Synthesis and biodegradation of copolyesterether of copoly(succinic anhydride/ethylene oxide) with triblock copolymer of poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene)

The thermal properties and biodegradability of the block copolyesterethers with copoly[succinic anhydride (SA)/ethylene oxide (EO)], synthesized by ring-opening copolymerization as a hard segment and the triblock copolyethers of poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) (PN) as a soft segment, were studied. The block copolyesterethers synthesized from higher than 8000 number-average molecular weight (M_n) of copoly(SA/EO)s showed a microphase separation structure as determined by the thermal properties [melting point (T_m) and glass transition (T_g)], at any polymer composition [EO/propylene oxide (PO)] or the determination of M_n of PN. A decrease in the M_n of copoly(SA/EO) or an increase in PO content in PN resulted in depression of heats of fusion (ΔH) of these block copolyesterethers. The enzymatic degradation of the block copolyesterethers by the lipase from Rhizopus arrhizus showed a substantial increase with a decrease in their ΔH, whereas it was depressed with an increase in the M_n of polyoxyethylene or polyoxypropylene segment in the block copolyesterethers. The block copolyesterethers were degraded by microorganisms in activated sludge. The biodegradability of the block copolyesterethers showed a pronounced drop, with an increase in the polyoxyethylene chain length or polyoxypropylene content in PN. The polycondensation was also conducted without a catalyst at 190°C, similarly, to the reaction catalyzed with Ti[OCH(CH₃)₂]₄ at 170°C. The effect of the residual titanium on the biodegradability of the block copolyesterethers was negligible. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 303–313, 1998     

Waterborne poly(urethane‐urea) gas permeation membranes for CO2/CH4 separation

In this work, dense membranes from aqueous dispersions of poly(urethane‐urea) (PUU) based on poly(propylene glycol) (PPG) and a block copolymer composed of poly(ethylene glycol) (PEG) and poly(propylene glycol) (PPG), EG‐b‐PG, with 7 wt % of the former were obtained. Nonpolluting formulations were synthesized with proportions of PPG and EG‐b‐PG as 1:0, 1:1, 1:3, and 3:1 in terms of equivalent number ratios. The effect of small and gradual increases in PEG segments was evaluated for the permeability of pure CO₂, CH₄, and N₂, at room temperature. Slight increases in PEG‐based segments in PUU promoted some remarkable properties, which led to a simultaneous increase in CO₂ permeability and ideal selectivity for CH₄ (300%) and N₂ (380%). Infrared spectroscopy showed that the PEG portions induced hydrogen bonds between ? NH of urethane and ether groups in the PEG portions, which promoted ordering of the flexible segments, confirmed by X‐ray diffractometry and small‐angle X‐ray scattering. Diffractometry techniques also confirmed the absence of crystalline domains, as did dynamic mechanical analysis. The produced membranes showed performance above Robeson's 2008 upper bound and seemed to be a superior polymeric material for CO₂/CH₄ and CO₂/N₂ separation. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46003.     

Investigation of phase behavior and water binding in poly(alkylene oxide) solutions

The aqueous solution properties of alkylene oxide polymers and copolymers are related to their interaction with water. In an attempt to better understand this behavior, differential scanning calorimetry has been employed to measure phase changes and water binding in solutions of polyethylene glycol (PEG), polypropylene glycol (PPG), and a 50/50 random copolymer of ethylene oxide and propylene oxide. PEG (M _n = 3510) forms a crystalline eutectic with water at 0.48 weight fraction of polymer. The liquidus curve for water can be fit accurately using the Flory–Huggins expression for solute activity with an interaction parameter of 0.05. PPG and the random copolymer do not crystallize and thus do not form a crystalline eutectic. Based on decreases in the heat of fusion of free water with added polymer, PEG binds more water than the copolymer which binds more water than PPG. The estimated hydration numbers per polymer segment are 1.5 for PPG, 2.3 for the copolymer, and 2.7 for PEG.     

Effect of polyhydric alcohols on the mechanical and thermal properties,porosities, and air permeabilities of polyurethane-blended films

Polyurethane (PU) and polyhydric alcohols composites were successfully prepared to be used as coating materials for fabrics. The effects of various polyhydric alcohols on the PU composites properties have been investigated. The tensile strengths, glass-transition temperatures, thermal-mechanical properties, and swelling capacities of the PU/polyhydric-alcohol-blended films are described in detail, along with their surface and cross-sectional morphologies. The tensile strengths and glass-transition temperatures of the PU/polyhydric-alcohol-blended films were found to decrease remarkably with increasing polyhydric-alcohol concentration. The swelling capacities and porosities of the PU/poly(propylene glycol) (PPG)-blended and PU/glycerol-blended films were observed to increase with increasing PPG or glycerol concentration. However, the poly(ethylene glycol) (PEG) concentration in the PU/PEG-blended film did not significantly affect its properties. The air and water-vapor permeability of nonwoven nylon fabrics coated with PU/PPG and PU/glycerol increased with increasing PPG or glycerol contents, while those coated with PU/PEG were unaffected by PEG content. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47429.     

Preparation of soluble copolyurethaneimide containing oxyethylene and oxypropylene units

Soluble copolyurethaneimides were synthesized by the isocyanate method in a solution of N‐methyl‐2‐pyrrolidone (NMP). The isocyanate‐terminated prepolyurethane prepared from low molecular weight poly(ethylene glycol) (PEG) or poly(propylene glycol) (PPG) and methylene diisocyanate was reacted with pyromellitic dianhydride at high temperature. The resulting copolyurethaneimides were soluble in polar solvents like N‐methyl‐2‐pyrrolidone and N,N'‐dimethylformamide. The film‐forming properties were investigated by changing the molecular weights of PEG and PPG. With PPG, the film‐forming property was enhanced. The inherent viscosity, solubility, thermal property, molecular weight distribution, and mechanical property were compared with the aromatic polyimide. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3502–3507, 2002     

The role of the ratio (PEG:PPG) of a triblock copolymer (PPG‐b‐PEG‐b‐PPG) in the cure kinetics,miscibility and thermal and mechanical properties in an epoxy matrix

The aim of this study was to evaluate the role of different poly(ethylene glycol):poly(propylene glycol) (PEG:PPG) molar ratios in a triblock copolymer in the cure kinetics, miscibility and thermal and mechanical properties in an epoxy matrix. The poly(propylene glycol)‐block‐poly(ethylene glycol)‐block‐poly(propylene glycol) (PPG‐b‐PEG‐b‐PPG) triblock copolymers used had two different molecular masses: 3300 and 2000 g mol^?1. The mass concentration of PEG in the copolymer structure played a key role in the miscibility and cure kinetics of the blend as well as in the thermal–mechanical properties. Phase separation was observed only for blends formed with the 3300 g mol^?1 triblock copolymer at 20 wt%. Concerning thermal properties, the miscibility of the copolymer in the epoxy matrix reduced the T_g value by 13 °C, although a 62% increase in fracture toughness (K_IC) was observed. After the addition of PPG‐b‐PEG‐b‐PPG with 3300 g mol^?1 there was a reduction in the modulus of elasticity by 8% compared to the neat matrix; no significant changes were observed in T_g values for the immiscible system. The use of PPG‐b‐PEG‐b‐PPG with 2000 g mol^?1 reduced the modulus of elasticity by approximately 47% and increased toughness (K_IC) up to 43%. Finally, for the curing kinetics of all materials, the incorporation of the triblock copolymer PPG‐b‐PEG‐b‐PPG delayed the cure reaction of the DGEBA/DDM (DGEBA, diglycidyl ether of bisphenol A; DDM, Q3‐4,4′‐Diaminodiphenylmethane) system when there is miscibility and accelerated the cure reaction when it is immiscible. All experimental curing reactions could be fitted to the Kamal autocatalytic model presenting an excellent agreement with experimental data. This model was able to capture some interesting features of the addition of triblock copolymers in an epoxy resin. © 2018 Society of Chemical Industry     

Biodegradable aliphatic/aromatic copoly(ester-ether)s: the effect of poly(ethylene glycol) on physical properties and degradation behavior

A series of high molecular weight copolymers based on poly(L-lactic acid) (PLLA) as the biodegradable aliphatic segments, poly(butylene terephthalate) (PBT) as the rigid aromatic segments and hydrophilic poly(ethylene glycol) (PEG) as the soft segments were synthesized with the aim of developing novel polymer materials which could combine high physical properties with good biodegradability. Via direct melt polycondensation of terephthalic acid (TPA), 1,4-butanediol (BDO), poly(L-lactic acid) oligomer (OLLA) and PEG, biodegradable aliphatic/aromatic copoly(ester-ether)s, poly(butylene terephthalate-co-lactate-co-ethylene glycol) (PBTLG), were prepared. The effect of the introduction of PEG soft segments on the synthesis, mechanical properties and thermal stabilities as well as the degradation behaviors of the final copolymers was investigated. When the PEG units were incorporated into the polymer main-chains, the weight-average molecular weight of the copolymers increased from 53,700 g/mol to 177,000 g/mol and the tensile strength (σ) improved by nearly two times from 6.5 MPa to 12.8 MPa for PBTLG1000-0.5. The glass-transition temperature (T _g) gradually decreased from 26.9 °C down to −5.5 °C and a depression of melting temperature was observed with the increase of PEG content. According to the in vitro hydrolytic degradation observation, all of the copolymers underwent significant degradation in phosphate buffer solution at 37 °C and the water absorption as well as the degradation rate of PBTLGs displayed a strong dependency on the PEG content.     

Plasticization of semicrystalline poly(l-lactide) with poly(propylene glycol)

Plasticization of semicrystalline poly(l-lactide) (PLA) with a new plasticizer - poly(propylene glycol) (PPG) is described. PLA was plasticized with PPG with nominal M_w of 425 g/mol (PPG4) and 1000 g/mol (PPG1) and crystallized. The plasticization decreased T_g, which was reflected in a lower yield stress and improved elongation at break. The crystallization in the blends was accompanied by a phase separation facilitated by an increase of plasticizer concentration in the amorphous phase and by annealing of blends at crystallization temperature. The ultimate properties of the blends with high plasticizer contents correlated with the acceleration of spherulite growth rate that reflected accumulation of plasticizer in front of growing spherulites causing weakness of interspherulitic boundaries. In PLA/PPG1 blends the phase separation was the most intense leading to the formation of PPG1 droplets, which facilitated plastic deformation of the blends that enabled to achieve the elongation at break of about 90-100% for 10 and 12.5 wt% PPG1 content in spite of relatively high T_g of PLA rich phase of the respective blends, 46.1-47.6 °C. Poly(ethylene glycol) (PEG), long known as a plasticizer for PLA, with nominal M_w of 600 g/mol, was also used to plasticize PLA for comparison.     

Structure–property relationships of poly(urethane–urea)s with ultra-low monol content poly(propylene glycol) soft segments. Part II. Influence of low molecular weight polyol components

Segmented poly(urethane–urea)s have been synthesized with mixed soft segments of ultra-low monol content poly(propylene glycol) (PPG) and tri(propylene glycol) (TPG) which allows the fabrication of quality elastomers without crosslinking. The narrow molecular weight distribution of the ultra-low monol content PPG polyols allows for the probing of the influence of the low molecular components of the molecular weight distribution through the inclusion of low molecular homologs of PPG such as TPG. Structure–property relationships for these materials were investigated as average soft segment molecular weight was varied by blending 8000 g/mol PPG with TPG to achieve molecular weights of 2500, 2000, and 1500 g/mol. Morphological features such as microphase separation, interdomain spacing and interphase thickness were quantified and revealed with SAXS. AFM was utilized to verify the microphase separation characteristics inferred by SAXS. The thermal and mechanical behavior was assessed through applications of DMA, DSC, and conventional mechanical tests. It was found that as the average soft segment molecular weight was decreased through the addition of TPG, the interdomain spacing distinctly increased contrary to the trend seen for decreasing soft segment molecular weight in PPG based systems without TPG. Additionally, the inclusion of TPG in the poly(urethane–urea) formulations resulted in the formation of larger hard domains as evidenced by AFM. These results and supporting evidence from DMA, DSC, birefringence, and mechanical testing led to the conclusion that TPG apparently acts more as a chain extender as well as, or in contrast to, a soft segment.     

Comparison of properties of thermoplastic polyurethane elastomers with two different soft segments

Two series of thermoplastic polyurethane elastomers [poly(propylene glycol) (PPG) based PP samples and poly(oxytetramethylene)glycol (PTMG) based PT samples] were synthesized from isophorone diisocyanate (IPDI)/1,4-butanediol (BD)/PPG and IPDI/BD/PTMG. The IPDI/BD based hard segments contents of polyurethane prepared in this study were 40–73 wt %. These polyurethane elastomers had a constant soft segment molecular weight (average M_n, 2000) but a variable hard segment block length (n, 3.5–17.5; average M_n, 1318–5544). Studies were made on the effects of the hard segment content on the dynamic mechanical thermal properties and elastic behaviors of polyurethane elastomers. These properties of PPG based PP and PTMG based PT samples were compared. As the hard segment contents of PP and PT samples increased, dynamic tensile modulus and α-type glass transition temperature (T_g) increased; however, the β-type T_g decreased. The permanent set (%) increased with increasing hard segment content and successive maximum elongation. The permanent set of the PT sample was lower than that of the PP sample at the same hard segment content. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1349–1355, 1998     

PEG、PPG改性PLA材料的性能研究

采用熔融共混法用聚乙二醇(PEG)对生物可降解材料聚乳酸(PLA)进行改性,研究了PEG的相对分子质量对共混体系热性能和力学性能的影响,对比了相同相对分子质量的PEG和聚丙二醇(PPG)由分子结构差异对共混体系性能的影响。结果表明,PEG的相对分子质量为2 000时,改性效果最好;相同相对分子质量的PEG改性效果优于PPG。     

The Effect of Glycol Type,Glycol Mixture,and Isocyanate/Glycol Ratio on Flexural Properties of Oil Palm Empty Fruit Bunch-Polyurethane Composites

Abstract

Oil palm empty fruit bunch (EFB)-polyurethane (PU) composites were produced. The effects of the isocyanate (NCO)/glycol (OH) ratio, glycol type, and mixtures (polyethylene glycol PEG 400 (M _w 400) and polypropylene glycol PPG 400 (M _w 400)) on the flexural properties were investigated. The NCO/OH ratio had a significant effect on the flexural properties of the EFB-PU composites. Composites made with PEG 200 exhibited higher flexural properties than with PEG 400 and PPG 400. The flexural properties were also found to be influenced by the PPG 400/PEG 400 ratio.     

改性聚醚结构对PU乳液及性能的影响

在聚环氧丙烷(PPG)链引入双酚A、环氧乙烷,进行了无规或有规嵌段聚合,调整丙氧基(PO)、乙氧基(EO)、双酚A在聚醚中的分布序列,得到S、SH和SPE 3种改性聚醚。结果表明,不同PO、EO和双酚A的分布对PU乳液外观及黏度有较大影响;有规嵌段的SPE聚醚对PU乳液的耐电解质性能有突出贡献,是S型的7.98倍、SH型的3.90倍、PPG型的3.69倍;双酚A对PU膜的力学性能有显著增强作用,SPE相对分子质量(Mr=3 000)较其他3种聚醚(Mr=2 000)大50%,在同等条件下得到的膜的力学性能好于其他3种。     

Structural Requirements for the Intercalation of Polyether Polyols into Sodium‐Montmorillonite: The Role of Oxyethylene Sequences

The structural requirements for the preparation of polyether polyol/Na⁺‐montmorillonite nanocomposites, which are used in polyurethane/NaMMT nanocomposites, were evaluated using X‐ray diffraction, thermogravimetric analysis and shear viscosity behavior. Nanocomposites based on homopolyetherols: poly(ethylene glycol) (PEG), poly(propylene glycol) (PPG), polytetrahydrofuran (PTHF), block‐type copolyetherols and a SAN‐grafted polymer polyol were prepared. Intercalation was observed only with oxyethylene (EO) units containing polyetherols. The amount of the intercalated polyetherol ranged from 15 to 30 wt.‐%. EO‐sequences of 5 to 6 units proved to be sufficient for intercalation, which suggests a crown‐ether type complexation of interlayer cations.

     

Preparation of waterborne polyurethanes using an amphiphilic diol for breathable waterproof textile coatings

The application of polyurethanes (PUs) on breathable waterproof fabric coatings requires a balance of water vapor permeability (WVP) and water resistance which can be achieved by tailoring hydrophilic and hydrophobic segments. PU prepolymers were prepared from isophorone diisocyanate, dimethylol butanoic acid, and a mixture of various ratios of amphiphilic PPG2050 (copolymer of ethylene oxide and propylene oxide with –OH end groups) and hydrophobic poly(tetramethylene ether glycol) (PTMEG). After neutralization with triethylamine, the prepolymers were chain-extended with ethylene diamine/1,4-butanediol (1:1 by molar). The WVP values of the fabric coatings prepared using various waterborne PUs were very similar (910–990 g/m² × 24 h). When waterborne PUs prepared using a mixture of PPG2050 and PTMEG were employed for the textile coatings, the resulting PU-coated textiles exhibited excellent waterproof properties (>10,000 mm H₂O). The textile coatings prepared from PPG2050/PTMEG-based waterborne PUs were significantly more waterproof than those prepared from poly(ethylene glycol) (PEG)/poly(propylene glycol) (PPG)/PTMEG-based waterborne PU. This is probably due to a more even distribution of hydrophobic segments in the PUs, even though the WVP values of the PEG/PPG/PTMEG-based PU coatings were considerably smaller than those of the PPG2050/PTMEG-based PU coatings.     

Microwave dielectric relaxation and molecular dynamics in binary mixtures of poly(propylene glycol) 2000 and poly(ethylene glycol)s of varying molecular weight in dilute solution

Molecular dynamics of binary mixtures of poly(propylene glycol) (PPG) and poly(ethylene glycol)s (PEGs) of varying molecular weight due to molecular interactions, chain coiling and elongation in dilute solution under various conditions, ie varying number of monomer units of PEG, method of mixing of polymers and solvent environment, has been explored using microwave dielectric relaxation times. The average relaxation time τ_o, relaxation time corresponding to segmental motion τ₁ and group rotations τ₂, of a series of binary mixtures of poly(propylene glycol) 2000 and poly(ethylene glycol) of varying molecular weight (ie PPG 2000 + PEG 200, PPG 2000 + PEG 300, PPG 2000 + PEG 400, and PPG 2000 + PEG 600 mixed by equal volume in the pure liquid states, and PPG 2000 + PEG 1500, PPG 2000 + PEG 4000 and PPG 2000 + PEG 6000 mixed equal weights in solvent) have been determined in dilute solution in benzene and carbon tetrachloride at 10.10 GHz and 35 °C. A comparison of the results of these binary systems of highly associating molecules shows that the molecular dynamics corresponding to rotation of a molecule as a whole and segmental motion in dilute solutions are governed by the solvent density when the solutes are mixed in their pure liquid state. Furthermore, the molecular motion is independent of solvent environment when the polymers are added separately in the solvent for the preparation of binary mixtures. It has also been observed that there is a systematic elongation of the dynamic network of the species formed during mixing of pure liquid polymers in lighter environment of solvent with increasing PEG monomer units, while the elongation behaviour of the same species in the heavier environment of carbon tetrachloride solvent is in contrast to the elongation behaviour of the polymeric species formed in pure PEG. The role of rotating methyl side‐groups in the PPG molecular chain has been discussed in term of the breaking and reforming of hydrogen bonds in complex polymeric species for the segmental motion. In all these mixtures, the relaxation time corresponding to group rotations is independent of the solvent environment and constituents of the binary mixtures. The effect of chain flexibility and coiling in these binary mixtures is discussed by comparing the relaxation times of the mixtures with their individual relaxation times in dilute solutions measured earlier in this laboratory. © 2001 Society of Chemical Industry     

Autoxidation of poly(alkylene glycols) in solution

Data reported for the autoxidation of poly(ethylene glycol) (PEG) and poly(propylene glycol) (PPG) in solution at relatively long reaction times were analyzed. A relatively simple and a more general kinetic scheme with corresponding rate expressions were used. It was found that the more general scheme gave somewhat more satisfactory agreement between calculated and observed values of several reaction variables. Limitations in the applications of both schemes to PEG and PPG autoxidations are mentioned.     

Melt Crystallization Behavior and Spherulitic Morphology of Poly(Trimethylene Terephthalate)/Poly(Propylene Glycol) Copolymers with Different Poly(Propylene Glycol) Molecular Weights

Poly(trimethylene terephthalate)/poly(propylene glycol) (PTT/PPG) copolymers with different PPG molecular weights (400–4,000?g?/mol) were successfully synthesized and characterized. Double melting endotherms during isothermal melt crystallization were observed by differential scanning calorimetry. Middle-temperature melting endotherms in all copolymers were stronger than that in PTT homopolymer and became smaller with the increasing PPG molecular weight. Nonisothermal crystallization kinetics of all samples were analyzed by Ozawa and Mo models. Polarized optical microscopy micrographs revealed that ring-banded spherulitic morphology was relatively easier to be observed in copolymers with higher PPG molecular weight at lower crystallization temperature, and PPG molecular weight nearly had no influence on the band spacing.     

Preparation of waterborne polyurethanes using an amphiphilic diol for breathable waterproof textile coatings

The application of polyurethanes (PUs) on breathable waterproof fabric coatings requires a balance of water vapor permeability (WVP) and water resistance which can be achieved by tailoring hydrophilic and hydrophobic segments. PU prepolymers were prepared from isophorone diisocyanate, dimethylol butanoic acid, and a mixture of various ratios of amphiphilic PPG2050 (copolymer of ethylene oxide and propylene oxide with –OH end groups) and hydrophobic poly(tetramethylene ether glycol) (PTMEG). After neutralization with triethylamine, the prepolymers were chain-extended with ethylene diamine/1,4-butanediol (1:1 by molar). The WVP values of the fabric coatings prepared using various waterborne PUs were very similar (910–990 g/m² × 24 h). When waterborne PUs prepared using a mixture of PPG2050 and PTMEG were employed for the textile coatings, the resulting PU-coated textiles exhibited excellent waterproof properties (>10,000 mm H₂O). The textile coatings prepared from PPG2050/PTMEG-based waterborne PUs were significantly more waterproof than those prepared from poly(ethylene glycol) (PEG)/poly(propylene glycol) (PPG)/PTMEG-based waterborne PU. This is probably due to a more even distribution of hydrophobic segments in the PUs, even though the WVP values of the PEG/PPG/PTMEG-based PU coatings were considerably smaller than those of the PPG2050/PTMEG-based PU coatings.     

Pressure-volume-temperature properties for binary and ternary polymer solutions of poly(ethylene glycol), poly(propylene glycol), and poly(ethylene glycol methyl ether) with anisole

Pressure-volume-temperature properties were measured for polymer solutions of poly(propylene glycol) (PPG)+anisole, polymer blends of PPG+poly(ethylene glycol methyl ether) (PEGME), and the blends of PPG+PEGME and poly(ethylene glycol) (PEG)+PPG with anisole at temperatures from 298.15 to 348.15 K and pressures up to 50 MPa. The Tait equation represents accurately the pressure effect on the liquid densities over the entire pressure range. The excess volumes change from positive to negative as increasing the mole fraction of PPG in the binary systems of PPG+anisole and PPG+PEGME. The volumetric data of the related binary systems were correlated with the Flory-Orwoll-Vrij and the Schotte equations of state to determine the binary parameters. By using these determined binary parameters, both equations predicted the specific volumes of the polymer blends with anisole to average absolute deviations of better than 0.13%.