酪素基rGO复合乳液的制备及其阻燃性能

为制备具有增强阻燃效果的皮革涂饰材料,首先以天然石墨为原料,采用Hummers法制备氧化石墨烯(GO),并采用NaBH4对其进行还原得到还原氧化石墨烯(rGO).通过FTIR,XRD和TEM等对其进行表征.结果表明,成功制备了rGO纳米材料.随后,采用物理共混法将rGO引入天然蛋白质酪素体系,制备酪素基rGO复合乳液并将其应用于皮革涂饰,对涂饰后革样的阻燃性能、力学性能和耐干湿擦性能进行测试.结果表明,当rGO的含量为酪素体系溶质质量的0.5％时,与未含rGO的酪素体系相比,涂饰后革样的燃烧速率下降47.2％,极限氧指数(LOI)由24.2％增加至26.3％,热释放速率(HRR)下降53.1％,总热释放速率(THR)也有所降低.rGO的引入对涂饰后革样的力学性能和耐干湿擦性能影响不大.     

改性酪素——明胶皮革涂饰剂的研究

以食用明胶及酪素为接枝混合母体,与丙烯酸丁酯、甲基丙烯酸甲酯、丙烯腈和苯乙烯等4种混和单体以K_2S_2O_8为引发剂进行接枝共聚,合成改性酪素—明胶皮革涂饰剂,建立了相应的标准及理化指标的检测方法。对所研究的改性酪素—明胶涂饰剂进行了理化指标检验及涂饰应用结果的感观评价。     

环氧有机硅改性酪素皮革涂饰剂的合成与应用探讨

本文提出了用环氧有机硅氧烷与酪素结构中的氨基(-NH2)、羧基(-COOH)反应，提高改性酪素的耐水、耐曲挠、耐摩擦等综合性能的新方法，该改性产品在多种鞋面革中进行了涂饰实验。     

新型聚氨酯乳液皮革涂饰剂的研究

本文详细阐述了新型聚氨酯乳液皮革涂饰剂的研究,新型聚氨酯乳液皮革涂饰剂是由2.2-双羟甲基丙酸,聚丁二醇与甲苯二异氰酸酯进行加聚反应,所得产物经皂化乳化而得到的。     

无皂乳液聚合法制备改性酪素乳液的研究进展

介绍了酪素的结构、性质及改性方法,着重论述了无皂乳液聚合法在酪素改性中的研究进展,并就该方面研究前景提出了展望。     

层层组装法制备抗菌-阻燃型生物质基复合涂层

为了赋予皮革更多功能，提高其使用价值，以己内酰胺（CPL）改性酪素（CA）（记为CPL-CA）、壳聚糖（CS）及植酸（PA）生物质材料为原料，引入无机组分氢氧化镁（MH），采用层层组装（LBL）技术在皮革上构筑具有阻燃及抗菌性能的涂层。对构筑涂层的革样进行了FTIR、SEM及EDS表征，并对其进行了抗菌性能及阻燃性能测试。结果表明，CS的引入明显改善了涂层的抗菌性，当CS溶液质量分数为1.0%时，涂层对金黄色葡萄球菌有良好的抑菌效果。固定CPL-CA溶液，在CS溶液质量分数为1.0%、浸渍层数3层的条件下，由质量分数为1.5%MH溶液和体积分数为0.4%PA溶液制得的复合溶液构筑涂层的革样的热释放速率（HRR）峰值和热释放总量（THR）分别比未浸渍革样降低了42.31%和40.97%，表明成功制备了具有良好抗菌及阻燃性能的生物质基复合涂层。     

皮革涂饰用丙烯酸树脂乳液的合成技术

介绍皮革涂饰用丙烯酸树脂乳液合成技术的发展变化,涉及制备丙烯酸树脂乳液的主要方法、技术要点及制品性能。     

聚丙烯酸酯/纳米二氧化硅Pickering复合乳液的制备及性能

以改性纳米SiO_2粉体作为稳定剂稳定丙烯酸酯类单体,采用Pickering乳液聚合法制备聚丙烯酸酯/纳米SiO_2复合乳液。以单体转化率和乳液凝胶率为指标,对乳液聚合条件进行了优化,通过光学显微镜观察了乳状液的形貌,用动态激光散射(DLS)和透射电镜(TEM)、傅里叶红外光谱仪(FTIR)和扫描电镜(SEM)对乳液及其成膜进行了表征。结果表明,SiO_2与乙烯基三乙氧基硅烷(A-151)的质量比为5∶1、甲基丙烯酸甲酯与丙烯酸丁酯的质量比为1∶4时,乳液性能最优。DLS和TEM结果表明,复合乳液的粒径在790 nm左右;FTIR结果表明,复合乳液中有纳米SiO_2的存在;SEM结果表明,纳米SiO_2分散在复合乳液成膜中。将复合乳液应用于皮革涂饰中,应用结果表明,与聚丙烯酸酯乳液涂饰革样相比,Pickering乳液聚合法制备的复合乳液涂饰后革样的透气性、透水气性及耐干湿擦性能都有所提升。     

PAA/ATP纳米复合材料的制备及其皮革阻燃性

采用γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH-570)改性纳米凹凸棒土(ATP),制得表面含双键的凹凸棒土(O-ATP),进而与丙烯酸发生共聚反应,制备了聚丙烯酸/凹凸棒土(PAA/ATP)纳米复合材料,采用FTIR、TEM、TGA对其结构进行分析,结果表明:成功制备了PAA/ATP纳米复合材料,ATP均匀地分散于PAA/ATP纳米复合材料中。当ATP用量为1%时(即ATP质量占丙烯酸质量的百分数,下同),PAA/ATP纳米复合材料的外观稳定性和热稳定性均最好。将PAA/ATP纳米复合材料应用于绵羊蓝湿革的复鞣工序中,结果表明:ATP的引入有利于提高革样的阻燃性能、增厚性能。当ATP用量为1%时,PAA/ATP纳米复合材料的极限氧指数提升至16.4%,燃烧速率降低至0.045 mm/s。     

螺环磷酰咪唑酯对棉布阻燃性能和力学性能的影响

采用自制膨胀型阻燃剂螺环磷酰咪唑酯通过浸轧方法对纯棉布进行阻燃整理,考察了阻燃剂、助剂的比例以及焙烘温度对整理棉布的极限氧指数(LOI)的影响。从中选取LOI值超过28%的阻燃棉布共8组,进行垂直燃烧和拉伸性能测试,进一步确定较优的阻燃整理工艺。结果发现,较优的阻燃整理条件为:整理液中w(阻燃剂)=30%,w(催化剂)=1.5%,w(交联剂)=1%,焙烘温度为150℃时,阻燃棉布的LOI值达到33.96%,阻燃等级达到B1级,拉伸性能测得断裂强力为312.50 N;对该条件下阻燃整理的棉布进行热重分析,结果表明,棉布的初始热分解温度提前了100℃,最大热分解速度降低,600℃下的残留量由几乎烧尽提高到30%。说明螺环磷酰咪唑酯阻燃体系对棉布具有很好的阻燃作用。     

模板法合成锡酸钴及其对PVC的阻燃应用

以活性炭为模板、五水四氯化锡和六水硝酸钴为原料,制备纯相的多孔锡酸钴（CoSnO3）阻燃剂,通过X射线衍射（XRD）和扫描电镜（SEM）对其结构、形貌进行表征,并将其应用于PVC的阻燃研究中。当CoSnO3的添加量为15份时,其极限氧指数（LOI）达到35.6％、烟密度等级（SDR）为75.2％、断裂伸长率为168.32%、拉伸强度为 22.50 MPa。通过热重分析（TGA）对阻燃前后PVC的热降解行为进行了初步探讨,研究发现： 经CoSnO3阻燃处理后,PVC样品的初始降解温度降低,高温时的剩炭量增加,表明CoSnO3对PVC材料具有较好的阻燃消烟性能。     

A low-density polyethylene composite with phosphorus-nitrogen based flame retardant and multi-walled carbon nanotubes for enhanced electrical conductivity and acceptable flame retardancy

Design and exploitation of flame retardant polymers with high electrical conductivity are desired for polymer applications in electronics. Herein, a novel phosphorus-nitrogen intumescent flame retardant was synthesized from pentaerythritol octahydrogen tetraphosphate, phenylphosphonyl dichloride, and aniline. Low-density polyethylene was combined with the flame retardant and multi-walled carbon nanotubes to form a nanocomposite material via a ball-milling and hot-pressing method. The electrical conductivity, mechanical properties, thermal performance, and flame retardancy of the composites were investigated using a four-point probe instrument, universal tensile machine, thermogravimetric analysis, and cone calorimeter tests, respectively. It was found that the addition of multi-walled carbon nanotubes can significantly improve the electrical conductivity and mechanical properties of the low-density polyethylene composites. Furthermore, the combination of multi-walled carbon nanotubes and phosphorus–nitrogen flame retardant remarkably enhances the flame retardancy of matrixes with an observed decrease of the peak heat release rate and total heat release of 49.8% and 51.9%, respectively. This study provides a new and effective methodology to substantially enhance the electrical conductivity and flame retardancy of polymers with an attractive prospect for polymer applications in electrical equipment.     

新型含磷阻燃剂的制备及性能

以双三羟甲基丙烷为原料合成一种新型含磷阻燃剂,该阻燃剂分子量较大,具有稳定的环状结构,热稳定性高于常用阻燃剂,阻燃效果好。探讨了原料配比、反应温度、反应时间对产率的影响,考察了目标产物的热稳定性能及其对不同织物的阻燃效果,用傅里叶变换红外光谱仪表征了中间体及目标产物的结构。结果表明,当原料配比为1∶3时,磷化温度为50℃,磷化时间5h,胺化温度为75℃时,反应效果较好,收率可达90%以上。目标产物对于锦纶的阻燃效果比较明显,对涤纶、棉有一定的阻燃效果,对于混纺、腈纶阻燃效果不明显。     

Butyltriphenylphosphine-based chelate borates influenced on flame retardancy of polystyrene composite containing self-expanded intumescent flame retardants

The polystyrene (PS) composite containing self-expanded intumescent flame retardant (polyphosphate ammonium and expandable graphite) was blended with three butyltriphenylphosphine-based chelate borates, respectively, to evaluate their effect on flame retardancy. The chemical structure of as-prepared three chelate borates was confirmed by nuclear magnetic resonance (NMR) and Fourier transform infrared spectrum (FTIR). The flame retardancy of various PS composites was evaluated by vertical burning test (UL-94), limited oxygen index (LOI), and cone calorimeter (CC). Flammability and combustion results suggested that one of chelate borates, named [BTP][BMB], made PS composite (PS4) obtain V-0 rating, 27.0 ± 0.3% LOI value, and reduction on heat release and smoke production with 17 wt% total flame retardants loading. The combustion residue was analyzed by scanning electron microscope and FTIR, and the pyrolysis gaseous products were investigated by TG-FTIR technique. Besides, complex viscosity of PS composites composed of various chelate borates from a rheology instrument indicated that the improvements of flame retardancy of PS composites depended on the temperature of construction of crosslinked network by expandable graphite, which the chelate borates showed distinctive influence. Accordingly, the flame-retarding mechanism about fast response to flame has been proposed.     

Synergistic effects of aluminium hypophosphite on the flame retardancy and thermal degradation behaviours of a novel intumescent flame retardant thermoplastic vulcanisate composite

ABSTRACT

The synergistic effects of aluminum hypophosphite (AHP) on the flame retardancy, thermal degradation behaviors of a novel intumescent flame retardant thermoplastic vulcanizate (TPV/IFR) composite were investigated. The results showed that the combination of AHP with IFR showed evident synergistic effects on the increase in the LOI value and reduction of the combustion parameters for the TPV/IFR/AHP composites at the optimum weight ratio of IFR/AHP (6/1) as evidenced by LOI, UL-94 and CCT. The TGA data revealed that AHP could change the degradation behavior of TPV/IFR composites and enhance the thermal stability of the TPV/IFR composites at high temperature. The results of FTIR, EDXS, LRS and SEM demonstrated that TPV/IFR/AHP composites could form more continuous, dense and stable char layer on the materials surface, and consequently improving the flame retardancy. Based on these results, the possible condensed flame retardant mechanism of TPV/IFR/AHP composites was concluded in detail.     

Preparation of novel biomass humate flame retardants and their flame retardancy in epoxy resin

Humic acid (HA), a biomass material with plentiful oxygen-containing functional groups, showed huge potential to be considered as a promising charring agent in flame retardancy. In this study, this HA was modified with four different metal ions like Fe²⁺, Mn²⁺, Al³⁺, and Cu²⁺ and finally, introduced into the epoxy resin (EP) to enhance the flame retardancy of the EP and the dispersion of these flame retardants into the EP matrix. When 10 wt% of HA-Fe and HA-Mn were incorporated into EP matrix, the limiting oxygen index (LOI) was increased from 21.2% for EP to 26.6 and 25.3% for the EP composites and the peak heat release rate (pHRR) was reduced by 36 and 35.5%, respectively. Such a significant improvement in flame retardancy was attributed to the catalytic charring of HA in the presence of metal ions, which ultimately increased the residual char formation and produced compact char layers during the combustion process to retard the transfer of heat and combustible gases between the EP composites and the flame zone. Finally, this kind of application provided a feasible way for the development of an environmentally friendly flame retardant with high efficiency, which improved the fire safety of EP matrix.     

Synthesis of a phenylene phenyl phosphine oligomer and its flame retardancy for polycarbonate

A novel flame retardant, phenylene phenyl phosphine oligomer (PPPO) was synthesized and its chemical structure was characterized using Fourier transform infrared spectroscopy, ¹H, ¹³C, ³¹P nuclear magnetic resonance spectroscopy and mass spectrometer. PPPO was used to impart flame retardancy to polycarbonate (PC). Combustion behaviors and thermal degradation properties of PC/PPPO system were assayed by limiting oxygen index (LOI), vertical burning test (UL‐94), cone calorimeter test, and thermogravimetric analysis. PC/6 wt % PPPO passed UL‐94 V‐0 rating with 3.0 mm samples and the LOI value was 34.1%, and PC/8 wt % PPPO also passed UL‐94 V‐0 rating with 1.6 mm samples and the LOI value was 36.3%. Scanning electron microscopy reveals that the char properties had crucial effects on the flame retardancy of PC. Mechanical properties and water resistance of PC/PPPO system were also measured. After water resistance test, PC/6 wt % PPPO with 3.0 mm samples and PC/8 wt % PPPO with 1.6 mm samples kept V‐0 rating and mass loss was only 0.2%. The results revealed that PPPO was an efficient flame retardant for PC. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Grafting multi-elements hybrid polymer brushes on graphene oxide for epoxy composite with excellent flame retardancy

In this paper, a silicon-oxygen coupling agent (MPS) with a double bond is hydrolyzed with graphene oxide (GO) to obtain MPS-GO. The polymerization of MPS-GO with the phosphorus-containing monomer (HEPO) is initiated with 2,2′-Azobis(2-methylpropionitrile) (AIBN) to obtain multi-elements hybrid polymer brushes grafting graphene oxide (HM-GO). As a flame retardant, different amounts of HM-GO are added to obtain EP composites. In this system, the properties of composite flame retardant obviously increase with the increasing of HM-GO. The limiting oxygen index (LOI) value of composites with 4 wt% addition of HM-GO is 31.0%, while the LOI value of EP-0 is only 23.9%. And the peak heat release rate (PHRR) value is reduced from 515.8 W g⁻¹ of pure epoxy resin to 376.9 W g⁻¹. In addition, with the increase of HM-GO addition, the T_g value, flexural strength and flexural modulus of EP composites are improved. Through calculation, it is proved that the rising of T_g was due to the increase of crosslink density of the system. The flame retardant performance and mechanical properties of the composite materials are steadily improved, indicating that such flame retardants are dispersed well in the epoxy resin. HM-GO is an efficient macromolecular modified graphene oxide halogen-free flame retardant, which can improve both flame retardant properties and mechanical properties.     

反应型阻燃剂DOPO-马来酸的合成及对醇酸树脂的阻燃研究

采用9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)和马来酸(MA)合成了反应型阻燃剂DOPO-MA,并将其引入到醇酸树脂分子链中,制备了不同含磷量的阻燃醇酸树脂,并表征了其结构,研究了燃烧和热分解性能。结果表明:随含磷量增加,醇酸树脂的残炭率逐渐提高,热释放速率峰值(PHRR)与总热释放量(THR)逐渐降低,辐射功率为50 k W/m2时,w(P)为2.5%的阻燃醇酸树脂的残炭率达12.96%,PHRR和THR比改性前分别降低36.9%,44.3%,且w(P)大于2.0%时醇酸树脂的热稳定性有所提高。