Structure and Mechanical Stability of Epoxy Modified Polyurethane Foam Under Heat and Stress

A series of phenolic epoxy resin (PEP) modified polyurethane foams (PUF) were prepared via an in-situ polymerization, one step process. It was found that the epoxy modified PUF foam exhibited a perforated network structure with larger cell size, higher open cell porosity and enhanced ovality compared with pure PUF. With increasing content of PEP, the tensile strength, elongation at break and low temperature modulus of PUF decreased. A single T_g was observed for PEP modified PUF, indicating that the two component phases of the polyurethane-epoxy were miscible. With increasing PEP content, the T_g of PUF shifted slightly to higher temperature, tan δ_max dropped to lower values, and the retention value of the storage modulus at ?20 and ?10?°C increased. For pure PUF, the cell walls degraded and the structure became disordered after aging under heat and stress, while for PUF/20wt%PEP, the degradation degree was obviously reduced, and an orientation of the cells along the stress direction and a density increase was observed. During aging at 200?°C, the retention of the mechanical properties of PUF/20wt% PEP was much higher than that of pure PUF, and it showed superior stability under heat and stress, attributed to incorporation of the thermally resistant oxazolidone rings and benzene rings in the PU backbones, the highly cross-linked networks of the polyurethane-epoxy systems and the obvious orientation of the cells under stress.     

Synthesis of polyphosphodiesters by ring‐opening polymerization of cyclic phosphates bearing allyl phosphoester protecting groups

The allyl phosphoester group is shown to be a protecting group for the synthesis of anionic polyphosphodiesters. Our strategy relies on the synthesis of a cyclic phosphate monomer bearing a pendant allyl phosphoester group, its easy purification by fractional distillation, its organocatalyzed ring‐opening polymerization by 1,8‐diazobicyclo[5.4.0]undec‐7‐ene (DBU) and 1‐[3,5‐bis(trifluoromethyl)phenyl]‐3‐cyclohexyl‐thiourea (TU). Finally, the deprotection of the allyl phosphoester group is carried out by reaction with sodium benzenethiolate in the absence of any detectable degradation. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2642–2648     

Synthesis of self‐healing polyurethane urea‐based supramolecular materials

Supramolecular polyurethane ureas are expected to have superior mechanical properties primarily due to the reversible, noncovalent interactions such as hydrogen bonding interactions. We synthesized polyurethane prepolymers from small molecular weight of poly(tetramethylene ether)glycol and isophorone diisocyanates, which were end capped with propylamine to synthesize polyurethane ureas with high contents of urea and urethane groups for hydrogen‐bonding formations to facilitate self‐healing. The effects of polyurethane urea molecular weight (3000 ≤ M_n ≤ 9000), crosslinking, and cutting direction were studied in terms of thermal, mechanical, and morphological properties with an emphasis on the self‐healing efficiency. It was found that the thermal self‐healability was more pronounced as the molecular weight of polyurethane urea decreased, showing a maximum of more than 96% with 3000 M_n when the sample was cut along the stretch direction. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 468–474     

Poly(ethylene glycol)-b-poly(1,3-trimethylene carbonate) Amphiphilic Copolymers for Long-Acting Injectables: Synthesis,Non-Acylating Performance and In Vivo Degradation

This article presents the evaluation of diblock and triblock poly(ethylene glycol)-b-poly(1,3-trimethylene carbonate) amphiphilic copolymers (PEG-PTMCs) as excipients for the formulation of long-acting injectables (LAIs). Copolymers were successfully synthesised through bulk ring-opening polymerisation. The concomitant formation of PTMC homopolymer could not be avoided irrespective of the catalyst amount, but the by-product could easily be removed by gel chromatography. Pure PEG-PTMCs undergo faster erosion in vivo than their corresponding homopolymer. Furthermore, these copolymers show outstanding stability compared to their polyester analogues when formulated with amine-containing reactive drugs, which makes them particularly suitable as LAIs for the sustained release of drugs susceptible to acylation.     

Design and development of self-repairable and recyclable crosslinked poly(thiourethane-urethane) via enhanced aliphatic disulfide chemistry

Thermoset polymer elastomers that are capable of autonomous repairability upon physical damage at ambient temperature are highly desirable because of their thermal and environmental resistance, outstanding mechanical toughness and stability. To aim at this goal, we demonstrated that tris(diethylamino)phosphine was initially proven as an efficient catalyst for the aliphatic disulfide exchange at mild condition. By making use of the aliphatic disulfide bond reshuffling and elasticity of polyurethane elastomers, the inherently cross-linked polysulfide-based poly(thiourethane-urethane) elastomers were prepared and exhibited the ability to mend without extrinsic stimuli in the presence of phosphorus catalyst at room temperature after artificially damaged. The self-healing efficiency via the mechanical recovery approach was investigated to be mainly dependent upon the cross-linking density of polysulfide and hard segments chemistry, which in turns determined the molecular chain diffusion and reshuffling that was corroborated by the stress-relaxation study. The thermoset elastomer based on asymmetric diisocynate showed a maximum self-healing efficiency of 85.6% compared to 71.6% for the elastomer with symmetric monomer building blocks. The self-healable polymer was confirmed to be recyclable and reprocessable through a cut-compression processing cycle under a quite mild pressure and temperature thanks to the disulfide bond reshuffling. Meanwhile, the recycled thermoset elastomer well maintained the mechanical properties to its original material.     

Relationships between molar mass and fracture properties of segmented urethane and amide copolymers modified by chemical degradation

This publication highlights the structure–property relationships in several thermoplastic elastomers (TPEs): one poly(ether-block-amide) and two thermoplastic polyurethane elastomers with ester and ether soft blocks. Structural changes are induced by chemical degradation from virgin samples through hydrolysis and oxidation. Molar mass measurements show an exclusive chain scission mechanism for all TPEs, regardless of the chemical modification condition. Mechanical behavior was nevertheless obtained from uniaxial tensile testing and fracture testing while considering the essential work of fracture (EWF) concept. During the macromolecular scission process, elongation at break shows a plateau followed by a drop, while stress at break decreases steadily. Once again, the trend is identical for all TPEs in all conditions considered. The βw_p parameter determined using the EWF concept exhibits an interesting sensitivity to scissions (i.e., molar mas decrease). Plotting elongation at break as a function of molar mass reveals a strong correlation between these two parameters. This master curve is particularly remarkable considering the range of TPEs and chemical breakdown pathways considered (hydrolysis and oxidation at several temperatures). Relevant structure–property relationships are proposed, highlighting that molar mass is a predominant parameter for determining the mechanical properties of thermoplastic elastomers.     

Synthesis and design of polyurethane and its nanocomposites derived from canola-castor oil: Mechanical,thermal and shape memory properties

The recent global pandemic and its tremendous effect on the price fluctuations of crude oil illustrates the side effects of petroleum dependency more evident than ever. Over the past decades, both academic and industrial communities spared endless efforts in order to replace petroleum-based materials with bio-derived resources. In the current study, a series of shape memory polymer composites (SMPC's) was synthesized from epoxidized vegetable oils, namely canola oil and castor oil fatty acids (COFA's) as a 100% bio-based polyol and isophorone diisocyanate (IPDI) as an isocyanate using a solvent/catalyst-free method in order to eventuate polyurethanes (PU's). Thereafter, graphene oxide (GO) nanoplatelets were synthesized and embedded in the neat PU in order to overcome the thermomechanical drawbacks of the neat matrix. The chemical structure of the synthesized components, as well as the dispersion and distribution levels of the nanoparticles, was characterized. In the following, thermal and mechanical properties as well as shape memory behavior of the specimens were comprehensively investigated. Likewise, the thermal conductivity was determined. This study proves that synthesized PU's based on vegetable oil polyols, including graphene nanoparticles, exhibit proper thermal and mechanical properties, which make them stand as a potential candidate to compete with traditional petroleum-based SMPC's.     

Nanocrystalline cellulose/fluorinated polyacrylate latex via RAFT‐mediated surfactant‐free emulsion polymerization and its application as waterborne textile finishing agent

A simple method for nanocrystalline cellulose (NCC)/fluorinated polyacrylate was developed by RAFT‐mediated surfactant‐free emulsion polymerization, in which the nanocomposites formed a core‐shell spherical morphology. The influence of the content of NCC‐g‐(PAA‐b‐PHFBA) (AA was acrylic acid, HFBA was hexafluorobutyl acrylate) on the properties of latex and film were systematically studied. The monomer conversion, the tensile strength, and water–oil repellency of film increased first and then decreased, the latex particle size decreased first and then decreased, when the content of NCC‐g‐(PAA‐b‐PHFBA) increased from 1 to 6 wt %. Elongation at break and thermal stability distinctly decreased when the content of NCC‐g‐(PAA‐b‐PHFBA) gradually increased. XPS showed that the fluorine‐containing groups well concentrated at the film–air interfaces during the annealing process. SEM analysis revealed that the treated fiber had a rugged surface, and the treated fabric had an excellent water repellency. In addition, this green grafting method in water offered a new perspective for the fabrication of exceptional NCC‐based nanocomposites with NCC as the core and also helped to promote the potential applicability of NCC in a range of multipurpose applications. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1305–1314     

Construction of Charring-Functional Polyheptanazine towards Improvements in Flame Retardants of Polyurethane

Nitrogen-containing flame retardants have been extensively applied due to their low toxicity and smoke-suppression properties; however, their poor charring ability restricts their applications. Herein, a representative nitrogen-containing flame retardant, polyheptanazine, was investigated. Two novel, cost-effective phosphorus-doped polyheptazine (PCN) and cobalt-anchored PCN (Co@PCN) flame retardants were synthesized via a thermal condensation method. The X-ray photoelectron spectroscopy (XPS) results indicated effective doping of P into triazine. Then, flame-retardant particles were introduced into thermoplastic polyurethane (TPU) using a melt-blending approach. The introduction of 3 wt% PCN and Co@PCN could remarkably suppress peak heat release rate (pHRR) (48.5% and 40.0%), peak smoke production rate (pSPR) (25.5% and 21.8%), and increasing residues (10.18 wt%→17.04 wt% and 14.08 wt%). Improvements in charring stability and flame retardancy were ascribed to the formation of P–N bonds and P=N bonds in triazine rings, which promoted the retention of P in the condensed phase, which produced additional high-quality residues.     

Thermally driven self-healing PEDOT conductive films relying on reversible and multiple Diels–Alder interaction

Thermally healing capability of cracks and defects is important and urgent for the safe operation and life extending of electric materials and devices. Here, by the combination of thermally driven reversible Diels–Alder (DA) interaction and in-situ chemical oxidative polymerization of 3,4-ethylenedioxythiophene (EDOT), a series of intrinsically conductive poly(3,4-ethylenedioxythiophene) (PEDOT)/DA composites possess intrinsically self-healing property under low-temperature (reverse DA reaction at 100°C; DA crosslinking at 60°C) stimulus were achieved. The crosslinking DA bonding reactions are multiple from the co-existence of pre-synthesized macromolecular polyurethane attached DA units (PU-DA) and 2,4-hexadiyne-1,6-diol (DADOL) in the films. PU-DA involved in the polymerization process of EDOT to endow PEDOT with outstanding solution-processability, uniform film making, and structural self-healing capability, while DADOL was added to enhance the cross bonding between polymer chains. This work will accelerate the research and application development of intrinsically self-healing conducting polymers for commercial capacitors, antistatic coatings, implantable, printable electronics, and so on.