Nondegradative melt functionalization of polypropylene with glycidyl methacrylate

The melt grafting of glycidyl methacrylate (GMA) onto powdered isotactic polypropylene (PP) in a Haake Rheocord RC90 mixer was studied. Grafting degrees were determined by nonaqueous back titration of trichloroacetic acid with sodium hydroxide. The extent of degradation and crosslinking of PP during grafting was indicated by the melt-flow rates (MFR) of the grafted samples. The influences of GMA concentration, initiator type and concentration on grafting degree, reaction efficiency, and degradation were evaluated. A novel method was developed to obtain a high grafting degree with little degradation of PP using acrylamide (AM) as the initiating agent. The grafting process occurred before or during the melting of PP (i.e., solid-state grafting), at which temperature crosslinking is preferred over chain scission. Primary free radicals generated from the rapid decomposition of AM have a higher tendency to attack GMA molecules than PP chains. At the same estimated amount of primary radicals, both grafting degree and grafting efficiency increase with decreasing decomposition temperature of the initiator (for the same decomposition half-life) in the order of AM > benzoyl peroxide (BPO) > 2,5-di(t-butylperoxy)-2,5-dimethyl-3-hexyne (LPO). FunctionalizedPP with the desired grafting degree and little degradation of PP could be obtained by the use of mixed initiators. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1957–1963, 1998     

Copolymerization of styrene and ethylene with mononuclear and dinuclear half-titanocenes

With mononuclear half-titanocenes such as CpTiCl₃, IndTiCl₃, and Me₅CpTiCl₃, as well as the constrained geometry catalyst (CGC) and a new dinuclear hexamethyltrisiloxanediylbis(cyclopentadienyltitanium trichloride) (TSDT), the copolymerization of styrene and ethylene was examined. The thermal properties and structure of copolymerization products were investigated with differential scanning calorimetry and ¹³C-nuclear magnetic resonance. In addition, the raw polymer was separated into homopolymer and copolymer with an extraction method and cross fractionation chromatography. With the above analysis, it was concluded that the raw polymer obtained with CpTiCl₃ and IndTiCl₃ was a mixture of syndiotactic polystyrene and polyethylene homopolymers with 10–30 wt % copolymer, whereas that produced by Me₅CpTiCl₃ and TSDT was a homopolymer mixture with a negligible amount of copolymer. Only CGC produced the copolymer of styrene and ethylene perfectly. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:2187–2198, 1998     

Influence of spacer groups on grafting ability,curing ability,and film properties of water-based radiation curable latexes

Film-forming polystyrene/poly(n-butyl acrylate-co-glycidyl methacrylate) [PS/P(BA-co-GMA)] core–shell latex particles were prepared via a two-stage emulsion polymerization procedure using a PS latex seed. A delayed addition of GMA was used to locate the functional epoxy groups near the surface of the particles. The surface-bound epoxy groups were used as grafting sites for unsaturated carboxyl functional monomers having the unsaturated groups and the carboxylic group separated by 1, 5, or 10 oxyethylene units. Grafting and curing characteristics and film properties after irradiation were investigated as a function of the number of oxyethylene units. A BA-GMA [P(BA-co-GMA)] copolymer was used as a model system for the core–shell latex particles for quantification of the grafting reactions. The grafting was demonstrated by FTIR and ¹H-NMR spectroscopy. The effects of crosslinking was studied by thermal mechanical analysis and dynamical mechanical analysis. Differential photocalorimetry was also used for evaluation of the curing ability. It was demonstrated that the reagent having five oxyethylene units in the spacer group was grafted onto the polymer backbones to a larger extent than the other two reagents, and a more thoroughly cured film was obtained upon irradiation. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 897–906, 1998     

Synthesis and properties of unsaturated polyoxyethylene and its graft copolymers with styrene

The unsaturated polyoxyethylene (PEO) was synthesized by copolymerization of ethylene oxide with allyl glycidyl ether in toluene using bimetallic-oxo-alkoxide as a catalyst. The effects of polymerization conditions on conversion and intrinsic viscosity of the copolymer were studied. The unsaturated copolymer was characterized with infrared spectra, ¹H NMR, and wide-angle X-ray diffraction. The relationship between crystallinity of the copolymers and conductivity of their LiClO₄ complexes were investigated. The copolymer with ∼ 65 wt % PEO content exhibits a room temperature conductivity of 1 × 10⁻⁴ S cm⁻¹ at a molar ratio of EO/Li = 20. The unsaturated PEO was graft-copolymerized with styrene using 2,2′-azobis(isobutyronitrile) as initiator in toluene, with grafting efficiency ∼ 50%. The purified graft copolymer was characterized with infrared spectra, ¹H NMR, and wide-angle X-ray diffraction, and was shown to have good emulsifying properties and a phase-transfer catalytic property. LiClO₄ complex of the graft copolymer with 70 wt % PEO content exhibits a room temperature conductivity approaching 1 × 10⁻⁴ S cm⁻¹ at molar ratio of EO/Li = 20/1. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2417–2425, 1998     

乳液聚合接枝效果的探讨

由于仅用接枝率表征不同粒径基础胶乳的乳液接枝效果有局限性,经定义和推导,提出了面积接枝率关系式。并以乳液聚合制备ＡＡＳ树脂为例,对关系式进行验证。结果表明Ｇａ关系式可以全面地评价接枝效果,并可对乳液接枝聚合实进行预测。     

马来酸酐与甲基丙烯酸甲酯混合改性SBS胶粘剂的研制

本文选用马来酸酐与甲基丙烯酸甲酯混合单体,对ＳＢＳ进行溶液接枝共聚,并配合增粘树脂制备了对聚烯轻薄膜有良好粘接性能的胶粘剂。探讨了引发剂用量、反应温度、反应时间、增粘树脂对胶液性能的影响．     

丙烯酸类高吸水性树脂的合成及性能研究

研究了以水为介质,丙烯酸——淀粉接枝共聚合成高吸水性树脂,讨论了交联剂用量、中和度、丙烯酸浓度、引发剂用量、淀粉用量等对树脂的吸水能力、保水能力、吸水速率、凝胶强度的影响。     

丙烯酸改性水性聚氨酯乳液的合成及表征

采用接枝法制备丙烯酸改性水性聚氨酯(PUA)乳液,研究了二羟甲基丙酸(DMPA)、甲基丙烯酸甲酯(MMA)对PUA乳液吸水率、黏度及涂膜硬度的影响,并用红外分析法表征了水性PUA与水性PU和共混型PU/PA在分子结构上的差异。     

光聚合壳聚糖基絮凝剂及其絮凝性能

壳聚糖是一种天然碱性氨基多糖物质,其分子上分布着许多功能性的氨基和羟基,使其能成为潜在的高效絮凝剂。采用紫外光引发壳聚糖(CS)与丙烯酰胺(AM)、丙烯酰氧乙基三甲基氯化铵(DAC)接枝共聚制备P(CS-AD)絮凝剂,探讨了单体浓度、壳聚糖百分比、阳离子度、光引发剂浓度、光照时间对P(CS-AD)的特性粘度的影响,确定了合成的优化条件:单体浓度为30%~40%、壳聚糖百分比为10%~20%、阳离子度为30%~40%、光引发剂浓度为0.3%~0.5%、光照时间为120min,优化后的制备的P(CS-AD)的特性粘度最高可达1 865mg/L。同时,采用红外光谱、扫描电镜(SEM)、差热热重分析(TG-DTA)对其进行表征。采用模拟硅藻土水样验证其絮凝性能,试验结果表明:P(CS-AD)的絮凝性能显著优于市售聚丙烯酰胺(PAM)。     

聚氨酯／丙烯酸酯复合弹性乳液的研究

通过粒径、热性能和力学性能的测定,研究了非共聚型及共聚型水性聚氨酯/丙烯酸酯(PUA)弹性树脂的结构和性能。发现PUA具有核/壳结构特征;共聚型PUA比非共聚型PUA具有更好的聚丙烯酸酯(PA)、聚氨酯(PU)之间的混溶性;PA复合PU后,不仅提高了乳液的固含量,而且体现出较好的弹性,适合于弹性建筑涂料等方面的应用。