膨胀型聚氨酯防火涂料阻燃机理的研究

用自制的新型成炭剂和聚磷酸铵复配作为聚氨酯防火涂料的阻燃体系。采用热失重分析、扫描电镜、红外光谱和元素分析等手段对膨胀型聚氨酯防火涂料的阻燃机理进行了较为深入的研究．     

三聚氰胺磷酸盐阻燃剂的合成及性能表征

以新方法合成了三聚氯胺磷酸盐自膨胀阻燃剂(MP)，其结构经元素分析、XRD，TG，DSC，IR等表征。测定了含MP阻燃材料的阻燃性能，讨论了其阻燃机理及特点。用MP对聚丙烯进行阻燃处理后其氧指数可达27．1；徐覆含MP自膨胀防火涂料的五层板在模拟火灾中的耐火极限达39min，发泡倍数为90倍-100倍。     

膨胀型环状类磷酸酯蜜胺盐阻燃剂的合成及阻燃聚丙烯的结构与性能

以双季戊四醇、三季戊四醇、多聚磷酸、五氧化二磷和三聚氰胺为原料,合成了膨胀型环状类磷酸酯蜜胺盐阻燃剂,并与聚丙烯共混制成阻燃聚丙烯.红外分析表明该阻燃剂具有环状结构.通过扫描电镜和X射线衍射对阻燃聚丙烯进行了结构分析和表面纹理的表征.实验结果表明：该阻燃剂阻燃性能良好,但在聚丙烯中的分散性较差;用甲基纤维素对该阻燃剂进行表面化学修饰以后,该阻燃剂在聚丙烯中的分散性及阻燃材料的机械性能得到了明显的改善.     

高耐盐性吸水树脂的紫外光引发合成及其性能

采用紫外光引发聚合法合成了聚乙烯醇与丙烯酸钠高耐盐性吸水树脂.用红外光谱和热重分析法对产物进行了表征,测定了该树脂的溶胀动力学、可逆性能及温度、pH、离子浓度和有机溶剂等因素对树脂吸附率的影响.结果表明:该树脂在蒸馏水中的吸水率为4 100 g/g,在w=0.9%的NaCl水溶液中的吸盐水率为405 g/g;树脂的吸液率与阳离子的价态有关,其吸液率大小顺序为NaCl＞CaCl2＞FeCl3;其溶胀动力学扩散过程中的膨胀指数0.5＜n＜1,属于non-Fickon扩散.     

环氧树脂水基化化学改性的研究

用对氨基苯甲酸改性环氧树脂 ,使其成为具有亲水性的树脂。测定了改性树脂的溶解性 ,发现改性后树脂在有机溶剂中的溶解性能变差 ,但在碱性溶剂中溶解性增强。对改性树脂进行了红外光谱表征 ,并根据环氧基特征峰的吸收对环氧基转化率进行了定量分析。测定了改性产物的DSC曲线 ,发现随着反应物中对氨基苯甲酸比例的提高 ,改性产物的玻璃化转变温度升高。涂膜的性能测试表明 ,对氨基苯甲酸改性环氧树脂水基涂料的机械力学性能和耐化学试剂性能比溶剂型纯环氧树脂要优越。     

不同囊材聚磷酸铵微胶囊在环氧树脂中的阻燃研究

采用原位聚合法合成制备了以蜜胺树脂(MF)、环氧树脂(EP)以及EP和MF为囊材的微胶囊阻燃剂MFAPP、EPAPP、EMFAPP,用红外光谱(FT-IR)和扫描电镜(SEM)表征微胶囊阻燃剂的核壳结构。采用极限氧指数(LOI)和垂直燃烧等级测试(UL94)对MFAPP、EPAPP、EMFAPP在环氧树脂中的阻燃特性进行了研究。当添加量大于7%时,阻燃复合材料均能通过UL 94 V-0级测试,极限氧指数大于27.0%,表明MFAPP、EPAPP、EMFAPP均为EP的高效阻燃剂,这些阻燃剂在EP阻燃过程中均形成了膨胀炭层,属于膨胀阻燃机理。另外在耐水性实验中发现,添加EPAPP、EMFAPP的EP复合材料具有更好的耐水性,经75℃水浸泡6天后,阻燃性能得到了较好的保持。     

有机硅-丙烯酸酯微乳液的合成与表征

采用高温乳化种子单体滴加法制备了有机硅-丙烯酸酯共聚微乳液。对合成条件及微乳液的性能进行了研究。用红外光谱(FT-IR)、透射电镜(TEM)、动态激光粒度仪(PCS)对微乳液的结构和粒子形态进行了表征。结果表明:有机硅氧烷与丙烯酸酯发生了共聚反应,生成的微乳液粒子大致为球形结构,粒子大小比较均一,粒径较小。     

膨胀型阻燃涂料的研究进展

本文综述了近年来膨胀型阻燃涂料的研究进展,从膨胀型阻燃涂料的构成(基料、膨胀阻燃体系、填料颜料、助剂)出发,详细介绍了国内外基料的研究现况;并对常用的主要膨胀型阻燃剂,包括炭化剂、脱水催化剂和发泡剂进行了总结和分类;结合国外的研究,将常用几种填料对膨胀型阻燃涂料的性能影响作了系统的总结,对阻燃协效剂和其它助剂的影响和使用情况也进行了归纳和论述,并在此基础上对未来膨胀型阻燃涂料的发展趋势提出了建议。     

含氧超高交联树脂制备及对苯胺和苯酚的吸附性能研究

分别以间苯三酚(THB)和二氯甲基芳烃为单体,无水ZnCl_2为催化剂合成了含氧超高交联树脂TX和TC。通过红外光谱分析、比表面积测定、热重分析、扫描电镜等手段对其结构和形貌进行了表征,研究了两种树脂对苯酚和苯胺的吸附性能。表征结果表明,该树脂为醚键型无定型态聚合物。两种树脂对苯酚的吸附为放热过程,对苯胺的吸附为吸热过程。对苯酚和苯胺的吸附动力学曲线均符合准二级动力学模型。树脂中存在的氧原子可以与苯酚和苯胺形成氢键作用,有利于其对苯酚和苯胺的吸附。     

新型环氧丙烯酸树脂增韧剂的合成

用马来酸酐和聚乙二醇1000合成具有反应活性端基的聚乙二醇,用红外与核磁共振进行了表征,并用其对环氧丙烯酸树脂进行改性;研究反应温度、反应时间对反应及产物性能的影响;用红外对反应性聚乙二醇和环氧丙烯酸树脂的固化物进行分析.结果表明,反应性聚乙二醇参与了环氧丙烯酸树脂的固化反应,可在交联网络中构成不同长度的柔性链段,显著地提高了环氧丙烯酸树脂的冲击强度.     

Fire Retardancy of Aluminum Hydroxide Reinforced Flame Retardant Modified Epoxy Resin Composite

A novel phosphorous containing flame retardant epoxy resin is synthesized by modifying the epoxy resin initially with phosphoric acid and further with aluminum hydroxide (ATH) to enhance the fire retardancy of the modified epoxy resin. The several phosphorous modified epoxy resin to ATH mass ratios were used to study the effect of ATH addition on epoxy. Thermal and mechanical properties. The structure of the modified flame retardant epoxy resin was characterized using Fourier-transform infrared spectroscopy (FTIR) while thermal degradation behavior and flame retardant properties were examined using thermo-gravimetric analysis (TGA) and UL-94 testing. Furthermore, ultimate tensile strength and young modulus were analyzed to study the effect of ATH addition on mechanical properties. The findings indicated that fire retardancy of ATH reinforced modified ep oxy resin is higher than virgin and phosphorous modified epoxy resin and depicted eminent flame retardant properties with suitable mechanical properties.

     

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%.     

微纳米钙钛矿型羟基锡酸钙的合成及对环氧树脂的阻燃性能

钙钛矿型羟基锡酸盐是近年来出现的新型高效阻燃消烟剂. 本文采用化学共沉淀法合成了微纳米钙钛矿型羟基锡酸钙[CaSn(OH)₆, CSH], 并利用扫描电子显微镜、 透射电子显微镜、 X射线衍射仪、 红外光谱仪和X射线光电子能谱仪等对其形貌和结构进行表征. 结果表明合成的CaSn(OH)₆为平均粒径500 nm的纯净正六面体, 粒径均一且分散性良好. 将CaSn(OH)₆应用于环氧树脂(EP)复合阻燃体系(CSH/EP), 并分别采用热重分析、 极限氧指数和锥形量热测试表征了其热降解行为和燃烧性能. 采用扫描电子显微镜、 红外光谱、 X射线衍射和拉曼光谱对EP复合材料的阻燃成炭机制进行探索. 结果表明, CaSn(OH)₆能显著提高EP复合材料的高温稳定性、 热释放速率、 热释放量、 烟释放量和极限氧指数数值. 特别是在很低添加量(0.5%, 质量分数)下, 阻燃消烟性能即得到极大提升, 热释放速率、 总放热量和一氧化碳释放量分别降低45.8%, 25.1%和31.3%. 此外, 由于CaSn(OH)₆在EP基体中的良好分散及较强的界面作用, CaSn(OH)₆在提升EP复合材料阻燃消烟性的同时还提升了EP复合材料的力学强度. 本文合成的CaSn(OH)₆可作为一种多功能的高效阻燃、 消烟和增强剂.     

Preparation of Poly(phosphoric acid piperazine) and Its Application as an Effective Flame Retardant for Epoxy Resin

A phosphorus-nitrogen containing flame retardant additive of poly(phosphoric acid piperazine),defined as PPAP,was synthesized by the salt-forming reaction between anhydrous piperazine and phosphoric acid,and the dehydration polymerization under heating in nitrogen atmosphere.Its chemical structure was well characterized by Fourier transform infrared (FTIR) spectroscopy,13C and 31p solid-state nuclear magnetic resonance measurements.The synthesized PPAP and curing agent m-phenylenediamine were blended into epoxy resin (EP) to prepare flame retardant EP thermosets.The effects of PPAP on the fire retardancy and thermal degradation behavior of cured EP/PPAP composites were investigated by limiting oxygen index (LOI),vertical burning (UL-94),thermogravimetric analysis/infrared spectrometry (TG-IR) and cone calorimeter tests.The morphologies and chemical compositions of char residues for cured epoxy resin were investigated by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS),respectively.The results demonstrated that the flame retardant EP thermosets successfully passed UL-94 V-0 flammability rating and the LOI value was as high as 30.8％ when incorporating 5wt％ PPAP into the EP thermosets.The TGA results indicated that the synthesized PPAP flame retardant additive possessed high thermal stability and excellent charring capability.Meanwhile,the incorporation of PPAP stimulated the epoxy resin matrix to decompose and charring ahead of time due to its catalytic decomposition effect,which led to a higher char yield at high temperature.The morphological structures and the analysis results of XPS for char residues of EP thermosets revealed that the introduction of PPAP benefited the formation of a sufficient,more compact and homogeneous char layer containing phosphorus-nitrogen flame retardant elements on the material surface during combustion.The formed char layer with high quality effectively prevented the heat transmission and diffusion,limited the production of combustible gases,and inhibited the emission of smoke,leading to the reduction of heat and smoke release.     

Effect of acrylic polymer and nanocomposite with nano-SiO2 on thermal degradation and fire resistance of APP-DPER-MEL coating

Acrylic nanocomposite and flame retardant coatings with different acrylic polymers were prepared. The effect of molecular structure and molecular weight of acrylic resins and nanocomposite with nano-SiO₂ on the interaction and char formation of ammonium polyphosphate-dipentaerythritol-melamine (APP-DPER-MEL) coating was investigated using differential thermal analysis (DTA), thermogravimetry (TG), Limiting Oxygen Index (LOI), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and fire protection test. The interaction of APP, DPER, MEL and 3F-1 acrylic resin led to the formation of intumescent coherent char at 300-450 °C. Owing to low molecular weight and lack of benzene rings, F-963 acrylic resin decomposed at lower temperature than APP, and hence their endothermic interaction was destroyed. The well-distributed nano-SiO₂ particles in acrylic nanocomposite could modify char formation and anti-oxidation of char structure at high temperature. It is noted that the fire protection properties of nanocoating with acrylic nanocomposite were better than those of flame retardant coatings with conventional acrylic resins.     

Intrinsically flame retardant epoxy resin - Fire performance and background - Part I

The flame retardant effect of newly synthesized phosphorus-containing reactive amine, which can be used both as crosslinking agent in epoxy resins and as a flame retardant, was investigated. The effect of montmorillonite and sepiolite additives on the fire induced degradation was compared to pristine epoxy resin. The effect of combining the organophosphorous amine with clay minerals was also studied. It could be concluded that the synthesized phosphorus-containing amine, TEDAP can substitute the traditional epoxy resin curing agents providing additionally excellent flame retardancy: the epoxy resins flame retarded this way reach 960 °C GWFI value, 33 LOI value and V-0 UL-94 rating - compared to the 550 °C GWFI value, 21 LOI value and “no rate” UL-94 classification of the reference epoxy resin. The peak of heat release was reduced to 1/10 compared to non-flame retarded resin, furthermore a shift in time was observed, which increases the time to escape in case of fire. The flame retardant performance can be further improved by incorporating clay additives: the LOI and the HRR results showed that the optimum of flame retardant effect of clay additives is around 1 mass% filler level in AH-16-TEDAP system. Applying a complex method for mechanical and structural characterization of the intumescent char it was determined that the flame retarded system forms significantly more and stronger char of better uniformity with smaller average bubble size. Incorporation of clay additives (owing to their bubble nucleating activity) results in further decrease in average bubble diameter.     

聚对苯二甲酸丙二醇酯的无卤阻燃化改性

聚对苯二甲酸丙二醇酯作为新型聚酯材料,具有非常优良的性能,但其易燃性很大的限制了它的应用范围。为了提高对苯二甲酸乙二醇酯的阻燃性能,本文以无卤膨胀型EPFR-300A为阻燃改性剂,马来酸酐接枝聚烯烃(POE-g-MAH)弹性体为增韧剂,对聚对苯二甲酸丙二醇酯树脂(PTT)进行阻燃改性。通过热重分析仪(TGA)、示差扫描量热仪(DSC)、扫描电子显微镜(SEM)、力学性能等技术手段研究了阻燃剂和增韧剂对PTT树脂力学、热学和阻燃性能的影响。结果表明,增韧剂POE和POE-g-MAH的添加提高了PTT树脂的综合力学性能。当质量分数相同时,POE-g-MAH对PTT树脂的增韧效果要优于POE,且当POE-g-MAH质量分数为7%时,综合力学性能最佳。当添加相同质量分数增韧剂,EPFR-300A质量分数达到20%时,阻燃PTT材料阻燃性能最佳,极限氧指数(LOI)达到28.0%,垂直燃烧阻燃等级达到UL94 V-0级。EPFR-300A阻燃剂与PTT树脂间相容性良好,可以有效地促进PTT树脂成炭并提高材料的阻燃性能。     

Synthesis and properties of a phosphorus-containing flame retardant epoxy resin based on bis-phenoxy (3-hydroxy) phenyl phosphine oxide

A reactive phosphorus-containing compound, bis-phenoxy (3-hydroxy) phenyl phosphine oxide (BPHPPO) was first successfully synthesized to produce the phosphorus-containing flame retardant epoxy resin (BPHPPO-EP). The chemical structures were characterized from FTIR, MS, NMR spectra and elemental analyses. Thermal degradation behaviors and flame retardant properties of the cured epoxy resins were investigated from the thermogravimetric analysis (TGA) and the limiting oxygen index (LOI) test using 4,4′-diaminodiphenylsulfone (DDS) as curing agent. The high char yields and the high limiting oxygen index values were found to certify the great flame retardancy of this phosphorus-containing epoxy resin.     

改性酚醛成炭剂的制备及其在氢氧化镁/聚酰胺6阻燃体系中的协效阻燃作用

氢氧化镁(MH)是一种重要环保型阻燃剂,针对MH阻燃效率低,添加量大,与树脂相容性差的特点,研制了硼改性酚醛基成炭剂(BPF)用于增强MH的凝聚相阻燃作用,以提高MH的阻燃效率.用XRD、红外、核磁等手段表征了BPF的化学结构.TGA研究表明BPF成炭性优异,750℃时残炭高达61%.阻燃PA6体系中,BPF与MH有显著的协效作用,材料能通过UL94-1.6 mm V0级别.BPF的阻燃增效机理分析表明,BPF燃烧时生成的B2O3可在燃烧材料表面富集形成玻璃态的有效阻隔层,使材料自熄.此外,BPF能显著提高材料加工流动性,具有较好增塑、润滑作用.BPF不会恶化材料力学性能,阻燃材料综合性能优良.     

含烯丙基六苯氧基环三磷腈的合成及其在阻燃丙烯酸酯树脂中的应用

以六氯环三磷腈（HCCP）、苯酚和2-烯丙基苯酚为原料,合成了新型含烯丙基的环磷腈阻燃单体（2-烯丙基苯氧基）五苯氧基环三磷腈（APPCP),用红外光谱、核磁氢谱、质谱和元素分析表征其组成和结构。 将APPCP与丙烯酸酯单体共聚制备了阻燃丙烯酸酯树脂,测试了共聚丙烯酸酯树脂的热稳定性和阻燃性,当APPCP用量为20%时,共聚丙烯酸酯树脂燃烧等级（UL-94）可达V-0级,极限氧指数（LOI）高达31.2%,在空气中600 ℃时残留质量提高至23.2%。