Preparations and Properties of Waterborne Polyurethane / Nanosilica Composites

Summary Aqueous dispersion of polyurethane(PU) ionomers, based on poly(tetramethylene glycol) as soft segment, isophorone diisocyanate as diisocyanate, 1,4-butanediol as chain extender, dimethylol propionic acid as potential ionic center, triethylene tetramine as crosslinker, and triethyl amine as neutralizer, were reinforced with hydrophobic nanosilica to give waterborne PU/nanosilica composites. The reinforcing effects of nanosilica were examined in terms of mechanical, dynamic mechanical, and thermal properties together with water swell and transparency of the dispersion cast films. With the addition of nanosilica to PU, tensile modulus and strength increased, and the rubbery modulus increased in magnitude and extended to higher temperature, and these enhanced mechanical and thermal properties, together with increased swell resistance were obtained without scarifying the transparency of the films.     

Polyurethane‐acrylic hybrid emulsions with high acrylic/polyurethane ratios: Synthesis,characterization, and properties

Allyl polyoxyethylene ether (APEE) was used as coupling agent between polyurethane (PU) and acrylic polymer (AC) to synthesize stable waterborne polyurethane‐acrylic (PU‐AC) hybrid emulsions with high AC/PU weight ratio ranged from 45/55 to 70/30. The effect of the AC/PU weight ratio and the acrylate type including methyl methacrylate (MMA), butyl acrylate (BA) and mixture of them on the properties of the synthesized emulsions and resultant films were investigated. The research results showed that the colloidal particle of the emulsions behaved core‐shell structure, and the copolymers were not crosslinked. An increase in the AC/PU weight ratio led to an increase in the average particles size and the particle size distribution, but decrease in the viscosity of the emulsions. Meanwhile, the molecular weight distribution of the copolymers became wide, and the tensile stress, shore A hardness, storage modulus, glass transfer temperature, water resistance, and water contact angle of the resultant films increased, except that the films of PU‐BA were too soft to determine their mechanical properties. MMA and BA can provide the PU‐AC hybrid emulsions with very different properties, and which can be adjusted according to the special application. It was suggested that APEE can not only built up chemical bonds between PU and AC, but also increase the self‐emulsifying ability in the emulsion polymerization due to its hydrophilic ethylene oxide and carboxylic groups, resulting in that PU‐AC hybrid emulsions with high AC/PU ratio can be obtained by this method. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44488.     

Modification of aqueous polyurethane dispersions via tetraphenylethane iniferters

Aqueous polyurethane (PU) dispersions containing tetraphenylethane iniferter groups were prepared from 4,4′‐diphenylmethane diisocyanate, poly(propylene oxide)glycols, dimethylol propionic acid, and 1,1,2,2‐tetraphenylethane‐1,2‐diol. To improve the water resistance of the dispersions, methyl methacrylate monomers were added into these dispersions and block‐copolymerized onto the main PU chain. The viscosity and particle size of the dispersions were determined. Dispersion‐cast films were characterized in terms of the contact angle, the swell in water, and the mechanical properties. Contact‐angle and water‐swell measurements showed that the hydrophilicity of the films was decreased significantly when methyl methacrylate was polymerized in the presence of tetraphenylethane containing aqueous PU dispersions. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2993–3000, 1999     

The effects of soft segments on the physical properties and water vapor permeability of H12MDI-PU cast films

This research was based on the study of the effects of H₁₂MDI-1, 4BD PU soft segments on the physical properties and water vapor permeability of films cast from solvent evaporation or wet coagulation method. The soft segments studied included polyether, polyester, and polycaprolactone polydiols. The NCO/OH mol ratios of prepolymer were prepared by 2, 3, 4, 5, and 8, respectively. The chain lengths of the soft segments used were: PTMG of molecular weights 650, 1000, 2000, and 2900; PBA of 1000, 2000, and 3000. The results revealed that the polyether-based PU cast films had lower T_gs than the polyester-based PU films. In general, the polyether-based PU films shows the characters of higher water vapor permeability, lower breaking elongation, and higher breaking strength. Films with higher molecular weight soft segments in the polymer chains exhibited lower T_gs, lower breaking strength, higher breaking elongation, and higher water vapor permeability. As the hard segment contents were increased, the films exhibited higher T_gs. Films with higher hard-segment ratios had the highest breaking strength but the water vapor permeability, on the other hand, became lower. Films cast from the solvent evaporation method had higher breaking strength and higher breaking elongation but lower water vapor permeability than films cast from the wet coagulation method. © 1994 John Wiley & Sons, Inc.     

The Influence of Macromolecular Structure and Composition on Mechanical Properties of Films Cast from Solvent‐Free Polyurethane/Acrylic Hybrid Dispersions

Polyurethane (PU) /acrylic dispersions are of great commercial interest due to the synergetic combination of the PU and acrylic polymers. In this work, a series of PU/acrylic dispersions is synthesized by a solvent‐free technique and the influence of colloidal structure, grafting between the two polymers, and the nature of the two polymer phases themselves on the mechanical properties of films cast from the dispersions is explored. TEM analysis shows that the particles have a PU shell/acrylic core structure which is translated into the morphology of films cast from the dispersions. This particle/film morphology leads to the acrylic copolymer acting as a filler material and allows high T_g copolymers to be employed, leading to films with very high mechanical strength. Grafting of the PU and acrylic phases leads to increased compatibility but has little effect on the mechanical properties which are largely determined by the hardness of both the diol used in the PU synthesis and more importantly the acrylic (co)polymer composition. This work allows us to propose a series of design principles in order to synthesize PU/acrylic hybrids with controlled mechanical properties.     

Hydrolytic Degradation of Aliphatic Polyesters Copolymerized with Poly(ethylene glycol)s

Poly(1,4-butanediol succinate) copolymers were prepared by melt polycondensation of succinic acid and 1,4-butanediol with 10–50mol% (in feed) of poly(ethylene glycol) (PEG), where molecular weight (MW) of PEG is 200–2000. The reduced specific viscosity of the copolymers increased with incorporation of the PEG component, but a higher PEG content in the copolymers reduced it. The temperature of melting (T_m) and crystallinity decreased with increasing PEG content. T_m depression of the copolymers followed approximately Flory’s equation, suggesting that these are random type copolymers. Tensile strength and elongation decreased with increasing MW and content of PEG. The weight loss of copolymer films in a buffer solution with or without lipase at 37°C, as well as water absorption, increased with increasing PEG content, implying that higher water absorption contributes to hydrolytic degradation of the films. However, the weight loss of copolymers with PEG of lower MW increased greatly in spite of lower water absorption, demonstrating that hydrolytic degradation is influenced by the concentration of degradable ester linkages between succinic acid and PEG segments rather than water absorption. © of SCI.     

Mechanical and surface properties of membranes prepared from waterborne cationic hydroxyl‐terminated polydimethylsiloxane/polyurethane surfactant‐free micro‐emulsion

With the action of catalyst and cosolvent, a series of hydroxyl‐terminated polydimethylsiloxane (HPMS) based polyurethane (PU) micro‐emulsion were gotten by surfactant‐free copolymerization. They were successfully prepared by reacting isophorone isocyanate, poly(tetramethylene glycol), and HPMS with N‐methyldiethanolamine (MDEA) as chain extender and trimethylolpropane (TMP) as crosslinker. After neutralizing with dimethyl sulfate and inversing the emulsion polymerization with deionized water, a series of microemulsions were obtained. The emulsions were then cast into membranes named as PU–HPMS. The mechanical properties and water absorption of the PU–HPMS were determined and simultaneously the effects of the content of hard segment, solvent, TMP, MDEA, HPMS, and the molecular weight of soft segment were studied. It is noticed that the tensile strength decreased and elongation at break increased in the HPMS/PU when compared with pure PU, which confirm that PU was end‐capped with PDMS. It is also noticed that water absorption increased in the HPMS/PU when compared with pure PU. As HPMS content increased from 0.0 to 25.0 wt %, the surface free energies decreased from 0.3446 to 0.2317 mN/cm and water absorption decreased from 11.2% to 0.14%. The surface free energies of the membranes were decreased by more than 32.76%, which demonstrate that the membrane surfaces have excellent water and oil repellency. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 40–46, 2006     

Contribution of soft segment entanglement on the tensile properties of silicone–urea copolymers with low hard segment contents

Novel, segmented thermoplastic silicone–urea (TPSU) copolymers based on rather high molecular weight aminopropyl terminated polydimethylsiloxane (PDMS) soft segments (<M_n> 10,800 and 31,500 g/mol), a cycloaliphatic diisocyanate (HMDI) and various diamine chain extenders were synthesized. Copolymers with very low urea hard segment contents of 1.43–14.4% by weight were prepared. In spite of very low hard segment contents, solution cast films showed very good microphase separation and displayed reasonable mechanical properties. Tensile strengths of TPSU copolymers showed a linear dependence on their urea hard segment contents, regardless of the structure of the diamine chain extender used. The modulus of silicone–urea copolymers is dependent on the urea concentration, but not on the extender type or PDMS molecular weight. When silicone–urea copolymers with identical urea hard segment contents were compared, copolymers based on PDMS-31,500 showed higher elongation at break values and ultimate tensile strengths than those based on PDMS-10,800. Since the critical entanglement molecular weight (M_e) of PDMS is about 24,500 g/mol, these results suggest there is a significant contribution from soft segment chain entanglement effects in the PDMS-31,500 system regarding the tensile properties and failure mechanisms of the silicone–urea copolymers.     

Synthesis and characterization of hydrogels based on gamma irradiation of acrylic acid and methacrylic acid

In this work, hydrogels based on different ratios of acrylic acid (AAc) and methacrylic acid (MAc) monomers were prepared by gamma radiation copolymerization. The hydrogels were characterized by IR spectroscopy and thermogravimetric analysis (TGA). The effect of temperature and pH on the degree of swelling of AAc/MAc hydrogels was also studied. The results showed that the gel fraction of AAc is relatively higher than MAc, while the gel fraction of AAc/MAc hydrogels decreased slightly with increasing the ratio of MAc monomer in the initial solution. The IR spectroscopic analysis indicates the formation of copolymer networks and the presence of hydrogen bonding. The thermal study showed that PAAc hydrogel displayed higher thermal stability than PMAc and AAc/MAc hydrogels, over the studied compositions. The results showed that PAAc hydrogel reached equilibrium swelling state in water after 4 h, whereas PMAc and AAc/MAc hydrogels reached the equilibrium after 7 h. In this regard, AAc/MAc hydrogels showed degree of swelling in water lower than PAAc and higher than PMAc hydrogels. It was found that the swelling of the hydrogels based on AAc and MAc monomers or their copolymers increases with increasing temperature up to 50°C. Moreover, it was observed that the degree of swelling of hydrogels were not affected by increasing the pH values up to 4 and increased greatly within the pH values from 5 to 9. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Biodegradability of poly(ethylene terephthalate) copolymers with poly(ethylene glycol)s and poly(tetramethylene glycol)

Poly(ethylene terephthalate) copolymers were prepared by melt polycondensation of dimethyl terephthalate and excess ethylene glycol with 10–40mol% (in feed) of poly(ethylene glycol) (E) and poly(tetramethylene glycol) (B), with molecular weight (MW) of E and B 200–7500 and 1000, respectively. The reduced specific viscosity of copolymers increased with increasing MW and content of polyglycol comonomer. The temperature of melting (T_m), cold crystallization and glass transition (T_g) decreased with the copolymerization. T_m depression of copolymers suggested that the E series copolymers are the block type at higher content of the comonomer. T_g was decreased below room temperature by the copolymerization, which affected the crystallinity and the density of copolymer films. Water absorption increased with increasing content of comonomer, and the increase was much higher for E1000 series films than B1000 series films. The biodegradability was estimated by weight loss of copolymer films in buffer solution with and without a lipase at 37°C. The weight loss was enhanced a little by the presence of a lipase, and increased abruptly at higher comonomer content, which was correlated to the water absorption and the concentration of ester linkages between PET and PEG segments. The weight loss of B series films was much lower than that of E series films. The abrupt increase of the weight loss by alkaline hydrolysis is almost consistent with that by biodegradation.     

Physical properties of water‐borne polyurethane blended with chitosan

Water‐borne polyurethanes based on 4,4‐diphenylmethane diisocyanate, poly(butylene adipate), and chain extender N‐methyldiethanolamine (MDEA) that provided tertiary amine groups were synthesized. The polyurethane–chitosan (PU/CS) blends can be dissolved in the acetic acid and cast into films. The mechanical properties including tensile strength and elongation, as well as the water absorption and thermal properties of the PU/CS films were evaluated. The tensile strength increased with the increased amount of chitosan, but the elongation decreased accordingly. The chitosan in the blends promoted the water absorption. Chitosan was more thermally‐stable than PU, as shown in the thermal gravity analysis. Chitosan also had higher crystallinity, as demonstrated by differential scanning calorimetry. The blends were partial compatible mixtures, based on the data obtained from a dynamic mechanical analysis. Biocompatibility test was conducted utilizing immortalized rat chondrocytes (IRC). After IRC were seeded onto the PU/CS films for 1.5 and 120 h, the number of cells was counted and the morphology of cells was observed by light microscopy and scanning electron microscopy. Blends containing 30% chitosan had more cells attached initially. However, the blends containing more than 70% chitosan appeared to promote the cell proliferation. IRC were round on PU/CS films with more PU, but spread when the chitosan content in blends was higher. Overall, PU/CS films with more chitosan had better mechanical properties as well as biocompatibility. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2683–2689, 2007     

HTPS改性聚氨酯乳液的表征及表面性能探讨

以烷羟基聚二甲基硅氧烷（HTPS）、聚醚和聚酯二醇作为复合软段,制备了系列有机硅改性的聚醚．聚酯型聚氨酯乳液。通过衰减全反射红外光谱及表面光电子能谱研究证实,有机硅链段已键入聚氨酯分子链中,且硅氧烷链段有表面富集的倾向。表面水接触角测试结果则表明,胶膜的水接触角随着有机硅含量的增加而增大,随着成膜温度的提高,先增大后降低。     

Eco-friendly protective coatings based on poly(urethane sulfone amide) dispersions for carbon steel

Eight eco-friendly protective coatings (PU, PUA1, PUA3, PUA5, T30PUA5, T60PUA5, T90PUA5, and T120PUA5), were formulated based on series of laboratory-synthesized poly(urethane co-sulfone amide) copolymer dispersions (CPDs) as binders. The first four formulations were based on CPDs prepared by the copolymerization reaction of PU based on castor oil (CO) with aromatic polyamide sulfone (APAS) in four different concentrations (0%, 1%, 3%, and 5% solid to solid). The other four formulations were based on CPDs synthesized by the copolymerization reaction of PU based on transesterified CO with triethanolamine (CON) at different time intervals (30, 60, 90, and 120 min) with APAS at only one concentration. The effect of the degree of copolymerization and transesterification reactions on the physical, chemical, and mechanical properties of the formulated coatings was studied. The results showed that the copolymerization and transesterification reactions led to an increase in the density and viscosity of the coating formulations. Additionally, the hardness of the dried films increased with copolymerization and transesterification reactions. The transesterification reaction decreased the adhesion force of the coated films. The copolymerization process caused a decrease in the water uptake of the coated films. However, the transesterification reaction increased the water uptake. The prepared formulations were applied on carbon steel substrates to estimate their efficiency as eco-friendly protective coatings for steel. The weight loss of the coated steel panels decreased with an increase in the amount of the copolymerized APAS within the PU chains, while it increased with an increase in the transesterification time of the CON used in the preparation of the coated copolymers. From the corrosion test results, PUA5 and T30PUA5 showed the best anticorrosive performance as estimated from the degree of rusting, weight loss measurements, and failure at scribe.     

Extrudate swell behavior of polypropylene composites filled with microencapsulated red phosphorus

The microencapsulated red phosphorus (MRP) filled polypropylene (PP) composites were prepared using a twin‐screw extruder. The effects of load and temperature on the extrudate swell behavior of the PP/MRP composite melts were investigated by means of a melt flow indexer. The test temperatures and loads were varied from 180 to 205°C and from 2.16 to 12.5 kg, respectively. The results showed that the die‐swell ratio (B) of the composite melts increased roughly linearly with increasing load while decreased slightly with a rise of test temperature. The sensitivity of the die‐swell ratio of the composite melts to load was significant. When the test temperature or load was constant, the values of the B of the composite melts decreased slightly with increasing MRP weight fraction. The findings can provide useful information for processing of these composites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Block copolymer of polyurethanes with poly(m-phenylene isophthalamide)

In this study,we modified two kinds of conventional polyurethane (PU) by the low molecular weight diamine-terminated wholly-rigid aromatic polyamide poly(m-phenylene isophthalamide) (PmIA) (Nomex). Two molecular weights (1000 and 2000) of poly(tetramethylene glycol) (PTMG) with 4,4-diphenylene methane diisocyanate (MDI) and with three different ratios of low molecular weight diamine-terminated PmIA prepolymer with different molecular weight of 346, 584, 823 were synthesized to form six PmIA-PU block copolymers. Various block copolymers were also obtained by different ratios of wholly-rigid PmIA prepolymers. Inherent viscosity results indicated that the block copolymers are more viscous than conventional polyurethanes, suggesting that the block copolymers had sufficiently high molecular weights. Moreover, results obtained from differential scanning calorimetry (DSC) and dynamic mechanical properties analysis (DMA) demonstrated that the block copolymers not only exhibited a glass transition temperature (T_g) under 0 °C, but also had a higher storage modulus (E) than those of the conventional PU. Opitical microscopy (OM), phase contrast microscopy (PCM), and transmission electron microscopy (TEM) analyses confirmed that all of the block copolymers had a dispersed phase structure. The mechanical properties, tensile strength and 300% modulus of the block copolymers were found to be better than those of conventional PU.     

Synthesis and characterization of hydroxypropyl terminated polydimethylsiloxane‐polyurethane copolymers

Polyurethane (PU) block copolymers were synthesized using prepared hydroxypropyl terminated polydimethylsiloxane (HTPDMS MW 990) and polyether diols (N‐210) as soft segment with 4,4′‐diphenylmethane diisocyanate (MDI) and 1,4‐butanediol. This low molecular weight polydimethylsiloxanes (PDMS) containing hydroxypropyl end‐groups displayed better compatibility with PU than common PDMS. In this article, we illustrate its synthesis routes and confirmed the proposed molecular structures using NMR and infrared radiation (IR). We varied the contents of HTPDMS and N‐210 in soft segments (HTPDMS—N‐210: 0 : 100, 20 : 80, 40 : 60, 60 : 40, 80 : 20, and 100 : 0) to synthesize a series of PDMS‐PU copolymer. IR spectroscopy showed the assignment characteristic groups of each peak in copolymers and confirmed that the desired HTPDMS‐PU copolymers have been prepared. The different thermal, dynamic mechanical and surface properties of the copolymers were compared by thermogravimetry, DMA, contact angle and solvent resistance. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Polyimide‐polyurethane/urea block copolymers for highly sensitive humidity sensor with low hysteresis

Polyimide (PI)‐polyurethane‐urea (PU) block copolymers (PI‐PU75/25, PI‐PU50/50, and PI‐PU25/75) were prepared by reaction between anhydride‐terminated poly(amic acid) prepolymers with various number‐average degree of polymerization = 73/49/25) and isocyanate‐terminated urethane‐urea prepolymers with various (11/21/31) to obtain high performance capacitive humidity sensors. Pure PI and PU were also prepared to compare with PI‐PU copolymers. This study examined the effect of PU content on the water absorption %/water vapor transmission rate, thermal and mechanical properties and sensing properties of PI‐PU block copolymers. The thermal stability and mechanical properties of the copolymer decreased markedly with increasing PU content. The sensitivity of sensor increased sharply with increasing PU content from 0 to 25 wt %, and then increased a little. The hysteresis of sensor decreased sharply with increasing PU content up to 50 wt %, and then decreased a little. These results demonstrate the apparent upside of using two copolymers (PI‐PU75/25 and PI‐PU50/50) compared to using pure PI, in terms of sensor performance. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44973.     

Synthesis and properties of polystyrene‐b‐poly(ethylene oxide)‐b‐polystyrene triblock copolymers

A series of well‐defined and property‐controlled polystyrene (PS)‐b‐poly(ethylene oxide) (PEO)‐b‐polystyrene (PS) triblock copolymers were synthesized by atom‐transfer radical polymerization, using 2‐bromo‐propionate‐end‐group PEO 2000 as macroinitiatators. The structure of triblock copolymers was confirmed by ¹H‐NMR and GPC. The relationship between some properties and molecular weight of copolymers was studied. It was found that glass‐transition temperature (T_g) of copolymers gradually rose and crystallinity of copolymers regularly dropped when molecular weight of copolymers increased. The copolymers showed to be amphiphilic. Stable emulsions could form in water layer of copolymer–toluene–water system and the emulsifying abilities of copolymers slightly decreased when molecular weight of copolymers increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 727–730, 2006     

Novel amphiphilic poly(ester‐urethane)s based on poly[(R)‐3‐hydroxyalkanoate]: synthesis,biocompatibility and aggregation in aqueous solution

BACKGROUND: The aim of this work was to develop polyhydroxyalkanoates (PHAs) for blood contact applications, and to study their self‐assembly behavior in aqueous solution when the PHAs are incorporated with hydrophilic segments. To do this, poly(ester‐urethane) (PU) multiblock copolymers were prepared from hydroxyl‐terminated poly(ethylene glycol) (PEG) and hydroxylated poly[(R)‐3‐hydroxyalkanoate] (PHA‐diol) using 1,6‐hexamethylene diisocyanate as a coupling reagent. The PEG segment functions as a soft, hydrophilic and crystalline portion and the poly[(R)‐3‐hydroxybutyrate] segment behaves as a hard, hydrophobic and crystalline portion. In another series of PU multiblock copolymers, crystalline PEG and completely amorphous poly[((R)‐3‐hydroxybutyrate)‐co‐(4‐hydroxybutyrate)] behaved as hydrophobic and hydrophilic segments, respectively. RESULTS: The formation of a PU series of block copolymers was confirmed by NMR, gel permeation chromatography and infrared analyses. The thermal properties showed enhanced thermal stability with semi‐crystalline morphology via incorporation of PEG. Interestingly, the changes of the hydrophilic/hydrophobic ratio led to different formations in oil‐in‐water emulsion and surface patterning behavior when cast into films. Blood compatibility was also increased with increasing PEG content compared with PHA‐only polymers. CONCLUSION: For the first time, PHA‐based PU block copolymers have been investigated in terms of their blood compatibility and aggregation behavior in aqueous solution. Novel amphiphilic materials with good biocompatibility for possible blood contact applications with hydrogel properties were obtained. Copyright © 2008 Society of Chemical Industry     

Preparation and characterization of electrospun poly(ε‐caprolactone)–pluronic–poly(ε‐caprolactone)‐based polyurethane nanofibers

In this study, amphiphilic poly(ε‐caprolactone)–pluronic–poly(ε‐caprolactone) (PCL–pluronic–PCL, PCFC) copolymers were synthesized by ring‐opening copolymerization and then reacted with isophorone diisocyanate to form polyurethane (PU) copolymers. The molecular weight of the PU copolymers was measured by gel permeation chromatography, and the chemical structure was analyzed by ¹H‐nuclear magnetic resonance and Fourier transform infrared spectra. Then, the PU copolymers were processed into fibrous scaffolds by the electrospinning technology. The morphology, surface wettability, mechanical strength, and cytotoxicity of the obtained PU fibrous mats were investigated by scanning electron microscopy, water contact angle analysis, tensile test, and MTT analysis. The results show that the molecular weights of PCFC and PU copolymers significantly affected the physicochemical properties of electrospun PU nanofibers. Moreover, their good in vitro biocompatibility showed that the as‐prepared PU nanofibers have great potential for applications in tissue engineering. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43643.