Reactive blending of polypropylene/polyamide-6 in the presence of tailor-made succinic anhydride-terminated oligopropene compatibilizers

Various anhydride-terminated isotactic and atactic oligopropenes of number average molecular weights ranging between 1,000 and 10,000 g/mole, prepared by maleinating vinylidene-terminated propene oligomers obtained with isospecific and nonstereospecific metallocene-based Ziegler–Natta catalysts, have been evaluated as blend compatibilizers of polypropylene/polyamide-6 (70 vol%/30 vol%) blends to study the role of blend compatibilizer molecular architecture. When added during processing, as shown by IR spectroscopic analysis, the anhydride-terminated oligopropenes react with the amine-terminated polyamide-6 to yield polypropylene-block-polyamide-6 in situ. Such block copolymers are efficient dispersing agents. While the polyamide dispersion in the polypropylene continuous phase is not affected by blend compatibilizer stereoregularities, both stiffness and yield stress as well as notched Charpy impact strength increase with increasing stereoregularities and molecular weights. With oligopropene molecular weights exceeding 1,150 g/mole, the average size of the dispersed polyamide microphases correlates with the volume fraction of the oligopropene-block-polyamide-6 blend compatibilizer and the dicarboxylic acid anhydride/amine molar ratio.     

Synthesis of Poly(methyl methacrylate)-poly(poly(ethylene glycol) methacrylate)-polyisobutylene ABCBA Pentablock Copolymers by Combining Quasiliving Carbocationic and Atom Transfer Radical Polymerizations and Characterization Thereof

Novel, unique amphiphilic pentablock terpolymers consisting of the highly hydrophobic polyisobutylene (PIB) mid-segment attached to the hydrophilic combshaped poly(poly(ethylene glycol) methacrylate) (PPEGMA) polymacromonomer chains, which are coupled to poly(methyl methacrylate) (PMMA) outer segments were synthesized by the combination of quasiliving carbocationic polymerization and atom transfer radical polymerization (ATRP). First, a bifunctional PIB macroinitiator was prepared by quasiliving carbocationic polymerization and subsequent quantitative chain end derivatizations. Quasiliving ATRP of PEGMAs with different molecular weights (M_n = 188, 300 and 475 g/mol) led to triblock copolymers which were further reacted with MMA under ATRP conditions to obtain PMMA-PPEGMA-PIB-PPEGMA-PMMA ABCBA-type pentablock copolymers. It was found that slow initiation takes place between the PIB macroinitiator and PEGMA macromonomers with higher molecular weights via ATRP. ATRP of MMA with the resulting block copolymers composed of PIB and PPEGMA chain segments led to the desired block copolymers with high initiating efficiency. Investigations of the resulting pentablock copolymers by DSC, SAXS and phase mode AFM revealed that nanophase separation occurs in these new macromolecular structures with average domain distances of 11-14 nm, and local lamellar self-assembly takes place in the pentablocks with PPEGMA polymacromonomer segments of PEGMAs with M_n of 118 g/mol and 300 g/mol, while disordered nanophases are observed in the block copolymer with PEGMA having molecular weight of 475 g/mol. These new amphiphilic block copolymers composed of biocompatible chain segments can find applications in a variety of advanced fields.     

Conducting Block Copolymer Nanowires Containing Regioregular Poly(3‐Hexylthiophene) and Polystyrene

Grignard Metathesis polymerization (GRIM) for the synthesis of regioregular poly(3‐alkylthiophenes) proceeds via a “living” chain growth mechanism. Due to the “living” nature of this polymerization regioregular poly(3‐alkylthiophenes) with predetermined molecular weight, narrow molecular weight distributions and desired chain end functionality are now readily available. Allyl terminated poly(3‐hexylthiophene) was successfully used as a precursor for the synthesis of di‐block copolymers containing polystyrene. The addition of “living” poly(styryl)lithium to the allyl terminated regioregular poly(3‐hexylthiophene) generated the di‐block copolymer. Poly(3‐hexylthiophene)‐b‐polystyrene was also synthesized by atom transfer radical polymerization. Integration of poly(3‐hexylthiophene) in di‐block copolymers with polystyrene leads to the formation of nanowire morphology and self‐ordered conducting nanostructured materials.     

Synthesis of polypropylene block copolymers from brominated styrene-terminated isotactic polypropylene

Isotactic polypropylene block copolymers, isotactic-polypropylene-block-poly (methyl methacrylate) (i-PP-b-PMMA) and isotactic-polypropylene-block-polystyrene (i-PP-b-PS), were prepared by atom transfer radical polymerization (ATRP) using a brominated styrene-terminated isotactic polypropylene macroinitiator synthesized from bromination of styrene-terminated isotactic polypropylene. The styrene-terminated isotactic polypropylene can be obtained by polymerization of propylene in the presence of styrene and hydrogen chain transfer agents using a rac-Me₂Si[2-methyl-4-(1-naphyl)Ind]₂ZrCl₂ as catalyst. The molecular weights of isotactic polypropylene block copolymers were controlled by altering the amount of hydrogen used in the polymerization of propylene and the amount of monomer used in the blocking reaction. The effect of i-PP-b-PS block copolymer on PP-PS blends and that of i-PP-b-PMMA block copolymer on PP-PMMA blends were studied by scanning electron microscopy.     

Characterization of amphiphilic hydrocarbon modified Poly(ethylene glycol) synthesized through ring-opening reaction of 2-(1-octadecenyl)succinic anhydride

Poly(ethylene glycol) (PEG) triblock and diblock amphiphilic block copolymers were synthesized from poly(ethylene glycol) and poly(ethylene glycol) monomethyl ether, respectively. The hydroxyl groups of PEG readily react with 2-(1-octadecenyl) succinic anhydride (OSA) at 140 °C through ring-opening reaction of the succinic anhydride. Both the PEG-OSA diblock and triblock copolymers are produced without use of any solvent or catalyst. The molecular structure of the copolymers was characterized by ¹H NMR and FTIR spectroscopy, and the thermal properties by DSC. The behavior of the copolymers in selective and nonselective solvents was studied by ¹H NMR spectroscopy in deuterium oxide and d-chloroform. The aggregation of the polymers in water was studied with a particle size analyzer and a transmission electron microscope (TEM) in bright field mode. The results show that the hydrophobic C₁₈ chain with intramolecular succinic anhydride linker can be attached to the hydrophilic PEG chain, an ester bond forming between the blocks. The copolymers exhibit flexible, liquid-like hydrophobic blocks even in water, which is a nonsolvent for OSA. PEG-OSA block copolymers self-organize in water, forming micellar polymer aggregates in nanoscale.     

Molecular characterization of maleic anhydride-functionalized polypropylene

This work deals with the molecular characterization of maleic anhydride melt-functionalized polypropylene (PP-g-MA). The functionalization mechanism, the nature, the concentration, and the location of grafted anhydride species onto the polypropylene chain are discussed. The polypropylene functionalization was performed using a pre-heated Brabender Plastograph (190°C, 4 min of mixing time). Several concentrations of maleic anhydride and organic peroxide were used for this study. In those experimental conditions, the organic peroxide undergoes an homolytic rupture and carries out a polypropylene tertiary hydrogen abstraction. The resulting macroradical undergoes a β-scission leading to a radical chain end which reacts with maleic anhydride. When a termination reaction occurs at this first step a succinic type anhydride chain end is obtained. However, oligomerization of maleic anhydride is found to occur more frequently leading to poly (maleic anhydride) chain end. Concentration of both anhydride types and minimal length of the grafted poly (maleic anhydride) were determined. A fraction of maleic anhydride does not react with polypropylene or homopolymerize leading to nongrafted poly (maleic anhydride). © 1995 John Wiley & Sons, Inc.     

Epoxy and hydroxy functional polyolefin macromonomers

Methods for preparing saturated polyolefin oligomers with Si(SINGLE BOND)H, epoxy groups, and with dihydroxy groups have been developed. Anionic polymerization of butadiene, then termination of the chains with chlorodimethylsilane leads to controlled molecular weight oligomers with silane functionality, and wherein the microstructure can be tailored. Hydrogenation of these materials proceeds smoothly using colloidal nickel catalysts to yield the corresponding saturated materials, which are stable to conditions used for melt polyesterifications. Hydrosilation of allyl glycidyl ether with the Si(SINGLE BOND)H end groups produces epoxy functional oligomers, and subsequent hydrolysis of the epoxy rings yields oligomers with a dihydroxy group at one end. Melt copolymerization of the olefin macromers with 1,4-butanediol and 1,4-dimethylcyclohexanedicarboxylate in the presence of titanium isopropoxide affords poly(ester-g-olefin) graft copolymers. These copolymers are under study as model interfacial agents for polyester/polyolefin blends and as suspension agents for polyester particles in nonpolar media. © 1996 John Wiley & Sons, Inc.     

Mediated melt functionalization of polypropylene

This work investigated the ability of several kinds of molecules to mediate the melt functionalization of polypropylene. N-Bromosuccinimide, nitroxides, iniferters, thiols and RAFT chain transfer agents were tested as potential mediators. The grafting of maleic anhydride onto polypropylene was carried out with and without mediator and the grafted polymers are discussed in terms of graft content, graft structure and molecular weights.     

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.     

α-甲基苯乙烯/苯乙烯/马来酸酐三元共聚物功能化聚丙烯及增容聚丙烯/尼龙6共混体系的研究

采用溶液聚合的方式合成了α-甲基苯乙烯/苯乙烯/马来酸酐三元共聚物(简称为PASM),研究了单体组成、反应温度和时间等因素对共聚的影响,并进一步研究了三元共聚物对聚丙烯的功能化作用和对聚丙烯/尼龙6(PP/Ny6)共混体系的原位增容作用.GPC和TG等技术对PASM的表征结果显示,随着单体组成中α-甲基苯乙烯(AMS)...     

温敏两亲性接枝物PAM-g-PNIPAm的合成及表征

以巯基乙胺为分子量调节剂,以丙烯酰氯作为链端转化剂合成了不同分子量的端丙烯酰胺基聚(N-异丙基丙烯酰胺)(PNIPAm)大分子单体;与丙烯酰胺共聚合,合成了以PNIPAm为侧链的接枝聚丙烯酰胺.用FTIR和¹HNMR方法表征了接枝聚合物与大分子单体的组成.该接枝聚合物在水溶液中具有热缔合特性及明显的温敏增稠性,水溶液的粘度在32～50℃之间随温度增加而增加.     

Synthesis of Propylene Diblock Copolymers via Metallocene and Borane Chemistry

An isotactic chain end unsaturated polypropylene was prepared by the homogeneous metallocene catalyst Et(Ind)₂ZrCl₂ with MAO. Herein, the chain end unsaturated polypropylene proceeded the hydroboration reaction to prepare borane‐containing polypropylene. The borane‐containing polypropylene could be transformed to hydroxyl‐terminated polypropylene, PPOH. And then the polypropylene‐nylon 6 diblock copolymer, PP‐b‐NY6, was synthesized from telechelic PPOH by converting this prepolymer with toluene diisocyanate and using the resulting materials as macroactivators for anionic caprolactam polymerization. Meanwhile, this investigation used borane‐containing polypropylene and oxygen to produce free radicals at the chain end on the polypropylene. Experimental results indicate that the free radical is an effective initiator for the polymerization of methyl methacrylate to produce diblock PP‐b‐PMMA. The block copolymers are characterized by IR, NMR, and DSC analyses. The diblock copolymer is a good compatibilizer for polymer blends.     

From NMP to RAFT and Thiol‐Ene Chemistry by In Situ Functionalization of Nitroxide Chain Ends

A straightforward, novel strategy based on the in situ functionalization of polymers prepared by nitroxide‐mediated polymerization (NMP), for the use as an extension toward block copolymers and post‐polymerization modifications, has been investigated. The nitroxide end group is exchanged for a thiocarbonylthio end group by a rapid transfer reaction with bis(thiobenzoyl) disulfide to generate in situ reversible addition–fragmentation chain transfer (RAFT) macroinitiators. Moreover, not only have these macroinitiators been used in chain extension and block copolymerization experiments by the RAFT process but also a thiol‐terminated polymer is synthesized by aminolysis of the RAFT end group and subsequently reacted with dodecyl vinyl ether by thiol‐ene chemistry.     

Living radical polymerization of diisopropyl fumarate to obtain block copolymers containing rigid poly(substituted methylene) and flexible polyacrylate segments

Living radical polymerizations of diisopropyl fumarate (DiPF) are carried out to synthesize poly(diisopropyl fumarate) (PDiPF) as a rigid poly(substituted methylene) and its block copolymers combined with a flexible polyacrylate segment. Reversible addition‐fragmentation chain transfer (RAFT) polymerization is suitable to obtain a high‐molecular‐weight PDiPF with well‐controlled molecular weight, molecular weight distribution, and chain‐end structures, while organotellurium‐mediated living radical polymerization (TERP) and reversible chain transfer catalyzed polymerization (RTCP) give PDiPF with controlled chain structures under limited polymerization conditions. In contrast, controlled polymerization for the production of high‐molecular‐weight and well‐defined PDiPF is not achieved by atom transfer radical polymerization (ATRP) and nitroxide‐mediated radical polymerization (NMP). The block copolymers consisting of rigid poly(substituted methylene) and flexible polyacrylate segments are synthesized by the RAFT polymerization. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2136–2147     

Amine/anhydride reaction versus amide/anhydride reaction in polyamide/anhydride carriers

Polyamide 6 (PA6) and poly(metaxylene adipamide) (PAmXD6) were blended in a batch mixer with anhydrides such as phthalic anhydride, n-octadecyl succinic anhydride, and anhydride-grafted ethylene propylene rubber. The melt viscosity, the solution viscosity, and chain end concentration were studied during the mixing. PA was first mixed 5 min to get an homogeneous melt prior to the anhydride addition. The introduction of the anhydride to the molten polyamide resulted in large decreases of melt and solution viscosities and of amine chain end concentrations. The anhydride units react with amine chain ends to form imide groups. The resulting low amine chain end concentration causes hydrolysis reaction to maintain the condensation equilibrium. As a consequence an increased carboxylic chain end concentration is observed. The imide concentration was studied by IR. It was shown that when most of the amine chain ends are consumed, the remaining anhydride reacts with amino groups formed by polyamide hydrolysis. © 1995 John Wiley & Sons, Inc.     

Crystalline-crystalline block copolymers of regioregular poly(3-hexylthiophene) and polyethylene by ring-opening metathesis polymerization

Block copolymers of regioregular poly(3-hexylthiophene) (P3HT) and polyethylene (PE) were synthesized through the chain transfer of olefin-terminated P3HT in the presence of cyclooctene via ring-opening metathesis polymerization (ROMP). Subsequent hydrogenation of the poly(cyclooctene) block yielded high molecular weight, crystalline-crystalline P3HT-PE block copolymers, which are thermally stable and resistant to solvents under ambient conditions. These copolymers were characterized by 1H NMR, DSC, and WAXS and represent the first materials of a class of crystalline-crystalline semiconducting-insulating block copolymers.     

Heterogeneous grafting of polypropylene and physical properties of graft blends

Polypropylene powder, as formed by typical Ziegler catalysts, can conveniently be hydroperoxidized in aqueous slurry. A cationic surfactant and potassium persulfate are used to achieve wetting and initiate oxidation. It is proposed that specific reaction between the quaternary ammonium cations and persulfate anion generates a water-insoluble persulfate which decomposes to yield a hydrophobic radical species which initiates oxidation. Graft copolymers were prepared by using this polypropylene hydroperoxide, a redox catalyst, and either dimethylaminoethyl methacrylate or n-butyl acrylate. These graft copolymers, dispersed in polypropylene, form two-phase systems in the solid state. Under synthesis conditions which are believed to yield long side chains, the dispersed, more polar polymer was found in larger domains than observed with shorter side chains. Polypropylene spherulites were also distorted, although per cent crystallinity of the continuous polypropylene phase was hardly affected by the presence of graft. Mixtures of poly(propylene-g-butyl acrylate) and polypropylene are rather extensible and of low modulus. Low temperature tensile impact values are only slightly higher than for pure polypropylene. Addition of poly(butyl acrylate) to these blends increases both the low-speed modulud and high-speed tensile impact relative to the two component blends.     

Thermal and photo induced reactions in blends of polypropylene and poly(methyl methacrylate)

Thermal Volatilization Analysis (TVA) demonstrates that poly(methyl methacrylate) (PMMA) is stabilized by blending with polypropylene (PP). Although well-defined radical reactions occur in both polymers under 2537 Å radiation, there is no evidence of the formation of block or graft copolymers when blends of the two are irradiated. Preirradiation suppresses the amount of monomeric methyl methacrylate formed on subsequent thermal degradation. The missing methyl methacrylate units appear in the chain fragment fraction. The characteristics of the thermal degradation of blends of unirradiated PP with preirradiated PMMA are similar to those of unirradiated rather than pre-irradiated blends, thus emphasizing the importance of the PP component in determining the thermal stability of blends after irradiation. These observations are discussed mechanistically.     

Synthesis of amphiphilic block copolymers via ring opening polymerization and reversible addition-fragmentation chain transfer polymerization

Amphiphilic block copolymers were synthesized via a dual initiator chain transfer agent (inifer) that successfully initiated the ring opening polymerization (ROP) of l -lactide (LLA) and subsequently mediated the reversible addition-fragmentation chain transfer (RAFT) polymerization of poly(ethylene glycol) ethyl ether methacrylate (PEGEEMA). The formation of each polymer block was confirmed using ¹H nuclear magnetic resonance spectroscopy, as well as gel permeation chromatography, and comprehensive kinetics studies provide valuable insights into the factors influencing the synthesis of well-defined block copolymers. The effect of monomer concentration, reaction time, and molar ratios of inifer to catalyst on the ROP of LLA are discussed, as well as the ability to produce poly(lactide) blocks of different molecular weights. The synthesis of hydrophilic PPEGEEMA blocks was also monitored via kinetics to provide a better understanding of the role the chain transfer agent plays in facilitating the complex and sterically demanding RAFT polymerization of PEGEEMA.     

Structure and properties of sequentially polymerized propylene-b-[ethylene-co-propylene]-b-propylene copolymers

The structure and properties of presumed block copolymers of polypropylene (PP) with ethylene-propylene random copolymers (EPR), i.e., PP-EPR and PP-EPR-PP, have been investigated by viscometry, transmission electron microscopy, dynamic mechanical analysis, differential scanning calorimetry, gel permeation chromatography, wide-angle x-ray diffraction, and other techniques testing various mechanical properties. PP-EPR and PP-EPR-PP were synthesized using δ-TiCl₃-Et₂-AlCl as a catalyst system. The results indicate that the intrinisic viscosity of these polymers increases with each block-building step, whereas the intrinsic viscosity of those prepared by chain transfer reaction (strong chain-transfer reagent hydrogen was introduced between block-building steps during polymerization) hardly changes with the reaction time. Compared with PP/EPR blends, PP-EPR-PP block copolymers have lower PP and polyethylene crystallinity, and lower melting and crystallization temperatures of crystalline EPR. Two relaxation peaks of PP and EPR appear in the dynamic spectra of blends. They merge into a very broad relaxation peak with block sequence products of the same composition, indicating good compatibility between PP and EPR in the presence of block copolymers. Varying the PP and EPR content affects the crystallinity, density, and morphological structure of the products, which in turn affects the tensile strength and elongation at break. Because of their superior mechanical properties, sequential polymerization products containing PP-EPR and PP-EPR-PP block copolymers may have potential as compatibilizing agents for isotactic polypropylene and polyethylene blends or as potential heat-resistant thermoplastic elastomers.