Mn^(3+)引发制得的淀粉与丙烯腈接枝共聚物中的交联键

通过淀粉丙烯腈接枝共聚物（ＳＰＡＮ）在二甲亚砜（ＤＭＳＯ）溶剂中溶解度变化情况推断，Ｍｎ３＋引发下，淀粉与丙烯腈接枝共聚反应生成的ＳＰＡＮ分子中存在有交联键，且这种交联键是由接枝共聚反应过程中共聚物自由基偶合反应形成的。

球碳钕系催化丁二烯-异戊二烯共聚物的红外光谱测定

红外光谱法（ＦＴＩＲ）测定了（Ｃ６０Ｘ）载体钕系催化剂引发不同丁二烯异戊二烯摩尔比所得共聚物的组成变化规律，提出了球碳９７３ｃｍ－１吸收带可能与共聚物主链上双键与Ｃ６０分子骨架间存在ππ相互作用有关的解释。

醋酸乙烯酯-丙烯酸丁酯乳液共聚乳胶粒形态演化过程的模拟

将簇迁移动力学拓展应用到共聚形态的研究中，对醋酸乙烯酯丙烯酸丁酯从间歇到不同加料速率下的半连续乳液共聚实验的乳胶粒形态演化过程进行了模拟，模拟从共聚均聚转折点开始．结果说明：半连续加料时，随着加料速率加快，相分离程度增加，间歇反应时形成了核壳结构．乳胶粒形态模拟结果与文献对此共聚乳胶粒形态的实验表征结果类似．

载体化Et(Ind)_2ZrCl_2催化乙烯-苯乙烯共聚

用均相亚乙基二（１－茚基）二氯化锆（Ｅｔ（Ｉｎｄ）２ＺｒＣｌ２）催化乙烯和苯乙烯共聚时，所得共聚物中苯乙烯链节含量和聚合活性不能同时满足聚乙烯功能化的要求［１，２］．因此我们用ＳｉＯ２对Ｅｔ（Ｉｎｄ）２ＺｒＣｌ２进行载体化，在保证较高聚合活性的同时，...

Synthesis and properties of soluble poly（aryl ether sulfone ether ketone）s copolymers containing pendant methyl groups

A series of Poly（arly ether sulfone ether ketone）s containing pendant methyl groups were synthesized by the reaction of 4,4＇-[sulfonylbis （1,4-phenylene）dioxy] dibenzoyl chloride （SODBC） with 4,4＇- diphenoxy diphenylsulfone （DPODPS）, 4,4＇- di（2-methylphenoxy） diphenylsulfone （o-Me-DPODPS）, 4,4＇- di（3-methylphenoxy） diphenylsulfone （m-Me-DPODPS）, 4,4＇- di （2,6-bimethylphenoxy） biphenylsulfone（o-Me2-DPODPS） respectively, in a mixture of 1,2-dichloroethane （DCE） and N-methylpyrrolidone （NMP）. These reactions were catalyzed by anhydrous aluminum chloride （AlCl）. The characteristic of copolymers were studied by means of advanced analytical techniques such as FT-IR,1H-NMR, DSC, TGA and WAXD. The results show glass transition temperature （Tg） in the range of 193-206℃, thermally stable in excess of 434℃ and excellent solubility in polar solvents. Methyl-substituted Poly（aryl ether sulfone ketone）s had higher glass transition temperatures, lower initial decomposition temperatures than the unsubstituted ones.

AlCl_3-Catalyzed Directional Conversion of some Polycyclic Aromatics

Special attention should be paid to the preparation of "special chemicals" from coal and the conversion of them. In this thesis, the alkylation and acylation of some polycyclic aromatics, naphthalene, acenaphthene and anthracene, catalyzed by Lewis acid AlCl 3 in carbon disulfide (CS 2) and nitrobenzene (PhNO 2), were investigated. The results show that some important organic intermediates and monomers can be selectively synthesized by controlling the reaction conditions.

颗粒淀粉与丙烯酰胺的接枝共聚

本文以小麦淀粉为骨架,丙烯酰胺为单体,溴酸钠为引发剂,使原淀粉与丙烯酰胺接枝共聚。对接枝过程中引发剂浓度、单体浓度、反应温度、反应时间、pH值,原料配比诸因素对产物的影响进行了讨论,并探讨了产物可以保持颗粒状态的条件。

Study on Structure and Crystallinity of A New Biodegradable Aliphatic-Aromatic Copolyester

A series of biodegradable aliphatic-aromatic copolyesters, poly(butylene terephthalate-co-butylene adipate-co- ethylene terephthalate-co-ethylene adipate) (PBATE), were synthesized from terephthalic acid (PTA), adipic acid (AA), 1,4-butanediol (BG) and ethylene glycol (EG) through direct esterification and polycondensation. The sequence structure and crystallinity of the copolyester were investigated by 1H NMR spectroscopy and the wide-angle X-ray diffractometry (WAXD). The analytical results showed that the PBATE copolyester was a random copolymer and the composition of PBATE copolyester was almost consistent with the feed molar ratios. The crystal structure of PBATE copolyester belonged to the triclinic crystalline system; The variation in melting point of the synthesized PBATE copolyester agreed well with the estimation obtained by the Flory equation and was applicable to the random copolymer.

Poly(aryl ether nitrile)s containing flexible side-chain-type quaternary phosphonium cations as anion exchange membranes

In order to effectively improve the properties of anion exchange membrane(AEM)materials,a series of novel poly(aryl ether nitrile)s with flexible side-chain-type quaternary phosphonium cations(PAEN-TPP-x)were designed and prepared on the basis of considering the influences of polymer backbone,cationic group species and the connection way between the cations and polymer chains.The synthetic method,structure and ion-exchange capacity,water absorption,swelling,hydroxide conductivity and alkaline stability of the obtained AEMs were studied.A comparative study with other reported AEMs was also performed for further exploration of the relationship between the structure and properties.These AEMs with flexible side-chain-type quaternary phosphonium cations displayed good comprehensive properties.Their water uptakes and swelling ratios were in the range of 11.6%–22.7%and 4.4%–7.8%at 60℃,respectively.They had hydroxide conductivity in the range of 28.6–45.8 mS cm^-1 at 60℃.Moreover,these AEMs also exhibited improved alkaline stability,and the hydroxide conductivity for PAEN-TPP-0.35 could remain 82.1%and 80.6%of its initial value at 60 and 90℃in 2 mol L^-1 NaOH solution for480 h,respectively.

Preparation and Characterization of Polysulfonamide Statistical Copolymers from Three Aromatic Diamines

Various polysulfonamide （PSA） statistical copolymers were synthesized by polycondensation of three aromatic diamines and terephthaloyl chloride. The inherent viscosities of the resulting PSA copolymers range from 1.54 to 1.66 dL/g. The precipitated PSA copolymers with feed content of p-phenylene diamine （PPD） being less than 50% （mole fraction） can be redissolved in N-methyl-2-pryrrolidone （NMP） or N, N-dimethylacetamide （DMAc） with lithium chloride of WLiC1 ： 0.02. All of the PSA copolymers exhibit enhanced tensile strength in comparison with PSA and still maintain excellent thermal stability in either air or nitrogen atmosphere

Thermal behavior and phase behavior in blends of liquid crystalline poly(aryl ether ketone) and poly(aryl ether ether ketone) containing thioether units

Thermal behavior and phase behavior in blends of liquid crystalline poly(aryl ether ketone) with lateral methoxy groups (M-PAEK) and poly(aryl ether ether ketone) containing thioether units (S-PEEK) have been investigated by differential scanning calorimetry (DSC) and polarized light microscopy (PLM) techniques. The results indicate that the composition of the blends has great effect on the phase behavior and morphology. Thin films of pure M-PAEK and S-PEEK crystallized from the melts exhibit typical mosaic and spherulitic structures, respectively. For the blends with higher M-PAEK contents (> 50%), an unusual ring-banded spherulite with structural discontinuity is formed. The bright core and rings of the ring-banded spherulites under PLM are composed of M-PAEK phase, while the dark rings consist mainly of S-PEEK phase. For the 50:50 M-PAEK/S-PEEK blend, the ring-banded spherulites and S-PEEK spherulites coexist, which implies that a partial phase separation between the two components takes place in the melting state. In S-PEEK-rich blends, a volume-filled spherulite is produced. In addition, the effect of isothermal crystallization temperature on the phase behavior, especially the ring-banded spherulite formation in the blends, is discussed.

Structure evolution of thiophene-containing conjugated polymer photocatalysts for high-efficiency photocatalytic hydrogen production

Conjugated polymer photocatalysts have received extensive attention in the field of photocatalytic hydrogen evolution owing to their tunable molecular structures and electronic properties.Herein,we developed three donoracceptor(D-A)type thiophene-containing narrow-band-gap conjugated polymers with pyrene as a donor and different fused-thiophene derivatives as acceptors via direct C-H arylation coupling polymerization.It was found that the band gap of the polymers can be tuned by adjusting the number of the fused-thiophene rings.The visible light absorption range can be extended by increasing the number of the thiophene rings,the planar molecular structure for both donor and acceptor units facilitates the charge transmission along the polymer skeleton,and the D-A type polymer structure promotes the dissociation of photo-induced electrons and holes.As a result,a high photocatalytic hydrogen evolution rate of 33.07 mmol h^(−1)g^(−1) was obtained by PyTP-2 with an optimized molecular structure under visible light irradiation(λ>420 nm)without the aid of Pt co-catalyst.In addition,PyTP-2 also shows a photocatalytic activity for oxygen evolution with an average oxygen evolution rate of 58.37µmol h^(−1)g^(−1).

Precursor synthesis strategy for polycyclic aromatic conjugated polymers on the application of supercapacitors

Polycyclic aromatics (PCAs) possess excellent photoelectric properties, but the construction of such compounds has been a quite challenging subject of study, mainly due to very low solubility. Herein we report a precursor synthesis strategy for polycyclic aromatic conjugated polymers. A soluble precursor polymer, that containing fusible "double U-shaped aromatic"(DUA) and perylenetetracarboxydiimide (PDI) units, was firstly synthesized by Suzuki coupling. The stereo aromatic units in polymer backbone were found to be converted into polycyclic aromatic units, i.e. hexa-peri-hexabenzocoronene (HBC), by chemical or electrochemical oxidation, which resulted in a formation of insoluble polycyclic aromatic conjugated polymers. The electrochemical oxidations that occurred at the interface of electrode and solution exhibited higher cyclization reactivity and leads to the formation of high quality films on the electrode surface. Characterization by Raman and UV-visible (UV-Vis) spectroscopy validated the successful formation of this HBC structure. Some potential applications of such thin films are being explored, and here we focus on the characteristics of supercapacitors based on their excellent electrochemical properties.

Enhance the performance of polymer solar cells via extension of the flanking end groups of fused ring acceptors

Two new fused ring electron acceptors(FREAs)IDT-IC-T and IDT-IC-B with thienyl or phenyl substituents at the terminal INCN unit are synthesized.Theoretical calculations indicate that the two acceptors dominantly favor an intermolecularπ-πstacking between the flanking terminal groups.The twist angle between the aryl substituent and INCN unit has a significant influence on theπ-πstacking distance of terminal unit.IDT-IC-T with a smaller twist angle has a shorterπ-πstacking distance than that of IDT-IC-B with a larger twist angle.In addition,extending the conjugation also affects the blend film morphology.IDT-IC-T and IDT-IC-B based photoactive films show appropriate nanoscale phase separations;whereas,blend films based on the parent compound IDT-IC show large-size acceptor domains.As expected,PBDB-T:IDT-IC-T blend films show higher and more balanced electron and hole mobilities.Moreover,these two acceptors present a good charge-transport connectivity arising from the extended conjugation and the increased intermolecular overlapping.Ultimately,IDT-IC-T demonstrates the highest electron mobility(1.47×10^(-4)cm^2V^(-1)s^(-1))and the best power conversion efficiency(PCE)of 9.43%.As for IDT-IC,which only shows an electron mobility of 7.33×10^(-5)cm^2V^(-1)s^(-1)and a PCE of 5.82%.These findings provide a facile and effective way to improve the photovoltaic performance.

Efficient and stable inverted perovskite solar cells enabled by inhibition of self-aggregation of fullerene electron-transporting compounds

Fullerene-based electron-transporting layers(ETLs)significantly influence the defect passivation and device performance of inverted perovskite solar cells(PSCs).However,theπ-cage structures of fullerenes lead to a strong tendency to self-aggregate,which affects the long-term stability of the corresponding PSCs.Experimental results revealed that[6,6]-phenyl-C61-butyric acid methyl ester(PCBM)-based ETLs exhibit a certain degree of self-aggregation that affects the stability of the device,particularly under continuous irradiation stress.To modulate the aggregation behavior,we replaced a methyl hydrogen of PCBM with a phenyl group to yield[6,6]-phenyl-C61-butyric acid benzyl ester(PCBB).As verified through X-ray crystallography,this minor structural modification results in more non-covalent intermolecular interactions,which effectively enhanced the electron-transporting ability of the PCBB-based ETL and led to an efficiency approaching 20%.Notably,the enhanced intermolecular forces of PCBB suppressed its self-aggregation,and the corresponding device showed significantly improved stability,retaining approximately 90%of its initial efficiency after 600 h under one-sun irradiation with maximum power point tracking.These findings provide a viable approach for the design of new fullerene derivatives to tune their intermolecular interactions to suppress self-aggregation within the ETL for highperformance PSCs.