PREPARATION AND CHARACTERIZATION OF SCHIFF BASE POLYMERS DERIVED FROM 4,4'-METHYLENEBIS(CINNAMALDEHYDE)

New Schiff base polymers poly[4,4＇-methylenebis（cinnamaldehyde）ethylenediimine] （PMBCen）, poly[4,4＇- methylenebis（cinnamaldehyde）1,2-propylenediimine] （PMBCPn）, poly[4,4＇-methylenebis（cinnamaldehyde）1,3-propylenediimine] （PMBCPR）, poly[4,4＇-methylenebis（cinnamaldehyde） 1,2-phenylenediimine] （PMBCPh）, poly[4,4＇-methylenebis（cinnamaldehyde）meso-stilbenediimine] （PMBCS）, poly[4,4＇-methylenebis（cinnamaldehyde）urea] （PMBCUR）, poly[4,4＇- methylenebis（cinnamaldehyde）semicarbazone] （PMBCSc）, poly[4,4＇-methylenebis（cinnamaldehyde）thiosemicarbazone] （PMBCTSc） and poly[4,4＇-methylenebis（cinnamaldehyde）hydrazone] （PMBCH） were formed by polycondensation of 4,4＇- methylenebis（cinnamaldehyde） with ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,2-phenylenediamine, meso-stilbenediamine, urea, semicarbazide, thiosemicarbazide and hydrazine, respectively. The dialdehyde and polymers have been characterized through elemental micro-analysis, IR, UV-Vis and ^1H-NMR spectroscopic techniques. Thermoanalytical studies and viscous flow of dilute solutions of dialdehyde and its polymers have been examined and compared.

Infuences of Different Admixtures on the Drying Shrinkage Characteristics of Metakaolin-based Geopolymer Mortar

To investigate the influences of different admixtures on the drying shrinkage of polymer mortar in a metakaolin base,the experiments of VAE(vinyl acetate ethylene copolymer),APAM(anionic polyacrylamide)and CPAM(cationic polyacrylamide)on the drying shrinkage properties of geopolymer mortar were designed under normal temperature curing conditions.An SP-175 mortar shrinkage dilatometer was introduced to measure the dry shrinkage of geopolymer mortar.Meanwhile,the drying shrinkage properties of geopolymer mortar are exhibited by the parameters of water loss rate,drying shrinkage rate,drying shrinkage strain and drying shrinkage coefficient.The experimental data are further fitted to obtain the prediction model of dry shrinkage of geopolymer mortar,which can better reflect the relationship between dry shrinkage rate and time.Finally,the experimental results demonstrate that the dry shrinkage of geopolymer mortar can be significantly increased by adding 4%VAE admixture,meanwhile under the condition that the polymer film formed by VAE reaction can strengthen and toughen the mortar.2.5%APAM admixture and 1.5%CPAM admixture can enhance the dry shrinkage performance of geopolymer mortar in a certain range.

Electrochemical Performance of Nickel Hydroxide/Activated Carbon Supercapacitors Using a Modified Polyvinyl Alcohol Based Alkaline Polymer Electrolyte

Polyvinyl alcohol （PVA）-sodium polyacrylate （PAAS）-KOH-H2O alkaline polymer electrolyte film with high ionic conductivity was prepared by a solution-casting method. Polymer Ni（OH）2/activated carbon （AC） hybrid supercapacitors with different electrode active material mass ratios （positive to negative） were fabricated using this alkaline polymer electrolyte, nickel hydroxide positive electrodes, and AC negative electrodes. Galvanostatic charge/ discharge and electrochemical impedance spectroscopy （EIS） methods were used to study the electrochemical performance of the capacitors, such as charge/discharge specific capacitance, rate charge/discharge ability, and charge/discharge cyclic stability. Experimental results showed that with the decreasing of active material mass ratio m（Ni（OH）2）/m（AC）, the charge/discharge specific capacitance increases, but the rate charge/discharge ability and the charge/discharge cyclic stability decrease.

Polymerization of isoprene catalyzed by neodymium heterocyclic Schiff base complex

Neodymium-based heterocyclic Schiff base complex was prepared and applied for the coordination polymerization of isoprene. This complex polymerized isoprene to afford products featuring high cis-1,4 stereospecificity （ca. 95%） and high molecular weight （ca, 10^5） in the presence of the triisobutyl aluminium （AliBu3） as cocatalyst, The microstructure of obtained polyisoprene was investigated by FTIR, 1^H NMR. Two different kinds of active centers in the catalyst system were examined by GPC method.

STUDY ON AB-CROSSLINKED POLYMERS Ⅰ. THE SYNTHESIS AND MECHANICAL PROPERTIES OF AB-CROSSLINKED POLYMERS BASED. ON PU/PS

The AB-crosslinked polymers (i.e. ABCP) with polystyrene as chain A and vinyl group blocked prepolymers of polyurethanes (PU) as chain B were synthesized and studied. The results of dynamic mechanical spectrometry (DMS) show that the compatibility between the components A and B can be improved greatly through chemical crosslinking during the formation of ABCPs. This effect is especially pronounced when short chain prepolymers is chosen as one of the components. It is apparent that the degree of crosslinking between the two components plays a major role in determining their compatibility. Copolymerizafion of styrene with maleic anhydride in chain A can improve the compatibility and broaden the damping temperature range. Mechanical properties of the sythesized ABCPs were also studied.

Synthesis,Crystal Structure and Characterization of a Nickel Complex Based on Phenoxyimine Ligand and Catalysis of the Vinyl Polymerization of Norbornene

The title complex N,O-bis{2-[[（2-benzhydryl-4,6-dimethylphenyl）imino]-methyl]-phenol}-nickel（II）（C56H48N2NiO2） has been synthesized by the reaction of 2-[[（2-benzhydryl-4,6-dimethylphenyl）mino]-methyl]-phenol with Ni（CH3COO）2·4 H2O, and characterized by elemental analysis and IR spectrum. The spatial structure of the complex has been confirmed by single-crystal X-ray diffraction analysis. The compound belongs to the monoclinic system, space group C2/c with a = 39.035（8）, b = 13.276（3）, c = 17.679（4） A°, β = 98.06（3）°, V = 9071（3） A°^3, C56H48N2NiO2, Mr = 839.67, Z = 8, Dc = 1.230 Mg/m^3, μ = 0.472 mm^-1, F（000） = 3536, T = 293（2） K, the final R = 0.0675 and w R = 0.1345（I 〉 2s（I））. The compound showed excellent catalytic activity up to 1.268 × 10^7 g of PNB（mol of Ni）^-1h^-1 for the addition polymerization of norbornene by using methylaluminoxane（MAO） as a cocatalyst.

Performance and Stability of Polymer Solar Cells Based on the Blends of Poly(3-Hexylthiophene) and Indene-C_(60) Bis-Adduct

The performance and morphology stability of polymer bulk heterojunetion solar cells based on poly（3-hexylthiophene） （P3HT） as the donor and indene-C6o bisadduct （ICBA） or methanofullerene [6,6]-phenyl C61-butyric acid methyl ester （PCBM） as the aeceptor are compared. Effect of the different donor and aeeeptor weight ratios on photo- voltaic performance of the P3HT：ICBA device is studied. The optimal device achieved power conversion emeiency of 5.51~o with dso of l0.86mA/cm2, Voc of 0.83 V, and fill factor （FF） of 61.1 % under AM 1.5G （lOOmW/cm2） simulated solar illumination. However, the stability measurement shows that cells based on P3HT：ICBA are less stable than those of the device based on P3HT：PCBM. Atomic force microscope results reveal that the morphol- ogy of the P3HT：ICBA film changed considerably during the storage periods due to unstable interpenetrating D-A network. This observation can be explained by the fact that there is lack of intermolecular hydrogen bonds in the P3HT：ICBA system. However, in the P3HT：PCBM system the molecules in the blend film are firmly held together in the solid state by means of intermoleeular hydrogen bonds originating from C-H. ~. Os bonds （where Os comes from the singly-bonded 0 atom of PCBM）, forming a stable three-dimensional network. The measured PL decay lifetimes for P3HT：PCBM and P3HT：ICBA systems are 33.66 ns and 35.34 ns, respectively, indicating that the P3HT：ICBA system has a less efficient exciton separation eftleiency than that of P3HT：PCBM, which may result in the interracial photogenerated charges accumulated on the D： A interface. Such progressive phase segregation between P3HT and ICBA eventually leads to the degradation in performance and deteriorates the stability of the device. We also present an approach to enhance the stability of P3HT：ICBA systems by adding PCBM as the second acceptor. Our results show that by carefully tuning the contents of PCBM as the second acceptor, more stable polymer solar cells can be obtained.

Oligomerization and Polymerization of Ethylene Initiated by a Novel Ni(Ⅱ)-Based Acetyliminopyridine Complexes as Single-Site Catalysts

Novel Ni（II）-based acetyliminopyridine complexes 1b, 2b, 3b （1-3b）, which are synthesized from ligands 1a, 2a, 3a （1-3a） and [NiCl2（DME）], are suitable precursors for the catalysts that are necessary for ethylene oligomerization and polymerization reactions, activated by methylaluminoxane （MAO）. The MAO-treated 1-3b presents an active catalytic center, which may oligomerize and polymerize ethylene to produce linear α-olefins and polyethylene, respectively. The molecular weight distributions of oligomers that are obtained are in good agreement with the Schulz-Flory rules for oligomers〉C4. The activity of 3b-MAO complex is 6.3×10^7 g/（molNi.h） at 50 ℃. The activities and molecular weight distributions of oligomers show significant reliance on the structures of catalyst precursors.

Synthesis, Crystal Structure and Norbornene Polymerization of a Palladium(Ⅱ) Complex Based on Phenoxyimine Ligand

The title complex N,O-bis{2-[[(2,6-benzhydryl-4-methylphenyl)imino]-methyl]-phenol}-palladium(II)(C_(80)H_(64)N_2O_2 Pd) has been synthesized by the reaction of 2-[[(2,6-benzhydryl-4-methylphenyl)imino]-methyl]-phenol with Pd(CH_3COO)_2, and characterized by IR spectrum and elemental analysis. The spatial structure of the complex has been verified by single-crystal X-ray diffraction analysis. The compound belongs to the monoclinic system, space group P21/n with a = 13.492(3), b = 16.924(3), c = 14.135(3) ?, β = 97.84(3)°, V = 3197.4(11) ?~3, C_(80)H_(64)N_2O_2 Pd, Mr = 1191.73, Z = 2, Dc = 1.238 Mg/m^3, μ = 0.339 mm^(-1), F(000) = 1240, T = 293(2) K, the final R = 0.0593 and wR = 0.1192(I > 2s(I)). The compound showed excellent catalytic activity up to 1.130 × 10~7 g of PNB(mol of Pd)^(-1)h^(-1) for the addition polymerization of norbornene by using methylaluminoxane(MAO) as a cocatalyst.

Polymerization of Norbornene via an Iron-Based Complex/MAO Catalytic System

Polynorbornenes were synthesized in the presence of an iron based catalyst, 2,6-bis[1-(2,6-diisopropyl-phenylimino)ethyl]pyridine iron(Ⅱ) dichloride. The FTIR, 1H NMR and 13C NMR analysis results revealed that the structure of the obtained polynorbornenes consisted of vinyl addition polymer substructures without any ring-opening structures. The polymers were amorphous with a short-range order, displayed in the WAXD(wide angle X-ray diffraction) diagrams. The glass transition temperatures ranged from 200 to 400 ℃. The effects of the polymerization reaction conditions, such as Al/Fe molar ratio and toluene/CH_2Cl_2 volume ratio, on the activity, intrinsic viscosity and T_g were also studied.

Lanthanum heterocyclic Schiff-base complex initiated ring-opening polymerization of ε-caprolactone

Lanthanum complex supported by the heterocyclic Schiff-base ligand of N-(2-pyridyl)-3,5-di-tert-butyl-salicylaldimine was prepared and employed for the ring-opening polymerization(ROP)ofε-caprolactone(ε-CL).The polymers obtained with this initiator showed a unimodal molecular weight distribution implied that only one active species was present.Mechanism study revealed that the polymerization proceeds via acyl-oxygen bond cleavage.

咪唑型离子液体催化α-烯烃聚合制备PAO的研究

合成了3种化合物1-乙烯基-3-苄基咪唑氯盐([VBzIm]Cl)、1-苄基-3-甲基咪唑氯盐([BzMIm]Cl)、1-苄基-3-乙基咪唑氯盐([BzEIm]Cl),分别与无水氯化铝(AlCl_(3))制备成离子液体催化剂(IL),探讨了阴阳离子摩尔比、反应温度、反应时间以及催化剂用量对PAO性能的影响。结果表明,以[VBzIm]Cl和AlCl_(3)制备的离子液体催化剂,有效地促进了1-癸烯的聚合反应,制得的聚α烯烃基础油(PAO)中,三聚体和四聚体的含量明显增加,优化实验条件,催化剂阴阳离子比例2∶1,催化剂质量分数7%,反应温度为80℃,反应时间3 h,1-癸烯的转化率在90%以上,聚α烯烃基础油40℃运动黏度为52.9 mm^(2)/s,100℃运动黏度为8.7 mm^(2)/s,黏度指数为142。

水基四元超分子微球功能评价及深部调剖适应性

为解决海上高含水油藏聚合物微球耐温、耐盐和抗剪切性能差导致应用效果变差的问题,采用分散聚合方法制备了一种水基四元超分子微球,并进行了性能表征及深部调驱能力评价。结果表明,该超分子微球在温度90℃、矿化度7×10^(4)mg/L、剪切速率3 000 s^(-1)条件下具有良好的稳定性,表现出良好的耐温、耐盐和抗剪切性能;在100~3 000 mD的岩心中具有良好的注入性与封堵性;对于高含水非均质岩心可实现采收率增幅达16.68%~20.56%,具有良好的应用潜力。

生物基聚酰胺510弹性体的制备及表征

以生物基戊二胺和癸二酸为单体采用熔融缩聚制备全生物基聚酰胺510。以双端羧基的聚酰胺510作为硬段,聚乙二醇为软段,采用两步熔融缩聚法制备生物基聚酰胺510弹性体。采用核磁共振氢谱和傅里叶变换红外光谱表征聚酰胺510弹性体的化学结构;通过差示扫描量热仪和热重分析仪测试聚酰胺510弹性体的热性能;利用万能试验机测试力学性能。结果表明,聚酰胺510弹性体的熔点、结晶温度、起始热分解温度、最大分解速率温度分别为210,163,395,452℃,低于聚酰胺510的217,177,410,456℃;在热学性能表征中,与聚酰胺510相比,聚酰胺510弹性体具有宽的加工窗口;在力学性能上,聚酰胺510弹性体的拉伸强度为42.7 MPa,低于聚酰胺510的拉伸强度60.3 MPa,断裂伸长率为224%,高于聚酰胺510的172%,聚酰胺510弹性体的柔韧性要高于聚酰胺510;在流变性能分析中,聚酰胺510弹性体低于聚酰胺510的储能模量、损耗模量及复数黏度,这是因为聚乙二醇影响了聚酰胺510的晶型结构及晶型的完整性。

生物基耐高温PA5T/56的高效制备及表征

目前,耐高温尼龙(PA)的生产主要采用“预聚合+固相后聚合”法,然而固相后聚合过程中存在的制备周期长、副反应多等技术难题长期得不到有效解决。笔者以生物基戊二胺(PDA)、对苯二甲酸(TPA)和己二酸(AA)为原料,通过在固相后聚合过程前期加入适量水,高效制备了生物基耐高温PA5T/56。研究了TPA与AA的物质的量比对产物熔点的影响,结果表明当其物质的量比为6∶4时,产物(P64)的熔点为309℃,可以作为耐高温工程塑料使用。考察了固相后聚合阶段用水量、反应温度、保温时间和预聚物粒径对固相后聚合产物相对黏度的影响,确定了优化工艺条件:用水量与设备的体积比为1∶300、反应温度为260℃、保温时间为6h、预聚物粒径<0.1mm。通过傅里叶变换红外光谱仪和核磁共振氢谱确认了产物的分子结构。热性能测试结果表明,P64的熔点为309℃,起始热分解温度为375℃,即样品具有很宽的温度加工区间和良好的熔融加工温度窗口。力学性能测试结果表明,P64拉伸强度为85.7 MPa、断裂伸长率15.4%、缺口冲击强度为5.56kJ/m^(2),这与商品化PA6T共聚物的性能相近,表明该样品可以部分代替PA6T共聚物使用,拓宽了应用领域。

Sulfur doped iron-nitrogen-hard carbon nanosheets as efficient and robust noble metal-free catalysts for oxygen reduction reaction in PEMFC

Transition metal-nitrogen-carbon(M-N-C)as a promising substitute for the conventional noble metalbased catalyst still suffers from low activity and durability for oxygen reduction reaction(ORR)in proton exchange membrane fuel cells(PEMFCs).To tackle the issue,herein,a new type of sulfur-doped ironnitrogen-hard carbon(S-Fe-N-HC)nanosheets with high activity and durability in acid media were developed by using a newly synthesized precursor of amide-based polymer with Fe ions based on copolymerizing two monomers of 2,5-thiophene dicarboxylic acid(TDA)as S source and 1,8-diaminonaphthalene(DAN)as N source via an amination reaction.The as-synthesized S-Fe-N-HC features highly dispersed atomic Fe Nxmoieties embedded into rich thiophene-S doped hard carbon nanosheets filled with highly twisted graphite-like microcrystals,which is distinguished from the majority of M-N-C with soft or graphitic carbon structures.These unique characteristics endow S-Fe-N-HC with high ORR activity and outstanding durability in 0.5 M H_(2)SO_(4).Its initial half-wave potential is 0.80 V and the corresponding loss is only 21 m V after 30,000 cycles.Meanwhile,its practical PEMFC performance is a maximum power output of 628.0 mW cm^(-2)and a slight power density loss is 83.0 m W cm^(-2)after 200-cycle practical operation.Additionally,theoretical calculation shows that the activity of Fe Nxmoieties on ORR can be further enhanced by sulfur doping at meta-site near FeN_(4)C.These results evidently demonstrate that the dual effect of hard carbon substrate and S doping derived from the precursor platform of amid-polymers can effectively enhance the activity and durability of Fe-N-C catalysts,providing a new guidance for developing advanced M-N-C catalysts for ORR.

聚合铝钛基絮凝剂的合成与应用

聚合铝钛基絮凝剂是一种新型的高分子聚合絮凝剂,研究证明其具有铝盐絮凝剂有机物去除效率高、成本低的优点,也具有钛盐混凝剂低毒性、生物相容性和沉降性能好的优点。研究通过慢速滴碱法与电渗析法制备了两种聚合氯化铝钛絮凝剂(PATC),对两种不同制备方法的PATC进行了絮凝剂结构、絮凝效果以及絮凝动力学三个方面的研究。实验结果表明E-PATC的中、高聚体比S-PATC多3.89%,Zeta电位高8.9 mV。对两者的絮凝动力学进行了对比,发现E-PATC的生长速度快,絮体粒径大,易沉降。综上,E-PATC与S-PATC的絮凝效果相差不大,但E-PATC絮凝产生的絮体粒径大,不易破碎,具有更好的沉降性。

纳米丁腈橡胶胶乳的制备与催化加氢

采用常规乳液聚合法结合低温间歇聚合工艺制备了丁腈橡胶胶乳,使用自制钌系催化剂对该胶乳进行乳液加氢,系统研究了催化剂用量和氢气压力对丁腈橡胶胶乳加氢效果的影响规律。结果表明,所制备丁腈橡胶胶乳的平均粒径为69.13 nm,加氢前后胶乳的粒径基本保持不变且胶乳稳定性良好;氢气压力越大催化加氢效果越好;当催化剂质量分数为0.017 5%时,可制得氢化度为99%以上且不含凝胶的产品。

端羟基叠氮呋咱醚氧杂丁烷-HTPE嵌段共聚物合成及内增塑性能

针对增塑剂易迁移、渗出进而严重影响聚合物基复合材料物化性能和机械性能的问题,研究通过3-硝基-4-羟基呋咱与3,3-二溴甲基氧杂丁环(BBMO)偶联合成2种新单体3-(4-硝基呋咱-3-氧甲基)-3-溴甲基氧杂环丁烷(BrNFMO)、3,3-二(4-硝基呋咱-3-氧甲基)氧杂环丁烷(BNFMO),以端羟基聚醚(HTPE)为大分子引发剂,在三氟化硼乙醚催化下分别与BrNFMO、BNFMO以及对照组BBMO共聚后叠氮化,制备得到三种内增塑嵌段共聚物,对其进行结构、热分解行为、内增塑性能测试,并对所设计目标共聚单元进行量化计算以评估其爆轰性能。最后对共聚工艺进行了优化,通过“假活性”聚合策略对引入嵌段的程度进行控制。结果表明,该系列新型含能共聚单元具有优于现有叠氮基氧杂环丁烷单体的能量水平。与直接将叠氮基团引入聚合物相比,通过呋咱醚桥联结构将叠氮基团进行引入能够通过内增塑策略获得具有更低玻璃化转变温度T_(g)与黏度的含能共聚物(T_(g)可降低5.27℃,黏度可降低4.90 Pa·s),其热稳定性也得到了提高(T_(d)可提高7.3℃)。