The effects of the selectivity of the toluene/ethanol mixture on the micellar and the ordered structures of an asymmetric poly(styrene-b-4-vinylpyridine)

The effects of the solvent selectivity of toluene/ethanol mixtures on the micellar and ordered structures of an asymmetric diblock copolymer of PS(19.6 K)-b-P4VP(5.1 K) in the dilute (1 wt%) and semi-dilute (8 wt%) solutions, as well as in the gel and solid films, were studied using small angle X-ray scattering (SAXS), generalized indirect Fourier transform (GIFT), and transmission electron microscopy (TEM) methods. The solvent selectivity was controlled by ? (weight percentage of ethanol in toluene/ethanol mixture). Individual micelles, space-filled micellar structure (without three-dimensional order), and three-dimensionally ordered gel and solid structures were observed from the 1 and 8 wt% solutions, the gel, and the solid film, respectively. In the 1 wt% solution, the individual micellar structures were strongly dependent on ?; the spherical micelles with P4VP core at ? = 0, the unimer state at 10 ≤ ? ≤ 50, the spherical micelles with PS core at ? = 60, the cylindrical micelles with PS core at ? = 70 and 80, and precipitation at ? = 90 and 100 were observed. The 8 wt% solution was close to overlap concentration with the unimer state in the regions of 20 ≤ ? ≤ 40. In the gel, the ordered structure was observed in the sequence of bcc, hexagonal, gyroid, lamellar, reverse hexagonal and random as ? increased, and could be explained by the change of the relative volume fraction of each block as ? changed, similar to the phase sequence in the phase diagram of the diblock copolymer. The solid films showed the various kinetically frozen ordered microstructures such as randomly packed sphere, hexagonal, gyroid, hexagonally perforated lamella, reversed hexagonal, and randomly packed cylinder, which were controlled by the solvent quality in the gel before solidification. We believe that these results can be applied to photonic crystals, self-assembled nano-patterning, and functional nanoparticles in which the structural control is most important.     

Adhesive properties of ABA poly(styrene-b-isoprene) block copolymers

ABA poly(styrene-b-isoprene) block copolymers with various molecular weight and elastomeric content were used as heat activated adhesives. The shear strength of glass to glass joints was tested. The influence of activation temperature and ageing on shear strength was also examined. Good adhesive and cohesive behaviour was found for copolymers with low total molecular weight and identical block lengths. These results were explained by the fact that phase separation does not easily occur in such copolymers.     

Synthesis of exfoliated poly(styrene-co-acrylonitrile) copolymer/silicate nanocomposite by emulsion polymerization; monomer composition effect on morphology

Two types of SAN/silicate nanocomposites were prepared to set up the relationship between the composition of monomers and the resultant morphology of the composites using a pristine sodium montmorillonite (Na-MMT). SAN I series were synthesized with acrylonitrile in initial stage and a mixture of styrene and acrylonitrile in increment stage. SAN II series were prepared with the mixture of styrene and acrylonitrile throughout polymerization. SAN I series showed exfoliated states but SAN II series exhibited intercalated states because SAN I series consisted of hydrophilic AN initially. The chemical affinity between monomer and silicate had a strong influence on the morphology of SAN/silicate nanocomposites. The exfoliated SAN I series had enhanced moduli and glass transition temperatures, T_g, compared to the intercalated SAN II series and pure SAN.     

Miscibility with positive deviation in Tg-composition relationship in blends of poly(2-vinyl pyridine)-block-poly(ethylene oxide) and poly(p-vinyl phenol)

Phase behavior and miscibility with positive deviation from linear T_g-composition relationship in a copolymer/homopolymer blend system, poly(2-vinyl pyridine)-block-poly(ethylene oxide) (P2VP-b-PEO)/poly(p-vinyl phenol) (PVPh), were investigated by differential scanning calorimetry (DSC), Fourier-transform infrared spectroscopy (FT-IR) and solid-state ¹³C nuclear magnetic resonance (¹³C NMR), optical microscopy (OM), and scanning electron microscopy (SEM). Optical and electron microscopy results as well as NMR proton spin-lattice relaxation times in laboratory frame () all confirmed the miscibility as judged by the T_g criterion using DSC. In comparison to the literature result on a homopolymer/homopolymer blend of P2VP/PVPh, fitting with the Kwei equation on the T_g-composition relationship for the block-copolymer/homopolymer blend of P2VP-b-PEO/PVPh blend system yielded a smaller q value (q = 120) for P2VP-b-PEO/PVPh than that for P2VP/PVPh blend (q = 160). The FT-IR and ¹³C NMR results revealed hydrogen-bonding interactions between the pendant pyridine group of P2VP-b-PEO and phenol unit in PVPh, which is responsible for the noted positive deviation of the T_g-composition relationship. Comparison of the shifts of hydroxyl IR absorbance band, reflecting the average strength of H-bonding, indicates a decreasing order of P2VP/PVPh > P2VP-b-PEO/PVPh > PEO/PVPh blends. The PEO block in the copolymer segment tends to defray the interaction strength in the P2VP-b-PEO/PVPh blends because of relative weaker interaction between PEO and PVPh than that between P2VP and PVPh pairs. A comparative ternary (P2VP/PEO)/PVPh blend was also studied as the controlling experiments for comparison to the P2VP-b-PEO/PVPh blend. The thermal behavior and interaction strength in (P2VP/PEO)/PVPh ternary blends are discussed with those in the P2VP-b-PEO/PVPh copolymer/homopolymer blend.     

Morphology and mechanical and dynamic mechanical properties of linear and star poly(styrene-b-isobutylene-b-styrene) block copolymers

The morphologies of solution cast linear and star poly(styrene-b-isobutylene-b-styrene) (SIBS) block copolymers, of ∼0.3-0.33 polystyrene (PS) volume fraction, were investigated using transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS) methods. The linear (L) and 4-arm star materials have hexagonal packed cylinder morphologies. TEM indicates more continuous domains for the 3-arm SIBS and SAXS indicates lamellar morphology. The diameters of the PS cylinders are 25-30 nm in all cases, but inter-domain distances increase in the order: L→3-arm star →4-arm star SIBS. Dynamic mechanical analysis shows a decrease of plateau modulus in the order L→3-arm →4-arm star. T_g for the PIB phase is independent of star-branching. T_g increases for the PS block phase from L- to 3-SIBS although T_g(PS) for 4-SIBS is not significantly greater than that of L-SIBS. A high temperature shoulder on the PIB block glass transition peak is associated with sub-Rouse motions. Tensile modulus is essentially the same for L- and 3-SIBS but considerably greater for 4-SIBS. Stress levels and energy-to rupture increase in the order: L-SIBS <3-SIBS <4-SIBS and this behavior is rationalized in terms of the covalent junction points, entanglements, and hard block domain reinforcement. The results of cyclic deformation studies of hysteresis vs. maximum percent strain per cycle are interpreted in terms of irreversible morphological rearrangements, chain slippage through entanglements, and the influence of degree of star branching on motional constraints. There is a permanent set that increases while the stress required to extend the sample to a given strain decreases with each cycle. For cycles of lower maximum strain, and before PS block domains are disrupted, microscopic deformation is viewed as somewhat reversible, accompanied by a measure of energy dissipated as a consequence of slow relaxation kinetics of chain rearrangement vs. rate of bulk deformation. At high strain, a major fraction of the energy loss is attributed to irreversible, longer ranged disruption of the PS domains leading to permanent morphological change and permanent set. Percent hysteresis for all three cases decreases—then increases—with increasing maximum percent strain per cycle. The initial decrease is thought of in terms of a progressive decrease in the entropy of stretched chains with consecutive extensions where the chains are increasingly less able to contribute to hysteresis until the PS domains become disrupted on a large scale, after which the curves begin to rise.     

Synthesis and properties of ABA-type triblock copolymers of poly(glycolide-co-caprolactone) (A) and poly(ethylene glycol) (B)

Poly(glycolide-co-caprolactone) (A)-poly(ethylene glycol) (B) ABA-type triblock copolymers (PGCE) were synthesized by bulk ring opening polymerization, using the hydroxyl endgroups of poly(ethylene glycol) (PEG) as initiator and stannous octoate as catalyst. The resulting copolymers were characterized by various analytical techniques. Gel permeation chromatographic analysis indicated that the polymerization product was free of residual monomers, PEG and oligomers. ¹H NMR and differential scanning calorimeter results demonstrated that the copolymers had a structure of poly(glycolide-co-caprolactone) (PGC) chains chemically attached to PEG segments. All the PGCE copolymers showed improved hydrophilicity in comparison with the corresponding PGC copolymers with the same molar ratio of glycolidyl and caproyl units. The microspheres of PGCE copolymer exhibited rough surfaces quite different from the smooth surface of PGC microspheres. This phenomenon was attentively ascribed to the highly swollen ability of PGCE copolymers and the freeze-drying process in the microspheres fabrication.     

Melt processed blends of poly(styrene-co-acrylonitrile) and poly(phenylene ether) compatibilized with polystyrene-b-polybutadiene-b-poly(methyl methacrylate) triblock terpolymers

Polystyrene-b-polybutadiene-b-poly(methyl methacrylate) triblock terpolymers (SBM) with equal (symmetric) and different (asymmetric) block lengths were used to compatibilize polymer blends based on poly(2,6-dimethyl-1,4-phenylene ether) (PPE) and poly(styrene-co-acrylonitrile) (SAN). First, the rheological behavior of the individual components and their binary mixtures was investigated. Based on the results, samples of PPE, SAN and SBM in weight ratios of 32/48/20 were melt blended and the morphology development during melt processing was investigated. It was found that a raspberry morphology, i.e. dispersion of PPE in SAN with rubbery PB domains at the PPE/SAN interface, could be achieved with a symmetric SBM with under sufficiently high shear rate, while a symmetric SBM with did not yield the desired morphology. Asymmetric SBMs with long PS blocks dissolved in the PPE phase did not display the expected compatibilization effect. In order to obtain a raspberry morphology with asymmetric copolymers it is suggested to pre-blend the SBM with SAN before adding the PPE. Finally it is shown that a commercial PPE containing High Impact Polystyrene (HIPS) as a toughness modifier can be compatibilized with SAN by melt processing using a symmetric SBM triblock terpolymer with      

Polymerization of ethylene oxide initiated by lithium derivatives via the monomer-activated approach: Application to the direct synthesis of PS-b-PEO and PI-b-PEO diblock copolymers

The anionic polymerization of ethylene oxide (EO) initiated by lithium derivatives is extremely sluggish and only yields very low molar mass EO oligomers because of the low reactivity of lithium alkoxide species. We show here that using the monomer-activated anionic polymerization approach, one can activate the C-O-Li bonds towards EO polymerization at low temperature and in non polar media. Starting from living polystyryllithium and polyisoprenyllithium, addition of triisobutylaluminum (i-Bu₃Al) in excess to lithium species triggers the propagation reaction of EO, allowing the direct synthesis, in a few hours, of poly(styrene-b-ethylene oxide) and poly(isoprene-b-ethylene oxide) diblock copolymers, with a molar mass of the PEO block up to 10 000 g/mol.     

Poly[(styrene-co-p-methylstyrene)-b-isobutylene-b-(styrene-co-p-methylstyrene)] triblock copolymers. 1. Synthesis and characterization

The synthesis of poly(isobutylene) (PIB)-based triblock copolymers having copolymer end blocks containing styrene and p-methylstyrene (pMSt) repeat units was investigated in an attempt to minimize chain-coupling reactions that occur at the 4-position on styrene repeat units during end block polymerization. Model end block copolymerizations using varying feed ratios of styrene and pMSt were conducted, and it was determined by ¹H NMR analysis that the addition of pMSt to the living chain end was favored slightly at low conversion. However, DSC revealed a single T_g that increased with increasing pMSt content verifying the absence of blockiness in the microstructure. Poly[(styrene-co-pMSt)-b-isobutylene-b-(styrene-co-pMSt)] triblock copolymers were synthesized using varying feed ratios of styrene and pMSt. The rate of end block propagation increased with increasing pMSt in the feed, and the end block copolymerizations initiated by PIB displayed longer reaction times and more curvature in their first order plots than did the model end block copolymerizations initiated by TMPCl. This effect was attributed to lower ionization equilibrium constant and higher degree of termination caused by the more non-polar local reaction medium provided by the PIB center blocks in block copolymerization. GPC analysis of the final BCPs revealed a decrease in a high molecular weight peak representing the chain-coupled product as the concentration of pMSt in the feed was increased.     

Precise preparation of four-arm-poly(ethylene glycol)-block-poly(trimethylene carbonate) star block copolymers via activated monomer mechanism and examination of their solution properties

The polymerization of trimethylene carbonate (TMC) in the presence of HCl·Et₂O via activated monomer mechanism was performed to synthesize 4a-PEG-b-PTMC star block copolymers composed of poly(ethylene glycol) (PEG) and poly(trimethylene carbonate) (PTMC) using four-arm (4a) PEG as an initiator. The TMC conversion and molecular weight of PTMC increased linearly with the polymerization time or the feed ratios of the TMC to 4a-PEG in the presence of HCl·Et₂O in CH₂Cl₂ at 25 °C. The obtained PTMC had molecular weights close to the theoretical value calculated from TMC to PEG molar ratio and exhibited monomodal GPC curve. We prepared successfully 4a-PEG-b-PTMC star block copolymers without metal catalyst at room temperature via living ring-opening polymerization (ROP) of TMC from 4a-PEG as an initiator in the presence of HCl·Et₂O as a monomer activator. The CMCs of the 4a-PEG-b-PTMC star block copolymers determined from fluorescence measurements. The CMCs of the 4a-PEG-b-PTMC star block copolymers decreased in the order of the increase in the PTMC segment. The partition equilibrium constant, K_v, which is an indicator of the hydrophobicity of the micelles of the 4a-PEG-b-PTMC star block copolymers in aqueous media, increased with the increase in the PTMC segment. In conclusion, we confirmed that the 4a-PEG-b-PTMC star block copolymers form micelles and hence may be potential hydrophobic-drug delivery vehicles.     

Synthesis and characterization of hexafluoroisopropylidene bisphenol poly(arylene ether sulfone) and polydimethylsiloxane segmented block copolymers

A series of hexafluoroisopropylidene bisphenol poly(arylene ether sulfone) (BAF PAES) segmented block copolymers with varying fractions of polydimethylsiloxane (PDMS) were synthesized by a condensation reaction of hydroxyl-terminated BAF PAES and dimethylamino endcapped PDMS. The segmented block copolymers have high thermal stability. The BAF PAES homopolymer exhibits a tensile modulus of 1700 MPa and an elongation at break of 16%. Copolymerizing BAF PAES with increasing molecular weight amounts of PDMS results in tensile properties ranging from plastic to elastomeric where the elongation is 417% for a segmented block copolymer with 64 wt% PDMS incorporated. The morphological properties of these segmented block copolymers were characterized by atomic force microscopy (AFM), small-angle X-ray scattering (SAXS), and transmission electron microscopy (TEM). AFM and TEM images show the segmented block copolymers were microphase separated, and comparison with bisphenol A (BA) PAES-b-PDMS segmented block copolymers revealed complex differences between the morphological behavior of the two systems. SAXS data of the segmented block copolymers supports AFM and TEM images, indicating microphase separation but little long-range order.     

Effects of micelle structures formed in selective solvents on crystallization behaviors of poly(ethylene glycol)-b-poly(styrene) copolymers

Well-defined amphiphilic block copolymers, poly(ethylene glycol) methyl ether-b-poly(styrene) (mPEG-b-PS), in which the PS blocks had different molecular weights, were synthesized by atom transfer radical polymerization (ATRP). Through introduction of selective solvents for the blocks, crystalline and amorphous blocks were self-assembled into different micelle structures in solutions. Atomic force microscopy (AFM) was used to characterize the micelle structures. It was observed that spherical micelles were always formed, whereas lamellar aggregates appeared only in the PS-selective solvent when the molecular weight of the PS block in mPEG-b-PS was low. The crystallizable mPEG blocks were self-assembled into either the core or corona of the micelles formed. The effects of the self-assembled structures on the crystallization behavior of mPEG blocks were then investigated with differential scanning calorimeter (DSC). When the PS molecular weight was much larger than that of mPEG, the result showed that the crystallinity of the mPEG block was lower when mPEG blocks crystallized in the corona than that in the core of the micelles. In this case, when mPEG blocks crystallized in micelle coronae, the micelle core formed by insoluble PS blocks was very big, so mPEG chains had to distribute sparsely in the micelle coronae. It was hard for mPEG chains in one micelle or among different micelles to gather together to crystallize. However, when the PS molecular weight was lower than that of mPEG, the crystallinity of mPEG was higher when the mPEG chains crystallized in the micelle corona, as the core formed by insoluble PS was small and the mPEG chains in the corona were easy to aggregate and crystallize.     

Disparate polymerization facilitates the synthesis of versatile block copolymers from poly(trimethylene carbonate)

A disparate polymerization technique is utilized for preparing versatile block copolymers from poly(trimethylene carbonate) (poly(TMC)). In this study, 4-(chloromethyl)benzyl alcohol (CBA) is used for the disparate polymerization. The hydroxyl group of CBA is involved in ring-opening polymerization and the benzyl chloride group is involved in incorporating dithiocarbamate for pseudo-living radical polymerization. First, TMC is polymerized from the hydroxyl group of CBA by using an organocatalyst. The benzyl chloride group in CBA is modified using a dithiocarbamate, and then vinyl and methacrylate monomers are polymerized by photo-driven pseudo-living radical polymerization. The resulting block copolymers are versatile and the molecular weight distribution is reasonably narrow. In the present study, N-isopropylacrylamide, acrylamide glycolic acid, and 2-hydroxyethyl methacrylate are used for the disparate polymerization. The resulting block copolymers could be well dissolved in water by incorporation of hydrophilic segment into hydrophobic poly(TMC). The solution property is characterized in terms of hydrophobic domain formation and phase transition under ambient conditions. Moreover, enzymatic degradation is evaluated by using a copolymer-coated substrate. The block copolymer synthesis technique is considerably versatile, and the resulting polymer function can be freely designed. The disparate polymerization technique is a promising approach that provides universal materials for integrating biodegradable polyesters and functional polymers.     

Controllable synthesis of poly(N-vinylpyrrolidone) and its block copolymers by atom transfer radical polymerization

At room temperature atom transfer radical polymerization (ATRP) of N-vinylpyrrolidone (NVP) was carried out using 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetra-azacyclo-tetradecane (Me₆Cyclam) as ligand in 1,4-dioxane/isopropanol mixture. Methyl 2-chloropropionate (MCP) and copper(I) chloride were used as initiator and catalyst, respectively. The polymerization of NVP via ATRP could be mediated by the addition of CuCl₂. The resultant poly(N-vinylpyrrolidone) (PNVP) has high conversion of up to 65% in 3 h, a controlled molecular weight close to the theoretical values and narrow molecular weight distribution between 1.2 and 1.3. The living nature of the ATRP for NVP was confirmed by the experiments of PNVP chain extension. With PNVP-Cl as macroinitiator and N-methacryloyl-N′-(α-naphthyl)thiourea (MANTU) as a hydrophobic monomer, novel fluorescent amphiphilic copolymers poly(N-vinylpyrrolidone)-b-poly(N-methacryloyl-N′-(α-naphthyl)thiourea) (PNVP-b-PMANTU) were synthesized by ATRP. PNVP-b-PMANTU copolymers were characterized by ¹H NMR, GPC-MALLS and fluorescence measurements. The results revealed that PNVP-b-PMANTU presented a blocky architecture.     

New miscible blends composed of polysulfone and poly(1-vinylpyrrolidone-co-acrylonitrile) copolymers and their phase behavior

The miscibility of polysulfone, PSf, blend with poly(1-vinylpyrrolidone), PVP, and that of PSf blend with poly(1-vinylpyrrolidone-co-acrylonitrile) copolymers, P(VP-AN), containing various amount of VP were explored. Even though PSf did not formed miscible blends with PVP when both components had high molecular weight, it formed miscible blend with PVP by decreasing molecular weight of PVP. PSf also formed homogeneous mixtures with P(VP-AN) containing AN from 2 to 16 wt%. These miscible blends underwent phase separation on heating caused by LCST-type (lower critical solution temperature-type) phase behavior. The phase separation temperature of miscible blends first increases with AN content, goes through a maximum centered at about 8 wt% AN. Interaction energies of binary pairs involved in blends were evaluated from the observed phase boundaries using the lattice-fluid theory. The decline of the contact angle between water and blend film by increasing P(VP-AN) content in blend indicated that the hydrophobic properties of PSf could be improved by blending with P(VP-AN) copolymers.     

Synthesis and characterization of graft copolymers with poly(epichlorohydrin-co-ethylene oxide) as backbone by combination of ring-opening polymerization with living anionic polymerization

Series of graft copolymers with [Poly(epichlorohydrin-co-ethylene oxide)] [Poly(ECH-co-EO)] as backbone and polystyrene (PS), poly(isoprene) (PI) or their block copolymers as side chains were successfully synthesized by combination of ring-opening polymerization (ROP) with living anionic polymerization. The Poly(ECH-co-EO) with high molecular weight (M_n = 3.3 × 10⁴ g/mol) and low polydispersity index (PDI = 1.34) was firstly synthesized by ring-ROP using ethylene glycol potassium as initiator and triisobutylaluminium (i-Bu₃Al) as activator. Subsequently, by “grafting onto” strategy, the graft copolymers Poly(ECH-co-EO)-g-PI, Poly(ECH-co-EO)-g-PS and Poly(ECH-co-EO)-g-(PI-b-PS) were obtained using the coupling reaction between living PI⁻Li⁺, PS⁻Li⁺ or PS-b-PI⁻Li⁺ species capped with or without 1,1-diphenylethylene (DPE) agent and chloromethyl groups on poly(ECH-co-EO). By model experiment, the addition of DPE agent was confirmed to have an important effect on the grafting efficiency at room temperature. Finally, the target graft copolymers and intermediates were characterized by SEC, ¹H NMR, MALLS and FTIR in detail, and thermal behaviours of the graft copolymers were also investigated by DSC measurement.     

Enhancement of the mechanical properties of poly(styrene-co-acrylonitrile) with poly(methyl methacrylate)-grafted multiwalled carbon nanotubes

Poly(methyl methacrylate) (PMMA) was grafted onto multiwalled carbon nanotubes (MWNTs). Composites of PMMA-grafted MWNTs and poly(styrene-co-acrylonitrile) (SAN) were prepared by solution casting from tetrahydrofuran. Since PMMA is miscible with SAN, the two polymers mix intimately to facilitate the dispersion of PMMA-grafted MWNTs in the SAN matrix. The intimate mixing is evidenced by the transparency of the composites. The incorporation of PMMA-grafted MWNTs to SAN (effective MWNT content=0.5-2 wt%) leads to increases in storage modulus at 40 °C, Young's modulus, tensile strength, ultimate strain, and toughness by 90, 51, 99, 184 and 614%, respectively. Such simultaneous increases in stiffness, strength, ductility and toughness of a polymer by rigid fillers are rarely observed.     

Electrospinning of poly(styrene-co-maleic anhydride) (SMA) and water-swelling behavior of crosslinked/hydrolyzed SMA hydrogel nanofibers

Random and alternating poly(styrene-co-maleic anhydrides) (SMAs) with respective maleic anhydride (MAh) content of 32 and 48% were synthesized through radical polymerization. SMA nanofibers with diameter down to 180 nm were generated by electrospinning from solvents acetone, dimethylformamide (DMF), and their mixtures. Fiber diameter increased dramatically when the SMA concentration in the spinning solution reached to a critical point where the SMA chains are extensively entangled. The diameter of SMA nanofiber decreased with increasing DMF content in the mixture, but beads are often accompanied as DMF content is over 50%. The optimum acetone/DMF ratio was found to be 2:1, in which continuous electrospinning was achieved and bead-free nanofibers were obtained. SMA nanofibers with MAh content of 32 and 48% were crosslinked with diethyleneglycol and subsequently hydrolyzed in NaOH/EtOH to turn SMA into crosslinked sodium form SMA (SMA-Na) hydrogel nanofiber. These hydrogel nanofibers were able to retain fiber form after immersing in water for 24 h. Their water absorption ratio was up to 37.6 and 8.2 g/g in distilled water and 0.25 N NaCl aq. solution, respectively.     

Facile synthesis of diphenylethylene end-functional polyisobutylene and its applications for the synthesis of block copolymers containing poly(methacrylate)s

The convenient synthesis of methoxy-free 1,1-diphenylethylene end-functionalized polyisobutylene (PIB-DPE) has been accomplished by capping living PIB with 1,4-bis(1-phenylethenyl)benzene, followed by hydride transfer reaction with tributylsilane. The proposed method eliminates the need for methylation of the capped living PIB in which large excess of dimethylzinc must be used, resulting in a large amount of inorganic salt contamination. The obtained PIB-DPE was quantitatively lithiated with 1.5-fold excess n-butyllithium in tetrahydrofuran (THF) at room temperature. The methine proton at the chain end remained intact during the lithiation procedure. The resulting macroanion efficiently initiated the polymerization of alkyl methacrylates. Poly(methyl methacrylate) (PMMA)-b-PIB-b-PMMA, poly(2-hydroxyethyl methacrylate) (PHEMA)-b-PIB-b-PHEMA and poly(tert-butyl methacrylate) (P^tBMA)-b-PIB-b-P^tBMA have been prepared with high blocking efficiency by the proposed methodology. Complete hydrolysis of P^tBMA-b-PIB-b-P^tBMA into poly(methacrylic acid) (PMAA)-b-PIB-b-PMAA was realized in THF/1,4-dioxane, as confirmed by FTIR, ¹H NMR, and DSC analyses.     

刚柔嵌段共聚物聚苯基喹啉-b-聚苯乙烯的合成

利用原子转移自由基聚合合成了端羧基聚苯乙烯,然后与4-氨基苯乙酮反应,生成末端为乙酰基的聚合物,以P2O5为催化剂,将功能化的聚合物与5-乙酰基-2-氨基二苯甲酮共聚,合成出刚柔嵌段共聚物聚苯基喹啉-b-聚苯乙烯(PPO-b-PS),用红外光谱(IR)、氢核磁共振(1HNMR)和热重分析(TGA)对其结构和性能进行了表征,并在三氟乙酸／二氯甲烷混合溶剂中进行了初步的自组装研究。