Synthesis and self-association in aqueous media of poly(ethylene oxide)/poly(ethyl glycidyl carbamate) amphiphilic block copolymers

New temperature sensitive AB, ABA, and BAB amphiphilic block copolymers consisting of hydrophilic poly(ethylene oxide) and hydrophobic poly(ethyl glycidyl carbamate) blocks were synthesized by anionic polymerization followed by chemical modification reactions. The self-association of the block copolymers in aqueous media was studied by UV-vis spectroscopy and dynamic and static light scattering. The obtained block copolymers spontaneously form micelles in aqueous media. The critical micellization concentration varied from 0.5 to 4 g/L depending on the copolymer architecture and composition. The influence of the temperature upon the self-association of the block copolymers was investigated. The increase of temperature did not affect the value of the critical micellization concentration, but led to the formation of better defined micelles with narrow size distribution.     

膦酰基羧酸共调聚物的阻垢性能研究

采用静态与动态试验方法,对新型阻垢剂膦酰基羧酸共调聚物抑制碳酸钙垢的性能进行了试验研究。静态试验研究表明,在水温低于60℃,钙硬度为600mg/L(以CaCO3计)的情况下,膦酰基羧酸共调聚物具有良好的阻垢性能,投加量为5mg/L时,阻垢率超过90%;在较高硬度时亦有较好的阻垢效果。动态试验研究表明,成垢溶液添加阻垢剂之后,污垢热阻大为减小,换热表面基本不结垢。因此,膦酰基羧酸共调聚物极适于工业循环冷却水系统的水处理过程。结合垢粒的扫描电镜照片对膦酰基羧酸共调聚物的阻垢机理进行了简要分析。     

Structural development in cycloolefin copolymers under uniaxial elongational flow

Development of structures in new cycloolefin copolymers (COCs) of ethylene–norbornene (E–NB) and ethylene–tetracyclododecene (E–TD) of different NB/TD compositions were investigated under uniaxial elongational flow. For E–NB copolymer, which has multiblock sequences, a shoulder in WAXD at 0.76 nm was evident besides its amorphous halo, and the relative intensity of the peak increased with increasing comonomer content (NB). The appearance of a new peak for E–TD copolymer, and a relatively higher intense peak for E–NB copolymer at the same position of 0.76 nm, indicated that local ordering of the segments occurred when the COC was subjected to uniaxial flow. A lower comonomer composition of elongated COC, at a constant Hencky strain rate, exhibited two T_g values, whereas a higher composition showed a single T_g. Both local ordering and segmentization occurred in low comonomer content COCs but only local ordering occurred in higher comonomer content COCs. Both the shear viscosity and roll processing experiments exhibited similar phenomena of segregation. A model is proposed to illustrate the structure of COC after uniaxial elongation/deformation. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3421–3427, 2004     

Synthesis and chain extension of nitroxide‐terminated styrene–maleimide copolymers

Thermal radical copolymerization of styrene (S) and maleimide (MI) at 125°C in diglyme in the presence of 2,2,6,6‐tetramethylpiperidin‐1‐yloxyl radical (TEMPO) was studied. Mole fractions of maleimide in the feed, F_MI, varied in the range 0.1–0.9. A quasiliving reaction process proceeded yielding copolymers with a low polydispersity (M_w/M_n = 1.17–1.41). The found azeotropic composition, (F_MI)_A = 0.46, did not differ substantially from that (0.5) in the conventional radical S‐MI copolymerization. At a higher conversion or MI content in the feed, deactivation of the copolymer chains occurred. The obtained TEMPO‐terminated S‐MI copolymers readily initiated polymerization of styrene; chain extension of the macroinitiators took place, giving poly(S‐co‐MI)‐block‐poly(S) diblock copolymers. The synthesized copolymers containing S and MI units were characterized by elemental analysis, NMR spectroscopy, size‐exclusion chromatography, and differential scanning calorimetry. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1863–1868, 2004     

Imide-aryl ether benzoxazole random copolymers

Novel imide-aryl ether benzoxazole copolymers were prepared and their morphology and mechanical properties investigated. A key feature of these copolymers is the incorporation of a benzoxazole moiety by the use of 2,2′-bis[4-(3-aminophenoxy)phenyl]-6,6′-bibenzoxazole or 2,2′-bis[4-(4-aminophenoxy)-phenyl]-6,6′-bibenzoxazole as co-diamines in polyimide syntheses. The preparation of these diamines involved the nucleophilic aromatic substitution of 2,2′-bis(4-fluorophenyl)-6,6′-bibenzoxazole with either 3- or 4-aminophenol in the presence of K₂CO₃. The diamines were co-reacted with various compositions of pyromellitic dianhydride (PMDA) and 4,4′-oxydianiline (ODA) to synthesize the desired poly(amic acids). Films were cast and cured (350°C) to effect the imide formation, affording films with elongations between 40 and 110% and moduli in the 2000–2750 MPa range. The copolymers exhibited good dimensional (T_g in excess of 300°C) and thermal stability. Wide-angle X-ray diffraction measurements on the copolymers showed that the ordered morphology characteristic of PMDA/ODA polyimide was retained. Improvements in the auto-adhesion were observed, particularly in those copolymers which displayed a T_g.     

Synthesis and properties of new polymerized monomer reactants matrix resins of pyrrolone–benzimidazole copolymers containing pyridine unit

A series of new polymerized monomer reactants (PMR) matrix resins of poly(pyrrolone‐benzimidazole)s containing a pyridine unit (PPBP) were synthesized by polycondensation of monoethyl ester of cis‐5‐norbornene‐endo‐2,3‐dicarboxylic acid, 2,6‐diphenyl ester pyridinedicarboxylic acid or 3,5‐diphenyl ester pyridinedicarboxylic acid, and diethyl ester of 4,4′‐oxydiphthalic acid with 3,3′‐diaminobenzidine in a mixing solution of anhydrous ethyl alcohol and N‐methylpyrrolidone under given temperature and pressure conditions. The resulting resin solutions showed good solubility in polar organic solvents and stability at room temperature. The corresponding PPBP matrix resin, molded powder, and molded plate were prepared by undergoing amidation, imidization, cyclization, and crosslinking reactions when the reaction temperature was increased from 80 to 350°C, successively; the crosslinking structure was formed by the reverse Diels–Alder reaction at 270–290°C under 50 MPa pressure (2.5–3.5 MPa displayed by the pressure meter). The chemical reactions and properties of the resulting PPBP were studied by means of FTIR, TGA, and DMA methods, and the results indicated that the kinds of PPBP materials retain excellent thermal stability and processability; when the initial decomposition temperature was above 620°C the T_g was at 413.5°C for 3,5‐PPBP‐20 molded plate. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3981–3990, 2004     

Vitamin A microencapsulation within poly(methyl methacrylate)‐g‐polyethylenimine microspheres: Localized proton buffering effect on vitamin A stability

To stabilize vitamin A in a cosmetic/dermatological formulation, we present here a new encapsulation method based on polymer microspheres having a localized “proton‐buffering” capacity. Poly(methyl methacrylate)‐g‐polyethylenimine (PMMA‐g‐PEI) was prepared by direct condensation grafting of PEI onto poly(methyl methacrylate‐co‐methyl acrylic acid). The reaction was confirmed by FT‐IR analysis showing the amide vibration at 1,550 cm^?1. Elemental analysis indicated that the weight content of the grafted PEI was 1.6% (w/w). Vitamin A was encapsulated into PMMA‐g‐PEI microspheres by using an oil‐in‐water (O/W) single emulsion method. The presence of PEI moiety dramatically improved the chemical stability of vitamin A in microspheres. Vitamin A encapsulated within PMMA‐g‐PEI microspheres maintained 91% of its initial activity after 30‐day incubation at 40°C, while only maintaining 60% within plain PMMA microspheres. This study demonstrates that proton‐buffering within hydrophobic polymer matrix is a useful strategy for stabilizing “acid‐labile” active ingredients. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 517–522, 2004     

Properties and crystallization kinetics of poly(ether ether ketone)‐co‐poly(ether ether ketone ketone) block copolymers

A series of block copolymers composed of poly(ether ether ketone) (PEEK) and poly(ether ether ketone ketone) (PEEKK) components were prepared from their corresponding oligomers via a nucleophlilic aromatic substitution reaction. Various properties of the copolymers were investigated with differential scanning calorimetry (DSC) and a tensile testing machine. The results show that the copolymers exhibited no phase separation and that the relationship between the glass‐transition temperature (T_g) and the compositions of the copolymers approximately followed the formula T_g = T_g1X₁ + T_g2X₂, where T_g1 and T_g2 are the glass‐transition‐temperature values of PEEK and PEEKK, respectively, and X₁ and X₂ are the corresponding molar fractions of the PEEK and PEEKK segments in the copolymers, respectively. These copolymers showed good tensile properties. The crystallization kinetics of the copolymers were studied. The Avrami equation was used to describe the isothermal crystallization process. The nonisothermal crystallization was described by modified Avrami analysis by Jeziorny and by a combination of the Avrami and Ozawa equations. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1652–1658, 2005     

Graft polymerization of vinyl acetate onto granular starch: Comparison on the potassium persulfate and ceric ammonium nitrate initiated system

This work was undertaken to discuss in depth the vital differences in the morphological development during synthesis, and properties of starch‐g‐poly‐(vinyl acetate) copolymers using two different initiators, potassium persulfate (KPS) and ceric ammonium nitrate (CAN). KPS‐initiated system gave relatively low values of grafting ratio and grafting efficiency, indicating a great tendency for the formation of poly(vinyl acetate) homopolymer (PVAc). Yet, higher values were seen for the CAN‐initiated system. Transmission electron microscope observations indicated a relatively broad distribution of latex particles for the KPS‐initiated system. The surface potential of latex particles was about ?3.5 mV, which turned out to be insufficient to maintain stability of latex particles. On the other hand, a uniform particle size distribution was found for the CAN‐initiated system, as the surface potential of latex particles was 21.5 mV. Moreover, radicals on starch molecules were generated directly through a redox reaction with positively charged ceric ion. The hydrophobic PVAc chains were thus grafted on starch, resulting in an amphiphilic graft copolymer, which provides a sufficient stabilization degree as a role of surfactant to render a relatively uniform distribution of latex particles. The synthesized starch‐g‐poly(vinyl acetate) copolymers were further converted to starch‐g‐poly(vinyl alcohol) through saponification, which were subjected to evaluations regarding the biodegradation and cell culture capability. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3017–3027, 2006     

Characterization of end‐functionalized styrene–butadiene–styrene copolymers and their application in modified asphalt

End amino, carboxylic acid, and hydroxyl functionalized styrene–butadiene–styrene (SBS) triblock copolymers were prepared with 1,5‐diazabicyclo[3.1.0]hexane, carbon dioxide, and epoxy ethane as capping agents, respectively. The effects of the end polar groups on the morphology and dynamic mechanical properties were investigated. Transmission electron microscopy images suggested that the group at the end of the polystyrene (PS) segment made the morphology of the PS domains disordered and incompact. Dynamic mechanical results showed that the storage and loss modulus increased after SBS was end‐functionalized. End amino and carboxylic acid groups improved the compatibility and storage stability of SBS‐modified asphalt. However, the effect of the end‐hydroxyl group on the improvement of the storage stability of SBS‐modified asphalt was not obvious. The differential scanning calorimetry analysis of SBS‐modified asphalt further showed that the compatibility and storage stability of SBS‐modified asphalt were improved by the attachment of amino or carboxylic acid groups through the anionic polymerization method. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 8–16, 2007