MSF-g-COOH/IFR阻燃复合薄膜的制备及性能研究

以季戊四醇(PEG)和三聚氰胺(MEL)为原料制备一种水溶性膨胀型阻燃剂(IFR),然后采用氯乙酸接枝剑麻纤维素微纤自制纳米纤维素(MSF-g-COOH)为基体,通过抽滤和自组装吸附的方法,制备了一种MSF-gCOOH/IFR阻燃复合薄膜。研究了IFR对MSF-g-COOH薄膜材料阻燃性和热性能的影响,并利用X射线分析仪(XPS)和扫描电子显微镜(SEM)对IFR的合成、MSF-g-COOH/IFR阻燃复合薄膜表面形貌的微观结构以及燃烧后的炭层结构进行分析。结果表明:当IFR自组装吸附在MSF-g-COOH薄膜表面后,MSF-g-COOH/IFR阻燃复合薄膜具有较好的阻燃性和热稳定性;其初始热分解温度相比纯MSF-g-COOH薄膜提高了20℃;经IFR自组装吸附后的MSF-g-COOH/IFR阻燃复合薄膜在燃烧过程中,其表面形成炭支撑保护层,可阻止火势蔓延。     

三嗪膨胀阻燃剂/硅酸镁协效阻燃TPU的制备及性能研究

以三嗪成炭发泡剂（CFA）及聚磷酸铵（APP）复配成膨胀阻燃剂(IFR),以硅酸镁(MgSiO3)为协效剂添加到热塑性聚氨酯弹性体(TPU)中制备阻燃TPU材料,研究了阻燃TPU材料的阻燃性能、力学性能、热降解行为和炭层的表面形貌。结果表明,纯TPU材料的极限氧指数仅为22.0 %,在空气中极易燃烧,当IFR添加量为28 %（质量分数,下同）,MgSiO3添加量5 %时,材料的极限氧指数提高到37.1 %,通过UL 94 V-0级,表现出很好的阻燃效果;但是IFR/MgSiO3的加入使材料的拉伸强度和断裂伸长率明显下降,也使得TPU材料的起始热分解温度提前,最大热降解速率峰值降低,同时材料的残炭量得到了很大程度的提高。     

烷基烯酮二聚体施胶体系对挂面再生纸表面不良施胶的成因剖析

针对某造纸厂再生纸抄造工程实际中,烷基烯酮二聚体（AKD）表面施胶挂面再生纸耐水性能提高不明显的质量问题,采用接触角、红外光谱（FTIR）、热重（TG）、X射线光电子能谱技术（XPS）、扫描电镜（SEM）、能谱（EDS）等研究方法,对纸厂生产的AKD施胶挂面再生纸纸样进行表征研究。结果表明,纸样接触角变化表现两面性差异,施胶纸样正面初期接触角为114.5°,反面初期接触角为118.5°,正面临界润湿接触角（≥90°）时间不足9min,反面临界润湿接触角为9min,纸样不具备长效耐水性,AKD施胶体系对纸张长效耐水性的贡献不明显;施胶后AKD特征官能团β-乙烯基丙内酯消失,施胶纸样和施胶萃取纸样在不同氛围下的失重行为不同,原子组成和原子价态化学环境不同,施胶纸样中含有可被四氢呋喃（THF）抽出的可溶物（AKD水解产物酮）,水解产物酮相对含量高于99.0%。AKD不良施胶的主要原因在于施胶体系配伍不当,导致AKD与纤维素酯化接枝反应的具有长效耐水产物的量不足。     

硅胶与膨胀型阻燃剂复配阻燃LGF/PP复合材料的性能研究

研究硅胶(SG)作为协效剂与IFR协同阻燃LGF/PP复合材料的性能。通过极限氧指数(LOI)、垂直燃烧(UL-94)、锥形量热仪(CONE)、热重分析法(TG)、扫描电子显微镜(SEM)、力学性能等测试表征LGF/PP/IFR/SG阻燃复合体系的性能。结果表明:当硅胶用量为2%时,阻燃复合材料的LOI为29.4%,且燃烧等级达到V-0级;CONE测试结果表明LGF/PP/IFR/SG阻燃复合材料的第一热释放速率峰值降低,而第二热释放速率峰消失;LGF/PP/IFR/SG阻燃复合材料具有较好的热稳定性,且产生致密均匀的炭层;并研究硅胶用量对复合材料力学性能的影响。     

超支化三嗪成炭剂阻燃聚丙烯

将自制的超支化三嗪成炭剂（CFA）与聚磷酸铵（APP）以1∶1的比例复配成膨胀型阻燃剂（IFR）,用于聚丙烯（PP）的阻燃。采用冲击实验、拉伸实验、极限氧指数仪、垂直燃烧（UL 94）和扫描电子显微镜 (SEM)等方法表征了PP阻燃复合材料的力学性能、阻燃性能,分析了断面形貌。结果表明,添加阻燃剂后,冲击强度呈先增加后降低的趋势,拉伸强度则随着阻燃剂含量的增加不断下降,但降幅不明显;含有15 % IFR的阻燃复合材料,其垂直燃烧等级即可通过UL 94 V-0级测试,显示出复合IFR具有优秀的阻燃效果。     

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。     

EG与IFR复合阻燃ABS的动态燃烧性和协同效应

将可膨胀石墨(EG)与P-N型膨胀阻燃剂(IFR)复合阻燃丙烯腈-丁二烯-苯乙烯共聚物(ABS)树脂,阻燃剂添加量为20%(质量分数,下同),通过极限氧指数(LOI)仪、垂直燃烧测试(UL-94)仪、锥形量热(CONE)仪和扫描电镜(SEM)研究了EG与IFR复合阻燃ABS的协同效应。结果表明,EG/IFR质量比为1/1为最佳配比,阻燃ABS的LOI达到29%,UL-94为V-0级;EG与IFR复合阻燃ABS,表现出一定的协同作用;通过SEM观察ABS/EG/IFR试样燃烧后样品发现,EG与IFR起到协同阻燃作用。     

硅酮粉与复合膨胀阻燃剂协同作用对聚丙烯阻燃性能的影响

研究了硅酮粉、聚磷酸铵(APP)与季戊四醇(PER)组成的复合膨胀阻燃剂(IFR)协同作用对聚丙烯(PP)热降解及阻燃性能的影响。通过TGA、LOI极限氧指数表征了PP材料热降解及阻燃性能。采用扫描电镜(SEM)表征了燃烧后残留炭层的表面形貌。结果表明:在PP燃烧过程中,硅酮粉能促进形成致密的,紧凑的膨胀阻燃炭层。当阻燃剂用量占体系的30%时,在聚丙烯阻燃体系中,硅酮粉与膨胀性IFR阻燃剂协同阻燃效果比单独使用IFR的阻燃效果好。硅酮粉与膨胀性IFR阻燃剂协同阻燃效果最佳用量为:硅酮粉为2%,IFR为28%。     

PP/LGF复合材料的膨胀性阻燃与协效阻燃性能

采用膨胀型阻燃剂(IFR)及协效剂海泡石(SP)对长玻璃纤维增强聚丙烯(PP/LGF)复合材料进行阻燃,通过双螺杆挤出机制备了PP/LGF母粒,IFR母粒和SP母粒,然后将这3种母粒通过注塑机制备了PP/LGF/IFR/SP复合材料,通过极限氧指数(LOI)、垂直燃烧测试、锥形量热仪、热重分析、扫描电子显微镜、力学性能测试等表征PP/LGF各阻燃复合体系的性能。结果表明,当IFR质量分数为22%时,PP/LGF/IFR阻燃复合材料的LOI为28.8%,且垂直燃烧等级达到V–0级;锥形量热仪测试结果表明加入IFR及SP后阻燃复合体系的第一热释放速率峰值降低,而第二热释放速率峰消失;SP质量分数为1%,IFR质量分数为21%的PP/LGF/IFR/SP阻燃复合材料LOI为29.6%,垂直燃烧等级达到V–0级,热释放速率峰值和总热释放量得到有效降低,热稳定性最好,且燃烧时产生致密的炭层覆盖于玻璃纤维表面,同时加入1%SP后复合材料的力学性能下降幅度相对较小。     

PPS与二乙基次膦酸铝协同阻燃GF增强PBT研究

采用聚苯硫醚(PPS)与二乙基次膦酸铝复配(ALDP),对玻璃纤维(GF)增强聚对苯二甲酸丁二酯(PBT)进行无卤阻燃改性,研究了复配阻燃体系对GF增强PBT阻燃性能和力学性能等的影响。结果表明,ALDP与PPS复配具有明显的协同阻燃效果,且随PPS含量的增加,阻燃GF增强PBT的力学性能呈现先降低后增加的趋势,而热变形温度、热分解温度和高温残留率逐渐提高,最大热分解速率逐渐降低。当添加PPS与ALDP的质量分数分别为10%,15%时,阻燃GF增强PBT的阻燃性能可达到UL94 V–0级(1.6 mm),拉伸强度为97.6 MPa,弯曲强度为149.1 MPa,缺口冲击强度为7.3 k J/m2,热变形温度为210.2℃,失重50%时的热分解温度(T50%)为513.5℃,700℃时的残留率为42.08%,最大热分解速率为9.53%/min。扫描电子显微镜测试表明,PPS的加入可以促进阻燃材料成炭,且对燃烧中形成的炭化层有加固作用,有效阻隔氧气和热量的传递,从而提高阻燃材料的阻燃性能。     

Synergistic flame‐retardant effect of halloysite nanotubes on intumescent flame retardant in LDPE

Synergistic flame‐retardant effect of halloysite nanotubes (HNTs) on an intumescent flame retardant (IFR) in low‐density polyethylene (LDPE) was investigated by limited oxygen index (LOI), vertical burning test (UL‐94), thermogravimetric analysis (TGA), cone calorimeter (CC) test, and scanning electronic microscopy (SEM). The results of LOI and UL‐94 tests indicated that the addition of HNTs could dramatically increase the LOI value of LDPE/IFR in the case that the mass ratio of HNTs to IFR was 2/28 at 30 wt % of total flame retardant. Moreover, in this case the prepared samples could pass the V‐0 rating in UL‐94 tests. CC tests results showed that, for LDPE/IFR, both the heat release rate and the total heat release significantly decreased because of the incorporation of 2 wt % of HNTs. SEM observations directly approved that HNTs could promote the formation of more continuous and compact intumescent char layer in LDPE/IFR. TGA results demonstrated that the residue of LDPE/IFR containing 2 wt % of HNTs was obviously more than that of LDPE/IFR at the same total flame retardant of 30 wt % at 700°C under an air atmosphere, and its maximum decomposing rate was also lower than that of LDPE/IFR, suggesting that HNTs facilitated the charring of LDPE/IFR and its thermal stability at high temperature in this case. Both TGA and SEM results interpreted the mechanism on the synergistic effect of HNTs on IFR in LDPE, which is that the migration of HNTs to the surface during the combustion process led to the formation of a more compact barrier, resulting in the promotion of flame retardancy of LDPE/IFR. In addition, the mechanical properties of LDPE/IFR/HNTs systems were studied, the results showed that the addition of 0.5–2 wt % of HNTs could increase the tensile strength and the elongation at break of LDPE/IFR simultaneously. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40065.     

Flame retardancy,mechanical, and thermal properties of waterborne polyurethane conjugated with a novel phosphorous‐nitrogen intumescent flame retardant

A novel phosphorous‐nitrogen intumescent flame retardant with reactive diamino groups, benzoguanamine spirocyclic pentaerythritol bisphosphonate (BSPB), was synthesized and used as a chain extender, and then a series of flame retardant waterborne polyurethanes (FRWPU) were prepared by covalently conjugating the BSPB into waterborne polyurethane (WPU) backbone. Their structures were characterized by Fourier transformed infrared spectrometry (FTIR), ¹H and ³¹P nuclear magnetic resonances (NMR), respectively. Simultaneously, the flame retardancy and the thermal stability of FRWPU were systematically investigated by limiting oxygen index (LOI) test, UL‐94 vertical burning test and thermogravimetric analysis (TGA). The results indicated that with the increase of BSPB content from 0 to 8 wt%, the LOI value of FRWPU increased from 18.6 to 27.3%, showing significant improvement by 8.7%. Compared with WPU, FRWPU showed decreased thermal stability but promoted char residue ratio. Conjugation of BSPB could obviously enhance the mechanical properties of FRWPU, the Young's modulus and tensile strength dramatically increased with the increase of BSPB. Investigation of char forming mechanism of BSPB through real time Fourier transform infrared spectra (RTFTIR) and scanning electronic microscopy (SEM) revealed that the polyphosphoric acid and phosphorus oxynitrides rich outer intumescent char layer could form protective shields to inhibit effectively internal polyurethane to heat and flame diffusion during contacting fire. POLYM. COMPOS., 38:452–462, 2017. © 2015 Society of Plastics Engineers     

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.     

Application of a novel halogen‐free intumescent flame retardant for acrylonitrile‐butadiene‐styrene

A novel intumescent flame retardant (IFR), containing ammonium polyphosphate (APP) and poly(tetramethylene terephthalamide) (PA4T), was prepared to flame‐retard acrylonitrile‐butadiene‐styrene (ABS). The flame retardation of the IFR/ABS composite was characterized by limiting oxygen index (LOI) and UL‐94 test. Thermogravimetric analysis (TGA) and TGA coupled with Fourier transform infrared spectroscopy (TG‐FTIR) were carried out to study the thermal degradation behavior of the composite and look for the mechanism of the flame‐retarded action. The morphology of the char obtained after combustion of the composite was studied by scanning electron microscopy (SEM). It has been found the intumescent flame retardant showed good flame retardancy, with the LOI value of the PA4T/APP/ABS (7.5/22.5/70) system increasing from 18.5 to 30% and passing UL‐94 V‐1 rating. Meanwhile, the TGA and TG‐FTIR work indicated that PA4T could be effective as a carbonization agent and there was some reaction between PA4T and APP, leading to some crosslinked and high temperature stable material formed, which probably effectively promoted the flame retardancy of ABS. Moreover, it was revealed that uniform and compact intumescent char layer was formed after combustion of the intumescent flame‐retarded ABS composite. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synergistic effects of 4A zeolite on the flame‐retardant properties and thermal stability of an efficient halogen‐free flame‐retardant EVA composite

The synergistic effects of 4A zeolite (4A) on the thermal degradation, flame retardancy, and char formation of an efficient halogen‐free flame‐retardant ethylene‐vinyl acetate copolymer composite (EVA/IFR) were investigated by limited oxygen index (LOI), vertical burning test (UL‐94), cone calorimeter test (CCT), digital photography, scanning electron microscopy (SEM), energy dispersive spectrometry (EDS), laser Raman spectroscopy (LRS) and thermogravimetric analytical (TGA) methods. It was found that a small amount of 4A clearly improved the LOI value of the EVA/IFR composite and reinforced the fire retardant performance with a great reduction in the combustion parameters of the EVA/IFR system from the CCT test. The entire composites passed the UL‐94 V‐0 rating test. The TGA and integral procedure decomposition temperature (IDPT) results showed that 4A enhanced the thermal stability of the EVA/IFR system and increased the char residue content effectively. The morphological structures observed by digital and SEM imaging revealed that 4A could promote EVA/IFR to form a more continuous and compact intumescent char layer. The LRS and EDS results demonstrated that by introduction of 4A into the EVA/IFR system, a more graphite structure was formed with increase phosphorus content in the char residue. POLYM. ENG. SCI., 56:380–387, 2016. © 2016 Society of Plastics Engineers     

笼型八苯基硅倍半氧烷对阻燃三元乙丙橡胶性能的影响

以聚磷酸铵和季戊四醇为膨胀阻燃体系(IFR),研究了笼型八苯基硅倍半氧烷(OPS)对阻燃三元乙丙橡胶(EPDM)力学性能及其阻燃性能的影响,并对燃烧残炭进行了表征。结果表明,与单独加入30份的IFR相比,同时加入20份OPS后,EPDM阻燃材料的综合性能得到改善,拉伸强度为2.47MPa,极限氧指数为24.2%,热释放速率峰值降低到331.2kW/m2,但生烟量增加到1058m2,且该材料的燃烧残炭结构相对致密均匀。     

Effect of charring agent THEIC on flame retardant properties of polypropylene

Tris(2‐hydroxyethyl) isocyanurate (THEIC) was used as charring agent and combined with ammonium polyphosphate (APP) to form an intumescent flame retardant (IFR) for polypropylene (PP). The flame retardancy and combustion performance of PP/IFR composite was tested by limiting oxygen index (LOI), UL‐94 vertical burning test and cone calorimeter. The results showed that PP/IFR composite had highest LOI of 34.8 and obtained V‐0 rating when 30 wt % IFR was loaded and mass ratio APP/THEIC was 2 : 1. The peak heat release (PHRR) and total heat release (THR) values of PP composite containing FRs were remarkably reduced compared with that of pure PP. However, water resistant test demonstrated the PP/IFR composite had poor flame retardant durability, both the LOI value and UL‐94 V‐rating decreased when PP/IFR composite was soaked in water at 70°C after 36 h. The degradation process and the char morphology of IFR and PP/IFR composite were investigated by TGA and SEM images. The possible reaction path between APP and THEIC in the swollen process was proposed. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41214.     

OMMT对LGFPP/IFR阻燃性能、燃烧性能及力学性能的影响

采用熔融共混技术制备了长玻璃纤维增强聚丙烯/膨胀阻燃剂/有机蒙脱土(LGFPP/IFR/OMMT)复合材料。利用极限氧指数(LOI)、锥形量热仪(CONE)以及万能力学试验机,表征了LGFPP/IFR/OMMT复合材料的阻燃性能、燃烧性能以及力学性能。氧指数测试结果表明,OMMT使LGFPP/IFR体系的氧指数提高。当添加2%OMMT时,LGFPP/IFR/OMMT复合材料的氧指数提高至24.2%。锥形量热仪测试结果表明,LGFPP/IFR体系的热释放速率峰值(PHRR)、烟雾生产率(THR)及引燃时间(TTI)均由于添加OMMT而大幅度降低。力学性能测试结果表明,LGFPP/IFR体系的拉伸强度、弯曲强度以及缺口冲击强度因OMMT的添加,分别提高了8.15%、9.04%和24%,使LGFPP/IFR体系中由于IFR引起LGFPP力学性能降低的弊端得到了明显改善。     

New intumescent flame‐retardant agent: Application to polyurethane coatings

The first part of this investigation focused on the synthesis and characterization of a new type of intumescent flame‐retardant (IFR) agent. Four steps were used in the synthesis process. The structure was characterized by FTIR, magic‐angle spinning nuclear magnetic resonance (MAS‐NMR) ¹³C spectroscopy, and elemental analysis. The addition of an IFR agent into polyurethane (PU) varnish led to an improvement in its carbonization and flame‐retardant (FR) properties. The second part focused on the evaluation of such characteristics as FR property, thermal stability of IFR/PU‐based coatings, rheology of IFR/PU‐based coating solutions, and mechanical properties such as hardness, adhesion, and flexibility of IFR/PU‐based dry coating films. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1193–1206, 2004     

Preparation of organic–inorganic intumescent flame retardant with phosphorus,nitrogen and silicon and its flame retardant effect for epoxy resin

According to the requirement of fire life cycle assessment (LCA), chitosan ethoxyl urea phosphate (CEUP), an organic–inorganic intumescent flame retardant (IFR) containing phosphorus, nitrogen, and silicon, was synthesized by the reaction of chitosan, phosphorus pentoxide, and urea. FTIR, ¹H NMR, SEM, and XRD were employed to characterize the compounds. As a result, CEUP was successfully prepared with higher thermal stability, favorable to enhance fire resistance. Combined with OMMT, the organic/inorganic IFR was applied as EP flame-retardant agents. The combustion behavior of EP composite was investigated by LOI, UL-94, CCT, SEM, TGA, and TG-IR. It was observed that using 15% CEUP and 3% OMMT (EP3), LOI value reached 34.8% and passed the UL-94 V-0 rating, while THR and TSP of EP composite reduced 65 and 72% compared with pure EP. The char residue of EP composite was up to 22.4%. The thermal decomposition mechanism was traced from 100 to 600°C by TG-IR. It was suggestive that CEUP decomposition commenced at 100°C to create phosphoric acid and sublimation of urea occurred at 300°C. EP3 exhibited a strong thermal stability, namely even at 600°C, the volatile substances were detectable. Dense and expanded carbon layer was confirmed in SEM images.