【作者】 刘文彬；

【导师】 张密林；

【作者基本信息】 哈尔滨工程大学 ， 材料学， 2008， 博士

【摘要】 双酚芴(BHPF)是一种含有Cardo不骨架结构的双酚类化合物，是合成聚碳酸酯、环氧树脂、聚酯或聚醚等缩聚产品的重要单体或改性剂。双胺芴为具有芴基骨架的芳香二元胺类化合物，可作为环氧树脂的固化剂。以BHPF为原料合成的耐热环氧树脂、聚碳酸酯等材料具有良好的热稳定性、高透明性、高折射率及易溶等特性，广泛用于航空航天、电子、汽车等领域。本文通过缩合反应合成了系列BHPF和双胺芴，以双酚芴为原料，制备出芴基环氧树脂；用IR、NMR、LC-MS和元素分析对产物结构进行表征。实验采用环境友好的固体酸作为缩合反应的催化剂，减少了废酸中和过程，催化剂可回收循环使用。当催化剂(阳离子交换树脂)用量为14％，酚酮比8：1，反应温度105℃，反应时间为8h时，双酚芴产率在85％左右，熔点222～223℃，纯度达到99．5％。双邻甲酚芴(BMPF)和双邻二甲酚芴(BDMPF)产率分别为67％和76．8％，熔点分别为217～219℃和289～291℃。双酚芴的合成机理属于亲核加成-消去反应历程。以二氯芴为原料，合成了BMPF。该反应是在甲烷磺酸催化剂存在下进行，二氯芴与邻甲酚摩尔比为1：3．4，反应温度低于30℃，BMPF产率达到67％，熔点218～219℃。该方法反应条件温和，反应时间短，可作为双酚芴的一种新的合成方法。分别以苯胺、邻甲苯胺、N-甲基苯胺和邻二甲基苯胺为原料，合成了双胺芴(BAF)、双邻甲胺芴(BMAF)、双-N-甲基胺苯基芴(BNMAF)和双二甲基胺苯基芴(BDMAF)，在芴酮、苯胺(或邻甲苯胺、N-甲基苯胺、邻二甲基苯胺)和催化剂物质的量比为1：8：1．0，甲烷磺酸为催化剂，反应温度150～175℃，反应时间12～16h，氮气气氛条件下，产物收率达到70％，熔点分别为236～237℃、230～232℃、205～207℃和120～121℃。以双酚芴和环氧氯丙烷为原料，合成了芴基环氧树脂。当BHPF、环氧氯丙烷、NaOH、相转移催化剂的摩尔比为1：12：3：0．1，反应温度65℃，反应时间3h，双酚芴环氧树脂(DGEBF)的环氧值达0．405 eq／100g。双邻甲酚芴环氧树脂(DGEMBF)和双二邻甲酚芴环氧树脂(DGEDMBF)的环氧值分别为0．368和0．334 eq／100g。采用DSC法对双酚A环氧(DGEBA)、脂环族环氧(TDE-85)、DGEBF、DGEMBF以及共混树脂进行固化工艺和非等温固化反应动力学研究，确定了各类固化体系的固化工艺；用Kissenger法、Ozawa法、Crane法计算了固化反应活化能和反应级数。Kissenger法计算的活化能低于Ozawa法，用Crane法求出的反应级数小于1，说明上述固化体系发生的是复杂反应。利用DMA、TGA研究了芴基环氧树脂以及双胺芴固化剂的结构与性能之间的关系。芴基具有庞大的Cardo环结构，使得苯基的旋转受到严重阻碍，聚合物链段的热运动和内旋转受到抑制，因此赋予了芴基聚合物具有更高的刚性，热分解活化能进一步提高，非极性官能团数量的增多以及固化交联密度的下降抑制了水分的侵入。双胺芴固化剂由于含有大体积的刚性芴基结构，增加了固化分子链的规整性和分子链间的相互作用，固化物的自由体积减小，空间位阻加大，链段的运动受到抑制，加上分子中非极性苯环数量多，交联密度低，产生羟基数量少，所以固化物的耐热性和耐湿热性较常规二胺基二苯亚砜(DDS)、二胺基二苯甲烷(DDM)和酸酐固化体系有较大提高。双酚芴环氧树脂与通用环氧树脂具有非常好的相容性，通过共混，可极大改善通用环氧树脂的热稳定性和耐湿热性能。DGEBF与DGEBA和TDE-85共混，经双胺芴固化，固化树脂的储能模量为2．65GPa，玻璃化转变温度约为240℃，在沸水中经72h浸泡的吸水率为2．28％，吸湿前后树脂性能变化小，具有良好的热稳定性，并可在200℃高温下长期使用。更多还原

【Abstract】 9,9-bis(4-hydroxyphenyl)-fluorene(BHPF) is a type of bisphenol fluorenecompounds with Cardo skeleton which is obtained by the condensation offluorenone with phenol in the presence of at least one acidic condensation agent.9,9-bis(4-aminophenyl)-fluorene(BAF) is a diamine compound used as curingagents of epoxy resins.BHPF can be used as monomer or modifier for thepreparation of high performance polycondensation products such as epoxy resins,polycarbonates,polyesters and polyethers,due to the unique properties of Cardorings such as thermal stability.The polymers obtained from bisphenol fluorenehave been found to exhibit desirable complex characteristics such as thermalstability,high transparency,high-refractive index and insulation,which makesthem useful in the applications in aerospace,electro-optics,electronic,automotiveand related industries.Relevant examples included but are not limited to:aircraftstructure articles,flame-retardant laminates,heat-resistant adhesives,high-temperature coatings,photoelectric conductors,fibre optics and films,et al.BHPF and BAF were synthesized from fluorenone and phenol or amine in thepresence of acidic catalyst,and the major factors affecting the reaction wereinvestigated.The chemical structures of products were confirmed by FTIR,NMR,MS and elemental analysis.The results showed that solid acid catalyst had highcatalytic activity and was easy to recover,and the process of waste acidneutralization was reduced.The mass percentage and yield of BHPF reached99.5% and about 85% respectively under optimal process conditions that themolar ratio of phenol to fluorenone was 8 to 1,the mass percentage of catalystwas 14% of the total reactants,reaction temperature was 105℃and reaction time was 12 h.The melting point(m.p.) of BHPF was 222-223℃.The yield and m.p.of BMPF and BDMPF were 67%,76.8%,217-219℃,289-291℃,respectively.The synthesis reaction of BHPF proceeds via nucleophilic addition-eliminatoin.BMPF was synthesized from 9,9-dichloro-fluorene in the presence ofmethanesulfonic acid with the dichloro-fluorene and o-cresol molar ratio from 1to 3.4 below 30℃.The yield of BMPF with m.p.of 218-219℃was 67%.Theprocess has been proved a novel method for the synthesis of BHPF with mildreaction conditions and short reaction time.Synthesis method of BAF,BMAF,BNMAF,and BDMAF is the same as thatof BHPF.A stream of nitrogen was introduced and the mixture includingfluorenone and amine,such as aniline,ortho-toluidine,N-methylaniline,dimethylaniline,was heated at 150-175℃for 12-16 h with vigorous stirring.Theyield of fluorenyl diamine was about 70%,and the m.p.was 236-237℃,230-232℃,205-207℃,and 120-121℃,respectively.Fluorene-containing epoxy resins,diglycidyl ether of 9,9-bis(4-hydroxy-phenyl)-fluorene(DGEBF),diglycidyl ether of 9,9-bis(3-methyl-4-hydroxy-phenyl)-fluorene(DGEMBF),and diglycidyl ether of 9,9-bis(2,6-dimethyl-4-hydroxyphenyl)-fluorene(DGEDMBF),was synthesized from BHPF,BMPF,or BDMPF and epichlorohydrin by the method reported previously.Epoxy valueof DGEBF,DGEMBF,and DGEDMBF was 0.405,0.368,and 0.334 eq/100g,respectively.The curing kinetics and curing craft of fluorenyl diamines with differentepoxy resins including DGEBF,DGEMBF,cycloaliphatic epoxy resin(TDE-85)and diglycidyl ether of bisphenol A(DGEBA),was investigated usingnon-isothermal differential scanning calorimetry(DSC),and determined byKissinger,Ozawa and Crane methods.The activation energy calculated by Kissinger method was less than that by Ozawa method.The reaction order wasless than 1.It showed that complex reations occurred in the above-mentionedsystem.The relationship of structure and performance about fluorenyl epoxy resinsand fluorenyl diamines was investigated by DMA and TGA.DGEBF have astructure in which a bulky fluorene unit protrudes vertically from the polymermain chain.This chemical structure of four phenyl rings connected to aquaternary carbon leads to severe rotational hindrance of the phenyl groups.Therefore,the stiff,bulky cardo moiety likely arise from the higher rigidity offluorene skeleton in the chain backbone,which would restrain the internalrotations and thermal motion of polymer segments.Heat resistance and thermaldecomposition activation energy of the cured polymers can be elevated drasticallyby introducing some rigid groups into the backbone of epoxy monomer.Thehydrophobic fluorene moieties might be responsible for the lower moistureabsorption for fluorenyl diamines.The average volume of fluorene ring isdeduced to be larger than those of methylene or cyclohexyl groups,and it mightcause a reduced crosslink density in the network of cured polymers to produceless hydroxyl groups,and finally leads to an improved hydrophobicity of thesystem.In addition,more contents of phenyl group than DDS,DDM,andanhydride decrease the polarity of cured polymers,and inhibit water to invade.Fluorenyl epoxy resins is compatible with current epoxy resins.The thermalstability and moisture resistance of commercial epoxy resins were modifiedthrough blending.The blend resin made from DGEBF,DGEBA,and TDE-85 wascured by BAF.The storage modulus,glass transition temperature and wateruptake(boiling water,72h) of cured resins were 2.65 GPa,210℃,and 2.28%,respectively.The polymer can be used for a long time at 200℃.Toughening agent,such as PU,CTBN,PES,et al,can improve toughness of cured resins.However,PU and CTBN can decrease the heat resistance of cured resins exceptPES.更多还原