透明阻燃环氧树脂的制备及研究

合成了一种新型含磷单体。以甲基二氯磷和双酚A为单体,通过熔融缩聚合成了分子量为1 316的聚甲基亚膦酸双酚A酯(PMPBE)。将合成的聚甲基亚膦酸双酚A酯添加环氧树脂(EP)中,制备了不同添加量的透明阻燃复合材料。通过极限氧指数仪、垂直燃烧仪、微型量热仪、扫描电子显微镜等测试了EP/PMPBE复合材料的结构和性能。结果表明,PMPBE和EP在120℃发生化学反应,得到的样条有良好透明性和热稳定性,与EP相容性好,说明PMPBE是良好的反应型阻燃剂。当添加20%PMPBE时,EP的极限氧指数从17.0%提高到27.6%,达到V-0级,最大放热速率和总热释放量均降低27.0%左右,能明显抑制EP的分解,提高EP的阻燃性能,以凝聚相机理实现阻燃。     

新型含磷环氧树脂的研究进展

有机和无机磷化物是新一代无卤、环保和绿色新型阻燃改性单体,可合成具有优异热稳定性、阻燃特性和物理机械性能的新型含磷环氧树脂。综述了DOPO的结构性能和化学反应性,以及以DOPO和氧氯化磷为原料合成新型含磷中间体和环氧树脂的结构、合成方法及性能等。     

新型磷硅改性环氧树脂阻燃性能研究

采用聚苯基硅氧烷(PPMS)、9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)与双酚A型环氧树脂合成了新型的含磷硅环氧树脂(Si-P-EP),通过红外谱确认了其结构。将Si-P-EP与纯环氧树脂复配制备得到复合物Si-P-EP/EP,对其进行了氧指数和水平燃烧测试并通过红外光谱对燃烧后的残炭结构进行了分析。结果表明,Si-P-EP/EP的氧指数有所提高,水平火蔓延速率由27.27 mm/min降低到20.13 mm/min,Si-P-EP/EP燃烧后生成了含磷硅的炭层,从而提高了环氧树脂的阻燃性能。     

改性环氧树脂对碳纤维表面上浆性能的影响

以双酚F型EP(环氧树脂)为基体、PMCB(含磷三聚氰胺席夫碱)为改性剂,合成了碳纤维表面上浆用新型含磷阻燃型EP上浆剂。研究结果表明:该上浆剂具有一定的阻燃性和热稳定性(其热分解温度为283.6℃),能有效提高碳纤维的综合性能;将该上浆剂应用于PAN(聚丙烯腈)基碳纤维表面,则上浆后的碳纤维复丝表面光滑、黏附性和集束性明显提高,并且其极限氧指数(29.4)提升了31.8%、拉伸强度(6 300 MPa)明显增大。     

阻燃型聚丙烯酸酯橡胶的制备和性能

用共聚法和共混法制得了2种阻燃环氧型聚丙烯酸酯橡胶 (EP -ACM ) ,研究了含磷共聚单体及添加无机阻燃剂对EP -ACM阻燃性能和力学性能的影响。结果表明 ,阻燃剂的引入虽可有效地提高胶料的阻燃性 ,但力学性能均有不同程度的下降。     

含磷共聚酯的合成及性能研究

用添加含磷共聚单体法合成了三种新四的含磷共聚酯。对萃洗后的反应产物进行了红外测试，对合成的反应条件进行了初步研究，并对所得产物的性能进行了对比。结果表明，含磷共聚单体的引入使共聚酯的玻璃化转变温度和熔点较聚酯降低，而冷结晶温度和结晶速度的变化则随引入的改性组分的不同而异。共聚酯的阻燃性、抗静电性均得到改善，染色性能也有所改善，表明该类共聚酯有可能用于制备多功能涤纶。     

含磷丙烯酸树脂的制备及其阻燃性能研究

采用甲基丙烯酸羟乙酯与五氧化二磷制备含磷单体—甲基丙烯酸羟乙酯磷酸酯(PMOE),并用于合成含磷丙烯酸乳液。研究含磷单体含量对乳液聚合过程稳定性及其树脂阻燃性能的影响。采用红外光谱(FTIR)分析含磷丙烯酸乳液的化学组成;通过热重分析(TGA)、极限氧指数(LOI)和UL-94方法测试含磷丙烯酸树脂的热稳定性和阻燃性能,并利用扫描电镜(SEM)观察含磷丙烯酸树脂残炭微观形貌。实验结果表明:当乳液体系中含磷单体的含量低于30%(wt)时,可以制备得到具有高单体转化率、低凝胶率且储存稳定良好的含磷丙烯酸乳液。随着含磷单体的提高,树脂的成碳率增大,LOI值提高,阻燃性能也得到提高。当含磷单体的用量为30%(wt)时,改性树脂的LOI值可以达到29.5%,并能通过UL-94测试的V-0级别,700℃下的成碳率可达54%(wt)。通过对树脂残炭的微观形貌分析,证明磷元素在丙烯酸树脂体系中主要起到凝聚相阻燃作用。     

环氧树脂改性丙烯酸酯乳液胶粘剂的制备及性能表征

以丙烯酸丁酯(BA)为软单体、甲基丙烯酸甲酯(MMA)为硬单体、丙烯酸(AA)为功能单体、EP(环氧树脂)为改性单体、十二烷基硫酸钠(SDS)和烷基酚聚氧乙烯醚(OP-10)为阴/非离子型复合乳化剂,采用半连续种子乳液聚合法合成了EP改性丙烯酸酯乳液胶粘剂。研究结果表明:当w(EP)=6%⁸%(相对于共聚单体总质量而言)时,改性胶粘剂的稳定性、耐水性、力学性能和粘接性能等均得到明显提高。     

环氧树脂和氧化锌对含磷化合物阻燃HIPS力学性能的影响

研究环氧树脂（EP）和氧化锌用量对含磷化合物阻燃高抗冲聚苯乙烯（HIPS）力学性能的影响。结果表明,EP可以改善含磷化合物在HIPS中的分散,提高含磷化合物阻燃HIPS的强度和刚度,但使材料的韧性下降：适量的氧化锌进一步提高了（EP-含磷化合物）复合阻燃HIPS的力学性能,当其用量为6份时,材料具有较好的综合力学性能。     

丙烯酸酯接枝改性环氧树脂乳液的合成与性能研究

以BA(丙烯酸丁酯)为软单体、St(苯乙烯)为硬单体、EP(环氧树脂)为基体、APS(过硫酸铵)为引发剂和三乙烯四胺为固化剂,采用乳液聚合法合成了丙烯酸酯接枝改性EP乳液。研究结果表明:当反应温度为80℃、m(BA)∶m(St)=1∶1、n(环氧基)∶n(氨基)=1∶1、w(引发剂)=0.8%、w(乳化剂)=4%和w(EP)=25%(均相对于单体总质量而言)时,合成的丙烯酸酯改性EP乳液具有良好的综合性能,其稳定性及涂膜强度均满足应用要求。     

全消光阻燃聚酯切片工业制造及性能表征

采用2-羧乙基苯基次磷酸(CEPPA)、[(6-氧(6H)-二苯并(c,e)(1,2)-氧磷杂己环-6-酮)甲基]-丁二酸(DDP),在连续化聚酯装置上工业化生产全消光阻燃聚酯切片。介绍了全消光阻燃聚酯切片的生产过程,并对产品性能进行了表征。结果表明:生产过程稳定,产品质量优异,全消光阻燃聚酯切片的结晶性能低于常规全消光切片,热稳定性能优于常规全消光切片,阻燃性能优良。     

结合磷阻燃型苯丙共聚乳液胶粘剂的合成及性能研究

以苯乙烯(St)、丙烯酸丁酯(BA)、丙烯酸乙酯(EA)、甲基丙烯酸甲酯(MMA)、丙烯酸(AA)和含磷单体为共聚单体,采用预乳化种子乳液聚合法制备PSA(结合磷型苯丙共聚乳液胶粘剂),并在PSA中添加少量无机阻燃剂APP(聚磷酸铵)制备CPSA(复合型阻燃胶粘剂)。系统研究了含磷单体和APP含量对乳液稳定性、胶膜剥离强度、涂层阻燃性和热性能等影响。结果表明:当m(St+BA+EA+MMA+AA)=40 g、m(St)∶m(BA)∶m(EA)∶m(MMA)∶m(AA)=16∶90∶60∶24∶5、w(含磷单体)=4%和w(APP)=12%(相对于单体总质量而言)时,可制成稳定性、剥离强度和阻燃性能俱佳的CPSA。     

Synthesis of phosphaphenanthrene derivatives as flame retardants and their properties in epoxy resin composites

In order to further improve the flame-retardant properties of epoxy resins (EPs), two hydroxyl-containing phospha-phenanthrene derivatives, DOPO-PHBA and DOPS-PHBA, were prepared from the molecular structure design by using 9,10-dihydro-9-oxa-10-phospha-phenanthrene-10-oxide (DOPO), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-sulfide (DOPS), and 4-hydroxybenzaldehyde (PHBA) as the raw materials. These composites of DOPO-PHBA/EP and DOPS-PHBA/EP were prepared by melt blending. The results showed that UL-94 V-0 was achieved with an LOI of 31.9% when just 7.5% DOPS-PHBA was added to EP, while a limited oxygen index of 35.2% was achieved with 10% DOPO-PHBA/EP. Moreover, in comparison with 7.5% DOPO-PHBA/EP, 7.5% DOPS-PHBA/EP has the lower peak of heat release rates, total heat release values, and fire growth rate, demonstrating that the flame-retardant DOPS-PHBA is more effective at reducing heat release, enhancing the material's flame retardancy, and lessening the intensity of EP burning. The Thermogravimetric-infraredspectrometry (TG-IR) results showed that the phosphorus-containing radicals generated by DOPS-PHBA/EP pyrolysis trapped the free radicals, such as H˙, O˙, or HO˙, thus providing free radical quenching. Furthermore, combining the macro and micro Scanning electron microscopy (SEM) test results, DOPS-PHBA/EP has a better char formation ability and a denser char layer, which can play a better role in heat and oxygen insulation.     

Cage–ladder-structure,phosphorus-containing polyhedral oligomeric silsesquinoxanes as promising reactive-type flame retardants for epoxy resin

We synthesized a novel cage–ladder-structure, phosphorus-containing polyhedral oligomeric silsesquinoxane (CLEP–DOPO–POSS) via the hydrolytic condensation of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO)–vinyl trimethoxysilane (VTMS) with 2-(3,4-epoxycyclohexyl) ethyl trimethoxysilane and then incorporated it into epoxy resins (EPs) in different ratios with thermal curing technology. The structure of CLEP–DOPO–POSS was confirmed by Fourier transform infrared spectroscopy, NMR spectroscopy (¹H-NMR and ²⁹Si-NMR), matrix-assisted laser desorption ionization time-of-flight, and X-ray diffraction. The thermal stability, mechanical properties and flame retardancy effect of CLEP–DOPO–POSS on EP were comprehensively evaluated via thermogravimetric analysis (TGA), dynamic mechanical analysis, universal tensile testing, limiting oxygen index (LOI) measurement, UL-94 testing, and cone calorimetry. The flame-retardant mechanism of the EP modified with CLEP–DOPO–POSS was investigated by TGA–IR, TGA–mass spectrometry, and scanning electron microscopy. The experimental results show that CLEP–DOPO–POSS was homogeneously dispersed in the EP matrix. The LOI value reached 31.9, and the UL-94 grade passed V-0 with the presence of only 0.28% P (2.91 phr CLEP–DOPO–POSS). In addition, the EP composite containing CLEP–DOPO–POSS exhibited a better thermal stability and mechanical properties. The flame-retardant mechanism was attributed to the quenching effect of the phosphorus-containing free radicals and the formation of phosphorus- and silicon-containing char layers in the condensed phase. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47607.     

Zirconium-Embedded Polyhedral Oligomeric Silsesquioxane Containing Phosphaphenanthrene-Substituent Group Used as Flame Retardants for Epoxy Resin Composites

A zirconium hybrid polyhedral oligomeric silsesquioxane derivative (Zr–POSS–bisDOPO) is synthesized by the corner-capping and Kabachnik–Fields reactions. It is characterized by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (NMR), and then used as a flame retardant in diglycidyl ether of bisphenol A (DGEBA) to endow epoxy resin (EP) with flame retardancy. The flame retardancy, thermal stability, and mechanical properties of the cured EP/Zr–POSS–bisDOPO composites are investigated. The results show that when Zr–POSS–bisDOPO is added by 5–7 wt%, the EP/Zr–POSS–bisDOPO composites pass the UL-94 V-0 rating test. In addition, they have a better flame-retardant effect than pure EP. The combination of Zr atom embedded in the Si O cubic cage and the two phosphaphenanthrene substituent groups in one corner of cubic cage is expected to realize the Zr/Si/P ternary intramolecular hybrid synergistic effect and achieve the possibility of dispersing metal–POSS cages at a sub-micrometer-scale level into polymer matrix. It also proves that Zr–POSS–bisDOPO produces phosphorus-containing free radicals and terminates the chain reactions in gas phase. Meanwhile the Si O Si and Zr O units are retained in the solid phase, which promote the char formation and enhance the flame retardancy. This kind of Zr-doped POSS will be helpful for developing the new metal–POSS hybrid flame-retardant and polymer composites.     

磷系阻燃聚酯纤维的制备与性能研究

本工作在制备磷系共聚/共混型聚酯的基础上,对磷系阻燃聚酯纤维进行了纺丝试验研究,并通过大角X衍射、声速和动态力学测试等手段对含磷阻燃PET纤维的结构性能进行了探讨。试验表明,含磷阻燃PET纤维的强度能达到2.8～3.0cN/dtex,LOI值达到32.5～34,但相应的结晶度和取向度低于常规PET纤维。     

Enhancement of fire safety in epoxy resin composites through incorporation of microencapsulated diatomite

Diatomite (DIA) particles are commonly employed as flame-retardant additives for polymers, yet their intrinsic inefficiency requires substantial quantities for optimal efficacy. To address this issue, we proposed a novel approach involving the microencapsulation of DIA with polyethylene glycol phosphate (PEGP) to enhance the flame retardancy of epoxy resin (EP). Characterization of the prepared DIA@PEGP utilized scanning electron microscopy with energy-dispersive x-ray spectrometry and Fourier transform infrared spectroscopy. The resulting EP composite, DIA@PEGP-4/EP, achieved a limiting oxygen index of 33.2% and achieved a V-0 level in vertical combustion tests. Compared to EP, DIA@PEGP-4/EP demonstrated significantly improved fire performance, with 38.6%, 47.8%, 25.0%, 41.3%, and 60.4% reduction in peak heat release rate, total heat release, peak smoke production rate, total smoke production, and CO yield. Furthermore, the highest FPI value of 0.080 m²·s/kW for DIA@PEGP-1/EP and the lowest FGI value of 8.734 kW/m²·s for DIA@PEGP-4/EP, indicate that the incorporation of DIA@PEGP into EP enhances its fire safety. The flame retardancy mechanism of DIA@PEGP-4 involves the formation of a phosphorus-containing aromatic carbon layer during EP char formation, capturing radicals in the gas phase during combustion.     

磷系阻燃改性共聚酯的热性能研究

选用主链含磷的阻燃剂2-羧乙基苯基次膦酸和侧链含磷的阻燃剂9,10-二氢-9-氧杂-10-[2,3-二(2-羟基乙氧基)羰基丙基]-10-磷杂菲-10-氧化物,在3 L聚合反应釜上分别合成了磷质量分数为0.6%的阻燃改性共聚酯。利用TGA、DSC对其热性能进行了分析,并对其切片干燥和熔融后的黏度降进行了测试。结果表明,随着反应型阻燃剂的添加,阻燃共聚酯的tg,tm下降,而Δt热和Δt冷则呈上升趋势,结晶能力下降;共聚酯的初始热分解温度有所下降,经切片干燥和熔融后的黏度降增大。     

An Itaconic Acid-Based Phosphorus-Containing Oligomer Endowing Epoxy Resins with Good Flame Retardancy and Toughness

With the aim to reduce the influence of flammability and brittleness of epoxy resin (EP) on its applications, a phosphorus-containing oligomer (BID) containing phosphophenanthrene group and flexible chain segment is designed and applied to methyltetrahydrophthalic anhydride (MeTHPA) curing EP systems. Compared with EP/MeTHPA, the glass transition temperature (T_g) declines after introducing BID. But the addition of BID endows EP/MeTHPA with good flame retardancy. When the dosage is only 19.2 wt.%, the limiting oxygen index (LOI) of EP/BID/MeTHPA increases by 77% to 36% (P content: 1.5 wt.%) compared with EP and reaches the vertical combustion (UL-94) V-0 rating. Cone calorimetry (CC) results reveal that PHRR and THR drop by 40% and 31%. The pyrolytic process and char residue data analysis show that BID plays flame-retardant role in gas phase and condensed phase. In addition, impact and flexural and tensile strength improve by 84%, 19% and 54% individually, proving that BID holds a potential on enhancing mechanical performance of EP/MeTHPA.     

磷系阻燃共聚酯流变性能探讨

采用日本岛津KOKA302型毛细管流变仪,对有光阻燃聚酯切片的流变性能进行了研究,并与普通有光聚酯切片的流变性能进行了比较。结果表明：阻燃聚酯熔体属非牛顿流体;与普通聚酯相比,阻燃聚酯熔体黏度偏低,对温度的敏感性相对较大,高磷含量阻燃聚酯对温度敏感性更大。流变性研究为磷系阻燃共聚酯切片的纺丝、成形、加工工艺条件的制订提供了依据。