脂肪族支化聚酰胺酯的合成与性能

以己二酸、1,4-丁二醇、己二胺和己内酰胺为原料,丙三醇为支化剂,采用熔融缩聚法合成了可生物降解的脂肪族支化聚酰胺酯(PEAs)。实验中发现,当丙三醇质量分数超过0．9％时,聚合物产生微交联。用差示扫描量热法表征了聚合物的热性能;考察了PEAs膜的拉伸性能;初步探讨了聚合物的水解降解性能。结果表明,随着丙三醇加入量的增大,聚合物的熔点和结晶温度降低;PEAs膜的拉伸强度下降,但降幅不大：将PEAs膜于50℃NaOH溶液(pH值为11)中降解,随聚合物支化度的增加,降解加快。     

Synthesis and properties of branched organosilicon-acrylate copolymer latexes

Summary Stable organosilicon-acrylate copolymer latexes with high silicon content were prepared by seeded semibatch emulsion polymerization of butyl acrylate (BA), methyl methacrylate (MMA) with a novel branched organosilicon monomer 3-methacryloxypropyl tris(trimethylsiloxy) silane (MPTS). Monomer conversion, evolution of the particle size and its distribution were monitored by dynamic light scattering. The effects of MPTS on the polymerization kinetics, the nucleation mechanism and properties of latex were investigated. The results indicated that, in addition to micellar nucleation, a coagulative nucleation step was also observed as a result of the addition of the organosilicon monomer, accordingly, the particle number of the silicon-acrylate latexes increased, the average particle diameter decreased and the polymerization rate accordingly increased compared to those of the acrylate latexes without organosilicon monomer. Moreover, the particle size distribution presented bimodal curves, which indicated that there were large particles formed at an early stage. However, the particle size distribution curves became monomodal at the later stage, and the final latex shows a narrow particle size distribution. It was found that the properties of latex and latex film were obviously influenced by MPTS content. With increasing MPTS content, latex film glass transition temperature and water absorption ratio decreased, the degradation temperature and water contact angle were increased. Hence, the resulting latex films containing MPTS showed lower glass transition temperature and excellent water-resistance, which probably due to the incorporation of the bulky branched hydrophobic group of MPTS into the copolymer chains.     

支化型水性聚氨酯胶黏剂的合成及性能

采用异佛尔酮二异氰酸酯(IPDI)、聚四氢呋喃醚二醇2000(PTMG2000)为原料,二月桂酸二丁基锡、1,4-丁二醇和2,2-二羟甲基丙酸分别为催化剂、小分子扩链剂和亲水单体,制得水性聚氨酯预聚体(PPU);接着以丙烯酸甲酯、二乙醇胺和三羟甲基丙烷为原料合成了超支化聚(胺-酯)(HPAE);最后制备出不同HPAE含...     

The rheological and physical properties of linear and branched polypropylene blends

The rheological, thermal, and mechanical properties of blends consisting of a linear high melt flow rate polypropylene (PP) and two branched PPs are characterized in detail. Blends containing branched PPs display evidence of miscibility in the melt state and exhibit high melt elasticity together with significant strain hardening in extensional deformation while retaining good flow properties. Out of the two blend systems examined the blends containing linear and branched PPs with similar melt flow rates have better mechanical properties, higher crystallization temperatures, and higher crystallinities. POLYM. ENG. SCI., 47:1133–1140, 2007. © 2007 Society of Plastics Engineers     

短支链型Extended表面活性剂的合成及性能研究

以异辛醇、环氧丙烷和气体三氧化硫为原料,经丙氧基化、硫酸化和中和3步反应合成了一种短支链型Extended表面活性剂异辛醇聚氧丙烯醚硫酸盐(i-OPS)。利用红外光谱和核磁氢谱对其结构进行了鉴定,并对其相关物化性能进行了研究。结果表明i-OPS在25℃时其临界胶束浓度(cmc)和最低表面张力(γ_(cmc))分别为15.6 mmol·L~(-1)和33.3 m N·m~(-1),其动态表面张力和动态接触角的降低幅度和降低速度均随浓度的增大而增大,在室温下其质量分数为1.0%水溶液对Na Cl的耐受性高于200 g·L~(-1)。     

The synthesis and two-photon excited fluorescence properties of novel branched fluorene derivatives

Two novel, V-shaped fluorene derivatives branched from triphenylamine and their linear analogue were synthesized via Cu-mediated Ullmann condensation and subsequent Pd-catalyzed Heck coupling reaction. Their two-photon excited fluorescence properties as well as their linear absorption and single-photon excited fluorescence properties were examined. When excited at 730 nm by a Ti:sapphire femtosecond laser, the compounds exhibited strong two-photon excited blue fluorescence. The two-photon excited fluorescence cross-sections of V-shaped derivatives in toluene at 730 nm were 506 GM in the case of N, N-bis{7-[4′-(N, N-diphenylamino)styryl]-9,9-diethyl-9H-fluorene-2-yl}-aniline) and 397 GM for N, N-Bis{7-[4′-(N, N-diphenylamino)styryl]-9,9-diethyl-9H-fluorene-2-yl}-4-acetyl-aniline), respectively.     

The synthesis and two-photon excited fluorescence properties of novel branched fluorene derivatives

Two novel, V-shaped fluorene derivatives branched from triphenylamine and their linear analogue were synthesized via Cu-mediated Ullmann condensation and subsequent Pd-catalyzed Heck coupling reaction. Their two-photon excited fluorescence properties as well as their linear absorption and single-photon excited fluorescence properties were examined. When excited at 730 nm by a Ti:sapphire femtosecond laser, the compounds exhibited strong two-photon excited blue fluorescence. The two-photon excited fluorescence cross-sections of V-shaped derivatives in toluene at 730 nm were ∼506 GM in the case of N, N-bis{7-[4′-(N, N-diphenylamino)styryl]-9,9-diethyl-9H-fluorene-2-yl}-aniline) and 397 GM for N, N-Bis{7-[4′-(N, N-diphenylamino)styryl]-9,9-diethyl-9H-fluorene-2-yl}-4-acetyl-aniline), respectively.     

枝状聚(苯基-二甲基)硅烷的合成及其性质研究

以苯基三氯硅烷、二甲基二氯硅烷为原料，利用伍兹反应使其共聚生成聚（苯基二甲基）硅烷。在不同投料比下，发现枝化度越高，聚合物分子量越小，分子量分布越宽，产率越高；并用红外光谱厦29Si—NMR谱对其结构进行表征，用紫外光谱和热失重表征其光学性质和热稳定性，发现聚合物在211nm处有尖锐吸收峰，并拖尾至380nm处，热分解温度约在500℃左右，高于一般的线形聚硅烷。     

溴肉桂醛衍生物的合成及其性质

以L-酪氨酸(L-Tyrosine)与溴肉桂醛为原料,首先合成了具有手性的新型席夫碱配体L、然后分别与乙酸铅和五水硫酸铜进行配位反应,生成了C₁₈H₁₅BrCuKNO₇S和C₂₂H₂₁BrKNO₇Pb两种新的氨基酸衍生物金属络合物。利用红外光谱、紫外光谱、质谱和荧光等进行表征和性质研究。结果表明,配体L在紫外区和可见区均可以作为光催化剂材料,配合物 C₂₂H₂₁BrKNO₇Pb只适合作为紫外光区的光催化剂材料。而C₁₈H₁₅BrCuKNO₇S络合产物不适合作为光催化剂材料。     

L-苏氨酸衍生物的合成及性质

以L-苏氨酸和香兰素为起始原料,设计并合成了9种新型光催化材料C₂₄H₂₈K₂N₂O₁₀Sn、C₂₄H₂₈FeK₂N₂O₁₀、C₂₄H₃₆FeK₂N₄O₁₀、C₂₄H₂₈Cl₂K₂N₂NiO₁₀、C₂₄H₂₈K₂N₄NiO₁₆、C₂₄H₂₈K₂N₂O₁₀Zn、C28H34K2N2NiO14、C₂₄H₂₈CoK₂N₂O₁₀和C₂₄H₂₈BaK₂N₂O₁₀,通过IR、MS(EI)、荧光分析和元素分析等对形成的希夫碱及其金属衍生物进行表征,推断其可能的化学结构,用紫外漫吸收研究光催化性质, 预测是一类潜在的环保性光催化材料。     

Synthesis, thermal and mechanical properties and biodegradation of branched polyamide 4

A series of linear and branched polyamide 4 were prepared and characterized in order to study the effect of the structure on thermal and mechanical properties. Polybasic acid chlorides were effective initiators for the synthesis of the branched polyamide 4. The melting points of the polyamide 4 for the high molecular weight region were near 265 °C and showed no significant difference depending on their chain structure. On the other hand, it was found that the branched polyamide 4 showed remarkable increase of tensile strength, compared to similar molecular weight of the linear polyamide 4 (e.g. four-branched type M_w=9.28×10⁴, tensile strength=72 MPa).When the initiator having branched structure were used, gel was also formed at the initiator concentration over a certain value (e.g. 3.0 mol% for 4-branched type).The biodegradation of the branched polyamide 4 was evaluated using a standard activated sludge (e.g. four-branched type M_w=8.25×10⁴, biodegradation 41%).     

The relationship between the structure of monoalkyl branched saturated triacylglycerols and some physical properties

Three different physical properties, the gel point (“solidification point”), the refractive index and the density, were determined and related to the structure of the branched triacylglycerols. A four-factor central composite face-centered design was constructed where the four variables were the length of the main chain, the branching position, the length of the side chain, and the number of branched fatty acyl groups attached to the glycerol backbone. Second-order models were calculated in which the three physical properties were related to the structure. Four additional branched triacylglycerols were analyzed in order to confirm the validity of each model. Contour plots are shown in order to visualize the prediction equations which were obtained.     

环氧树脂改性高度支化水性聚氨酯的合成与性能研究

用甲苯-2,4-二异氰酸酯(TDI)、聚碳酸酯二醇(PCDL)、二羟甲基丙酸(DMPA)等为原料,制备了线性水性聚氨酯(LWPU,A2),并通过A2+B3的方式,将其滴加到聚醚胺(T403)的四氢呋喃–异丙醇(THF–IPA)溶液(B3)中,合成出端氨基高度支化水性聚氨酯(HBWPU)。用核磁共振仪表征了HBWPU的结构,证实合成成功。考察了TDI、DMPA和T403的用量对HBWPU的乳液粒径、外观和力学性能的影响,得到最优配方为:n(NCO)∶n(OH)=1.3,w(DMPA)=6.0%,n(B3)∶n(A2)=0.8。以双酚A型环氧树脂(EP)改性最优配方所得的HBWPU,用红外光谱研究了产物HBWPU/EP的结构,通过热重分析(TGA)和应力-应变曲线探讨了EP用量对其热稳定性和力学性能的影响。结果表明,引入EP明显提升了HBWPU的热稳定性及力学性能。当m(EP)∶m(HBWPU)=0.2,HBWPU/EP的拉伸强度达38.30 MPa,断裂伸长率为252%。但当EP用量过多,拉伸强度反而下降。     

苯并咪唑型离子液体的合成及物理性质研究

由1-乙基-2-甲基苯并咪唑和苄氯合成了中间体氯化苯并咪唑盐,经离子交换得到4种不同阴离子的目标化合物,1HNMR、13CNMR、MS和FT-IR表征了其结构,并探讨了这4种离子液体的水溶性、熔点、粘度和溶解性等性质.     

邻菲啉衍生物的合成及光谱性质的研究

合成了4,5-二氮杂芴-9-酮缩氨基硫脲和4,5-二氮杂芴-9-酮缩氨基脲两种邻菲啉的衍生物.用1HNMR、IR、MS表征了其结构,通过紫外可见光谱和荧光光谱研究了其光谱性质,发现两种新化合物具有良好的荧光特性.     

Synthesis and radioprotective properties of pulvinic acid derivatives

A high-throughput screening method has highlighted the marked antioxidant activity of some pulvinic acid derivatives (PADs) towards oxidation of thymidine, under γ and UV irradiation, and Fenton-like conditions. Here, we report the synthesis of a series of new hydrophilic PADs and the evaluation of their radioprotective efficacy in cell culture. Using a cell-based fluorescent assay, we show that some of these compounds have a pronounced ability to prevent cell death caused by radiation and to allow the subsequent resumption of proliferation. Thus, PADs may be considered as a novel class of radioprotective agents.     

The relationship between the structure of monoalkyl branched saturated fatty acids and some physical properties

The gel point and the refractive index of monoalkyl branched saturated fatty acids were determined and related to the structure of the acids. A three-factor central composite face-centered design was constructed where the three variables were the length of the main chain, the branching position and the length of the side chain. Second-order models were calculated in which the two properties were related to the structure. In order to confirm the validity of the models, two additional fatty acids were analyzed. The gel point was found to be proportional to the length of the main chain and the square of the branching position whereas the refractive index was proportional to the length of both the main and the side chain and also to the square of the main chain.     

Synthesis and physical properties of cuphea-oleic estolides and esters

Cuphea-oleic estolides and esters were synthesized from cuphea and oleic FA with various amounts of perchloric acid (0.01 to 0.40 equiv) at 60°C. Estolide yields ranged from 30 to 65% after Kugelrohr distillation. Estolide number (EN), the average number of FA units added to a base FA, varied with reaction conditions. Cuphea-oleic estolides were esterified with 2-ethylhexanol to obtain high yields of the corresponding ester. A streamlined, one-pot process was used to synthesize the estolide and its ester with 0.05 equiv of HClO₄, with, esterification incorporated into an in situ second step to provide a functional fluid at a very reasonable cost. The physical properties of the cuphea-oleic estolides and estolide esters, including their viscosities, pour points, and cloud points, were related directly to the amount of oligomerization (EN), i.e., viscosity increased with higher oligomerization. The viscosity index ranged from 132 to 166 cSt for the free-acid estolides, whereas the complex estolide 2-ethylhexyl esters had slightly high viscosity indices that ranged from 165 to 181 cSt. These new cuphea-oleic estolide esters displayed good low-temperature properties (pour point −42°C and cloud point −41°C).     

Effect of branched PP content on the physical properties and cell growth during foaming of TPOs

Linear/branched PP blends at various ratios were used as the matrix for thermoplastic olefin (TPO) compounds, containing an ethylene–octene copolymer dispersed phase. A detailed investigation of the physical properties of these blends revealed that addition of branched PP (BPP) resulted in improved stiffness and flexural properties. Given that the phase morphology of the blends and the interfacial tension between their components remained virtually unaffected, these improvements are attributed to the higher stiffness of the BPP‐containing matrices. Talc‐filled TPOs containing branched PPs exhibited further improvements in the stiffness and flexural properties. An investigation into the bubble growth process during foaming using a batch foaming simulation system revealed that the presence of BPP resulted in a slight delay in cell nucleation, whereas the rate of bubble growth was not significantly altered. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

支化PE的结构与性能

采用均相和负载α-二亚胺镍配合物催化乙烯聚合制备不同支化度的聚乙烯(PE),探讨支化度对PE密度、熔融行为、结晶度和晶型、热稳定性等的影响。随着支化度的增加,PE密度近于线性减小,熔点随之下降,结晶度呈线性下降,但热稳定性并不是单调下降。PE的差示扫描量热法升温曲线的熔融峰随着支化度增大而变低,熔融区域变宽;支化度达到48个/1 000 C时出现双峰,此时PE结晶度下降至13.0%,且衍射角为23°附近时,(200)晶面衍射峰消失,表明己转变为非结晶态的PE。