新型含磷阻燃剂的合成及阻燃PC/ABS的热稳定性能

通过9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)、乙烯基甲基二甲氧基硅烷(WD-23)和γ-氨丙基甲基二乙氧基硅烷(DB902)之间的反应,合成了一种新型含磷阻燃剂:10-(乙基甲基二甲氧基硅烷)-9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物/γ-氨丙基甲基二乙氧基硅烷共聚物(DPWDF).利用热重分析(TGA)研究了阻燃剂及阻燃PC/ABS的热稳定性.结果表明:480 ℃以后,阻燃剂在空气氛围中的残炭量比在氮气氛围中的高;阻燃剂提前于基体PC/ABS分解,有利于促进基体成炭,提高基体的高温残炭量.     

新型单组份磷-氮膨胀型阻燃剂的热分解动力学

利用热重分析法研究了在不同升温速率下新型单组份磷-氮膨胀型阻燃剂六(4-(9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物)-羟甲基苯氧基)环三磷腈(DOPOMPC)在氮气气氛和空气气氛中的热分解动力学.采用Kissinger和Flynn-Wall-Ozawa(FWO)法分别计算出DOPOMPC在相应气氛下的活化能和指前因子.     

磷杂菲类阻燃剂的合成及其与聚磷酸铵复合膨胀体系对环氧树脂的阻燃性能研究

以9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)、五硫化二磷(P2S5)为原料合成9,10-二氢-9-氧杂-10-磷杂菲-10-硫化物(DOPS),并将DOPS与聚磷酸铵(APP)组成复合阻燃剂,用于环氧树脂(EP)的阻燃改性.通过氧指数(LOI)、垂直燃烧(UL-94)、热失重(TGA)、锥形量热(CONE)和扫描电镜(SEM)等方法对改性后的环氧树脂的阻燃性能和阻燃机理进行了测试和分析.实验结果表明,DOPS/APP阻燃体系对EP具有很好的阻燃性能,且复配阻燃剂的阻燃效果比单一的阻燃剂阻燃效果好;其中,当阻燃剂的总添加量达到30%时即W_(DOPS)=10%、W_(APP)=20%时,阻燃EP复合材料的LOI值可达到29.2%,垂直燃烧等级达到UL-94 V-0级,残炭量可达49.3%.     

银铜双金属/组氨酸功能化石墨烯量子点/石墨烯杂化物的制备及其在电化学法测定黄瓜中毒死蜱、克百威和多菌灵上的应用北大核心CSCD

为了提高金属纳米粒子在石墨烯片上的分散度,通过组氨酸功能化石墨烯量子点(His-GQD)作为桥梁,设计合成银铜双金属/His-GQD/石墨烯杂化物(AgCu/His-GQD/G)。His-GQD通过π-π堆积作用固定到氧化石墨烯上,然后与银离子和铜离子结合形成复合物,最后在氮气保护下热还原获得AgCu/His-GQD/G。形成的杂化物表现出独特的三维结构,且银、铜纳米粒子均匀分散在石墨烯片上。基于该杂化物构建了电化学适配体传感器,适配体与杂化物上的银、铜纳米粒子通过Ag-N和Cu-N键连接而修饰到电极表面上,用于毒死蜱、克百威和多菌灵的测定,表现出高的灵敏度和选择性。毒死蜱、克百威和多菌灵标准曲线的线性范围分别为1.00×10^(-2)~1.00×10^(3)pmol·L^(-1)、1.00×10^(-1)~1.00×10^(4)pmol·L^(-1)和1.00~1.00×10^(6)pmol·L^(-1),检出限(3S/N)分别为3.2×10^(-3)pmol·L^(-1)、2.3×10^(-2)pmol·L^(-1)和2.9×10^(-1)pmol·L^(-1)。该适配体传感器用于黄瓜样品中克百威、毒死蜱和多菌灵的测定,仅检出多菌灵,检出量为1.21 pmol·L^(-1)和1.25 pmol·L^(-1);并按标准加入法进行回收试验,回收率为99.3%~100%。     

磺化侧苯基杂萘联苯聚醚酮酮的合成与性能

以4-(3-苯基-4-羟基苯基)-2,3-二氮杂萘-1-酮(DHPZ-P)、 4-(4-羟基苯基)-2,3-二氮杂萘-1-酮(DHPZ)和1,4-二(4'-氟苯甲酰基)苯(BFBB)为原料, 经溶液亲核取代缩聚反应, 通过调节DHPZ-P和DHPZ的比例, 合成了一系列侧苯基杂萘联苯聚醚酮酮(PPEKK-P), 然后以浓硫酸为磺化剂, 制备出一系列磺化侧苯基杂萘联苯聚醚酮酮(SPPEKK-P). 利用傅里叶变换红外光谱(FTIR)和氢核磁共振谱(¹H NMR)对聚合物结构进行表征, 结果表明, 磺酸基团引入到聚合物链的侧苯基上. 采用溶液浇铸法制备SPPEKK-P质子交换膜. SPPEKK-P膜的吸水率、 溶胀率和质子传导率均随离子交换容量(IEC)的增加而增加, 且具有较好的耐氧化性. IEC最高的SPPEKK-P-100膜的质子传导率在95℃能达到7.44×10^-2 S/cm, 且甲醇渗透系数为5.57×10^-8 cm²/s, 阻醇性能优于Nafion117膜.     

环状和网络状有机硼化合物的研究 Ⅱ.1,2-氧硼杂戊环类化合物的合成与性质

2-烯丙氧基-1,2-氧硼杂戊环(1)的侧链有较大化学活性。(1)可与醇类酯交换制得2-烷氧基-1,2-氧硼杂戊环,如2-正戊氧基-、2-环己氧基-、2-环辛氧基、2-氨基乙氧基-1,2-氧硼杂戊环;与乙二醇反应可制得2,2′-次乙二氧基-双-(1,2-氧硼杂戊环)(6),同样,也可制得1,2-丙二醇和2,3-丁二醇衍生物(7)(8)。(1)与三丁基硼和三烯丙基硼热交换可制得2-正丁基-1,2-氧硼杂戊环和2-烯丙基-1,2-氧硼杂戊环(10)。(10)的侧链活性更大,易与醇、胺类反应制得相应衍生物,如2-正丁氧基-和2-烯丙胺基-1,2-氧硼杂戊环,反应机理可能是烯丙基型重排。(1)与氯化亚砜作用可制得2-氯-1,2-氧硼杂戊环(13),另外还有二个破环、氯转位的副产物,3-氯丙基硼酸二烯丙酯及酐。(6)、(7)、(8)的双环相互作用可能形成网络状结构以及(13)的X-衍射结晶结构正在深入研究中。通过1,2-氧硼杂戊环类侧链的交换反应,合成侧链上具有碳、氮、氧、氯的衍生物,不仅表明侧链的多变性,而且表明环本身有相对稳定性。     

氮杂菲及其10-取代衍生物的~1H及~(13)C核磁共振谱

本文测定并研究了氮杂菲和它的10-羟基,7,9-二溴-10-羟基,7,9-二氯-10-羟基,10-乙酰基,10-甲氧基衍生物的~1H及~(13)C NMR谱。在XL-200型仪器上使用标准的FT技术、分辨率增强和自旋模拟法,识别了~1H和~(13)C谱峰,测得J_(HH)。氮杂菲的10-H显著去屏蔽。当忽略10-H时,δ_O和δ_H相关很好。还测得氮杂菲~(13)C的T_1值。     

聚磷酸酯阻燃剂复配蒙脱土及聚磷酸铵对环氧树脂阻燃性能的影响

本文以二氯化磷酸对甲基苯酯和10-(2,5-二羟基苯基)-10-氢-9-氧杂-10-磷杂菲-10-氧化物(ODOPB)为原料,合成了一种新型聚磷酸酯阻燃剂聚磷酸-2-10-氢-9-氧杂-10-磷杂菲-10-氧化物基对苯二酚对甲苯酯(POTP),并采用傅里叶变换红外光谱(FTIR)和核磁共振(~(31)P-NMR,~1H-NMR和~(13)C-NMR)对其结构进行表征.将POTP与蒙脱土(MMT)及聚磷酸铵(APP)组成复合阻燃剂对环氧树脂(EP)进行阻燃改性,通过垂直燃烧(UL-94)、氧指数(LOI)、热失重(TGA)、锥形量热(CONE)和扫描电镜(SEM)等方法研究其对EP的热性能和阻燃性能的影响.结果表明,当阻燃剂添加量为7%时, EP复合材料UL-94测试等级可达V-0级;当添加阻燃剂为9%时,其LOI值可达到27.6%,最大热释放速率(Pk-HRR)下降了50.1%,热释放总量(THR)下降了27.4%,其残炭量高达29%. CONE测试后的残炭形貌研究显示阻燃EP在高温下形成较稳定的致密膨胀炭层,能有效抑制烟毒性气体释放,隔绝可燃气体与空气的交换,从而提高阻燃EP在高温下的热稳定性和阻燃性能.     

火安全环氧树脂材料的制备及其阻燃性能研究

针对“十四五”规划对高等教育人才培养的需求,为促进学生全面发展,加强交叉类学科的推广,改善传统教学实验中直观性、交叉性、创新性和实践性不足的问题,设计了制备安全环保材料的新创类综合实验。首先,利用9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)结构中P―H键的反应活性,与二苯甲烷双马来酰亚胺(BMI)分子发生加成反应,合成阻燃剂(BMP)。最后,通过熔融共混法将阻燃剂BMP均匀分散到环氧树脂固化物中,制得阻燃环氧树脂。该综合实验不仅将基础知识与科学前沿相结合,而且将合成实验与应用实践相结合,培养学生发现并解决问题的能力、学习新事物的能力、理论联系实际的能力。     

多胺配体及其配合物的合成与热力学性质研究

合成并表征了5个多胺配体N，N′-二(1，10-菲罗啉-2-亚甲基)-1，2-乙二胺(L1)，1，7-二(1，10-菲罗啉-2-亚甲基)-1，4，7-三氮杂庚烷(L2)，1，10-二(1，10-菲罗啉-2-亚甲基)-1，4，7，10-四氮杂癸烷(L3)，1，13-二(1，10-菲罗啉-2-亚甲基)-1，4，7，10，13-五氮杂十三烷(L4)，N，N′-二(1,10-菲罗啉-2-亚甲基)-1，3-丙二胺(L5)。利用pH电位滴定法在25.0 ± 0.1 ℃时测定了这5个配体的质子化常数及其与Co(Ⅱ)，Ni(Ⅱ)，Cu(Ⅱ)和Zn(Ⅱ)形成配合物的稳定常数，并且试图解释了这5个系列配合物的差异。     

Synergistic effect between a novel hyperbranched charring agent and ammonium polyphosphate on the flame retardant and anti-dripping properties of polylactide

A novel hyperbranched polyamine charring agent (HPCA), a derivative of triazines, was synthesized and well characterized by ¹H NMR and FTIR. HPCA and ammonium polyphosphate (APP) were added into polylactide (PLA) resin as an intumescent flame retardant (IFR) system to impart flame retardancy and dripping resistance to PLA. The flammability and thermal stability of IFR-PLA composites were investigated by limiting oxygen index (LOI), UL-94 vertical burning, cone calorimetry and thermogravometric analysis (TGA) tests. The results showed that the IFR system had both excellent flame retardant and anti-dripping abilities for PLA. The TGA curves suggested that HPCA has good ability of char formation and when combined with APP, would induce synergistic effect which could be clearly observed. This effect greatly promoted the char formation of IFR-PLA composites, hence improved the flame retardant property. Additionally, the structure and morphology of char residues were studied by XPS, FTIR and SEM.     

Synthesis of functionalized α-zirconium phosphate modified with intumescent flame retardant and its application in poly(lactic acid)

A novel functionalized α-zirconium phosphate (F-ZrP) modified with intumescent flame retardant was synthesized by co-precipitation method and characterized. Poly (lactic acid) (PLA)/F-ZrP nanocomposites were prepared by melt blending method. The thermal stability and combustion behavior of PLA/F-ZrP nanocomposites were investigated by thermogravimetric analysis (TGA), limiting oxygen index (LOI), vertical burning test (UL-94), scanning electronic microscopy (SEM), and cone calorimeter test (CCT). The results showed that the addition of flame retardant F-ZrP slightly affect PLA's thermal stability, but significantly improve the flame retardancy of PLA composites. In comparison with neat PLA, the LOI value of PLA/F-ZrP was increased from 19.0 to 26.5, and the UL-94 rating was enhanced to V-0 as the loading of F-ZrP at 10%. SEM results suggested the introduction of F-ZrP in the PLA system can form compact intumescent char layer during burning. All these results showed that the F-ZrP performed good flame retardancy for PLA.     

Synthesis of organo-modified α-zirconium phosphate and its effect on the flame retardancy of IFR poly(lactic acid) systems

Novel intumescent flame-retardant poly(lactic acid) (PLA/IFR)/organo-modified α-zirconium phosphate(OZrP) nanocomposites were prepared via incorporation of charring agent (CA), ammonium polyphosphate (APP) and OZrP into PLA. OZrP was synthesized directly by a solvent thermal method. The morphological characterization of PLA/IFR/OZrP nanocomposites was conducted by wide angle X-ray diffraction (WXRD) and transmission electron microscopy (TEM). The effect of the OZrP on flame retardancy and the thermal stability of PLA/IFR composites were studied by thermogravimetric analysis (TGA), limiting oxygen index (LOI), vertical burning test (UL-94) and cone calorimeter test. The TGA data illustrated that the OZrP could increase the residue and significantly improve the flame retardancy of PLA/IFR/OZrP nanocomposites showing an excellent synergistic effect. The addition of OZrP to the flame-retardant PLA increases the LOI and enhances the UL-94 rating. Cone calorimeter tests gave clear evidence that the incorporation of OZrP into PLA/IFR composites resulted in the significant reduction of the heat release rate (HRR), low total heat release (THR) and high amount of char residues during combustion. The flame-retardant mechanism of PLA/IFR/OZrP nanocomposites may correspond to the intumescent flame-retardant mechanism and catalyzed carbonization mechanism caused by OZrP.     

Fire retarded polyurethane foam composites based on steel slag/ammonium polyphosphate system: A novel strategy for utilization of metallurgical solid waste

A series of FR-RPUF composites were prepared by a one-step water foaming process with ammonium polyphosphate (APP) and steel slag (SS) as flame retardants. Thermogravimetric analysis (TG), limiting oxygen index (LOI), UL-94 vertical combustion test, microscale combustion calorimetry (MCC), TG-Fourier transform infrared spectrometry (TG-FTIR), scanning electron microscopy (SEM), Raman spectra and FTIR were used to investigate the thermal stability, flame retardancy, combustion performance, gas phase products, and char residue morphology of FR-RPUF composites. TG test results showed that the initial decomposition temperature (T_-5wt%) and char residue rate at 700°C of RPUF/APP/SS composites were significantly enhanced by the addition of APP and SS, and the thermal stability of the composites was improved. Flame retardant test results confirmed the significantly increased LOI values of RPUF/APP/SS composites with V-0 rating. TG-FTIR also confirmed the obviously decreased release of toxic gases and flammable gases in the combustion of RPUF/APP/SS composites. SEM and Raman spectra of char residues for the composites suggested that APP/SS system improved the compactness and graphitization degree of char layer for RPUF/APP/SS composite. The above researches provide a new strategy for the utilization of SS in fire safety engineering.     

磷腈类衍生物改性磷酸锆的合成及其复配聚磷酸铵对硅橡胶阻燃性能和力学性能的影响

利用原位插层反应制得磷腈类衍生物修饰的改性磷酸锆(F-ZrP),并用机械共混工艺制得阻燃硅橡胶复合材料(FRSR).采用X射线衍射(XRD)、透射电子显微镜(TEM)、傅立叶红外光谱(FTIR)、热重(TG)、扫描电子显微镜(SEM)分别对磷酸锆的结构及其在硅橡胶基体的分散进行表征,并结合FRSR的垂直燃烧(UL-94)、极限氧指数(LOI)、锥形量热测试及残渣表面形貌的观察,研究了不同份数的F-ZrP复配聚磷酸铵对FRSR阻燃性能的影响并和添加未改性磷酸锆的样品性能对比,并对阻燃机理进行初步探讨;最后分析FRSR的力学性能.结果表明:F-ZrP拥有更大的层间距,而且在FRSR中分散的更好;当1 phr F-ZrP和19 phr APP复配使用时,UL-94达V-0级且LOI值为31.4,热释放速率峰值为265.3 kW/m~2,拉伸强度达8.11 MPa,FRSR的阻燃性能和力学性能得到明显的改善.适量的F-ZrP和APP复配使用能在气相和固相发挥协效阻燃作用,F-ZrP与APP的并用能提高残渣质量并且使阻隔层更加紧实,致密.     

Flame retardant properties and mechanism of an efficient intumescent flame retardant PLA composites

The charring agent (CNCA‐DA) containing triazine and benzene rings was combined with ammonium polyphosphate (APP) to form intumescent flame retardant (IFR), and it was occupied to modify polylactide (PLA). The flame retardant properties and mechanism of flame retardant PLA composites were investigated by the limited oxygen index (LOI), vertical burning test (UL‐94), thermogravimetric analysis, microscale combustion calorimetry, scanning electron microscopy, laser Raman spectroscopy analysis and X‐ray photoelectron spectroscopy. The analysis from LOI and UL‐94 presented that the IFR was very effective in flame retardancy of PLA. When the weight ratio of APP to CNCA‐DA was 3:1, and the IFR loading was 30%, the IFR showed the best effect, and the LOI value reached 45.6%. It was found that when 20 wt% IFR was loaded, the flame retardancy of PLA/IFR still passed UL‐94 V‐0 rating, and its LOI value reached 32.8%. The microscale combustion calorimetry results showed that PLA/IFR had lower heat release rate, total heat release, and heat release capacity than other composites, and there was an obvious synergistic effect between APP and CNCA‐DA for PLA. IFR containing APP/CNCA‐DA had good thermal stability and char‐forming ability with the char residue 29.3% at 800°C under N₂ atmosphere. Scanning electron microscopy observation further indicated that IFR could promote forming continuous and compact intumescent char layer. The laser Raman spectroscopy analysis and X‐ray photoelectron spectroscopy analysis results indicated that an appropriate graphitization degree of the residue char was formed, and more O and N were remained to form more cross‐linking structure. Copyright © 2016 John Wiley & Sons, Ltd.     

Combustion properties and thermal degradation behavior of polylactide with an effective intumescent flame retardant

An intumescent flame retardant spirocyclic pentaerythritol bisphosphorate disphosphoryl melamine (SPDPM) has been synthesized and its structure was characterized by Fourier transformed infrared spectrometry (FTIR), ¹H and ³¹P nuclear magnetic resonances (NMR). A series of polylactide (PLA)-based flame retardant composites containing SPDPM were prepared by melt blending method. The combustion properties of PLA/SPDPM composites were evaluated through UL-94, limiting oxygen index (LOI) tests and microscale combustion calorimetry (MCC) experiments. It is found that SPDPM integrating acid, char and gas sources significantly improved the flame retardancy and anti-dripping performance of PLA. When 25 wt% flame retardant was added, the composites achieved UL-94 V0, and the LOI value was increased to 38. Thermogravimetric analysis (TGA) showed that the weight loss rate of PLA was decreased by introduction of SPDPM. In addition, the thermal degradation process and possible flame retardant mechanism of PLA composites with SPDPM were analyzed by in situ FTIR.     

聚磷酸酯阻燃剂复配聚磷酸铵对环氧树脂阻燃性能的影响

合成了一种9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)的衍生物——聚苯氧基磷酸-2-10-氢-9-氧杂-磷杂菲基对苯二酚酯(POPP), 以间苯二胺(m-PDA)为固化剂, 环氧树脂(EP)为基料, POPP为阻燃剂, 复配聚磷酸铵(APP), 制备了不同磷含量的阻燃环氧树脂. 利用极限氧指数(LOI)和垂直燃烧(UL94)实验表征了环氧树脂的阻燃性能; 以热重分析、 锥型量热和扫描电镜分析了阻燃环氧树脂的热性能和表面形态. 研究结果表明, 阻燃剂总加入量(质量分数)为5%时即可达到UL94 V-0级, 同时LOI值为27.7%; 当总加入量为15%, 即w_POPP=5%, w_APP=10 %时, 其LOI值可达到33.8%. 随着磷含量的增加, 阻燃环氧树脂的初始降解温度略有降低, 但高温下的残炭率明显增加. POPP/APP的加入在很大程度上降低了环氧树脂的热释放速率、 有效燃烧热、 烟释放量和有毒气体释放量. 阻燃环氧树脂在高温下形成比较稳定的致密膨胀炭层, 为底层的环氧树脂主体隔绝了分解产物及热量和氧气交换, 增强了高温下的热稳定性.     

Synergistic effect between expandable graphite and ammonium polyphosphate on flame retarded polylactide

Synergistic effect was observed between expandable graphite (EG) and ammonium polyphosphate (APP) on flame retarded polylactide (PLA) in this paper using limiting oxygen index (LOI), thermal gravimetric analysis (TGA), scanning electron microscopy (SEM) and X-ray spectroscopy (XPS) and cone calorimeter tests etc. In the experiments, PLA composites with 15 wt% of APP/EG(1:3) combinations showed a LOI value of 36.5 and V-0 rating in UL-94 tests, greatly improved flame retardant properties from composites with APP or EG alone. Results from TGA and cone calorimeter demonstrated that APP/EG combination could retard the degradation of polymeric materials above the temperature of 520 °C by promoting the formation of a compact char layer. This char layer protects the matrix effectively from heat penetrating inside and prevents its further degradation, resulting in lower weight loss rate and better flame retarded performance.     

Synergistic effect of boron containing substances on flame retardancy and thermal stability of intumescent polypropylene composites

The synergistic effect of four different boron containing substances, zinc borate (ZnB), borophosphate (BPO₄), boron silicon containing preceramic oligomer (BSi) and lanthanum borate (LaB), were studied to improve the flame retardancy of a polypropylene (PP) intumescent system composed of ammonium polyphosphate (APP) and pentaerythritol (PER). The flame retardancy of PP composites was investigated by limiting oxygen index (LOI), UL-94 standard, thermogravimetric analysis (TGA) and cone calorimeter tests. The addition of 20 wt% intumescent flame retardant (IFR) improves the flame retardancy by increasing the char formation. According to LOI and UL-94 test, boron compounds show their highest synergistic effect at 1 wt% loading. BPO₄ containing composite shows the highest LOI (30), lowest maximum heat release rate (HRR) and lowest total heat release rate (THR) value. Although the char yield increases as the amount of boron compounds increases, the flame retarding effect decreases. Cone calorimeter and TGA data indicate that the boron compounds are likely to show their synergistic effect by reinforcing the integrity of char which improves its barrier effect rather than increasing the char yield.