Physico-chemical characterization of hybrid polymers obtained by 2-hydroxyethyl(methacrylate) and alkoxides of zirconium

Hybrid monolithic materials were prepared through polymerisation of 2-hydroxyethyl methacrylate (HEMA) mixed with zirconium alkoxides (Zr(OBuⁿ)₄, Zr(OPrⁿ)₄ and Zr(OEt)₄), modified by acetylacetonate groups. The molar ratio HEMA/Zr varied between 1 and 4. Thermo-Gravimetry coupled with Mass Spectroscopy (TG-MS) analyses, ¹³C MAS NMR and Dynamical Mechanical Thermal Analysys (DMTA) indicated the polymeric chains were interconnected by the inorganic component.The presence of zirconium alkoxides modified substantially the poly-HEMA properties. Glass transition temperature of hybrid materials derived from butoxy and propoxy was found in the range 50-80 °C, depending on the composition. The typical swelling of p-HEMA in the water, was suppressed by the presence of zirconium compounds. After immersion in distilled water, hybrid polymers showed an initial slight weight increase, followed by a small mass loss, which increases proportionally to the length of alkoxyl group (ethoxide(propoxide(butoxide) and reaches a constant value after about 40 days. The hybrids remained always rigid and transparent. Flexural modulus and strength of about 400-900 and 4-8 MPa were measured.     

共聚物水凝胶的合成及其溶胀性能研究

以过氧化二苯甲酰(BPO)为引发剂，合成了N-乙烯基吡咯烷酮(NVP)-甲基丙烯酸肛羟乙酯(HEMA)-甲基丙烯酸丁酯(BMA)共聚物水凝胶，可作为软性角膜接触镜材料。探讨了不同比例的NVP、HEMA、BMA对材料溶胀性能的影响。     

甲状腺素T4免疫传感器的研究

报道以甲基丙烯酸羟乙酯与甲基丙烯酸甲酯的共聚物为载体膜材料，研制成非酶标记的Ｔ４免疫传感器，并对载体膜材料的共聚方法及共聚物共聚比与传感器灵敏度的关系进行了探讨。     

HEMA共聚物水凝胶中水的存在状态

用过氧化二苯甲酰(BPO)作为引发剂，合成了N-乙烯基吡咯烷酮(NVP)／甲基丙烯酸β-羟乙酯(HEMA)和NVP/HEMA／甲基丙烯酸甲酯(MMA)共聚物水凝胶，用差热扫描量热法(DSC)和热重法(TG)对这些亲水凝胶中吸附水的状态进行了研究．结果表明，水凝胶中水的状态大致可分为自由水、可冻结的结合水和非冻结的结合水．不同用量的MMA与NVP和HEMA共聚，溶胀度不同，其吸附水中不同状态水的含量也有所差异，结果表明，随着MMA含量的增加，水凝胶中非冻结结合水的含量也增加。     

Tuning the thermoresponsive properties of poly(oligo(propylene glycol) methacrylate) hydrogels via gradient copolymerization with 2-hydroxyethyl methacrylate

Gamma radiation was used to prepare copolymer hydrogel libraries based on oligo(propylene glycol) methacrylate (OPGMA) and 2-hydroxyethyl methacrylate (HEMA); a complete screening in composition of P(OPGMA/HEMA) copolymers was elaborated from 0% to 100% of OPGMA. Determination of gel fraction was performed as the first step after radiation induced synthesis. Tuning of the volume phase transition temperature (VPTT) of P(OPGMA/HEMA) copolymeric hydrogels was investigated by swelling study. Additional characterization of structure and properties was conducted by FTIR, DSC, and UV-Vis spectroscopy. All results indicate that new P(OPGMA/HEMA) copolymeric hydrogels have wide diversity in thermoresponsive properties which strongly depend on their composition.     

Aspects of enamel bonding using experimental silanes for orthodontic adhesion

This in vitro study investigates bonding to enamel using experimental silane-based primers with and without 2-hydroxyethylmethacrylate (HEMA) under various artificial ageing methods. One hundred and fifty sound extracted human premolars were used and randomly assigned to three experimental study groups. They were first acid-etched for 15 s, rinsed with water spray, air dried, and applied 0.3 ml of artificial saliva on the enamel surfaces. Two groups of enamel surfaces were primed using silane-based experimental primers (1.0 vol% of 3-isocyanatopropyltrimethoxysilane and 0.5 vol% of bis-1,2-(triethoxysilylethane) with and without 25% HEMA) while one group was served as control. Then, stainless steel premolar orthodontic brackets were fixed onto teeth with orthodontic resin composite. The specimens from each group (n=10) were stored under different ageing conditions: thermo-cycling (500, 2000, and 6000 cycles), storage in artificial saliva for 24 h, and for one year. The shear adhesion (bond) strength (SBS) was tested by using a universal testing machine at a crosshead speed of 1.0 mm/min. Surface morphology and failure modes at the debonded interfaces were examined using SEM. Two-way ANOVA and post hoc tests were used to compare the SBS (α=0.05). The results suggested that an experimental primer with 25% HEMA, after 24 h storage in artificial saliva, produced the highest mean SBS (22.1 MPa, SD 2.2 MPa). The lowest mean value (5.8 MPa, SD 1.1 MPa) was obtained with the control group thermo-cycled (6000 cycles). There was a significant difference between the experimental primers (p<0.001) and artificial ageing (p<0.001). We conclude that 25% HEMA inclusion in silane primer could provide satisfactory adhesion strength, and 500 cycles of thermo-cycling (ISO TR 11450) does not correlate with 1-year artificial saliva storage for enamel bonding test.     

Mechanical and tribological properties of poly(hydroxyethyl methacrylate) hydrogels as articular cartilage substitutes

Poly(hydroxyethyl methacrylate) (p(HEMA)) hydrogels have been proposed as promising biomaterials to replace damaged articular cartilage. A major obstacle to their use as replacement bearing tissue is their poor mechanical properties in comparison with healthy articular cartilage. The purpose of this study was to obtain p(HEMA) hydrogels with physicochemical and mechanical properties close to healthy articular cartilage, by introducing a hydrophilic monomer, namely acrylic acid (AA). Formulations of hydrogels with different amounts of hydrophilic monomer (acrylic acid, AA) were synthesized and tested: p(HEMA), p(HEMA-co-5%AA), p(HEMA-co-25%AA). The macro-mechanical tests were reproduced at nanoscale in order to verify if the superficial properties of the hydrogels are similar to the bulk ones.     

Atom transfer radical polymerization (ATRP): A versatile and forceful tool for functional membranes

The progress in atom transfer radical polymerization (ATRP) provides an effective means for the design and preparation of functional membranes. Polymeric membranes with different macromolecular architectures applied in fuel cells, including block and graft copolymers are conveniently prepared via ATRP. Moreover, ATRP has also been widely used to introduce functionality onto the membrane surface to enhance its use in specific applications, such as antifouling, stimuli-responsive, adsorption function and pervaporation. In this review, the recent design and synthesis of advanced functional membranes via the ATRP technique are discussed in detail and their especial advantages are highlighted by selected examples extract the principles for preparation or modification of membranes using the ATRP methodology.     

AM与HEMA共聚制备水凝胶接触镜材料及其溶胀性能

采用丙烯酰胺(AM)与甲基丙烯酸β-羟乙酯(HEMA)进行本体共聚制备水凝胶接触镜材料,研究了水凝胶的溶胀性能及其温度和pH值敏感性。结果表明,引发剂过氧化苯甲酰(BPO)用量为反应单体总质量的0.3%、反应温度80℃,产物溶胀之后为无色透明的玻璃状水凝胶;共聚物水凝胶具有较好的pH值敏感性,水凝胶在酸性溶液中溶胀,在碱性溶液中收缩:含有AM的水凝胶,其pH值敏感性较大:随AM的含量增大,共聚物水凝胶的溶胀速度和饱和含水量增大,随温度升高,水凝胶的饱和含水量下降,共聚物水凝胶中AM的含量对其温度敏感性无显著影响:SEM照片显示,AM与HEMA共聚物存在均匀的纤维状结构,并且共聚物中AM的含量越大,这种纤维状结构越大、越明显。     

DMAEMA/NVP/HEMA共聚物水凝胶的合成与性能研究

以甲基丙烯酸N,N-二甲氨基乙酯(DMAEMA)、N-乙烯基吡咯烷酮(NVP)和甲基丙烯酸β-羟乙酯(HEMA)为共聚单体,采用自由基水溶液聚合法制备了化学交联的三元共聚水凝胶,并对水凝胶在不同温度和不同离子强度及不同pH介质中的溶胀性能进行了测定。结果表明,在不同离子强度(I)的水溶液中,随着I的增大,水凝胶的平衡溶胀比ESR不断降低;但当I>0.2后,对凝胶ESR的影响不显著;当外界环境酸度较大(pH<2)时,凝胶ESR较大,但pH值稍有增大,凝胶ESR迅速下降;温度升高,凝胶ESR减少。