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.

Structure-Property Studies on a Series of Polycarbonate-Polydimethylsiloxane Block Copolymers

1980 ◽  
Vol 53 (5) ◽  
pp. 1160-1169 ◽  
Author(s):  
S. H. Tang ◽  
E. A. Meinecke ◽  
J. S. Riffle ◽  
J. E. McGrath
Keyword(s):  
Block Copolymers ◽  
Bisphenol A ◽  
Elevated Temperatures ◽  
In Situ Polymerization ◽  
Soft Segment ◽  
Thermoplastic Elastomers ◽  
Structure Property ◽  
Polydimethyl Siloxane ◽  
Bisphenol A Polycarbonate ◽  
Siloxane Oligomers

Abstract Block copolymers composed of hard and soft segments form an interesting class of materials ranging from thermoplastics to thermoplastic elastomers depending on their composition and/or the size of segments. These materials have attracted much attention in the past decade because by careful tailoring, polymers of desired properties can be obtained. Yet they are thermoplastic in nature and can be processed and even reprocessed thermally. Among the common elastomers that can be used as the soft segment in a block copolymer, polydimethyl-siloxane is of special interest due to its great thermal stability at elevated temperatures and high flexibility at low temperatures. Block copolymers containing polydimethylsiloxane as the soft segment and various thermoplastics such as poly(α-methylstyrene), polystyrene, and polysulfone, etc., as the hard segment, have been synthesized and studied. A group of randomly alternating block copolymers of bisphenol-A polycarbonate and polydimethylsiloxane have also been prepared by in situ polymerization of dichloro-terminated siloxane oligomers and bisphenol-A and phosgene. The properties of these block copolymers as well as those of the others have been discussed to some extent in a general review. This work reports the results of a study on the structure-property relationship of a series of perfectly alternating block copolymers of bisphenol-A polycarbonate and polydimethylsiloxane synthesized via different routes. They were prepared by silylamine-hydroxyl reaction. Slightly less than the stoichiometric quantity of siloxane oligomers was incrementally added to a hydrated solution of the polycarbonate in refluxing chlorobenzene. The reaction can be represented by the simple scheme:

scholarly journals RELAXATION PROPERTIES OF COMPOSITE MATERIALS BASED ON MIXTURES OF EPOXY POLYMERS AND THERMOPLASTIC ELASTOMERS

2020 ◽  
pp. 85-95
Author(s):  
Y. Kochergin ◽  
Tatyana Grigorenko ◽  
V. Zolotareva
Keyword(s):  
Molecular Weight ◽  
High Temperature ◽  
Block Copolymers ◽  
Thermoplastic Elastomer ◽  
Thermoplastic Elastomers ◽  
Relaxation Processes ◽  
Polybutylene Terephthalate ◽  
Dynamic Mechanical ◽  
Epoxy Polymers ◽  
Polytetramethylene Oxide

The influence of thermoplastic elastomers, which are two-block statistical block copolymers based on polybutylene terephthalate and polytetramethylene oxide with a different ratio of rigid and elastic blocks, on the static and dynamic mechanical properties of epoxy polymers is studied. The initial compounds for the synthesis of block copolymers are dimethyl terephthalate, 1,4-butanediol and polytetramethylenoxide with a molecular weight of 2000. The tetrabutoxide is used as catalyst. The process of interaction of the initial components is carried out in two stages, the reaction of transesterification and copolycondensation is consistently carried out. The composition of BSP is set by the ratio of initial reagents. The total molecular weight of block copolymers is 30–40 thousand. The method of dynamic mechanical analysis shows that the introduction of modifiers leads to a decrease in molecular mobility in a wide temperature range from low-temperature (at 220K) to high-temperature (at 380K) relaxation transitions. The magnitude of the effect depends on the ratio of rigid and flexible blocks in the block copolymer. It is assumed that the decrease in the tangent of the angle of mechanical losses at temperatures below the glass transition temperature and especially in the region of the β-transition, may be associated with the slowdown of relaxation processes at the interface of the epoxide matrix with rigid blocks of thermoplastic elastomer. The observed effects in the region of high-temperature transition may be associated with the restriction of freedom of conformational rearrangements near the interface of the epoxy polymer with polybutylene terephthalate and polytetramethylene oxide blocks and an increase in the cross-linking density of the epoxy. A noticeable decrease in the magnitude and creep rate of epoxy composites is found when thermoelastoplast is introduced.

Research on In Situ Anionic Polymerization of PA6/PI Alloy

2011 ◽  
Vol 295-297 ◽  
pp. 21-25
Author(s):  
Hong Kai Zhao ◽  
Li Guang Xiao ◽  
Hong Jie Wang
Keyword(s):  
Molecular Weight ◽  
Bisphenol A ◽  
High Performance ◽  
Hot Spot ◽  
Microscopic Analysis ◽  
Infrared Analysis ◽  
Elongation At Break ◽  
System Temperature ◽  
Lamellar Crystals

High performance trend of plastics has become a hot spot of current research. Select bisphenol A dianhydride and bisphenol A diamine with excellent water resistance as the reactant monomers to obtain anhydride-terminated polyimide with very high molecular weight by two-step polymerization, graft the active radicals of acyl caprolactam using the activity of anhydride and obtain PI modified nylon resin by polymerization.When the system temperature is above 160 °C and the added modifiers are greater than 10%, the system viscosity increases very fast; when the system temperature reaches 140 °C and the added modifiers are at 5%, the system viscosity increases very slowly. It is proved that the reaction in each above step is successful through infrared analysis. The mechanical properties of modified PI nylon increases with the increase of consumption and molecular weight of polyimide, when the molecular weight is selected to be about 8000~10000 and the adding amount is 10wt%~15 wt%, the tensile strength reaches over 85MPa, the notch impact strength is increased to 19.6kJ.m-2 and the elongation at break reaches 18%, which are remarkably better than general engineering plastics.Through microscopic analysis, the molecules of polyimide does not enter crystallization phase of nylon resin, but forms compact lamellar crystals existing in nylon matrix.

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.

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