GMA改性水性光固化不饱和聚酯乳液的合成

以三羟甲基丙烷单烯丙基醚(TMPME)、新戊二醇(NPG)、二羟甲基丙酸(DMPA)、己二酸(AD)为主要原料进行聚合得到UV固化不饱和聚酯预聚体,然后用甲基丙烯酸缩水甘油酯(GMA)进行接枝改性,经N,N-二甲基乙醇胺(DMEA)中和,以去离子水分散后制得一种稳定的且具有良好光固化活性的水性光固化不饱和聚酯乳液。研究了DMPA、GMA、光引发剂用量以及中和度、接枝温度及工艺对乳液和涂膜性能的影响。结果表明:当DMPA为24%,GMA为15%,中和度为80%,光引发剂为固含的4%时,水性光固化不饱和聚酯乳液的稳定性好,涂膜的综合性能较好。     

氧化铋对环状膦酸酯阻燃棉织物的协效阻燃抑烟作用

通过阻燃性能测试、热重分析、锥形量热分析等研究手段,考察了氧化铋对环状膦酸酯阻燃棉织物的阻燃抑烟协效作用。结果发现,在阻燃整理剂中添加0.4 g/L的氧化铋,可以使阻燃棉布的极限氧指数从43%提高到52%;损毁炭长缩短到5 cm,垂直燃烧达到B1级;而对断裂强度影响不大。热重分析表明,氧化铋的加入进一步降低了阻燃棉织物的初始分解温度和最大热解速率,500℃时的成炭量有所增加;扫描电镜显示,添加氧化铋后,棉织物燃烧成炭更致密;氧化铋具有明显的抗燃烧变形能力;锥形量热测试表明,氧化铋的添加不仅降低了阻燃棉织物的总热释放速率,而且使阻燃棉织物的总烟释放量降低了60%。     

GMA/St双组分单体熔融接枝聚丙烯的研究

分别以甲基丙烯酸缩水甘油酯（GMA）和马来酸酐（MAH）为接枝单体，苯乙烯（St）为接枝共单体，过氧化二异丙苯（DCP）为引发剂对聚丙烯（PP）进行熔融接枝，研究了接枝单体的种类、组分配比等因素对PP的接枝率和熔体流动速率等的影响，并研究了接枝PP的力学性能和耐热变形性能。实验结果表明：作为接枝单体，GMA比MAH更具有优越性；双组分单体熔融接枝PP的接枝率和性能优于单组分单体熔融接枝；接枝PP的结晶参数受其接枝率的影响；当PP／GMA／St／DCP=100／6／3／0、3时，PP—g^-（GMA—CO—St）的接枝率最高，力学性能和耐热变形性能最好。     

聚磷酸酯膨胀阻燃剂复配有机蒙脱土阻燃改性环氧树脂

以间苯二胺为固化剂,聚苯氧基磷酸210氢9氧杂磷杂菲对苯二酚酯（POPP）、聚磷酸铵（APP）为阻燃剂, 复配质量分数为1 %有机蒙脱土（OMMT）为膨胀阻燃体系,对环氧树脂（EP）进行阻燃改性。通过极限氧指数测定仪、垂直燃烧测定仪同步热分析仪、锥形量热等研究改性EP的阻燃性能、热性能和力学性能。结果表明,当膨胀阻燃体系（2.5 %POPP/APP+1 %OMMT）添加量为3.5 %时,改性EP可达UL 94 V-0级,同时LOI为25.2 %;当膨胀阻燃体系添加量为11 %时,改性EP的LOI值进一步升高到31.7 %;阻燃剂的加入,使EP的初始分解温度略有降低,但残炭量明显增加;POPP/APP/OMMT的加入很大程度上降低了EP的热释放速率、烟释放量和平均热释放速率。     

阻燃改性苎麻增强环氧树脂复合材料制备及性能研究

采用紫外光接枝的方法,将甲基丙烯酸缩水甘油酯(GMA)接枝到苎麻织物上,再胺化、磷酸化,对苎麻织物进行阻燃改性,并利用手糊成型的方法制备了阻燃改性苎麻增强环氧树脂(EP)复合材料。用拉伸试验机和氧指数仪等研究了复合材料的力学性能和阻燃性能,用扫描电子显微镜观察了复合材料的拉伸断面形貌和燃烧残炭,并讨论了不同GMA接枝率对复合材料力学性能和阻燃性能的影响。结果表明,阻燃改性的苎麻织物与EP之间的粘结效果明显改善,提高了复合材料的力学性能和阻燃性能,接枝45%GMA的苎麻胺化、磷酸化后与EP复合,可使复合材料的极限氧指数达到25.6%。     

反应挤出法制备POE—g-（GMA—co—St）的研究

以甲基丙烯酸缩水甘油酯（GMA）为接枝单体,苯乙烯（St）为接枝共单体,在双螺杆挤出机上对乙烯-辛烯共聚物（POE）进行熔融接枝,制备了POE—g-（GMA—co—St）。研究了引发剂用量、单体用量、共单体用量和抑交联剂亚磷酸三苯酯等对POE接枝物接枝率和熔体流动速率的影响,利用红外光谱对接枝物进行了表征。研究袭明,St的加入能有效提高GMA的接枝率,亚磷酸三苯酯有效抑制了POE的交联。最佳配方为：过氧化二异丙苯（DCP）为0．15份,GMA为3份,St为3份,亚磷酸三苯酯为1份。     

溶液法制备EPDM-g-GMA／CaCO3复合材料及表征

采用溶液法,以甲基丙烯酸缩水甘油酯（GMA）为接枝单体,过氧化苯甲酰（BPO）为引发剂,二甲苯为溶剂,与三元乙丙橡胶（EPDM）进行了接枝反应,在此基础上加入补强剂CaCO3,制备了EPDM—g—GMA／CaCO3复合材料。分别探讨了BPO与GMA用量对接枝率的影响以及CaCO3用量对拉伸强度的影响,并相应对上述复合材料进行红外分析、热重分析及相形态表征。     

偶联剂表面改性对膨胀阻燃聚丙烯性能的影响

采用硅烷偶联剂、钛酸酯偶联剂、铝钛、铝硅复合偶联剂对无卤膨胀型阻燃剂（IFR）进行表面改性,对比了表面改性前后IFR堆积密度和休止角的变化,研究了表面改性对IFR阻燃聚丙烯（PP）分散性能、力学性能及阻燃性能的影响,并采用锥形量热仪对比了表面改性前后IFR阻燃PP的燃烧行为。结果表明,4种表面改性剂中铝硅复合偶联剂的改性效果最优;可显著改善IFR在PP中的分散性,提高了PP的极限氧指数和UL 94阻燃级别,材料的断裂伸长率提升了200 %,冲击强度提升了50 %;还可抑制IFR的析出,材料燃烧时的热释放速率及总量、生烟速率及总量下降幅度达到30 %左右。     

DOPO接枝氢氧化镁阻燃超高分子量聚乙烯研究

采用9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物（DOPO）接枝氢氧化镁（MH）制备新型接枝型复合阻燃剂（D-MH）,并用于超高分子量聚乙烯（UHMWPE）阻燃改性,对D-MH的化学结构进行表征,对阻燃改性后UHMWPE热释放、烟释放、热降解过程及力学性能进行分析。结果表明：D-MH对UHMWPE的阻燃效果明显优于未经过改性的MH阻燃剂,D-MH阻燃UHMWPE材料的热释放速率峰值和总热释放量与MH阻燃UHMWPE材料相比下降53.7%和69.3%,烟释放速率峰值和总烟释放量下降74.0%和86.8%,拉伸强度和无缺口冲击强度提高0.5倍和6.3倍。     

单体自增溶原位固相接枝法合成三单体接枝物PE-g-（GMA／St／BA）的研究

采用单体自增溶原位固相接枝技术合成PE—g-（GMA＋St＋BA）的三单体固相接枝物，采用傅立叶变红外光谱分析接枝物的结构，并探讨单体配比、单体总质量、引发剂用量等反应条件对接枝率和凝胶率的影响。结果表明，当三种单体的配比GMA／St/BA（质量比）：6／6／2，BPO用量为2phr，单体的总用量在50phr左右时，接枝率较高；苯乙烯能降低凝胶含量，BPO为2phr时凝胶含量较低。     

A facile one‐step synthesis of flame‐retardant coatings on cotton fabric via ultrasound irradiation

This article reports a facile one‐step methodology to increase fire resistance properties of cotton fabric. The flame‐retardant coating for cotton fabric was synthesized with methyltriethoxysilane and organophosphates (M102B) through an ultrasound irradiation process. The coating structure and surface morphology of uncoated and coated fabrics were investigated by Fourier transform infrared spectroscopy and scanning electron microscope, respectively. The flame‐retardant properties, bending modulus, air permeability and thermal stability were studied by vertical burning test, cantilever method, air permeability test and thermogravimetric analysis (TGA). As a result, the cotton fabric coated with 29.2% (mass increased) of flame‐retardant coating was able to balance the flame retardant property and wearing comfort of the fabrics. The TGA results showed that the residue char of cotton was greatly enhanced after treatment with the coating, which has a high char forming effect on cellulose during testing. Furthermore, flame‐retardant property of coated fabrics did not change significantly after 10 washing cycles. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45114.     

Aqua-mediated in situ synthesis of highly potent phosphorous functionalized flame retardant for cotton fabric

Flame retardancy in various materials is becoming an increasingly important performance feature. In the textile industries, fire-related problems have become an important concern over the decade. Herein, the polyvinyl alcohol (PVA) and graphene-supported material were functionalized with trimethyl phosphate (TMP) for the synthesis of flame retardant (FR) composite material [graphene polymer functionalized trimethyl phosphate (GPTMP)] in the aqueous medium, which improves the stability of cotton fabric against flame. Graphene and PVA fabricated with phosphorus functional groups make the fabric more comfortable against fire and help to avoid further spreading of fire. The composite-coated fabric sustains for a long time on continuous flame with maintaining its initial shape and size. The GPTMP-coated fabric shows flame retardancy for up to 540 s on constant flame exposure, whereas control samples such as PVA-, graphene oxide-, and TMP-coated fabrics resist for up to 15, 20, and 14 s, respectively. The limiting oxygen index (LOI) and vertical flammability test (VFT) for synthesized composites were performed to confirm and support the flame retardancy property of GPTMP. The GPTMP shows the 35% LOI value and forms the char length of 2.6 cm during VFT. This work provides a simple and eco-friendly method to obtain novel GPTMP, which has a high potential as a FR for different fabrics, including cotton.     

多层阻燃织物整体热防护性能初探

研究了消防服用多层阻燃织物复合系统的整体热防护性及外层织物的阻燃性。将阻燃织物国产间位芳纶、杜邦NomexⅢ和芳纶3A面料与国产间位芳纶毡和阻燃棉布组合,模拟构成消防服的多层织物结构,通过垂直燃烧实验测试分析了阻燃外层织物的阻燃性能,通过热辐射和热对流综合热防护性能(TPP)实验测试分析了多层复合织物的整体热防护性能。实验结果表明:整体热防护性能最好的是国产间位芳纶织物、面密度200 g/m2的芳纶毡和阻燃棉布的组合,但最适宜用于消防服的是NomexⅢ织物、面密度200 g/m2的芳纶毡和阻燃棉布。     

Flame retardant finishing of the polyester/cotton blend fabric using a cross‐linkable hydroxy‐functional organophosphorus oligomer

Blend fabrics of cotton and polyester are widely used in apparel, but high flammability becomes a major obstacle for applications of those fabrics in fire protective clothing. The objective of this research was to investigate the flame retardant finishing of a 50/50 polyester/cotton blend fabric. It was discovered previously that N,N′‐dimethyloldihydroxyethyleneurea (DMDHEU) was able to bond a hydroxy‐functional organophosphorus oligomer (HFPO) onto 50/50 nylon/cotton blend fabrics. In this research, the HFPO/DMDHEU system was applied to a 50/50 polyester/cotton twill fabric. The polyester/cotton fabric treated with 36% HFPO and 10% DMDHEU achieved char length of 165 mm after 20 laundering cycles. The laundering durability of the treated fabric was attributed to the formation of polymeric cross‐linked networks. The HFPO/DMDHEU system significantly reduced peak heat release rate (PHRR) of cotton on the treated polyester/cotton blend fabric, but its effects on polyester were marginal. HFPO/DMDHEU reduced PHRR of both nylon and cotton on the treated nylon/cotton fabric. It was also discovered that the nitrogen of DMDHEU was synergistic to enhance the flame retardant performance of HFPO on the polyester/cotton fabric.     

Studying smoldering to flaming transition in polyurethane furniture subassemblies: Effects of fabrics,flame retardants,and material type

The transition from smoldering to flaming was studied on fabric, batting, and foam assemblies via an electric spot ignition source of similar intensity to a cigarette. The materials studied included four different fabrics (cotton, polyester, cotton/polyester blend, flame retardant cotton/polyester blend), two types of batting (cotton, polyester), and three types of polyurethane foam (nonflame retardant, flame retardant by FMVSS 302 testing, flame retardant by BS5852 testing). The results from testing found that materials highly prone to smoldering could propagate smoldering into foams and lead to ignition, whereas materials that tended to melt back from the ignition source did not. Flame retardant fabrics or foam can and do prevent the transition from smoldering to flaming provided sufficient levels of flame retardants are incorporated in the upholstery fabric or foam. The transition from smoldering to flaming of cotton fabric/nonflame retardant foam assembly was also studied using temperature measurements and evolved gas analysis. It was determined that the transition takes place when the oxygen consumption by accelerating smoldering front exceeds the oxygen supply. At this point, the solid fuel gasification becomes driven by thermal decomposition rather than by surface oxidation which leads to high enough concentrations of fuel for flaming combustion to occur.     

阻燃型磷酸酯聚硅氧烷的合成与应用

该文以N-β-氨乙基-γ-氨丙基聚二甲基硅氧烷(ASO-1)、环氧氯丙烷、磷酸三丁酯为原料合成了阻燃型磷酸酯聚硅氧烷(PPSO),经红外光谱(IR)和核磁共振氢谱(1HNMR)证实了产物及中间体的化学结构,将PPSO进行乳化得到了透明乳液(PPSE),用马尔文纳米粒度仪及Zeta电位仪测出乳液平均粒径为62.5 nm,Zeta电位+53.71 mV.将所得硅乳应用于棉织物,探讨了阻燃剂用量对整理后织物性能的影响.结果表明,整理后的织物具有了阻燃性,最佳阻燃剂用量为200 g?L-1.为了进一步解释纤维阻燃的机理,通过热重分析研究了织物的热裂解过程,结果表明,阻燃剂对纤维起到了脱水、炭化作用,提高了剩炭率.     

Thermal properties and combustion behavior of POSS‐ and bohemite‐finished cotton fabrics

A finishing process with polyhedral oligomeric silsesquioxane (POSS) and bohemite nanoparticles has been exploited for enhancing the thermal stability and flame retardancy of cotton fabrics. The thermal behavior of flame retardant treated cellulosic fabric has been studied by thermogravimetric analyses (TGAs). It has been found that such nanoparticles favor the carbonization of the cellulose and slow down the kinetics of thermo‐oxidation in air. At the same time, the finished fabrics have turned out to be more efficient with respect to neat cotton as far as the flame retardancy is concerned, pointing out an increase of the time to ignition (TTI) and a decrease of the heat release rate (HRR). Furthermore, a comparison between the fire performances of the nanoparticles under study and a commercial phosphorus‐based flame retardant has been investigated. The morphology and elemental composition present in the treated fabrics have been also investigated using scanning electron microscopy (SEM) coupled to the energy dispersive spectroscopy (EDS), and the results have been compared with the untreated fabric. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis of carborane acrylate and flame retardant modification on silk fabric via graft copolymerization with phosphate‐containing acrylate

A novel carborane acrylate monomer (1‐acryloyloxyethyl carborane) was synthesized by addition reaction, hydrolysis, and esterification and characterized by proton nuclear magnetic resonance (¹H NMR) spectroscopy and Fourier transform infrared spectroscopy (FT‐IR) analysis. Subsequently, the carborane monomer and a phosphate‐containing methacrylate monomer were applied on the modification of a silk fabric. The heat resistance and flame retardancy of the silk fabric before and after modification were compared. Energy‐dispersive X‐ray spectrometer (EDS) and FT‐IR showed that carborane monomer and phosphate‐containing methacrylate were grafted onto the surface of the fibers. The cross‐sectional morphology of silk fabrics after burning was observed by scanning electron microscope (SEM), and the flame‐retardant mechanism was analyzed. Thermal‐gravimetric analysis (TGA) and differential scanning calorimetry (DSC) analysis revealed that the thermal stability of the modified silk increased with the increase of the grafting yield. The MCC‐2 microcalorimeter (MCC) test showed that, when using 1‐acryloyloxyethyl carborane as monomer and blending with phosphate‐containing methacrylate, the maximum heat release rate (PHRR) of the modified silk fabric decreased from 97.6 W/g (before grafting) to 51.3 and 45.8 W/g, respectively, and the total heat release (THR) decreased from 10.2 kJ/g (before grafting) to 5.9 and 5.2 kJ/g, respectively. The limiting oxygen index (LOI) test revealed that using 1‐acryloyloxyethyl carborane and phosphate‐containing methacrylate as mixed monomers to modify the silk fabric obtained good flame retardancy, whose LOI value reached 29.8%.     

Flame‐retardant fabric systems based on electrospun polyamide/boric acid nanocomposite fibers

To examine the feasibility of developing flame‐retardant‐textile coated fabric systems with electrospun polyamide/boric acid nanocomposites, fiber webs coated on cotton substrates were developed to impart‐fire retardant properties. The morphology of the polyamide/boric acid nanocomposite fibers was examined with scanning electron microscopy. The flame‐retardant properties of coated fabric systems with different nanoparticle contents were assessed. The flame retardancy of the boric acid coated fabric systems was evaluated quantitatively with a flammability test apparatus fabricated on the basis of Consumer Product Safety Commission 16 Code of Federal Regulations part 1610 standard and also by thermogravimetric analysis. The 0.05 wt % boric acid nanocomposite fiber web coated on pure cotton fabric exhibited an increment in flame‐spreading time of greater than 80%, and this indicated excellent fire protection. Also, the coated fabric systems with 0.05% boric acid nanocomposite fiber webs exhibited a distinct shift in the peak value in the thermal degradation profile and a 75% increase in char formation in the thermooxidative degradation profile, as indicated by the results of thermogravimetric analysis. The results show the feasibility of successfully imparting flame‐retardant properties to cotton fabrics through the electrospinning of the polymer material with boric acid nanoparticles. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012