Organized Nanostructures of Thermoresponsive Poly(N-isopropylacrylamide) Block Copolymers Obtained Through Controlled RAFT Polymerization

Kontrolloidut radikaalipolymerointimenetelmät, kuten RAFT-polymerointi, ovat moderni tapa valmistaa polymeerejä säädellysti. RAFT-polymeroinnilla polymeerien ketjunpituutta, moolimassajakaumaa, mikrorakennetta (taktisuus, järjestys), koostumusta ja funktionaalisuutta kyetään hallitsemaan. Siten menetelmällä voidaan valmistaa uudenlaisia polymeeriarkkitektuureja, kuten blokki- ja tähtipolymeerejä, sekä hybridimateriaaleja ja biokonjugaatteja. Polymeeristen rakennuspalikoiden itsejärjestyminen, missä huolellisesti syntetisoidut polymeerit järjestyvät halutulla tavalla nanoskaalassa, on suosittu tutkimuskohde materiaalitieteessä. On huomattava, että blokkipolymeerien itsejärjestyminen on vielä suhteellisen nuori tutkimusaihe. Tämän hetkiset polymeeriset nanomateriaalit ovat suhteellisen yksinkertaisia luonnon luomuksiin verrattuina, tarjoten jatkuvasti uusia mahdollisuuksia seuraavan sukupolven polymeereille. Tässä työssä RAFT-polymeroinnilla syntetisoitiin amfifiilisiä di- ja triblokkikopolymeerejä sekä tutkittiin niiden järjestymistä nanorakenteiksi. Kaikissa blokkikopolymeereissä käytettiin lämpöherkkää poly(N-isopropyyliakryyliamidia). Siten polymeerit ja tutkitut materiaalit reagoivat lämpötilanmuutokseen ympäristössä eli ovat ns. ympäristöherkkiä. Työssä tutkittiin taktisuuden kontrollointia N-isopropyyliakryyliamidin RAFT-polymeroinnissa. Polymeerin taktisuutta sekä ketjunpituutta ja blokkijärjestystä säätämällä voitiin hallita polymeerin itsejärjestymistä vesiliuoksessa. Amfifiiliset polymeerit järjestyivät laimeissa vesiliuoksissa erilaisiksi misellirakenteiksi, muodostaen ns. mikrosäiliöitä. Tällaisilla polymeereillä odotetaan olevan sovelluksia esim. lääkeainevapautuksessa. Amfifiilejä käytetään myös esimerkiksi apuaineina pinnoitteissa ja kosmetiikassa. Kiinteässä tilassa tutkitut triblokkikopolymeerit muodostivat teoreettisesti ennustettuja morfologioita. Lämpöherkän materiaalin hydrogeelit toimivat suodatinmembraanina nanokokoluokassa. RAFT-polymeroinnilla syntetisoituja polymeereja voidaan sellaisenaan käyttää kultananopartikkeleiden päällystämiseen. Kultananopartikkelit ovat erittäin kiinostavia mm. niiden stabiilisuuden ja ainutlaatuisten pintaominaisuuksien vuoksi. Kun amfifiilisiä polymeerejä kiinnitettiin kultapartikkelin pinnalle, sen liuos- ja optisia ominaisuuksia voitiin säädellä pH:n ja lämpötilan avulla. Tällaisilla kultananopartikkeleilla on sovelluksia mm. diagnostiikassa, sensoreina ja solukuvauksessa.

Study of morphology and phase diagram of the H-shaped (AC)B(CA) ternary block copolymers using self-consistent field theory

By using a combinatorial screening method based on the self-consistent field theory (SCFT) for polymer systems, the micro-phase morphologies of the H-shaped (AC)B(CA) ternary block copolymer system are studied in three-dimensional (3D) space. By systematically varying the volume fractions of the components A, B, and C, six triangle phase diagrams of this H-shaped (AC)B(CA) ternary block copolymer system with equal interaction energies among the three components are constructed from the weaker segregation regime to the strong segregation regime, In this study, thirteen 3D micro-phase morphologies for this H-shaped ternary block copolymer system are identified to be stable and seven 3D microphase morphologies are found to be metastable.

A self-consistent field theory study on the morphologies of linear ABCBA and H-shaped (AB)(2)C(BA)(2) block copolymers

By using a combinatorial screening method based on the self-consistent field theory, we investigate the equilibrium morphologies of linear ABCBA and H-shaped (AB)(2)C(BA)(2) block copolymers in two dimensions. The triangle phase diagrams of both block copolymers are constructed by systematically varying the volume fractions of blocks A, B, and C. In this study, the interaction energies between species A, B, and C are set to be equal. Four different equilibrium morphologies are identified, i.e., the lamellar phase (LAM), the hexagonal lattice phase (HEX), the core-shell hexagonal lattice phase (CSH), and the two interpenetrating tetragonal lattice phase (TET2). For the linear ABCBA block copolymer, the reflection symmetry is observed in the phase diagram except for some special grid points, and most of grid points are occupied by LAM morphology. However, for the H-shaped (AB)(2)C(BA)(2) block copolymer, most of the grid points in the triangle phase diagram are occupied by CSH morphology, which is ascribed to the different chain architectures of the two block copolymers. These results may help in the design of block copolymers with different microstructures.

Comparing the morphology and phase diagram of H-shaped ABC block copolymers and linear ABC block copolymers

By using a combinatorial screening method based on the self-consistent field theory (SCFT) for polymers, we have investigated the morphology of H-shaped ABC block copolymers (A(2)BC(2)) and compared them with those of the linear ABC block copolymers. By changing the ratios of the volume fractions of two A arms and two C arms, one can obtain block copolymers with different architectures ranging from linear block copolymer to H-shaped block copolymer. By systematically varying the volume fractions of block A, B, and C, the triangle phase diagrams of the H-shaped ABC block copolymer with equal interactions among the three species are constructed. In this study, we find four different morphologies ( lamellar phase ( LAM), hexagonal lattice phase ( HEX), core-shell hexagonal lattice phase (CSH), and two interpenetrating tetragonal lattice (TET2)). Furthermore, the order-order transitions driven by architectural change are discussed.

Compatibilization of polyamide-6/syndiotactic polystyrene blends using styrene/glycidyl methacrylate copolymers

Blends of polyamide-6 (PA6) with syndiotactic polystyrene (sPS) were prepared using a series of styrene/glycidyl methacrylate (SG) copolymers as compatibilizers. These copolymers are miscible with sPS, and the epoxide units in SG are capable of reacting with PA6 end groups. These copolymers thus have the potential to form SG-g-PA6 graft copolymers at the PA6/sPS interface during melt processing. This study focuses on the effects of functionality and concentration of the compatibilizer on the morphological, mechanical and crystallization behaviors of the blends.. In general, SG copolymers are effective in reducing the sPS domain size and improving the interfacial adhesion. About 5 wt% glycidyl methacrylate (GMA) is the optimum content in SG copolymer that produces the best compatibilization. Both the strength and modulus of the blend have been improved on addition of the SG copolymers, accompanying a loss in toughness when higher concentration copolymer is added. Incorporation of SG compatibilizers to PA6/sPS blend has little influence on the crystallization behavior of PA6 component but resulted in a steady reduction in intensity of crystallinity peak of sPS and simultaneous crystallization of sPS with PA6 is observed.

COMPATIBILIZATION OF HIGH-DENSITY POLYETHYLENE/POLYISOPRENE BLENDS WITH POLYETHYLENE/POLYISOPRENE THREAD-THROUGH COPOLYMERS

The compatibilization of high density polyethylene (HDPE)/polyisoprene (PI) blends with polyethylene/polyisoprene (PE/PI) ''thread-through'' copolymers was investigated. The proliferating structure of PE/PI with segments chemically identical to HDPE and PI, respectively, is different from that of graft copolymers. Studies showed that the dispersed domain size in the blends was significantly reduced and interfacial adhesion was improved by the compatibilization action of the copolymer. In the differential scanning calorimetry (DSC) analysis, the crystallization peak of HDPE in the blends became broad with adding the copolymer and fractionated crystallization appeared in the HDPE/PI blend compatibilized with the copolymer at a weight ratio of 30/70 while it appeared in the blend without copolymer at a weight ratio of 20/80. DMA results showed that by adding the copolymer, both the glass transition temperature (T-g) of the PI component and the alpha-relaxation of HDPE shifted to lower temperature, demonstrating the enhanced penetration of the two components. Mechanical properties of the blends were improved, especially the elongation at break, by the presence of the copolymers. The characteristic yielding at the fractured surface of the blends compatibilized with the copolymer indicates the fractural behavior of the material changed from brittle to tough.

PREPARATION AND PROPERTIES OF THREAD-THROUGH COPOLYMERS OF POLYETHYLENE WITH POLYISOPRENE

Graft copolymers of polyethylene (PE) with polyisoprene (PI) were synthesized through polymerization of ethylene in toluene solution of PI (cis-1,4-: 95%; 3,4-: 5%) using a homogeneous V(acac)3/Et3Al2Cl3 catalyst. Copolymers are formed when the growing po

An investigation of cadmium(II) and nickel(II) adsorption by chitin graft covolymer

Chitin hydrogels of poly(vinylpyrrolidone) (VP) were prepared by means of the hydrogen peroxide graft copolymerization process. The effect of the VP grafted chain on water diffusion through the biopolymer was studied. Fourier transform infrared spectra of the VP-g-Ch showed an increase in the intensities of the hydroxyl and carbonyl stretching bands indicating a reduction in the hydrogen bonding of chitin. An investigation was undertaken regarding the adsorption of nickel(II) and cadmium(II) ions from aqueous solutions by the VP grafted chitin and the effects of the grafting degree on the Cd2+ and Ni2+ sorption were studied. The Cd2+ and Ni2+ adsorption equilibrium data correlate well with the Freundlich equation. The results indicate that the Ch-g-VP graft copolymer under investigation is a potentially powerful chelating material that can be employed for Ni2+ and Cd2+ ion removal from wastewater effluents. (C) 2004 Wiley Periodicals, Inc.

Morphological, mechanical and rheological properties of nylon 6/acrylonitrile-butadiene-styrene blends compatibilized with MMA/MA copolymers

The morphological, mechanical and rheological properties of nylon 6/acrylonitrile-butadiene-styrene blends compatibilized with MMA-MA [poly(methyl methacrylate-comaleic anhydride)] copolymers were studied. A twin screw extruder was used for melt-blended the polymers and the injection moulding process was used to mold the samples. The main focus was on nylon 6/ ABS blends compatibilized with one MMA-MA copolymer. This copolymer has PMMA segments that appear to be miscible with the styrene-acrylonitrile (SAN) phase of ABS and the anhydride groups can react with amine end groups of the nylon 6 (Ny6) to form graft copolymers at the interface between Ny6 and ABS rich phases. Tensile and impact and morphological properties were enhanced by the incorporation of this copolymer. Transmission electron microscopy (TEM) observations revealed that the ABS domains are finely dispersed in nylon 6 matrix and led to the lowest ductile-brittle transition temperatures and highest impact properties. It can be concluded that the MMA-MA copolymer is an efficient alternative for the reactive compatibilization and can be used as a compatibilizer for nylon 6/ABS blends.© 2003 Kluwer Academic Publishers.

The accelerating effect of additives on radiation-induced graft polymerization : final report /

"Category No. UC-4 ; Chemistry ; TID-4500."

Thermoplastic Elastomers Based on Compatibilized Poly(butylene terephthalate) Blends: Effect of Functional Groups and Dynamic Curing

Two sets of graft copolymers were prepared by grafting glycidyl methacrylate (GMA) or ally] (3-isocyanate-4-tolyl) carbamate (TAI) onto ethylene/propylene/diene terpolymer (EPDM) in an internal mixer. These graft copolymers were used as the compatibilizer to prepare the thermoplastic elastomers (TPEs) containing 50 wt%, of poly(butylene terephthalate), PBT, 30 wt% of compatibilizer, and 20 wt% of nitrile-butadiene rubber, NBR. The indirect, two-step mixer process was chosen for dynamic curing.

Rheology, morphology and mechanical properties of LLDPE/PS blends catalyzed by combined Lewis acids

The rheological, morphological and mechanical properties of LLDPE/PS blends with a combined catalyst, Me3SiCl and InCl3 center dot 4H(2)O, were studied in this work. The higher complex viscosity and storage modulus at low frequency were ascribed to the presence of graft copolymers, which were in situ formed during the mixing process. From the rheological experiments, the complex viscosity and storage modulus of reactive blends were higher than the physical blends. The dispersion of LLDPE particles of reactive blending becomes finer than that of physical blends, consistent with the rheological results. As a result of increased compatibility between LLDPE/PS, the mechanical properties of reactive blends show much higher tensile and Izod impact strength than those of physical blends.

Copolymerizations of ethylene with alpha-olefin-omega-ols by highly active vanadium(III) catalysts bearing [N,O] bidentate chelated ligands

The copolymerizations of ethylene with polar hydroxyl monomers such as 10-undecen-1-ol, 5-hexen-1-ol and 3-buten-1-ol were investigated by the vanadium(III) catalysts bearing bidentate [N,O] ligands (1, [PhN=C(CH3)CHC(Ph)O]VCl2(THF)(2): 2, [PhN=CHC6H4O]VCl2(THF)(2); 3, [PhN=CHC(Ph)CHO]VCl2(THF)(2)). The polar monomers were pretreated by alkylaluminum before the polymerization. High catalytic activities and efficient comonomer incorporations can be easily obtained by changing monomer masking reagents and polymerization conditions in the presence of diethylaluminium chloride as a cocatalyst. The longer the spacer group, the higher the incorporation of the monomer. Under the mild conditions, the incorporation level of 10-undecen-1-ol reached 13.9 mol% in the resultant copolymers was obtained. The reactivity ratios of copolymerization (r(1) = 41.4, r(2) = 0.02, r(1)r(2) = 0.83) were evaluated by Fineman-Ross method. According to C-13 NMR spectra, polar units were located both on the main chain and at the chain end.

Synthesis of a (sic)-shaped amphiphilic block copolymer by the combination of atom transfer radical polymerization and living anionic polymerization

The functionalization of monomer units in the form of macroinitiators in an orthogonal fashion yields more predictable macromolecular architectures and complex polymers. Therefore, a new there exists E-shaped amphiphilic block copolymer, (PMMA)(2)-PEO-(PS)(2)-PEO-(PMMA)(2) [where PMMA is poly(methyl methacrylate), PEO is poly (ethylene oxide), and PS is polystyrene], has been designed and successfully synthesized by the combination of atom transfer radical polymerization (ATRP) and living anionic polymerization. The synthesis of meso-2,3-dibromosuccinic acid acetate/diethylene glycol was used to initiate the polymerization of styrene via ATRP to yield linear (HO)(2)-PS2 with two active hydroxyl groups by living anionic polymerization via diphenylmethylpotassium to initiate the polymerization of ethylene oxide. Afterwards, the synthesized miktoarm-4 amphiphilic block copolymer, (HO-PEO)(2)-PS2, was esterified with 2,2-dichloroacetyl chloride to form a macroinitiator that initiated the polymerization of methyl methacrylate via ATRP to prepare the there exists E-shaped amphiphilic block copolymer.

Suppression of phase separation in PC/PMMA blend film by thermoset oligomer

Phase separation of bisphenol A polycarbonate (PC) and poly(methyl methacrylate) (PMMA) thin blend film is suppressed by addition of solid epoxy oligomer. Epoxy has strong intermolecular interactions with both PC and PMMA, while PC and PMMA are quite incompatible with each other. Consequently, phase separation in the PC/PMMA blend film pushes epoxy to the interface; at the same time, PC and epoxy react readily at the interface to form a cross-linking structure, binding PMMA chains together. Therefore, the interface between PC and PMMA is effectively reinforced, and the PC/PMMA thin blend film is stabilized against phase separation. On the other hand, only an optimal content of epoxy (i.e., 10 wt %) can serve as an efficient interfacial agent. In contrast to the traditional reactive compatibilization, here we observed that the cross-linking structure along the interface is much more stable than block or graft copolymers. Atomic force microscopy (AFM) is used to characterize the morphological changes of the blend films as a function of annealing time. Two-dimensional fast Fourier transform (2D-FFT) of AFM data allows quantitative investigation of the scaling behavior of phase separation kinetics.