聚磷腈改性沸石咪唑酯骨架材料的制备及其在聚酯阻燃中的应用

为提高聚对苯二甲酸乙二醇酯(PET)的阻燃性能,以六水合硝酸锌和2-甲基咪唑制备沸石咪唑酯骨架材料(ZIF-8),之后用六氯环三磷腈和4,4 -二羟基二苯砜对ZIF-8进行表面修饰合成一种ZIF-8聚环三磷睛-共磺酰基双酰/(PZS)亚微米颗粒,并与PET通过熔融共混制备PET阻燃复合材料。借助热重分析仪、极限氧指数仪、垂直燃烧仪、万能材料试验机以及扫描电镜等对复合材料的热稳定性、阻燃抗熔滴性、力学性能以及阻燃机制进行分析。结果表明:添加6%的ZIF-8/PZS亚微米颗粒使PET的极限氧指数(LOI值)提高到29.2%,并通过UL-94 V-0等级,而复合材料的力学性能没有受到严重影响;ZIF-8/PZS可以在气相和凝聚相中同时发挥效用,从而赋予PET复合材料优异的阻燃性能。     

Structures and flammability properties of polyethylene terephthalate(PET) fibers containing encapsulated carbon materials

In this paper, carbon nanotubes (CNTs) and carbon microspheres (CMSs) have been microencapsulated to obtain microencapsulated carbon nanotubes (MCNTs) and microencapsulated carbon microspheres (MCMSs). Moreover, a series of PET fibers with CNTs/CMSs or MCNTs/MCMSs were prepared by melt spinning. Morphologic structures, mechanical, thermal, and flame retardant properties of MCNTs/MCMSs /PET fibers have been studied by TEM, SEM, electronic tension meter, DSC, TG, limiting oxygen index (LOI), and vertical flammability instruments. The results show that the tensile strength of MCNTs/MCMSs/PET fibers are increased because of better dispersion and compatibility of MCNTs/MCMSs in PET and enhanced orientation degrees of fibers, compared with CNTs/CMSs/PET fibers. Moreover, the highest values of mechanical properties are observed with 0.4 wt% content. Meanwhile, the MCNTs/MCMSs/PET fibers have good thermal stabilities and their fabrics have higher LOI value of 25.3%, reaching B1 class of China standard GB 17591-2006. Overall, this method endowed the MCNTs/MCMSs/PET fibers with the good mechanical and flame-retardant properties.     

磷杂菲基共聚协效阻燃聚酰胺6纤维的制备及其性能

为提高聚酰胺6(PA6)纤维的阻燃性能,以10-(2,5-二羧基苯氧基)-10-氢-9-氧杂-10-磷杂菲-10-氧化物(DOPODP)为共聚阻燃剂,复配二硫化钼(MoS₂)或硫化锌(ZnS),制备DOPODP共聚协效阻燃PA6,经熔融纺丝制备阻燃PA6纤维,并对其结构、性能及阻燃机制进行研究。结果表明:DOPODP经共聚法成功引入PA6,DOPODP可提高PA6的阻燃性能,但其熔融温度、结晶温度等下降;引入协效阻燃剂后,阻燃PA6垂直燃烧(UL94)级别为V-0级,极限氧指数(LOI值)达30%以上;DOPODP对PA6主要表现为气相阻燃作用,DOPODP分解产生含磷自由基可捕获活性自由基,协效阻燃剂可促进PA6成炭;相比PA6纤维,阻燃PA6纤维力学性能下降,而织物的LOI值提高。     

Enhancing the flame retardant of polyethylene terephthalate (PET) fiber via incorporation of multi-walled carbon nanotubes based phosphorylated chitosan

Phosphorylated chitosan (PCS) were first deposited on the multi-walled carbon nanotubes (MWNTs) surface via chemical modification to obtain functionalized MWNTs-based PCS (PCS-MWNTs). Then, a series of PET fibers with MWNTs or PCS-MWNTs were prepared via melt spinning. The microstructure and molecular structure of PCS-MWNTs were characterized by field emission scanning electron microscopy (FESEM) and Fourier transform infrared spectroscopy. The morphological structures, mechanical, thermal, and flame-retardant properties of the PET fibers containing MWNTs or PCS-MWNTs were analyzed by FESEM, therogravimetry, differential scanning calorimetry, cone and electronic tension meter method. The results showed that MWNTs were coated with PCS. Compared to PET fiber, when the content of PCS-MWNTs was 0.9 wt.%, the PCS-MWNTs/PET fibers exhibited an efficient flame-retardant capacity, with the lower heat release rate and total release rate values of 81.03 kW/m² and 39.05 MJ/m², respectively, decreasing by 130.06 kW/m² and 11.87 MJ/m². The thermal stability of PCS-MWNTs/PET fibers strengthened, and the char residue increased from 7.21 to 13.52%. Compared to MWNTs/PET fiber, the crystallization property and tensile strength of PCS-MWNTs/PET fiber improved, because of the good dispersion and strong interface binding force with the PET fiber. Overall, the PCS layer endowed the MWNTs with good dispersion and flame-retardant characteristics.     

Preparation of microencapsulated carbon microspheres coated by magnesium hydroxide/polyethylene terephthalate flame–retardant functional fibers and its flame retardant properties

In order to improve the compatibility between the flame retardants of carbon microspheres coated by magnesium hydroxide (MH@CMSs) and the PET matrix and improve the spinnability of the masterbatch, MH@CMSs have been microencapsulated by PET to obtain microencapsulated carbon microspheres coated by magnesium hydroxide flame retardants – MMH@CMSs.Morphologies and structures of MMH@CMSs have been studied by scanning electron microscope (SEM), transmission electron microscopy (TEM), and FTIR, which showed that an organic shell layer of PET as capsule wall was coated on the surface of MH@CMSs. A series of MMH@CMSs/PET fibers with different MMH@CMSs contents were successfully prepared through the melt-spinning method. The morphology and structure of MMH@CMSs/PET fibers were characterized by SEM and FTIR. The flame retardancy of MMH@CMSs/PET fibers was determined via limiting oxygen index (LOI) test and cone calorimeter. Results showed that the MMH@CMSs/PET fibers possessed optimum flame retardancy when the MMH@CMSs content is 0.6 wt.%, at which the LOI reached a maximum of 25.8, and the pk-HRR, total heat release, and total smoke release were reduced by 27.4, 20, and 13.6%, compared with pure PET fibers, respectively. Moreover, the flame-retardant mechanism was studied by thermogravimetric analysis, thermogravimetric analysis-infrared spectrometry, and the SEM of the residue char, which disclosed that MMH@CMSs enhanced the thermal stability of PET fibers, and promoted PET fibers to form a dense and continuous protective char layer that effectively blocked heat transfer and combustible gas release.     

涤纶耐久阻燃剂TEX-3的合成及应用

采用两步法合成涤纶耐久阻燃剂TEX-3,并将其用于涤纶织物的阻燃整理。分析阻燃剂用量、工作液pH值、焙烘温度和焙烘时间等对阻燃效果的影响。结果表明:当阻燃剂用量为150 g/L,工作液pH值为6时,涤纶织物具有良好的阻燃效果(达到国家标准B1级)和优异的耐水洗性能(可耐50次以上水洗),且不影响织物的色泽和手感。     

新型含锌离子阻燃共聚酯的合成及其性能表征

利用新型含锌离子阻燃剂2-羧乙基苯基次膦酸乙二醇酯锌盐（CEPPA-Zn）合成阻燃聚酯,由于含金属离子的阻燃剂加入,聚合反应过程中,缩聚反应的时间缩短,缩聚反应的温度降低,利用差示扫描量热（DSC）测试阻燃聚酯的热性能,发现阻燃聚酯的玻璃化转变温度、结晶化温度及熔点均提高,热重测试（TGA）显示聚酯的热稳定性能提高,而且由于Zn离子的存在使得残炭量增加,极限氧指数（LOI）测试显示,当含Zn离子的阻燃剂质量含量达到7 %时,阻燃聚酯的LOI值达到36.7。     

聚酯/棕榈基多孔碳纤维杂化膜的结晶和力学性能

为提高静电纺丝聚酯纤维膜的力学性能,根据多孔碳纤维的高强度和高模量特性,在聚对苯二甲酸乙二醇酯(PET)溶液中添加自制棕榈基多孔碳纤维(PACF),制得PET/PACF杂化纤维膜,并研究了PACF含量对杂化纤维膜形貌、结晶行为和力学性能的影响。结果表明:添加PACF后,纤维牵伸效果明显改善,类竹节状纤维消失,纤维间黏连减少,直径更均匀;随PACF含量的增加,杂化纤维膜的玻璃化温度较纯PET提高约10℃,结晶度约提高6.7%,证明PACF的加入改善了电场对射流的牵伸效果,使得取向度提高;结晶温度提高约13.7℃,说明PACF异相成核作用促进了纤维膜的结晶。随取向度的提高,当PACF含量为2.5%时,纤维膜断裂强度达4.22 MPa,较纯PET静电纺膜提高了366.3%。     

阻燃涤纶织物和毛织物及其混纺试样的性能研究

涤纶燃烧因出现熔滴现象而甚少被用于阻燃防护服,文章采用自制阻燃剂对涤纶和毛织物进行阻燃处理,阻燃效果较好,并探讨了毛/涤混纺织物的阻燃性及断裂强度。结果表明:自制的氮磷复合阻燃剂对涤纶的阻燃级别可达B2阻燃级别,极限氧指数可达28.4%;对毛织物的阻燃效果可达到B1阻燃级别,极限氧指数可达34.7%;阻燃涤纶织物的断裂强力明显高于阻燃毛织物;阻燃毛/涤混纺织物极限氧指数均能达到难燃材料级别,当涤纶含量高于50%时,混纺织物断裂强力高于芳纶等织物。     

环三磷腈和三嗪衍生物协同阻燃对聚酯性能的影响

为提高聚对苯二甲酸乙二醇酯（PET） 的阻燃性能,合成了阻燃剂（4?烯丙氧羰基苯氧基） 环三磷腈（HACP）和三（4?烯丙氧羰基苯氧基）?1,3,5?三嗪（TATZ）,并与PET通过熔融共混制备了PET/HACP/TATZ复合材料。采用极限氧指数仪、垂直燃烧仪、微型量热仪、热失重分析测试仪、差示扫描量热仪和拉伸试验机等测试仪器对复合材料的阻燃性能、热稳定性能、力学性能和成炭性能进行测试与分析。结果表明：HACP和TATZ的协同阻燃性不仅提高了PET材料的阻燃效率,而且降低了对基材PET力学性能的负面影响,复合材料的极限氧指数值达到32.4%,垂直燃烧性能达到V-0 级,热释放速率较纯PET下降了30.9%。     

溶胶-凝胶法改性阻燃粘胶纤维的制备及其性能

为提升粘胶/二硫代焦磷酸酯(VF/DDPS)纤维的阻燃性能,通过溶胶-凝胶法,采用正硅酸四乙酯(TEOS)对VF/DDPS纤维表面进行阻燃改性,得到阻燃粘胶纤维(VF/DDPS/TEOS)。借助扫描电子显微镜、X射线光电子能谱仪、热重分析仪、锥形量热仪、微型量热仪、单纤强力仪等对改性纤维的结构和性能进行分析。结果表明:改性后VF/DDPS/TEOS纤维的阻燃性能提高,其在750 ℃时的残炭量从3.23%增加到7.93%,引燃时间从4 s延长至16 s,热释放速率峰值和总热释放量分别下降了19.3%和16.0%,极限氧指数从28.2%升高至29.3%;VF/DDPS/TEOS纤维表面形成了致密的氧化硅保护膜,二氧化硅在纤维燃烧过程中显著增强了纤维表面炭层的热质阻隔作用;阻燃整理后纤维的断裂强度、断裂伸长率及吸湿性能均有所降低。     

共聚型磷系阻燃聚酯聚合反应动力学及其性能

为探究共聚型磷系阻燃聚酯的反应规律及其影响因素,以2-羧乙基苯基次磷酸(CEPPA)为阻燃剂制备不同磷含量的阻燃共聚酯,建立了聚酯反应动力学模型并分析其影响因素。借助红外光谱仪、差示扫描量热仪、热失重测试仪、极限氧指数仪、锥形量热仪对聚酯的结构及性能进行测试与分析。结果表明:随着CEPPA质量分数的增加,缩聚反应活化能逐渐增大,最高增加至106.83 kJ/mol;聚合物的玻璃化转变温度、熔点均呈下降趋势;阻燃剂中磷元素以共价键形式共聚到PET分子链中,抑制了分子链的结晶;当磷含量为1%时,阻燃共聚酯的极限氧指数达到31%,引燃时间明显延长,最大热释放速率降低了24%,阻燃效果显著。     

导热结构对聚对苯二甲酸乙二醇酯非等温结晶行为的影响

针对聚对苯二甲酸乙二醇酯(PET)中的导热结构会影响纤维材料加工成形、纺织品加工过程以及纤维性能的问题,通过熔融共混法分别制备得到含有碳纳米管、石墨烯的PET复合材料,借助差示扫描量热仪对PET的非等温结晶动力学进行研究.结果表明:掺杂的碳纳米管、石墨烯在PET中起成核剂作用,其质量分数的增加对PET的结晶温度、结晶速...     

高效无卤阻燃棉织物的制备及其结构与性能

为了提高棉织物的阻燃效果与耐久性,以磷酸二氢铵(NH₄H₂PO₄)和尿素为原料,经磷酸化改性制备无卤耐久阻燃棉织物。通过研究原料物质的量比、反应时间、反应温度对阻燃棉织物接枝率与白度的影响,确定了最佳工艺条件:脱水葡萄糖单元(AGU)、NH₄H₂PO₄与尿素的量比为1∶2.5∶15,反应温度为130 ℃,反应时间为90 min。测试了阻燃棉织物的阻燃性能与耐水洗性能及力学性能等。结果表明:阻燃棉织物的极限氧指数(LOI)由原棉织物的18%提高到50.9%,达到不燃级别;经800 ℃热分解,残炭量上升到40.0%左右,具有优异的热稳定性;经30次标准洗涤测试后,LOI值仍可达到28.5%,表现出较好的耐洗涤性;该法实现了棉织物的高效耐久阻燃。     

分子内阻燃PET纤维的结构性能

 以反应性无卤阻燃剂CEPPA为第三单体,通过共聚改性制备了分子内阻燃PET树脂,并经熔融纺丝纺制阻燃PET纤维。利用元素分析和核磁共振分析了阻燃PET树脂中的磷含量,结果表明大部分CEPPA聚合到PET分子链中。对阻燃PET纤维结晶性能、染色行为、力学性能及燃烧性能也进行了研究,结果表明阻燃PET纤维的结晶度随着磷含量的增加而降低,这导致了纤维染色性能的提高。阻燃PET纤维采用分散染料在常压沸染条件下上染率可达90%以上。此外纤维具有优异的阻燃性能,极限氧指数(LOI)值约为35%,并且抗熔滴性能得到了改善.     

皮芯结构微纳米纤维复合纱线的制备及其性能

为探究纺丝液质量分数对皮芯结构微纳米纤维复合纱线结构与性能的影响,利用双针头水浴静电纺丝法连续制备了以聚对苯二甲酸乙二醇酯(PET)长丝为芯、外包聚酰胺6(PA6)的皮芯结构微纳米纤维复合纱线,通过扫描电子显微镜、差示扫描量热仪和万能材料试验机对其形貌结构、热性能和力学性能等进行测试与表征。结果表明:不同PA6纺丝液质量分数制备的微纳米纤维复合纱线均具有良好的皮芯结构;当PA6纺丝液质量分数从10%提高到20%时,纳米纤维复合纱线的平均直径从(61.99±13.08) nm增加到(150.22±21.53) nm,结晶度由16.28%提高至20.63%;当PA6纺丝液质量分数为20%时复合纱线的结晶度达到了常规PA6纤维的结晶范围,增加纺丝液质量分数一定程度上可提高复合纱线的力学性能。     

阻燃聚酯的研制及其结构和性能

首先用磷系阻燃剂2-羧乙基苯基次膦酸(CEPPA)与乙二醇(EG)合成2-羧乙基苯基次膦酸乙二酯(CEPPA-EG),再加入到对苯二甲酸乙二醇酯的缩聚体系中合成含磷阻燃聚酯。借助IR、SEM、DSC、TGA、LOI等测试方法对其结构以及热性能、成炭情况、燃烧性能进行研究。结果表明,阻燃剂以共聚的方式结合到聚酯大分子链上,并且随着阻燃剂添加量的增多,阻燃聚酯的Tg、Tm下降,而Tc则呈上升趋势,同时阻燃聚酯高温处理后成炭情况良好,炭粒均匀,相对未添加阻燃剂的纯聚酯,极限氧指数(LOI)有很大程度提高,阻燃效果得到较好的改善。     

氧化石墨烯协同二硫代焦磷酸酯阻燃粘胶纤维的制备及其性能

为提高粘胶/二硫代焦磷酸酯(VF/DDPS)纤维的阻燃及力学性能,以氧化石墨烯(GO)作为协同阻燃剂添加到VF/DDPS基体中,通过湿法纺丝工艺制得VF/DDPS/GO复合纤维。借助热重分析仪、极限氧指数仪、微型量热仪和单丝强力仪研究GO对VF/DDPS复合纤维热性能、阻燃性能和力学性能的影响。结果表明:与VF/DDPS纤维相比,当GO质量分数为2.0%时,VF/DDPS/GO复合纤维的残炭量从20.0%增加到29.7%,极限氧指数从27.8%升高到29.1%,热释放速率峰值从141.5 W/g降低到99.4 W/g,干、湿断裂强度分别从2.08、0.96 cN/dtex增加到2.20、1.17 cN/dtex;GO的添加可提高VF/DDPS炭渣的石墨化程度和致密度,增强炭渣的热质阻隔作用。     

三聚氰胺氰尿酸盐对阻燃PET的影响

使用三聚氰胺氰尿酸盐（MCA）分别与聚对苯二甲酸乙二醇酯（PET）及含磷共聚酯（CP-PET）合成PET-MCA复合物和CP-PET-MCA复合物。借助TGA、LOI、垂直燃烧仪（UL-94）、锥形量热仪、SEM和EDS等测试方法对其热稳定性、阻燃性能和成炭情况等进行研究,并初步分析了其作用机理。研究结果表明,PET-MCA复合物和CP-PET-MCA复合物的初始热分解温度有所降低,燃烧后残炭量提高,极限氧指数（LOI）有所提高,并且CP-PET-MCA复合物在UL-94测试中达到V-0级标准,成炭情况良好,MCA与2-羧乙基苯基次膦酸（CPEEA）复合使用对PET具有一定的氮-磷协效阻燃作用。     

阻燃超疏水涤/棉混纺织物的制备及其性能

为实现涤/棉混纺织物同时具有阻燃和超疏水功能,以生物基的壳聚糖(CS)和植酸(PA),采用层层自组装方法在涤/棉混纺织物上构建阻燃涂层,并采用含氟的超疏水整理剂处理涤/棉混纺织物。测定了织物的阻燃和超疏水性能及热稳定性;并观察了阻燃处理前后织物及其垂直燃烧后残炭的外观形貌。结果表明:经CS/PA阻燃处理后织物的极限氧指数(LOI值)可以达到30.6%,经超疏水处理会使其LOI值有所降低,但静态接触角可以达到150°以上,可获得阻燃超疏水功能,并具有一定的水洗耐久性;织物经阻燃超疏水处理,有利于提高其高温稳定性和促进其成炭,CS/PA阻燃涂层可发挥膨胀阻燃作用。