Influence of molecular weight and degree of segregation on local segmental dynamics of ordered block copolymers

2016 ◽  
Vol 54 (9) ◽  
pp. 859-864 ◽  
Author(s):  
Vaidyanathan Sethuraman ◽  
Victor Pryamitsyn ◽  
Venkat Ganesan
Keyword(s):  
Molecular Weight ◽  
Block Copolymers ◽  
Segmental Dynamics

Elastomeric Polycarbonate Block Copolymers

1965 ◽  
Vol 38 (2) ◽  
pp. 431-449
Author(s):  
Eugene P. Goldberg
Keyword(s):  
Molecular Weight ◽  
Block Copolymers ◽  
Bisphenol A ◽  
Flexural Modulus ◽  
Softening Temperature ◽  
Thermoplastic Elastomers ◽  
Partial Replacement ◽  
Initial Increase ◽  
Copolymer Composition ◽  
Moderate Degree

Abstract Polycarbonate block copolymers were prepared by phosgenating pyridine solutions of polyether glycol-bisphenol-A mixtures. Copolycarbonates derived from poly(oxyethylene) glycols (Carbowaxes) were studied in detail for property-structure effects as a function of glycol molecular weight (1000–20,000) and copolymer composition (5–70 weight per cent or 0.3–10.0 mole per cent of a 4000 molecular weight glycol). Remarkable strength (>7000 psi) and snappy elasticity (>90 per cent immediate recovery) were observed at poly(oxyethylene) block concentrations greater than 3 mole per cent. These thermoplastic elastomers also exhibited high softening temperatures (>180° C) and tensile elongations up to about 700 per cent. Both Tg and softening temperature varied linearly with comonomer mole ratio over the composition range studied, with Tg displaying much greater polyether concentration sensitivity. It is suggested that the observed property effects result to a large extent from the variation in poly(bisphenol-A carbonate) block length that accompanies the changing of copolymer composition. An initial increase in flexural modulus (stiffness) was observed at low polyether concentrations (0–1 mole per cent). This phenomenon is considered to be related to similar modulus effects found in plasticized rigid thermoplastics at low plasticizer concentrations. A moderate degree of molecular order, due to bisphenol carbonate segments rather than the normally crystalline polyether, was detected by x-ray analysis. Elastomeric carbonate-carboxylate tetrapolymers were also prepared by partial replacement of carbonate with isophthalate, terephthalate or adipate linkages in polyether-bisphenol systems. The dramatic softening temperature depression observed in this class of polymers is attributed to the disruption of long bisphenol carbonate block sequences that exist in the simpler polyether glycol-bisphenol carbonate copolymers.

Effect of Block Molecular Weight on the Mechanical Properties of PA1010-b-PEG Segmented Block Copolymers

2012 ◽  
Vol 512-515 ◽  
pp. 2127-2130
Author(s):  
Li Huo ◽  
Cai Xia Dong
Keyword(s):  
Mechanical Properties ◽  
Molecular Weight ◽  
Block Copolymers ◽  
Microphase Separation ◽  
Soft Segment ◽  
Mechanical Measurements ◽  
Wide Range ◽  
Hard Block ◽  
Higher Temperature ◽  
Hard Segments

The mechanical properties were investigated of a series of PA-PEG thermalplastic elastomer based on PA1010 and polytetramethylene glycol (PEG) with varying hard and soft segment content. Dynamic mechanical measurements of these polymers have carried out over a wide range of temperatures. The block copolymers exhibit three peaks, designated as α, β and γ in the tanδ-temperature curve. The α transition shifts to higher temperature with increasing hard block molecular weight. However, at a constant hard molecular weight, the α transition shifts to higher temperature and the damping increases on increasing the soft segment molecular weight. DMA results show that the block copolymers exhibit a microphase separation structure and both soft and hard segments were found to be crystallizable. The degree of phase separation increases with increasing hard block molecular weight.

Amphiphilic Block Copolymers as Stabilizers in Emulsion Polymerization: Effects of the Anchoring Block Molecular Weight Dispersity on Stabilization Performance

2016 ◽  
Vol 50 (1) ◽  
pp. 315-323 ◽  
Author(s):  
Sean R. George ◽  
Rachel Champagne-Hartley ◽  
Gary A. Deeter ◽  
J. D. Campbell ◽  
Bernd Reck ◽  
...  
Keyword(s):  
Molecular Weight ◽  
Block Copolymers ◽  
Emulsion Polymerization ◽  
Amphiphilic Block Copolymers

Rheology of Block Copolymers

2007 ◽  
Author(s):  
Chang Dae Han
Keyword(s):  
Mechanical Properties ◽  
Molecular Weight ◽  
Block Copolymers ◽  
Small Angle ◽  
Volume Fraction ◽  
Synthesis Methods ◽  
Chemical Structures ◽  
X Ray Scattering ◽  
Transmission Electron ◽  
Molecular Weight Form

Block copolymer consists of two or more long blocks with dissimilar chemical structures which are chemically connected. There are different architectures of block copolymers, namely, AB-type diblock, ABA-type triblock, ABC-type triblock, and AmBn radial or star-shaped block copolymers, as shown schematically in Figure 8.1. The majority of block copolymers has long been synthesized by sequential anionic polymerization, which gives rise to narrow molecular weight distribution, although other synthesis methods (e.g., cationic polymerization, atom transfer radical polymerization) have also been developed in the more recent past. Owing to immiscibility between the constituent blocks, block copolymers above a certain threshold molecular weight form microdomains (10–50 nm in size), the structure of which depends primarily on block composition (or block length ratio). The presence of microdomains confers unique mechanical properties to block copolymers. There are many papers that have dealt with the synthesis and physical/mechanical properties of block copolymers, too many to cite them all here. There are monographs describing the synthesis and physical properties of block copolymers (Aggarwal 1970; Burke and Weiss 1973; Hamley 1998; Holden et al. 1996; Hsieh and Quirk 1996; Noshay and McGrath 1977). Figure 8.2 shows schematically four types of equilibrium microdomain structures observed in block copolymers. Referring to Figure 8.2, it is well established (Helfand and Wasserman 1982; Leibler 1980) that in microphase-separated block copolymers, spherical microdomains are observed when the volume fraction f of one of the blocks is less than approximately 0.15, hexagonally packed cylindrical microdomains are observed when the value of f is between approximately 0.15 and 0.44, and lamellar microdomains are observed when the value of f is between approximately 0.44 and 0.50. Some investigators have observed ordered bicontinuous double-diamonds (OBDD) (Thomas et al. 1986; Hasegawa et al. 1987) or bicontinuous gyroids (Hajduk et al. 1994) at a very narrow range of f (say, between approximately 0.35 and 0.40) for certain block copolymers. Figure 8.2 shows only one half of the symmetricity about f = 0.5. Transmission electron microscopy (TEM), small-angle X-ray scattering (SAXS), and small-angle neutron scattering (SANS) have long been used to investigate the types of microdomain structures in block copolymers.

scholarly journals Enhancing the biocompatibility of siliconepolycarbonate urethane based implant materials

2019 ◽  
Vol 5 (1) ◽  
pp. 453-455 ◽  
Author(s):  
Kiriaki Athanasopulu ◽  
Larysa Kutuzova ◽  
Joana Thiel ◽  
Günter Lorenz ◽  
Ralf Kemkemer
Keyword(s):  
Molecular Weight ◽  
Cell Proliferation ◽  
Hyaluronic Acid ◽  
Cell Growth ◽  
Block Copolymers ◽  
Cytotoxic Potential ◽  
Implant Surface ◽  
Characterization Methods ◽  
Hard Segments

AbstractPolyurethane-bases block copolymers (TPCUs) are block-copolymers with systematically varied soft and hard segments. They have been suggested to serve as material for chondral implants in joint regeneration. Such applications may require the adhesion of chondrocytes to the implant surface, facilitating cell growth while keeping their phenotype. Thus, aims of this work were (i) to modify the surface of soft biostable polyurethane-based model implants (TPCU and TSiPCU) with high-molecular weight hyaluronic acid (HA) using an optimized multistep strategy of immobilization, and (ii) to evaluate bioactivity of the modified TPCUs in vitro. Our results show no cytotoxic potential of the TPCUs. HAbioactive molecules (Mw =700kDa) were immobilized onto the polyurethane surface via polyethylenimine (PEI) spacers, and modifications were confirmed by several characterization methods. Tests with porcine chondrocytes indicated the potential of the TPCU-HA for inducing enhanced cell proliferation.

scholarly journals Synergistic toughening of polypropylene with ultra-high molecular weight polyethylene and elastomer-olefin block copolymers

RSC Advances ◽  
2019 ◽  
Vol 9 (41) ◽  
pp. 23994-24002 ◽  
Author(s):  
Lucheng Qi ◽  
Lei Wu ◽  
Ren He ◽  
Hui Cheng ◽  
Boping Liu ◽  
...  
Keyword(s):  
Molecular Weight ◽  
Block Copolymers ◽  
Rheological Properties ◽  
High Molecular Weight ◽  
Twin Screw Extruder ◽  
Screw Extruder ◽  
Twin Screw ◽  
Ultra High Molecular Weight

Blends of polypropylene (PP) and ultra-high molecular weight polyethylene (UHMWPE) with elastomer-olefin block copolymers (OBC) were prepared using an ultrasonic twin-screw extruder, and their mechanical and rheological properties were investigated.

Novel phenylacetylene based ketonic resins

2015 ◽  
Vol 44 (4) ◽  
pp. 198-204 ◽  
Author(s):  
N. Kizilcan ◽  
B. Erson
Keyword(s):  
Molecular Weight ◽  
Block Copolymers ◽  
Technical Information ◽  
Fluorescence Properties ◽  
Formaldehyde Resin ◽  
Step Method ◽  
Content Type ◽  
Naoh Solution ◽  
Copolymer Structure

Purpose – This paper aims to report the synthesis of resins having fluorescence properties, with the help of phenylacetylene (PhAc) by one-step method of in situ modification of ketonic resin. Cyclohexanone-formaldehyde resin (CFR) and acetophenone formaldehyde resin (AFR) were in situ modified with PhAc, in presence of sodium hydroxide (NaOH) by condensation polymerisation. Design/methodology/approach – Ketone, formalin and phenylacetylene were mixed and then 20% aqueous NaOH solution was added to produce the phenylacethylene modified ketonic resin. The solubility, molecular weight and thermal properties of the products were investigated. Findings – These new PhAc-modified ketonic resins (PAc-CFR and PAc-AFR) have fluorescence properties. Research limitations/implications – This study focuses on obtaining a fluorescence resin using a cyclohexanone, acetophenone and PhAc monomer which is an insulator. Practical implications – This study provides technical information for the synthesis of fluorescence comonomers. The modified resins contain acetylene groups. A chemical redox or radical system can be used to polymerise these acetylene groups and resins with much higher molecular weight. The resins may also promote the adhesive strength of a coating and corrosion inhibition to metal surfaces of a coating. Social implications – The resins will be used for the preparation of AB- and ABA-type block copolymers. These block copolymers may exhibit different properties due to incorporation of monomer into the block copolymer structure. Originality/value – PAc-CFR and PAc-AFR have been synthesised in the presence of a basic catalyst. Higher solubility and fluorescence intensity of the modified ketonic resins may increase their applications in the field of electroactive polymers and open new areas. These comonomers have fluorescence property.

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