水溶性丙烯酸树脂的合成及表征

用于水性油墨的水溶性丙烯酸树脂可以由丙烯酸丁酯（A），甲基丙烯酸甲酯（MMA），丙烯酸（AA）3种单体采用传统的自由基溶液聚合方式合成，通过大量的对比实验，获得了最佳合成工艺，包括引发剂，溶剂，加料方式，聚合的时间和温度，对影响树脂性能的指标如共聚物组成，玻璃化转变温度（Tg)等因素，采用DSC，IR等分析方法进行了表征。     

Synthesis and Characterization of First Generation Dendritic Azidoesters

A new class of first generation azido‐terminated dendritic esters have been synthesized by four step processes. The final products and the intermediates are characterized by IR, ¹H NMR, and elemental analysis. Thermal studies revealed that these dendritic esters were thermally stable up to ∼190 °C and the glass transition temperature was found to be −54 and −32 °C, respectively.     

聚合物/CO2混合物的玻璃化转变温度

基于经典热力学与统计热力学理论,结合实验结果,构建了聚合物／二氧化碳混合物的玻璃化转变温度与二氧化碳含量以及聚合物特性(包括单体相对分子质量、摩尔体积以及纯聚合物玻璃化转变温度,玻璃化转变时摩尔定压热容增量)之间关系的模型。采用该模型计算出的结果与实验结果吻合较好：对于聚苯乙烯(PS),最大偏差为6K,聚氯乙烯(PVC)最大偏差为10K,聚甲基丙烯酸甲酯(PMMA)最大偏差为7K。     

Application of Azido Esters as Energetic Plasticizers for LOVA Propellant Formulations

The study of a cyclotrimethylene trinitramine‐based low vulnerable ammunition (LOVA) propellant having cellulose acetate (CA) and nitrocellulose (NC) combinations as binders is described herein. Two propellant compositions ( 1 and 2 ) were prepared by replacing the non energetic plasticizer triacetin (TA) with the novel tetraazido ester plasticizers tetraazido malonate and tetraazido glutarate, respectively, and their ballistic, mechanical, and thermal properties were studied. Both compositions 1 and 2 showed thermal stability up to 200 °C with a heat release of 1752.81 and 1774.34 J g⁻¹, respectively. Both compositions have high impact insensitivity (h₅₀: 39 cm), friction insensitivity up to 36 kg, and an ignition temperature greater than 250 °C. The flame temperatures of 1 and 2 are 3164 and 3243 K with linear burn rate coefficients of 0.117 and 0.122 cm s⁻¹ MPa⁻¹, respectively. Similar percentage elongations at three different temperatures (−20 °C, +27 °C, and +55 °C) conditions were recorded for both compositions.     

一种新型叠氮含能固化剂的合成及性能

为提高黏合剂体系的力学性能,通过叠氮聚醚多元醇与六亚甲基二异氰酸酯（HDI）反应合成了一种新型叠氮多异氰酸酯含能固化剂（EC）。研究了料比、反应温度、后处理方法等因素对反应的影响。DSC结果表明,EC的最大热分解温度为252．89℃,玻璃化温度为-47．13℃。EC／GAP胶片的最大热分解温度为254．56℃,玻璃化温度为-45．78℃。EC／GAP／50％TEGDN体系具有良好的物理和化学相容性,制备的胶片有两个分解放热峰,对应的最大热分解温度分别为213．05℃和250．89℃,玻璃化温度为-69．08℃。GAP／EC胶片在＋20℃下的拉伸强度和断裂伸长率分别为0．67MPa和129％,优于GAP／N100体系的0．53MPa和56．5％。     

Synthesis and Characterization of Azido Plasticizer

In order to get a good compatibility with azidopolymers, plasticizers are required with a similar chemical structure. The energetic plasticizers EGBAA, DEGBAA, TMNTA and PETKAA were synthesized and characterized. They are liquid and the glass-transition temperatures are between −70.8°C and −34.1°C. The differential scanning calorimetry (DSC) analysis shows an acceptable thermal stability for practical applications. The infrared spectrum shows distinctly the functional groups C-N₃, ester, carbonyl and nitrate. The elemental analysis and NMR agree with the molecular structures. As a practical example, EGBAA was combined with the energetic binder Poly Nimmo. The viscosity, glass-transition point and stability of 50% mixtures were investigated.     

An Azido Ester Plasticizer, 1,3‐Di(Azidoacetoxy)‐2,2‐Di(Azidomethyl)Propane (PEAA): Synthesis,Characterization and Thermal Properties

A polyazido compound, 1,3‐di(azidoacetoxy)‐2,2‐di(azidomethyl)propane (PEAA) was synthesized and identified. Thermal properties of PEAA, such as the glass transition temperature (T_g), differential scanning calorimetry (DSC) and thermogravimetric analysis (DTG) were investigated in detail. Two steps in the course of thermal decomposition of PEAA were observed clearly, and some gases, carbon monoxide, carbon dioxide, nitrogen, hydrocyanic acid, methane and 2‐methyl‐1,3‐butadiene were identified as decomposition products by in situ cell FTIR. The pyrolysis mechanism was also proposed.     

Synthesis,Characterization and Properties of Nitropolybutadiene as Energetic Plasticizer for NHTPB Binder

The nitration of low molecular weight polybutadiene (PB) by a convenient and inexpensive procedure was investigated. To retain the unique physico‐chemical properties of the plasticizer, it was nitrated to an extent of 10 % double bonds. The product nitropolybutadiene (NPB) was characterized by FT‐IR and ¹H NMR spectroscopy as well as GPC, DSC, and TGA methods. The kinetic parameters for the decomposition of NPB from room temperature to 400 °C were obtained from non‐isothermal DSC. The changes in glass transition temperature (T _g) and inert uncured binder systems were used for determination of its efficiency as plasticizer. NPB was used in cured and unfilled nitro‐hydroxyl terminated polybutadiene (NHTPB) binder. Isothermal thermogravimetric analysis (Iso‐TGA) was employed to determine the migration rate in cured and unfilled HTPB binder systems compared to the dioctyladiphate (DOA) plasticizer. It was found that the exudation of the NPB plasticizer is slower than that of the DOA plasticizer. Thus, the NHTPB/NPB binder system (binder/plasticizer) presents more convenient mechanical properties than HTPB/DOA and is a promising new energetic binder system for polymer bonded explosives.     

Diffusion in polymers below the glass transition temperature: Comparison of two approaches based on free volume concepts

Theories based on free-volume concepts have been developed to characterize the self and mutual diffusion coefficients of low molecular weight penetrants in rubbery and glassy polymer-solvent systems. These theories are applicable over a wide range of temperatures and concentrations. In this paper, two alternative freevolume based approaches used to evaluate the solvent self-diffusion in glassy polymer-solvent systems are compared in terms of their differences and applicability     

鞋材用聚丙烯酸酯乳液及其醇溶性港宝的研制

为了适应环保和市场的要求,筛选出聚合物性能优良的醇溶性单体,采用预乳化乳液聚合法合成了鞋材用聚丙烯酸酯乳液,研制开发了新型鞋材醇溶性港宝胶片。讨论了醇溶性单体用量、引发剂加入工艺对乳液聚合物性能的影响,分析了填料种类对胶片性能的影响。通过DSC、GPC对乳液聚合物进行了表征。结果表明：单体组成质量比为MMA：EA：MAA=45：40：15时,所得乳液聚合物能满足使用性能要求;种子引发剂加入量控制在单体量的0．3％,而总的引发剂用量在0．8％较适宜;以滑石粉作填料,可克服工作液增稠严重的缺陷,工作液的配比按胶乳：滑石粉：水质量比200：80：60能得到理想港宝胶片。     

增塑剂对聚乳酸性能的影响

对不同增塑聚乳酸体系的力学性能、脆韧转变现象和增塑剂的迁移性能进行了研究。实验表明：增塑剂品种不同对聚乳酸的增塑效果不同,三种增塑剂中柠檬酸三丁酯(TBC)的增塑效果最佳；TBC的质量分数小于10%时,增塑体系的脆性基本不变,TBC的质量分数在10%～13%时,材料出现脆韧转变；增塑聚乳酸体系增塑剂迁移率随增塑体系相容性的增加而减小,随增塑剂用量增加而增大。     

硝酸酯类含能黏合剂绿色合成研究进展

对3种具有发展潜力的硝酸酯类含能黏合剂聚(3-甲基硝酸酯-3-甲基环氧丁烷)(Poly-NIMMO)、聚缩水甘油硝酸酯(PolyGLYN)和硝化端羟基聚丁二烯(NHTPB)的绿色合成工艺和性质进行了简要评述,分析了这些黏合剂的发展前景。并采用以五氧化二氮为硝化剂的绿色合成路线制备得到NHTPB黏合剂,考察了不同官能团对其热稳定性和玻璃化转变温度的影响规律。     

GAP基含能热塑性弹性体的合成与表征

以聚叠氮缩水甘油醚(GAP)为软段,1,4-丁二醇(BDO)和4,4′-二苯基甲烷二异氰酸酯(MDI)为硬段,采用熔融预聚体法合成了GAP基含能热塑性弹性体(ETPE)。研究了扩链剂加料方式、催化剂用量、异氰酸酯指数、硬段含量等因素对弹性体力学性能的影响。采用傅里叶变换红外光谱(FT-IR)、凝胶渗透色谱(GPC)、热台显微镜、差示扫描量热(DSC)、热重分析(TG)表征了ETPE的性能。结果表明,采用恒速滴加扩链剂方法合成的ETPE具有良好的热稳定性和力学性能。当催化剂质量分数为0.6‰,异氰酸酯指数(R)为0.98,硬段质量分数(Y)为35%时,热塑性弹性体的数均相对分子质量为52 312,软化点为96℃,拉伸强度为14.52MPa,断裂伸长率为518.78%。     

含能中间体5-肼基四唑的合成及表征

以5,5’-偶氮四唑钠为原料,采用盐酸酸化、乙酸钠重结晶的方法得到了5-肼基四唑产物。利用傅里叶变红外、熔点和元素分析表征了其结构,讨论了合成中影响酸化和重结晶的关键因素。结果表明,酸化过程中,5,5＇-偶氮四唑钠溶液的质量分数应为10％,HCl溶液的质量分数应为10％～15％。最终产物得率为55％～60％,熔点196～198．9℃。     

槲皮素苯甲酸酯的合成与表征

以槲皮素为原料、浓硫酸作催化剂,85℃与苯甲酰氯反应,TLC板监测反应完毕,过滤、氯仿/甲醇重结晶合成标题化合物。UV表征显示,槲皮素的两个特征吸收峰均发生蓝移,这是形成新化合物共轭体系引起的。IR中ν—OH峰明显减弱,说明槲皮素的5个羟基中有的羟基发生了反应;νCO位于1 745.32 cm-1,酯羰基峰明显增强;νC—O位于1 259.66cm-1,峰变宽增强。1HNMR中3-OH、3'-OH、4'-OH上面的氢消失,说明与苯甲酰氯发生了酯化反应;同时,在δ6.7~8.4处有苯甲酰基的多重峰。MS中m/z 615.2为槲皮素三苯甲酸酯的分子离子峰。因此,槲皮素与苯甲酰氯反应可以得到标题化合物。     

六烷基胍TADC含能离子液体的合成与表征

采用离子交换法合成了4种六烷基胍4,5-二氰基-1,2,3三唑([Cn-guan][TADC],n=3,4,5,6)含能离子液体,用红外光谱和核磁共振对结构进行了表征,测试了其在常用有机溶剂中的溶解性,用表面界面张力仪和TG、DSC分别研究了其密度和热性能。结果表明,六烷基胍TADC离子盐在极性较大的有机溶剂中具有良好的溶解性,最大分解温度在370℃左右,表明[C3-6-guan][TADC]具有良好热稳定性,([Cn-guan][TADC],n=3,4,5)在DSC的二次升温过程中经历了玻璃态、过冷态、结晶固态和液态4种相态。     

糖基化三氮唑香草酸白杨素酯的合成与结构表征

以叠氮糖、炔丙基溴、香草醛和白杨素为原料,通过醚化、Click chemistry氧化、酯化4步反应得到4个糖基化三氮唑香草酸白杨素酯,反应路线简单,条件温和,收率较高,总收率为51%~62%(以香草醛计),产物结构通过1H NMR、IR、ESI-MS和元素分析确认。     

Synthesis and Characterization of Novel Betti Type Cyanate Esters

Several aromatic diols bearing amino benzyl linkage in the main chain have been synthesized through high yield Betti reaction, which involves the reaction of an aldehyde with p-amino phenol and 8-hydroxy quinoline. Five different aldehydes have been used to prepare five new bisphenols. These bisphenols were converted to their corresponding cyanate esters by the treatment of cyanogen bromide in the presence of triethyl amine. The structures of the diols and dicyanate esters were confirmed by FT-IR, ¹H-NMR, ¹³C-NMR spectral studies and elemental analysis. The cyclotrimerization reactions of cyanate esters have been studied by differential scanning calorimetry (DSC). The maximum curing temperatures of these cyanate esters are in the range of 186-201^oC. T_gvalues of the polycyanurate networks are above 270^oC. Thermogravimetric analysis (TGA) shows that the 10% weight loss of all the cured cyanate esters is above 400^oC in N₂ atmosphere. The char yield is in the range of 66-73%. The flame retardancy of the cyanate ester resins have been studied using Limiting Oxygen Index (LOI) value which is in the range of 43.9-46.7% at 700^oC.     

木器涂料用环氧-丙烯酸乳液T_g设计及与单体转化率的关系

本试验合成了水性环氧-丙烯酸酯杂化乳液,通过对引发剂用量、乳化剂用量、不同乳化剂配比、种子乳液以及搅拌速度等聚合反应条件的考察,得出了聚合反应的最佳工艺条件,并简单探讨了单体转化率与乳胶膜玻璃化转变温度之间的关系。结果表明,当引发剂质量分数为0.8%、乳化剂质量分数为3%、m(OP-10):m(SDS)=2:1、种子乳液的用量为预乳化液的20%(质量分数)、转速为180r/min时,乳液聚合单体的最终转化率可以达到98%。且最终转化率的提高使乳胶膜玻璃化转变温度更接近于理论计算值。     

原位聚合PLA/HA复合材料的性能研究

采用原位聚合法和超声波辅助分散溶液共混法,分别制备了羟基磷灰石质量分数为30％的聚乳酸（PLA）／羟基磷灰石（HA）生物可降解复合材料,对其结构与力学性能进行了研究。结果表明,HA的存在对乳酸的聚合有一定的影响,使其摩尔质量降低、分布变宽。与共混法相比,原位聚合法改善了HA在复合材料中的分散性,在PLA与HA之间形成了较强的结合界面,从而提高了PLA玻璃化温度和力学性能。