反应型转光剂制备及其与聚乙烯接枝研究
文献类型：学位论文
| 作者 | 林泽森 |
| 学位类别 | 硕士 |
| 答辩日期 | 2015-04 |
| 授予单位 | 中国科学院研究生院 |
| 授予地点 | 中国科学院长春应用化学研究所 |
| 导师 | 姚占海 |
| 关键词 | 线性低密度聚乙烯 预辐照与熔融接枝联用技术 萘酰亚胺 苝酰亚胺 迁移 |
| 中文摘要 | 有机染料类转光剂制备的转光棚膜相较稀土类具有透光性好等优点，但是存在转光剂与聚乙烯等常用基材相容性低导致喷霜等问题，因此需要对有机染料和基材分别进行改性。本论文以制备耐迁移的有机染料类转光膜为目的，合成了两种反应型转光剂N-烯丙基-4-甲氧基-1,8-萘酰亚胺(MOANI)和N, N’-二烯丙基-1,6,7,12-四(4-叔丁基苯氧基)-苝-3,4,9,10-四甲酰二亚胺(DAPBI)，并采用预辐照与熔融接枝联用技术，将两种反应型转光剂接枝到了线性低密度聚乙烯(LLDPE)上，发展了接枝率的测定及转光膜耐迁移性的测试方法，最终制备出了比常规掺混转光膜耐迁移性能更高的荧光有机染料类转光膜。 首先，以4-氯-1,8-萘二甲酸酐为原料通过一锅法一步制得了MOANI；以N,N’-二正丁基-1,6,7,12-四(4-叔丁基苯氧基)-苝-3,4,9,10-四甲酰二亚胺为原料，经水解、烯丙基化，两步制得DAPBI。采用质谱，红外光谱，核磁共振证明了两种产物的组成结构。采用紫外可见及荧光分光光度法测试了产物在溶液中的吸收及发射光谱，两种光谱证明MOANI及DAPBI可以作为转光剂。 随后，将MOANI及DAPBI分别与预辐照的线性低密度聚乙烯进行熔融接枝，纯化后，采用紫外可见、荧光、红外光谱法以及氢核磁共振波谱法对接枝物的结构进行了表征，结果证明MOANI及DAPBI已经分别接枝到了LLDPE分子链上。通过紫外可见分光光度法建立了一套接枝率(GD)的测定方法，测定了两种接枝聚合物的接枝率并计算了接枝效率(GE)，并用其研究了初始单体浓度、反应温度、反应时间三种因素对GD及GE的影响。结果表明，两种单体的接枝率均随这三种因素的增加而增加，但初始单体浓度对MOANI接枝率的影响最大，反应温度对DAPBI的影响最大；相同反应温度及时间的条件下，MOANI的初始单体浓度在1.5wt%时接枝效率最大，DAPBI在0.3wt%时GE最大。对两种接枝物的流变性能、热学性能和样品表面性质的研究表明：1. pi-LLDPE在熔融状态下会发生分子链交联，从而产生长支链，而两种单体的接枝会减少交联过程的发生；2. 接枝上的单体起到了异相成核剂的作用；3. 纯化后的接枝聚合物在与共混物相同荧光性能的条件下不会发生喷霜现象。 最后，为了更贴近工业生产的实际，我们通过预辐照与反应挤出接枝连用技术及色母粒技术制备了一系列浓度未经纯化的接枝聚合物，并研究了它们吹塑成膜后的紫外耐候性能和迁移析出性能。一、紫外耐候性能的研究：我们将紫外耐候试验仪不同时间老化后的样品用荧光分光光度计及万能拉力机测试，得到了老化条件下薄膜的荧光衰减性质及力学老化性质。研究表明：1.接枝上的单体减小了荧光的衰减速率；2.MOANI起到了紫外线吸收剂的作用，但DAPBI却起到了光敏剂的作用。二、薄膜转光效果的评价：我们以氙灯为光源，通过光谱验证仪对所有薄膜样品的透过光谱进行了研究，研究表明：未经纯化的LLDPE-g-MOANI膜起到了紫外转蓝作用，增强了聚乙烯薄膜在400~500nm间的透过光强，初始MOANI浓度为0.15 wt%的膜在该范围内透过光强与300~750nm总透过光强的积分相较LLDPE增加了2.5%；未纯化LLDPE-g-DAPBI膜起到了黄绿转橙红的作用，增强了聚乙烯薄膜在600~750nm间的透过光强，初始DAPBI浓度为0.09 wt%的膜在该范围内透过光强与300~750nm总透过光强的积分比较LLDPE增加了1.7%，此外其红光/远红光量比相较LLDPE膜增加了0.033。三、迁移析出性能的研究：结合转光膜实际使用的特点，我们用流滴膜的测试装置——加速流滴仪结合荧光分光光度计测定了两种接枝聚合物薄膜因单体迁移析出造成的荧光衰减性质。经60℃加速诱导，22天后，初始单体浓度为0.15wt%的未纯化LLDPE-g-MOANI膜（所用1wt%色母粒GD=0.17wt%）的蓝色荧光占初始强度的百分数为64.5%，而对比的同初始浓度的共混膜只有41.6%；相同条件下，47天后，含有流滴剂且初始单体浓度为0.13wt%未纯化LLDPE-g-DAPBI膜（所用1wt%色母粒GD=0.10wt%）的红色荧光占初始强度的百分数为58.4%，而对比的同初始浓度的共混膜只有42.0%。结果表明：接枝上的单体抑制了未接枝单体的迁移析出过程。此外通过复配我们发现，两种接枝物的复配更能延缓未接枝单体的迁移渗出过程。 |
| 英文摘要 | As one kind of light-converting agents, fluorescent organic dyes are widely used, because they are molecular dispersion in the polymer than rare earth type light-converting agents. Unfortunately, fluorescent organic dyes lack an affinity for aliphatic hydrocarbons, consequently migrate to the surface of polyolefins and even crystallize on the surface, so the dyes or polyethylene need to be modified. In this work, we synthesized two polymerisable light-converting agents, 4-methoxy-N-allyl-1,8-naph -thalimide (MOANI) and N,N'-diallyl-1,6,7,12-tetra(4-tert-butylphenoxy)-perylene-3,4, 9,10-tetracarboxylic bisimide (DAPBI), grafted them onto linear low density polyethylene (LLDPE) with the pre-irradiation and melt grafting joint technology and finally the two modified LLDPEs showed the potential application in long-term light-converting films. Firstly, MOANI was synthesized from 4-chloro-1,8-naphthalic anhydride through using a one-pot method. DAPBI was synthesized from N,N'-di-n-butyl-1,6,7,12-tetra(4 -tert-butylphenoxy)-perylene-3,4,9,10-tetracarboxylic bisimide through using hydrolyzation and allylation reaction successively. The chemical structures of products were proved through using MS, FTIR and NMR. The absorption and emission spectra were obtained through using UV/vis spectrometer and fluorospectrometer, and they prove that MOANI and DAPBI can be as light-converting agents. Secondly, MOANI and DAPBI were respectively grafted onto pre-irradiated linear low density polyethylene (LLDPE) with a melt reactive mixing process, and charactered spectral, thermo and rheological properties of two grafting polymers (LLDPE-g-MOANI, LLDPE-g-DAPBI) obtained in mixer after purification. By comparing UV/vis, fluorescence, FTIR, 1HNMR spectra of the LLDPE, two grafting polymers and two polymerisable light-converting agents, it was proved that MOANI and DAPBI were grafted on LLDPE. The grafting degree (GD) of MOANI or DAPBI in LLDPE-g-MOANI or LLDPE-g-DAPBI was determined by UV/Vis spectra and relevant grafting efficiency (GE) was also calculated. The effects of monomer concentration, chamber temperature and reaction time on GD and GE were systematically studied. The results show that GDs of MOANI and DAPBI increased with increasing initial monomer concentration, chamber temperature and reaction time. However, the initial monomer concentration and chamber temperature are the main processing parameters for controlling the GD to MOANI and DAPBI, respectively. In the same chamber temperature and reaction time, the highest GE of MOANI was reached in 1.5wt% of initial monomer concentration of MOANI, but in 0.3wt% of initial monomer concentration of DAPBI. The rheological behaviors of LLDPE-g-MOANI and LLDPE-g-DAPBI suggest that the crosslinking of LLDPE can be inhibited effectively by graft of MOANI and DAPBI. The grafted monomer acts as a nucleation agent, which improves the crystallization rates of LLDPE molecular chains. Surface morphologies of LLDPE-g-MOANI and LLDPE-g-DAPBI demonstrating the grafted monomer are difficult to migrate to the surface of the films. Finally, accelerated migration and UV weathering of blown films of unpurified LLDPE-g-MOANI and LLDPE-g-DAPBI obtained in extruder were tested in order to close to actual industrial production. Mechanical properties of unpurified LLDPE-g-MOANI films as function of UV weathering period mean that MOANI acts as the role of ultraviolet absorber and inhibited the aging process of LLDPE. But for unpurified LLDPE-g-DAPBI films, DAPBI acts as the role of sensitizer and accelerated the aging process of LLDPE. The test results of spectrograph suggest that unpurified LLDPE-g-MOANI and LLDPE-g-DAPBI films can increase light intensity of blue-violet light and orange-red light compared with LLDPE film, respectively. Besides, the intensity ratio of red and far-red light of unpurified LLDPE-g-DAPBI film with 0.09 wt% DAPBI initial concentration increased by 0.033, compared with LLDPE film. The test results of accelerated migration and UV weathering indicate that migration processes of the free MOANI or DAPBI in unpurified LLDPE-g-MOANI or LLDPE-g-DAPBI films were delayed effectively by the grafted MOANI or DAPBI in these films. Through blown films of mixture of unpurified LLDPE-g-MOANI and LLDPE-g-DAPBI, migration processes of the free MOANI or DAPBI were delayed further, compared with unpurified LLDPE-g-MOANI or LLDPE-g-DAPBI with same MOANI or DAPBI initial concentration. |
| 语种 | 中文 |
| 公开日期 | 2016-05-03 |
| 源URL | [http://ir.ciac.jl.cn/handle/322003/64460]  |
| 专题 | 长春应用化学研究所_长春应用化学研究所知识产出_学位论文 |
| 推荐引用方式 GB/T 7714 | 林泽森. 反应型转光剂制备及其与聚乙烯接枝研究[D]. 中国科学院长春应用化学研究所. 中国科学院研究生院. 2015. |
入库方式： OAI收割
来源：长春应用化学研究所
浏览0
下载0
收藏0
其他版本
除非特别说明，本系统中所有内容都受版权保护，并保留所有权利。