Preparation of UV curable emulsions using PEG-modified urethane acrylates and their coating properties III: Effects of epoxy acrylate

Water-dispersible UV-curable urethane acrylate emulsions were prepared with polyethylene glycol (PEG)-modified urethane acrylates (PMUA), containing terminal hydrophilic polyoxyethylene chains. To improve physical properties of PMUA, epoxy acrylate (EA) having high thermal stability and hardness, was mixed with five kinds of PMUA containing different chain lengths of polyoxyethylene (POE). For PMUA/EA mixtures, the composition ratio of EA to PMUA and the chain length of POE greatly influenced the size of droplets of emulsions and the physical properties of their cured films. At higher EA to PMUA ratio, the physical properties decreased, which was due to phase separation between EA and PMUA. Phase separation was confirmed by scanning electron microscopy. Received: 13 September 1996/Revised: 27 November 1996/2 December 1996     

Preparation of UV-curable emulsions using PEG-modified urethane acrylates: The effect of nonionic and anionic groups

To prepare self-emulsificable urethane acrylate resin, PEG-modified urethane acrylates (PMUA), containing polyoxyethylene chains as a terminal hydrophilic group and urethane acrylate anionomers (UAA) incorporated dimethylolpropionic acid (DMPA) as a pendant hydrophilic one were synthesized. For PMUA emulsions, the reaction molar ratio of PEG to 2-hydroxyethyl methacrylate (2-HEMA) significantly influenced the viscosity and droplet size of the emulsion and tensile strength of cured films. These emulsions were stable to pH change and the addition of electrolyte, but coagulated around 60°C. In the case of UAA, emulsions, however, were very stable to elevated temperatures and coagulated in adding even a little bit of electrolyte. For soap-free emulsions of the mixture of PMUA and UAA, emulsion stabilities of these mixtures against temperature, pH change, the addition of electrolyte, and the rate of shear and freeze–thaw increased synergetically. Additionally, the tensile strength of cured films was also improved. © 1996 John Wiley & Sons, Inc.     

Plasticized poly(3‐hydroxybutyrate) with improved melt processing and balanced properties

The widespread application of poly(3‐hydroxybutyrate) (PHB) in the food packaging and biomedical fields has been hindered by its high brittleness, slow crystallization, poor thermal stability, and narrow processing window. To overcome these limitations, a mixture of biodegradable and biocompatible plasticizers was used to modify PHB. Epoxidized soybean oil (ESO), acetyl tributyl citrate, poly(ethylene glycol) 4000 (PEG4000), and poly(ethylene glycol) 6000 (PEG6000) were tested to improve PHB melt processing and to achieve balanced thermal and mechanical properties. These plasticizers increased the flexibility and decreased the melt viscosity, improving the processability. The tensile strength was maintained within the limit of experimental error for ESO and decreased slightly (6–7%) for the other plasticizers. PEG6000 and ESO delayed the decomposition process of PHB. The plasticizers did not hinder the crystallization, and poly(ethylene glycol)s increased the crystallinity. The change in the interplanar distance and crystallite size, correlated with lamellar stack dimensions, gave more information on the plasticizers' effects in PHB. The blend with 5 wt % ESO was considered suitable for the fabrication of marketable PHB films. This study showed that it is possible to tailor the rheological, thermal, and mechanical behavior of a commercial PHB through the addition of a second plasticizer. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44810.     

Swelling behavior of novel polyurethane hydro-xerogels

Summary Polyurethane hydro-xerogels derived from PEG-modified urethane acrylates (PMUA), containing hydrophilic segment (polyoxyethylene groups) and hydrophobic segment at the same molecule, were prepared and their swelling behaviors were evaluated.Hydro-xerogels of PMUA were prepared using gelation process of PMUA emulsions. these gels could be swelled at both of water and dioxane, moreover, the swelling ratio of these gels at dioxane and water were changed with composition ratio of water to PMUA in the preparation of gel. In aqueous medium, swelling ratio of these gels increased with the increase in composition ratio of water to PMUA. However, in organic medium (Dioxane), swelling ratio decreased as the composition ratio of water increased. Additionally, as the reaction molar ratio of PEG to 2-HEMA increased, swelling ratio of gels at water increased. These results were due to microstructure of PMUA gels, which was formed by phase separation between hydrophilic and hydrophobic segments in the course of gelation.     

Modification of zein films by incorporation of poly(ethylene glycol)s

The thermal and mechanical properties of corn (maize) (CZ) films plasticized with poly(ethylene glycol) (PEG) of two different molar masses (400 and 1000 g mol⁻¹) were studied using differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), tensile strength, moisture absorption isotherms and water vapour transmission rate measurements. The glass transition temperature (T_g) of plasticized films is determined primarily by the amount of moisture contained in the film. DMTA data show contraction of films with loss of absorbed water during heating/cooling cycles. The moisture absorption behaviour of films plasticized with PEG400 and PEG1000 is similar at low relative humidities but significantly different at higher relative humidities. Incorporation of up to about 30 wt% PEG substantially enhances the tensile strength and the resistance to water vapour transmission of the protein film, and PEG1000 is more effective than PEG400. © 2000 Society of Chemical Industry     

Conductive graphite/polyurethane composite films using amphiphilic reactive dispersant: Synthesis and characterization

Well-dispersed and conductive graphite (GP)/polymer composites films were fabricated using two different polymerizable amphiphilic dispersion agents namely urethane acrylate nonionomer (UAN) and polyethylene oxide (PEO) modified urethane acrylate (PMUA). Our GP/polymer composites were fabricated via in situ polymerization of unmodified GP and UAN or PMUA mixtures where UAN and PMUA acted not only as dispersion agents but also as macromonomer for the formation of the polymeric matrix. Dispersibility of GP in the polymeric matrix strongly depended on the type of amphiphilic dispersion agent, which was confirmed by SEM measurements. Fabricated composite films exhibited electrical conductivities of 10⁻¹ S/cm for UAN and 10⁻² S/cm for PMUA at 50 wt% of GP loading. From the thermogravimetric analysis, the introduction of graphite exhibits a beneficial effect on the thermal stability of poly(UAN) and poly(PMUA).     

Studies on water-swellable elastomers. II. Thermal properties and crystalline behavior of amphiphilic graft copolymers with poly(ethylene glycol) side chains

The thermal properties and crystalline structure of the amphiphilic graft copolymers CR-g-PEG600, CR-g-PEG2000, and CR-g-PEG6000 using chloroprene rubber (CR) as the hydrophobic backbone and poly (ethylene glycol) (PEG) with different molecular weights as the hydrophilic side chains were studied by DSC and WAXD. The results showed that a distinct phase-separated structure existed in CR-g-PEGs because of the incompatibility between the backbone segments and the side-chain segments. For all the polymers studied, T_m2, which is the melting point of PEG crystalline domains in CR-g-PEG, decreased compared to that of the corresponding pure PEG and varied little with PEG content. For CR-g-PEG600 and CR-g-PEG2000, T_m1, which is the melting point of the CR crystalline domains, increased with increasing PEG content when the PEG content was not high enough, and at constant PEG content, the longer were the PEG side chains the higher was the T_m1. The crystallite size L_o11 of CR in CR-g-PEGs increased compared to that of the pure CR and decreased with increasing PEG content. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 2441–2447, 1997     

聚乙二醇改性聚乳酸/乙酰柠檬酸三丁酯复合薄膜的结构及性能

以聚乳酸（PLA）为基材、乙酰柠檬酸三丁酯（ATBC）为增塑剂、聚乙二醇（PEG）为增韧剂采用溶液共混法涂覆制备PLA复合薄膜。采用红外吸收光谱、热分析、X射线衍射、扫描电子显微镜及拉伸测试表征PLA复合薄膜的结构和性能。结果表明,适量的PEG改性PLA/ATBC复合薄膜后,使其拉伸强度从29.52 MPa增加到33.40 MPa,断裂伸长率从262 %增加到292 %,薄膜的柔韧性得到增强;PEG的端羟基与PLA的羰基发生缔合反应形成氢键,提高了PLA/ATBC复合薄膜的热稳定性和结晶度;观察90 d后的薄膜表面SEM图像,发现PEG改性后的PLA/ATBC复合薄膜表面没有龟裂纹的产生,延长了其使用寿命;加入微量的爽滑剂乙撑双硬脂酰胺（EBS）改善了PLA复合薄膜的相容性和加工性能。     

Effects of nonreactive resins on the properties of a UV-curable methacrylated urethane resin

The effects of two nonreactive conventional-type resins, a bisphenol-A-based phenoxy resin PAPHEN-301 and aromatic-based PETROLEUM RESIN, on the mechanical, thermal, and physical properties of methacrylated urethane resin-based UV-curable formulations were studied. A methacrylated urethane prepolymer was synthesized from isocyanatoethyl methacrylate (IEM) and polytetrahydrofurandiol (PTHF) via a one-step reaction. An increase in PAPHEN-301 content caused an increase both in tensile strength and elongation values of UV-cured polymeric films. On the other hand, an increase in PETROLEUM RESIN content caused a decrease both in tensile strength and elongation values of the polymeric films. However, thermooxidative properties were not affected by the introduction of either resin. It was also found that the water-absorption capacities of the UV-cured methacrylated urethane films depended on the type and amount of the nonreactive resins. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1837–1845, 1998     

Improvement of biocompatibility and biodegradability of poly(ethylene succinate) by incorporation of poly(ethylene glycol) segments

Poly(ethylene glycol) (PEG) segments were incorporated into poly(ethylene succinate) (PES) by chain-extension reaction of PEG with PES using 1,6-hexamethylene diisocyanate as a chain-extender, forming a poly(ester ether urethane) (PEEU). The chemical structures and molecular weights of the PEEUs were determined by ¹H NMR and GPC, respectively. The composition dependence of thermal transitions, crystallization, hydrophilicity, in vitro biocompatibility, in vitro biodegradation and tensile properties of the PEEUs were systematically investigated. The glass transition temperature and degree of crystallinity of PEEU decreased with increase of PEG content. The hydrophilicity increased with PEG content as proved by the decreased water contact angle and increased water absorption. The results of cell culturing suggested that the in vitro biocompatibility increased with PEG content. Hydrolytic degradation demonstrated that degradation rate of PEEU increased with PEG content, which was caused by the increased hydrophilicity and decreased degree of crystallinity with increase of PEG content. The tensile results proved that the tensile strength and modulus decreased while elongation at break increased with PEG content.     

Synthesis,characterization, and evaluation of carboxyl‐terminated poly(ethylene glycol) adipate‐modified epoxy networks: Effect of molecular weight

A series of carboxyl‐terminated poly(ethylene glycol) adipate (CTPEGA) was synthesized by polycondensation of poly(ethylene glycol) (PEG) of various molecular weights (“2000,” “4000,” “6000,” “8000,” “10,000” g/mol) and adipic acid. CTPEGA was incorporated into the epoxy by a prereaction method. The CTPEGA and modified epoxy samples were thoroughly characterized by Fourier transform infrared spectroscopy, ¹H NMR spectroscopy, differential scanning calorimetry, and gel permeation chromatography. The effects of molecular weight of CTPEGA on thermomechanical and viscoelastic properties of the modified epoxy networks were investigated. Maximum improvement in impact strength was found for the epoxy network modified with CTPEGA containing PEG of molecular weight 2000 g/mol. With further increase in molecular weight of CTPEGA, the impact strength of the modified network decreases. However, in case of higher molecular weight CTPEGA, the improvement in toughness was achieved without any reduction in T_g due to the complete phase separation. The results were explained in terms of morphology studied by scanning electron microscopy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1723–1730, 2007     

Synthesis and characterisation of polyurethanes derived from waste black liquor lignin

Waste black liquor lignin, obtained from bagasse from the small-scale paper industry, can be utilized for the synthesis of polyurethanes (PUs). Several polyurethane samples were prepared from laboratory black liquor (LBL) by reacting varying amounts of lignin ranging from 5 to 70% (w/v) in poly(ethylene glycol) (PEG) (having molecular weights of 200, 600, 1000, 1500 and 4000) with tolylene 2,4-diisocyanate (TDI). The effects of lignin concentration and molecular weight of PEG on mechanical and thermal properties of PUs obtained were investigated. The polyurethanes synthesised were characterized for different properties such as shear strength, adhesion and thermal stability. The shear strength of PU joints with aluminum was found to decrease with increase in both lignin concentration and molecular weight of PEG. Maximum shear strength, i.e. 3.6 N/mm², was shown by 50% (w/v) lignin in PEG of molecular weight 200.     

Properties of Poly(vinyl chloride)/poly(ethylene oxide)/polyaniline Conductive Films: The Effect of Poly(ethylene glycol) Diglycidyl Ether

The effect of polyaniline and poly(ethylene glycol) diglycidyl ether on tensile properties, morphology, thermal degradation, and electrical conductivity of poly(vinyl chloride)/poly(ethylene oxide)/polyaniline conductive films was studied. The poly(vinyl chloride)/poly(ethylene oxide)/polyaniline conductive films were prepared using a solution casting technique at room temperature until a homogeneous solution was produced. Poly(vinyl chloride)/poly(ethylene oxide)/polyaniline/poly(ethylene glycol) diglycidyl ether conductive films exhibit higher electrical properties, tensile strength, modulus of elasticity but lower final decomposition temperature than poly(vinyl chloride)/poly(ethylene oxide)/polyaniline conductive films. Scanning electron microscopy morphology showed that the polyaniline more widely dispersed in the poly(vinyl chloride)/poly(ethylene oxide) blends with the addition of poly(ethylene glycol) diglycidyl ether as surface modifier.     

丙烯酸六氟丁酯用量对改性水性聚氨酯性能的影响

采用聚氧化丙烯二醇(PPG2000)、异佛尔酮二异氰酸酯(IPDI)、二羟甲基丙酸(DMPA)、1,4-丁二醇(BDO)、丙烯酸羟乙酯(HEA)和丙烯酸六氟丁酯(FA)为主要原料合成了含氟水性聚氨酯(WPU)。讨论了FA用量对WPU乳液、胶膜及WPU处理后棉织物疏水性能的影响。结果表明,随着FA用量的增加,胶膜的热稳定性能提高,拉伸强度增大,耐水性能提高,棉织物的疏水性能也得到提高。     

Novel amphiphilic polyurethane networks: gelation mechanism and swelling behaviors

Amphiphilic polyurethane gels can be prepared using poly(ethylene glycol)-modified urethane acrylate (PMUA) through two types of methods. When PMUA gels were prepared at an aqueous phase, droplet coalescence and gelation occurred at the same time, so the microstructure of these gels (UAHG) was similar to that of PMUA emulsion which was formed by the microphase separation between hydrophilic and hydrophobic domains. In the case of UAHG gels, as the composition ratio of water to PMUA increased, swelling in water increased, but swelling in dioxane was slightly decreased. For the other kind of PMUA gels prepared using dioxane through a conventional gelation process (UADG), swelling in dioxane greatly increased with increasing of the composition ratio of dioxane; however, swelling of these gels in water was very low. The difference in swelling behavior between UAHG and UADG gels was due to the difference of microstructures between these gels which also influenced the mechanical properties. Additionally, the microstructures of UADG and UAHG gels were able to be confirmed using scanning electron microscopy (SEM) and contact angle measurement. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 821-832, 1997     

聚乙烯醇/聚乙二醇复合材料的热塑加工性能

通过热塑加工方法制备了增塑改性聚乙烯醇(mPVA)/聚乙二醇(PEG)复合材料,研究了PEG相对分子质量和含量对mPVA/PEG复合材料热性能、热塑加工性能,转矩流变性能和力学性能的影响.结果表明:加入适量PEG可降低mPVA的熔点,表明PEG对mPVA有一定的增塑作用;随着PEG用量的增加,mPVA的熔体流动速率增大...     

Synthesis and characterization of PMMA/PEG-TPE semi-interpenetrating polymer networks

Two-component semi-interpenetrating polymer networks (Semi-IPNs) of thermoplastic urethane elastomer based on poly(ethylene glycol) and polymethyl methyacrylate were synthesized by the sequential technique. The Semi-IPNs obtained were characterized with respect to their mechanical properties such as tensile strength, elongation. Glass transition temperatures were carried out using dynamic mechanical thermal analysis. Phase morphology was studied by scanning electron microscopy. The effect of the compositional variation on the above-mentioned properties was examined. The results demonstrate that the components are immiscible, phase separation at the micrometer scale is observed, the extent of interpenetrating is dependent on variations in composition.     

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     

Improved processability and performance of biomedical devices with poly(lactic acid)/poly(ethylene glycol) blends

To improve the processability of micropolymer‐based devices used for biomedical applications, poly(lactic acid) (PLA) was melt‐blended with poly(ethylene glycol)s (PEGs) of different molecular weights (MWs; weight‐average MWs = 200, 800, 2000, and 4000; these PEGS are referred to as PEG200, PEG800, PEG2000, and PEG4000, respectively, in this article). The thermal properties, mechanical properties, and rheological properties of the PLA and the PLA–PEG blends were investigated. The tensile samples’ morphologies showed that the low‐MW PEGs filled molds well. The rheological properties confirmed that the low‐MW PEGs decreased the complex viscosity, and improved the processability. With decreasing PEG MW, the PLA glass‐transition temperature decreased. The nanoindenter data show that the addition of PEG decreased the modulus and hardness of PLA. The morphologies of the tensile samples showed that with increasing PEG MW, the thicknesses of the core layers increased gradually. The elongation at break was improved by approximately 247% with the addition of PEG200. Such methods can produce easily processed biological materials for producing biomedical products. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45194.     

Synthesis and characterization of new optically active poly(amide‐imide‐urethane) thermoplastic elastomers,derived from 4,4′‐(hexafluoroisopropylidene)‐N,N′‐bis(phthaloyl‐L‐leucine‐p‐aminobenzoic acid) and PEG‐MDI

A new class of optically active poly(amide‐imide‐urethane) was synthesized via two‐step reactions. In the first step, 4,4′‐methylene‐bis(4‐phenylisocyanate) (MDI) reacts with several poly(ethylene glycols) (PEGs) such as PEG‐400, PEG‐600, PEG‐2000, PEG‐4000, and PEG‐6000 to produce the soft segment parts. On the other hand, 4,4′‐(hexafluoroisopropylidene)‐N,N′‐bis(phthaloyl‐L ‐leucine‐p‐amidobenzoic acid) (2) was prepared from the reaction of 4,4′‐(hexafluoroisopropylidene)‐N,N′‐bis(phthaloyl‐L ‐leucine) diacid chloride with p‐aminobenzoic acid to produce hard segment part. The chain extension of the above soft segment with the amide‐imide 2 is the second step to give a homologue series of poly(amide‐imide‐urethanes). The resulting polymers with moderate inherent viscosity of 0.29–1.38 dL/g are optically active and thermally stable. All of the above polymers were fully characterized by IR spectroscopy, elemental analyses, and specific rotation. Some structural characterization and physical properties of this new optically active poly(amide‐imide‐urethanes) are reported. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2288–2294, 2004