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%.     

磷酸腺苷对蚕丝织物的生物阻燃耐久整理

为了满足对蚕丝织物生态阻燃的需求，以1-(3-二甲氨基丙基)-3-乙基碳二亚胺 (EDC)和 N-羟基琥珀酰亚胺(NHS)为催化剂将磷酸腺苷(AMP)引入蚕丝织物。采用FTIR、SEM、EDS等对改性前后丝织物的化学结构、表面形貌和元素含量进行表征，采用极限氧指数仪、垂直燃烧测试仪、锥形量热仪和热重分析仪对其阻燃性能和热稳定性进行测试，同时对改性前后丝织物的拉伸断裂性能和织物风格等物理机械性能进行测试。结果表明，改性丝织物表面呈现颗粒状覆盖物，且均匀分布着磷元素。改性丝织物增重率达13.3%时，极限氧指数达30.10%，相比于原丝织物失重率降低13.1%，热释放速率降低30.6%，损毁长度减少11.1 cm，并出现明显炭层。经50 次洗涤后，改性丝织物极限氧指数仍能达到25%以上，说明改性丝织物具有较好的耐洗性能。     

Flame retardancy finish with an organophosphorus retardant on silk fabrics

The paper mainly deals with flame retardancy of silk fabrics treated with a commercial organophosphorus flame retardant [N‐hydroxymethyl (3‐dimethyl phosphono) propionamide (HDPP), also known as Pyrovatex CP], using the pad‐dry‐cure‐wash method. The structures and properties of the treated and control sample are discussed. The Limiting Oxygen Index (LOI) value of the modified sample is above 30%. After 50 laundry cycles, it still has some flame retardancy left. HDPP and a cross‐linking agent (HMM) were bound to silk fabrics which is confirmed by FT‐IR spectra and amino analysis. The reaction degree of the flame retardant with silk is also high; almost all the tyrosine units have reacted, which can be confirmed by amino acid analysis. The reaction between flame retardant and silk only occurs in the amorphous region of silk fibre, which is confirmed by X‐ray diffraction analysis and amino acid analysis. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) analysis show that the flame retardant causes silk fabrics to decompose below its ignition temperature (600°C) and formed carbonaceous residue or char when exposed to fire. The char behaves as a thermal barrier to fire, so silk fabrics show good flame retardancy. The treatment has a little effect on the whiteness of the silk fabrics and the tensile strength of treated silk fabrics slightly decreased; both effects are negligible. Copyright © 2006 John Wiley & Sons, Ltd.     

The surface characterization of mulberry silk grafted with acrylamide by plasma copolymerization

The effects of plasma-induced graft copolymerization and simultaneous plasma-treated graft copolymerization with acrylamide (AAm) on the structure of mulberry silk are investigated. Through scanning electron microscopy, transmission infrared (IR), and attenuated total reflectance-IR and x-ray photoelectron spectroscopy (XPS) studies, changes of the surface morphology, structure, and composition are observed. The results show that plasma-induced graft copolymerization has more influence on the original structure of silk than does simultaneous plasma-treated graft copolymerization. The former brings the AAm branch polymer into the main chain of silk by the initiation of some kind of oxygen and nitrogen groups formed by the plasma, but the latter directly forms the AAm branch or cross-linking polymers with oxygen and nitrogen groups on the silk surface. This is the reason for the high elastic recovery angle of silk fabric modified by the two plasma graft copolymerizations. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1713–1717, 1997     

阻燃-阳离子染料易染涤纶短纤维的研制

采用磷系阻燃剂、SIPM与DMT、EG共聚方式合成了阻燃 阳离子染料易染聚酯 (FR CDP) ,并进行了热性能研究。通过对纺丝工艺的探索 ,成功地研制出了FR CDP短纤维 ,其常规物理指标合格 ,并具有优良的染色性能和阻燃性能 ,在 10 0℃下 ,经 90min ,上染率达 89 3 % ,极限氧指数LOI为 3 0 0 %。     

接枝共聚技术提高ABS、SBS聚合物成炭率

通过接枝共聚提高高聚物的成炭率 ,是改善材料阻燃性的有效技术措施。将丙烯酸或甲基丙烯酸及它们的钠盐接枝到某些ABS和SBS上 ,可明显提高接枝共聚物的热稳定性、成炭率及阻燃性。     

Graft copolymerization coating of methacryloyloxyethyl diphenyl phosphate flame retardant onto silk surface

This paper reports an efficient surface modification methodology to increase fire resistance properties of silk fabric performed by radio frequency (RF) plasma-induced graft copolymerization of vinyl phosphate ester as nanometer coating. Methacryloyloxyethyl diphenyl phosphate (MEDP) monomer was prepared and graft-copolymerized onto the surface of silk fabric by argon RF plasma at ambient temperature. Under optimum RF power (30 W), amounts of MEDP and N,N methylenebisacrylamide cross linking agent were varied to obtain optimum graft copolymerization conditions. Untreated and treated silk were characterized by attenuated total reflectance infrared (ATR-IR) spectroscopy to investigate their functional group characteristics. This showed a strong covalent attachment between the surface of silk and flame retardant material as the carbonyl functionality of the MEDP was clearly observed in the spectra. Scanning electron microscopic (SEM) analysis also showed grafted material as nanometer residue on silk surface. Thermogravimetric analysis (TGA) revealed that the decomposition of phosphorus compound which occurs at lower temperature than that of silk itself resulted in the formation of char which covers the surface of the fabrics. This protects the fabric surface from further burning, therefore, higher amounts of remaining materials were observed as char in all cases. Furthermore, the limiting oxygen index (LOI) increased from 25.5 for untreated to 28.0 (ca. 10%) for the MEDP-grafted silk. Higher amounts of char were also observed in the case of MEDP-treated silk. After 5 dry cleaning cycles, the LOI of the treated silk dropped only very slightly. Detailed analysis on structural and thermal properties as well as surface grafting efficiency are presented.     

PET共聚阻燃改性研究进展

该文综述了近年来聚对苯二甲酸乙二醇酯(PET)以共聚改性方式制备高性能阻燃PET的最新研究进展,主要从磷系共聚阻燃、高温交联、高温重排、高温离子聚集和高温端基捕获链扩展5个方面对阻燃改性PET的阻燃机理和阻燃性能进行阐述,并总结了不同阻燃共聚改性方法的特点,对未来PET共聚阻燃的研究方向提出展望.     

Intercalated kaolinite with ammonium dihydrogen phosphate as an effective flame retardant to enhance the flame retardance and smoke suppression of epoxy resins

To improve the compatibility and flame retardance of kaolinite (Kaol) in polymeric materials, ammonium dihydrogen phosphate (ADP) was intercalated into kaolinite to obtain a novel intercalated kaolinite (K-ADP) for enhancing thermal stability, flame retardance, smoke suppression, and mechanical performance of epoxy resins (EPs). The results show that the presence of K-ADP exerts a more positive effect on reducing the heat release and smoke generation of EPs than the same addition of Kaol. Condensed phase analysis shows that EP/K-ADP composite generates more aromatic cross-links in the condensed phase to reinforce the compactness and intumescence of char compared to EP/Kaol composite. Especially, 5 wt% K-ADP confers a 43.7% reduction in peak heat release rate value and a 36.3% reduction in peak smoke production rate value to EP. Toxic gases analysis shows that K-ADP conduces to inhibiting the release of combustible gases including isocyanates and aromatic volatiles, and generating incombustible gases including ammonia and carbon dioxide to reduce the intensity of EP combustion. The mechanical test shows that K-ADP imparts less adverse impact on mechanical behavior to EP composites than Kaol due to the good dispersion and compatibility between K-ADP with EP matrix.     

Compatibilization of acrylic polymer–silk fibroin blend fibers. I. Graft copolymerzation of acrylonitrile onto silk fibroin

To synthesize effective compatibilizers for the compatibilization of acrylic polymer–silk fibroin blend fibers, the homogeneous graft copolymerization of acrylonitrile onto silk fibroin, initiated by potassium persulfate–sodium bisulfite redox system in 60 wt % ZnCl₂ aqueous solution was investigated. The percentage graft, percentage efficiency, and molecular weight of the grafted polyacrylonitrile increase with the increase of the concentration of initiator, the concentration of acrylonitrile, and the temperature to optimum values, respectively, and then decrease. With the increase of reaction time, the percentage graft and percentage efficiency increase, whereas the molecular weight of the grafted polyacrylonitrile decreases. The influence of the reactionconditions on the molecular architecture of the graft copolymers is also discussed. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1089–1097, 1998     

膨胀型阻燃剂/二乙基次磷酸铝阻燃改性不饱和树脂基复合材料

采用密胺包覆聚磷酸铵（APP）、季戊四醇（PER）和三聚氰胺（MEL）作为膨胀型阻燃剂（IFR）对不饱和树脂（UP）进行改性,研究了APP、PER和MEL不同复配比例及用量对不饱和树脂基复合材料阻燃性能和力学性能的影响。基于IFR最佳用量,以二乙基次磷酸铝（ADP）为协效剂,研究了ADP用量对IFR/UP阻燃复合材料阻燃性能、力学性能及热稳定性的影响。结果表明,当APP∶PER∶MEL复配比例为4∶1∶1,IFR添加量为15 %（质量分数,下同）时,复合材料综合性能最佳,其极限氧指数为27.4 %,UL 94垂直燃烧达到V?1等级,弯曲强度和冲击韧性分别为100.3 MPa和6.3 kJ/m²;ADP的引入能够进一步提高IFR/UP复合材料阻燃性能,且随着ADP质量分数的增加而增强;当ADP质量分数为2 %时,IFR?ADP/UP复合材料极限氧指数为28.5 %并达到V?0阻燃等级,弯曲强度和冲击韧性分别为110 MPa和7.8 kJ/m²,与IFR/UP复合材料相比,分别提高了9.7 %和23.8 %;ADP能够促进IFR/UP复合材料表面成炭,缓解基体的热降解。     

涤纶织物浸轧用阻燃剂环状磷酸酯的合成

以亚磷酸三乙酯、三羟甲基丙烷和甲基磷酸二甲酯为原料合成了环状磷酸酯,可作为涤纶织物浸轧用的环保型耐久阻燃剂。利用正交实验讨论了反应过程中各因素对结果的影响。结果表明:亚磷酸三乙酯:三羟甲基丙烷:甲基磷酸二甲酯的摩尔比为1.05:1:1.2,自制复合有机酸为酯交换反应催化剂,质量分数为0.1%,反应温度85℃,反应时间3 h,自制复合有机碱为加成反应的催化剂,质量分数为1.0%,反应温度200℃,反应时间8 h,酯交换反应收率95.0%,加成反应收率90.0%。合成的阻燃剂具有良好的阻燃性能和耐洗性能,用量超过100 g/L时,处理的织物经50次水洗可达GB/T5455—1997 B1级。     

阻燃吸湿改性PET的制备及性能研究

在聚对苯二甲酸乙二醇酯(PET)合成过程中添加不同配比的共聚单体2-羧乙基苯基次磷酸(CEP-PA)、间苯二甲酸双羟乙酯-5-磺酸钠(SIPE)及聚乙二醇(PEG),制得阻燃吸湿改性PET;分析了改性PET的热性能、结晶行为、阻燃和吸湿性能等。结果表明:采用CEPPA为阻燃剂合成阻燃PET过程中,添加SIPE,改性PET的结晶速率和结晶度下降,含水率提高,耐热性及极限氧指数(LOI)降低;同时引入CEPPA和PEG,改性PET的结晶速度、阻燃性和吸湿性都得到提高;添加了CEPPA、SIPE和PEG的改性PET的含水率为0.61%,LOI为25%,具有良好的阻燃性能。     

MPP无卤阻燃聚丙烯纤维的辐照改性研究

采用自制季戊四醇螺环磷酸酯双蜜胺盐(MPP)无卤阻燃剂与聚丙烯(PP)进行共混纺丝,制备了无卤阻燃PP纤维,采用低能电子辐照对无卤阻燃PP纤维进行改性,并对MPP的结构、PP纤维的力学性能及阻燃性能进行了表征。结果表明:自制MPP为预期结构;随着MPP含量的增加,PP纤维的极限氧指数(LOI)增大,但其断裂强度有所下降;MPP质量分数为8%时,纤维断裂强度为6.02 cN/dtex,LOI为24.5%;随低能电子辐照量的增大,MPP质量分数8%的阻燃PP纤维的LOI大幅度增加;当电子辐照量为200 kGy时,阻燃PP纤维的LOI为33.8%,断裂强度为3.08 cN/dtex,起始分解温度和残炭率比纯PP纤维均有较大幅度增加,燃烧形成连续致密的炭层。     

Effect of a novel phosphorus‐containing compound on the flame retardancy and thermal degradation of intumescent flame retardant polypropylene

A novel flame retardant, tetra(5,5‐dimethyl‐1,3‐ dioxaphosphorinanyl‐2‐oxy) neopentane (DOPNP), was synthesized successfully, and its structure was characterized by FT‐IR, ¹H NMR, and ³¹P NMR. The thermogravimetric analysis (TGA) results demonstrate that DOPNP showed a good char‐forming ability. Its initial decomposition temperature was 236.4°C based on 1% mass loss, and its char residue was 41.2 wt % at 600°C, and 22.9 wt % at 800°C, respectively. The flame retardancy and thermal degradation behavior of novel intumescent flame‐retardant polypropylene (IFR‐PP) composites containing DOPNP were investigated using limiting oxygen index (LOI), UL‐94 test, TGA, cone calorimeter (CONE) test, and scanning electron microscopy (SEM). The results demonstrate that DOPNP effectively raised LOI value of IFR‐PP. When the loading of IFR was 30 wt %, LOI of IFR‐PP reached 31.3%, and it passed UL‐94 V‐0. TGA results show that DOPNP made the thermal decomposition of IFR‐PP take place in advance; reduced the thermal decomposition rate and raised the residual char amount. CONE results show that DOPNP could effectively decrease the heat release rate peak of IFR‐PP. A continuous and compact char layer observed from the SEM further proved the flame retardance. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

无卤本质阻燃热塑性共聚酯

介绍了由9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物二元酸衍生物与对苯二甲酸二羟乙基酯(BHET)或2,6-萘二甲酸二羟乙基酯(BHEN)直接酯化生成的含磷热塑性共聚酯的制备方法及性能。磷的质量分数为0．5％(BHEN共聚酯)或0．75％(BHET共聚酯)时,共聚酯的阻燃性可达UL 94 V-0级,700℃下空气中的成炭率接近20％,且燃烧时产生较少烟雾及有毒和腐蚀性气体。     

Graft copolymerization of acrylate monomers onto sulfonated jute–cotton blended fabric

Graft copolymerization of acrylate monomers, e.g., methyl methacrylate and ethyl methacrylate, onto bleached sulfonated jute–cotton‐blended fabric was carried out in an aqueous medium, using potassium persulfate as an initiator under the catalytic influence of ferrous sulfate in a nitrogen atmosphere. The parameter variables, e.g., concentrations of monomer, potassium persulfate, ferrous sulfate, reaction time, and reaction temperature, directly influenced the percent graft yield. The percent graft yield increased to a certain value in each variable, and the percent graft yield of methyl methacrylate and ethyl methacrylate was about 15.9 and 17.1%, respectively. Polymer grafting was characterized by thermogravimetric analysis, infrared spectroscopy, and X‐ray diffractometry. Grafting improved the thermal stability, protected from photo‐oxidative degradation, decreased the dyeability, and had positive impact on fastness characteristics. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4393–4398, 2006     

Surface photografting: New application for flame retardant finishing of polyamide6.6 (PA6.6) fabric

Surface photografting modification with maleic anhydride (MAn) under UV irradiation in association with a post reaction with triethanolamine has been used to improve the flame retardancy of polyamide6.6 (PA6.6) fabric in this study. The effects of irradiation time and monomer concentration on the fabric surface grafting were investigated. The flame retardancy and thermal decomposition behavior of the samples were characterized by limiting oxygen index test (LOI), thermogravimetric analysis (TGA), and differential scanning calorimetric (DSC), and the results indicate that flame retardancy of the treated PA6.6 fabric samples has been significantly improved. The chemical structures of the treated samples' surface were characterized by attenuated total reflection infrared spectroscopy (ATR‐FTIR), and the possible photochemical mechanisms were discussed. It is suggested that this could be the first time to use photografting technology to enhance the flame retardancy of PA6.6 fabric. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

过硫酸钾引发羧甲基甲壳素和丙烯酸钾溶液接枝聚合

以过硫酸钾为引发剂,水为介质,制备了羧甲基甲壳素接枝丙烯酸钾共聚物,讨论了反应温度、反应时间、引发剂用量、单体用量对接枝率的影响,获得了最佳反应条件。结果表明：在含羧甲基甲壳素0．3g的30．0mL水溶液中,加入过硫酸钾50．0mg,丙烯酸钾水溶液8．0mL,于60℃反应120min时接枝率最高,达305．1％。接枝共聚物具有水溶性。接枝共聚改性反应可以扩展羧甲基甲壳素的应用价值。     

丙烯酰氧基螺噁嗪接枝羧甲基甲壳素反应条件的研究

采用接枝共聚法合成了一种具有螺噁嗪侧基的羧甲基甲壳素水溶性衍生物。讨论了反应温度、反应时间、引发剂用量、溶剂用量、单体用量对丙烯酰氧基螺噁嗪接枝羧甲基甲壳素反应的影响。接枝效率最高时反应条件为:羧甲基甲壳素0.4 g,溶剂水50.0 mL,引发剂0.35 mmol,单体3.0 mmol,反应温度70℃,反应时间4.0 h,接枝率为65.0%,接枝效率为25.2%。