摘要
聚甲基丙烯酸甲酯(PMMA)是一种透明材料,与无机透明材料相比,它具有很多优异的性能,但耐热性差是其主要缺点。提高PMMA耐热性,拓宽其应用领域已成为当今众多科研工作者的热门研究课题。
本文采用两种途径对PMMA进行耐热改性:一是通过共聚在PMMA大分子链上引入刚性的N-环己基马来酰亚胺(CHMI),增大链内旋转阻力,从而提高其耐热性;二是利用有机-无机纳米复合技术,通过性能互补,实现PMMA的高性能化。
本文首先研究了N-环己基马来酰亚胺单体合成的最佳条件,采用高温脱水法合成出了高产率、高纯度的单体(熔点为90.2℃,文献值90.2℃)。在此基础上,利用本体聚合法制备了MMA/CHMI二元共聚物。热分析测试表明,N-环己基马来酰亚胺的引入使PMMA的玻璃化转变温度、热分解温度显著提高。但随着CHMI用量的增加,产物的黄色指数增大。研究表明,导致产物变黄的主要原因是体系中CHMI的残留。为此,将苯乙烯(St)作为第三单体引入上述共聚体系,制备了MMA/CHMI/St三元共聚物。St的引入提高了CHMI参与共聚的活性,降低了产物的黄色指数,当St用量合适时,可得到热学性能、力学性能良好的透明材料。
本文研究的另一个重要内容是活性有机蒙脱土的制备。将水溶性阳离子自由基引发剂偶氮二异丁基脒盐酸盐(AIBA)和十六烷基三甲基溴化铵(CTAB)或十六烷基三正丁基溴化鳞(HTPB)两次插层蒙脱土制备了既有较大层间距,又有引发活性的有机蒙脱土ANMMT(AIBA和CTAB改性MMT)和APMMT(AIBA和HTPB改性MMT)。AIBA在蒙脱土中的含量主要取决于两种插层剂的比值,与长碳链阳离子的种类关系不大。活性有机蒙脱土层间距的大小不仅与两种插层剂比值有关,还受阳离子种类的影响,在其它条件相同时,季鳞盐改性蒙脱土的层间距大于季铵盐。此种活性有机蒙脱土用于纳米复合材料的制备将从热力学和动力学两方面为蒙脱土片层的打开提供必要及充分的条件。
甲基内烯酸甲酷一N一环己基马来酞亚胺一苯乙烯共聚物及其蒙脱土纳米复合材料的制备、结构和性能
将MMA分别与上述两种活性有机蒙脱土进行原位本体聚合,制备了PMMA/
ANMMT和PMMA/APMMT纳米复合材料。XRD和TEM测试表明,两种复合材料均实
现了纳米复合;蒙脱土的加入使PMMA/ANMMT复合材料的玻璃化转变温度Tg提高,
而PMMA/APMMT复合材料未出现明显的玻璃化转变;两种复合材料都表现出较高的热
分解温度,尤其是PMMA/APMMT复合材料;PMMA/ANMMT复合材料的透光性变差,
而PMMA/APMMT表现出良好的透光率和雾度值。
为进一步提高蒙脱土片层的剥离程度,增大聚合物基体与蒙脱土片层的界面作用,采
用共聚插层复合,将耐热改性单体CHMI引入插层复合体系,制备了MMA一CHMI共聚
物/ANMMT和MMA一CHMI共聚物/APMMT复合材料。CHMI的引入使蒙脱土片层有
了更大程度的分散。共聚物/蒙脱土纳米复合材料的耐热性及透明性比均聚物/蒙脱土纳
米复合材料有明显的提高,而且MMA一CHMI/ APMMT复合材料的透明性优于MMA-
CHMI/ANMMT复合材料。
本文还探讨了无机蒙脱土存在下AIBA引发MMA一CHMI一St的三元共聚反应,考察
了MMT用量、AIBA浓度、反应温度对聚合反应速率、共聚物分子量和产物Tg的影响;
采用连续加料法制备了MMA一CHMI一St/MMT复合材料;将其作为耐热改性剂与PVC
共混,共混后PVC的耐热性有所提高。
Poly (methyl methacrylate) (PMMA) is a kind of transparent materials. It has a variety of interesting and desirable properties compared to inorganic materials. But the poor thermal properties of PMMA have been point out to be a main disadvantage of these materials. In order to extent it's application fields, more and more attentions have been focused on the research of improving heat resistence for PMMA.
In our work, two ways were adopted to improve the thermal properties of PMMA: incorporating rigid N-cyclohexyl maleimide into the chain of PMMA by copolymerization and compounding the organic-inorganic components by means of nanocompouding technique.
Firstly, N-cyclohexyl maleimide was synthesized in high yield and purity (mp: 90.2C, literature: 90.2C) by dehydration of maleimic acid at hight temperature. Binary copolymers of MMA / CHMI at different feed content were synthesized by bulk copolymerization. The results show that as the content ratio of CHMI increased, the glass transition temperature and thermal decomposition temperature of copolymers are all higher than PMMA, and the yellow index of the copolymer is also increased. The resident CHMI in the copolymer leads to the yellow index of the materials. The introduce of St as the third monomer into the copolymerization improves the activity of the CHMI, so the yellow index of the copolymer decreased. Transparent materials with well integration properties will be obtained by controlling the ratios of monomers properly.
Secondly, a new two-step intercalation with aqueous soluble cationic free-radical initiator 2,2'-azobi(2-methyl-propionamide) hydrochloride (AIBA) and hexadecyltrimethyammonium bromide (CTAB) or hexadecyltri-n-butylphosphonium bromide (HTPB) was used to modify montmorillonite (MMT), and two kinds of active organic montmorillonite ANMMT (AIBA-CTAB-MMT) and APMMT (AIBA-HTPB-MMT) were obtained. The absorption
amounts of AIBA in the above montmorillonite maining depended on the content ratio of AIBA, and the interlayer distance of the active organic montmorillonite was influenced by the ratio of intercalation agents and the cationic character.
PMMA / ANMMT and PMMA / APMMT nanocomposites were prepared by bulk intercalation polymerization. XRD and TEM studies showed that montmorillonite is as nanostructure in PMMA matrix. The glass transition temperature of PMMA / ANMMT nanocomposites was increased with the addition of ANMMT while no glass transition could be observed for PMMA / APMMT nanocomposites, but their heat decomposition temperature were all increased with the introduce of active organic montmorillonite. PMMA / APMMT nanocomposites exhibited better light transmittance than PMMA / ANMMT nanocomposites.
We introduced CHMI into the bulk intercalation copolymerization and prepared MMA-CHMI / ANMMT and MMA-CHMI / APMMT nanocomposites. It was found that the dispersibility of montmorillonite in polymer matrix and the interaction of between the montmorillonite layers with copolymer was greatly improved with the incorporation of polar unit CHMI. Thermal properties and light transmittance of copolymer nanocomposites were superior to those of the homopolymer nanocomposites .
Methyl methacrylate (MMA)-jV-cyclohexylmaleimide (CHMI)-styrene (St) copolymer / Na-montmorillonite (MMT) composites were prepared by soap-free emulsion copolymerization using 2,2'-azobi (2-methyl-propionamide) dehydrochloride (AIBA) as initiator. The influences of the amount of montmorillonite, initiator and the temperature of reaction on the copolymerization rate, molecular weight of copolymer and the glass transition temperature (Tg) of the composite were investigated. The results indicated that MMT can accelerate the copolymerization rate, increase the molecular weight of the copolymer, and enhance the thermal properties of composites. MMA-CHMI-St / MMT composites, using as heat resistance modifier, can improve the thermal property of PVC.
引文
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