滑石粉对PC韧性、刚性、热性能等性能的影响规律。结果表明,碱性滑石粉对PC有明显的催化降解作用,降低了PC的热分解温度及玻璃化转变温度并使其冲击性能显著降低,因此降低滑石粉对PC的催化降解作用是提高滑石粉填充PC材料性能的关键。为此自制了一种含有长链烷烃和羧酸、马来酸酐及丙烯酸酯类基团的羧酸类助剂,该助剂可与PC发生一定反应,但主要通过与滑石粉的酸碱反应达到保护PC、减少PC降解程度的目的。当助剂质量分数为0.5%时,制得了刚韧平衡的质量分数25%滑石粉填充PC材料,其悬臂梁缺口冲击强度达到180 J/m,弯曲弹性模量达到6 490 MPa,能够满足电子产品薄壁化设计要求。     

耐溶剂聚碳酸酯/聚酰胺1010共混物的制备及其性能探讨

用碳链较长、韧性较好的聚酰胺（PA）1010对聚碳酸酯（PC）进行改性。对PC/PA1010合金体系的力学性能、耐热性能、耐溶剂性能以及动态流变性能等进行了研究,并探讨了PA1010及相容剂聚乙烯接枝甲基丙烯酸缩水甘油酯（PE-g-GMA）对PC/PA1010合金的性能影响。结果发现,PA1010能够较好地保持合金的冲击强度,同时明显改善了PC的耐溶剂性能;PE-g-GMA对PC/PA1010有很好的反应增容作用;当PC/PA1010/PE-g-GMA的配比为80/15/5（质量比,下同）时,合金获得最佳综合性能。     

SNP阻燃剂对聚碳酸酯热分解与老化寿命的影响

采用热重(TG)分析法研究了不同升温速率下,SNP阻燃剂对聚碳酸酯(PC)热降解行为的影响,并且通过Kissinger和Flynn-Wall-Ozawa两种方法对PC/SNP复合材料的热分解动力学进行了探讨,两种方法计算结果一致,均表明阻燃剂SNP的加入降低了PC的热分解活化能,相比PC分别降低了9.9%和9.0%。采用时–温等效原理对阻燃PC的老化寿命进行了预估,结果发现,SNP阻燃剂的加入使PC的老化寿命明显缩短,表明SNP阻燃剂能加快PC的热降解速率,使PC的初始分解温度提前了6.46%,促使PC更早地降解成炭,成炭量增加了28%,从而提高了PC的阻燃性能。     

Synthesis,flame‐retardancy testing,and preliminary mechanism studies of nonhalogenated aromatic boronic acids: A new class of condensed‐phase polymer flame‐retardant additives for acrylonitrile–butadiene–styrene and polycarbonate

This study describes the syntheses and thermal properties of aromatic boronic acids and their use as flame retardants. The possible flame‐retardancy mechanisms are also discussed. The materials were synthesized from aromatic bromides using one of two procedures. The first procedure involved traditional approaches to boronic acids, using lithium–halogen exchange and quenching with trimethylborate followed by hydrolysis. The second procedure used a nickel catalyst and a dialkoxy borane to generate aromatic dialkoxyboronates that were converted to boronic acids by acid hydrolysis. The thermal properties of these aromatic boronic acids were studied using differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). These materials were blended into acrylonitrile–butadiene–styrene (ABS) and polycarbonate (PC) resins and tested for ignition resistance, using the UL‐94 flame test. A 10 wt % loading of 1,4‐benzenediboronic acid in polycarbonate gave a UL‐94 V‐0 result. This same diboronic acid showed flame retardancy and char formation in ABS, but this result was not quantifiable by the UL‐94 test. Burn times for the ABS samples often exceeded 5 min, thereby showing unusual resistance to consumption by fire. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1257–1268, 2000     

Surface modification of polymer structures by an imido-alkylene substitution reaction. I. Polycarbonate

The surface characteristics of molded polycarbonate sheet was altered via an imidoalkylene substitution reaction. The reaction was effected by contacting the surface with N-hydroxymethylmaleimide and a Friedel-Crafts alkylation catalyst in the presence of a mixture of solvents having limited solubility for polycarbonate. The substitution reaction suggested an aromatic electrophilic substitution mechanism. When N-hydroxymethylmaleimide was used in the surface treatment of polycarbonate sheet, imido-alkylene substitution not only took place but pendent C?C bonds were also incorporated along the polymer chain. When these C?C bonds were photochemically reacted with each other, the surface of the polycarbonate sheet became crosslinked and solvent resistant.     

A comparison of the thermal stabilities of a siloxane substituted polycarbonate with a standard polycarbonate and a polydimethylsiloxane

The thermal stability in inert and oxidising atmosphere of an aromatic polycarbonate with a siloxane side chain has been compared with those of a polycarbonate and a poly-(dimethylsiloxane) using thermogravimetry. The presence of the siloxane side chain is seen to marginally enhance the thermal stability compared to that of the unsubstituted polycarbonate.     

硬段对PCDL型水性聚氨酯的结构与性能的影响

以聚碳酸酯二元醇(PCDL)为软段,分别以异氟尔酮二异氰酸酯(IPDI)、甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)、六亚基二异氰酸酯(HDI)为硬段,采用丙酮法制备了四种不同硬段组成的PCDL型水性聚氨酯(WPU).综合对比,研究了硬段类型对PCDL型WPU结构与性能的影响.结果表明,芳香族WPU的力学...     

Synthesis and characterization of polycarbonate/polydimethylsiloxane multiblock copolymer prepared from dimethylsiloxane and various aromatic dihydroxyl monomers

This study utilizes different types of bisphenol monomers instead of bisphenol‐A to synthesize phenol terminated polydimethylsiloxane‐polycarbonate block copolymers. The copolymers were synthesized by interfacial phosgenation of α, ω‐phenol‐organofunctional polydimethylsiloxane oligomer with various aromatic dihydroxyl monomers. In addition,the thermal properties, flammability, and mechanical properties of the synthesized copolymers after extrusion and injection molding were investigated. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 545–552, 2000     

Measurement of the residual mechanical properties of crazed polycarbonate. II: Design of experiments analysis

The Design of Experiments (DOE) approach was used to build quantitative empirical models of the residual mechanical properties of crazed polycarbonate as functions of relative craze density, crazing stress, and strain rate. Crazing did not affect the yielding behavior of polycarbonate, but increasing the strain rate increased the yield stress according to the Eyring theory. The Eyring activation volume for yielding of crazed polycarbonate was measured to fall between reported values for conformational changes of a dilute solution of polycarbonate chains and yielding of uncrazed polycarbonate. Also, with as little as 1% relative craze density, the failure stress was approximately 10% lower and the ductility was, on the average, 50% lower than for uncrazed polycarbonate properties. It was also found that increasing the crazing stress from 40 to 45 MPa increased the failure stress and ductility for a given magnitude of relative craze density.     

透明PC用阻燃剂的研究与应用进展

综述了目前国内外能保持聚碳酸酯(PC)透明性的环保阻燃剂的研究进展,具体包括芳香族磺酸盐、磷酸酯、含溴聚碳酸酯齐聚物及硅酮化合物等。概述了各类阻燃剂的阻燃机理、制备方法及透明阻燃PC的市场应用情况,介绍了各类阻燃剂在使用过程中存在的优缺点且提出今后的发展方向。     

Characterization of polyester/polycarbonate blends by size exclusion chromatography and melt rheometry

A major obstacle to the study of polymer blends has been the lack of a convenient technique for measurement of molecular weight. Melt rheometry, while giving useful information related to processing and end-use performance, is incapable of providing detailed information on the individual components. This work describes the use of size exclusion chromatography (SEC) to study the molecular-weight distributions of polycarbonates and aromatic polyesters in blends of the two. SEC of the polycarbonate is achieved in a solvent which dissolves the polycarbonate, but not the polyester, while SEC is performed in a solvent which dissolves both components, but using selective detection. Thus, SEC is used to examine the individual components of the blend, while rheometry can be used to study the blend as a whole. This combination of techniques has been successfully used to analyze the effect of moisture, processing conditions, and recycling on blend properties.     

Self-Reinforced melt processible polymer composites: Extrusion,compression, and injection molding

Rheological properties, extrusion, fiber spinning, compression, and injection molding of blends of polycarbonate and two thermotropic liquid crystal polymers based on wholly aromatic copolyesters have been studied. Blends were prepared using an internal Banbury mixer and static Koch mixer. Based upon differential scanning calorimetry and dynamic mechanical measurements, these blends have been shown to be incompatible in the entire range of concentrations. During extrusion and injection molding at high strain rates, it has been observed that thermotropic liquid crystal polymer at concentrations 2.5, 5, and 10 percent by weight in situ forms high modulus and high strength fibers within the polycarbonate matrix leading to self-reinforced polymer composites. The tensile strength of the composite containing 10 percent of liquid crystal polymer exceeds that of the pure components. In addition, anisotropy of properties of the injection molded parts has been found to substantially reduce in a comparison with that of liquid crystal polymer. The processing conditions and technique for the production of self-reinforced polymer composite during processing of the blends have been identified. This has been done by measurements of mechanical properties, direct observation of morphology, and by theoretical calculation using simplified composite theory for the unidirectional continuous fiber-reinforced composites. At the high concentrations, 25 and 50 percent by weight, thermotropic liquid crystal polymer forms large spherical droplets inside polycarbonate leading to highly brittle material. This is in distinction from the fibrous, high modulus tough composites formed at the lower concentrations.     

聚酯共混改性聚碳酸酯研究进展

综述近年来国内外聚酯共混改性聚碳酸酯的研究进展，分类介绍聚碳酸酯／半芳香族聚酯、聚碳酸酯／脂肪族或脂环族聚酯及聚碳酸酯／液晶聚酯等各共混体系，讨论了各体系的相行为、相容性、力学性能及光学性能等。而脂肪族或脂肪族聚酯共混改性聚碳酸酯是提高其综合性能的一条好途径。