Solid-phase grafting of glycidyl methacrylate onto polypropylene

Free-radical grafting of glycidyl methacrylate (GMA) onto polypropylene (PP) powder was studied in a batch mixer. The reaction temperature was below the melting point of PP so that PP was modified in the solid phase. The graft yield of GMA obtained under various experimental conditions allowed for a good appreciation of the effects of chemical parameters (the concentration of monomer, initiator, and interfacial agent) and those of processing parameters (reaction time and temperature). Toluene was used as an interfacial agent to etch the surface of PP powder to provide more sites for reaction. Quantitative determination of the graft level was performed by wet chemical methods. The results showed that the solid-phase grafting could take place over a temperature range of 100–140°C in the initiation of benzoyl peroxide (BPO). The ultimate GMA grafting level achieved was higher than that obtained in the melt state with dicumyl peroxide (DCPO) as a radical initiator. The grafting of GMA affected the crystalline morphology of PP and speeded up the crystallization process. The energy of activation and initial decomposition temperature of grafted samples were higher than those of ungrafted PP. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 1905–1912, 1997     

Polypropylene–phenol formaldehyde‐based compatibilizers. I. Preparation and characterization

This work deals with the synthesis of a new type of compatibilizer suitable for blends or alloys of polypropylene and engineering polymers having aromatic residues or functionality complimentary to hydroxyl. Polypropylene–phenol formaldehyde graft copolymers from thermoplastic phenol formaldehyde (PF) resins and functionalized polypropylene (f‐PP) were synthesized by reactive extrusion. The content of PF in the graft copolymer was determined by reaction variables like type and density of functionality on PP, molecular weight of PF, and viscosity ratio of f‐PP and PF. The results showed that the viscosity ratio is of primary importance for such reactive processing. Also, type and concentration of the functional groups were important variables. The glycidyl methacrylate functionality resulted in higher conversions than did PP‐g‐maleic anhydride within the available reaction times. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 347–354, 2000     

Selective plasma‐induced grafting of polystyrene onto polyolefin blends

Plasma pretreatment has been used to generate reactive radicals and oxygenated groups on polymer surfaces for graft polymerization. The polymer substrates studied were composed of a polypropylene–polyethylene (PP–PE) copolymer, which was predominantly PP, and also contained blended ethylene–propylene rubber (EPR) as either about 15 or about 60 mol %. A pure PP substrate was also studied for comparison. The grafted polymer was polystyrene (PS). Raman microspectroscopic 2‐dimensional mapping was used to elucidate the role of crystallinity and EPR in the plasma treatment and graft polymerization process. It was found that the plasma pretreatment favored the EPR component of the substrate and the graft yield was related to the EPR content. Crystallinity seemed to have a much less significant effect on the grafting reaction. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1643–1652, 2003     

Surface modification by continuous graft copolymerization. II. Photoinitiated graft copolymerization onto polypropylene film surface

A method for photochemically induced graft copolymerization of acrylamide (AM) onto polypropylene (PP) film surface by a continuous presoaking process under nitrogen atmosphere has been developed. After removal of homopolymer formed, ESCA, UV spectroscopy, contact angle, and adhesion measurements confirmed a photografted layer on the surface of the PP film. The results from spectral analysis and surface properties measurements were consistent. The best grafting yield was obtained for 7–10 s irradiation time. Stabilizing additives in the PP film had no evident effect on the photografting. Benzophenone was an efficient photoinitiator for photografting of PP film with AM. An AM concentration of 0.5–1.3M in the presoaking solution was appropriate in the present case. Acetone was the best solvent among the three alifatic ketones tested (acetone, methylethylketone, and methylpropylketone).     

Graft copolymerization studies. III. Methyl methacrylate onto polypropylene and polyethylene terephthalate

The tert‐butoxy radical‐facilitated grafting of methyl methacrylate (MMA) onto commercial polypropylene (PP) pellets and fiber was investigated in heterogeneous conditions similar to practical systems. Free‐radical grafting of several other monomers onto PP fiber was also investigated. Also, preliminary data from the grafting of MMA onto poly(ethylene terephthalate) pellets is presented. The PP‐graft‐PMMA residues were detected by solid‐state ¹³C‐NMR and photoacoustic IR spectroscopy. There was a good correlation between the degree of grafting (DG) determined from these spectroscopic techniques and the results from gravimetric methods. A maximum grafting efficiency of over 50% was found, whereas DG (20%) remained constant at various PP pellet, initiator, and monomer concentrations. However, at relatively low PP fiber concentrations, the DG was 27%; the increase was most likely due to the greater surface area of the fiber. There was also a reduction in DG (14%) at relatively low initiator concentrations. The reaction conditions were altered to favor grafting by the addition of more polymer substrate. When the ratio of tert‐butoxy radicals to PP was decreased, more of the substrate remained unmodified, and empirical calculations showed the formation of grafts with up to 40 monomer units. At high initiator concentrations, calculations showed that the graft residues were 1–2 units long. Therefore, variation of the polymer, initiator, and monomer concentrations was shown to have a significant effect on grafting. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 898–915, 2002     

Influence of an annealing treatment on the solid‐state grafting of styrene onto spherical isotactic polypropylene granules

The main place of solid‐state graft polymerization in polypropylene (PP) granules has been believed to be the amorphous region of PP. In this work, the solid‐phase morphology of nascent spherical PP (N‐PP) granules was found to be markedly changed by an annealing treatment. The crystallinity of PP granules was almost doubled after annealing at 150°C for 12 h, whereas the porosity of the granules was unchanged. Solid‐state grafting polymerizations of styrene initiated by tert‐butyl perbenzoate in both N‐PP and annealed polypropylene (A‐PP) granules were compared under different reaction conditions. The formation of gel in the product could be completely depressed at a low concentration of the initiator when A‐PP granules were used as the matrix and graft‐polymerized at 120°C. Both the introduction of styrene and the annealing treatment of the PP granules led to a depression of polymer degradation in the process of the grafting reaction. However, using A‐PP as the matrix caused an increase in the grafting degree at a relatively high concentration of the initiator. A reduction in the amorphous phase in the PP granules was thought to be the main reason for the effects of the annealing treatment on the structure of the graft polymerization products. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of premade and in situ compatibilizers in polypropylene/ethylene–propylene–diene terpolymer thermoplastic elastomeric olefins and thermoplastic vulcanizates

During dynamic vulcanization of polypropylene (PP)/ethylene–propylene–diene terpolymer (EPDM) blends with dicumyl peroxide/triallyl cyanurate, there is a possibility of the generation of in situ graft links at the interface. Three potential compatibilizers (PP‐grafted EPDM, styrene–ethylenebutylene–styrene, and trans‐polyoctenamer) for PP/EPDM blends were first investigated as references to obtain a quantified insight into the effects to be expected from in situ graft links. Only the first compatibilizer showed some compatibilizing action in straight, unvulcanized blends, as evidenced by a slight increase in the tensile strength of the blend and a somewhat smaller EPDM particle size within the PP matrix. Also, dynamic mechanical testing, in particular, the glass‐transition temperatures of the PP and EPDM components, showed some signs of compatibilization. The PP‐grafted EPDM resembled most closely the structures of PP and EPDM. In the spectra obtained with high temperature, solid‐state NMR, there was an indication that PP–EPDM graft links were generated during the dynamic vulcanization process that still remained after the extraction of the free PP phase from the thermoplastic vulcanizate film. NMR relaxation experiments gave further evidence for the graft links formed in situ. In all cases, only qualitative indications could be achieved because of the extremely low number of graft links formed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3877–3888, 2006     

Comparison of maleic anhydride grafting onto powder and granular polypropylene in the melt by reactive extrusion

The grafting of powder and granular polypropylene (PP) with maleic anhydride (MA) was investigated in a reactive extrusion process with dicumyl peroxide (DCP) as an initiator. The effects of the MA and DCP contents in the feed on grafting were investigated. Under the experimental conditions applied in this study, the grafted monomer unit content was varied from 0.023 to 0.5%. The MA grafting efficiency of powder PP was higher than that obtained for the granular form of PP. In general, the grafting degree first increased with the MA or DCP content in the feed, then reached a maximum value, and finally decreased because of several possible alternative reactions during the grafting. The grafting of powder PP was more successful because of better initial mixing and less diffusional resistance during the grafting. An increase in the MA content in the feed caused significant reductions in the melt‐flow index of the graft copolymers. The results obtained with Fourier transform infrared, differential scanning calorimetry, and X‐ray powder diffraction analyses indicated that the structure, macrotacticity, crystallinity, crystallization, and thermal behavior of PP changed with grafting and depended on the grafting degree. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3675–3684, 2004     

Synthesis of polypropylene graft copolymers from a hydroxyl‐groups‐containing polypropylene precursor via atom‐transfer radical polymerization

Isotactic polypropylene graft copolymers, isotactic[polypropylene‐graft‐poly(methyl methacrylate)] (i‐PP‐g‐PMMA) and isotactic[polypropylene‐graft‐polystyrene] (i‐PP‐g‐PS), were prepared by atom‐transfer radical polymerization (ATRP) using a 2‐bromopropionic ester macro‐initiator from functional polypropylene‐containing hydroxyl groups. This kind of functionalized propylene can be obtained by copolymerization of propylene and borane monomer using isospecific MgCl₂‐supported TiCl₄ as catalyst. Both the graft density and the molecular weights of i‐PP‐based graft copolymers were controlled by changing the hydroxyl group contents of functionalized polypropylene and the amount of monomer used in the grafting reaction. The effect of i‐PP‐g‐PS graft copolymer on PP‐PS blends and that of i‐PP‐g‐PMMA graft copolymer on PP‐PMMA blends were studied by scanning electron microscopy. Copyright © 2006 Society of Chemical Industry     

Preparation of epoxy functionalized PP with unique structure and its post‐ring open reaction

This article discusses a convenient chemical approach named in situ chlorination graft copolymerization (ISCGC) to prepare epoxy functionalized isotactic polypropylene (iPP) with a unique structure. This method was carried out in the gas‐solid state, and chlorine was used as radical initiator as well as terminate agent. The effect of influence factors on the structure of the functionalized PP was investigated, and it was determined by levels of grafted GMA moieties. The results showed that PP modified with GMA could obtain higher grafting level. Crystallinity and mechanical properties of the functionalized PP were also investigated. For the purpose of researching the reactivity of epoxy groups located at the grafted side chains, trichloroacetic acid and hydroxyl‐terminated butadiene–acrylonitrile rubber (HTBN) were used as models to explore the ring open reaction of the epoxy groups of the functionalized PP. The structure and property of the modified PP that has undergone post‐ring open reaction was characterized by FTIR, dynamic property analysis. The results indicated that epoxy groups of the graft side chains have successfully undergone ring open reaction in the presence of carbonyl and hydroxyl groups. Additionally, the compatibilization of PP with HTBN is enhanced after PP was modified by GMA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Blends of i‐PP and SBS. II. Influence of in situ compatibilization on the mechanical properties

This article concerns the in situ compatibilization of immiscible isotatic polypropylene/styrene–butadiene–styrene triblock copolymer blends (i‐PP/SBS) by use of a reactive mixture. For this purpose, maleated PP (PP–MAH) and SBS (SBS–MAH) were used as functionalized polymers and 4,4′‐diaminediphenylmethane was used as a coupling agent between maleated polymers, resulting in a graft copolymer. Binary blends of i‐PP/SBS, nonreactive ternary blends of i‐PP/PP–MAH/SBS, and reactive ternary blends of i‐PP/PP–MAH/SBS–MAH with varying diamine/anhydride molar ratios were prepared. The mechanical properties of the blends were determined by tensile and impact‐resistance tests. The optimum improvement in the mechanical properties was found when the diamine/anhydride molar ratio in the ternary reactive blends was 0.5/1. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 516–522, 2003     

Studies on grafting of acrylic acid onto polypropylene melt‐blown nonwovens induced by electron‐beam preirradiation

We report the graft copolymerization of acrylic acid onto the polypropylene (PP) melt‐blown nonwovens induced by electron beam (EB) preirradiation in this article. The occurrence of the graft copolymerization was confirmed by means of XPS, FTIR, and SEM. The effects of preirradiation dose, monomer concentration, bath ratio, reaction time, and temperature on the graft ratio were investigated. The water conservation, water absorption rate, and K⁺ exchange capacity were also determined on the grafted PP melt‐blown nonwovens, which showed that EB preirradiation‐induced grafting was an effective way to improve the hydrophicility of PP melt‐blown nonwovens. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4971–4977, 2006     

超临界二氧化碳协助双单体接枝聚丙烯

采用氧化法制备氢过氧化聚丙烯(HPP),然后用超临界二氧化碳(SC CO2)将单体苯乙烯(St)和季戊四醇三丙烯酸酯(PETA)溶胀到HPP颗粒内,再通过热引发将单体接枝到HPP上.考察了溶胀温度、压力、接枝反应温度、时间及单体用量对产物接枝率与单体接枝效率的影响,并采用红外光谱(FT-IR)、热重-差热分析(TG-DTA)、扫描电子显微镜(SEM)对接枝共聚物进行了表征.结果表明,合适的反应条件为30 g聚丙烯和0.5 g过氧化苯甲酰(BP0)在80℃反应2 h生成HPP,HPP与9 g苯乙烯(St)和季戊四醇三丙烯酸酯(PETA)的混合物(St与PETA物质的量之比为1:1)在37℃,8.5 MPa的超临界CO2中溶胀3 h,再在80℃常压下反应8 h,得到双单体接枝聚丙烯,接枝率达到28%,接枝效率大于90%,且PETA和St同时接枝到了PP分子链上,聚合物的耐热性增强.     

聚丙烯固相接枝技术的研究进展

综述了聚丙烯(PP)固相接枝技术的最新发展,重点介绍了PP固相接枝的原理,讨论了接枝单体．接枝基体、引发剂、溶剂．催化剂．反应温度．反应时间对接枝率的影响。PP固相接枝技术在PP复合材料与共混合金中具有良好的使用效果和广阔的应用前景。     

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.     

Grafting of cyclodextrins onto polypropylene nonwoven fabrics for the manufacture of reactive filters. I. Synthesis parameters

A novel method for the preparation of immobilized α‐, β‐, and γ‐cyclodextrins (α‐, β‐, or γ‐CD) on polypropylene (PP) nonwoven fabrics is presented. These new materials were prepared by graft‐polymerization of glycidyl methacrylate (GMA) onto PP filters using the electron‐beam technique, followed by coupling of α‐, β‐, and γ‐CDs with the epoxide group. Optimization of various reaction parameters such as time, temperature, irradiation dose, monomer, and CD concentration was carried out. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2118–2125, 2000     

Ammonia adsorption behavior of polypropylene nonwoven fabric grafted with acrylic acid

An attempt was made to synthesize an adsorbent by the photoinduced grafting of acrylic acid (AA) onto polypropylene nonwoven fabrics using benzophenone (BP) as a photosensitizer in a CH₃OH/H₂O medium. As the BP concentration was increased, the graft yield was increased up to a specific value and then decreased, and the effect of AA concentration showed the same tendency. It was also found that the graft yield increased with the reaction time and temperature. The amounts of ammonia adsorbed onto polypropylene nonwoven fabrics grafted with AA (PP‐g‐AA) were dependent on the graft yield, adsorption time, and ammonia gas pressure. The adsorption capacity of PP‐g‐AA was 5.86 mmol/g at the graft yield of 116.6%, which was much higher than that of active carbon or silica gel. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 295–301, 2002; DOI 10.1002/app.10328     

Polypropylene/clay nanocomposites: An innovative one‐pot process

This work discloses a novel one‐pot preparation method of polypropylene (PP)/clay nanocomposites with high degree of clay delamination and improved thermal, mechanical and rheological properties. The in situ simultaneous synthesis of carboxylate clay from native clay and ionomer of PP‐graft maleic anhydride (PP‐g‐MA) through trihydrate sodium acetate addition, combined with water injection in the extrusion process, appears to be a valuable alternative to the use of organoclay for producing PP/PP‐g‐MA/clay nanocomposites. The influence of PP‐g‐MA graft content, and of its ionomer form, onto the clay dispersion has been especially investigated. PP‐g‐MA of low graft content is compared to a home‐made highly grafted PP‐g‐MA synthesized in the presence of N‐bromosuccinimide (NBS). The nanocomposites prepared by combining the use of NBS‐mediated PP‐g‐MA, trihydrate sodium acetate and water injection exhibit the highest clay dispersion. Thermal, rheological, and mechanical properties of the nanocomposites have been measured. POLYM. COMPOS., 36:644–650, 2015. © 2014 Society of Plastics Engineers     

Development and physicochemical characterization of modified polymeric surfaces for bacterial adhesion

Radiation‐induced graft polymerization was used to modify the surfaces of polypropylene (PP) sheets for bacterial adhesion. For the experiments, two monomers were mixed: the quaternary ammonium salt (QAS) [2‐(methacryloyloxy)ethyl]trimethylammonium chloride and acrylic acid (AAc). The PP sheets were activated by electron‐beam radiation before the grafting reaction. Different AAc/QAS comonomer mixture ratios (50 : 10, 40 : 20, 30 : 30, 20 : 40, and 10 : 50) were used to determine the degree of grafting and to make the PP surfaces hydrophilic. The graft level increased with an increase in the percentage of AAc in the comonomer mixtures. Synergism was investigated during graft polymerization to quantify the poly(acrylic acid) and poly{[2‐(methacryloyloxy)ethyl]trimethylammonium chloride} graft fractions in the resulting graft copolymers. An approximation of the graft fractions was made with an analytical technique based on acid–base volumetric titration. The wettability of the modified surfaces was determined by the measurement of the water contact angles. The surfaces prepared with higher percentages of QAS in the comonomer mixtures had lower contact angles than those prepared with lower percentages of QAS. The presence of oxygen and nitrogen on the modified PP surfaces was investigated with X‐ray photoelectron spectroscopy. Structural changes in unmodified and modified PP were characterized with differential scanning calorimetry. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Kinetic studies and process analysis of the reactive compatibilization of nylon 6/polypropylene blends

This article describes a study on the reactive compatibilization of nylon 6 (N6) and polypropylene (PP) blends through a functionalized PP. A graft copolymer was formed in-situ by reacting an acid modified PP with N6 during blend compounding. The compatibilization reactions are studied in detail. Kinetics were estimated by means of experiments in a batch mixer. Three time constants were estimated, corresponding to (a) reactions, (b) melting of polymers, and (c) melt mixing. The effects of temperature and rotor speed on the reaction kinetics were also measured. There was a substantial increase in initial reaction rate, as the rotor speed was increased. Increasing the temperature did not significantly affect the reaction rate. Process parameters important for such a reactive compatibilization process were identified by statistically designed experiments in a co-roatating intermeshing twin-screw extruder. Screw speed, presence of venting, and sequence of feeding were shown to have a noticeable effect on the reactive compatibilization process during continuous compounding.