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%。     

水脱型UV防护油墨的制备及性能研究

通过将环氧树脂E44、丙烯酸、2-丙烯酰胺-2-甲基丙磺酸反应,合成了一种改性环氧丙烯酸树脂。将改性的环氧丙烯酸树脂作为主体树脂,复配活性单体、引发剂、助剂、填充料等进行混合、分散、研磨,制备得到热水脱膜UV防护油墨。将该树脂与其他丙烯酸树脂进行性能对比,并进一步探究不同活性单体、膜层厚度与光固化能量对防护油墨的性能影响。实验表明,该树脂具有较好的热水脱膜性能,当采用活性单体二乙二醇二甲基丙烯酸酯,膜层厚度为30?m及固化能量为1 500 mJ/cm2时,防护油墨综合性能最佳。     

密胺树脂/硼酸锌双层包覆微胶囊化红磷的制备及其在阻燃聚烯烃中的应用

描述了采用密胺树脂和硼酸锌连续双层包覆微胶囊化红磷(MRP)的最新制备方法。采用红外光谱、电子能谱和透射电镜等分析手段对其进行了表征，并证实红磷已被完全包覆。实验数据表明：经包覆的MRP的热稳定性获得了明显改善，吸水率和磷化氢的发生量均大大减少。MRP作为阻燃助剂应用于聚烯烃阻燃材料表现出了良好的阻燃效果。实时红外和热失重测量以及扫描电镜观察表明：其阻燃机制是红磷受热时与树脂反应促进了含磷膨胀炭层的形成，从而提高了材料的热稳定性，碳层起到了隔氧、隔热作用，而且主要在凝聚相中发挥其阻燃作用。     

环状单体与乙烯基单体的杂化共聚

本文研究了在膦腈碱(t-BuP4)催化下各种环状单体和乙烯基单体的杂化共聚,发现己内酯、丙交酯或环碳酸酯与丙烯酸酯或甲基丙烯酸酯能够进行杂化共聚,但环硅氧烷与乙烯基单体、丙烯腈与内酯不能杂化共聚.研究表明,单体与活性中心的匹配决定了杂化共聚能否进行.     

粘胶纤维接枝含磷阻燃单体的研究

用含磷、硫的阻燃共聚单体O,O-二乙基-O-烯丙基硫代磷酸酯与粘胶纤维在四价铈离子作引发剂的条件下,通过自由基共聚的方式制备了含磷、硫的改性粘胶纤维。通过红外光谱(FTIR)、热重分析(TG)、差热分析(DTA)、差示扫描量热分析(DSC)、X射线分析以及扫描电子显微镜(SEM)分析对所制备的改性粘胶纤维进行了表征及性能研究。结果表明,阻燃共聚单体接枝到了粘胶纤维的表面;改性后的粘胶纤维的热分解温度较未改性的粘胶纤维提前,且热性能显著提高。     

超临界二氧化碳中含氟聚合物的合成*

超临界二氧化碳是廉价、低毒、不易燃、易回收、环境友好的惰性聚合介质,是传统有机溶剂的替代品。尤其是有望成为含氟单体的聚合溶剂,以替代目前使用的氟氯烃。本文详细地介绍了近年来以超临界二氧化碳为介质的氟烷基丙烯酸酯类单体和氟烯烃类单体的聚合反应研究,其中涉及氟烷基丙烯酸酯类单体的均聚和共聚,可熔融加工的四氟乙烯聚合物,离子交换树脂,偏氟乙烯的均聚和共聚合等。研究表明在超临界二氧化碳中的含氟单体的聚合反应有其它溶剂体系无法比拟的优点。     

一种新型无卤阻燃覆铜箔板基板材料的制备

以苯并噁嗪树脂与含磷环氧树脂作基体，外加磷酸酯类阻燃剂，KH平纹玻璃布作增强材料，制备了一种新型无卤阻燃覆铜板，其玻璃化转变温度为160℃，加强耐热性PCT(2p^a水蒸气处理2h后，经288℃浸锡)试验达到385秒，径向弯曲强度为630．6MPa，阻燃性达到UL94V0级。     

阻燃有机玻璃研究进展

有机玻璃属于易燃材料,存在严重的火灾隐患,其阻燃配方设计需要同时对聚甲基丙烯酸甲酯进行耐热改性和阻燃设计,并兼顾热变形性和机械性能等方面.改善耐热性主要通过在聚甲基丙烯酸甲酯上增加链段刚性、主价交联和副价交联,从而减缓甲基丙烯酸甲酯的分解,减少阻燃配方设计时阻燃剂用量.为了设计高玻璃化转变温度的材料,提高阻燃有机玻璃的力学性能,应尽可能降低添加型和可聚合型磷酸酯类阻燃剂的用量,其中可聚合磷酸酯类阻燃剂是今后阻燃有机玻璃技术发展的重要方向.在透明度要求不高的领域,采用二氧化硅纳米粉、氧化锌纳米棒、磷酸铝和石墨烯片状纳米材料与阻燃剂复配也可以得到良好的阻燃效果.     

阻燃型含磷环氧树脂体系的研究进展

将磷导入环氧树脂体系而赋予其阻燃性能是目前热门的研究课题。本文简述了含磷阻燃剂的阻燃机理，详细讨论了含磷阻燃环氧的类型及固化物的阻燃特性，以及磷和氮、硅等元素的协同效应。     

巯基/(甲基)丙烯酸(甲基)烯丙酯光固化特性

通过对羧酸盐法改进后合成同时含有高活性的丙烯酸酯型C=C和低自由基活性的烯丙基型C=C的烯类单体(甲基)丙烯酸(甲基)烯丙酯,以实现(甲基)丙烯酸酯类紫外光固化与巯/烯光聚合结合在二元体系中;并以1173为光引发剂,利用实时红外(RT-IR)跟踪此类烯烃与三羟甲基丙烷三(3-巯基丙酸酯)(TMMP)光固化过程,探究烯烃结构、光强和引发剂用量对含有两类碳碳双键的烯类单体与巯基化合物二元体系的光固化行为的影响.研究发现,这类二元巯-烯光聚合反应中均有(甲基)丙烯酸酯双键的反应活性最大,(甲基)烯丙基次之,巯基的反应活性最小;甲基取代在烯烃的不同C=C上,对巯-烯光固化特性影响不同,甲基取代在烯丙基C=C上比甲基取代在丙烯酸基C=C上对巯-烯光固化行为影响更大;巯基最终转化率随甲基取代基数目增多而减少;丙烯酸甲基烯丙酯体系中两类双键(丙烯酸型/甲基烯丙基型)反应活性几乎相同且均具有高的转化率.     

有机磷类阻燃剂的合成及应用进展

由于有机磷阻燃剂具有高效、低毒、无污染及无烟等特点,该领域的研究在国内外得到极大的关注,已经在合成和应用等方面取得了显著成就。 本文对磷系阻燃剂的阻燃机理及近年来磷系阻燃剂的应用进展作了简要综述。 分别综述了各类有机含磷阻燃剂的研究进展,并提出了有机磷阻燃剂今后的发展方向。     

Solubilities,thermostabilities and flame retardance behaviour of phosphorus-containing flame retardants and copolymers

Thirteen phosphorus-containing flame retardants were synthesized in this work. The solubilities of flame retardant [(6-oxide-6H-dibenz[c,e][1,2]oxaphosphorin-6-yl)-methyl]-butanedioic acid (DDP) in selected solvents are measured. TGA measurements of the 13 phosphorus-containing flame retardants were carried out and thermal stabilities of three flame-resistant PET (FRPET) resins were investigated. A FRPET incorporated by DDP with terephthalic acid and ethylene glycol reported in literature was also discussed and compared. The thermal stability of the FRPET is improved by the incorporation of phosphorus-containing flame retardants. The LOI values of all phosphorus-containing polyesters are higher than 27%. The improvement of the flame-resistant ability is due to the formation of the char that is not only caused by the existence of phosphorus elements in the resin but also by the relative large number of carbon atoms of the phenyl group in the flame retardants.     

Self-extinguishing cotton fabric with minimal phosphorus deposition

The phosphorus-containing acrylate monomer, 2-acryloyloxyethyl diethyl phosphate (ADEP), was synthesized and applied to cotton fabric by using the admicellar polymerization technique. A cationic surfactant (cetylpyridinium chloride, CPC) was used as the surfactant for admicellar polymerization. Results from FTIR-ATR and SEM showed that PADEP polymer film was successfully formed on the cotton fabric surface. TGA and DTG analyses showed that the phosphorus-containing PADEP lowered the decomposition temperature of the treated fabric resulting in a higher char yield than in the case of untreated cotton. The flammability tests showed that PADEP-coated cotton with the phosphorus content 4.18 mg/g cotton was self-extinguishing, with the flame extinguishing right after the removal of the ignition source leaving a small area of char formation.     

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.     

Brazilian clays as synergistic agents in an ethylenic polymer matrix containing an intumescent formulation

The effect of two different Brazilian montmorillonitic clays in intumescent ammonium polyphosphate and pentaerythritol formulations was evaluated. Ethylene and butyl acrylate copolymer was used as polymeric matrix. The clays were added both to the pure polymer and to the polymer containing intumescent mixture. The influence of these mineral fillers on flame retardancy was investigated by thermogravimeric analysis (TG). The results show that these inorganic additives have a synergist effect in the polymeric composite containing the intumescent formulation.     

Thermal properties and combustion behaviors of a novel UV-curable flame retarded coating containing silicon and phosphorus

A silicon-based acrylate (SHEA) was synthesized via the reaction between 2-hydroxylethyl acrylate and dimethyldichlorosilane, and characterized by Fourier transform infrared (FTIR), ¹H NMR spectroscopy and ²⁹Si NMR spectroscopy. The SHEA was blended with phosphorus-containing tri(acryloyloxyethyl) phosphate (TAEP) at different ratios to obtain a series of UV-curable flame retarded resins. The final unsaturation conversion of the SHEA films was determined by FTIR. Their combustion behaviors were examined by microscale combustion calorimetry (MCC). The thermal degradations of TAEP/SHEA composites were characterized using thermogravimetric analysis/infrared spectrometry (TG–IR). The MCC results present that the addition of TAEP into SHEA was able to decrease the HRR, HRC, T_max and THC. Among the TAEP/SHEA resins, Si1 (TAEP:SHEA is 1:1) owns the highest initial decomposition temperature and leaves the most char residue at 800 °C. The change of chemical structure during the thermal degradation process was monitored by real-time FTIR analysis to study the condensed-phase flame retarded mechanism.     

Copolymerization of （10-oxo- 10-hydro-9-oxa- 10λ^5-phosphaphenanthrene-lO-yl）-methyl acrylate with styrene

A phosphorus-containing monomer (10-oxo-10-hydro-9-oxa-10λ⁵-phospha-phenanthrene-10-yl)-methyl acrylate (M₁) was copolymerized with styrene to give a potential flame retardant copolymer of high thermal stability. The structures of monomer and copolymer were characterized by FT-IR and ¹H NMR measurements. The reactivity ratios for free-radical of the monomer (M₁) and styrene (M₂) were studied. The calculated results are as follows:r₁=0.225, r₂=0.503; Q₁=0.413, e₁=0.476; azeotropic point=0.37. TGA and DTG curves indicated that M₁ is a potential flame retarding monomer for styrenic polymers.     

Effects of phosphorus-containing thermotropic liquid crystal copolyester on pyrolysis of PET and its flame retardant mechanism

In order to compare their inherent flame retardancy and thermal stability, two phosphorus-containing thermotropic liquid crystalline copolyesters (P-TLCP) were synthesized by melting transesterification. Additionally based on the facts that the P-TLCP can work as a functional additive to enhance the flame retardancy and mechanical property of PET, we further studied the flame retardant mechanism. Scanning Electronic Microscope (SEM) observations show that the char from PET/P-TLCP is more compact, therefore more efficiently resists fire and heat attack than pure PET. Moreover, Fourier Transform Infrared Spectroscopy (FTIR) measurements of evolved gas, indicate that P-TLCP decomposes to produce phosphorus-containing small molecular compounds during the pyrolysis process, such that P-TLCP could play a flame retardant role in vapour phase. Furthermore, P-TLCP strongly inhibits the generation of combustible compounds in the pyrolysis of PET, which also helps to resist fire propagation.     

有机磷系及石墨烯阻燃环氧树脂研究进展

环氧树脂作为一种优异的树脂基体,被广泛地应用于众多领域,但因其极易燃烧,所以常常需要对其进行阻燃处理。本文简要综述了近几年有机磷系化合物及石墨烯阻燃环氧树脂的研究进展,其中有机磷系化合物阻燃部分重点介绍了以阻燃剂中间体9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)及其衍生物和聚磷酸铵(APP)为代表的含磷阻燃剂在环氧树脂中的阻燃机理和阻燃进展;同时也介绍了石墨烯及其衍生物在环氧树脂阻燃领域的最新研究进展,并对其发展前景进行了展望。     

Flame retardant epoxy polymers based on all phosphorus-containing components

A phosphorus-containing epoxy resin, bis(3-t-butyl-4-glycidyloxyphenyl-2,4-di-t-butylphenyl)resorcinol diphosphate, was synthesized and subsequently cured with non-phosphorus containing amines, and/or novel phosphorus-containing aromatic or polyoxyalkylene amines. Chemical structures of these materials were characterized with FTIR, NMR, elemental analysis, and amine titration. The introduction of soft -P-O- linkage, polyoxyalkyene, or hard aromatic group into the backbones of the synthesized phosphorus-containing amines provides epoxy polymers with high phosphorus contents and tailored flexibility. Thermal analysis of differential scanning calorimeter and thermal gravimetric analysis (TGA) reveals that these resulted epoxy polymers possess moderate T_gs and thermal stability. Furthermore, high char yields in TGA analysis and high limited oxygen index values indicate that these phosphorus-containing epoxy polymers possess excellent flame retardant properties.