PBT/AlPi/MPP/CB复合材料结晶及流变性能研究

以聚对苯二甲酸丁二醇酯(PBT)为基材,二乙基次膦酸铝(AlPi)以及三聚氰胺次膦酸盐(MPP)为阻燃剂、导电炭黑(CB)为抗静电剂,通过密炼熔融共混得到PBT/AIPi/MPP/CB阻燃抗静电复合材料。通过差示扫描量热分析(DSC),动态力学分析(DMA)和动态流变分析考察了阻燃抗静电PBT/AIPi/MPP/CB复合材料的熔融结晶性能,动态力学性能和动态流变性能。结果表明:阻燃剂和CB都会使复合材料提前结晶,结晶度提高;阻燃剂的添加使PBT的玻璃化转变温度升高,CB的加入会降低材料的内耗峰,阻燃剂和CB超过一定用量会使材料的储能模量降低;PBT/AIPi/MPP/CB复合材料的储能模量对剪切频率的依赖性不明显,而其复数黏度呈现强烈的剪切频率依赖性。     

聚乳酸/苯基次膦酸铈复合材料的制备及性能

采用简单方法合成苯基次膦酸铈(CeP),并将其作为阻燃剂加入聚乳酸(PLA)中,通过熔融共混技术制备聚乳酸/苯基次膦酸铈(PLA/CeP)复合材料。通过热重(TG)、极限氧指数(LOI)、UL-94垂直燃烧(UL-94)、微型量热(MCC)研究复合材料的热稳定性、阻燃性能和燃烧性能。通过阻燃测试发现,CeP能够提高复合材料阻燃性能,PLA/CeP20极限氧指数能达到24.3%并通过UL-94 V-2级别。热重分析的结果表明,CeP显著提高了PLA/CeP复合材料初始分解温度和成炭率。MCC测试结果表明,CeP能明显降低PLA/CeP复合材料火灾危险性。PLA/CeP20热释放速率峰值(PHRR)和总热释放(THR)分别为397 W/g和13.6 kJ/g,与纯聚乳酸相比,分别下降了13.9%和28.0%。因此,苯基次磷酸铈对聚乳酸具有良好的阻燃效果。     

环氧树脂/二烷基次膦酸锌阻燃体系热分解动力学研究

利用热重分析法,采用Flynn-Wall-Ozawa(FWO)法和Kissinger法计算出了甲基环己基次膦酸锌(Zn(MHP))、环氧树脂(EP)以及复合材料(EP/Zn(MHP))阻燃体系在氮气中的热分解活化能以及指前因子,在此基础上利用Coast-Redfern法选取不同的机理模型,确定了热降解动力学机理。研究结果表明:Kissinger法和FWO法所得到的活化能值相近,Zn(MHP)、EP/Zn(MHP)和EP平均热分解活化能依次减小。Zn(MHP)的加入,能增加EP的热稳定性以及热分解活化能。Coats-Redfern法推断EP,Zn(MHP)/EP具有相似的热分解机理,热分解符合函数g(a)=[-ln(1-a)]~(2/3),反应级数n=2/3,Zn(MHP)的热分解符合函数g(a)=-ln(1-a)机理,反应级数n=1。     

苯基次膦酸锌阻燃改性聚乳酸材料

采用共沉淀法合成了苯基次膦酸锌(ZnP)并对其进行表征,在此基础上通过熔融共混技术制备了一系列聚乳酸/苯基次膦酸锌(PLA/ZnP)复合材料,采用热重分析,极限氧指数测试（LOI）,UL 94垂直燃烧测试、微型量热(MCC)研究ZnP对复合材料热稳定性、阻燃性能以及燃烧性能的影响。研究表明,ZnP可以提高复合材料的热分解温度和成炭性,30 %（质量分数,下同）ZnP使得复合材料的分解温度相对于纯PLA上升8 ℃,750 ℃成炭率达到18.5 %;此外,ZnP可以提高复合材料阻燃性能,PLA/ZnP30的极限氧指数达到24.0 %,并通过UL 94 V-2级别,热释放速率峰值相对于PLA降低了24.9 %,有效提高了复合材料火灾安全性。     

聚酯中亚甲基含量对其热性能影响研究

以聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丙二醇酯(PTT)、聚对苯二甲酸丁二醇酯(PBT)为研究对象,采用差示扫描量热仪考察了其亚甲基含量对聚酯的玻璃化转变、熔融结晶行为、冷结晶行为等热性能的影响,通过Avrami方程、Arrhenius方程计算了3种聚酯的结晶物理常数;采用热失重分析仪分析了PET,PTT,PBT的热稳定性。结果表明:PET的玻璃化转变温度为77.24℃,而PTT,PBT未见明显的玻璃化转变;随着亚甲基含量增加,聚酯的熔点下降,冷结晶峰温度上升,其中PTT在67.8,192.0℃处存在两个冷结晶峰;3种聚酯的熔融结晶行为均符合Avrami方程;随着亚甲基含量增加,聚酯的熔融结晶热焓、Avrami指数依次增大,半结晶时间依次减小,校正后的非等温结晶动力学常数变化不大;3种聚酯的冷结晶程度均弱于熔融结晶,PET,PTT,PBT的冷结晶程度分别约为熔融结晶的70%,10%,7%,冷结晶速度依次变快;随着聚酯中的亚甲基含量增加,聚酯的热稳定性变差;3种聚酯的热降解过程可分为3个阶段,PTT,PBT初始分解温度低于PET,第一、第二降解活化能高于PET,但第三降解活化能低于PET。     

异氰酸酯基硅氧烷树脂/硅藻土/PBT复合材料研究

采用熔融共混方法制备异氰酸酯基硅氧烷树脂/硅藻土/聚对苯二甲酸丁二醇酯(PBT)复合材料,通过傅里叶红外光谱(FTIR)、力学性能测试和扫描电子显微镜(SEM)研究了相容剂异氰酸酯基硅氧烷树脂和硅藻土对PBT复合材料微观结构及性能的影响。FTIR结果表明,异氰酸酯硅氧烷树脂和PBT、硅藻土发生反应,起到"分子桥"的作用。SEM分析显示,异氰酸酯基硅氧烷树脂改变PBT和硅藻土两相之间的黏结状态。当异氰酸酯基硅氧烷树脂/硅藻土/PBT质量比为6/10/90时,硅藻土粒子被PBT树脂基体包埋,分散均匀,在两相之间没有明显的界面,异氰酸酯基硅氧烷树脂是PBT和硅藻土良好增容剂,此时复合材料综合性能最好。和纯PBT相比,异氰酸酯基硅氧烷树脂/硅藻土/PBT复合材料的冲击强度、弯曲强度和拉伸强度分别提高73.80%、46.86%和32.41%。     

阻燃PLA复合材料的制备及其阻燃性能研究

采用熔融共混技术,将二乙基次膦酸铝（ADP）引入聚乳酸(PLA)中,制备了一系列阻燃聚乳酸复合材料(FR-PLA)。在此基础上,采用热重分析、极限氧指数、UL 94垂直燃烧、微型量热测试研究了二乙基次膦酸铝对阻燃聚乳酸复合材料热稳定性、阻燃性能以及燃烧性能的影响。结果表明,ADP可以有效提高复合材料的阻燃性能,30 %（质量分数,下同）的ADP使得PLA/ADP30通过UL 94 V-0级别,极限氧指数达到31.6 %（体积分数,下同）; ADP使得阻燃PLA复合材料的初始分解温度降低,但明显提高复合材料的成炭性; ADP使得复合材料的热释放速率峰值明显下降,PLA/ADP30热释放速率峰值为290 W/g,相对于PLA下降37.1 %,明显降低复合材料的火灾危险性。     

磷系阻燃剂NYP3对PBT阻燃性能影响的研究

经由新型磷系阻燃剂氨基三亚甲基膦酸铝(NYP3)与二乙基次膦酸铝(BEP-22E)复配使用,制备了无卤阻燃的增强PBT复合材料,并研究了材料的阻燃性能和燃烧残余物表面形貌。结果表明,添加质量分数为6%NYP3、10.5%BEP-22E时,材料UL 94垂直燃烧1.5 mm测试可达到V-1,LOI值高达37.1%;添加质量分数为4%NYP3、12.5%BEP-22E时,材料UL 94垂直燃烧1.5 mm测试可达到V-1,LOI值高达39.5%。由锥形量热分析可知,NYP3和BEP-22E复配使用可以有效降低复合材料的HRR及THR值,燃烧时有助于在材料表面形成致密炭层。     

ALPi/MPP/FeCo-MOF协效阻燃PBT/PP复合材料的研究

制备了一种双金属协效阻燃剂(FeCo-MOF),研究了二乙基次膦酸铝(ALPi)/三聚氰胺聚磷酸盐(MPP)/FeCo-MOF协效阻燃聚对苯二甲酸丁二醇酯/聚丙烯(PBT/PP)复合材料的性能。结果表明：当ALPi/MPP/FeCo-MOF的质量比为13.00∶6.50∶0.60时,阻燃PBT/PP复合材料的极限氧指数为32%,UL-94垂直燃烧阻燃等级为V-0级,800℃时残炭率达8.97%。     

一种高效单一组分磷-氮协效型阻燃剂的合成及其在PA6中的应用

以2-甲基-2,5-二氧-1,2-氧磷杂环戊烷(OP)、对硝基苯胺以及异丙醇铝为原料,经两步反应合成了一种高效单一组分磷-氮(P-N)协效型阻燃剂——对硝基丙酰苯胺基甲基次膦酸铝[Al(NNPMP)]。采用核磁共振、傅里叶红外光谱等技术表征了目标产物,并通过熔融共混法制备Al(NNPMP)/PA6阻燃复合材料。添加质量分数为20%的Al(NNPMP)可使PA6的极限氧指数由20.8%提高至29.5%,垂直燃烧等级达到UL94 V-0级别。微形量热测试表明Al(NNPMP)对PA6的热释放速率有明显的抑制作用。扫描电子显微镜-X射线能谱(SEM-EDX)分析证实Al(NNPMP)在PA6的热降解过程中兼具气相和凝聚相阻燃机理。     

PBT-b-PEO-b-PBT triblock copolymers: Synthesis,characterization and double-crystalline properties

We demonstrated here a facile method to synthesize novel double crystalline poly(butylene terephthalate)-block-poly(ethylene oxide)-block-poly(butylene terephthalate) (PBT-b-PEO-b-PBT) triblock copolymers by solution ring-opening polymerization (ROP) of cyclic oligo(butylene terephthalate)s (COBTs) using poly(ethylene glycol) (PEG) as macroinitiator and titanium isopropyloxide as catalyst. The structure of copolymers was well characterized by ¹H NMR and GPC. TGA results revealed that the decomposition temperature of PEO in triblock copolymers increased about 30 °C to the same as PBT copolymers, after being end-capped with PBT polymers. These triblock copolymers showed double crystalline properties from PBT and PEO blocks, observed from DSC and WAXD measurements. The melting and crystallization peak temperatures corresponding to PBT blocks increased with PBT content. The crystallization of PBT blocks showed the strong confinement effects on PEO blocks due to covalent linking of PBT blocks with PEO blocks, where the melting and crystallization temperatures and crystallinity corresponding to PEO blocks decreased significantly with increment of PBT content. The confinement effect was also observed by SAXS experiments, where the long distance order between lamella crystals decreases with increasing PBT length. For the triblock copolymer with highest PBT content (PBT₅₄-b-PEO₂₂₇-b-PBT₅₄), this effect shows a 30 °C depression on PEO crystals' melting temperature and 77% on enthalpy, respectively, compared to corresponding PEO homopolymer. The crystal morphology was observed by POM, and amorphous-like spherulites were observed during PBT crystallization.     

聚对苯二甲酸甲二酯的热分解行为及其动力学研究

研究了惰性气氛下聚对苯二甲酸甲二酯(PMT)的非等温热分解行为及其动力学,并与聚对苯二甲酸丁二酯 (PBT)进行了对比。研究发现,PMT的热降解过程包括两个主要失重阶段,其热分解反应不是一级反应。第一阶段的起始分解温度较低是由于产物的分子链末端基中含有Br或Cl能催化聚合物的降解反应;第二阶段为分子链主体的热分解过程,由于分子链中苯环的密度较大,分子链的热稳定性比具有较低苯环密度的PBT要高。而PBT的降解失重过程仅为一个阶段,为一级反应。     

溴化环氧树脂协同三氧化二锑阻燃PBT热分解动力学研究

利用热重分析法研究了聚对苯二甲酸丁二醇酯(PBT)及溴化环氧树脂(BER)协同三氧化二锑(Sb2O3)阻燃PBT在不同升温速率下的热稳定性及热分解动力学;采用Kissinger及Flynn-Wall-Ozawa方法计算出了PBT和阻燃PBT的热分解活化能;利用Coats-Redfern方法确定了PBT和阻燃PBT的热分解动力学机理及其模型,得出了聚合物主降解阶段的非等温动力学方程。结果表明:BER协同Sb2O3阻燃体系的添加提高了PBT的阻燃性能;通过Kissinger和FWO法的分析可知,阻燃PBT在主分解阶段的活化能明显提高;PBT的热分解机理函数为g(α)=1-(1-α)1/3,阻燃PBT的热分解机理函数为g(α)=2[(1-α)-1/2-1],反应级数n=1.5。     

Synthesis of aluminum methylcyclohexylphosphinate and its use as flame retardant for epoxy resin

A novel aluminum phosphinate—aluminum methylcyclohexylphosphinate (Al(MHP))—was synthesized by reacting n‐butyl methylphosphonite with cyclohexene, followed by reacting with anhydrous AlCl₃. The products were characterized with gas chromatography, Fourier transform infrared spectroscopy, hydrogen nuclear magnetic resonance, phosphorus nuclear magnetic resonance, X‐ray fluorescent spectroscopy, and thermogravimetric (TG) analyses. After blending with epoxy resin (EP), flame retardancy was estimated with the use of limited oxygen index (LOI) and UL‐94 test, and thermal stability was investigated using TG analysis. The morphologies and composition of the char obtained after being heated at 300 °C for 20 min followed by 500 °C for 3 min in the muffle furnace were characterized by scanning electron microscopy (SEM) with energy‐dispersive X‐ray (EDX) analysis. Results showed that Al(MHP) is an efficient flame retardant for EP, and Al(MHP)/EP can pass UL‐94V‐0 rating with an LOI of 28.8% by adding 15 wt.% of Al(MHP). TG results showed that the presence of Al(MHP) in EP increases the char yield and depresses the thermal decomposition. SEM‐EDX analysis showed that the char obtained at 300 °C is coherent and consists of P‐rich components; at higher temperature (500 °C), the char becomes tiny and loose and phosphorus element is released into gas. Compared with neat EP, composites have lower water absorption. Copyright © 2012 John Wiley & Sons, Ltd.     

溶液共混法制备PBT/石墨烯复合材料及其性能研究

摘要：采用溶液共混法制备石墨烯（GS）/聚对苯二甲酸丁二醇酯（PBT）复合材料和表面功能化石墨烯（GS-KH550）/聚对苯二甲酸丁二醇酯（PBT）复合材料,并对PBT、GS/PBT、GS-KH550/PBT的性能进行研究。结果表明,石墨烯和表面功能化石墨的加入均使PBT的熔融温度（Tm）和结晶温度(Tc)均略有升高,促进了PBT的结晶,PBT的结晶度和晶粒尺寸略有增加,使结晶更完善,但并未改变PBT结晶的类型;表面功能化石墨烯（GS-KH550）/聚对苯二甲酸丁二醇酯（PBT）复合材料的缺口冲击强度有明显的提高。     

Polymer blends of PBT and PP compatibilized by ethylene-co-glycidyl methacrylate copolymers

The ethylene-co-glycidyl methacrylate (EG) copolymer is an efficient reactive compatibilizer for polymer blends of poly(butylene terephthalate) (PBT) and polypropylene (PP). During melt processing, the epoxy functional group of the EG copolymer can react with the PBT carboxylic acid and/or hydroxyl terminal groups at the interface to form various EG-g-PBT copolymers. These in situ formed grafted copolymers tend to concentrate along the interface to reduce the interfacial tension at the melt and result in finer phase domains. Higher glycidyl methacrylate (GMA) content in the EG copolymer or a higher quantity of the EG compatibilizer in the blend results in a better compatibilized blend in terms of finer phase domains, higher viscosity, and better mechanical properties. The presence of only 50 ppm catalyst (ethyltriphenyl phosphonium bromide) in the EG compatibilized blend further improves the blend compatibility substantially. © 1996 John Wiley & Sons, Inc.     

含酰胺基的次膦酸金属盐阻燃剂在PBT中的应用

比较了β (N 苯基甲酰胺)乙基甲基次膦酸的锌、镁、铝盐\[Zn(CEMP)、Mg(CEMP)和Al(CEMP)\]对聚对苯二甲酸丁二醇酯(PBT)阻燃性能的影响。结果表明,相比于Zn(CEMP)和Mg(CEMP),Al(CEMP)表现出较好的阻燃效果,当其添加量为20 %(质量分数,下同)时,可使PBT的极限氧指数达到39.5 %,垂直燃烧达到UL 94 V 0级;Al(CEMP)能够降低PBT的热分解速率,提高其残炭率;热分解过程中的残留物主要含磷和碳组分,初步推断Al(CEMP)主要通过凝聚相发挥阻燃作用。     

国内聚对苯二甲酸丁二酯纤维的应用领域分析与预测

聚对苯二甲酸丁二酯(PBT)纤维是一种新型的聚酯纤维。介绍了国内PBT纤维的发展状况以及PBT纤维的优良综合性能,指出近年来PBT纤维在弹力牛仔布、毛衫、运动服饰、泳衣等领域用量快速增长。预计未来几年,PBT纤维市场会保持超过30%的年增长率,"十二五"期末,将有15万t左右的需求量。     

PBT/OMMT纳米复合材料的性能研究

采用原位聚合方法制备了聚时苯二甲酸丁二酯(PBT)/有机膨润土(OMMT)纳米复合材料.结果表明,含质量分数3%左右OMMT的PBT/OMMT纳米复合材料的拉伸强度、缺口冲击强度、弯曲强度较纯PBT分别提高16.5%、11.3%和9.9%,热稳定性小幅提高.OMMT与阻燃剂混合使用,可大幅提高材料的阻燃性能,较纯PBT...     

Depolymerization of poly(butylene terephthalate) using high‐temperature and high‐pressure methanol

Poly(butylene terephthalate) (PBT) was depolymerized in excess methanol at high‐temperature (473–523 K) and high‐pressure (4–14 MPa) conditions. Considering the critical point of methanol (512.6 K, 8.09 MPa), the reaction pressure was varied over the range of 6–14 MPa at the reaction temperature of 513 K. As a result, ca. 20 min was required to recover dimethyl terephthalate and 1,4‐butanediol, quantitatively, at any pressure, indicating that the supercritical state of methanol is not a key factor of degradation of PBT and that the effect of pressure is little. On the contrary, when the reaction temperature was varied over the range of 473–523 K at the pressure 12 MPa, the decomposition rate constant of PBT at the reaction temperatures (503–523 K) higher than the melting temperature of PBT (500 K) was much higher than that at 473–483 K. This result indicates that melting of PBT is an important factor for the short‐time depolymerization of PBT. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 3228–3233, 2000