Block and graft copolymers by selective cationic initiation. III. Synthesis and characterization of bigraft copolymers

The synthesis and characterization of new bigraft copolymers poly[(ethylene-co-propylene-co-1,4-hexadiene)-g-styrene-g-α-methylstyrene] (Nordel-g-PSt-g-PαMeSt) and poly[(ethylene-co-propylene-co-1,4-hexadiene)-g-isobutylene] (Nordel-g-PSt-g-PIB) are described. The synthesis involves the use of a polyhydrocarbon backbone containing allylic chlorines and bromines (chlorobrominated Nordel) in conjunction with a suitable alkylaluminum compound to initiate selectively the polymerization of a monomer (generally styrene) from the chloride sites and subsequently to initiate the polymerization of another monomer (α-methylstyrene or isobutylene) from the bromide sites. Conditions conductive to selective and sequential initiation have been worked out. The pure bigrafts are obtained by selective solvent extraction and their homogeneity (by gel permeation chromatography), overall composition (by nuclear magnetic resonance spectroscopy) and molecular weight (by osmometry) are determined.     

PMMA-AES Blends Prepared by in situ Polymerization

Blends of poly(methyl methacrylate) (PMMA) and poly(acrylonitrile-g-(ethylene-co-propylene-co-diene)-g-styrene) (AES) were prepared by in situ polymerization. AES, a commercial elastomer obtained by radical copolymerization of styrene and acrylonitrile in the presence of ethylene-propylene-diene terpolymer (EPDM), was dissolved in methyl methacrylate and the in situ polymerization was conducted at 60 °C. The blends were characterized by CHN analysis, infrared spectroscopy (FTIR), carbon-13 nuclear magnetic resonance (¹³C NMR), dynamic mechanical analysis (DMA) and transmission electron microscopy (TEM). These blends are immiscible and present complex phase behavior. Selective extraction of the blends’ components showed that a fraction of the material is crosslinked and grafting reactions on EPDM chains take place during MMA polymerization. Syndiotactic PMMA was obtained in the presence of AES and this syndiotactic-specificity increased with increasing amount of AES. The morphology of polymerized specimens showed irregular domains of elastomeric phase and in some cases inclusions of PMMA could be observed.     

Synthesis and properties of poly(oxyethylene)s containing thioether,sulfoxide, or sulfone groups

Poly[oxy(ethylthiomethyl)ethylene] (ETE) was prepared from poly[oxy (chloromethyl)ethylene] (CE) by reaction with sodium ethanethiolate. Sulfoxide and sulfone analogues were synthesized by oxidation of the poly[oxy(ethylthiomethyl)ethylene]. By changing the chloromethyl/sodium ethanethiolate ratio, poly[oxy (chloromethyl)ethylene-co-oxy(ethylthiomethyl)ethylene] (CE-ETEs) were easily made. Poly[oxy(ethylsulfinylmethyl)ethylene] (ESXE), poly[oxy(chloromethyl)ethylene-co-oxy(ethylsulfinylmethyl)ethylene] (CE-ESXEs), poly[oxy(ethylsulfonylmethyl)ethylene] (ESE), and poly[oxy(chloromethyl)ethylene-co-oxy(ethylsulfonylmethyl)ethylene] (CE-ESEs) were obtained by oxidation of ETE or CE-ETEs. There was little if any chain degradation. The (co)polymer structures were confirmed by FTIR and ¹H-NMR spectroscopic studies. Their thermal properties were studied by DSC and TGA. T_gs of ETE, ESXE, and ESE were -57, 36, and 57°C, respectively, and T_d,os (initial decomposition temperature, TGA) were 331, 198, and 308°C, respectively. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 793–801, 1998     

Surface degradation of poly(ethylene-co-propylene-co-5-ethylidene-2-norbornene) terpolymer by ozone in water

Saturated olefinic rubbers have been widely used as materials for not only municipal waterworks, but also for household uses. As a sanitizing agent for water, chlorine will be replaced by ozone in the near future from an environmental point of view. However, the ozone treatment in water seriously damages saturated olefinic rubbers, which are necessary for the infrastructure of daily life. Here, we report the surface degradation of cross-linked poly(ethylene-co-propylene-co-5-ethylidene-2-norbornene) terpolymer (EPDM) by ozone treatment, both in water and air. We also discuss how the presence of water impacts the ozone oxidation of EPDM, resulting in macroscopic damage to EPDM.     

Synthesis of polypropene-block-poly(ethylene-co-propene) by short-period polymerization with MgCl2-supported Ziegler catalyst

The short-period polymerization method was successfully applied to the synthesis of a novel diblock copolymer, polypropene-block-poly(ethylene-co-propene). The polymerization was carried out for ca. 0,1 s with a MgCl₂-supported Ziegler catalyst. The copolymers obtained showed unimodal curves in gel-permeation chromatography without any peak in the low-molecular-weight region. After extraction with heptane, the fraction of poly(ethylene-co-propene) remained unchanged in the copolymer but disappeared in a commercial so-called block-type copolymer. All the results the formation of polypropene-block-poly(ethylene-co-propene), in which poly(ethylene-co-propene) is chemically linked with polypropene.     

The synthesis of poly(3,4-dihydroxystyrene) and poly[(sodium 4-styrenesulfonate)-co-(3,4-dihydroxystyrene)]

Poly(2-methoxy-4-vinylphenol), polyMVP, and poly[(sodium 4-styrenesulfonate)-co-(2-methoxy-4-vinylphenol)], poly(SSS/MVP), were synthesized by radical polymerization using Vazo-64 or tributylborane as initiator. Poly(3,4-dihydroxystyrene) and poly[(sodium 4-styrenesulfonate)-co-(3,4-dihydroxystyrene)] were obtained by demethylation of polyMVP and poly(SSS/MVP) using HBr and trimethylsilyl iodide, respectively. (Co)polymer structures were confirmed by ¹H and ¹³C NMR spectra. About 30 wt.-% gel formed in the polyMVP polymerizations, whereas only a small amount (0.5 mol-%) of gel formed in the copolymerizations.     

Synthesis and characterization of polymers of 1,4-hexadienes

The homopolymerization of trans-1,4-hexadiene, cis-1,4-hexadiene, and 5-methyl-1,4-hexadiene was investigated with a variety of catalysts. During polymerization, 1,4-hexadienes undergo concurrent isomerization reactions. The nature and extent of isomerization products are influenced by the monomer structure and polymerization conditions. Nuclear magnetic resonance (NMR) and infrared (IR) data show that poly(trans-1,4-hexadiene) and poly(cis-1,4-hexadiene) prepared with a Et₃Al/α-TiCl₃/hexamethylphosphoric triamide catalyst system consist mainly of 1,2-polymerization units arranged in a regular head-to-tail sequence. A 300-MHz proton NMR spectrum shows that the trans-hexadiene polymer is isotactic; it also may be the case for the cis-hexadiene polymer. These polymers are the first examples of uncrosslinked ozone-resistant rubbers containing pendant unsaturation on alternating carbon atoms of the saturated carbon-carbon backbone. Polymerization of the 1,4-hexadienes was also studied with VOCl₃- and β-TiCl₃-based catalysts. Microstructures of the resulting polymers are quite complicated due to significant loss of unsaturation, in contrast to those obtained with the α-TiCl₃-based catalyst. In agreement with the literature, there was no discernible monomer isomerization with the VOCl₃ catalyst system.     

Novel 3D printed shape-memory PLLA-TMC/GA-TMC scaffolds for bone tissue engineering with the improved mechanical properties and degradability

The biodegradable substitution materials for bone tissue engineering have been a research hotspot. As is known to all, the biodegradability, biocompatibility, mechanical properties and plasticity of the substitution materials are the important indicators for the application of implantation materials. In this article, we reported a novel binary substitution material by blending the poly(lactic-acid)-co-(trimethylene-carbonate) and poly(glycolic-acid)-co-(trimethylene-carbonate), which are both biodegradable polymers with the same segment of flexible trimethylene-carbonate in order to accelerate the degradation rate of poly(lactic-acid)-co-(trimethylene carbonate) substrate and improve its mechanical properties. Besides, we further fabricate the porous poly(lactic-acid)-co-(trimethylene-carbonate)/poly(glycolic-acid)-co-(trimethylene-carbonate) scaffolds with uniform microstructure by the 3D extrusion printing technology in a mild printing condition. The physicochemical properties of the poly(lactic-acid)-co-(trimethylene-carbonate)/poly(glycolic-acid)-co-(trimethylene-carbonate) and the 3D printing scaffolds were investigated by universal tensile dynamometer, fourier transform infrared reflection (FTIR), scanning electron microscope (SEM) and differential scanning calorimeter (DSC). Meanwhile, the degradability of the PLLA-TMC/GA-TMC was performed in vitro degradation assays. Compared with PLLA-TMC group, PLLA-TMC/GA-TMC groups maintained the decreasing T_g, higher degradation rate and initial mechanical performance. Furthermore, the PLLA-TMC/GA-TMC 3D printing scaffolds provided shape-memory ability at 37 ℃. In summary, the PLLA-TMC/GA-TMC can be regarded as an alternative substitution material for bone tissue engineering.     

Functionalization of Styrene-Olefin Block Copolymers by Melt Radical Grafting of Glycidyl Methacrylate and Reactive Blending with PET

Blocks copolymers styrene-b-(ethylene-co-butylene)-b-styrene (SEBS) and styrene-b-(ethylene-co-propylene) (SEP, SEPSEP), with different styrene content and number of blocks in the chain, were functionalized with glycidyl methacrylate (GMA) by melt radical grafting. The influence of monomer concentration, radical initiator and copolymer structure on the grafting degree was examined. The grafted copolymers were characterised by DSC and capillary rheometry. Blends of PET with functionalized SEBS and SEPSEP showed a marked improvement of phase morphology and elongation at break when compared to blends with unfunctionalized copolymers.     

Preparation and functionalization of reactive monodisperse macroporous poly(chloromethylstyrene-co-styrene-co-divinylbenzene) beads by a staged templated suspension polymerization

Reactive monodisperse porous poly(chloromethylstyrene-co-styrene-co-divinylbenzene) beads have been prepared by a staged templated suspension polymerization method with different concentrations of linear polystyrene porogen and chloromethylstyrene in the polymerization mixture. The presence of a small amount of linear polystyrene in the polymerization mixture leads to a dramatic increase in both the pore size and the pore volume of the resulting beads. In contrast, addition of chloromethylstyrene leads to lower surface areas and smoother surfaces due to the reduced compatibility between the polystyrene porogen and the newly formed crosslinked chains. The modification of chloromethylstyrene beads by Gabriel synthesis to obtain aminated beads has also been studied. The final number of primary amino groups is related to the starting concentration of functional benzyl chloride moieties rather than to the porous properties. Both π-basic and π-acidic type chiral selectors, (R)-1-(1-naphthyl)-ethylamine and (R)-N-(3,5-dinitrobenzoyl)phenylglycine, respectively, have been attached to the amino functionalized beads, and the resulting chiral beads have been used in the model HPLC separations of enantiomers. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2631–2643 1997     

Accelerating effect of poly(methyl methacrylate) on rubber oxidation, Part 1: A chemiluminescence study

The oxidative stability of blends of poly(methyl methacrylate) (PMMA) with four types of rubber, poly(ethylene-stat-propylene-stat-5-methylene-2-norbornene) (EPDM), poly(ethylene-stat-vinyl acetate) (EVA), dicarboxy terminated poly(acrylonitrile-stat-butadiene) (NBR) and poly(1,3-butadiene-stat-styrene) (SBR), has been investigated as models for rubber-toughened PMMA. Chemiluminescence was used to monitor the oxidation of the rubber in the blends, revealing an unexpected accelerating effect of PMMA on the oxidation of all the rubbers investigated. The effect varies according to the type of rubber and the temperature. The thermo-oxidative stability of PMMA has also been found to decrease in the presence of the rubber as proved by thermogravimetry, confirming mutually antagonistic effects of PMMA and rubber in the blend oxidation. On the basis of results from all techniques, including identification of oxidation products by FTIR spectroscopy, a possible mechanism is suggested, involving the formation of mobile radicals in PMMA induced by rubber oxidation. These radicals are suggested to play a crucial role in enhancing rubber phase oxidation.     

Synthesis and properties of the ionomer diblock copolymer poly(4‐vinylbenzyl triethyl ammonium bromide)‐b‐polyisobutene

A new amphiphilic diblock copolymer containing an ionomer segment, poly[(4‐vinylbenzyl triethyl ammonium bromide)‐co‐(4‐methylstyrene)‐co‐(4‐bromomethylstyrene)]‐b‐polyisobutene [poly(4‐VBTEAB)‐b‐PIB], was synthesized by the chemical modification of poly(4‐methylstyrene)‐b‐polyisobutene [poly(4‐MSt)‐b‐PIB]. First, the 4‐methylstyrene moiety in poly(4‐MSt)‐b‐PIB was brominated with azobisisobutyronitrile as an initiator at 60 °C in CCl₄, and then the highly reactive benzyl bromide groups were ionized by a reaction with triethylamine in a toluene/isopropyl alcohol (80/20 v/v) mixture at about 85 °C to produce the ionomer diblock copolymer poly(4‐VBTEAB)‐b‐PIB. The solubility of the ionomer block copolymer was quite different from that of the corresponding poly[(4‐methylstyrene)‐co‐(4‐bromomethylstyrene)]‐b‐polyisobutene {poly[(4‐MSt)‐co‐(4‐BrMSt)]‐b‐PIB}. Transmission electron microscopy observations demonstrated that all three diblock copolymers had microphase‐separation structures in which polyisobutene (PIB) domains existed in the continuous phase of the poly(4‐methylstyrene) segment or its derivative segment matrix. Dynamic mechanical thermal analysis measurements showed that poly[(4‐MSt)‐co‐(4‐BrMSt)]‐b‐PIB had two glass‐transition temperatures (T_g's), ?56 °C for the PIB segment and 62 °C for the poly[(4‐MSt)‐co‐(4‐BrMSt)] domain, whereas poly(4‐VBTEAB)‐b‐PIB showed one T_g at ?8 °C of the PIB domain; T_g of the poly[(4‐vinylbenzyl triethyl ammonium bromide)‐co‐(4‐methylstyrene)‐co‐(4‐bromomethylstyrene)] domain was not observable because of the strong ionic interactions resulting in a higher T_g and a retention of modulus up to 124 °C. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2755–2764, 2003     

Synthesis, characterization and degradability of the comb-type poly(4-hydroxyl-ε-caprolactone-co-ε-caprolactone)-g-poly(l-lactide)

The novel comb-type biodegradable graft copolymers based on ε-caprolactone and l-lactide were synthesized. Firstly, 2-oxepane-1,5-dione (OPD) was synthesized by the Baeyer-Villiger oxidation of 1,4-cyclohexanedione, and was subsequently copolymerized with ε-caprolactone (CL) to produce poly(2-oxepane-1,5-dione-co-ε-caprolactone) (POCL) catalyzed by stannous(II) 2-ethylhexanoate in toluene. Then, POCL was converted into poly(4-hydroxyl-ε-caprolactone-co-ε-caprolactone) (PHCL) using sodium borohydride as reductant. Finally, poly(4-hydroxyl-ε-caprolactone-co-ε-caprolactone)-g-poly(l-lactide) (PHCL-g-PLLA) were prepared successfully by bulk ring-opening polymerization of l-lactide using PHCL as a macro-initiator. All the copolymers have been characterized by ¹H and ¹³C NMR, DSC, and GPC. Compared with the random copolymer of poly(CL-co-LA), the elongation is highly increased. And the thermal analysis showed that the crystallization rate of the PCL backbone in the graft copolymers was greatly reduced compared to the PCL homopolymer. The hydrolytic degradation of the copolymer was much faster in a phosphate buffer (pH = 7.4) at 37 °C, which is confirmed by the weight loss and change of intrinsic viscosity.     

Preparing a functionalized thermoplastic elastomer—bromination and synthesis of poly(p-methylstyrene-co-styrene)-block-poly(ethylene-co-butene)-block-poly(p-methylstyrene-co-styrene)

A poly(p-methylstyrene-co-styrene)-block-poly(ethylene-co-butene)-block-poly(p-methylstyrene-co-styrene) thermoplastic elastomer was prepared via anionic synthesis of poly(p-methylstyrene-co-styrene)-block-polybutadiene-block-poly(p-methylstyrene-co-styrene) followed by a hydrogenation of the polybutadiene midblock. The sequential method used for the synthesis has resulted in a nearly monodispersed polymer with a polydispersity of 1.03. Bromination of such synthesized copolymer was next, conducted using two different methods. In the presence of a FeCl₃ catalyst in CCl₄ solvent, bromination occurred through forming a carbocationic complex to undergo an electrophilic substitution reaction on the aromatic rings of the end blocks. Nevertheless, the bromination occurred exclusively on the p-methyl groups of the end blocks when conducted in cyclohexane using photoinitiated free radicals. The microstructure of the brominated molecules were analyzed using ¹H-NMR and ¹³C-NMR, and bromination efficiencies of 48 and 44% have been attained from the two methods, respectively. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4108–4116, 1999     

Synthesis of repeating sequence copolymers of lactic,glycolic, and caprolactic acids

Repeating sequence copolymers of poly(lactic‐co‐caprolactic acid) (PLCA), poly(glycolic‐co‐caprolactic acid) (PGCA), and poly(lactic‐co‐glycolic‐co‐caprolactic acid) (PLGCA) have been synthesized by polymerizing segmers with a known sequence in yields of 50–85% with M_ns ranging from 18–49 kDa. The copolymers exhibited well‐resolved NMR resonances indicating that the sequence encoded in the segmers used in their preparation is retained and that transesterification is minimal. The exact sequences allowed for unambiguous assignment of the NMR spectra, and these standards were compared with the data previously reported for random copolymers. The glass transition temperatures (T_gs) of the PLCA and PGCA copolymers were found to depend primarily on monomer ratio rather than sequence. Sequence dependent T_gs were, however, noted for the PLGCA polymers with 1:1:1 L:G:C ratios; poly LGC and poly GLC exhibited T_gs that differed by nearly 8 °C. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis and characterization of AgBr nanocomposites by templated amphiphilic comb polymer

A novel amphiphilic graft copolymer, poly(vinylidene fluoride-co-chlorotrifluoroethylene)-g-poly(4-vinyl pyridine) (P(VDF-co-CTFE)-g-P4VP) at 65:35 wt.%, respectively, was synthesized via atom transfer radical polymerization (ATRP), as confirmed by nuclear magnetic resonance (¹H NMR) and transmission electron microscopy (TEM). Silver bromide (AgBr) nanoparticles were in situ generated within the self-assembled P(VDF-co-CTFE)-g-P4VP graft copolymer. TEM, UV–visible spectroscopy and X-ray diffraction (XRD) analyses support the successful formation of P(VDF-co-CTFE)-g-P4VP nanocomposites consisting of stabilized AgBr nanoparticles mostly 20–40 nm in size, which is presumably due to the capping action of the coordinating pyridine groups of the graft copolymer. The wavenumber of pyridine nitrogen in FT-IR spectra and the glass transition temperature (T_g) of the graft polymer measured by DSC shifted upon the formation of AgBr nanoparticles, indicating specific interactions between the nanoparticles and the graft copolymer matrix.     

Surface tension of polymer mixtures and copolymers

Contact angles θ of liquids of different polarity were measured on a series of mixtures of solid high polymers and a series of copolymers. The mixtures were composed of an alternating poly(ethylene-co-maleic anhydride) (EMA), and its addition product with n-octadecylamine, poly(ethylene-co-N-n-octadecylmaleamic acid) (EOM). The co-polymers were composed of the same monomeric units as the mixtures. The surface tension γ_s of EOM, calculated from θ by the Good-Fowkes-Owens-Wendt treatment, decreased slightly with increasing molecular weights and then reached a limiting value. Plots of γ_s against EOM concentration indicated large negative excess surface tension of the units with lower surface tension, EOM, in both series studied. For the mixture series, γ_a first sharply decreased with the EOM concentration; then it reached a limiting value, the γ_s of pure EOM, at a very low EOM concentration. This indicates phase separation of the two polymers, and the thickness of a monomolecular surface layer was calculated from these data. For the copolymers, γ_s varied logarithmically with the EOM concentration. Throughout the whole concentration range, the data fitted the equation developed by Belton and Evans for ideal mixtures.     

Aromatic and rigid rod polyelectrolytes based on sulfonated poly(benzobisthiazoles)

Aromatic polyelectrolytes based on sulfonated poly(benzobisthiazoles) (PBTs) have been synthesized by a polycondensation reaction of sulfo-containing aromatic dicarboxylic acids with 2,5-diamino-1,4-benzenedithiol dihydrochloride (DABDT) in freshly prepared polyphosphoric acid (PPA). Several sulfonated PBTs, poly[(benzo[1,2-d:4,5-d′]bisthiazole-2,6-diyl)-2-sulfo-1,4-phenylene] sodium salt (p-sulfo PBT), poly[(benzo[1,2-d:4,5-d′]bisthiazole-2,6-diyl)-5-sulfo-1,3-phenylene] sodium salt (m-sulfo PBT), their copolymers, and poly[(benzo[1,2-d:4,5-d′]bisthiazole-2,6-diyl)-4,6-disulfo-1,3-phenylene] potassium salt (m-disulfo PBT), have been targeted and the polymers obtained characterized by ¹³C-NMR, FT-IR, elemental analysis, thermal analysis, and solution viscosity measurements. Structural analyses confirm the structures of p-sulfo PBT and m-disulfo PBT, but suggest that the sulfonate is cleaved from the chain during synthesis of m-sulfo PBT. m-Disulfo PBT dissolves in water as well as strong acids, while p-sulfo PBT dissolves well in strong acids, certain solvent mixtures containing strong acids, and hot DMSO. TGA indicates that these sulfonated PBTs are thermally stable to over 500°C. Free-standing films of p-sulfo PBT, cast from dilute neutral DMSO solutions, are transparent, tough, and orange in color. Films cast from basic DMSO are also free standing, while being opaque and yellow-green. p-Sulfo PBT was incorporated as the dopant ion in polypyrrole, producing conductive films with conductivities as high as 3 S/cm and electrical anisotropies as high as 10. © 1996 John Wiley & Sons, Inc.     

Tight binding of poly(carboxylate) ligand to calcium carbonate with intramolecular NH…O hydrogen bond

Novel poly(carboxylates), partially amidated poly(acry late), poly{[1-carboxylate-2-(N-t-butyl)carbamoyl)]ethylene-alt-ethylene}, poly[1-(N-oxysuccinyl-aminomethenyl)ethylene], poly[1-(N-oxymalenyl-aminomethnyl)ethylene] and poly[1-(N-oxyphthalyl-aminomethnyl)ethylene] with intramolecular NH…O hydrogen bond between amide NH and coordinating oxygen were synthesized as model ligands for CaCO₃ biominerallization. The FE/SEM and its backscatter of the CaCO₃ composite of gold colloid-conjugated poly{[1-carboxylate-2-(N-p-methylthiophenyl)carbamoyl]ethylene-alt-ethylene} indicate that the polymer ligand is located at the surface of vaterite crystals and the oriented carboxylate ligands control the CaCO₃ polymorph.     

Synthesis of bottlebrush block copolymers from bottlebrush polystyrene and bottlebrush random copolymer of ω-end-norbornyl polymethacrylates and their self-assembly

Six different bottlebrush block copolymers (BBCPs) (A-b-(B-co-C)) from bottlebrush polystyrene (A) and bottlebrush random copolymers (B-co-C) of polymethacrylates were synthesized through living anionic polymerization and ring-opening metathesis polymerization. To induce the phase separation of bottlebrush polystyrene (PNB-g-PS) (A) and bottlebrush poly(benzyl methacrylate) (PNB-g-PBzMA) (C)-based BBCP with an extremely low Flory–Huggins interaction parameter (χ), three kinds of bottlebrush polymethacrylates (B): poly(norbornene-g-methyl methacrylate) (PNB-g-PMMA), poly(norbornene-g-tert-butyl methacrylate) (PNB-g-PtBMA), and poly(norbornene-g-methacrylic acid) (PNB-g-PMAA), respectively, were randomly combined with C. An order–disorder phase transition of the BBCPs (A-b-(B-co-C)) was observed with a change in mole ratios of PMMA, PtBMA, or PMAA to PBzMA of 25, 50, and 75% in random copolymer blocks using field-emission scanning microscopy. While the BBCP with 25% of PMAA in the random copolymer block showed an ordered lamellar nanostructure, a disordered morphology was revealed at 75% PMAA. SEM showed that the incorporation of PtBMA and PBzMA showed better-ordered lamellar morphologies than was the case with PMMA and PBzMA at the same mole ratios.