Synthesis of block copolymers for surface functionalization with stimuli-responsive macromolecules

Using block copolymers with poly(n-butyl acrylate) (PBA) as anchor block being capable to tether the temperature-responsive block poly(N-isopropylacrylamide) (PNIPAAm) to the surface, polysulfone (PSf) films were functionalized applying an adsorption/surface entrapment process. Homo and block copolymer synthesis was investigated applying atom transfer radical polymerization (ATRP) using tris(2-(dimethylamino)ethyl)amine (Me₆TREN), CuCl and N,N-dimethylformamide (DMF). On basis of the determined critical micelle concentration of the block copolymers, surface functionalization of PSf was performed from an aqueous solution containing 25 vol% dimethylacetamide. These functionalized surfaces exhibit reversible temperature dependent properties due to the lower critical solution temperature (LCST) of PNIPAAm as can be proven by contact angle measurement. Furthermore, the beneficial effect of the PBA block with adjusted molecular weight on the stability of these coatings was proven. This surface functionalization method has various potential applications and the resulting surfaces are anticipated to exhibit actively triggerable ‘chaotic’ properties as basis of an efficient anti-biofouling strategy.     

Synthesis of well-defined star polymers and star block copolymers from dendrimer initiators by atom transfer radical polymerization

Novel polyarylether dendrimers with 1,3,5-tri(4-hydroxyphenoxy)benzene core, polybenzylether interior, and benzyl 2-bromoisobutyrate surface group (CMGn-Br, n=1-3, with functionality of 6, 12, and 24, respectively) were prepared by convergent procedure. ATRP of tert-butyl acrylate (tBA) and styrene (St) with CMGn-Br dendrimer initiators in the presence of CuBr/pentamethyldiethylenetriamine catalytic system was investigated in detail, and a series of well-defined dendrimer-like star PtBA and PSt with precise arm numbers were synthesized under suitable conditions. The quantitative initiation of the dendrimer initiators was demonstrated by high initiation efficiency, ¹H NMR spectra, hydrolysis, and MALLS/SEC approach. Star block copolymers comprising PSt and PtBA segments with low polydispersity (1.08<M_w/M_n<1.18) were also successfully synthesized using functional macroinitiators by block copolymerization. In addition, the thermal properties of the resultant polymers were characterized by DSC and TGA.     

Poly[(2-ethylhexyl acrylate)-ran-(tert-butyl acrylate)]-block-poly(2-cinnamoyloxyethyl acrylate) synthesis and properties

Poly[(2-ethylhexyl acrylate)-ran-(tert-butyl acrylate)]-block-poly(2-cinnamoyloxyethyl acrylate) or P(EXA-r-tBA)-PCEA was synthesized by atom transfer radical polymerization. Reactivity ratios of EXA and tBA for copolymerization were determined. The specific refractive index increments of six diblocks were measured as a function of their composition. The diblocks were thermally stable and formed micelles in an automobile engine oil. Such micelles may be useful as an anti-friction additive in lubricating oils.     

Amphiphilic block copolymers bearing strong push-pull azo chromophores: Synthesis, micelle formation and photoinduced shape deformation

In this work, a series of amphiphilic diblock copolymers bearing strong push-pull type azo chromophores was synthesized through post-polymerization azo-coupling reaction scheme. The copolymers (P(CNAZO_m-b-MAA_n)), composed of 2-(N-ethyl-N-(4-(4′-cyanophenylazo)-phenyl)amino)ethyl methacrylate (CNAZO) and methacrylic acid (MAA) blocks, were obtained through four-step reactions. Firstly, precursor diblock copolymers (P(EMA_m-b-tBMA_n)) were obtained through sequential two-stage ATRP reactions of 2-(N-ethyl-N-phenylamino)ethyl methacrylate (EMA) and tert-butyl methacrylate (tBMA). Then, 4-amino-4′-cyanoazobenzene chromophores were introduced by azo-coupling reaction of P(EMA_m-b-tBMA_n) with diazonium salt of 4-aminobenzonitrile. Finally, P(CNAZO_m-b-MAA_n) was obtained through selective hydrolysis of the tert-butyl ester linkages in the tBMA blocks. Three block copolymers with the same CNAZO block length (m = 100) and different MAA block lengths (n = 5, 13, 23) were prepared by this method. The polymer and copolymers prepared in the process were characterized by GPC, ¹H NMR, UV-vis, DSC and TGA measurements. Results show that P(CNAZO_m-b-MAA_n) forms spherical micellar aggregates by gradually increasing the water content in THF/H₂O mixtures. The diameters of the spherical aggregates are related to the composition of the block copolymers and the water-adding rate. The block copolymer with larger molecular weight of the hydrophilic MAA block forms the aggregates with the smaller average size. The increase of the water-adding rate also shows an effect to reduce the diameters. Upon irradiation with a linearly polarized Ar⁺ laser beam, the spherical aggregates can be elongated in the light polarization direction. The deformation degree shows an almost linear dependence on the light irradiation time in the testing period. The deformed aggregates can recover the original spherical shape after thermal annealing at a temperature above T_g of the block copolymer.     

The amphiphilic block copolymers of 2-(dimethylamino)ethyl methacrylate and methyl methacrylate: Synthesis by atom transfer radical polymerization and solution properties

Amphiphilic di- and tri-block copolymers of poly(methyl methacrylate) (PMMA) and poly(2-dimethylamino)ethyl methacrylate (PDMAEMA) have been synthesized by atom transfer radical polymerization (ATRP) at ambient temperature (35 °C) in the environment-friendly solvent, aqueous ethanol (water 16 vol%) using CuCl/o-phenanthroline as the catalyst. The PDMAEMA blocks are contaminated with ethyl methacrylate (EMA) residues to the extent of 1-2 mol% of DMAEMA depending on the length of the PDMAEMA block. The EMA forms through the autocatalyzed ethanolysis of the DMAEMA monomer and undergoes random copolymerization with the latter. The rate of ethanolysis is unexpectedly greater in the aqueous ethanol than in neat ethanol, which has been attributed to the higher polarity of the former than of the latter. In contrast to the ethanolysis no hydrolysis of DMAEMA in the aqueous ethanol medium could be detected for 133 h. The block copolymers form micelles in water. Their solubility and CMC in neutral water have been studied. Dynamic light scattering (DLS) studies reveal that for a fixed degree of polymerization (DP) of the PMMA block the hydrodynamic diameter of the micelles in methanolic water (water 95 vol%) increases at a faster rate with the DP of the PDMAEMA block when it is much greater than that of the PMMA block compared to when it is less than or close to that of the latter.     

Synthesis of thermoresponsive poly(N-isopropylmethacrylamide) and poly(acrylic acid) block copolymers via post-functionalization of poly(N-methacryloxysuccinimide)

Polymers exhibiting a thermoresponsive, lower critical solution temperature (LCST) phase transition have proven to be useful for many applications as “smart” or “intelligent” materials. A series of poly(N-isopropylmethacrylamide) (PNIPMAM) polymer, poly(N-isopropylmethacrylamide)-b-poly(acrylic acid) (PNIPMAM-b-PAA) diblock, and poly(acrylic acid)-b-poly(N-isopropylmethacrylamide)-b-poly(acrylic acid) (PAA-b-PNIPMAM-b-AA) triblock copolymer samples were synthesized via ATRP. A facile post-functionalization route was developed that uses an activated ester functionality to convert poly(N-methacryloxysuccinimide) (PMASI) blocks to LCST capable polyacrylamide, while poly(t-butyl acrylate) (PtBA) blocks were converted to water-soluble poly(acrylic acid) (PAA). The post-functionalization was monitored via ¹H NMR and ATR-FTIR. The aqueous solution properties were explored and the PNIPMAM polymers were shown to have a LCST phase transition varying from 35 to 60 °C. The ability to synthesize block copolymers that are thermoresponsive and water-soluble will be of great benefit for broader applications in drug delivery, bioengineering, and nanotechnology.     

Synthesis and characterization of pH/temperature-sensitive block copolymers via atom transfer radical polymerization

In order to prepare well-defined pH-sensitive block copolymers with a narrow molecular weight distribution (MWD), we synthesized a pH-sensitive block copolymer via atom transfer radical polymerization (ATRP) of sulfamethazine methacrylate monomer (SM) and amphiphilic diblock copolymers by the ring-opening polymerization of d,l-lactide/?-caprolactone (LA/CL), and their sol-gel phase transition was investigated. SM, which is a derivative of sulfonamide, was used as a pH responsive moiety, while PCLA-PEG-PCLA was used as a biodegradable, as well as a temperature sensitive one, amphiphilic triblock copolymer. The pentablock copolymer, OSM-PCLA-PEG-PCLA-OSM, was synthesized using Br-PCLA-PEG-PCLA-Br as an ATRP macroinitiator. The number average molecular weights of SM were controlled by adjusting the monomer/initiator feed ratio. The macroinitiator was synthesized by the coupling of 2-bromoisobutyryl bromide with PCLA-PEG-PCLA in the presence of triethyl amine catalyst in dichloromethane. The resultant block copolymer shows a narrow polydispersity. The block copolymer solution shows a sol-gel transition in response to a slight pH change in the range of 7.2-8.0. Gel permeation chromatography (GPC) and NMR were used for the characterization of the polymers that were synthesized.     

Synthesis of amphiphilic rod-coil ABC triblock copolymers with oligo(para-phenyleneethynylene) as the middle rigid block

An amphiphilic rod-coil ABC triblock copolymers using rigid oligo(para-phenyleneethynylene) (OPE) as the middle rod segment, poly(ethylene oxide)-block-oligo(para-phenyleneethynylene)-block-polystyrene (PEO-b-OPE-b-PS), was designed and successfully synthesized. In the synthetic route, a kind of macroinitiator, PEO-b-OPE-Br was achieved by stepwise coupling of iodo-terminated poly(ethylene oxide) and oligo(para-phenyleneethynylene) with amino end group, capping with 2-bromopropionyl bromide. Subsequently, from this macroinitiator atom transfer radical polymerization (ATRP) of styrene was performed to obtain PEO-b-OPE-b-PS. The resulting copolymers were characterized by nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC). All these novel copolymers were affirmed to have well-defined structures and narrow molecular weight distributions.     

Preparation and surface properties of fluorine-containing diblock copolymers

Two series of semifluorinated fluorocarbon diblock copolymer poly(butyl methacrylate-co-perfluoroalkyl acrylate) have been synthesized by atom transfer radical polymerization (ATRP). The ¹H NMR, F-EA, GPC and FTIR were used to characterize copolymer structure. Contact angle measurements on the thin polymer films showed low critical surface tensions and low dispersion force contributions to the surface energy, which indicated the presence of the fluorinated block at the surface. The results showed that the water- and oil-repellency increased with the fluorine content in the diblock copolymers. After annealing at different temperatures or different times, the water- and oil-repellent properties of diblock copolymer were increased to approach maximum values. This phenomenon proves the propensity of polymer for fluorine enrichment at air-polymer surface.     

Synthesis and characterization of side-chain liquid crystalline homopolymers and block copolymers containing biphenyl-4-ylthiophene and biphenyl-4-ylfluorene pendants

A series of new liquid crystalline homopolymers (P1 and P2) and block copolymers (P3 and P4) composed of methacrylates containing pendant biphenyl-4-ylthiophene (M1) and biphenyl-4-ylfluorene (M2) units were synthesized by atom transfer radical polymerization (ATRP). The number-average molecular weights (M_n) of the homopolymer (P2) and diblock copolymers (P3 and P4) were in the range of 5153-8713 g mol⁻¹ with polydispersity indices (PDIs) between 1.17 and 1.25. The thermal, mesogenic, and photoluminescence (PL) properties of all polymers were investigated. Except for the absence of mesogenic properties in block copolymer P4, polymers P1 and P3 possessed the smectic A phase and polymer P2 exhibited the nematic phase. Moreover, the mesomorphism and the layer d-spacing values of the smectic A phase in polymers P1 and P3 were confirmed and characterized by X-ray diffraction (XRD) patterns.     

Synthesis and applications of triblock and multiblock copolymers using telechelic oligopropylene

Isotactic polypropylene (iPP)-polystyrene (PS) and iPP-poly(methyl methacrylate) (PMMA) multiblock copolymers were synthesized by atom transfer radical coupling (ATRC) of PS-iPP-PS and PMMA-iPP-PMMA triblock copolymers obtained by atom transfer radical polymerization (ATRP) of styrene (St) and methyl methacrylate (MMA), respectively, using α,ω-dibromoisobutyrateoligopropylene (iPP-Br) as a bifunctional macroinitiator. The iPP-Br was prepared by hydroxylation and subsequent esterification of telechelic oligopropylene having terminal vinylidene double bonds at both ends obtained by controlled thermal degradation of iPP. ATRP of St and (meth) acrylic monomers using iPP-Br formed the corresponding triblock copolymers. It was confirmed that the PMMA-iPP-PMMA triblock copolymer was effective as the compatibilizer for the iPP/PMMA blend. An iPP-PS multiblock copolymer (M_n: 25?000 g/mol and M_w/M_n: 4.1) was prepared by ATRC of PS-iPP-PS triblock copolymer (M_n: 8900 g/mol and M_w/M_n: 1.3). ATRC with St of PMMA-iPP-PMMA triblock copolymer (M_n: 13?000 g/mol and M_w/M_n: 1.4) provided an iPP-PMMA multiblock copolymer containing St chains (M_n: 39?000 g/mol and M_w/M_n: 2.8).     

A new strategy for the one-step synthesis of block copolymers through simultaneous free radical and ring opening polymerizations using a dual-functional initiator

Block copolymers are fascinating and complex materials that have been used in a range of diverse scientific and technological capacities. We demonstrate that a single one-step approach based on dual simultaneous polymerizations is a viable technique for the synthesis of a wide range of block copolymers by combining two dissimilar polymerization systems and using a dual-functional initiator. The main advantage of this methodology is that a simple, one-step, and simultaneous polymerization occurs in the bulk, which makes this process very attractive from both industrial and academic points of view. We plan to study the reaction kinetics and evaluate how well the ring opening catalyst [in this case, Sn(oct)₂] works under reverse ATRP conditions.     

Synthesis and characterization of dendritic-linear-dendritic triblock copolymers based on poly(amidoamine) and polystyrene

Dendritic-linear-dendritic triblock copolymers composed of linear polystyrene (PSt) and poly(amidoamine) dendrons have been successfully synthesized. Two bromines-terminated PSt with M_n = 13,000 was prepared by atom transfer radical polymerization (ATRP) using α,α′-dibromo-p-xylene as initiator. Then the terminal bromines at both ends of PSt chains were replaced by one imine group of piperazine (PZ), and further Michael addition reaction of terminal PZ with excess 1,3,5-triacryloylhexahydro-1,3,5-triazine (TT) produced the first generation (G₁) of the triblock copolymer. Continuous growth of dendrons from G1.5 to G4 at the both ends of PSt chains was carried out by the iterative Michael addition reactions with excess PZ and following TT. The ABA triblock copolymers composed of the G₁-G₄ dendrons and the linear PSt were obtained. Structures of the triblock polymers were characterized by GPC and ¹H NMR spectra. Thermal phase transitions of the polymers were studied by DSC measurements, and all of the copolymers displayed a glass transition temperature.     

Block and star block copolymers by mechanism transformation. VIII Synthesis and characterization of triblock poly(LLA-b-St-b-MMA) by combination of ATRP and ROP

Block copolymers, poly(LLA-b-St)s and triblock copolymes, poly(LLA-b-St-b-MMA)s have been synthesized by the combination of the atom transfer radical polymerization (ATRP) with ring-opening polymerization (ROP) using bifunctional initiator β-hydroxylethyl α-bromoisobutyrate (HEBIB) without intermediate function transformation. The molecular weight (MW) and the molecular weight distribution (MWD) can be controlled. The structures of the copolymers were confirmed by ¹H NMR spectroscopy and GPC.     

Comparison of thermomechanical properties of statistical, gradient and block copolymers of isobornyl acrylate and n-butyl acrylate with various acrylate homopolymers

Well-defined statistical, gradient and block copolymers consisting of isobornyl acrylate (IBA) and n-butyl acrylate (nBA) were synthesized via atom transfer radical polymerization (ATRP). To investigate structure-property correlation, copolymers were prepared with systematically varied molecular weights and compositions. Thermomechanical properties of synthesized materials were analyzed via differential scanning calorimetry (DSC), dynamic mechanical analyses (DMA) and small-angle X-ray scattering (SAXS). Glass transition temperature (T_g) of the resulting statistical poly(isobornyl acrylate-co-n-butyl acrylate) (P(IBA-co-nBA)) copolymers was tuned by changing the monomer feed. This way, it was possible to generate materials which can mimic thermal behavior of several homopolymers, such as poly(t-butyl acrylate) (PtBA), poly(methyl acrylate) (PMA), poly(ethyl acrylate) (PEA) and poly(n-propyl acrylate) (PPA). Although statistical copolymers had the same thermal properties as their homopolymer equivalents, DMA measurements revealed that they are much softer materials. While statistical copolymers showed a single T_g, block copolymers showed two T_gs and DSC thermogram for the gradient copolymer indicated a single, but very broad, glass transition. The mechanical properties of block and gradient copolymers were compared to the statistical copolymers with the same IBA/nBA composition.     

Synthesis and characterization of ABC ternary segregated H-shaped copolymers

The synthesis of a novel ABC ternary segregated H-shaped copolymer is described, of which a central poly(ethylene glycol) (PEG) chain is terminated on both sides by polystyrene (PS) and poly(tert-butylacrylate) (PtBA) chains. The synthetic procedure involves functionalization of PEG by 2-bromosuccinic anhydride followed by esterification of 1,6-hexanediol, which gives its ends the bifunctional nature that allows sequential growth of two PS, then two PtBA arms via atom transfer radical polymerization (ATRP). The resulting segregated H-shaped copolymers were characterization by NMR spectroscopy and gel permeation chromatography (GPC). All these copolymers were affirmed to have well-defined structures and narrow molecular weight distributions.     

Synthesis of block copolymers from PDMS macroinitiators

The synthesis of polystyrene‐b‐polydimethylsiloxane‐b‐polystyrene (PSt‐b‐PDMS‐b‐PSt) copolymers is described. Commercially available difunctional PDMS containing vinylsilyl terminal species was reacted with hydrogen bromide resulting in the PDMS macroinitiators. The terminal alkyl bromide groups were then used as initiators for atom transfer radical polymerization (ATRP) to produce block copolymers. Using this technique, triblock copolymers consisting of a PDMS centre block and polystyrene terminal blocks were synthesized. ATRP of St from those macroinitiators showed linear increases in M_n with conversion, demonstrating the effectiveness of ATRP to synthesize a variety of inorganic/organic polymer hybrids. Copyright © 2004 Society of Chemical Industry     

Heterografted PEO-PnBA brush copolymers

A series of P[(HEMA-TMS)-co-PEOMA] graft copolymers with different amounts of incorporated macromonomer grafts were prepared by copolymerization of a PEO macromonomer (PEOMA, MW_av=1100 g/mol, DP_PEO=23) with 2-(trimethylsilyloxy)ethyl methacrylate (HEMA-TMS) using various initial ratios of the comonomers via atom transfer radical polymerization. After transformation of the HEMA-TMS units to 2-(2-bromopropionyloxy)ethyl methacrylate (BPEM), the resulting P(BPEM-co-PEOMA) copolymers were used as macroinitiators for the controlled polymerization of nBA in a ‘grafting from’ reaction. The resulting densely heterografted brush copolymers with a uniform length of PEO grafts (DP_PEO=23) and a range of lengths for the PnBA side chains (DP_PnBA=15-60) depending solely on the reaction time. Analysis of the bulk properties showed that the specific architecture of the copolymers suppresses crystallization of the PEO, and consequently leads to amorphous, homogeneous materials.     

Synthesis of symmetric H-shaped block copolymer by the combination of ATRP and living anionic polymerization

A novel fluorescent dye labeled H-shaped block copolymer, (PMMA-Fluor-PS)₂-PEO-(PS-Fluor-PMMA)₂, is synthesized by the combination of atom transfer radical polymerization (ATRP) and anionic polymerization (AP). To obtain the designated structure of the copolymer, a macroinitiator, 2,2-dichloro acetyl-PEO-2,2-dichloro acetyl (DCA-PEO-DCA), was prepared from DCAC and poly(ethylene oxide). The copolymer was characterized by ¹H NMR, GPC and fluorescence spectroscopy.     

Synthesis of block copolymers by combination of ATRP and photoiniferter processes

BACKGROUND: Block copolymers of monomers polymerizing by different mechanisms can be prepared by the transformation approach. A wide range of combinations of different polymerization modes has been reported in the literature. In this work, the transformation approach was further extended to the preparation of block copolymers by combining atom transfer radical polymerization (ATRP) and photoiniferter processes. RESULTS: Photoactive morpholine‐4‐dithiocarbamate‐terminated polystyrene (MDC‐PS‐MDC) was prepared by the reaction of dibrominated polystyrene, obtained by ATRP, with morpholine‐4‐dithiocarbamate sodium salt in dimethylformamide. The structure of MDC‐PS‐MDC was confirmed by ¹H NMR and UV‐visible spectral analysis. The ability of MDC‐PS‐MDC to act as a photoiniferter for the block copolymerization of methyl acrylate was examined. The polymerization shows a ‘living’ character at up to 25% conversion and produces well‐defined polymers with molecular weights close to those predicted from theory and relatively narrow polydispersities (M_w/M_n ≈ 1.40). CONCLUSION: It is demonstrated that the end groups of polymers obtained by ATRP can be converted into morpholino‐4‐dithiocarbamate groups which act as photoiniferters. In this way, the desired mechanistic transformation between two controlled free radical polymerization methods can be achieved. Copyright © 2008 Society of Chemical Industry