活性聚合法制备大分子表面改性剂及应用

综述了大分子表面改性剂的优点,并系统介绍了目前大分子改性剂的开环聚合、基团聚合法、原子转移自由基聚合、可逆加成断裂-链转移聚合等合成工艺。同时对目标大分子表面改性剂的结构选择、设计及应用前景进行了分析和展望。     

活性聚合法制备大分子表面改性剂及应用

综述了大分子表面改性剂的优点,并系统介绍了目前大分子改性剂的开环聚合、基团聚合法、原子转移自由基聚合、可逆加成断裂-链转移聚合等合成工艺。同时对目标大分子表面改性剂的结构选择、设计及应用前景进行了分析和展望。     

聚烯烃表面改性剂

本文简单介绍近年来国外开发的聚烯烃表面改性剂的结构、性能及在二次加工方面的使用效果。     

自制的含氟大分子表面改性剂对纳米Si_3N_4粉末的表面化学修饰研究

采用设计合成的含氟大分子表面改性剂,对纳米S i3N4粉体进行了表面包覆改性处理。应用TEM,FTIR,NMR,TGA等对含氟大分子表面改性剂和表面改性前后的纳米S i3N4粉体进行了表征和分析比较。结果表明,包覆在纳米S i3N4粉体表面的含氟大分子表面改性剂,与其发生了化学键合,有效地阻止了纳米S i3N4粉体的团聚。当含氟大分子表面改性剂用量为7%时,包覆改性后的纳米S i3N4粉体的粒径较小,为64.5 nm,分布最窄,分散性最好。     

纳米氮化硅粉体的大分子改性剂表面修饰研究

从分子设计的角度合成了一种新型的大分子表面改性剂(LMPB-g-MAH):采用溶液聚合法将极性单体马来酸酐(MAH)接枝到低分子量的聚丁二烯液体橡胶(LMPB)分子长链中,并用其对纳米氮化硅粉体进行表面修饰;对合成的大分子表面改性剂、改性前后的纳米氮化硅粉体,运用FT-IR、TEM、TGA、粒径分析、沉降实验等方法进行了表征.实验结果表明:马来酸酐已经接枝到低分子量的聚丁二烯液体橡胶分子长链中;当大分子表面改性剂的接枝率为9%～11%、用量为10%～12%、反应温度为65℃、反应时间为3 h时,表面修饰后的纳米氮化硅粉体颗粒粒径减小,有效阻止了纳米颗粒的团聚.     

纳米TiN表面改性的研究及其在ACM胶中的应用

采用自制的大分子表面改性剂对纳米TiN进行表面改性,对改性前后的纳米TiN进行红外光谱分析（FTIR）、热重分析（TGA）、粒径分析、接触角等表征。结果表明,大分子改性剂和纳米TiN的表面发生化学键合,有效地阻止了纳米TIN的团聚,使得纳米T．N疏水性提高。用改性后的纳米TiN填充丙烯酸酯橡胶（ACM）,制备纳米TiN／ACM复合材料,透射电镜（TEM）观察到纳米TiN颗粒在ACM基体中分散良好;复合材料性能检测结果显示：材料的常规力学性能、耐油、耐热空气老化和耐磨性能均有明显提高。     

表面原位化学组合改性Al（OH）3／PVC复合材料的制备与性能

基于Al(OH)_3粉体与PVC基体的界面设计和调控,采用表面原位化学组合改性方法,在Al(OH)_3表面依次化学键合烷基酚醛树脂、丁腈橡胶等几种大分子改性剂,形成极性逐渐过渡的梯度界面层。当改性Al(OH)_3在PVC复合材料中的用量为80份时,材料的缺口冲击强度达到最大值,分别为添加等量偶联剂改性Al(OH)_3、未改性Al (OH)_3复合材料的2．5和2．7倍,是基体树脂的1．5倍,获得了具有高阻燃消烟性能,同时改善了力学和加工性能的综合性能良好的高填充复合材料。通过扫描电镜分析表明,Al(OH)_3粒子经过表面原位化学组合方法处理,在PVC中分散均匀,与塑料基体结合良好,并形成了以Al(OH)_3粒子为核、以多层大分子改性剂为壳的软壳硬核结构。     

糖基季铵盐表面活性剂的研究进展

糖基季铵盐表面活性剂是一类含有糖结构单元的新型阳离子表面活性剂.针对糖基季铵盐结构的不同和合成方法的差异,进行比较和归纳,阐述了单疏水基双亲水基、双疏水基双亲水基和聚糖基3类糖基季铵盐表面活性剂合成方法的研究现状,并对其性能如表面活性、抗硬水性、与阴离子表面活性剂的配伍性、对人体的毒性和生物降解性以及应用作了介绍.     

Gemini表面活性剂合成进展

Gemini表面活性剂是一类新型的双亲水基、双疏水基两亲表面活性剂,按照其结构特点,Gemini表面活性剂可分为阳离子、阴离子、非离子以及高分子表面活性剂。介绍了Gemini表面活性剂的研究进展和合成现状。     

超细水镁石粉的表面改性及在聚烯烃中的应用

采用4种表面改性剂烷基多磷酸酯、硬脂酸钠、柠檬酸单甘酯、十二烷基磷酸酯对超细水镁石粉进行表面改性,通过吸水率、接触角等表征手段考察了改性剂种类和用量对超细水镁石粉表面改性的影响。2,2,4-三甲基戊烷洗涤后改性水镁石粉的接触角发生了变化,表明改性后的超细水镁石粉由亲水性转变为疏水性,吸附方式既有化学吸附又有物理吸附。将硬脂酸钠改性后的水镁石粉填充到聚烯烃中,结果表明,硬脂酸钠的较佳用量为2 %,硬脂酸钠改性水镁石粉的加入使聚烯烃的氧指数从29.3 %提高到32.9 %,断裂伸长率提高了30 %。     

改性纳米Si3N4的制备及在PU合成革中的应用

采用自制的丙烯酸丁酯-甲基丙烯酸甲酯-乙烯基三乙氧基硅氧烷（BA-MMA-VTES）大分子表面改性剂对纳米氮化硅（Si3N4）陶瓷粉体进行表面包覆改性,将改性后的纳米Si3N4粉体加入到耐水解聚氨酯（Pu）树脂中成革,并进行傅立叶变换红外光谱、透射电子显微镜等分析及力学性能测试。结果表明,BA—MMA—VTES与纳米Si3N4发生化学健合;BA—MMA—VTES质量分数为5％时,纳米Si3N4粒径最小,改性后的纳米Si3N4有良好的分散性能。添加改性纳米Si3N4粉体的PU合成革的力学性能明显提高。     

Surface modification of MWNTs with BA‐MMA‐GMA terpolymer by single‐step grafting technique

In this article, a facile strategy was developed to prepare BA‐MMA‐GMA/MWNTs (multiwalled carbon nanotubes) hybrid nanoparticles as nanofillers in rubber by single‐step grafting technique. First, a new macromolecular surface modifier butyl acrylate (BA)‐α‐methyl methacrylate(MMA)‐glycidyl methacrylate (GMA) terpolymer was synthesized via radical copolymerization. Afterward, this terpolymer modifier was covalently grafted onto the surface of crude MWNTs by single‐step grafting technique. The structure, surface properties, and thermal stability of modified MWNTs were systematically investigated by FTIR, TGA, and TEM. FTIR results showed that BA‐MMA‐GMA terpolymer was successfully grafted onto the surface of MWNTs. TGA indicated that the optimum mass fraction of macromolecular modifier coated on the surface of MWNTs was 9 wt %. TEM images revealed that an organic coating layer was formed and the modified MWNTs showed good dispersibility in acetone. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

碳纳米管/丙烯酸酯橡胶复合材料的制备及性能研究

采用自制的大分子表面改性剂对多壁碳纳米管(MWNTs)进行表面改性,制备改性MWNTs/丙烯酸酯橡胶(ACM)复合材料,研究改性MWNTs用量对复合材料性能的影响,并与炭黑补强的ACM性能进行对比.结果表明:用MWNTs填充ACM制备的材料,其性能远优于炭黑补强的ACM橡胶的性能;随着改性MWNTs用量的增大,复合材料...     

含活性硅氧烷型大分子改性剂BA-MMA-VTES的合成与表征

针对弱极性天然/丁苯橡胶复合体系,从分子设计的角度出发,选择乙烯基三乙氧基硅氧烷(VTES)、丙烯酸丁酯(BA)、甲基丙烯酸甲酯(MMA)为单体,通过自由基溶液聚合并优化了反应条件:在85℃和115℃分别加入两种不同量的引发剂BPO和DCP,均保温反应2h,合成了三元共聚物BA-MMA-VTES大分子表面改性剂,用于纳米碳化硅、氮化硅陶瓷粉体的表面改性。采用FTIR、NMR、GPC、DSC、TGA等对所合成的三元共聚物的结构、性质和数均相对分子质量进行了分析和表征。通过FTIR、NMR测试结果,证实了BA-MMA-VTES三元共聚物的结构;通过GPC测试,证明BA-MMA-VTES三元共聚物的数均相对分子质量控制在3000～10000;DSC显示合成的大分子只有一个Tg,在3.3℃左右,表明它是无规共聚物,柔性适中;TGA显示三元共聚物主要热分解区间在280～500℃,热稳定性良好。     

Synthesis and characterization of macromolecular surface modifier PP-g-PEG for polypropylene

A novel macromolecular surface modifier, polypropylene-grafted-poly(ethylene glycol) copolymer (PP-g-PEG), was synthesized by coupling polypropylene containing maleic anhydride with monohydroxyl-terminated poly(ethylene glycol). The effects of the reaction condition on the graft reactions were studied. The copolymers were characterized by IR, ¹H NMR, thermogravimetry (TG) and differential scanning calorimetry (DSC). The results indicated that the graft reactions were hindered by increasing the molecular weight of PP or PEG. The graft copolymer was found to have a higher initial thermal degradation temperature and lower crystallization capacity as compared with pure PP, and the side chain of PEG hindered the PP chain from forming a perfect β crystal. The thermal stability of PP-g-PEG decreased with the increasing content or molecular weight of PEG. The copolymers were blended with polypropylene to modify the surface hydrophilicity of the products. The results of attenuated total reflectance FTIR spectroscopy (ATR-FTIR) showed that PP-g-PEG could diffuse preferably onto the surface of the blends and be suitable as an effectual macromolecular surface modifier for PP. __________ Translated from Acta Polymerica Sinica, 2007, (2): 203–208 [译自:高分子学报]     

Surface enrichment of polypropylene-graft-poly(methyl methacrylate) on polypropylene

To overcome disadvantage of polypropylene induced by its low surface energy, poly(methyl methacrylate) was grafted onto polypropylene and entrapped into polypropylene as macromolecular surface modifier. The effects of copolymer structures, contact dies and content of modifiers on their surface enrichment were studied by attenuated total reflection infrared spectroscopy (ATR-FTIR), contact angle measurements (CDA) and scanning electron microscopy (SEM). Lower content and higher surface energy dies were in favor of the copolymer to enrich on the PP surface. PPw-g-PMMA with low PMMA graft density, long length of PMMA was distributed in PP with smaller phase domains and concentration gradient, especially at lower loadings in blends, which favored its selective enrichment on the surface of PP. The modified material exhibited excellent solvent-resistance. The results indicated that PPw-g-PMMA can transfer to the surface of blends and effectively increase the hydrophilicity of PP, which offer a convenient technique to functionalize the surface of polymers with lasting-effectiveness compared with modification by homopolymers.     

Synthesis and characterization of macromolecular surface modifier PP--PEG for polypropylene

A novel macromolecular surface modifier, polypropylene-grafted-poly(ethylene glycol) copolymer (PP-g-PEG), was synthesized by coupling polypropylene containing maleic anhydride with monohydroxyl-terminated poly(ethylene glycol). The effects of the reaction condition on the graft reactions were studied. The copolymers were characterized by IR, ¹H NMR, thermogravimetry (TG) and differential scanning calorimetry (DSC). The results indicated that the graft reactions were hindered by increasing the molecular weight of PP or PEG. The graft copolymer was found to have a higher initial thermal degradation temperature and lower crystallization capacity as compared with pure PP, and the side chain of PEG hindered the PP chain from forming a perfect ? crystal. The thermal stability of PP-g-PEG decreased with the increasing content or molecular weight of PEG. The copolymers were blended with polypropylene to modify the surface hydrophilicity of the products. The results of attenuated total reflectance FTIR spectroscopy (ATR-FTIR) showed that PP-g-PEG could diffuse preferably onto the surface of the blends and be suitable as an effectual macromolecular surface modifier for PP.     

氢化聚丁二烯/聚甲基丙烯酸甲酯接枝共聚物的合成及表征

采用溶液法将极性单体马来酸酐在隔氧条件下对聚丁二烯进行接枝，通过氢化反应及马来酸酐与端羟基PMMA的酯化反应，合成了氢化聚丁二烯／聚甲基丙烯酸甲酯接枝共聚物。考察了反应时间等因素对接枝反应的影响，测定了聚合物的接枝率，同时对其结构进行了表征。结果表明，所合成的接枝共聚物具有良好耐热性和表面迁移特性，适合用作PP的太分子表面改性剂。