含氟丙烯酸酯共聚物防粘剂的制备及其表面性能研究

以甲基异丁基甲酮为溶剂,偶氮二异丁腈为引发剂,全氟烷基乙基丙烯酸酯、丙烯酸十八酯、丙烯酸丁酯和甲基丙烯酸羟乙酯为原料,溶液聚合制得了均一的含氟丙烯酸酯共聚物防粘剂,并研究了其表面性能。结果表明:全氟烷基乙基丙烯酸酯单体的加入显著降低了共聚物的表面能,提高了共聚物膜的硬度、耐水、耐碱、耐溶剂等性能。当加入ω(氟单体)为30%时,表面能降低至14.7 mN/m,低于有机硅类防粘剂的表面能,含氟丙烯酸酯共聚物膜与压敏胶的的剥离力较低,剩余粘附率为93.2%,该共聚物膜的防粘等综合性能最好。     

“活”的α-甲基苯乙烯共聚物:聚合反应新化学和材料工程新技术

高于临界聚合反应温度时,α-甲基苯乙烯(AMS)单体和其聚合物处于聚合-解聚平衡.基于AMS聚合物在受热时可裂解生成大分子链自由基的特性,提出了含AMS结构单元的共聚物是一种"活"的,可作为大分子自由基引发剂的概念,并通过实验对AMS共聚物的引发性能和应用进行了研究.首先,合成了AMS与(甲基)丙烯酸酯类单体、丙烯酸、苯乙烯和马来酸酐等的共聚物.然后以上述共聚物为大分子引发剂,在90℃引发(甲基)丙烯酸酯类单体和苯乙烯等的本体聚合、溶液聚合和乳液聚合,得到了嵌段共聚物.用ESR谱证明了AMS的共聚物在加热时能裂解生成以碳原子为中心的大分子链自由基.此外,在聚合物的熔融共混中,AMS分解产生的大分子链自由基通过偶合反应形成接枝链,原位生成相容剂.AMS共聚物还可以对碳纳米管及无机粒子进行表面原位接枝改性.AMS共聚物是一类无小分子残留的绿色自由基引发剂,可以用于低成本制备两嵌段共聚物,也可以用于聚合物的熔融共混增容.     

含氟丙烯酸酯共聚物结晶性与涂膜表面润湿性能研究

以甲基丙烯酸2-全氟辛基乙酯( FOEMA)分别和不同烷烃链长丙烯酸酯(RA,CH2=CHCOOCnH2n+1,n=4,8,12,16,18)为单体,用自由基聚合法合成了一系列的含氟丙烯酸酯共聚物,通过X射线衍射(XRD)和示差扫描量热法(DSC)对共聚物进行了表征,发现结晶性与丙烯酸酯的烷烃链长度密切相关,当n=4,...     

双官能团引发剂进行的基团转移嵌段共聚

嵌段共聚物的合成技术有较大的可靠性和预见性,并可提供别的聚合物所不能达到的特殊性能。用基团转移聚合的方法进行丙烯酸酯类极性单体室温下的活性聚合,能得到具有预定链长、嵌段纯度和多分散性指数小的嵌段共聚物。用双官能团引发剂进行基团转移嵌段共聚,可减少加单体的次数,避免引进杂质,且能合成用单官能团引发剂所无法得到的A—B—     

核壳型含氟丙烯酸酯共聚物的合成及性能

采用饥饿态半连续种子乳液聚合方法, 在十二烷基硫酸钠(SDS)/辛基苯基聚氧乙烯醚(TX-10)复合乳化剂的作用下, 分别选用甲基丙烯酸三氟乙酯(TFEM)、甲基丙烯酸六氟正丁酯(HFBM)和甲基丙烯酸十二氟庚酯(DFHM)为含氟单体, 合成以丙烯酸正丁酯(BA)、甲基丙烯酸甲酯(MMA)和含氟单体为原料的核壳型结构含氟丙烯酸酯共聚物乳液. FTIR, 1H NMR, TEM和DSC分析结果显示, 获得了BA/MMA/含氟单体的共聚物乳液, 且乳液具有明显的核壳结构. DSC, TGA和SEM-EDX的分析显示, 核壳型结构的共聚物具有优异的热力学稳定性能和成膜性能; 长侧链或短侧链含氟单体对共聚物的热稳定性影响不明显, 但侧链较长的含氟单体所获得的聚合物在成膜过程中更易向表面迁移, 更能体现含氟聚合物的优点.     

含mPEG侧链的水溶性梳状聚合物的合成及其侧链受限结晶行为研究

采用大单体与小单体共聚的技术,通过自由基引发溶液聚合,合成了一系列水溶性梳状聚合物———聚丙烯酸接枝聚乙二醇单甲醚(PAA-g-mPEG).制备过程分两步进行,首先合成大单体聚乙二醇单甲醚丙烯酸酯,然后将大单体与丙烯酸单体共聚,合成了梳状聚合物.通过控制反应条件,获得了一系列主链和支链组成比不同的接枝共聚物.用傅立叶变换红外光谱(FT-IR)和核磁共振氢谱(1H-NMR)表征了共聚物的结构,并对其侧链的结晶行为进行了研究.采用差热扫描量热法(DSC)表征并分析了不同侧链长度的mPEG的热性能及其结晶情况.利用相差显微镜和原子力显微镜(AFM)观察薄膜的结晶形貌,表明梳状聚合物的侧链mPEG在受限条件下的薄膜结晶形貌为高度支化的晶体,初步分析了mPEG链长及其在共聚物中的重量百分含量对晶体形貌的影响.     

含氟接枝共聚物为助稳定剂的苯乙烯细乳液聚合反应

以含氟接枝共聚物(PSG)单独作为助稳定剂,十二烷基硫酸钠(SDS)为乳化剂,过硫酸钾(KPS)为引发剂引发苯乙烯(St)的细乳液聚合。考察了聚合温度、乳化剂用量、引发剂用量和PSG用量对细乳液聚合转化率的影响。结果表明,以PSG单独作为助稳定剂,细乳液聚合过程较稳定,起始单体液滴数目与成核粒子数目几乎相等。最终转化率随着乳化剂用量和反应温度的提高而增加,引发剂用量影响不明显。在相同的反应条件下,分别以相同用量(w.t.%=0.091%时,占单体和水的总质量)的PSG和十六醇为助稳定剂用于苯乙烯细乳液聚合,反应290min后,PSG体系的聚合转化率达到87.2%,而十六醇体系的聚合转化率只有78.2%。     

两亲性丙烯酸酯共聚物的聚合研究

利用过氧化苯甲酰为引发剂探讨了甲基丙烯酸β－羟乙酯和丙烯酸长链烷基酯的自由基共聚合。重点讨论了合成条件如溶剂、沉淀剂、引发剂用量、单体配比、反应时间等对共聚反应的影响以及各种聚合条件对该共聚物的组成、结构和性能的影响。并用ＩＲ，ＧＰＣ，＾１３ＣＮＭＲ等手段对共聚物进行了表征。     

优化含氟丙烯酸酯共聚物乳胶膜表面性能的方法研究

含氟丙烯酸酯乳液由于氟的引入具有优异的表面性能,在涂料、胶粘剂、纺织助剂等领域得到广泛应用.然而含氟单体成本较高,而且产物中乳化剂的存在影响了含氟丙烯酸酯乳液涂膜的抗污、疏水疏油等特性.如何采取有效措施提高含氟丙烯酸酯共聚物乳胶膜的表面性能,是其走向产业化急需解决的问题.针对这方面问题,本文主要从含氟单体的利用率、设计乳胶粒结构、共聚物链结构以及乳胶膜的后处理等方面对近年来的研究成果进行了综述.     

超临界二氧化碳光聚合制备可交联含氟聚合物颗粒及应用

通过自由基无规共聚和酰化反应两步法制备了两类侧链含丙烯酸酯双键的含氟低聚物,并通过调节反应物种类、配比和链转移剂用量,制备出一系列不同双键含量、氟含量的多官能度低聚物。以制备的含氟低聚物为原料,进行超临界二氧化碳光聚合制粒。聚合得到的含氟颗粒作为增强相,加入TPGDA光固化配方中,可实现颗粒与树脂的化学交联,显著提高基材的交联密度,改善疏水性,降低吸水率,并增强热稳定性。     

A model study on the mechanism and kinetics for the dissociation of water anion

Quantum chemical computations using both density functional theory (B3LYP functional) and wavefunction (MP2 and CCSD(T)) methods, with the 6-311++G(3df,2p) and aug-cc-pVnZ (n = D,T,Q) basis sets, in conjunction with a polarizable continuum model (PCM) method for treating structures in solution, were carried out to look again at a series of small negatively charged water species [(H₂O)_n]^•–. For each size n of [(H₂O)_n]^•– in aqueous solution with n = 2, 3, and 4, two distinct structural motifs can be identified: a classical water radical anion formed by hydrogen bonds and a molecular pincer in which the excess electron is directly interacting with H atoms. In aqueous solution, both motifs have comparable energy content and likely coexist and compete for the ground state. Some water anion isomers can dissociate when interaction with a water molecule, [(H₂O)_n]^•– + H₂O → H^•(H₂O)_m + OH^–(H₂O)_n–m, through successive hydrogen transfers with moderate energy barriers. This reaction can also be regarded as a water-splitting process in which the H transfers involved take place mainly within a water trimer, whereas other water molecules tend to stabilize transition structures through microsolvation rather than direct participation. Calculated absolute rate constants for the reversed reaction H^•(H₂O)₂ + OH^–(H₂O)₂ → [(H₂O)₄]^•־ + H₂O with both H and D isotopes agree well with the experimentally evaluated counterpart and lend a kinetic support for the involvement of a tetramer unit.     

从物质本原到干水:水的概念的发展史

在古代哲学中,水被视为一种物质本原。17世纪化学学科形成后,水被定义成一种化学元素。18世纪的化学革命中,水被发现是氢氧化合物。19世纪原子分子论的创立,使水的概念得到微观表征。至20世纪,重水的发现和干水的发明使水的概念有了新的发展。总之,水的概念的发展史,反映了化学思想的发展和科学技术的进步,对化学研究和化学教育均有重要的启示。     

Interaction of water with the regenerated cellulose membrane studied by DSC

One to three endothermal peaks atributted to melting of bulk and interfacial water were observed by DSC in the regenerated cellulose — water system. The profiles of thermal effects depend on water content, time of conditioning, film pretreatment and the conditions applied during the preceding freezing-thawing cycles. The occurrence might be deduced of melting-crystallisation processes. A large amount of non-freezable strongly bounded water was also detected. Although cellulose absorbs water quickly after immersion, the structural changes consisting on ordering of polymer fraction occur during further conditioning due to increase in strength of water binding. Using the membranes in the separation module at 90°C causes weakening of these bonds. Differences between interaction of particular cellulose films with water can be detected during the first, the second and the third heating. This revised version was published online in July 2006 with corrections to the Cover Date.     

Effects of Amplitude of the Radiofrequency Electromagnetic Radiation on Aqueous Suspensions and Solutions

The effects of radiofrequency (RF) (1–4) and magnetic fields (5–9) on the behavior of aqueous solutions and suspensions have been a popular subject in recent years. The mechanism of the magnetic “water memory” effect, though, is still largely unknown (5). In this work, we present evidence that the primary “receptor” of the electromagnetic radiation is a gas/liquid interface. Gas can be either already present in water or produced by the effects of electromagnetic fields. Perturbed gas/liquid interfaces require hours to equilibrate. Certain RF and magnetic signals also produce reactive oxygen and hydrogen species (superoxide, hydrogen peroxide, hydrogen, atomic hydrogen). The perturbed gas/liquid interface modifies the hydrogen bonding networks in water and also the hydration of ions and interfaces. Careful outgassing removes all of the effects of the electromagnetic fields, including the magnetic memory effect. The amplitude of the applied field influences the observed effects. Different amplitudes of RF radiation perturb the interfacial water in different ways and consequently affect the behavior of colloids and ions in specific manners. For instance, the bulk and template precipitation of calcium carbonate, zeta potentials of suspended colloids, rate of dissolution of colloidal silica, and attachment of colloidal silica to metal surfaces are modified in specific ways with the low amplitude or high amplitude RF treatments described in this paper. The solubility/diffusivity of gas species is also modified in a different manner, and it is probably at the core of the specificity of the RF amplitude effects.     

离子强度对P(HEMA-co-MMA)水凝胶溶胀性能及水的状态的影响

对甲基丙烯酸-β-羟乙酯(HEMA)与甲基丙烯酸甲酯(MMA)共聚水凝胶扩散行为、聚合物-溶剂相互作用及水的状态进行了研究。考察了不同NaCl离子强度下水凝胶平衡含水率、扩散系数及聚合物-溶剂相互作用参数的变化关系。研究结果表明,随着NaCl离子强度增大,平衡含水率降低,扩散系数下降,聚合物-溶剂相互作用参数升高。通过DSC测定了水凝胶中冻结水和非冻结水的组成。     

Selective water sorbents for multiple application, 6. Freshwater production from the atmosphere

In this communication we consider an application of new selective water sorbents for freshwater production from the atmosphere. We present a general scheme of water production and discuss its efficiency in different climatic areas. The results of our lab-scale tests have demonstrated the feasibility of this method with the output of 3–5 kg of water per 10 kg of the dry sorbent per day.     

Effects of the Water Quantity on the Solventless TEOS Hydrolysis Under Ultrasound Stimulation

The acid hydrolysis under ultrasound stimulation of solventless tetraethoxysilane(TEOS)-water mixtures was studied at 40°C, by means of a heat flux calorimetric method, as a function of the initial water/TEOS molar ratio (r) ranging from 2 to 10. The method is based on the time record of the exothermic heat peak of hydrolysis, arising after an induction time under ultrasound stimulation, which is a measure of the reaction rate. The hydrolysed quantity was found to be approximately independent of the water/TEOS molar ratio, even for r < 4. Polycondensation reaction takes place mainly for low water/TEOS molar ratio in order to supply water to allow almost complete hydrolysis. The overall process of dissolution and hydrolysis has reasonably been described by a previous modelling. The dissolution process of water in TEOS, under ultrasound stimulation and acid conditions, was found to be rather dependent of the alcohol produced in the hydrolysis reaction instead of the initial water quantity present in the mixture.