Structure‐property relationships of degradable polyurethane elastomers containing an amino acid‐based chain extender

A series of degradable polyurethanes of variable soft segment chemistry and content were synthesized and characterized. An amino acid‐based diester chain extender was used to confer degradability and both polycaprolactone diol (PCL) and polyethylene oxide (PEO) were used as soft segments. In addition, the diisocyanate component was a potentially nontoxic diisocyanate (2,6‐diisocyanato methyl caproate, LDI). The physicochemical properties of these unique series of polyurethanes were investigated. It was found that the PEO containing polyurethanes were generally weak, tacky amorphous materials. In contrast, the PCL polyurethanes were relatively strong, elastomeric materials which ranged from completely amorphous to semicrystalline as noted by differential scanning calorimetry. The PCL containing polyurethanes exhibited increasing tensile strength, modulus, and ultimate strain with increasing PCL molecular weight because of increasing phase separation and increasing soft segment crystallinity. Fourier transform infrared analysis showed significant hard segment urea and urethane hydrogen bonding which increased with hard segment content, although interphase bonding is believed to be significant for the PCL polyurethanes. Surface characterization carried out by contact angle analysis and X‐ray photoelectron spectroscopy indicated soft segment surface enrichment for all of the polyurethanes. The PEO‐based polymers were very hydrophilic whereas the PCL‐based polymers displayed significantly higher contact angles, indicating greater surface hydrophobicity. The observed diversity in material properties suggests that these polyurethanes may be useful for a wide range of applications. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1522–1534, 2000     

Structure–properties relationship of starch/waterborne polyurethane composites

The blend materials from waterborne polyurethane (WPU)/starch (ST) with different contents (10–90 wt %) were satisfactorily prepared by using the solution casting method. Their miscibility, structure, and properties were investigated by wide‐angle X‐ray diffraction (WAXD), scanning electron microscope (SEM), different scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), and the tensile tests, respectively. The results indicated that tensile strength of composite materials not only depended on the starch content, but also related to the microstructure of WPU. The sample WPU2 (1.75 of NCO/OH molar ratio) exhibited hard‐segment order, but WPU1 (1.25 of NCO/OH molar ratio) had no hard‐segment order. The appropriate starch filled into WPU not only decreased the ordered region of soft‐segment matrix, but also hindered the formation of hard‐segment ordered structure. The blend material from 80 wt % WPU1 and 20 wt % starch exhibited better tensile strength (27 MPa), elongation at break (949%), and toughness than others. With an increase of starch content, the WPU matrix with dispersed starch in the blends transited to dual‐phase continuity and then to starch matrix with dispersed WPU. The results suggested that a certain extent of miscibility existed between WPU and starch in the blend materials on the whole composition ratio. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3325–3332, 2003     

蓖麻油作交联剂的聚氨酯弹性体的合成及性能

以不同摩尔比的四氢呋喃均聚醚（PTMG）和1,6-亚己基二异氰酸酯（HDI）合成聚氨酯（PU）预聚体,再分别用丁二醇（BD）、蓖麻油（CO）以及BD和CO混合物进行扩链交联,合成了一系列不同CO含量的PU.通过FTIR、AFM、拉伸实验和TGA,对不同硬段含量和CO含量PU的氢键化程度、相形态结构、力学性能和热性能进行了比较。结果表明,二异氰酸酯和扩链剂的种类及用量对PU的性能均有很大的影响。随着PU中二异氰酸酯用量的增加,其力学性能和热稳定性能提高。随着扩链剂中CO用量的增加,PU氨酯键的氢键化程度降低,其软、硬段的微相分离程度降低,导致其力学性能降低。但CO用量的增加会提高PU分子链的交联和支化,因而其热稳定性能得到提高。     

Structure–property relationship of polyimide fibers containing ether groups

The copolyimide (co‐PI) fibers with outstanding mechanical properties were prepared by a two‐step wet‐spinning method, derived from the design of combining 4,4′‐oxydianiline (ODA) with the rigid 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA)/p‐phenylenediamine (p‐PDA) backbone. The mechanical properties of PI fibers were drastically improved with the optimum tensile strength of 2.53 GPa at a p‐PDA/ODA molar ratio of 5/5, which was approximately 3.7 times the tensile strength of BPDA/p‐PDA PI fibers. Two‐dimensional wide‐angle X‐ray diffraction indicated that the highly oriented structures were formed in the fibers. Two‐dimensional small‐angle X‐ray scattering revealed the existence of the needle‐shaped microvoids aligned parallel to the fiber axis, and the introduction of ODA led to the reduction in the size of the microvoids. As a result, the significantly improved mechanical properties of PI fibers were mainly attributed to the gradually formed homogeneous structures. The co‐PI fibers also exhibited excellent thermal stabilities of up to 563°C in nitrogen and 536°C in air for a 5% weight loss and glass transition temperatures above 279°C. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42474.     

Processing‐structure‐property relationship in rigid polyurethane foams

Rigid polyurethane (PU) foam is used as a thermal insulating and supporting material in domestic refrigerator/freezers and it is produced by reaction injection molding (RIM) process. There is a need to improve the thermal property of rigid PU foam but this is still a challenging problem. Accordingly, this work investigates the RIM process parameters to evaluate their effects on rigid PU foam's structure and hence property. It has been found that mold temperature is a key parameter whereas curing time has negligible effect on structure of PU foam. Cell size, strut thickness, and foam density have been found very critical in controlling the thermal and mechanical properties. Upper and lower values of 30 to 32 kg/m³ density are critical to observe contribution of radiation and solid conductivity separately. Finally, PU foam with 160 µm average cell size, 16 µm strut thickness, below 10% open cell content, and 30 to 32 kg/m³ density allow obtaining better thermal insulation without significant reducing in the compressive strength. The presented work provides a better understanding of processing‐structure‐property relationship to gain knowledge on producing high‐quality rigid PU foams with improved properties. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44870.     

Structure–property relationship of polyetheramines as clay‐swelling inhibitors in water‐based drilling fluids

The influences of structure parameters of polyetheramines as clay‐swelling inhibitors in water‐based drilling fluids on the application performances were studied. Interactions of polyetheramines with clays were investigated through elemental analysis (EA), X‐ray diffraction (XRD), and thermogravimetric analysis (TGA). The results showed that lower molecular weight, hydrophobic oxypropylene segment, and plentiful amino group of polyetheramines favored improvement of inhibitive properties, enhancement of adsorption abilities, and expelling interlayer bound waters of clays (as confirmed by cutting rolling test, bentonite inhibition test, EA, XRD, and TGA studies). Simultaneously, the polyetheramines did not produce adverse effect to filtration control of the drilling fluids. In addition, XRD patterns revealed that these polyetheramines could intercalate into interlayer spaces of clays and display a monolayer arrangement. The corresponding basal spacing of clays was correlated only with molecular weight of polyetheramines. The dense loading of polyetheramines in the interlayer of clays was beneficial in improving inhibitive properties. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Structure–property relationship of starch‐filled chain‐extended polyurethanes

Chain‐extended polyurethane (PU) elastomers were prepared using castor oil with 4,4′‐methylene bis (phenyl isocyanate) (MDI) as a crosslinker and 4,4′‐diamino diphenyl sulphone (DDS) as an aromatic diamine chain extender. A series of starch‐filled (from 5 to 25% wt/wt) diamines chain‐extended PUs have been prepared. The starch‐filled PU composites were characterized for physico‐mechanical properties viz, density, surface hardness, tensile strength, and percentage elongation at break. Thermal stability of PU/starch have been carried out by using thermogravimetric analyzer (TGA). Thermal degradation process of PU/starch were found to proceed in three steps. TGA thermograms of PU/starch shows that all systems were stable upto 235°C, and maximum weight loss occur at temperature 558°C. The microcrystalline parameters such as crystal size (〈N〉) and lattice strain (g in %) of PU/starch have been established using wide‐angle X‐ray scattering (WAXS) method. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2945–2954, 2003     

Structure–property relationship of electron‐beam‐modified EPDM rubber

Electron‐beam‐initiated grafting of trimethylolpropane triacrylate (TMPTA) onto the bulk ethylene propylene diene monomer (EPDM) was carried out with varying concentrations of TMPTA at a constant irradiation dose of 100 kGy and over a wide range of irradiation doses (0–500 kGy) at a fixed concentration (10%) of TMPTA. The rubber was also modified in the bulk by tripropylene glycol diacrylate (TPGDA, 10%) and tetramethylol methane tetraacrylate (TMMT, 10%) at an irradiation dose of 100 kGy. The modified rubbers were characterized by IR spectroscopy, crosslinking density measurements, and mechanical, dynamic mechanical, and electrical properties. The IR studies indicated increased peak absorbances at 1730, 1260, and 1019 cm⁻¹ due to increased 〉CO and C O C concentrations up to certain levels of TMPTA and irradiation dose. These are accompanied by an increase in the crosslinking density. The tensile strength of the samples increases gradually with increasing both the concentration of the monomer and radiation dose up to a certain level. The values of the modulus also increase at the expense of the elongation at break. An increase in the number of double bonds from two in the case of the diacrylate to four in the case of the tetraacrylate also brings about an increase in the tensile strength and moduli values. The elongation at break, however, decreases. The DMTA measurements indicate changes in the glass transition temperature, T_g, and tan δ_max on modification. The T_g shifts to a higher temperature with a simultaneous lowering of the tan δ_max values as the TMPTA level is increased. A similar trend is observed when the irradiation dose is increased and the nature of the monomer changes from di‐ to tetraacrylate. The dielectric loss tangent registers an increase on modification by irradiation of TMPTA while the permittivity is decreased. All the results could be explained on the basis of the structural modification and crosslinking density. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 323–337, 2000     

Structure‐property relationship in polyaniline‐filled castor oil based chain extended polyurethanes

A series of polyaniline (Pani)‐filled chain extended polyurethanes (PUs) were prepared by condensation polymerization of castor oil with methylene diisocyanate (MDI) as crosslinker and diamino diphenyl sulfone (DDS) as chain extender. The effect of different amounts of Pani (varying from 5% to 25%) on the chain extended PUs has been reported. The Pani‐filled chain extended PU sheets were characterized by their physico‐mechanical properties such as density, tensile strength, percentage elongation at break and surface hardness. Electrical properties, such as volume and surface conductivity, also have been reported. These results are corroborated with microcrystalline parameters of PU/Pani estimated using wide angle X‐ray scattering (WAXS). Polym. Eng. Sci. 44:772–778, 2004. © 2004 Society of Plastics Engineers.     

Structure‐property relationship of substituted pyrrolidine functionalized CNT epoxy nanocomposite

Carbon nanotubes (CNTs) based polymer nanocomposites hold the promise of delivering exceptional mechanical properties and multifunctional characteristics. However, the realization of exceptional properties of CNT based nanocomposites is dependent on CNT dispersion and CNT‐matrix adhesion. To this end, we modified MWCNTs by Prato reaction to yield aromatic (phenyl and 2‐hydroxy‐4‐methoxyphenyl) substituted pyrrolidine functionalized CNTs (fCNT1 and fCNT2) and aliphatic (2‐ethylbutyl and n‐octyl) substituted pyrrolidine functionalized CNTs (fCNT3 and fCNT4). The functionalization of CNTs was established by Thermogravimetric analysis (TGA), Raman Spectroscopy, and XPS techniques. Optical micrographs of fCNT epoxy mixture showed smaller aggregates compared to pristine CNT epoxy mixture. A comparison of the tensile results and onset decomposition temperature of fCNT/epoxy nanocomposite showed that aliphatic substituted pyrrolidine fCNT epoxy nanocomposites have higher onset decomposition temperature and higher tensile toughness than aromatic substituted pyrrolidine fCNT epoxy nanocomposites, which is consistent with the dispersion results of fCNTs in the epoxy matrix. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42284.     

Structure‐property relationship of L‐tyrosine‐based polyurethanes for biomaterial applications

The structure‐property relationship of L ‐tyrosine‐based polyurethanes was demonstrated by using different polyols and diisocyanates. L ‐tyrosine‐based chain extender, desaminotyrosyl tyrosine hexyl ester (DTH), was used to synthesize a series of polyurethanes. Polyethylene glycol (PEG) or poly caprolactone diol (PCL) was used as the soft segment and hexamethylene diisocyanate (HDI) or dicyclohexylmethane 4,4′‐diisocyanate (HMDI) was used with DTH as the hard segment. The polyurethanes were characterized to investigate the effect of structure on different polyurethane properties. From FTIR and DSC, these polyurethanes exhibit a wide range of morphology from phase‐mixed to phase‐separated structure. The decreasing molecular weight of the PEG soft segment leads to relatively more phase mixed morphology whereas for PCL‐based polyurethanes the extent of phase mixing is less with decreasing PCL molecular weight. Results show that PCL‐based polyurethanes are mechanically stronger than PEG‐based polyurethanes but PCL‐based polyurethanes degrade slower and absorb less water compared with PEG‐based polyurethanes. The HMDI‐based polyurethanes are less crystalline and comparatively more hydrophobic than HDI‐based polyurethanes. The characterization results show that the polyurethane properties are directly related to the structure and can be varied easily for a different set of properties that are pertinent for biomaterial applications. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Structure–property relation in polyvinyl alcohol/starch composites

A series of polyvinyl alcohol (PVA)/starch films were cast by the solvent method. Mechanical, optical, wide‐angle X‐ray scattering (WAXS), and biodegradation studies of starch‐filled PVA films were carried out. With the addition of starch there was an increase in haze and diffusion of light, whereas there was only slight change associated with tensile behavior and burst strength of the PVA film. Microstructural parameters, such as crystal size (〈N〉) and lattice distortion (g, in %) were estimated using one‐dimensional Hosemann's paracrystalline model along with WAXS data. These parameters quantify the changes in the PVA/starch systems, which resulted in the observed physical properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 12: 630–635, 2004     

Structure–property relationships in bibenzoxazole polymers containing fluorocarbon linkages

A series of bibenzoxazole polymers with general formula where R′f and Rf are fluorocarbon-containing linkages has presented a unique opportunity to determine relationships between physical transitions and molecular structure. The results of oscillatory thermomechanical experiments (～1 Hz) show two glassy-state and a glass transition as amorphous transitions for each material above ?180°C. Each glassy-state transition is correlated with onset of motion of specific linkages, the flexibilities of which depend on the structure and molecular positions of the linkages. The glass transition temperatures depend on the two relaxations (T < T_g) in a systematic manner.     

Structure–property relationships for azo disperse dyes on polyurethane fibre

Using two series of monoazo disperse dyes, the relationships between the molecular structure of dye and its dyeing properties, such as adsorption behaviour, fastness properties and distribution on polyurethane–polyester blends, were thoroughly investigated. Correlation analysis of experiment data revealed that the partition coefficient between octanol and water (CLogP) is the main factor affecting dye sorption. A greater level of CLogP tends to have a greater isotherm coefficient and better rubbing and washing fastness on polyurethane fibre, as well as a greater distribution ratio between the components of the blend. The dye dipole moment is negatively correlated with various degrees of washing fastness. The dye with two terminal hydroxy groups exhibited notable sorption on the polyurethane component and has the largest partition ratio on polyurethane–polyester in the blend. Corresponding regression analysis equations were identified.     

Effect of pyridazine content and crosslinker structure on the properties of polyurethane elastomers

This article studies the development of a series of heterocyclic polyurethanes (PUs) with various pyridazine content and different crosslinker structure in their main chains. All of the isocyanate‐terminated PU prepolymers were prepared from poly(tetramethylene oxide) glycol of molecular weight 1400 (Terathane 1400) and 1,6‐hexamethylene diisocyanate. The properties of the obtained linear and crosslinked pyridazine‐based PU were compared with the properties of common PUs obtained by chain extension with 1,4‐butanediol. All the obtained PUs were characterized through spectral and thermal behavior. The pyridazine‐based PU showed improved thermal stability with 10% weight loss at temperatures above 370–400°C. With the increase of pyridazine content the values of Young's modulus are higher and the strain at break decreases. Increasing pyridazine content leads to increased films surface hydrophilicity. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Structure‐property relationships in commercial polyetheretherketone resins

Key relationships between molecular structure and final properties are reported for standard flow and high flow grades of commercially‐available polyetheretherketone (PEEK) resins that differ primarily in molecular weight and molecular weight distribution. Despite similar chemistry and composition, the molecular size‐dependent structural differences associated with the PEEK resins in this study are shown to influence the crystallization rate, final crystallinity, and melt rheology during processing, which subsequently affects mechanical properties, including strength, ductility, and impact resistance. These structure‐property relationships provide fundamental understanding to aid in the design and manufacturing of industrial and medical devices that leverage both the advantages common to all PEEK resins, including chemical and thermal resistance, mechanical strength, and biocompatibility, as well as more subtle differences in crystallization kinetics, melt rheology, ductility, and impact resistance. POLYM. ENG. SCI., 57:955–964, 2017. © 2016 Society of Plastics Engineers     

Structure–property relationship in polybutadiene–polyamide multiblock copolymers

Two kinds of aromatic–aliphatic polyamide oligomers were newly prepared by the reactant pairs of 3,4′-oxydianiline–adipic acid and 3,4′-oxydianiline–azelaic acid. These oligomers were then condensed separately with α, ω-polybutadienedicarboxylic acid giving two series of polybutadiene–polyamide multiblock copolymers. Properties of four series of polybutadiene–polyamide multiblock copolymers, whose polyamide blocks consisted of not only newly prepared polyamides but also previously synthesized aromatic polyamides derived from 4,4′-oxydianiline–isophthalic acid and 3,4′-oxydianiline–isophthalic acid, were investigated on the view point of structure-property relationship. A larger extent of the T_g depression of polybutadiene phase, and higher tensile strength and modulus were observed in the block copolymers having aromatic polyamides compared with those having aliphatic ones.     

Structure–tensile property relationship of knitted fabric composites

This paper reports some further studies on the tensile properties of plain weft knitted DuPont Kevlar fiber fabric reinforced epoxy matrix composites. One aim of this work is to investigate systematically the anisotropy of knitted fabric composites. Tensile tests were conducted at different off‐axial angles (0°, 30°, 45°, 60° and 90°) with respect to the wale direction. Fracture modes corresponding to this off‐axial variation were clearly identified. The elastic modulus and tensile strength were found to be the highest in the wale direction (0°), but decreased gradually towards the course direction (90°). This anisotropic study was carried out on both single layered and multilayered (four layered) knitted fabric composites. Another aim is to study the effect of specimen width (or number of loops per specimen width) on the tensile properties. This study indicated an optimum number of loops per sample width required to obtain meaningful tensile test results. Further, edge effect on the tensile properties of the knitted fabric composites was also investigated in the paper. This was achieved through comparative studies on cut and uncut four layered specimens. In the cut specimens the continuity of the yarns is lost at the cut edges, which show a marginal variation in the properties compared with the uncut specimens where the yarns are continuous throughout the specimen. Finally, a study was also carried out to investigate the effect of loop size (or stitch density) on the tensile strength and stiffness of the single layered composites.     

Structure–property relationships in one‐component polyurethane adhesives for wood: Sensitivity to low moisture content

The causes of strength loss of wood joints and their consequent delamination from one‐component polyurethane adhesives used for bonding structural wood when used at a low moisture content was investigated by testing wood joint strength and elongation at rupture at different wood moisture contents and by ¹³C‐NMR spectroscopy and scanning electron microscopy of the hardened bond line. The combination of the relative proportion of the still‐reactive free ? NCO groups on the polyurethane, of the wise choice of degree of polymerization of the resin, and of a slower rate of reaction were the three parameters found to be important in overcoming the problem of poor or no bonding of wood at low to very low moisture contents from one‐component polyurethane adhesives. The results obtained indicated that one‐component polyurethane adhesives that had a combination of a higher proportion of still‐unreacted ? NCO groups, a lower degree of polymerization, and a slower reaction rate were capable of overcoming the problem of the high sensitivity of polyurethane gluing at low to very low wood moisture contents. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4181–4192, 2006     

Structure‐property relationships in copolyester elastomer‐layered silicate nanocomposites

While the field of polymer–clay nanocomposites is reaching maturity, some parts of the studied systems still present researchers with possibilities for the improvement of material properties. This study entails the understanding of the relationships in copolyester elastomer/organically modified layered silicate nanocomposite and the structure–property relationships within the system of the nanocomposite. A series of these nanocomposites was prepared via twin‐screw extrusion melt compounding. The experiments included the following three types of synthetic organosilicates: high aspect ratio Somasif (ME100) fluoromica and two lower aspect ratio Laponite synthetic hectorites, (WXFN) and (WXFP). These organosilicates were modified with quaternary octadecyltrimethylammonium bromide (ODTMA) and were used to prepare the nanocomposites. The nanocomposite structure on a micro‐ and nanometre scales was evaluated by two techniques, such as X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The mechanical properties of the nanocomposites were examined to determine the impact aspect ratio of the nanofiller and wt % loading have on performance. The addition of the 2 wt % high aspect ratio of ME100‐ODTMA, in particular, showed statistically improved tensile strength, tear resistance, creep resistance, and water vapor permeation barrier enhancement. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41742.