聚芳醚腈的合成与性能

本文以二氯苯甲腈，对苯二酚和间苯二酚为原料，制备了一种新型的聚芳醚腈ＰＥＮ－ＨＱＲＳ，采用流延法制备了较高力学性能的ＰＥＮ－ＨＱＲＳ薄膜，并对其合成与性能进行了研究。     

聚芳酮的合成与性能

本文综述了一类新型的热塑性工程塑料─—聚芳酮的合成方法，并对其性能进行了分析和讨论。     

含柔性链端炔基POSS(POSS-LA)的合成及对含硅芳炔树脂的改性

通过水解缩聚、巯烯加成及酯化反应合成了八(十一烷酸丁炔醇酯基硫醚丙基)笼型倍半硅氧烷(POSS-LA),并通过红外光谱、核磁共振谱、差示扫描量热法等对POSS-LA的结构及性能进行了表征。用POSS-LA与含硅芳炔树脂(PSA)共混制得改性树脂LP-PSA,并对改性LP-PSA树脂进行了表征。研究表明,改性LP-PSA固化物的强度及韧性随POSS-LA的加入而提高。当POSS-LA的质量分数为15%时,弯曲强度可提升86%,冲击断裂能可提升91%。此外,LP-PSA固化物还显示了良好的热稳定性(热分解温度T_(d5)436℃)。     

含硝基噁二唑聚炔的合成及三阶非线性光学性能

设计合成了一种含硝基噁二唑功能基的聚炔材料。通过红外光谱(IR)和核磁共振(1H-NMR)对该聚炔化合物进行了结构表征。利用紫外光谱(UV-vis)和热重分析(TGA)对其性能进行了评价。TGA显示其热稳定性相对于单体有很大提高,UV-vis表明它在500 nm以上长波区吸收很弱。该聚炔化合物的非线性光学性能借助Z-scan技术进行研究,其χ(3)达3.25×10-11(esu)。与含烷基的同类聚炔比较,拉电子基团硝基有效地提高了含噁二唑聚炔的三阶非线性光学性能。     

新型含炔基苯并(口恶)嗪的合成及性能研究

为了提高苯并(口恶)嗪的热稳定性,以对碘苯胺、3-氨基苯乙炔、苯酚及多聚甲醛为原料合成了新型的含炔基苯并(口恶)嗪(PA-an-ba),并通过傅里叶变换红外光谱仪和核磁共振仪(~1 H-NMR,~(13) C-NMR)对其结构进行表征,通过差示扫描量热仪和热重分析仪对其固化行为和热性能进行了测试。结果表明:炔基的引入能显著提高聚苯并(口恶)嗪的耐热性,其失重率为5%和10%时的温度分别为437℃和464℃,800℃的残炭率为73%,比传统苯并(口恶)嗪提高了40%。     

新型杂环氯代聚芳醚的合成与性能

以自制的新型氯代类双酚化合物4-(3-氯-4-羟基苯基）-2,3-二氮杂萘-1-酮（OC-HPPZ）为单体,分别与4,4/-二氟二苯酮、4,4/-二氯二苯砚和1,4-双-（4-氯代苯甲酰基）苯进行缩聚反应,合成了一类新型的具有较高分子质量的聚芳醚材料。利用FTIR、1H NMR等分析手段研究了类双酚化合物OC-HPPZ及其聚合物的结构;采用差示扫描量热仪（DSC）、热重分析仪（TGA）研究了聚合物的耐热性能,结果表明,新型聚芳醚砜、聚芳醚酮和聚芳醚酮酮具有优异的耐热性能和热稳定性能,其玻璃化转变温度为234～287℃,在氮气氛中5%热失重温度均高于420℃,新型氯代聚芳醚在氯仿、N、N-二甲基乙酰胺等极性有机溶剂中可溶解并浇铸得到透明、韧性的薄膜。     

新型含酰基结构炔胺的合成

N-取代炔烃是一种应用非常广泛的化学合成分子,能够参与到化学反应的各个环节中,是一种具有非常显著的立体选择性以及区域选择性的合成子。酰基炔胺是一种比N-取代炔烃更加稳定的有机化合物,在化工行业中有着非常重要的作用。本次研究通过实验对新型含氨基结构炔胺及其衍生物进行合成,旨在为化工行业提供更加简单方便的操作方法。     

新型含氰侧基氯取代聚芳醚醚酮酮的合成及表征

在无水AlCl3及N-甲基吡咯烷酮(NMP)/1,2-二氯乙烷(DCE)复合溶剂的存在下,将2,6-二苯氧基苯甲腈(DPOBN)与2,5-二氯对苯二甲酰氯(DCC)进行低温缩聚反应,合成了一类新型含氰侧基氯取代的聚芳醚醚酮酮.用IR、DSC、TG、WAXD等方法对其结构和性能进行了表征.结果表明,所合成的聚合物为非晶态聚合物;其玻璃化转变温度(Tg)为229℃,热分解5%的温度(Td)为445℃,说明其具有突出的耐高温性能;聚合物能在NMP、DMF、DMSO等强极性非质子溶剂及DCE、THF、CHCl3等普通溶剂中溶解或溶胀.     

含叔丁基新型聚芳醚砜薄膜的制备及性能研究

以双酚A(BPA)、叔丁基对苯二酚(TBHQ)、4,4'-二氯二苯砜(DCDS)为共聚单元,在分子主链侧基中引入大体积疏水性的叔丁基,通过调整BPA与DCDS的比例制备了系列聚芳醚砜薄膜,并对薄膜进行了红外表征和性能测试.结果 表明:系列薄膜综合性能优异,介电常数(1MHz,2.76～3.05)、介电损耗(＜0.75％...     

几种新的杂环取代丁二炔类衍生物的三阶非线性光学性能

用简并四波混顿法测试了一系列新合成的丁二炔（ＰＤＡ）类衍生物的三阶非线性极化率，其γ值在１０－３４ｅｓｕ～１０－３０ｅｓｕ之间。其中ｐｏｌｙ－ＰＤＭＡ［聚５－（２－硫甲基－４－甲基）－嘧啶基－戊二炔－１－醇－α－甲基丙烯酸甲酸］的χ（３）值为１２７．１５８×１０－１３ｅｓｕ（０．５３２μｍ），对应的γ值为１１８４５．１９８×１０－３４ｅｓｕ，已接近目前文献所见的最大值１０－２９ｅｓｕ数量级。从ｐｏｌｙ－ＰＤＭＡ的ＵＶ－ｖｉｓ吸收光谱（λｍａｘ，＝３０７ｎｍ）及透射率（０．５３２ｕｍ，Ｔ＝０．０６５）来看，虽所测得的为部分共振γ值，但也是不同寻常了。     

含苯并硒二唑组分的聚对苯撑乙炔类共轭聚合物的合成及性能研究

通过钯催化的Sonagashira偶合反应合成出了3种带有不同链长烷氧基侧链,主链中含有2,1,3-苯并硒二唑纽分的聚苯乙炔类共轭聚合物并对其化学结构进行了表征确认.此类聚合物在常用的有机溶剂中具有较好的溶解性和成膜性.通过紫外可见光谱、荧光光谱、循环伏安等对所得聚合物的基本性能进行了探讨.聚合物P7、P9和P12在溶液状态下的紫外吸收分别为421、450和450nm,相对应最大发射分别位于475、482和481nm;固态下聚合物的吸收分别为433、486和486nm,相对应最大发射为575、583和590nm.聚合物的循环伏安测试表明聚合物P7、P9、P12的起始电位为1.19、1.19、1.18V.聚合物非线性光学性能研究表明取代基为十二碳烷氧基的聚合物显示出了良好的三阶非线性光学性能,其三阶非线性光学系数为3.54×10-12esu.     

Synthesis and characterization of novel poly(aryleneethynylene)s derived from squaraines for photovoltaic applications

Two novel π-conjugated polymers composed of alkyl carbazole/dialkoxyphenylene and squaraine units were synthesized by Sonogashira cross-coupling reactions. The structures and properties of these copolymers were characterized using FT-IR, NMR, UV–Vis, gel permeation chromatography and cyclic voltammetry (CV). Both polymers possess adequate thermal stability and exhibit good solubility in common organic solvents such as chloroform, THF, and toluene. The polymer films show intense and broad visible and near IR absorption with the long wavelength absorption maximum peaks of 796 and 851 nm for P ₁ and P ₂ , respectively, which are apparently red-shifted compared with poly(phenyleneethynylene). CV studies reveal that the band gaps of these copolymers are about 1.45 eV, implying that the resulted polymers may be promising candidates for solar cells.     

超支化聚对苯共聚物的合成及表征

利用Suzuki缩聚反应,合成了以1,3,6,8-(N-己基)咔唑为核的新型超支化聚对苯撑共聚物.用红外、核磁共振对聚合物的结构进行测定,表明咔唑以及吡啶单元成功引入聚合物中.聚合物可溶于四氢呋喃、氯仿和甲苯等有机溶剂.用凝胶渗透色谱法测得超支化聚合物的分子量在40000～110000之间,分子量随着1,3,6,8-(N-已基)咔唑含量的增加逐渐增加.超支化聚合物在溶液和薄膜状态下的吸收峰分别位于315～334nm和402～410nm之间.随着支化咔唑单元含量的增加,超支化聚合物的吸收峰均发生一定程度的蓝移.超支化聚合物在溶液和薄膜状态下的最大发射峰分别位于402～410nm和402～415nm之间,并且随着引入的支化咔唑单元含量的增加,分子内发生更加有效的分子内电荷转移,PL光谱发生略微的红移.     

Composite electronic materials based on poly(3,4-propylenedioxythiophene) and highly charged poly(aryleneethynylene)-wrapped carbon nanotubes for supercapacitors

Supercapacitor charge storage media were fabricated using the semiconducting polymer poly(3,4-propylenedioxythiophene) (PProDOT) and single-walled carbon nanotubes (SWNTs) that were helically wrapped with ionic, conjugated poly[2,6-{1,5-bis(3-propoxysulfonicacidsodiumsalt)}naphthylene]ethynylene (PNES). These PNES-wrapped SWNTs (PNES-SWNTs) enable efficient dispersion of individualized nanotubes in a wide range of organic solvents. PNES-SWNT film-modified Pt electrodes were prepared by drop casting PNES-SWNT suspensions in MeOH; high stability, first-generation PProDOT/PNES/SWNT composites were realized via electropolymerization of the ProDOT parent monomer (3,4-propylenedioxythiophene) in a 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide/propylene carbonate solution at the PNES-SWNT-modified electrode. The electrochemical properties of PProDOT and PProDOT/PNES/SWNT single electrodes and devices were examined using cyclic voltammetric methods. The hybrid composites were found to enhance key supercapacitor figures of merit (charge capacity and capacitance) by approximately a factor of 2 relative to those determined for benchmark Type I devices that exploited a classic PProDOT-based electrode material. The charge/discharge stability of the supercapacitors was probed by repeated rounds of cyclic voltammetric evaluation at a minimum depth of discharge of 73%; these experiments demonstrated that the hybrid PProDOT/PNES/SWNT composites retained ~90% of their initial charge capacity after 21,000 charge/discharge cycles, contrasting analogous data obtained for PProDOT-based devices, which showed only 84% retention of their initial charge capacity.     

聚乙二醇改性聚乳酸的合成与性能表征

以外消旋乳酸(D,L-LA)和不同数均分子量(Mn)的聚乙二醇(PEG)为原料,通过熔融缩聚法,合成了系列聚乳酸聚乙二醇(PLEG)。最佳工艺条件为:以(Sn(Oct)2)为催化剂,m(Sn(Oct)2)为0.8%,n(PEG)∶n(D,L-LA)=1∶600,聚合温度170℃,压力0.096 MPa条件下,反应8h。用特性粘度测试、FT-IR、XRD、接触角等对其进行表征,实验结果表明系列PLEG中PLEG-800接触角为63°,表明其亲水性能最好;PEG-800和乳酸共聚合成的PLEG的粘均分子量最大,可达48997,与PDLLA相比,结晶度有较大提高,亲水性得到改善。     

Synthesis and characterization of nitrated and aminated poly(phenylene sulfide) derivatives for advanced applications

Nitrated and aminated poly(phenylene sulfide) (PPS) derivatives with different extent of modification were synthesized in a one-pot reaction in suspension. Their substitution degree was determined from both elemental analysis and TGA curves. FT-IR and NMR spectra demonstrated the effectiveness of the functionalization reactions, showing the appearance of bands related to the substituent groups. A progressive reduction in thermal stability was observed as the number of functional groups increased. Aminated derivatives were thermally less stable and exhibited higher solubility in aprotic polar solvents than the corresponding nitrated polymers. DSC thermograms revealed a diminution in the crystallization temperature and a rise in the glass transition with increasing functionalization degree, since the presence of substituent groups inhibits the rotation of consecutive elements of the polymer chain. The level of crystallinity decreased upon increasing chain modification, as evidenced from X-ray diffractograms. The steric hindrance of the substituents disrupts the chain packing, leading to smaller crystals. These derivatives are expected to have applications in electromembranes and as matrix materials for the fabrication of high-performance composites suitable for structural and non-structural components.     

高分子量聚L-乳酸的合成和表征

采用丙交酯开环聚合合成聚L-乳酸(PLLA),研究了引发剂用量、聚合时间对聚L-乳酸分子量的影响.采用FTIR、DSC、TG分析方法对聚乳酸的结构和热性能加以表征.研究结果表明通过对聚合时间以及引发剂用量的控制,合成出高分子量聚L-乳酸.FTIR分析结果证实了聚L-乳酸的结构,DSC分析表明合成出的聚L-乳酸玻璃化转变温度为62℃,结晶度达到42.3%;TG分析表明聚L-乳酸热分解温度为299℃.     

Synthesis and characterization of conducting poly (1-aminonaphthalene), poly (2-aminonaphthalene) and poly (aniline-co-1-aminonaphthalene)

Poly (1&2)-aminonaphthalene and poly (aniline-co-1-aminonaphthalene) have been synthesized in high yields by chemical oxidative polymerization method. The polymers are soluble in polar solvents such as DMSO, NMP etc. In PNA-2 as head-to-tail coupling cannot occur, the electrical conductivity is lower than PNA-1. The copolymer exhibits distinct morphology, higher viscosity, characteristic exciton peak, appreciable thermal stability and electrical conductivity compared to PNA-1.     

Synthesis of poly(2,5-Thienylene Vinylene) and its derivatives: Low band gap materials for photovoltaics

Poly-(2,5-Thienylene Vinylene) (PTV) derivatives have been synthesised via the “dithiocarbamate precursor route” in good yield and satisfactory molecular weight. Structural characterisations of the conjugated PTV polymers reveal an optical band gap around 1.8 eV. Organic field effect transistors and organic based photovoltaic devices were made with the plain PTV, via a precursor approach. More specifically, solar cells were produced using a blend of the precursor PTV polymer and PCBM (1-(3-methoxycarbonyl) propyl-1-phenyl [6,6] C₆₁) at various ratios, converted in situ in thin film. A promising power efficiency of 0.76% was achieved.     

酪氨酸改性聚乳酸共聚物的合成及降解研究

以乳酸(D,L-LA)和L-酪氨酸(Tyr)为原料[n(D,L-LA)/n(Tyr)=95/5],氯化亚锡(Sn(cl)2)为催化剂,采用梯度升温法,通过直接熔融缩聚合成聚(乳酸-酪氨酸)共聚物(PLA-co-Tyr).用特性粘度测试、FT-IR、1 H-NMR、GPC、DSC、XRD、TG等对其进行表征,通过SEM、XRD等方法研究了降解前后材料的表面形态、结晶度及失重率的变化.结果表明:系列共聚物中的重均相对分子量Mw最大可达2900,与聚乳酸相比具有较小的Tg和结晶度,分解温度高于180℃,具有良好热稳定性且降解性能优于聚乳酸.