十二烷基/羧基改性聚硅氧烷乳液的制备及应用性能

以八甲基环四硅氧烷、γ-氨丙基甲基二乙氧基硅烷、十二烷基甲基二甲氧基硅烷、六甲基二硅氧烷、顺丁烯二酸酐为原料,合成了十二烷基/羧基改性聚硅氧烷(RCAS);并用非离子表面活性剂脂肪醇聚氧乙烯醚(AEO)将其乳化,制得外观透明的RCAS微乳液。运用透射电子显微镜、纳米粒度仪、Zeta电位分析仪、电脑测控柔软度仪等对RCAS乳液的粒径等物化指标进行测定,并考察了RCAS乳液在棉织物上的应用性能。结果表明:RCAS乳液的离心、弱酸碱及电解质稳定性良好,乳胶粒平均粒径为28 nm,粒径呈单峰分布,Zeta电位为-37.88 mV。经RCAS乳液整理的棉织物柔软性能较之经羧烃基改性聚硅氧烷(CAS)、十二烷基改性聚硅氧烷(RSO)整理的织物及未整理织物均有所增加,亲水性较之经氨基改性聚硅氧烷(ASO)整理的织物显著增加,白度最为优异,综合应用性能优于经CAS、RSO及ASO乳液整理的织物,同时赋予被整理织物软滑、蓬松增厚的独特手感;采用二次浸轧工艺整理的织物白度和亲水性基本保持不变,而柔软性能提升,获得了更佳的整理效果;RCAS乳液整理棉织物的最佳用量为1.0 g/100 mL水。     

端羧基聚硅氧烷(FRCAS)的合成及性能研究

本文先通过D4、MM、D3F和氨基硅烷等的本体聚合反应制备含氨基及三氟丙基的系列聚硅氧烷(FRASO),然后在催化剂作用下,使聚硅氧烷侧链氨基与马来酸酐作用,将羧基引入聚硅氧烷侧链制得新型羧基改性聚硅氧烷(FRCAS)。用非离子表面活性剂T-99对FRASO及FRCAS进行乳化,并分别将其用于织物整理中。用红外光谱仪(FT-IR)、核磁共振仪1H-NMR、Zeta电位仪等仪器对产物结构及乳液物化性能进行表征和测试。结果表明:FRASO、FRCAS与预先设计的分子结构一致。FRCAS乳液平均粒径为101.5 nm,粒径分布窄。Zeta电位为-43.6 mV,乳液稳定性强。织物经整理后,柔软度和白度均有所提高,具有一定的疏水性,FRCAS处理过的织物疏水性明显低于FRASO处理过的织物。     

生丝用柔软剂CAPES的合成及应用

摘要：以环氧基封端的聚二甲基硅氧烷(α,ω-ESO)、聚醚胺为原料合成中间体氨基聚醚硅油(APES),再用马来酸酐(MAn)对APES改性,合成了一种羧基化聚醚硅油(CAPES)。用非离子表面活性剂脂肪醇聚氧乙烯醚,将自制的羧基化聚醚硅油(CAPES)乳化,制得白色半透明泛蓝的乳液并将该乳液用于生蚕丝的柔软浸泡整理中。利用红外(IR)光谱、纳米粒度仪、Zeta电位分析仪、扫描电镜(SEM)对CAPES及其乳液进行表征、测定,观察CAPES在生丝表面的膜形貌,并考察CAPES浴液的pH、浸丝时间和硅乳的用量对生丝性能的影响。结果表明：CAPES乳液平均粒径84.6nm,Zeta电位-21.5mV,且在丝样纤维表面的成膜性良好;当pH为6,浸丝时间为30min,CAPES用量为5g/L左右时,整理效果最佳。     

生丝用柔软剂CAPES的合成及应用

以环氧基封端的聚二甲基硅氧烷(α,ω-ESO)、聚醚胺为原料合成中间体氨基聚醚硅油(APES),再用马来酸酐(MAn)对APES改性,合成了一种羧基化聚醚硅油(CAPES)。用非离子表面活性剂脂肪醇聚氧乙烯醚,将自制的羧基化聚醚硅油(CAPES)乳化,制得白色半透明泛蓝的乳液并将该乳液用于生蚕丝的柔软浸泡整理中。利用红外(IR)光谱、纳米粒度仪、Zeta电位分析仪、扫描电镜(SEM)对CAPES及其乳液进行表征、测定,观察CAPES在生丝表面的膜形貌,并考察CAPES浴液的p H、浸丝时间和硅乳的用量对生丝性能的影响。结果表明:CAPES乳液平均粒径84.6 nm,Zeta电位-21.5 m V,且在丝样纤维表面的成膜性良好;当p H=6,浸丝时间为30 min,CAPES用量为5 g/L左右时,整理效果最佳。     

季铵化改性氨基聚硅氧烷的合成及应用性能

采用氯乙酸乙酯对N,N-二甲基-γ-氨丙基-γ-氨丙基聚二甲基硅氧烷(ASO-121)进行季铵化改性,合成了一种季铵化改性氨基聚硅氧烷(QASO-121)。利用红外光谱(IR)、核磁共振氢谱(1HNMR)、扫描电镜(SEM)、纳米粒度仪等仪器对QASO-121及其乳液进行了表征和纤维表面的成膜性分析,并讨论了氨值、黏度及硅乳用量对所整理织物应用性能的影响。结果表明,QASO-121乳液平均粒径为75.3 nm,电位为+21.2mV,且其在织物纤维表面具有良好的成膜性。经氨值为0.6 mmol/g、黏度为2.600 Pa·s、硅乳用量为4 g/L的QASO-121整理的布样,织物柔软性提高,亲水性增强,白度基本不变。将QASO-121与未季铵化ASO-121进行应用性能对比,发现两者整理织物的柔软性相近,但经QASO-121所整理织物具有良好的亲水性且富有弹性,其抗黄变性能也得到了改善。     

长链烷基聚醚/氨基硅的合成、表征与应用

以含氢硅油(PHMS)、烯丙基环氧基聚醚(AEH)和1-十六碳烯(C16)为原料,在氯铂酸催化作用下通过硅氢化加成反应得到长链烷基环氧聚醚硅油(PCA),再与聚醚胺反应,制备一种长链烷基聚醚/氨基硅(PCAD)。利用红外光谱(IR)、核磁共振氢谱(1HNMR)、阿贝折射仪、扫描电镜(SEM)和纳米粒度仪对PCAD及其乳液进行了表征和纤维表面的成膜性分析,并探讨了1-十六碳烯和环氧基聚醚的摩尔比,乳液用量以及焙烘温度对所整理织物应用性能的影响。结果表明,PCAD乳液的平均粒径为83.7 nm,并且在织物纤维表面上具有良好的成膜性。当十六碳烯和烯丙基环氧基聚醚的摩尔比为8∶2,乳液用量为15 g/L,焙烘温度为150℃时,经PCAD整理的织物柔软性提高,具有一定防水性,而白度基本不变。     

核壳乳液的合成及对蔗渣纤维的疏水化改性

采用半连续种子乳液聚合法,以苯乙烯(St)、丙烯酸丁酯(BA)、甲基丙烯酸缩水甘油酯(GMA)为单体,十六烷基三甲基氯化铵(CTAC)为阳离子乳化剂,二甲基丙烯酸乙二醇酯(EGDMA)为交联剂,2,2-偶氮二(2-甲基丙基咪)二盐酸盐(AIBA)为阳离子引发剂,制备阳离子乳液。研究了乳化剂用量、引发剂用量、保温时间以及反应温度条件对乳液性能的影响。结果表明:在反应温度80℃、乳化剂用量为单体质量的6%、引发剂用量为单体质量的0.5%、保温时间为2 h时,单体转化率达到98.03%,核壳结构由透射电镜、纳米激光粒度仪表征,结果表明:乳胶粒子的平均粒径为57.21 nm,粒径分布窄(PDI=0.051),乳液的Zeta电位为47.62 m V。利用该乳液对蔗渣纤维进行表面疏水改性,并进行亲水性测试,结果表明,改性后蔗渣纤维接触角由0°提高至98°,疏水改性效果明显。     

羧基化聚醚有机硅紫外线吸收剂CPE-MUVS的合成、表征及应用

在无溶剂条件下,制备了一种羧基化聚醚有机硅紫外线吸收剂CPE-MUVS。用红外光谱、核磁共振氢谱、紫外光谱对其结构进行了表征。将CPE-MUVS进行乳化得到了透明乳液,用马尔文公司的纳米粒度及Zeta电位仪测出乳液平均粒径为33.08 nm,Zeta电位-41.24 mV。氨基硅乳(ASO-1)/CPE-MUVS复配体系用于棉织物后整理的结果表明,ASO-1/CPE-MUVS能改善棉织物的紫外线吸收性能,并能明显降低棉织物的弯曲刚度,增强棉织物的亲水性,对棉织物的白度无影响。     

季铵化聚醚改性聚硅氧烷的应用性能研究

采用含氢聚硅氧烷(PHMS)先与烯丙基环氧基聚醚(AH307030)进行硅氢加成反应,再与三乙醇胺进行季铵化反应,合成了一种季铵化聚醚改性聚硅氧烷(QASO)。利用红外光谱(IR)、纳米粒度仪等仪器对QASO及其乳液进行了表征分析,并探讨了分子结构及QASO用量对整理织物应用性能的影响。结果表明,QASO乳液平均粒径为53.3 nm,电位为+21.1 mV。当固体质量分数为30%的QASO乳液用量为3 g/L时,所整理布样的织物柔软性、亲水性及白度的综合性能最佳。     

水性封闭异氰酸酯乳液的合成及稳定性研究

采用甲苯二异氰酸酯(TDI)、三羟甲基丙烷(TMP)、二羟甲基丙酸(DMPA)为原料,2-甲基咪唑为封闭剂,三乙胺为中和剂制备了水分散封闭异氰酸酯(WBI)乳液,考察了中和剂和Zeta电位(ζ-电位)对WBI乳液稳定性的影响,探讨了乳液耐电解质能力及其温敏特性对其解封温度及双组分聚氨酯漆膜性能的影响。实验结果表明:用三乙胺作为中和剂时,乳液粒径较小,稳定性及贮存稳定性均较好,最佳中和度为100%。随DMPA用量的增加,乳液的ζ电位绝对值增大,乳液粒径减小、耐电解质能力增强,乳液的稳定性提高。乳液的Zeta电位及粒径受温度影响较小,说明乳液较为稳定。DMPA用量为20%～25%(摩尔分数)较适宜。差示扫描量热法(DSC)分析表征其解封温度为125.6～138.1℃,应用表明此类WBI作为固化剂可以赋予涂料较好的耐水性、耐醇性、硬度及耐冲击性。     

GMA改性磷酸腺苷的制备及其对棉织物的阻燃整理

为了提高磷酸腺苷单体在棉织物上的接枝改性程度及其阻燃效果,采用甲基丙烯酸缩水甘油酯（GMA）对一磷酸腺苷（AMP）、二磷酸腺苷（ADP）、三磷酸腺苷（ATP）进行改性,制得三种带有不饱和双键的阻燃单体AMP-m-GMA、ADP-m-GMA、ATP-m-GMA;然后通过紫外光接枝法将三种阻燃单体分别接枝到棉织物上,制备光接枝AMP-m-GMA、ADP-m-GMA和ATP-m-GMA阻燃棉织物;对三种阻燃单体进行了结构表征和热稳定性分析,并探究了三种阻燃单体光接枝阻燃棉织物的热稳定性、阻燃性能、燃烧行为和残炭结构。结果表明,三种磷酸腺苷通过GMA环氧基开环引入不饱和双键,且具有良好的热稳定性。相比于原棉织物,三种阻燃棉织物的最大热降解速率分别降低了60.0%、52.0%、60.0%,极限氧指数由16.1%分别提升到25.4%、27.4%、26.4%,织物热释放速率分别下降了15.09%、60.47%、37.82%,说明三种磷酸腺苷阻燃单体均有助于棉织物形成致密炭层,阻止热量扩散,获得良好的阻燃效果。其中,光接枝ADP-m-GMA阻燃棉织物的增重率可达22.4%,燃烧后损毁长度由30 cm缩短至14.2 cm,表现出更优异的阻燃性能。     

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.     

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.     

Effect of chicken‐feather protein‐based flame retardant on flame retarding performance of cotton fabric

A new kind of eco‐friendly chicken‐feather protein‐based phosphorus–nitrogen‐containing flame retardant was synthesized successfully with chicken‐feather protein, melamine, sodium pyrophosphate, and glyoxal. And its structure was characterized by Fourier transform infrared spectroscopy, and the thermogravimetry of the agent was analyzed. Then the flame retarding performances of the chicken‐feather protein‐based flame retardant and in combination with the borax and boric acid in application to a woven cotton fabric were investigated by the vertical flammability test and limited oxygen index test. In addition, the surface morphologies of the treated and untreated fabrics were conducted by the scanning electron micrographs (SEM), and the thermogravimetric analyses of the treated and untreated cotton were explored, and the surface morphologies of char areas of the treated and untreated fabrics after burnt were tested by the SEM. The results showed that the flame retardancy of the cotton fabric treated by the chicken‐feather protein‐based flame retardant in combination with borax and boric acid was improved further, and the combination of the chicken‐feather protein‐based flame retardant and borax and boric acid could facilitate to form a homogenous and compact intumescing char layer, and the combination of them plays a good synergistic effect in the improvement of the flame retardancy of the treated cotton fabric. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40584.     

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%。     

Effect of condensed-phase and gas-phase flame retardants on the ignition behaviour of cotton fabric

The purpose of this study is to evaluate the effect of some well-known flame retardants on the ignition behaviour of cotton fabric. Two types of flame retardants acting in different phases (e.g. condensed phase and gas phase) were used. At low add-on of the retardant acting in the condensed phase the ignition behaviour of the cotton is different from that treated with retardant acting in the gas phase. The condensed-phase retardant caused cotton to burn more rapidly than untreated fabrics. This was attributed to the fact that small add-on of the retardant makes the fuel for the flame available at a lower temperature. However, in the presence of sufficient amounts of retardant, the decomposition of cellulose becomes more directed towards the dehydration mechanism and thus the concentration of the flammable gases is insufficient to reach the flammability limits required. When gas-phase flame retardants were used, a linear dependency of ignition time on the concentration of additive was found. This is explained in terms of the dilution effect of this retardant on the fuel produced from the decomposing fabric.     

Synthesis of phosphorus-containing flame retardants and investigation of their flame retardant behavior in textile applications

Flame retardants are a growing area of research interest. Nonhalogenated, durable, and nonleachable flame retardants are one of the main strategies used in the research of flame retardant polymers. In this regard, the covalent attachment of phosphorus-containing flame retardants onto cotton fabric has been developed. Two types of reactive phosphorus-containing flame retardants (MKT-1 and MKT-2) have been synthesized and used as a surface coating for cotton fabric. MKT-1 possesses anhydride and acid functionalities that can react with the  OH functionalities in cellulose. In addition, MKT-2 has both acid and organosilicon groups that can also react with the hydroxy group present in cellulose. The structures of the reactive flame retardants (MKT-1 and MKT-2) were characterized using ¹³C and ³¹P nuclear magnetic resonance spectroscopy. Thermal properties of the coated and uncoated cotton fabrics were investigated using thermogravimetric analysis. Surface characterization was carried out using scanning electron microscopy and X-ray photoelectron spectroscopy. A standard test method used to evaluate the flammability of blankets (BS 5852) was also applied to characterize the fire retardant properties of the coated and uncoated cotton fabrics studied. Different loadings of MKT-1 and MKT-2 on the fabric (10, 20, and 30% by weight in dimethylformamide solution) were applied in the dip coating process. The cotton fabric coated with 30% MKT-2 does not burn after being subjected to a propane burner for 20 s and also produced the highest char yield (36%) at 500 °C. Inductively coupled plasma–optical emission spectrometry showed that MKT-1 contains 8.23 ± 0.33 P% whereas MKT-2 contains 3.88 ± 0.15 P%. Although MKT-1 possess a higher P content than MKT-2, the additive effect caused by the organosilicon and nitrogen groups present in MK-2 enhance its flame retardant properties. Furthermore, the covalently attached flame retardant materials are durable and do not hydrolyze during washing. The mechanical properties of coated fabrics were characterized by a tensile test and significant change in elongation at break was observed. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47935.     

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.     

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     

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。