以不同聚合物和有机前驱体模板法制备纳米孔炭及其热性能(英文)

以糠醇(FA)、4,4-双马来酰亚胺二苯基甲醇(BM)、BM与二乙烯基苯共聚物(BM-DVB)和蔗糖(S)为炭前驱体,硅胶为硬模板制备了六种纳米孔炭。在氦气气氛中800℃～1 000℃炭化30 min,炭化后利用质量分数40%HF脱除模板。利用元素分析、氮气吸附、热分析和漫反射红外表征产物的孔结构和化学结构及它们对多孔炭热性能的影响。结果表明,前驱体对多孔炭的性能有一定的影响。前驱体的化学结构和热处理条件对炭的孔隙结构,亲水性和热稳定性都有影响。最稳定的产物中含有氮和磷元素。     

聚碳硅烷和二乙烯基苯的交联及纳米SiC陶瓷的制备

碳化硅基复合材料是理想的高温结构材料,以聚碳硅烷(PCS)作为碳化硅陶瓷的先驱体,二乙烯基苯(DVB)为交联体,通过改变二者的配比研究了PCS与DVB的交联反应以及PCS/DVB交联体的热裂解过程。通过傅立叶红外光谱详细研究了PCS/DVB配比变化对PCS与DVB的交联反应和交联体微观结构的影响,PCS/DVB配比最终决定碳化硅陶瓷的产率,当PCS/DVB配比为1∶0.5时,经1500℃热裂解后碳化硅陶瓷产率最高,达到63.1%,热裂解产物为纳米碳化硅,粒径为10-40nm。用SEM和XRD研究了不同PCS/DVB配比交联体热裂解产物的微观结构和相组成,通过热重分析研究了PCS/DVB配比为1∶0.5时交联体的热裂解过程,在400-800℃,PCS/DVB交联体失重显著,在800℃热裂解过程基本完成,PCS/DVB配比为1∶0.5时能够制备出纳米碳化硅基复合材料。     

一体化膨胀型防火涂料的热解机理研究

为解决传统防火涂料的装饰性问题,设计并合成了一种一体化膨胀型防火涂料.采用热红联用技术对该防火涂料的热解行为进行了研究,发现其热解过程可以分为4个阶段:第1阶段后期,炭化反应开始;第2阶段不稳定磷酸酯结构的断裂释放出CO2等气体,使熔融炭化物发生初步膨胀;第3阶段气体产物使炭化层进一步膨胀,最后硬化形成多孔炭化层;最终阶段炭化层高温热解.研究发现该防火涂料的热解反应发生顺序符合膨胀防火体系的要求,可以顺利地形成具有多孔结构的炭化层来保护基材.     

酚醛泡沫衍生多孔炭的制备及其电化学性能研究

以苯酚、甲醛为原料，利用水热合成法制备酚醛泡沫前驱体，经炭化和KOH活化后制备具有高比表面积的多孔炭PAFc。采用X射线衍射、扫描电镜和N₂吸附-脱附等方法对多孔炭进行表征。结果表明：当炭化温度为800℃、活化比例为1∶2时制备的多孔炭含有丰富的孔结构和高比表面积(1692.24m²/g)。此外，多孔炭也表现出优异的电化学性能，电流密度为1A/g时多孔炭的比电容达255.6F/g,循环5000次后，电容保持率为97.3%。     

己二酸-1,4-丁二醇-尿素共聚物的合成与表征

以己二酸、1,4-丁二醇和尿素为原料,在氩气环境下,通过高温熔融缩聚反应合成了一种新型可降解的己二酸-丁二醇-尿素共聚物,并对反应时间、催化剂种类及其用量、原料配比、反应温度等因素对聚合产物的影响进行了研究。采用红外光谱(FT-IR)、核磁共振(1H-NMR)、凝胶渗透色谱(GPC)、热重分析(TG)、差示量热扫描(DSC)对产物的结构与性能进行了表征。结果表明,当丁二醇和尿素的总量与己二酸(n(丁二醇+尿素)∶n(己二酸))的摩尔比为1.16∶1,丁二醇和尿素(n(1,4-丁二醇)∶n(尿素))的摩尔比为5∶1,最高反应温度为220℃,二月桂酸二丁基锡为催化剂且用量为原料总量的0.03%,总反应时间10h,所得到产物的重均分子量(Mw)可达12700,其颜色、热稳定性和降解性能等较好。     

己二酸/酚醛树脂共聚炭化制备多孔炭材料及其电性能研究

以酚醛树脂(PF)为炭前驱体, 己二酸(DA)为致孔链段, 利用聚合物共聚炭化法制备双电层电容器用多孔炭材料. 通过红外和热重分析证实己二酸与酚醛树脂发生了化学反应, DA以链段或支链的形式存在于酚醛树脂固化体系中, 并在后续炭化过程中热解逸出. 氮气吸附分析表明酚醛树脂固化体系中的DA起到了一定的造孔作用, 随着DA加入量增加, 多孔炭比表面积先增大后减小, 当w(PF)/w(DA)=3:1时所得多孔炭的比表面积为550 cm²/g, 孔容为0.27 cm³/g. 采用直流充放电法、交流阻抗法和循环伏安法测定以上述多孔炭为电极材料的双电层电容器的电化学性能, 结果表明: w(PF)/w(DA)=3:1时制得的多孔炭电极在30% KOH电解液中比电容为145 F/g, 电流密度增大50倍, 比电容保持率达到70 %.     

加热法和常温催化法固化的GAP力学性能研究

采用加热法和常温催化法,将固化剂2,2-丙炔基丙二酸二甲酯(DDPM)与聚叠氮缩水甘油醚(GAP)按摩尔比2∶1、4∶1和8∶1的配比进行固化反应。利用微机控制电子试验机测试制得样品的拉伸及压缩性能,并对数据进行了分析比较。结果表明：增加固化剂可以提高固化产物的抗拉及抗压强度;DDPM与GAP的摩尔比为2∶1和4∶1时,常温催化法制得样品的抗拉和抗压性能较优;DDPM与GAP的摩尔比为8∶1时,加热法制得样品的抗拉和抗压性能较优,但弹性较差。     

共聚炭化法制备多孔炭材料及其电容性能研究

采用酚醛树脂(PF)为热稳定聚合物, 端环氧基的聚合物(QS)为热不稳定聚合物, 利用聚合物共聚炭化法制备多孔炭。经红外光谱分析及热重分析证实, 在酚醛树脂与QS的共聚固化物中, QS链段上的环氧基与酚醛树脂链段上的酚羟基发生反应生成醚键, QS接枝到酚醛树脂的链段上。BET比表面积、孔结构和电化学性能分析表明: 在共聚固化物PF/QS的炭化过程中, QS的热解逸出能起到造孔作用, 并随着QS用量的增加多孔炭的比表面积先增大后减小。QS加入量为15%的多孔炭具有最大的比表面积609.0 m²/g、总孔容0.28 cm³/g和微孔孔容0.22 cm³/g, 与聚合物共混炭化法相比, 在相同热不稳定聚合物加入量条件下, 多孔炭的比表面积和孔容都有所提高。该多孔炭电极在30wt% KOH电解液中的比电容达177.5 F/g, 具有良好的电容特性。     

高亲水性聚(苯乙烯-二乙烯基苯)多孔微球的制备及亲水性研究

以环状马来酸酐为改性剂,分别采用改进的二步种子溶胀法和悬挂双键接枝法制得了高亲水性的聚(苯乙烯-二乙烯苯)/马来酸酐共聚多孔微球(PSt-DVB-co-MAH)及聚(苯乙烯-二乙烯苯)接枝马来酸酐多孔微球(PSt-DVB-g-MAH)。用FT-IR证明了改性产物中马来酸酐的存在;用TEM、SEM观察了改性前后微球的内、外部形貌;酸碱滴定法考查了MAH加入量对微球孔径的影响;用极性熊果苷的吸附对比实验验证了改性效果。结果表明,两种方法制得的改性微球在形态上与没改性前的微球略有差别,但当共聚法St∶DVB∶MAH=10∶8∶2及接枝法P(St-DVB)微球∶MAH=5∶3时,所得亲水微球均保持了较好的多孔形貌且亲水性比未改性的增大5倍以上。     

不饱和三元聚醚橡胶的合成及其某些性能EI

以Al(i-Bu)_8-H_8PO_4-H_2O-DMA(二甲基苯胺)四元催化剂合成了环氧氯丙烷(ECH)/环氧乙烷(EO)/烯丙基缩水甘油醚(AGE)三元不饱和氯醇醚橡胶。当四元催化剂的摩尔比为1∶0.15∶0.15∶0.10,在10～30℃,24hr,所得产物的ηi在3.0～4.5之间,共聚转化率在95％以上。试验表明:ECH、EO、AGE的三元共聚反应速度略低于ECH与AGE的二元共聚。X-射线衍射显示ECH/EO/AGE三元胶为无定形结构。硫化胶的力学性能(抗张力强度280kg/cm^2,伸长率360％,永久形变16％)和辊筒行为均优于ECH/AGE二元胶。     

Investigation of the degree of crystallinity of acrylonitrile-divinylbenzene copolymers

Using the wide-angle X-ray scattering method, the degree of crystallinity of suspension copolymers and terpolymers of acrylonitrile (AN) and divinylbenzene (DVB) were determined. Copolymers with various degrees of cross-linking (5%–50% DVB) were prepared in the presence of thermodynamically different solvents added in order to obtain porous structure. It was found that copolymers with a degree of cross-linking of 0.1% DVB have a crystallinity index below 0.2, although the crystallinity index of PAN obtained under the same conditions is 0.5. Owing to the solvation conditions, even in copolymers with a degree of cross-linking of 20% DVB, ordered regions occur, and dilution of the polymerization mixture with poor solvents cause a decrease in the degree of crystallinity of these copolymers. Terpolymers AN, butyl acrylate (BA) or vinyl acetate (VA) have less ordered structure for the same amount of DVB. Methacrylonitrile and DVB copolymers obtained under the same conditions as AN and DVB are amorphous.     

Bisphenol A imprinted polymer adsorbents with selective recognition and binding characteristics

Imprinted copolymers, which highly recognized and bound bisphenol A (Bis A), were synthesized by using covalent imprinting technique. Bisphenol A dimethacrylate (BADM) was used as a template monomer in the copolymerization with a crosslinkable monomer of divinyl benzene (DVB), ethylene glycol dimethacrylate (EGDM) or N,N’-methylenebisacrylamide (MBAA). The resultant copolymer was hydrolyzed in acidic or basic condition. It was found that the Bis A imprinted copolymers of EGDM and MBAA had no selectivity to Bis A, because the crosslinker dissociated by the hydrolysis reaction and thus comprehensive imprinted sites were not formed. On the other hand, imprinted copolymer of DVB showed excellent selectivity to differentiate Bis A from bisphenol E and bisphenol F (Bis F). Characterization of the copolymers suggested that the DVB copolymer had resistance to the acid and alkali conditions. Effect of recognition by the Bis F imprinted polymer was also compared with that of the Bis A imprinted polymer, when DVB and bisphenol F dimethacrylate were copolymerized. The Bis F imprinted copolymer was able to recognize Bis F in ethanol solution, however showed higher binding capacity for both Bis A and Bis F in water solution without recognition. Therefore, hydrophobic interaction between Bis A and the imprinted site enhanced the binding capacity with high selectively for the BADM-co-DVB imprinted copolymer.     

The incorporation of polar monomers in copolymers based on styrene and divinylbenzene obtained from glycerol suspension polymerization

Porous copolymer networks based on styrene (STY) and divinylbenzene (DVB) containing polar monomer (methacrylamide — MAM, methacrylic acid — MAA or acrylonitrile — ACN) were prepared by suspension polymerization using glycerol as a dispersant medium. Poly(styrene-co-methacrylamide-co-divinylbenzene), poly(styrene-co-methacrylic acid-co-divinylbenzene) and poly(styrene-co-acrylonitrile-co-divinylbenzene) were synthesized using mixtures of toluene with 2-butanone, toluene and 2-butanone and n-heptane with ethylacetate, respectively at different dilutions: 50%, 100% and 120% (v/v). The copolymers were characterized by bulk density, infrared spectrometry (FTIR) and elemental analysis (CHN). Morphological features of the copolymer pearls were evaluated by microscopic analysis and correlations between porous structure and parameters of reaction were found. The copolymers presented high incorporation of polar monomers. The pearl porosities and visual appearances had a strict relation with the monomer type and the dilution degree employed in synthesizing them.     

交联剂对可膨胀小球制备的影响

以丙烯腈为主要单体,以氢氧化镁为无机分散剂,采用常压聚合法,制备了膨胀倍率达到20-30倍的可膨胀小球。系统研究了二丙二醇二丙烯酸酯(DPGDA)、三缩丙二醇二丙烯酸酯(TPGDA)、新戊二醇二丙烯酸酯(NPGDA)、三羟甲基丙烷三丙烯酸酯(TMPTA)和二乙烯基苯(DVB)等5种交联单体对可膨胀小球制备的影响。通过扫描电子显微镜、热重分析、交联密度测定等手段研究了可膨胀小球的形貌、粒径、发泡剂的含量、交联密度、发泡倍率。确定DPGDA为最佳的交联剂种类,用量为1.7%。采用DPGDA作为交联剂的小球既具有较完好的球状形貌,又有较小的粒径,较高的发泡剂含量和较高的交联度,膨胀倍率可达30倍。     

Electrochemical copolymerization of benzanthrone and 3-methylthiophene and characterization of their fluorescent copolymer

Poly(3-methylthiophene-co-benzanthrone), a novel copolymer, was successfully achieved by electrochemical oxidation of the monomer mixtures of 3-methylthiophene (3MeT) and benzanthrone in the binary solvent system containing boron trifluoride diethyl etherate and acetonitrile. A series of experiments with different monomer feed ratios were carried out to investigate the influence of monomer feed ratio on the electrochemical copolymerization and the overall properties of the copolymer films. The resulting copolymer possesses the advantages of both polybenzanthrone and poly(3-methylthiophene), such as considerable fluorescence property, good redox activity, high thermal stability, and relatively high electrical conductivity. Ultraviolet–visible, FT-IR, and thermal analysis were used to characterize and investigate the structure and thermal stability of the copolymers. Fluorescence spectroscopic studies revealed that the copolymer dissolved in common organic solvents was a good green or yellow-green light emitter, with a strong emission at 499 nm in doped state and 529 nm in dedoped state.     

MA/ATMP共聚物的微观结构及其热稳定性研究

采用不同配比的反应型受阻胺4-丙烯酰氧基-2,2,6,6-四甲基哌啶醇酯(ATMP)与丙烯酸甲酯(MA)进行溶液光引发共聚合.用核磁共振对共聚物的组成及其序列分布进行了表征.在此基础上,对不同微观结构的共聚物进行了热稳定性及玻璃化温度的测定,确定了共聚物中各基团的断裂分解温度、材料的玻璃化转变,以及这些变化与共聚物链组成和序列分布的关系.     

Electrochemical copolymerization of dibenzo-18-crown-6 and carbazole and characterization of their copolymer

The electrochemical copolymerization of carbazole (CZ) and dibenzo-18-crown-6 (DBC) was successfully achieved in pure boron trifluoride diethyl etherate (BFEE) by direct anodic oxidation of the monomer mixtures on the platinum or stainless steel electrodes. The optimal feed ratio together with the suitable applied potential for their copolymerization was determined. The copolymer films, which were electrosynthesized with a feed ratio of CZ/DBC = 1:5, owned both the advantages of poly(dibenzo-18-crown-6) (PDBC) and polycarbazole (PCZ), such as nice electrochemical behavior, excellent fluorescence properties and good mechanical properties. Besides, the copolymers possessed better thermal stability and higher electrical conductivity than those of PDBC or PCZ. The structure of the copolymers was investigated by UV–vis and FT-IR spectroscopy. Fluorescent spectral studies revealed that the dedoped copolymer film was a good blue-light emitter with strong emission at 410 nm. With these advantageous properties, as-formed poly(CZ-co-DBC) films may be a good candidate for optoelectronic devices.     

Effects of molar substitution of AA pendant on poly(MMA-co-GMA) under UV curing

The molar substitution of an acrylic acid (AA) pendant group on a glycidyl methacrylate–methyl methacrylate copolymer was investigated to evaluate its affects on mechanical properties and thermal stability under UV curing. Structural analysis was conducted by Fourier transform infrared spectroscopy and proton nuclear magnetic resonance spectroscopy (¹H-NMR) to study the synthetic route of the acrylate copolymer. The mechanical behaviors of AA substituted copolymers were interpreted in terms of both their loss tangent and elongation at the break point, because AA increases the cross-linking density, which is directly proportional to the degree of homopolymerization; this relationship was monitored by ¹H-NMR with various molar substitutions. In addition, the optical and mechanical properties of the copolymers were also characterized by the extent of AA molar substitution. The optimal behavior was obtained at a molar substitution of 94.3% (equivalent to an AA/GMA molar ratio of 1.4) and satisfied both the transparency (>89.3%) and elongation (>7.4%) requirements for the complex-shaped coatings.     

Electrochemical copolymerization of indole and 3,4-ethylenedioxythiophene

The copolymerization of indole and 3,4-ethylenedioxythiophene (EDOT) was achieved electrochemically in acetonitrile containing lithium perchlorate as supporting electrolyte by direct anodic oxidation of the monomer mixtures on platinum and stainless steel electrodes. As-formed copolymers own both the advantages of polyindole (PIn) and poly (3,4-ethylenedioxythiophene) (PEDOT), i.e., good thermal stability, good electrochemical behavior, high conductivity and excellent ambient stability. The structure and morphology of the copolymer were investigated by UV-vis, infrared spectroscopy, thermal analysis and scanning electron microscopy (SEM), respectively.     

新型二元含氟共聚乳液的制备

以甲基丙烯酸-β-(全氟烷氧基酰基)乙脂均聚物、甲基丙烯酸甲酯为主要原料,制备固相质量分数为23%,乳胶粒子粒径为76¹00 nm的一系列稳定的二元含氟共聚物乳液,并对聚合物结构进行红外光谱表征,讨论单体配比对聚合物玻璃化转变温度、热稳定性及乳胶膜对水接触角的影响。结果表明,随着含氟单体用量的增加,聚合物的玻璃化转变温度降低;新型含氟共聚物较原含氟均聚物有较好的热稳定性;随着含氟单体的增加,乳胶膜对水的接触角增大。