An atomic-force microscopy study of the formation of vinyl and acryl graft polymers on a polypropylene film surface

Changes in the surface structure of oriented polypropylene (PP) films in conditions of graft copolymerization of acrylamide, vinylpyridine, and styrene on a PP surface preliminary subjected to plasmochemical activation in oxygen plasma or in a plasma-electrolyte solution system are investigated by atomic-force microscopy. It is shown that the latter soft conditions of activation are superior to the hard conditions with oxygen plasma in retaining original lamellar structure of oriented PP films. It is established that the subsequent graft copolymerization of the vinyl and acryl monomers on the PP surface yields amorphous phases of respective polymers.     

Synergistic mechanical effects of calcite micro- and nanoparticles and β-nucleation in polypropylene copolymers

For improving the understanding of mechanical effects in micro- and nanocomposites based on polypropylene (PP) copolymers and precipitated or ground calcium carbonate (PCC or GCC), especially in the presence of significant portions of the β-modification, a set of compounds based on different PP grades and fillers with optional β-nucleation prepared by melt compounding was studied. A synergistic improvement of mechanical properties by a combination of calcite particles and β-nucleation was found for two of the investigated high-impact base polymers up to 20 wt.% of nanofiller. While in the past research positive toughness effects were always limited to PP homopolymers with a moderate original impact strength and to particles of less than 100 nm average diameter, the toughness of high impact ethylene–propylene impact copolymers could be increased by more than 150% even at sub-zero temperatures where the failure behaviour is determined by the disperse elastomer phase.     

Amphiphilic Triblock Copolymers Containing Polypropylene as the Middle Block

The synthesis of stereoregular telechelic polypropylene (PP) and their use to access triblock amphiphilic copolymers with the PP block located in the center is described. The strategy consists of selectively copolymerizing propylene and a di-functional co-monomer (1,3-diisopropenylbenzene) to yield a α,ω-substituted polypropylene. Initiation of the copolymerization favors insertion of DIB over propylene; propagation steps favor insertion of propylene. Termination via a chain-transfer reaction yields the terminal unsaturation of the polymer. The telechelic polypropylene is then converted into α,ω-hydroxyl-terminated polypropylene and used as a macroinitiator for the synthesis of triblock copolymers. Water-soluble amphiphilic triblock polymers are also synthesized. The use of catalytic reactions simultaneously provides the stereocontrol of the polypropylene and high productivity (multiple chains of block copolymer per metal center).     

Synthesis and applications of olefin-contaning polymers

The problems of ionic coordination polymerization of higher α-olefins are summarized briefly. During the polymerization such monomers as 3-methyl-butene-1, vinylcyclohexane and others isomerize into unreactive isomers, and the rate of polymerization and final yield of polymer are sharply decreased as compared with the polymerization of lower olefins. The modification of polypropylene by ionic coordination copolymerization of propylene with higher α-olefins and polar monomers is considered. Significant modification of carbochain polymers may be obtained by the insertion of heteroatoms in the backbone. New possibilities for chemical “modification” of olefins by direct interaction with sulphur and the unusual aspects of the polymerization of olefin sulfides are also considered. The subsequent transformation of polyolefin sulfide gives polymers which have properties drastically differing from those of polyolefins. In conclusion, some new application areas are described.     

Exchange and free radical grafting reactions in reactive extrusion

The potential of two types of reactions for reactive extrusion was evaluated in our laboratory: exchange reactions of copolyesters and free radical grafting of monomers onto polyolefins. Specifically, the alcoholysis of ethylene and vinyl acetate copolymers, the transesterification of ethylene and alkyl acrylate copolymers (EAA) and the aminolysis of alkyl acrylate copolymers were investigated as the exchange reactions while the grafting of maleic anhydride (MA) onto polypropylene (PP) as the free radical reactions. The exchange reactions are very slow without catalysts. Tin derivatives, such as dibutyl tin dilaurate (DBTDL) and dibutyl tin oxide (DBTO), are good catalysts for the alcoholysis and the transesterification, but not for the aminolysis. For the latter, tautomeric compounds, such as 2-pyridone and 2-mercaptopyridone, are efficient. Comparative kinetic studies showed that, for all the three exchange reactions, the reacting medium (solution or the homogeneous melt) does not affect their reaction mechanisms nor their intrinsic rate constants. Additionally, mechanical mixing does not contribute to the overall reactions. As for the free radical grafting of MA, the presence of electron-donating monomers and styrene (ST) in particular was shown to be very effective in improving the grafting yield while minimising the degradation of PP. This was proven to be due to the formation of a charge transfer complex between MA and such a monomer.     

橡胶相具有交联结构的新型抗冲聚丙烯合金

利用具有"颗粒反应器技术(RGT)"特征的Ziegler-Natta催化剂进行丙烯多相共聚(丙烯均聚+乙烯/丙烯无规共聚),通过在乙丙共聚阶段引入双烯烃单体1,9-癸二烯,使乙丙共聚物在聚合的同时实现交联,制备了新型抗冲聚丙烯合金.聚合反应结果表明,1,9-癸二烯可参与乙丙共聚,同时对聚合反应速率和共聚物组成影响较小;1,9-癸二烯使乙丙共聚物发生支化/部分交联,合金聚合物的熔体流动速率在引入1,9-癸二烯后显著降低,且凝胶含量随1,9-癸二烯用量的增加而增大.形态研究结果表明,乙丙共聚物的交联显著降低了其在聚丙烯基体中的分散尺度,提高了分散均匀性,分散相粒径随支化/交联程度提高而减小.力学性能测试结果表明,乙丙共聚物的交联使合金聚合物在保持较高韧性的同时显著提升了刚性,有利于实现抗冲聚丙烯合金的刚韧平衡.     

A novel efficient Ti(O-<Emphasis Type="Italic">iso</Emphasis>-C<Subscript>3</Subscript>H<Subscript>7</Subscript>)<Subscript>4</Subscript>-based olefin polymerization catalyst system

The polymerization of ethylene and propylene and the copolymerization of ethylene and hexene-1 with a Ti(O-iso-Pr)₄–AlR₂Cl/MgBu₂ catalyst system have been studied. The advantages of this system over metallocene and postmetallocene catalysts are high activity, low cost, and ease of synthesis. The resulting polymers and copolymers are characterized by a broad molecular-mass distribution, which reflects the heterogeneity of the active sites with respect to kinetic parameters. As a consequence, the ethylene/hexene-1 copolymers exhibit compositional heterogeneity. The active sites of the system produce copolymers with a pronounced tendency toward alternation of monomer units. The propylene polymerization product is mostly amorphous atactic polypropylene.     

Copolymerization of Ethylene and Polar Monomers by Using Ni/IzQO Catalysts

The replacement of precious metals in catalysis by earth‐abundant metals is currently one of the urgent challenges for chemists. Whereas palladium‐catalyzed copolymerization of ethylene and polar monomers is a valuable method for the straightforward synthesis of functionalized polyolefins, the corresponding nickel‐based catalysts have suffered from poor thermal tolerance and low molecular weight of the polymers formed. Herein, we report a series of neutral nickel complexes bearing imidazo[1,5‐a]quinolin‐9‐olate‐1‐ylidene (IzQO) ligands. The Ni/IzQO system can catalyze ethylene polymerization at 50–100 °C with reasonable activity in the absence of any cocatalyst, whereas most known nickel‐based catalysts are deactivated at this temperature range. The Ni/IzQO catalyst was successfully applied to the copolymerization of ethylene with allyl monomers to obtain the corresponding copolymers with the highest molecular weight reported for a Ni‐catalyzed system.     

Surface and bulk modification of polyolefins by functional aryl nitrenes as highly reactive intermediates

Aromatic azides with hindered amine light stabilizer (HALS) residues or hydrophilic groups such as glucose, sucrose and dextrine residues were synthesized and used for surface modification of polyolefins. By UV‐irradiation nitrenes were formed, which are able to react with polyolefin surfaces. By photochemical immobilization of the carbohydrates hydrophilicity of PE and PP was strongly increased (surface tensions > 44mN/m). Light stability of PP surfaces modified with HALS azides was comparable with PP, stabilised with Tinuvin 770. Bulk modification of ethylene‐propylene and ethylene‐octene copolymers was achieved by grafting nitrenes formed by thermal decomposition of azido benzoic acid. In a circulating air oven up to 1.55 wt% amino benzoic acid residues could be bonded covalently to ethylene‐propylene‐copolymers, less than half of it to ethylene‐octene‐copolymers. Reactive extrusion resulted in grafting yields of more than 50% for both types of copolymers.     

添加型聚丙烯大分子表面改性剂PP-g-PEG的制备及其应用

以马来酸酐为桥联剂,通过其与单端羟基聚乙二醇的反应,合成了大分子表面改性剂聚丙烯-聚乙二醇接枝共聚物,探索了反应条件对接枝反应的影响,用IR、NMR、TGA、DSC对接枝物的结构及性能进行研究,并通过共混研究了接枝物对聚丙烯的表面改性效果.结果表明,提高马来酸酐接枝聚丙烯或聚乙二醇的分子量,会阻碍接枝反应的进行,接枝率明显下降;接枝聚乙二醇降低了接枝物的结晶能力;聚丙烯-聚乙二醇接枝共聚物的热稳定性随着聚乙二醇的含量增加及侧链聚乙二醇长度的增加略有下降;聚丙烯-聚乙二醇接枝共聚物组分在共混物中具有明显的向外择优迁移特性,可以作为聚丙烯的添加型表面改性剂使用.     

Functionalization of polyolefins by reactive processing: influence of starting reagents on content and type of grafted groups

Previous studies carried out in our laboratory on the functionalization of ethylene polymers (homo and copolymers) through free radical processes, using mechanical mixers and/or extruders with diethylmaleate (DEM) and dicumyl peroxide (DCP), have shown that the presence of branched α-olefin blocks favours degradation versus functionalization and crosslinking whereas these last are more effective with linear ethylene blocks. In this contest the present paper reports about attempts to extend the same processes to propylene polymers by benefitting of the indications of previous results. In particular the one step functionalization of EPM with two or more different groups was carried through the use of different monomers. Moreover the procedure was extended to polypropylene thus obtaining a significant functionalization degree flanked by a remarkable decrease of molecular weight.     

Characterization of polyolefins by comprehensive high-temperature two-dimensional liquid chromatography (HT 2D-LC)

Temperature rising elution fractionation hyphenated to size exclusion chromatography (TREF × SEC) is a routine technique to determine the chemical heterogeneity of semicrystalline olefin copolymers. A serious limitation is its applicability to non crystallizing samples. Comprehensive high temperature two-dimensional liquid chromatography (HT 2D-LC) gives an alternative to characterize the chemical heterogeneity of copolymers irrespective of their crystallizability. We have hyphenated interactive HPLC, which separates polyolefins according to their chemical composition, with high-temperature size exclusion chromatography (SEC), which distinguishes polyolefins with regard to their molar mass at 160 °C. The first separation step was based on a selective adsorption of macromolecules on a Hypercarb® column packed with porous graphite particles and subsequent desorption by a gradient 1-decanol → 1,2,4-trichlorobenzene at 160 °C. The SEC column was calibrated with polypropylene (PP) and polyethylene (PE) standards and it turned out that the injection solvent from the first dimension influenced the elution of PP in the SEC column, while the retention of PE was virtually constant. HT 2D-LC was then used to separate a broad variety of polyolefin blends containing PE, PP with different microstructure, ethylene–propylene (EP) and ethylene–propylene–diene (EP(D)M) rubber and ethylene/1-hexene copolymers. For the first time it has been shown that the elution of iPP in the gradient HPLC is molar mass dependent. The results from the HT 2D-LC separation were compared to those from TREF × SEC-experiments. The particular advantage of HT 2D-LC over TREF × SEC is the fact that HT 2D-LC is also applicable to non crystallizing polyolefin samples. The new technique therefore resolves the problem to analyze the chemical heterogeneity of non crystallizing olefin copolymers like EP and EP(D)M copolymers.     

Production of high melt strength polypropylene by gamma irradiation

High melt strength polypropylene (HMS-PP) has been recently developed and introduced in the market by the major international producers of polypropylene. Therefore, BRASKEM, the leading Brazilian PP producer, together with EMBRARAD, the leading Brazilian gamma irradiator, and the IPEN (Institute of Nuclear Energy and Research) worked to develop a national technology for the production of HMS-PP. One of the effective approaches to improve melt strength and extensibility is to add chain branches onto polypropylene backbone using gamma radiation. Branching and grafting result from the radical combinations during irradiation process. Crosslinking and main chain scission in the polymer structure are also obtained during this process. In this work, gamma irradiation technique was used to induce chemical changes in commercial polypropylene with two different monomers, Tri-allyl-isocyanurate (TAIC) and Tri-methylolpropane-trimethacrylate (TMPTMA), with concentration ranging from 1.5 to 5.0 mmol/100 g of polypropylene. These samples were irradiated with a ⁶⁰Co source at dose of 20 kGy. It used two different methods of HMS-PP processing. The crosslinking of modified polymers was studied by measuring gel content melt flow rate and rheological properties like melt strength and drawability. It was observed that the reaction method and the monomer type have influenced the properties. However, the concentration variation of monomer has no effect.     

Asymmetric Cationic [P,O] Type Palladium Complexes in Olefin Homopolymerization and Copolymerization

Metal‐catalyzed ethylene homopolymerization and ethylene‐polar monomer copolymerization to produce new kinds of polyolefins with novel microstructures are of great interest. So far, there are some disadvantages for traditional transition metal catalyst systems. Therefore, it is critical to develop new catalysts or alternative strategies. In recent years, some cationic [P, O] palladium complexes have been demonstrated with the abilities to obtain oligomers and the high molecular weight polymers. Most importantly, these complexes showed high activity and generated polymers with specific microstructures when used for copolymerization of ethylene with industrially relevant polar monomers. This review summarizes several types of high performance cationic [P, O] palladium catalysts in ethylene oligomerization, ethylene homopolymerization and the copolymerization of ethylene with polar monomers. Specially, the regulation of steric and electronic effects at specific sites of the metal complexes was focused.     

Supramolecular Copolymerization as a Strategy to Control the Stability of Self‐Assembled Nanofibers

A major challenge in supramolecular polymerization is controlling the stability of the polymers formed, that is, controlling the rate of monomer exchange in the equilibrium between monomer and polymer. The exchange dynamics of supramolecular polymers based on benzene‐1,3,5‐tricarboxamide (BTA) can be regulated by copolymerizing molecules with dendronized (dBTA) and linear (nBTA) ethylene glycol‐based water‐soluble side chains. Whereas nBTAs form long nanofibers in water, dBTAs do not polymerize, forming instead small spherical aggregates. The copolymerization of the two BTAs results in long nanofibers. The exchange dynamics of both the BTA monomers in the copolymer are significantly slowed down in the mixed systems, leading to a more stable copolymer, while the morphology and spectroscopic signature of the copolymers are identical to that of nBTA homopolymer. This copolymerization is the supramolecular counterpart of styrene/ maleic anhydride copolymerization.     

Advances in the catalyses of polymerizations

Abstract

Nearly all technical processes for the production of polymers are carried out in the presence of catalysts. In the case of addition polymerization reactions, two mechanisms are possible: Start of the reaction via an initiator (e.g., peroxides) or start via a true catalyst (e.g., Ziegler/ Natta systems). In both areas remarkable progress has been made: Cationic “living” polymerizations of oxacycloalkanes, group transfer polymerization, metal-catalyzed alternating copolymerization of ethylene with carbon monoxide, and metallocene-catalyzed polymerizations of alpha-olefins. The polymerization of alpha-olefins with metallocene catalysts not only leads to the improvement of well-known polymers like polyethylene and polypropylene, but also enables the production of new polymers like syndiotactic polypropylene, syndiotactic polystyrene, and cycloolefin copolymers on an industrial scale.     

Syntheses and flame retarding properties of DOPO polymers,melamine polymers,and DOPO‐melamine copolymers

The 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) polymers, melamine polymers, and DOPO‐melamine copolymers have been successfully synthesized, and their flame retarding properties have also been investigated by blending with polypropylene (PP)/styrene‐ethylene‐butylene‐styrene (SEBS) alloys. Experimental results establish that all of them are good polymeric flame retardants. No blooming or color stains occur when they are incorporated into PP/SEBS alloys. Among lab‐made polymeric flame retardants, DOPO‐ melamine copolymers exhibit the best thermal stability and nonflammability. PP/SEBS alloys containing DOPO‐melamine copolymers display comparable thermal resistance and flame retarding behavior (T_d = 290°C; char yield: 15.6%, LOI: 23, and flammability: UL‐94 V0) as the alloys containing common commercial flame retardants (i.e., DOPO, melamine, and ammonium polyphosphate). Copyright © 2013 John Wiley & Sons, Ltd.     

Bidentate Pyridyl-Amido Hafnium Catalysts for Copolymerization of Ethylene with 1-Octene and Norbornene

Polyolefin elastomers ( POEs ) and cyclic olefin copolymers ( COCs ) are high-performance polyolefin materials of wide interest. It is crucial to develop low-cost and high-performance transition metal catalysts to prepare these polyolefin materials. In this contribution, we designed and synthesized a series of bidentate pyridyl-amido hafnium catalysts and used them in ethylene polymerization and copolymerization with comonomers including 1-octene and norbornene. These catalysts exhibited high activities of up to 16.3×10⁶ g mol⁻¹ h⁻¹ and produced polyethylene with a high molecular weight of up to 24.5×10⁴ g mol⁻¹ in ethylene polymerization at 150 °C. More importantly, these catalysts produced ethylene/1-octene copolymers with incorporation of up to 13.7 mol % and molecular weight of up to 72.7×10⁴ g mol⁻¹, and prepared ethylene/norbornene copolymers with incorporation of up to 50.3 mol %, along with glass transition temperature of up to 184.3 °C and molecular weight of up to 187.6×10⁴ g mol⁻¹. The ease of synthesis, high versatility and great copolymerization properties of these hafnium catalysts make them highly attractive for future studies.     

Degradation of Polyolefins Prepared with Fischer-Tropsch Derived Olefins

Degradation of some copolymers of ethylene with Fischer-Tropsch derived olefins was investigated. Hydroperoxide and carbonyl formation in samples of ethylene copolymers with heptene-1, and ethylene multiple polymers with the Fischer-Tropsch derived 3,4 methyl-pentene and linear olefins were monitored by IR spectroscopy. The results correlated with results obtained from thermogravimetry, multiple extrusion and rheology in previous studies. It was shown that degradation of ethylene with Fischer-Tropsch derived olefins is related to the type of branch introduced into the chain by the copolymerization with the particular olefin.     

The Influence of Copolymerization Condition on Rheology,Morphology and Thermal Behavior of Polypropylene Heterophasic Copolymers

In this work, the polypropylene impact copolymers were synthesized by a modified sequential polymerization process. The copolymerization of ethylene and propylene was carried out between two homopolymerization stages at two different pressures and temperatures and the rheology, morphology and thermal properties of reactor alloys were studied. It is found that the ethylene propylene rubber (EPR) content increased up to 32 wt% by increasing the copolymerization time to 20 min. At a fixed copolymerization time of 10 min, the addition of 50 ppm hydrogen (H₂), increased the EPR content from 9.7 to 12.8 wt%. By doubling H₂ concentration, no considerable change in EPR wt% was observed. It is found that the zero shear viscosity of the alloys is significantly under the influence of EPR wt%, not the molecular weight of matrix. The molecular weight of PP matrices determined by rheological data, mildly decreased from 463000 to 458000 g/mol by increasing the copolymerization time from 10 min to 15 min. At high copolymerization time/high H₂ concentration, a melting peak in the differential scanning calorimetry test around 165°C for isotactic PP and also an endothermic peak around 127°C for the block copolymer with long ethylene segments, is observed. The study of interfacial strength by theoretical emulsion models showed that 15 min copolymerization time is optimum considering EPR wt%.