Metalization of polypropylene. I. Synthesis and melt free‐radical grafting of novel maleimides and methacrylates containing chelating moieties

Several chelating monomers with methacrylate and maleimide residues as polymerizable groups and diketone and aspartic acid residues as metal‐bonding groups were synthesized. A long‐chain aliphatic spacer was introduced to increase the solubility of the monomers in the polymer melt and to enhance the compatibility of grafted side chains and homopolymers with polypropylene (PP). PP was functionalized by melt free‐radical grafting, and some properties of the modified polymer were investigated. The grafting of a chelating methacrylic ester by injection molding afforded grafting yields of 30–50%. A comparison with products obtained by the grafting of commercially available acetoacetoxy methyl methacrylate showed the beneficial effect of the aliphatic spacer with respect to the grafting yield as well as the tensile strength and flexural modulus. The grafting of an aspartic acid based maleimide in an extruder afforded grafting yields of 80–95% and a significant increase in the surface wettability, as shown by contact‐angle measurements. A comparative study using samples obtained by the grafting of maleimidobenzoic acid indicated that the homogeneity‐increasing effect of the spacer was neutralized by the detrimental effect of the dicarboxylic chelating group. Nevertheless, the results showed that the maleimides were well suited for grafting by reactive extrusion because of their low susceptibility to homopolymerization under melt‐processing conditions. Preliminary metalization experiments showed the feasibility of plating without the use of corrosive etchants. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3400–3413, 2003     

Styrene-assisted melt free radical grafting of glycidyl methacrylate onto polypropylene

The free radical grafting reactivity of glycidyl methacrylate (GMA) onto polypropylene (PP) in the molten state is low. This article shows that adding styrene as a second monomer (or comonomer) increases both the rate and yield of GMA grafting and reduces PP chain scission. The proposed mechanism is that when St is added to the PP/GMA/peroxide grafting system, St reacts first with PP macroradicals to form stable styryl macroradicals. These latter then react (or copolymerize) with GMA to form GMA grafted PP. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1053–1063, 1998     

Polymerization of vinyl monomers in the presence of silica having surface functional groups

The surface of silica was modified by mercaptopropyl, chloropropyl, aminopropyl, and methacryloxypropyl groups by the treatment of silica with the corresponding silane coupling agents, and the effects of functional groups on the surface on the polymerization of vinyl monomers initiated by benzoyl peroxide or 2,2-azobisisobutyronitrile were investigated. Although the rate of the polymerization of vinyl monomers in the presence of silica was almost equal to that in the absence of silica, a part of polymer formed was grafted onto silica surface. The polymerization was considerably retarded in the presence of these functionalized silicas and the corresponding polymers were effectively grafted onto the surface. The molecular weight of ungrafted polymer formed in the presence of the functionalized silica was lower than that formed in the presence of unmodified silica. This indicates that the chain transfer reaction of growing polymer radical to functionalized silica surface forms radicals on the surface, which then couples with growing polymer radical and/or reinitiates the polymerization to give rise to the grafting of polymers onto the surface. In the case of silica having methacryloxypropyl groups, the grafting based on the copolymerization of vinyl monomer with the surface methacryloxypropyl groups was considered to successfully proceed.     

Compositions à base de polypropylène possedant une résistance au choc améliorée

Polypropylene-homopolymer (PP), modified with SBR and BS-latex, has been investigated. The best results were obtained using PP-powder, mixed with BS-latex with continuous stirring. In this case, the process is significantly facilitated because of the retained dispersity of the base product. Three-component compositions, comprising PP-inorganic filler-other polymer, have been tested. It was found that impact resistance increased with content of polymeric modifier. Better results were obtained with BS-latex. In this case, the inorganic filler was treated with latex. This material possessed the initial dispersity so that the composition preparation was facilitated.     

Solid‐state modification of polypropylene (PP): grafting of styrene on atactic PP

Grafting of unsaturated vinyl monomers onto polypropylene (PP) is a convenient route to develop new polymeric materials with synergistic properties. Particular attention must be paid to the formation of graft copolymer relative to the formation of homopolymer, since the final properties are dependent both on the dispersion of the new polymer into the iPP matrix, which is controlled by the degree of grafting, as well as on the chemical nature of the in‐situ formed polymer chains. In the present work the grafting reaction of styrene on atactic PP (aPP), considered as good model system for the more studied solid‐state modification of isotactic PP (iPP), has been investigated in the presence of two different radical initiators in order to get a first insight into the grafting reactions onto PP. Several grafting reactions were carried out by changing the chemical compositions of the starting polymerization mixture, whose homogeneity was accurately investigated by Raman spectroscopy. Infrared‐spectroscopy (FT‐IR) was used for qualitative and quantitative characterization of the reaction product. A quantitative separation procedure, based on the concept of selective solvent extraction, has been established which enables the determination of the grafting efficiency (Φ) as well as the exact chemical composition of the final product. Finally, all products were characterized by means of Differential Scanning Calorimetry (DSC) in order to study their thermal behaviour.     

甲基丙烯酸缩水甘油酯/苯乙烯固相接枝聚丙烯

以苯乙烯(St)为共单体，过氧化苯甲酰(BPO)为引发剂，采用固相接枝反应将甲基丙烯酸缩水甘油酯(GMA)接枝到聚丙烯(PP)大分子链上。研究了反应时间、单体用量、引发剂用量等因素对接枝率的影响。采用凝胶渗透色谱(GPE)测定了PP和接枝物PP-g-(GMA-St)的分子量和分子量分布。结果 表明固相接枝PP反应条件为[GMA／[St]=2，反应3．5h，加入GMA 10份，BPO 5份。St的加入有助于GMA与PP的接枝，同时在一定程度上抑制了PP的降解。     

熔体自由基反应法制备聚丙烯/碳纳米管复合材料

以2,5-二甲基-2,5-双（叔丁基过氧基）己烷（DHBP）在聚丙烯体系中引发形成自由基,以二硫化四甲基秋兰姆（TMTD）调控自由基反应,通过熔融共混一步法制备了共价接枝的聚丙烯/碳纳米管（PP/CNTs）复合材料。 通过拉曼光谱和透射电子显微镜证明发生了共价接枝反应,并研究了PP/CNTs的结晶性能、热性能与力学性能。 结果表明,发生共价接枝的PP/CNTs与未接枝的PP/CNTs及PP相比,其结晶温度分别提高了2.6和12.0 ℃,热分解温度T5%分别提高了6.4和34.8 ℃,其拉伸强度和拉伸模量略有提高,冲击强度分别提高了56.7%和58.1%。     

Graft-copolymerization of styrene on polypropylene in the solid phase

The graft-copolymerization of styrene on PP in the solid phase has been studied under various reaction conditions using a radical initiator. Polymerization kinetics were investigated by DSC experiments and reactions in glass ampoules. The conversion rate and grafting efficiency of styrene appeared to be strongly influenced by the presence of the PP matrix and the styrene/PP ratio. From reactions in a lab scale reactor the concentrations of styrene and initiator, the dosing rate and the temperature were investigated to be critical parameters determining the grafting efficiency and the average length and number of grafts. The phenomena observed were explained by describing the process in relative rates of diffusion and polymerization, including swelling of the polymer by styrene monomer and diffusion limitations (Trommsdorff effect).     

1,6-己二醇二丙烯酸酯和苯乙烯多单体熔融接枝制备长支链聚丙烯研究

采用哈克转矩流变仪制备了1,6-己二醇二丙烯酸酯(HDDA)和苯乙烯(St)多单体熔融接枝聚丙烯(PP)体系.红外测试结果表明St的加入能够促进HDDA接枝到PP主链,提高接枝率.动态流变行为研究结果也表明采用多单体熔融接枝PP更有利于体系在熔融接枝中生成长支链(LCB).随着St单体添加量的增加,HDDA的接枝率增大...     

马来酸酐-苯乙烯熔融接枝聚丙烯的影响因素及其性能研究

用单螺杆挤出机制备了马来酸酐 (MAH) 苯乙烯 (St)对聚丙烯 (PP)的多组分单体自由基熔融接枝体系 .研究证实了当两种单体物质的量比约为 1∶1时 ,接枝物的接枝率最高 ,而熔体流动速率 (MFR)最大 .对反应体系影响因素的研究表明单体用量和引发剂用量对不同单体用量比的系列接枝物的接枝率会产生不同的影响 ;另外 ,单体用量增加 ,接枝物的MFR减小 ,过氧化二异丙苯 (DCP)用量增加 ,接枝物的MFR增加 .对多单体熔融接枝聚丙烯PP g (MAH co St)的力学性能研究发现 ,选用合适的单体用量比、单体用量和DCP用量时 ,所制备的接枝物可具有与纯PP相当或更佳的力学性能     

Formation of Polymer Nanolayers with Special Properties at Polymer Surfaces

A principal possibility of the utilization of polymer peroxides for the modification of polymer surfaces that provides an immobilization of the tailored quantity of peroxide groups at them has been established. The processes of polymer surface activation with following “grafting from” or “grafting to” utilizing immobilized peroxide groups has been studied using a FTIR-ATR spectroscopy, ellipsometry and measurements of contact angles. The proposed technique of polymer surface activation is based on the universal ability of carbon chain polymer to participate the free radical reactions.     

聚丙烯熔融接枝中共单体的作用机理

聚丙烯树脂是当今最具发展前途的热塑性高分子材料之一,在聚烯烃与工程塑料,如与聚酰胺或聚酯的共混合金中,聚丙烯接枝共聚物则广泛地被用为相容剂．此外,聚丙烯接枝共聚物还广泛应用于极性添加物等,用于改善制品的表面喷涂性能．聚丙烯接枝共聚物是通过自由基熔融接...     

Emulsion Polymerization of Vinyl Monomers in Presence of Chitosan with Peroxide Groups

Peroxychitosans with ditertiary peroxide fragments were synthesized via radical reactions of chitosan and 5-tert-butylperoxy-5-methyl-l-hexen-3-in. They can be used as macroinitiators and coemulsifiers for emulsion polymerization of vinyl monomers. It is shown that peroxychitosans are grafted to the surface of latex particles and impart antibacterial properties to emulsion polymer.     

Monitoring polyolefin modification along the axis of a twin‐screw extruder. II. Maleic anhydride grafting

The physico‐chemical phenomena developing along the screw axis of a twin‐screw extruder during the grafting of maleic anhydride (MA) onto polyolefins [polyethylene (PE), ethylene–propylene rubber (EPM), and polypropylene (PP)] were investigated. For this purpose, sampling devices located along the extruder barrel were used to collect polymer samples that were subsequently characterized to follow the degrees of grafting and crosslinking or degradation. A similar evolution of MA grafting was observed regardless of the polyolefin type or MA and peroxide concentration when grafting was performed under identical conditions, that is, the same peroxide type and set temperature. A correlation between the MA grafting and the calculated peroxide decomposition was established. Chemical reactions occurred along the extruder axis until the peroxide was fully converted. More detailed quantitative measurements of the peroxide decomposition and MA grafting would allow the development of accurate process models. The final MA content depended on the polyolefin composition (PE > EPM ≫ PP). As expected for PE, crosslinking occurred in addition to grafting, but after a certain residence time, the PE network degraded. The PP viscosity reduction after MA grafting was due to the conversion of tertiary PP radicals into primary PP radicals after grafting. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3919–3932, 2000     

Reactive processing of polymers: Effect of bifunctional and tri-functional comonomers on melt grafting of glycidyl methacrylate onto polypropylene

Two reactive comonomers, divinyl benzene (DVB) and trimethylolpropane triacrylate (TRIS), were evaluated for their role in effecting the melt free radical grafting reaction of the monomer glycidyl methacrylate (GMA) onto polypropylene (PP). The characteristics of the GMA-grafting systems in the presence and absence of DVB or TRIS were examined and compared in terms of the yield of the grafting reaction and the extent of the main side reactions, namely homopolymerisation of GMA (poly-GMA) and polymer degradation, using different chemical compositions of the reactive systems and processing conditions. In the absence of the comonomers, i.e. in a conventional system, high initiator concentrations of peroxides were typically required to achieve the highest possible GMA grafting levels which were found to be generally low. Concomitantly, both poly-GMA and degradation of the polymer by chain scission takes place with increasing initiator amounts. On the other hand, the presence of a small amount of the comonomers, DVB or Tris, in the GMA-grafting system, was shown to bring about a significant increase in the grafting level paralleled by a large reduction in poly-GMA and PP degradation. In the presence of these highly reactive comonomers, the optimum grafting system requires a much lower concentration of the peroxide initiator and, consequently, would lead to the much lower degree of polymer degradation observed in these systems. The differences in the effects of the presence of DVB and that of TRIS in the grafting systems on the rate of the GMA-grafting and homopolymerisation reactions, and the extent of PP degradation (through melt flow changes), were compared and contrasted with a conventional GMA-grafting system.     

Preparation of rechargeable biocidal polypropylene by reactive extrusion with diallylamino triazine

Biocidal polypropylene (PP) was prepared by using a reactive extrusion process, in which PP was grafted with an N-halamine precursor, 2, 4-diamino-6-diallylamino-1, 3, 5-triazine (NDAM). After chlorination the grated PP was converted to biocidal halamine structures. Effects of monomer and initiator concentration on grafting yield, thermal properties, and biocidal efficacy were studied. The Fourier transformed spectroscopy (FTIR) results and nitrogen analysis confirmed the graft polymerization on PP backbone during the reactive extrusion. The results also indicated that at low monomer concentration, increase in initiator concentration led to increase in PP chain scission and decrease in mixing torque, or polymer chain length. As the monomer concentration increases, grafted monomer content in the products showed a steady increase, indicating more grafting copolymerization in the system. The halogenated products exhibited potent antimicrobial properties against Escherichia coli, and the antimicrobial properties were durable and regenerable.     

多单体熔融接枝聚丙烯的微相分离结构

用熔融接枝方法制备了一系列不同接枝率的GMA(甲基丙烯酸缩水甘油酯)/St(苯乙烯)多单体接枝聚丙烯[PP-g-(GMA-co-St)],基体聚丙烯包括均聚聚丙烯和共聚聚丙烯(乙烯的摩尔分数分别是6.0%,12%,33%).接枝聚丙烯经过分离提纯后,用四氧化钌(RuO₄)进行染色,然后用透射电子显微镜(TEM)观察其微观形态.发现在接枝聚丙烯中形成了长程有序的、球状的微相分离结构,这种在分子量和分子结构都是多分散体系中形成的微相分离结构尚未见报道.同时,研究了基体聚丙烯中乙烯链段的含量以及接枝率对于接枝聚丙烯微观形态的影响.     

Synthesis and characterization of anhydride-functional polycaprolactone

Polycaprolactone-graft-maleic anhydride (PCL-g-MA) copolymer was prepared by grafting maleic anhydride onto PCL in a batch mixer and in an extruder using dicumyl peroxide as the initiator. The graft content was determined with the volumetric method by converting the anhydride functions to acid groups and then titrating with ethanolic potassium hydroxide. The grafted polymer was extracted with xylene to remove any unreacted monomer before the estimation step. The effect of temperature and the various concentrations of the initiator and monomer used for the grafting reaction were investigated. The presence of residual initiator in the reaction product was checked using thin-layer chromatography. Molecular weight determination was carried out for the pure and grafted polymer using gel permeation chromatography to determine if chain scission was present. Results indicate that maleic anhydride is grafted onto PCL using free radical initiators. The grafting reaction was confirmed by FTIR and NMR techniques. FTIR spectra showed absorption bands around 1785 and 1858 cm⁻¹. NMR spectra gave signals for methine proton at 3.47 ppm. For a given peroxide level, a higher temperature or residence (reaction) time gave higher percentage of grafted MA. There was an optimum temperature and initiator concentration after which the percentage of MA grafted on PCL decreased. The number-average molecular weight, tensile strength, and the percent elongation of PCL-g-MA were comparable to those of PCL before grafting. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1139–1148, 1997     

Influence of polypropylene topological structure evolution during melt branching reactive processing on its melt performances

Gel‐free long‐chain‐branched polypropylene (LCBPP) was prepared by the melt radical branching reaction in the presence of peroxide initiator 2,5‐dimethyl‐2,5‐di(tert‐butylperoxy) hexane peroxide, zinc dimethyldithiocarbamate, and trimethylolpropane triacrylate in a torque rheometer. It could be inferred that recombination between PP chains via radical coupled reaction took place and trimethylolpropane triacrylate was grafted onto PP backbone by the torque curves and Fourier transformed infrared spectroscopy results. The presence of long chain branches (LCB) for modified PP was verified by the gel permeation chromatography measurements and vGP plots. On the other hand, it was found that the topological structure of PP chains transformed from linear form to a long star‐like shape during the reaction progress, and the topological structure was directly determined by the radical reaction time. The topological structure of PP would further impact its melt behaviour. After complete melting of raw PP, “sparse and long” LCBPP firstly generated which possessed high melt strength owing to the increasing entanglement of long branching chains. And at the time corresponding to the summit of reaction peak on the torque curve, the modified LCBPP possess the highest melt strength owing to its long star topological structure. While as reaction time was prolonged, severe degradation of the LCBPPs would take place under too long mixing time and “dense and short” branches generated due to the residual radicals, with a sharp decline in melt strength.     

Effect of comonomer sorption on radiation-induced copolymer grafting onto polyethylene and EVA films in the vapor phase

Radiation-induced copolymer grafting of acenaphthylene and maleic anhydride onto polyethylene or EVA film in the vapor phase was carried out and the effect of comonomer sorption on the grafting was studied. When polyethylene film was used as a backbone polymer, the sorption of the binary monomers during the grafting increased linearly as the grafting reaction proceeded. The marked increase was probably caused by the formation of a grafted layer. Particularly, the sorption of maleic anhydride was brought about by the existence of a grafted layer. In grafting onto EVA film, the content of maleic anhddride in the grafted copolymer increased with the increasing content of vinyl acetate in EVA. Continuous measurements of sorption of the comonomers onto EVA and grafted EVA films were carried out by use of an electrobalance. The distinctive feature of the sorption was that the equilibrium sorption of acenaphthylene or maleic anhydride onto the grafted EVA film increased and the diffusion constants for both comonomers decreased markedly with increasing percentage of graft. The copolymer grafting was explained from these results by assuming that the monomer molecules are supplied to the propagating chain ends mostly through a sorbed state on the polymer film.