Barrier properties of vinylidene chloride copolymers

The permeability coefficients of a series of copolymers of vinylidene chloride (VDC) with methyl acrylate (MA), butyl acrylate (BA) or vinyl chloride (VC) (as comonomer) to oxygen and carbon dioxide have been measured at 1.0 MPa and 30 degrees C, while those to water vapor have been measured at 30 degrees C and 100% relative humidity. All the copolymers are semicrystalline. VDC/MA copolymers have lower melting temperature compared with VDC/BA copolymers, while that melting temperature of VDC/VC copolymer is higher than that of VDC/acrylate copolymers with the same VDC content. The barrier property of the copolymers is predominantly controlled by crystallite, free volume fraction, and cohesive energy. The permeability coefficients of VDC/MA copolymers to oxygen, carbon dioxide, and water vapor were successfully correlated with the ratio of free volume to cohesive energy.

Control led/living free-radical copolymerization of 4-(azidocarbonyl) phenyl methacrylate with methyl acrylate under Co-60 gamma-ray irradiation

A new vinyl acyl azide monomer, 4-(azidocarbonyl) phenyl methacrylate, has been synthesized and characterized by NMR and FTIR spectroscopy. The thermal stability of the new monomer has been investigated with FTIR and thermal gravimetry/differential thermal analysis (TG/DTA), and the monomer has been demonstrated to be stable below 50 degrees C in the solid state. The copolymerizations of the new monomer with methyl acrylate have been carried out at room temperature under Co-60 gamma-ray irradiation in the presence of benzyl 1-H-imidazole-1-carbodithioate. The results show that the polymerizations bear all the characteristics of controlled/living free-radical polymerizations, such as the molecular weight increasing linearly with the monomer conversion, the molecular weight distribution being narrow (< 1.20), and a linear relationship existing between In([M](0)/[M]) and the polymerization time. The data from H-1 NMR and FTIR confirm that no change in the acyl azide groups has occurred in the polymerization process and that acyl azide copolymers have been obtained. The thermal stability of the polymers has also been investigated with TG/DTA and FTIR.

A novel approach to synthesis of functional CPVC and CPE or graft copolymers - in situ chlorinating graft

A new process of graft copolymerization of poly(vinyl chloride) (PVC) and polyethylene (PE) with other monomers was developed. The grafted chlorinated poly(vinyl chloride) (CPVC) and chlorinated polyethylene (CPE) were synthesized by in situ chlorinating graft copolymerization (ISCGC) and were characterized. Convincing evidence for grafting and the structure of graft copolymers was obtained using FT-IR, H-1-NMR, gel permeation chromatography (GPC), and the vulcanized curves. Their mechanical properties were also measured. The results show that the products have different molecular structure from those prepared by other conventional graft processes. Their graft chains are short, being highly branched and chlorinated. The graft copolymers have no crosslinking structure. The unique molecular structure will make the materials equipped with special properties.

Poly(ethylene glycol)-block-poly(butyl acrylate). II. Characterization and properties

Poly(ethylene glycol)-block-poly(butyl acrylate) synthesized by radical polymerization in a one-step procedure were characterized by gel permeation chromatography, infrared, IH-NMR spectroscopy, and differential scanning calorimetry (DSC). The crystalline property, emulsifying property, and phase transfer catalytic effect in the Williamson reaction were studied. It was found that the crystallinity of the copolymer increased with an increase in both the content and molecular weight of poly( ethylene oxide) (PEO) sequences. DSC curves showed two distinct crystallization temperature due to the heterogeneous nucleation and homogeneous nucleation crystallization. The casting solvent significantly affected the morphology and crystallinity of the solvent cast films. Both the emulsifying volume and the phase transfer catalytic efficiency in the Williamson reaction increased with the amount and PEO content of the block copolymers used, but decreased with an increase in the molecular weight of PEO sequences. (C) 1998 John Wiley & Sons, Inc.

Barrier properties of vinylidene chloride methyl acrylate copolymer

A series of vinylidene dichloride (VDC) copolymers with methyl acrylate (MA) as comonomer (3-12wt%), was prepared by free-radical suspension copolymerization. The permeability coefficients of the copolymers to oxygen and carbon dioxide were measured at 1.0 MPa and at 30 degrees C, and those to water vapor were measured at 30 degrees C and 100% relative humidity. All the VDC/MA copolymers studied are semicrystalline. As the MA content increases, the permeability coefficients of the copolymers to oxygen, carbon dioxide, and water vapor are progressively increased, caused by decrease in crystalline fraction and increase in free volume of VDC/MA copolymers.

Barrier property and structure of acrylonitrile/acrylic copolymers

A series of acrylonitrile (AN) copolymers with methyl acrylate (MA) or ethyl acrylate (EA) as comonomer (5-23 wt%) was prepared by free-radical copolymerisation. The permeability coefficients of the copolymers to oxygen and carbon dioxide were measured at 1.0 MPa and at 30 degrees C, and those to water vapor also measured at 100% relative humidity and at 30 degrees C. All the AN/acrylic copolymers are semicrystalline. As the acrylate content increase, the permeability coefficients of the copolymers to oxygen and carbon dioxide are increased progressively, but those to water vapor are decreased progressively. The gas permeability coefficients of the polymers were correlated with free-volume fractions or the ratio of free volume to cohesive energy.

Poly(ethylene glycol) block poly(butyl acrylate) .1. Synthesis

Prepolymers of poly(ethylene oxide) (Pre-PEG) were synthesized by reacting azoisobutyronitrile (AIBN) with poly(ethylene glycol) (PEG), and their structures were characterized by IR and UV. The molecular weight of pre-PEG was related to the feed ratio and reaction time. These prepolymers can be used to prepare block copolymers - poly(ethylene oxide)-block-poly(butyl acrylate) (PEO-b-PBA) by radical polymerization in the presence of butyl acrylate (BA). Solution polymerization was a suitable technique for this step. The yield and the molecular weight of the product were related to the ratio of the prepolymer to BA, the reaction time, and temperature. GPC showed that the molecular weight increased with a higher ratio of BA to pre-PEO. The intrinsic viscosity of the copolymers was only slightly dependent on reaction time, but decreased at higher reaction temperatures, as did the amount of PEA homopolymer. (C) 1997 John Wiley & Sons, Inc.

Structure and thermal properties of vinylidene chloride/acrylics copolymers

A series of vinylidene chloride (VDC) copolymers with methyl acrylate (MA) or butyl acrylate (BA) as comonomer (not more than 10%) was prepared by free-radical suspension copolymerization. The effects of comonomer structure, copolymer composition, and reaction condition (such as polymerization temperature on crystallinity) and thermal properties (such as melting temperature and decomposition temperature) were investigated. All VDC/acrylics copolymers studied here are semicrystalline and have more than one crystalline structure. The melting temperature of MA/VDC copolymers is decreased progressively with increase in MA content. The decomposition temperature of MA/VDC copolymers is slight increased gradually with increase in MA content. MA/VDC copolymers have lower melting temperature compared with BA/VDC copolymers with same VDC composition. The melting temperature of VDC copolymers increases with increase in polymerization temperature and decomposition temperature of those is almost independent of polymerization temperature. (C) 1996 John Wiley & Sons, Inc.

Synthesis and properties of two kinds of CPVC carboxylated ionic copolymers

In the present work, two kinds of CPVC carboxylated ionic copolymers were prepared by a new method. First, a graft copolymer (CPVC-cg-AA) comprising of polyacrylic acid (PAA) as branched chains and chlorinated polyvinyl chloride (CPVC) as backbone was synthesized by in-situ chlorinating graft copolymerization (ISCGC). Second, the acid groups of the graft copolymer were neutralized by sodium hydroxide and aluminium hydroxide, respectively in order to prepare carboxylated ionic copolymers.

Study on structure and molecular dynamics of starch/poly(sodium acrylate)grafted superabsorbent by C-13 solid state NMR

The domain-structure of samples containing a series of starch/poly(sodium acrylate)-grafted superabsorbents, pure starch, pure poly(sodium acrylate), and blend of starch/poly(sodium acrylate) has been studied by high-resolution solid-state C-13 NMR spectroscopy at room temperature. The result shows that the crystallinity of starch decreases greatly in the grafted and blended samples.

A strategy for synthesis of ion-bonded supramolecular star polymers by reversible addition-fragmentation chain transfer (RAFT) polymerization

We have developed a novel strategy for the preparation of ion-bonded supramolecular star polymers by RAFT polymerization. An ion-bonded star supramolecule with six functional groups was prepared from a triphenylene derivative containing tertiary amino groups and trithiocarbonate carboxylic acid, and used as the RAFT agent in polymerizations of tert-butyl acrylate (tBA) and styrene (St). Molecular weights and structures of the polymers were characterized by H-1 NMR and GPC. The results show that the polymerization possesses the character of living free-radical polymerization and the ion-bonded supramolecular star polymers PSt, PtBA, and PSt-b-PtBA, with six well-defined arms, were successfully synthesized.

A strategy for synthesis of ion-bonded amphiphilic miktoarm star copolymers via supramolecular macro-RAFT agent

Amphiphilic supramolecular miktoarm star copolymers linked by ionic bonds with controlled molecular weight and low polydispersity have been successfully synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization using an ion-bonded macromolecular RAFT agent (macro-RAFT agent). Firstly, a new tetrafunctional initiator, dimethyl 4,6-bis(bromomethyl)-isophthalate, was synthesized and used as an initiator for atom transfer radical polymerization (ATRP) of styrene to form polystyrene (PSt) containing two ester groups at the middle of polymer chain. Then, the ester groups were converted into tertiary amino groups and the ion-bonded supramolecular macro-RAFT agent was obtained through the interaction between the tertiary amino group and 2-dodecylsulfanylthiocarbonylsulfanyl-2-methyl propionic acid (DMP). Finally, ion-bonded amphiphilic miktoarm star copolymer, (PSt)(2)-poly(N-isopropyl-acrylamide)(2), was prepared by RAFT polymerization of N-isopropylacrylamide (NIPAM) in the presence of the supramolecular macro-RAFT agent. The polymerization kinetics was investigated and the molecular weight and the architecture of the resulting star polymers were characterized by means of H-1-NMR, FTIR, and GPC techniques. (c) 2008 Wiley Periodicals, Inc.

Synthesis and Properties of Carbazole Main Chain Copolymers with Oxadiazole Pendant toward Bipolar Polymer Host: Tuning the HOMO/LUMO Level and Triplet Energy

Three new carbazole copolymers, poly(9-(2,5-diarene-[1,3,4]oxadiazole)-carbazole-alt-9-(2-ethylhexyl)-carbazole-3,6-diyl)s (P1), poly(9-(2,5-diarene-[1,3,4]oxadiazole)-2, 7-carbazole-alt-9-(2-ethylhexyl)-3, 6-carbazole-diyl)s (P2), and poly(9-(2,5-diarene-[1,3,4]oxadiazole)-carbazole-alt-9-(2-ethylhexyl)-carbazole-2,7-diyl)s (P3), were synthesized by the Suzuki coupling reaction

The influence of variant PE-b-PEO segments on physical properties of LLDPE graft copolymers

A method was adopted to fix a series of polymers of PE-b-PEO with different PEO/PE segments on the chains of LLDPE. Maleic anhydride (MA) reacting with hydroxyl group of PE-b-PEO (mPE-b-PEO) was used as the intermediate. The structures of intermediates and graft copolymers were approved by H-1 NMR and FTIR. XPS analysis revealed a great amount of oxygen on the surface of grafted copolymers although the end group of PEO was fixed on the LLDPE chains through MA. Thermal properties of the graft copolymers as determined by differential scanning calorimetry (DSC) showed that PE segments in the grafted monomers could promote the heterogeneous nucleation of the polymer, increase T., and crystal growth rate.