一种新星型大分子——六对甲酰胺乙酸甲酯苯氧基环三磷腈的合成及其热性能、水解性能的表征

本文以六氯环三磷腈（HCCP）为原料合成了一种以甘氨酸甲酯苯氧基为侧基的新星型环三磷腈化合物六对甲酰胺乙酸甲酯苯氧基环三磷腈（HGPCP）及其中间体,并采用^1H NMR,^13CNMR,^31PNMR,FFIR和元素分析技术对其结构进行了确认．通过TGA、DSC、FrIR技术和测定水解液的紫外光谱,水解残余物剩余质量,残余物的磷含量方法分别对化合物的热性能和水解性能进行了表征．通过比较HGPCP在酸碱环境下的水解结果,发现水解504h,样品的水解过程尚处于化合物侧链断裂阶段,其37℃在酸性缓冲溶液（pH1．0）下较中性缓冲溶液（pH1．0）更易水解．由于其可能在高温下生成交联结构,六对醛基苯氧基环三磷腈（HCPCP）,六对羧基苯氧基环三磷腈（HCPCP）和HGPCP在800℃时碳残余量分别为75％、47％和47％,都表现出良好的热稳定性．     

光固化阻燃单体、树脂合成及其阻燃机理研究

本文综述了过去十余年间中国科技大学施文芳教授研究组在光固化阻燃技术领域的工作成果，主要包括活性单体、稀释剂、光固化树脂配方等体系，品类有磷酸酯类单体、含磷丙烯酸酯、超支化丙烯酸酯树脂、膦酸酯类单体和树脂、丙烯酸化环状磷腈、甲基丙烯酸化三聚氰胺、含磷环氧单体等十余种。同时介绍了这些配方体系的合成、性能和应用方法，以及对其热降解、阻燃性能评价和阻燃机理的研究。     

六对羧基苯氧基环三磷腈的合成及其热性能

羧基苯氧基磷腈及其衍生物由于具有优良的生物活性并能降解成无毒产物,因而在生物医用材料的应用上潜力巨大。本文采用两步法合成了六对羧基苯氧基环三磷腈(HCPCP),首先以六氯环三磷腈和对羟基苯甲醛为原料,采用亲核取代反应制得六对醛基苯氧基环三磷腈（HAPCP）,再用KMnO4氧化法合成HCPCP。通过红外光谱、高效液相色谱、核磁共振及元素分析等确证了产物的结构;用TGA和DSC对其热性能进行了研究。     

新型树状单分子磷-氮膨胀阻燃剂的合成及阻燃性能研究

以六氯环三磷腈、对羟基苯甲醚、新戊二醇以及三氯氧磷等为原料, 合成一种新型树状单分子磷-氮膨胀阻燃剂六(4-(5,5-二甲基-1,3-二氧杂环己内磷酸酯基苯氧基))环三磷腈(Ⅵ). 标题化合物结构经IR、MS 及¹H NMR 证实. 热失重分析表明标题化合物具有较高的热稳定性和良好的成炭性, 氮气氛下的起始分解温度为270 ℃, 600 ℃时炭残余量达45.2%. 实验表明, 标题化合物对环氧树脂呈现出良好的阻燃效果.     

六苯氧基环三磷腈的合成及其在层压板中的阻燃应用

以六氯环三磷腈（HCCTP）粗产物、苯酚、NaOH为反应原料,四丁基氯化铵（TBAC）为相转移催化剂,氯苯和水为溶剂,合成了六苯氧基环三磷腈（HPCTP）,考察了反应温度、反应时间、反应溶剂、物料配比对收率的影响。结果表明,在最佳原料配比n(NaOH): n(苯酚): n(TBAC): n(HCCTP粗产物)=7.5: 6.3: 0.15: 1,30 ℃反应4 h,回流反应6 h,HPCTP的收率达到75％。采用红外光谱、核磁氢谱、碳谱、磷谱、X射线衍射分析、示差扫描量热分析、热重分析测试技术对产物进行了表征分析,并首次用于苯并噁嗪树脂玻璃布层压板,当HPCTP的质量分数为10％时,燃烧等级达到V-0级,平行击穿电压为47 kV,热态弯曲强度为596 MPa。     

含环三磷腈衍生物的辐照交联聚乙烯基复合材料的制备及阻燃性能

将具有阻燃剂和辐照敏化剂双重功能的含烯丙基环三磷腈（CP-Allyl）,通过熔融共混的方式引入到由低密度聚乙烯和乙烯-醋酸乙烯共聚物组成的基体中,制备了一系列基于有机-无机阻燃复配剂的新型无卤阻燃聚乙烯基复合绝缘材料。进一步通过100~190 kGy剂量下的电子束辐照,实现了复合材料的辐照交联,并建立了辐照剂量与交联度以及材料性能的关系。研究结果表明,含有功能性环三磷腈衍生物的辐照交联复合材料具有优良的力学强度、阻燃性和电绝缘性能。力学强度在14.5 MPa以上,极限氧指数为28.2%~32.4%,电阻达到2.47×10¹² Ω以上,因而有希望在电线电缆领域获得应用。     

环三磷腈类阻燃剂的合成及应用研究进展

简要介绍了制备环三磷腈类阻燃剂所需起始原料六氯环三磷腈的合成方法、合成及取代反应机理;介绍了环三磷腈阻燃剂的阻燃机理;着重阐述了近20年间反应型的羟基/氨基环三磷腈、环氧基环三磷腈、含不饱和双键的环三磷腈、羧基环三磷腈阻燃剂,以及添加型烷氧基环三磷腈、芳氧基环三磷腈的合成及阻燃应用,同时综述了其应用材料的热稳定性能和阻燃性能,并对其发展趋势作了总结和展望。     

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.     

星型绿色磷腈阻燃剂的制备及阻燃环氧树脂性能

从分子结构设计出发,以六氯环三磷腈、对羟基苯甲醛、三氯氧磷及新戊二醇等为原料,制备了一种新型阻燃剂六[4-(5,5-二甲基-1,3,2-二氧杂己内磷酰基)苯氧基]环三磷腈(HDDCPPCP),并将其与聚磷酸铵(APP)和多壁碳纳米管(MWCNT)复配,应用于环氧树脂(EP)中,制备了HDDCPPCP/APP/MWCNT/EP阻燃复合材料.利用极限氧指数(LOI)、水平燃烧(UL-94)、锥形量热(CONE)、拉伸、弯曲和冲击等方法研究该阻燃复合材料的燃烧性能、热性能及力学性能.实验结果表明,保持阻燃体系总质量分数为30%,当MWCNT质量分数为2%时,EP2(HDDCPPCP/APP/MWCNT/EP)的各项燃烧参数综合表现较好,其LOI值达到42. 8%,热释放速率峰值(pk-HRR)、热释放速率平均值(av-HRR)、有效燃烧热平均值(av-EHC)及一氧化碳释放率平均值(av-CO)相对EP0分别降低92. 5%,93. 0%,65. 2%和66. 6%,呈现出良好的阻燃、抑烟和抑毒性能; EP2的拉伸强度、断裂伸长率、弯曲强度和弯曲模量较好,分别为110. 46 MPa,6. 24%,1259. 99 MPa,377. 72 MPa.     

磷腈化合物阻燃高分子材料研究进展

磷腈化合物是一类骨架由磷、氮单双键交替排列而成,侧基由有机基团组成的有机-无机化合物.由于其结构特殊、性能优异而被应用于防火阻燃、生物医用、高分子导体及液晶、燃料及催化剂等各种领域.磷腈有高含量的磷、氮元素,因而具有优异的阻燃性能.近年来,环三磷腈阻燃剂被越来越广泛地应用于高分子阻燃材料中.本文阐述了近10年来具有不同取代基的环三磷腈阻燃剂的合成及应用,重点介绍了其对环氧树脂、丙烯腈-丁二烯-苯乙烯共聚物(ABS)、聚烯烃、聚酯等高分子材料的阻燃性能及热稳定性的影响,并对其影响规律和阻燃机理进行了总结,对其应用前景进行了展望.     

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。     

Flame retardance and shrinkage reduction of polystyrene modified with acrylate-containing phosphorus and crosslinkable spiro-orthoester moieties

Styrene was radically copolymerized with a spiro-orthoester with an acrylate group (SOE-AC), and terpolymerized with SOE-AC and diethyl(methacryloyloxymethyl)phosphonate (DEMMP). This was done for several different feed ratios, to obtain polymers with spiro-orthoester moieties in the side chain. These polymers were then crosslinked with ytterbium triflate, as cationic initiator, via the double ring-opening polymerization. The thermal stability and fire retardant properties of these materials were evaluated by TGA and LOI. The DEMMP-containing polymers give materials which were significantly more flame retardant than the nonphosphorus-containing materials, as indicated by the LOI measurements. The volume changes measured upon crosslinking of the polymers were evaluated by density measurements with a gas pycnometer. In all the cases, expansion was observed. This indicates that SOE-AC is an effective monomer for crosslinkable polymers without volume changes.     

硅溶胶改性水性超薄型钢结构防火涂料的研究

以过硫酸铵为引发剂,OP-10为乳化剂,在聚乙烯醇保护下,用甲基丙烯酸甲酯、丙烯酸丁酯进行共聚,合成乳液型丙烯酸酯树脂,并用红外光谱表征.用磷酸、五氧化二磷、季戊四醇反应生成的酯型中间体与三聚氰胺混合,制得膨胀型阻燃剂,用红外光谱表征并对其进行热重分析.用自制膨胀型阻燃剂与乳液型丙烯酸树脂及少量硅溶胶按一定比例混合调匀,制备超薄型钢结构防火涂料,根据国家标准对涂料性能进行检测,其基本性能达到防火涂料要求.     

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%.     

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.     

Flame retardancy of epoxy resin nanocomposite with a novel polymeric nanoflame retardant

A wrapped nanoflame retardant, designated as polyhedral oligomeric silsesquioxane (POSS)‐poly(4‐bromostyrene) (PBS)‐carbon nanotubes (CNTs), was synthesized via π‐π stacking interactions between the walls of multiwalled carbon nanotubes and the silicon‐bromine containing hybrid copolymer (designated as POSS‐PBS) that was copolymerized by 4‐bromostyrene and acryloyloxyisobutyl polyhedral oligomeric silsesquioxane. The POSS‐PBS‐CNTs exhibited good dispersibility in epoxy resin (EP) without obvious aggregation. Furthermore, the fire behaviors of this flame‐retardant EP (FR‐EP) nanocomposites were examined via limited oxygen index (LOI) and cone calorimeter (CONE) tests. The FR‐EP had an ideal LOI value of 35.3% and its residual char yield obtained from CONE test was significantly enhanced from 5.9% to 15.3% with the incorporation of 4 wt% POSS‐PBS‐CNTs and 1.33 wt% Sb₂O₃ into EP matrix. Additionally, the addition of 4 wt% POSS‐PBS‐CNTs or POSS‐PBS can efficiently decrease the peak heat release rate (PHRR) of EP matrix by 41.0% or 45.6%, respectively.     

Immobilization of flame retardant onto silica nanoparticle surface and properties of epoxy resin filled with the flame retardant‐immobilized silica

To prepare silica nanoparticle having flame retardant activity, the immobilization of flame retardant onto hyperbranched poly(amidoamine) (PAMAM)‐grafted silica was investigated. Grafting of PAMAM onto a silica surface was achieved in a solvent‐free dry‐system using PAMAM dendrimer synthesis methodology. The immobilization of bromine flame retardant, poly(2,2′,6,6′‐tetrabromobisphenol‐A) diglycidyl ether (PTBBA), was successfully achieved by the reaction of terminal amino groups of PAMAM‐grafted silica (Silica‐PAMAM) with epoxy groups of PTBBA. The immobilization of PTBBA was confirmed by FTIR and thermal decomposition GC‐MS. The amount of PTBBA immobilized onto Silica‐PAMAM was determined to be 60 wt %. PTBBA‐immobilized Silica‐PAMAM (Silica‐PAMAM‐PTBBA) was dispersed uniformly in a epoxy resin, and the epoxy resin was cured in the presence of hexamethylenediamine. Flame retardant activity of the epoxy resin filled with Silica‐PAMAM‐PTBBA was estimated by limiting oxygen index (LOI). The LOI of epoxy resin filled with Silica‐PAMAM‐PTBBA was higher than that filled with untreated silica and free PTBBA. It was confirmed that the flame retardant activity of epoxy resin was improved by the addition of the Silica‐PAMAM‐PTBBA. The elimination of PTBBA from the epoxy resin filled with Silica‐PAMAM‐PTBBA into boiling water was hardly observed by immobilization of PTBBA onto silica surface. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6145–6152, 2009     

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.     

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.

     

Influence of oxidation state of phosphorus on the thermal and flammability of polyurea and epoxy resin

The focus of this study is an investigation of the effect of oxidation state of phosphorus in phosphorus-based flame retardants on the thermal and flame retardant properties of polyurea and epoxy resin. Three different oxidation states of phosphorus (phosphite, phosphate and phosphine oxide) additives, with different thermal stabilities at a constant phosphorus content (1.5 wt.%) have been utilized. Thermal and flame retardant properties were studied by TGA and cone calorimetry, respectively. The thermal stability of both polymers decreases upon the incorporation of phosphorus flame retardants irrespective of oxidation state and a greater amount of residue was observed in the case of phosphite. Phosphate was found to be better flame retardant in polyurea, whereas phosphite is suitable for epoxy resin. Phosphite will react with epoxy resin by trans-esterification, which is demonstrated by FTIR and ³¹P NMR. Further, TG–FTIR and XPS studies also provide information on flame retardancy of both polymers with phosphorus flame retardants.