Synthesis of multi-arm star polystyrene with hyperbranched polyether core

Multi-arm star polystyrenes with hyperbranched poly(3-ethyl-3-oxetanemethanol) (PEOM, 3) core were synthesized by atom transfer radical polymerization (ATRP) method. The structures of polymers were confirmed by FT-IR and ¹H NMR. GPC results showed that the resultant polymers had relatively low polydispersity indices (PD = 1.47-2.03). DSC analysis indicated that polystyrene star polymers had a glass transition temperature (T_g = 42.2-91.5 °C) that changed with the amount of the polystyrene in the polymers. In addition, the aggregation behavior of the multi-arm star polystyrenes in a selective solvent (THF/cyclohexane) was probed with polystyrene arms that encapsulated in the aggregates and PEOM cores hidden in the center of the micelles.     

Synthesis and characterization of H-type amphiphilic liquid crystalline block copolymers by ATRP

H-type amphiphilic liquid crystalline block copolymers containing azobenzene were synthesized by atom transfer radical polymerization （ATRP）. Macroinitiators prepared by the esterification between poly（ethylene oxide） （PEG） and 2,2-dichloroacetyl chloride were utilized to initiate the polymerization of 6-[4-（4-ethoxyphenylazo）phenoxy]hexyl rnethacrylate （M6C）. The resulting macroinitiators and block copolymers were characterized by ^1H NMR, gel permeation chromatography （GPC）. Polarizing optical microscopy （POM） and differential scanning calorimetry （DSC） preliminarily revealed the liquid crystalline property of these block copolymers. This series of liquid crystalline block copolymers are promising in some areas, such as optical data storage, optical switch, and molecular devices.     

Synthesis by ATRP and effects of molecular weight on photomechanical properties of liquid crystalline polymers containing side-chain azobenzene chromophores

The synthesis of a series of azobenzene containing liquid crystalline methacrylic homopolymers, poly(4-ω-methacryloyloxy-hexyloxy-4′-ethoxyazobenzene) [Poly(M6A)], with distinct average chain lengths and low polydispersity has been achieved by Atom Transfer Radical Polymerization (ATRP) in THF solution using allyl 2-bromoisobutyrate as initiator and Cu(I)Br as catalyst. Under the adopted conditions the living centers concentration is found to be constant throughout the polymerization process and well defined chain end-groups are obtained. All the obtained polymeric samples, having average molecular mass ranging from 3300 to 14000 g/mol, exhibit smectic and nematic liquid-crystalline phases on heating, with transition temperatures strongly dependent on polymerization degree, as characterized by differential scanning calorimetry and polarized optical microscopy.The photomechanical effects (i.e. the dependence of volume and density) exhibited upon trans-to-cis and cis-to-trans photoisomerization of the azobenzene mesogenic groups have been investigated by ellipsometry and related to molecular weight, with particular attention to important parameters for potential applications such as the relative variation of total volume, response time, stability and reproducibility.     

Synthesis of a novel star liquid crystal polymer using trifunctional initiator via atom transfer radical polymerization

In this paper, two types of three-arm star mesogen-jacketed crystal polymers (MJLCPs) with different core (that is hard core and soft core) were synthesized by 2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene (MPCS), which was initiated by two different trifunctional initiators 1,3,5-(2′-bromo-2′-methylpropionato)benzene (I_a) and 1,1,1-tris(2-bromoisobutyryloxymethyl)propane (I_b), respectively. Characterization of these polymers by ¹H NMR and GPC clearly supported the formation of a three-arm star-shaped PMPCS. The resulting three-arm star PMPCS possessed narrow molecular weight distribution, and its molecular weight (M_n,NMR) agreed well with the theoretical value, which reveals the quantitative initiation efficiency. The liquid-crystalline behaviors of the two types of three-arm star polymer with different structure were also investigated by differential scanning calorimeter (DSC) and polarized optical microscope (POM). We found that the liquid-crystalline behavior was incorrelated with structure of core but correlated with the length of three-arm star polymer arm. Only each arm of the three-arm star-shaped polymers with a M_n,GPC beyond 0.90 × 10⁴ g/mol could form a liquid crystalline phase,which was found to be stable up to the decomposition temperature of these tri-arm MJLCPs.     

Synthesis of hyperbranched-linear star block copolymers by atom transfer radical polymerization of styrene using hyperbranched poly(siloxysilane) (HBPS) macroinitiator

Hyperbranched-linear star block copolymers, hyperbranched poly(siloxysilane)-block-polystyrene (HBPS-b-PSt), were prepared by atom transfer radical polymerization (ATRP) of styrene in xylene, using bromoester-terminated HBPS (HBPS-Br (P3), M_n = 7500, M_w/M_n = 1.76) as a macroinitiator. The number-average molecular weights of the obtained polymers (M_n) were in the range of 21,800-60,000 and molecular weight distributions were unimodal throughout the reaction (M_w/M_n = 1.28-1.40). These polymers showed 5 wt.% decomposition temperature (T_d5) over 300 °C. The DSC thermograms of the resulting polymers indicated two glass transition temperatures (T_g). The T_g of HBPS segment shifted to higher value while the T_g of PSt segment shifted to lower value compared with those of the homopolymers. Preliminary physical characterization related to the solution viscosity of the resulting block copolymers is also reported.     

Cellulose acetate graft copolymers with nano-structured architectures: Synthesis and characterization

Cellulose acetate is a very good film-forming polymer with major applications in cigarette filters, photographic films, cosmetics and pharmaceutics formulations and membrane separation processes. Nevertheless, its rigidity and relative hydrophobic character can be limiting drawbacks for some applications. In this work, new cellulose acetate materials with highly flexible and hydrophilic grafts were obtained with different hydrophilic/hydrophobic balances. Cellulose acetate was grafted with methyl diethylene glycol methacrylate (MDEGMA) from brominated macroinitiators by atom transfer radical polymerization (ATRP) in two steps. The first step consisted of introducing ATRP initiator groups on cellulose acetate by reacting hydroxyl side groups with 2-bromoisobutyryl bromide. A preliminary study was then carried out to determine the experimental conditions for the controlled ATRP of MDEGMA homopolymerization in a solvent (cyclopentanone) compatible with cellulose acetate grafting. In these conditions, the MDEGMA homopolymerization followed Hanns Fischer’s kinetics model accounting for the radical persistent effect. The ATRP grafting was then investigated for two cellulose acetate macroinitiators differing in the number of their ATRP initiator groups. Two families of graft copolymers with nano-structured architectures were obtained. The first family corresponded to copolymers with a high number of short grafts. The copolymers of the second family had almost the same graft weight fractions but a small number of long grafts. The morphology of the graft copolymers was then investigated by synchrotron X-ray scattering. The most informative results showed that the phase segregation depended upon the number and length of the poly(MDEGMA) grafts. The copolymer with 44 wt.% of long grafts showed a segregated morphology of nano-domains with sharp interfaces and a radius of gyration of 11.5 nm (from Guinier’s law). These cellulose acetate copolymers eventually led to strong films with potential applications in membrane separations.     

Effect of spacer length on the liquid crystalline property of azobenzene-containing ABA-type triblock copolymers via ATRP

The effect of flexible spacer length on the liquid crystalline property of ABA-type triblock copolymers containing azobenzene groups was investigated.For the study,the monomers,n-[4-(4-ethoxyphenylazo)phenoxy]alkyl methacrylates with varying methylene groups(n=0,2,6)were used to synthesize a series of azobenzene-containing amphiphilic triblock copolymers PAnC-PEG-PAnC by atom transfer radical polymerization(ATRP).Differential scanning calorimetry(DSC),polarizing optical microscopy(POM),and one-dimensional X-ray diffraction(1D WAXD)have shown that the glass transition temperatures of these copolymers decreased with increasing n,PAOC-PEG-PAOC has no mesophase,while both PA2C-PEG-PA2C and PA6C-PEG- PA6C have a nematic mesophase.These differences derive from the length of spacer groups between the polymer backbone and side-chain LC monomers.     

Synthesis,liquid crystalline mesophases and morphologies of diblock copolymers composed of a poly(dimethylsiloxane) block and a nematic liquid crystalline block

In this study, a series of liquid crystalline diblock copolymers, composed of a soft poly(dimethylsiloxane) (PDMS) block with a de?ned length and a side-on liquid crystalline poly(3??-acryloyloxypropyl 2,5-di(4?-butyloxybenzoyloxy) benzoate) (P3ADBB) block with different lengths, are synthesised by the atom transfer radical polymerisation. The macromolecular structures, liquid crystalline properties and the microphase-separated morphologies of the diblock copolymer are investigated by ¹H NMR, FT-IR, GPC, POM, DSC and TEM. The results show that the well-de?ned diblock copolymers (PDMS_n-b-P3ADBB_m) possess four different soft/rigid ratios (n = 58, m = 10, 25, 42, 66) and relatively narrow molecular distributions (PDI ≤ 1.30). P3ADBB blocks of the copolymers show nematic sub-phases, which are identical to the mesomorphic behaviour of the homopolymer P3ADBB. After being annealed at 90°C in a vacuum oven for 48 h, the copolymers form a lamellar morphology when m = 10 and morphologies of PDMS spheres embedded in P3ADBB matrix when m = 25, 42 and 66.     

Synthesis and characterization of 4‐arm star side‐chain liquid crystalline polymers containing azobenzene with different terminal substituents via ATRP

4‐Arm star side‐chain liquid crystalline (LC) polymers containing azobenzene with different terminal substituents were synthesized by atom transfer radical polymerization (ATRP). Tetrafunctional initiator prepared by the esterification between pentaerythritol and 2‐bromoisobutyryl bromide was utilized to initiate the polymerization of 6‐[4‐(4‐methoxyphenylazo)phenoxy]hexyl methacrylate (MMAzo) and 6‐[4‐(4‐ethoxyphenylazo)phenoxy]hexyl methacrylate (EMAzo), respectively. The 4‐arm star side‐chain LC polymer with p‐methoxyazobenzene moieties exhibits a smectic and a nematic phase, while that with p‐ethoxyazobenzene moieties shows only a nematic phase, which derives of different terminal substituents. The star polymers have similar LC behavior to the corresponding linear homopolymers, whereas transition temperatures decrease slightly. Both star polymers show photoresponsive isomerization under the irradiation with UV–vis light. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3342–3348, 2007     

Polysiloxane side-chain liquid crystalline polymers prepared by alkyne hydrosilylation

We describe in this work an alkyne-hydrosilylation approach to synthesize a series of novel polysiloxane sidechain LCPs attaching end-on or side-on mesogenic side groups. Their properties are characterized by NMR, FTIR, gel permeation chromatography, thermogravimetric analysis, differential scanning calorimetry, polarized optical microscopy and small-angle X-ray scattering. These obtained alkenylsilane linked novel LCPs exhibit higher glass transition temperatures and clearing points, and especially display the tendency of forming smectic phases, in strong contrast with the nematic phases of their comparative conventional alkylsilane linked analogues, which manifests more rigid features of the alkenylsilane linkages and their significant influence on the mesomorphic properties.     

Synthesis and characterization of liquid crystalline side‐chain block copolymers containing luminescent 4,4′‐bis(biphenyl)fluorene pendants

A series of new liquid crystalline homopolymers, copolymers, and block copolymers were polymerized from styrene‐macroinitiator ( SMi ) and methacrylates with pendent 4,4′‐bis(biphenyl)fluorene ( M1 ) and biphenyl‐4‐ylfluorene ( M2 ) groups through atom transfer radical polymerization (ATRP). The number‐average molecular weights (Mn) of polymers P1 ‐ P4 were 10,007, 14,852, 6,275, and 10,463 g mol^?1 with polydispersity indices values of 1.21, 1.15, 1.31, and 1.22, respectively. All polymers exhibit the nematic phase. The thermal, mesogenic, and photoluminescent properties of all polymers were investigated. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4564–4572, 2007     

Synthesis and supramolecular self‐assembly of thermosensitive amphiphilic star copolymers based on a hyperbranched polyether core

A novel amphiphilic thermosensitive star copolymer with a hydrophobic hyperbranched poly (3‐ethyl‐3‐(hydroxymethyl)oxetane) (HBPO) core and many hydrophilic poly(2‐(dimethylamino) ethyl methacrylate) (PDMAEMA) arms was synthesized and used as the precursor for the aqueous solution self‐assembly. All the copolymers directly aggregated into core–shell unimolecular micelles (around 10 nm) and size‐controllable large multimolecular micelles (around 100 nm) in water at room temperature, according to pyrene probe fluorescence spectrometry and ¹H NMR, TEM, and DLS measurements. The star copolymers also underwent sharp, thermosensitive phase transitions at a lower critical solution temperature (LCST), which were proved to be originated from the secondary aggregation of the large micelles driven by increasing hydrophobic interaction due to the dehydration of PDMAEMA shells on heating. A quantitative variable temperature NMR analysis method was designed by using potassium hydrogen phthalate as an external standard and displayed great potential to evaluate the LCST transition at the molecular level. The drug loading and temperature‐dependent release properties of HBPO‐star‐PDMAEMA micelles were also investigated by using indomethacin as a model drug. The indomethacin‐loaded micelles displayed a rapid drug release at a temperature around LCST. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 668–681, 2008     

Synthesis of miktoarm star (block) polymers based on a heterofunctional initiator via combination of ROP, ATRP and functional group transformation

Versatile miktoarm three-arm star polymers, (polystyrene)(polyε-caprolactone)₂ ((PS)(PCL)₂), (PS-b-poly(n-butyl acrylate))(PCL-b-PS-b-poly(n-butyl acrylate))₂ ((PS-b-PnBA)(PCL-b-PS-b-PnBA)₂) and (PtBA-b-PS)(PCL-b-PtBA-b-PS)₂ were synthesized via combination of atom-transfer radical polymerization (ATRP), functional group transformation technique and ring opening polymerization (ROP) using 1,1-dihydroxymethyl-1-(2-bromoisobutyryloxy)methyl ethane (DHB) as a heterofunctional initiator. In the synthesis of (PS)(PCL)₂ by combination of ROP of ε-caprolactone (ε-CL) and ATRP, the implementation sequence, ROP followed by ATRP, was proved to be effective to get a well-defined miktoarm star polymer than the reverse one. The two miktoarm star block polymers, (PS-b-PnBA)(PCL-b-PS-b-PnBA)₂ and (PtBA-b-PS)(PCL-b-PtBA-b-PS)₂, were prepared by one ROP step, one group transformation and ATRP steps using the same initiator. All the polymers have defined structures and their molecular weights are adjustable with good controllability.     

AB_2型星形杂臂偶氮液晶聚合物的合成及表征

通过原子转移自由基聚合(ATRP)与ATRP衍生物化学修饰结合的方法,合成了一系列AB2型星形杂臂偶氮液晶聚合物.其中,A为聚苯乙烯,B为聚6-[4-(4′-甲氧基苯基)偶氮苯氧基己酯](PMMAZO).合成分三步进行.首先,以ATRP方法得到ω-溴聚苯乙烯活性链PS(Br).然后对PS(Br)进行化学改性,得到带两个末端溴原子的聚苯乙烯活性链PS(Br)2·最后,以PS(Br)2作为双官能团大分子引发剂,引发6-[4-(4′-甲氧基苯基)偶氮苯氧基]己酯(MMAZO)发生ATRP聚合,得到星形杂臂PS(PMMAZO)2聚合物.进一步对聚合产物进行了GPC和1H-NMR分析.结果表明合成产物是预期的星形杂臂聚合物,产物分子量可控且分子量分布狭窄.同时,以DSC和POM表征了星形杂臂聚合物的液晶性.     

Synthesis and thermal properties of side-chain liquid crystalline polyethers with racemic and chiral backbone

Racemic and chiral [(4-cyano-4′-biphenyl)oxy] and [(4-methoxy-4′-biphenyl)oxy]methyloxiranes were prepared from racemic epichlorohydrin or racemic and chiral glycidols and polymerized in dimethylsulfoxide (DMSO) with Bu^tOK as the initiator system. Initial phase identifications were made by differential scanning calorimetry (DSC) and optical microscopy techniques and confirmed by X-ray diffraction measurements. Upon heating, all the monomers show only a crystal–isotropic phase transition. The racemic and chiral [(4-cyano-4′-biphenyl)oxy]methyloxiranes exhibit a nematic and a cholesteric monotropic phase, respectively. Methoxybiphenyl substituted polyethers are crystalline and insoluble in virtually all common solvents. Cyanobiphenyl substituted polyethers are soluble under the same experimental conditions and show enantiotropic liquid crystalline properties. The racemic polymer exhibits a nematic phase, while the optically active polymer forms a cholesteric phase.     

Photoinduced chirality in achiral liquid crystalline azobenzene polymers containing different polar side groups

Circular dichroism (CD) was induced in the films of two achiral liquid crystalline polymers, poly[(4′-(6-(methacryloyloxy)hexyl)oxy)-(4-X)azobenzene] (PM6X, X = C and N for cyano and nitro, respectively), by irradiation with one handed circularly polarized light (CPL) at 442 nm. The CD and UV spectra of the polymeric films suggest that left-CPL induces a left helical structure and right-CPL reverses the resulting structure into a right helix. For PM6C, the photoinduced CD values of the nematic film are much higher than in the casting and isotropic film. The photoinduced chirality of PM6C films is higher than PM6N due to a higher polarity of nitro groups in PM6N. The PM6N’s CD intensity around 450 nm is increased with the irradiation time of linearly polarized light (LPL) followed by left-CPL irradiation. The correlation between azobenzene chromophores and circularly polarized light will be discussed in the paper.     

Tailoring the liquid crystalline property via controlling the generation of dendronized polymers containing azobenzene mesogen

The first‐ and second‐generation dendronized polymers containing azobenzene mesogen were designed and successfully synthesized via free radical polymerization. The chemical structures of the monomers were confirmed by elemental analysis, ¹H NMR, and ¹³C NMR. The molecular characterizations of the polymers were performed with ¹H NMR and gel permeation chromatography. The phase structures and transition behaviors were studied using differential scanning calorimetry, polarized light microscopy, and small‐angle X‐ray scatter experiments. The experiment results revealed that the first‐generation dendronized polymer exhibited liquid crystalline behavior of the conventional side‐chain liquid crystalline polymer with azobenzene mesogen, that is, the polymer exhibited smectic phase structure at lower temperature and nematic phase structure at higher temperature. However, the second‐generation dendronized polymers exhibited more versatile intriguing liquid crystalline structures, namely smectic phase structure at lower temperature and columnar nematic phase structure at higher temperature, and moreover, the phase structure still remained before the decomposition temperature. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1149–1159, 2010     

Synthesis and characterization of side‐chain liquid crystalline ABC triblock copolymers with p‐methoxyazobenzene moieties by atom transfer radical polymerization

A series of novel side‐chain liquid crystalline ABC triblock copolymers composed of poly(ethylene oxide) (PEO), polystyrene (PS), and poly[6‐(4‐methoxy‐4′‐oxy‐azobenzene) hexyl methacrylate] (PMMAZO) were synthesized by atom transfer radical polymerization (ATRP) using CuBr/1,1,4,7,7‐pentamethyldiethylenetriamine (PMDETA) as a catalyst system. First, the bromine‐terminated diblock copolymer poly(ethylene oxide)‐block‐polystyrene (PEO‐PS‐Br) was prepared by the ATRP of styrene initiated with the macro‐initiator PEO‐Br, which was obtained from the esterification of PEO and 2‐bromo‐2‐methylpropionyl bromide. An azobenzene‐containing block of PMMAZO with different molecular weights was then introduced into the diblock copolymer by a second ATRP to synthesize the novel side‐chain liquid crystalline ABC triblock copolymer poly(ethylene oxide)‐block‐polystyrene‐block‐poly[6‐(4‐methoxy‐4′‐oxy‐azobenzene) hexyl methacrylate] (PEO‐PS‐PMMAZO). These block copolymers were characterized using proton nuclear magnetic resonance (¹H NMR) and gel permeation chromatograph (GPC). Their thermotropic phase behaviors were investigated using differential scanning calorimetry (DSC) and polarized optical microscope (POM). These triblock copolymers exhibited a smectic phase and a nematic phase over a relatively wide temperature range. At the same time, the photoresponsive properties of these triblock copolymers in chloroform solution were preliminarily studied. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4442–4450, 2008     

Synthesis and application of functional polyethylene graft copolymers by atom transfer radical polymerization

This investigation attempts to elucidate the copolymerization reaction ethylene and p-methylstyrene via the homogeneous metallocene catalyst, Et(Ind)₂ZrCl₂. With increasing of p-methylstyrene concentration, the poly[ethylene-co-(p-methylstyrene)] copolymer shows systematical decrease of melting temperature and crystallinity and increase of glass transition temperature. The benzylic protons of p-methylstyrene are ready for numerous chemical reactions, such as halogenation and oxidation, which can introduce functional groups at the p-methyl group position under mild reaction conditions. With the bromination reaction of poly[ethylene-co-(p-methylstyrene)], polyethylene graft copolymers, such as polyethylene-g-poly(methyl methacrylate) and polyethylene-g-polystyrene can be prepared via atomic transfer radical polymerization. The following selective bromination reaction of p-methylstyrene units in the copolymer and the subsequent radical graft-from polymerization were effective methods of producing polymeric side chains with well-defined structure. The products were characterized by nuclear magnetic resonance, gel-permeation chromatography, differential scanning calorimetry, and thermal gravimetric analysis. Additionally, the morphology of PE/PMMA and PE/PMMA/PE-g-PMMA blend are compared by using scanning electron microscope.