聚(N-异丙基丙烯酰胺)均聚凝胶的合成及其性能研究

采用自由基聚合反应,在20℃调节单体的浓度及交联剂的用量合成了聚N-异丙基丙烯酰胺均聚凝胶,对材料的结构进行了表征和分析,同时研究了单体浓度及交联剂用量对材料的温敏性、光学性能以及溶胀性能等的影响。实验结果表明:凝胶的温敏性及透射比随单体浓度及交联剂用量的增加而降低,其初始溶胀度随单体浓度及交联剂用量的增加而增加,体积相转变温度保持为34℃,不随单体浓度及交联剂用量而改变。     

PEGDA交联PAA-K高吸水树脂制备及性能研究

采用紫外引发、微波引发方法分别制备聚丙烯酸钾(PAA-K)高吸水树脂,研究了交联剂聚乙二醇二丙烯酸酯(PEGDA)、光引发剂2,2二甲氧基苯基乙酮(BDK)、引发剂过硫酸铵(APS)以及丙烯酸(AA)中和度对PAA-K高吸水树脂吸水性能的影响以及两种方法制备PAA-K树脂性能的比较。采用傅里叶变换红外光谱仪、热失重分析仪、扫描电子显微镜等仪器对PAA-K高吸水树脂进行表征。结果表明,在最佳优化条件下,紫外引发PAA-K高吸水树脂在蒸馏水和生理盐水中的最大吸水倍率分别为3297 g/g和419 g/g;微波引发PAA-K高吸水树脂在蒸馏水和生理盐水中的最大吸水倍率分别为2861 g/g和414 g/g。     

聚甲基丙烯酸水凝胶的制备研究

以甲基丙烯酸为原料,N,N’-亚甲基双丙烯酰胺为交联剂,过硫酸钾为引发剂,自由基引发聚合制备聚甲基丙烯酸水凝胶。研究了聚甲基丙烯酸水凝胶的溶胀率、保水率,讨论了交联剂、引发剂的用量以及pH、盐溶液浓度对溶胀性能的影响。实验结果表明,当合成温度为70℃,pH=8,盐溶液浓度为0,交联剂、引发剂用量分别为反应物质量的0.6%、1.0%时,制备出来的水凝胶的溶胀性能最好。     

聚丙烯酸水凝胶的制备研究

以丙烯酸为单体,N,N＇-亚甲基双丙烯酰胺为交联剂,过硫酸铵为引发剂,通过自由基聚合制备了聚丙烯酸水凝胶.考察了交联剂、引发剂、单体中和度、聚合温度以及盐溶液对水凝胶溶胀性能的影响.结果表明,引发剂为单体质量的0.6％,交联剂为0.8％,单体的中和度为70％时,凝胶的溶胀性能最佳,吸水率达到了3 000％以上,聚丙烯酸水凝胶的溶胀性能随着盐溶液浓度的增大而降低.     

负载芹菜素壳聚糖凝胶珠的制备及其性能研究

为实现芹菜素有效利用,以柠檬酸钠为交联剂,采用离子聚沉法制备了芹菜素水凝胶珠,通过FT-IR、TGA和XRD等手段对其表征,并利用UV-Vis测定了芹菜素的包封率、负载率、溶胀度及其释药行为。实验条件下,芹菜素负载率为20.58%,包封芹菜素后,芹菜素形态未发生变化,但由于壳聚糖与芹菜素之间发生相互作用,热稳定性略降低。凝胶珠中芹菜素可持续释放,并且对pH有明显的响应性。累积释放率在pH 8.0时最高。在0.1 mol/L酸度下,24 h后,空白和载药凝胶珠都可降解,但随着酸度增大到1、2 mol/L,降解反而减缓,负载芹菜素凝胶珠比空白凝胶珠更不易降解。这些为利用凝胶珠运载药物进一步提供了实验依据。     

交联大豆蛋白凝胶的溶胀性能的研究

制备了大豆蛋白凝胶与戊二醛交联大豆蛋白凝胶,研究了凝胶的溶胀性及其影响因素,以质构仪、扫描电镜对凝胶的质构和断面微观结构进行了表征,结果表明:大豆蛋白浓度为13%,其凝胶溶胀率为15.00g/g;当大豆蛋白浓度为12%,25%戊二醛用量为50μL,交联大豆蛋白凝胶溶胀率为25.1g/g,;氯化钠浓度和水的温度对交联大豆蛋白凝胶的溶胀率有影响,氯化钠浓度从0升至0.1M,交联凝胶溶胀率从25.1减小为5.34g/g;水的温度从20升至60℃,凝胶的溶胀率从21.81增至49.12g/g;质构分析和扫描电镜结果显示,戊二醛交联凝胶比大豆蛋白凝胶具有更高的硬度、弹性、内聚性、破裂强度和更有序的微观结构。     

甲苯二异氰酸酯交联阳离子型丙烯酸酯树脂的制备及性能

用自由基聚合法制备了阳离子型羟基丙烯酸酯树脂,以甲苯-2,4-二异氰酸酯(TDI)和丁酮肟合成出半封端型TDI,将两种产物混合反应,制备出系列聚氨酯改性的丙烯酸酯树脂分散液.分散液成膜后,在高温(140 ℃)下解封的异氰酸酯官能团与丙烯酸酯树脂上的羟基反应得到异氰酸酯交联丙烯酸酯树脂膜.结果表明,随着交联度的提高,丙烯酸酯树脂的玻璃化转变温度升高,凝胶含量增加,拉伸性能、邵尔A硬度、耐腐蚀性及耐水性得以提高.     

苯乙烯乳液共聚聚丙烯酸复合凝胶制备及溶胀性能

以丙烯酸(AA)为亲水单体、苯乙烯、二乙烯苯为疏水单体,OP-10为乳化剂,在水中进行自由基共聚得到改性凝胶。测定了不同试剂原料配比下的复合结构凝胶的平衡溶胀率、溶胀速率,发现复合结构凝胶(MCG)平衡溶胀率随疏水单体用量增加和乳化剂用量减小而增加,溶胀速率随疏水单体用量增加先增加后降低,随乳化剂用量增加而加快。复合结构凝胶具有弹性体特征,避免了小分子交联剂交联的常规凝胶的脆性。     

聚乙烯醇水凝胶的制备及其溶胀性能

采用化学交联方法制备了PVA水凝胶，研究了PVA聚合度、醇解度等分子结构参数，反应温度、反应时间等合成工艺参数，交联剂用量、疏水单体用量、阴离子单体用量等化学组成对PVA水凝胶溶胀性能的影响。结果表明，采用聚合度为1700、醇解度为95％的PVA1795为基体，当交联剂用量为1mL，反应温度为80℃，反应时间为8h，所制得的PVA水凝胶具有较高的溶胀率。     

Fabrication of speedy and super‐water‐absorbing non‐woven cloth with hierarchical three‐dimensional network structure

A novel speedy and super‐water‐absorbing non‐woven cloth with hierarchical three‐dimensional network (3D‐SS‐PET) was fabricated through the induction of UV copolymerization on polyethylene terephthalate (PET) fibers followed by a volume phase transition. The macroscopic three‐dimensional network implied that the PET non‐woven substrates are complicated three‐dimensional fibrous materials including oriented fibers in preferential or random directions. The microscopic three‐dimensional network is poly(acrylic acid‐co‐acrylamide) (poly(AA‐co‐AM)) crosslinked copolymer layers on the fiber surface. The rapid volume phase transition was achieved by immersing the swelled non‐woven poly(AA‐co‐AM) modified PET (PET‐g‐AA‐co‐AM) in ethanol. The above process was an essential step to prepare the copolymer chain; after that the fiber surface was extended to form abundant capillary channels and plenty of space between fibers. The water contact angle decreased remarkably from 130° to 0°, while the absorbing capacity of the saturated water and the average water‐absorbing rate experienced an increasing trend, rising from 300 to 324.6 g g^?1 in 24 h and 18.6 and 222 g (g min)^?1 in 40 s, respectively. It was concluded that surface hydrophilicity and capillaries of the hydrophilic modified macroscopic fibrous structure enhanced the water‐absorbing rate and the swelling process contributed to the higher water absorption capacity. This speedy and super‐water‐absorbing material exhibits great potentiality in diapers, sanitary napkins, wound dressings, surgical pads, and hygroscopic and sweat‐free underwear in extremely cold areas. © 2018 Society of Chemical Industry     

Preparation and swelling properties of crosslinked sodium polyacrylate

Crosslinked sodium polyacrylate as a superabsorbent was prepared by inverse suspension polymerization with cyclohexane as the continuous phase and sorbite anhydride monostearic acid ester (span‐80) as the dispersant. The crosslinking degree was regulated by NaOH. The distilled water absorbency (WA) of the polymer gel was about 700 times its own weight if the gel was allowed to swell at room temperature for 24 h. WA under various conditions, such as varying pH, temperature, reaction time, neutralization, and cyclohexane concentration, was investigated and optimized. Our results revealed that the optimal reaction conditions were 55°C, 25‐min reaction time, 85% neutralization, and a 7:1 (v/v) cyclohexane/monomer ratio. Our results also showed that such synthesized polymer gels have a high WA and a good water‐retention ability under different pressures. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1515–1520, 2001     

聚亚苯基硅氧烷交联网络的热性能

用Si—H/Si—OR缩聚的方法制备了含可交联乙烯基的聚亚苯基硅氧烷-二甲基硅氧烷共聚物(PTMPS-DMS),用硅氢加成、BPO热交联两种方法进行交联得到交联网络,并用热重分析(TG)、300℃恒温热分析和DSC等方法对其热性能进行了研究。结果表明,交联方法对PTMPS-DMS交联网络的热稳定性影响很大,BPO热交联网络的热稳定性远远高于硅氢加成交联网络,两种交联网络在空气中的5%热失重温度分别是480℃和368℃,Tg则没有显著差异,分别是-55℃和-49℃。H2PtCl6能显著降低PTMPS-DMS及其交联网络在空气中的热稳定性。     

Study of pH/temperature dual stimuli‐responsive nanogels with interpenetrating polymer network structure

Nanogels with interpenetrating polymer network (IPN) structure based on poly(N‐isopropylacrylamide) (PNIPAM) and poly(acrylic acid) (PAA) were synthesized by in situ polymerization of acrylic acid and N, N′‐methylenebisacrylamide within the PNIPAM nanogels. Their IPN structure was confirmed using transmission electron microscopy after staining by uranyl acetate. The temperature‐ or pH‐dependent hydrodynamic diameters measured using dynamic laser light scattering show that the IPN nanogels have pH and temperature dual stimuli‐responsive properties. As compared to previously reported pH/temperature dual stimuli‐responsive nanogels, these IPN nanogels have the advantage of less mutual interference between the temperature‐responsive and pH‐responsive components, which is beneficial for their applications in controlled drug release and sensors. The temperature‐ and pH‐triggered volume phase transition mechanisms of the IPN nanogels were tested by probing the microenvironment change of their PNIPAM and PAA chains upon phase transition using infrared (IR) absorption spectra measured at different pH values and IR difference spectra obtained by subtracting the IR spectrum obtained before temperature‐induced phase transition from that obtained after phase transition. Copyright © 2012 Society of Chemical Industry     

Mechanical properties of interpenetrating polymer network hydrogels based on hybrid ionically and covalently crosslinked networks

Hydrogels are polymer networks swollen in water. Because of their soft and wet nature, and their ability to show large volume changes, hydrogels can be useful in many biomedical and actuator applications. In these applications, it is crucial to tune the mechanical and physical properties of a hydrogel in a controllable manner. Here, interpenetrating polymer networks (IPNs) made of a covalently crosslinked network and an ionically crosslinked network were produced to investigate the effective parameters that control the physical and mechanical properties of an IPN hydrogel. Covalently crosslinked polyacrylamide (PAAm) or poly(acrylic acid) (PAA) networks were produced in the presence of alginate (Alg) that was then ionically crosslinked to produce the IPN hydrogels. The effect of ionic crosslinking, degree of covalent crosslinking, AAm : Alg and AA : Alg ratio on the swelling ratio, tensile properties, indentation modulus, and fracture energy of IPN hydrogels was studied. A hollow cylindrical hydrogel with gradient mechanical properties along its length was developed based on the obtained results. The middle section of this hydrogel was designed as a pH triggered artificial muscle, while each end was formulated to be harder, tougher, and insensitive to pH so as to function as a tendon‐like material securing the gel muscle to its mechanical supports. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2504–2513, 2013     

Bituminous polyurethane network: Preparation,properties, and end use

Industrial‐grade bitumen (85:25) was treated with 4,4′‐diphenyl methane diisocyanate as a blocking agent to make it compatible with polyurethane resin. Optimization of treatment conditions for the bitumen such as isocyanate dose (～3 wt % of bitumen), reaction temperature (180°C), and treatment time (120 min) was done on the basis of estimating its residual acid value and unreacted ? NCO groups. Formation of the urethanized bituminous species after treatment resulted in a reduction in the glass‐transition temperature of the base bitumen from ?9.63°C to ?17.09°C and in moisture vapor transmission from 16.95 to 12.21 g 24 h^?1 m^?2. The bituminous networks were prepared from these treated/SBS‐modified treated bitumen and polyurethane prepolymers by in situ and conventional liquid blending methods. Lack of low‐temperature flexibility in the bituminous network made from the blending method restricted its use for waterproofing/sealing purposes. Modulated differential scanning calorimetry showed the presence of two overlapping glass‐transition temperatures and an endothermic peak in the in situ prepared networks similar to the base bitumen, evidence of a close intermixing of the bitumen constituents with the polyurethane phases. Rheological studies revealed that the SBS‐modified bituminous polyurethane network exhibited superior behavior than that of other systems in terms of stiffness and elasticity over a wide range of frequencies. The compounded bituminous networks satisfied the requirements of standard specifications and can be suitably used for waterproofing purpose and sealing of concrete joints. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 217–226, 2006     

Properties of crosslinked polyurethanes synthesized from 4,4′‐diphenylmethane diisocyanate and polyester polyol

Polyurethanes were synthesized using the high functional 4,4′‐diphenylmethane diisocyanate (MDI), polyester polyol, and 1,4‐butane diol. The synthesized polyurethanes were analyzed using differential scanning calorimeter (DSC), dynamic mechanical thermal analysis (DMTA), Fourier transform infrared (FTIR) spectrometer, and swelling measurement using N,N′‐dimethylformamide. From the result of thermal analysis by DSC and DMTA, single T_gs were observed in the polyurethane samples at all the formulated compositions. From this result, it is suggested that the polyurethanes synthesized in this study have crosslinked structure rather than the phase‐separated segmented structure because of the high functionality (f = 2.9) of the MDI. By annealing the polyurethane samples using DSC, the T_gs were increased by 4.7∼16.0°C at the various annealing temperatures. From the results of FTIR and swelling measurement of polyurethanes, it is suggested that the increase of T_g of the polyurethanes by annealing is not due to increase of the hydrogen bond strength but mainly due to the increase of the crosslink density. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 624–630, 2000     

Atomistic molecular simulations of structure and dynamics of crosslinked epoxy resin

Many excellent thermal and mechanical performances of cured epoxy resin products can be related to their specific network structure. In this work, a typical crosslinked epoxy resin was investigated using detailed molecular dynamics (MD) simulations, in a wide temperature range from 250 K to 600 K. A general constant-NPT MD procedure widely used for linear polymers failed to identify the glass transition temperature (T_g) of this crosslinked polymer. This can be attributed to the bigger difference in the time scales and cooling rates between the experiments and simulations, and specially to the highly crosslinked infinite network feature. However, by adopting experimental densities appropriate for the corresponding temperatures, some important structural and dynamic features both below and above T_g were revealed using constant-NVT MD simulations. The polymer system exhibited more local structural features in case of below T_g than above T_g, as suggested by some typical radial distribution functions and torsion angle distributions. Non-bond energy, not any other energy components in the used COMPASS forcefield, played the most important role in glass transition. An abrupt change occurring in the vicinity of T_g was also observed in the plots of the mean squared displacements (MSDs) of the crosslinks against the temperature, indicating the great importance of crosslinks to glass transition. Rotational dynamics of some bonds in epoxy segments were also investigated, which exhibited great diversity along the chains between crosslinks. The reorientation functions of these bond vectors at higher temperatures can be well fitted by Kohlrausch-Williams-Watts (KWW) function.     

Synthesis and swelling properties of new crosslinked polyorthocarbonates

Crosslinked polyorthocarbonates were synthesized by the condensation of tetraethyl orthocarbonate and hydroxyl functional monomers. The main goal of this study was to produce a solvent‐absorbent polymer with a high absorption capacity and to use these polymers for the removal of organic solvents from the environment and the recovery of these solvents. The synthesized polymers were characterized by Fourier transform infrared spectroscopy, solid‐state ¹³C‐NMR spectroscopy, thermogravimetric analysis, and differential scanning calorimetry. All of the polymers (except Poly 1 and Poly 2 ) had a high and fast uptake ability for organic solvents, such as tetrahydrofuran, dichloromethane, benzene, and acetone. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

超高分子量聚乙烯树脂的溶胀性的检测分析

通过上海化工研究院设计的在线检测装置对超高分子量聚乙烯(UHMWPE)溶胀过程中的温度、黏度进行测试,形成了UHMWPE树脂溶胀工艺的检测方法,对黏均分子量分别为3.261×106(A),3.833×106(B),3.455×106(C)3种不同树脂的溶胀温度、溶胀时间、溶胀比等参数进行了分析。结果表明:A,B,C树脂的溶胀温度分别为121,120,119℃;对溶胀釜加热系统设定统一温度,釜内温度达120℃时,A,B,C树脂的溶胀时间分别为60,30,3 min,溶胀比分别为2.37,2.51,2.31。