快速升温条件下聚甲基丙烯酸甲酯的燃烧机理

用色谱和质谱研究了快速升温条件下PMMA以及单体MMA在空气和氩气中的不同温度下的热反应，推测了PMMA在空气中燃烧的主要历程。结果表明，在快速升温条件下，PMMA首先降解为单体MMA，而后MMA分解，生成甲醇、甲烷、丙烯、2-甲基丙烯和丙酮等可燃性气态小分子，最后气态小分子与氧反应发生燃烧。在较高温度下，MMA也可直接与氧反应，生成丙酮酸甲酯、甲醛和丙酮，但此反应在PMMA的燃烧历程中处于次要地位。     

高原和平原环境下宽度对保温材料PS火蔓延特性的影响

分别在拉萨高原地区和合肥平原地区开展了一系列保温材料PS(聚苯乙烯)火蔓延对比实验研究,通过对火蔓延过程中一些重要特性参数(火蔓延速度、表面火焰区和池火区火焰高度等)的测量,分析了高原地区和平原地区保温材料PS的火灾危害特性。结果表明,对于同种宽度的EPS或XPS,在拉萨的火蔓延速度均小于在合肥情况下;而当保温材料的宽度为10cm左右时,在两地火蔓延速度均出现了最小值,这主要为空气卷吸程度与热量损失共同作用的结果。研究同样表明,对于EPS和XPS,在宽度比较小的情况下,无论在拉萨还是在合肥,表面火焰区的火焰高度呈现出略大于池火区火焰高度的特点;随着宽度的增加,池火区的火焰高度逐渐大于表面火焰区的火焰高度,并且具有逐渐增高的特性。     

聚甲基丙烯酸甲酯的电场纺丝行为

研究了聚甲基丙烯酸甲酯(PMM A)的电场纺丝行为。结果表明,溶液的浓度对纤维的形貌起了主导作用,当以N,N二-甲基甲酰胺(DM F)为溶剂,PMM A的质量分数低于12%时只能得到液滴,PMM A的质量分数为15%时,得到珠串状结构的纤维,只有当PMM A的质量分数提高到20%时,才有可能得到形貌比较均匀的纤维;纤维的直径随施加电压的增大而增大,收集距离的增大而减小;染料溶液的加入使纤维倾向于形成珠串状结构,但所得纤维的直径在100 nm至300 nm之间,对研究纳米纤维在2维方向上对荧光分子的压缩效应有利。     

高分子量聚甲基丙烯酸甲酯的制备

通过悬浮聚合法制取了分子量在100万～150万范围的聚甲基丙烯酸甲酯(PMMA).研究了温度、引发剂浓度、转化率对聚合物分子量的影响情况,用粘度法测量了PMMA的分子量.结果表明:温度升高、引发剂用量增加使得聚合物分子量降低;随反应的进行和单体转化率提高,聚合物分子量增大并趋于定值.在单体:水相=1:5(质量比),过氧类引发剂浓度1%,反应温度60～70℃,反应时间5h左右的实验条件下,制备得到了高分子量PMMA.     

聚甲基丙烯酸甲酯乳胶粒子流变特性及零切粘度的研究

在描述聚甲基丙烯酸甲酯乳胶粒子体系的流动特性及相应流变实验的基础上，阐述了高聚物溶液／熔体流动特性与流变性质的对应关系，并依据这种对应关系确定了流体层间的零切粘度求值方法。同时依据实验数据，得到了不同粒径聚甲基丙烯酸甲酯乳胶粒子体系的零切粘度值。     

多孔聚甲基丙烯酸甲酯与羟基磷灰石复合材料的制备及表征

在传统聚甲基丙烯酸甲酯(PMMA)制备的基础上,以羧甲基纤维素(CMC)和羟基磷灰石(HA)分别作为成孔剂和生物活性填料,制备多孔PMMA和多孔PMMA/HA复合材料,并用热电偶、显微CT、MTS材料试验系统和扫描电镜等比较改良后的PMMA合成物与传统PMMA最高聚合温度、抗压强度、弹性模量以及体外矿化能力等。结果显示:CMC水凝胶能显著降低传统PMMA聚合时的产热,也能使致密PMMA形成相互联通的孔径结构从而使其力学特性与人松质骨更匹配。HA颗粒的载入不会影响多孔PMMA支架的力学性能,但却能显著提高所形成复合材料的体外矿化能力。改良后的多孔PMMA/HA复合材料作为骨缺损修复材料具有良好的应用前景。     

窄分子量分布聚甲基丙烯酸甲酯的研究进展

对比不同窄分子量分布PMMA的制备方法,从自由基聚合、阴离子聚合及活性自由基聚合3种体系角度分析:自由基聚合操作条件温和、适用范围广,但分子量分布的极限是2.0左右;阴离子聚合能够得到分子量分布小于1.2的PMMA,然而反应条件苛刻;活性自由基聚合兼具两者优势,能够在温和条件下获得极窄分子量分布的PMMA,展现出了明显的优越性,是未来工业化开发的方向。     

纳米粒子改性聚甲基丙烯酸甲酯的制备及应用

本文主要论述了用纳米粒子SiO2 、TiO2 及石墨、蒙脱土等改性PMMA的方法以及表征手段和材料的用途及展望 ,纳米改性PMMA赋予PMMA很好力学、光学及导电性能。     

聚偏氟乙烯/聚甲基丙烯酸甲酯共混物的老化性能

对聚偏氟乙烯(PVDF)/聚甲基丙烯酸甲酯(PMMA)共混物的老化性能进行了研究,对试样进行湿热老化和紫外老化的加速老化实验,得到了拉伸强度和色差值随老化时间的变化规律。结果表明:在湿热老化过程中,拉伸强度随时间的延长先增加后减小,且PVDF与PMMA的质量比为70∶30时最大,但此时材料脆性太大;而在老化121 d后,随PM-MA含量的增加,试样的熔融指数增加;在老化152 d内,四组试样色差值ΔE<1.5,属于可接受的范围。同样两组薄膜样品在紫外光老化实验中,拉伸强度先增大后减小,且在紫外老化的1040h内,色差值ΔE<1,耐紫外效果较好。     

氰酸酯/聚甲基丙烯酸甲酯互穿聚合物网络的探究

用同步法合成一系列氰酸酯/聚甲基丙烯酸甲酯(CE/PMMA)体系的互穿聚合物网络(IPN).研究了甲基丙烯酸甲酯(MMA)的含量对CE/PMMA-IPN体系的力学性能及密度的影响.结果表明:CE/PMMA-IPN体系的性能比单一树脂的优异,但其工艺条件有待进一步改进.     

聚偏氟乙烯/聚甲基丙烯酸甲酯交替多层材料的热稳定性

利用微层共挤出技术制得不同层数(2,16,64层)的聚偏氟乙烯(PVDF)/聚甲基丙烯酸甲酯(PMMA)交替多层材料,通过偏光显微镜、垂直燃烧测试、热失重分析、红外光谱分析、微型量热测试研究了层数的变化对体系热分解和热释放行为的影响。结果表明,PVDF层与PMMA层沿层状样品的厚度方向交替排列,层结构明显,层界面清晰,随着层数的增加,层界面数增加,材料的垂直燃烧行为几乎不变,但表现出更高的热稳定性;高层数样品中热稳定性优异的PVDF层对易热解的PMMA层保护作用增强,且在热释放过程中,更多的层界面为PVDF炭层的形成提供了更丰富的空间,使材料的热释放速率减小,总热释放降低。     

聚甲基丙烯酸甲酯/二氧化硅复合材料的热性能

聚甲基丙烯酸甲酯/二氧化硅(PMMA/Si O_2)复合材料可以通过简便的单体浇铸、本体聚合方法制备,二氧化硅用硅烷偶联剂3-(异丁烯酰氧)丙基三甲氧基硅烷(γ-MPS)进行表面修饰,并用红外光谱表征其甲苯抽提后的组成。当加入量为11.76%时,PMMA/Si O_2复合材料的导热率达到0.23 W/(m·K),比基体PMMA提高了27.78%。用PMMA红外光谱的侧甲基弯曲振动峰(δCH3)与羰基(νC=O)的伸缩振动峰比值可以表示PMMA大分子的偶合终止与歧化终止的比例,随着二氧化硅含量的增加,歧化终止比例升高,从而使PMMA/Si O_2复合材料的热稳定性提高,与热重分析结果一致。     

Modification on crystallization of poly(vinylidene fluoride) (PVDF) by solvent extraction of poly(methyl methacrylate) (PMMA) in PVDF/PMMA blends

The crystallization modification of poly(vinylidene fluoride) (PVDF) was investigated for the blend films of PVDF and poly(methyl methacrylate) (PMMA). The mass crystallinity (χ_c) and further, the β-phase content (F_(β)) of PVDF, were studied for the as-prepared blend films with different mass ratios. In addition, the variations of χ_c and F_(β) were systematically probed once the PMMA component was removed from the related blend systems. DSC, FTIR and XRD measurements all indicated that 1) χ_c, F_(β) and even the content of α-phase (F_(α)) decreased with the addition of PMMA; 2) with the extraction of PMMA, both χ_c and F_(β) increased while F_(α) decreased. It is worth noting that the increase of χ_c and F_(β) depended on the relative amount of extracted PMMA (E_PMMA), i.e., the more PMMA was removed, the more χ_c and F_(β) increased. These results reveal the hindrance effect from the PMMA constituent to the crystallization of PVDF, and consequently, this restriction would be released when the PMMA was extracted.     

Si+ and N+ ion implantation for improving blood compatibility of medical poly(methyl methacrylate)

Si⁺ and N⁺ ion implantation into medical poly(methyl methacrylate) (PMMA) were performed at an energy of 80 keV with fluences ranging from 5×10¹² to 5×10¹⁵ ions/cm² at room temperature to improve blood compatibility. The results of the blood contacting measurementsin vitro showed that the anticoagulability and anticalcific behaviour on the surface morphology were enhanced after ion implantation. No appreciable change in the surface morphology was detected by scanning electron microscopy (SEM). X-ray photoelectron spectroscopy (XPS) analysis indicated that ion implantation broke some original chemical bonds on the surface to form some new Si- and N-containing groups. These results were considered responsible for the enhancement in the blood compatibility of PMMA.     

Effect of hydrophilic–hydrophobic balance on biocompatibility of poly(methyl methacrylate) (PMMA)–hydroxyapatite (HA) composites

The purpose of this study is to put in evidence the correlation between hydrophilic/hydrophobic balance and biocompatibility of PMMA–HA composites, in order to select the best composites for futures clinical applications. For this purpose, PMMA–HA cements with different compositions were prepared and static contact angle measurements, water absorption and gingival fibroblasts cell culture were performed and discussed.     

偶氮二异丁基盐酸脒引发甲基丙烯酸甲酯微球的无皂乳液聚合

采用偶氮二异丁基盐酸脒(AMPMDHC)为引发剂,用无皂乳液聚合方法制备单分散性PMMA微球,合成粒径为500nm的单分散PMMA微球的聚合条件是:MMA/H2O=20:100(m1),温度为70℃,AMPMDHC用量为0.06g,反应时间为1.5h.实验结果表明:(1)引发剂用量越多,PMMA微球粒径越小,但对微球粒径分布影响较小;(2)反应温度升高,微球粒径增大,单分散性降低;(3)微球的粒径随着水的用量增大而降低,当MMA/H2O小于1/6时,微球粒径趋于180nm.     

Study of d.c. electrical conductivity of paranitroaniline doped (1:1) polyvinylchloride and poly(methyl methacrylate) polyblends

Electrical properties of PVC, PMMA and their 1: 1 polyblends, before and after adding paranitroaniline into them, have been investigated as a function of temperature, electric field and dopant concentration, to study the mechanism of electrical conduction. The current was measured by applying d.c. voltage in the range 25–800 V at various thermostatically controlled temperatures (313–373 K). The results obtained predict the Schottky-Richardson conduction mechanism to be operative and d.c. conductivity of the blend lies intermediate between those of individual components. Further, the conductivity of the blend increases with temperature and applied electric field and also with the increase in concentration of dopant. To identify the mechanism governing the conduction, the activation energies in low temperature (LTR) and high temperature (HTR) regions have been calculated. The dielectric constant of the sample at various temperatures have been calculated which increased with increase in temperature. This is indicative of the diffusion of ions in space charge polarization at higher temperature. The study of XRD and FTIR supports the changes occurring in the conductivity of the blend.     

聚甲基丙烯酸甲酯基网络稳定铁电液晶的制备及性能

通过热引发聚合制备了聚甲基丙烯酸甲酯基网络稳定铁电液晶(PNSFLC)材料。采用热台偏光显微镜观察了由不同含量的甲基丙烯酸甲酯(MMA)制备的PNSFLC样品的网络织构。采用紫外分光光度计在0～30V的电压条件下研究了PNSFLC样品的电光性能。采用阿贝折射仪在0～70℃范围内,研究了PSFLC的折射率随温度变化的关系。结果表明:随着(MMA)含量的增加,聚合物网络结构由稀疏至致密。当MMA含量为7%时,所制备的PNSFLC样品的电光响应比小分子液晶的电光性能成线性好,且该MMA含量的PNSFLC样品的热稳定性较好。     

Mössbauer studies of iron doped poly(methyl methacrylate) before and after ion beam modification

High-energy MeV ions from accelerators are known to produce drastic modifications in polymers. The typical effects include chain scissions, crosslinks, molecular emission and double bond formation. Poly(methyl methacrylate) was doped with Fe(III) and irradiated with 95 MeV O⁷⁺ ions.⁵⁷Fe-Mössbauer studies were done on the doped samples before and after irradiation. Before irradiation, no Mössbauer absorption was observed. The irradiated samples showed a good Mössbauer absorption, which seems to indicate that there is a significant interaction between the metal ion and the polymer matrix. Two possibilities exist at these doses (～ 22 × 10¹² ions/cm): Fe(III) ions may be bridging the various polymer segments through crosslinking or amorphization of the sample leading to Fe-C bonding. Studies of FTIR, conductivity and glass transition temperatures on these samples support these observations.