Electro‐optic properties of CO2 fixed‐polymer/nematic LC composite films

Bis(cyclic carbonate) was obtained from the epoxide and CO₂ reaction with a quaternary ammonium halide salt catalyst. Cyclic carbonate derivatives were then reacted with amine to obtain quantitatively poly(hydroxy)urethanes that were reacted with isophorone diisocyanate (IPDI) and end capped with acrylate to form prepolymers. These prepolymers were mixed with reactive diluents and nematic LCs, and subjected to UV cure to form polymer/LC composite films in a transparent cell. Three types of diglycidyl ether [poly(propyleneglycol), cyclohexane, bisphenol A], three types of end‐capping acrylates [2‐hydroxyethyl acrylate (HEA), 2‐hydroxypropyl acrylate (HPA), and 2‐hydroxyethyl methacrylate (HEMA)], three types of multyfunctional diluents [tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA), dipentaerythritol hydroxy penta/hexa acrylate (DPHPA)], and three types of photoinitiators (Irgacure‐651, Irgacure‐184, Darocure‐1173) were incorporated to control the morphology, and hence, the electro‐optic properties of the polymer/nematic LC composite films. Poly(propylene glycol) diglycidyl ether segment of polyurethane acrylate (PUA) showed lower viscosity and gave larger domain size resulting in lower threshold (V₁₀) and driving (V₉₀) voltages, together with larger nematic–isotropic transition temperature depression. HEA end‐capped PUA gave larger polymer–LC phase separation and smaller V₁₀ as well as V₉₀. TPGDA‐based PUA showed the lowest V₁₀ and V₉₀ and the shortest response time. Among the three types of photoinitiators used Irgacure‐651 showed the larger LC domain, and smaller V₁₀ and V₉₀. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2744–2753, 2001     

Preparation and properties of UV-curable polyurethane acrylates

UV-curable polyurethane (PU) acrylates have been synthesized from polypropylene glycol (PPG), isophoron diisocyanate (IPDI), and three types of reactive diluents, i.e., 2-hydroxyethylacrylate (HEA), tripropyleneglycol diacrylate (TPGDA), and trimethylolpropane triacrylate (TMPTA). The effects of soft segment length, type, and concentration of reactive diluent on the mechanical and dynamic mechanical properties have been determined. When the soft segment length was short (750) tensile strength (σ_b) decreased, and elongation at break (ϵ_b) generally increased with increasing HEA concentration, due respectively to the inferior strength of HEA homopolymer, and increased molecular weight between crosslinks (M_c). Initial modulus (E) and σ_b increase and elongation at break (ϵ_b) decreased with the increase of TPGDA concentration, and the effect was more pronounced as the soft segment length decreased. The hardness and σ_b increase with diluent concentration in PPG 2000-based materials was more pronounced with higher functionality diluent, due to the increased crosslinking density. The lower temperature glass transition peak of PU was not influenced by the TPGDA incorporation, whereas the higher temperature one moved toward still higher temperature. This was interpreted in terms of possible compatibility of hard segments and acrylates due to their similar polarity and hydrogen bonding. © 1996 John Wiley & Sons, Inc.     

Aqueous dispersion of polyurethanes from H12MDI,PTAd/PPG,and DMPA: Particle size of dispersion and physical properties of emulsion cast films

Aqueous dispersions of ionic/nonionic polyurethane (PU) were prepared from hydrogenated diphenylemthane diisocyanate (H₁₂MDI), poly(tetramethylene adipate) glycol (PTAd), polypropylene glycol (PPG), monofunctional ethylene-propylene oxide ether, and dimethylol propionic acid (DMPA). The effects of DMPA, PTAd/PPG ratio, and the average molecular weight of PPG on the state of dispersion, mechanical, and viscoelastic properties of the emulsion cast films were determined using Authosizer, Instron, and Rheovibron.     

Preparation and properties of segmented thermoplastic polyurethane elastomers with two different soft segments

Thermoplastic polyurethane elastomers were prepared from 4,4‐diphenylmethane diisocyanate (MDI)/1,4‐butanediol (BD)/poly(propylene glycol) (PPG) and MDI/BD/poly(oxytetramethylene glycol) (PTMG). The MDI/BD‐based hard‐segment content of polyurethane prepared in this study was of 39–65 wt %. These polyurethane elastomers had a constant soft‐segment molecular weight (M_n , 2000), but a variable hard‐segment block length (n, 3.0–10.1; M_n , 1020–3434). The effects of the hard‐segment content on the thermal properties and elastic behavior were investigated. These properties of the PPG‐based MPP samples and the PTMG‐based MPT samples were compared. The polyurethane prepared in this study had a hard‐segment crystalline melting temperature in the range of 185.5–236.5°C. With increasing hard‐segment content, the dynamic storage modulus and glass transition temperature increased in both the MPP and MPT samples. The permanent set (%) increased with increasing hard‐segment content and successive maximum elongation. The permanent set (%) of the MPP samples was higher than that of MPT samples at the same hard‐segment content. The value of K (area of the hydrogen‐bonded carbonyl group/area of the free carbonyl group) increased with increasing hard‐segment content in both the MPP and MPT samples, and the K value of the MPT samples was higher than that of the MPP samples at the same hard‐segment content. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 345–352, 1999     

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     

Syntheses and properties of urethane prepolymers and their corresponding crosslinked films

Trimethylol propane (TMP), polyglycol (PG), and toluene diisocyanate (TDI) were reacted in various molar ratios to produce TMP–TDI–PG–urethane prepolymers and then mixed with equivalent isocyanate generator (Desmodur AP-Stable) in a mixture of m-cresol and naphtha to give polyurethane varnishes which finally became crosslinked films by the casting method. The mechanical properties and viscoelasticities of the PG-modified and PG-free polyurethane crosslinked films and the practicability of magnet wires coated with them were studied in this article. Three different PGs used in this experiment were polyethylene glycol, PEG(#400), polypropylene glycols, PPG(#1000) and PPG(#2000). In the case of adding PEG(#400) for modification, strength at break increased but elongation did not change. Meanwhile, glass transition temperature (T_g) shifted to lower temperature with increasing molar ratio. In the case of adding PPG(#1000) and PPG(#2000) for modification, the samples changed their mechanical properties from hard and brittle to soft and tough. With increasing molar ratios, strength at break initially increased and then decreased gradually, and elongation varied a lot and was consistently contrary to strength at break. T_g occurred at two regions: one at high temperature above 100°C for small molar ratios and the other at low temperature below 100°C for high molar ratios. Besides, for all PG-modified polyurethane crosslinked films, strength at break showed a local maximum at TMP/TDI/PG = 1/1/0.5, which indicated their homogeneous structures. The molar ratios of PG-modified urethane prepolymers, which are suitable for manufacturing practical magnet wires according to testing method JIS-C-3211, are as follows: TMP/TDI/PPG(#100) = 1/1/0.15–0.35 and TMP/TDI/PPG(#2000) = 1/1/0.10. PEG(#400)-modified magnet wires were not accepted on the aging test. The properties of crosslinked films of practical magnet wires are generally as follows: strength at break at 200–700 kg/cm², elongation less than 41%, and T_g at 100–200°C.     

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.     

Influence of polyurethane properties on mechanical performances of magnetorheological elastomers

Magnetorheological elastomers (MREs) are mainly composed of magnetizable particles and elastic polymer. The polymer matrix plays an important role in mechanical performances of MREs. In this study, the polyurethane (PU), which is synthesized by using toluene diisocyanate (TDI) and poly (propylene glycol) (PPG‐220), is selected as a matrix because it has better degradation stability than natural rubber and higher mechanical stability than silicone rubber. Four different MRE samples were fabricated by adjusting the reaction molar ratio of TDI to PPG to change the property of PU matrix. Structural characterization of the PU matrix was described by Fourier transform infrared analysis. The microstructures of samples were observed by using an environmental scanning electron microscope. The mechanical performances of samples, including shear modulus, magnetorheological effect (MR) effect, loss factor, and glass transition temperature (T_g), were characterized with dynamic mechanical analyzer. The results show that the shear modulus, the relative magnetic residual shear modulus and glass transition temperatures of samples increase with the increment of toluene diisocyanate, while the relative MR effects and loss factors decrease steadily. The experimental results indicate that optimal molar ratio (TDI : PPG) is 3 : 1. The field‐induced shear modulus of sample with molar ratio 3 : 1 is 4.9 MPa, and the relative MR effect is 121% under an external magnetic field of 800 mT at room temperature. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Waterborne polyurethane dispersions obtained by the acetone process: A study of colloidal features

Waterborne polyurethane (PU) dispersions were prepared from isophorone diisocyanate (IPDI), 2‐bis(hydroxymethyl) propionic acid (DMPA), 1,4‐butane diol (BD), poly(propylene glycol) (PPG), and triethylamine (TEA) by means of phase inversion through the acetone process. Changes in DMPA content, initial PU content in acetone, phase‐inversion temperature, evaporation conditions, and solvent nature were found to have a great impact on dispersion properties. Using a DMPA concentration of 0.30 mmol/g_pol, stable PU dispersions could only be obtained when the initial PU content in acetone was at least 60 wt %, and phase‐inversion temperature was lower than 30°C. However, when increasing the PU content to 75 wt %, stable dispersions were obtained using DMPA concentrations three times lower. Finally, viscosity curves during the water addition step as well as a phase diagram were determined to understand the particle formation mechanism. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Thermal characteristics of IPNs composed of poly(propylene glycol) and poly(acrylic acid)

Interpenetrating polymer networks (IPNs) based on poly(propylene glycol) (PPG) and poly(acrylic acid) (PAAc) were prepared by UV irradiation and characterized using fourier transform infrared (FTIR), differential scanning calorimetry (DSC), dielectric analysis (DEA), and thermogaravimetry (TGA). The glass transition temperatures (T_gs) of these IPNs exhibited a relatively higher temperature with an increased PAAc content. The decomposition temperature of PAAc is lower than that of PPG. PAAc affects the thermal stability of IPN more than PPG. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2570–2574, 2003     

Preparation and properties of MDI/H12MDI‐based water‐borne poly(urethane‐urea)s—Effects of MDI content and radiant exposure

Water‐borne poly(urethane‐urea)s (WBPUs) were prepared by a prepolymer mixing process using aromatic diisocyanate (MDI, 4,4′‐diphenylmethane diisocyanate)/aliphatic diisocyanate (H₁₂MDI, 4,4′‐methylenebis cyclohexyl isocyanate), polypropylene glycol (PPG, M_n = 1000), dimethylol propionic acid, and ethylene diamine as a chain extender, and triethylamine as a neutralizing agent. The effect of MDI on the molecular weight, chemical structure, dynamic thermo, and tensile properties of WBPUs was investigated. The yellowness index (YI, photo‐oxidation behavior) change of WBPUs under accelerated weathering exposure was also investigated. The WBPUs containing higher MDI content showed lower molecular weight, which verified the participation of some high reactive isocyanate groups of MDI into side reaction instead of chain growing reaction. As the MDI content increased, the storage modulus and tensile modulus/strength of WBPUs film increased, and their glass transitions of soft segments (T_gs) and hard segments (T_gh) were shifted to higher temperature. The intensity of tan δ peak of all three samples increased with increasing radiant exposure. The YI of H₁₂MDI‐based WBPU sample (WBPU‐0) was not occurred. The YI of WBPUs containing MDI increased with increasing MDI content and radiant exposure. However, the YI of sample WBPU‐25 containing 25 mol % of MDI at 11.3 MJ/m² (radiant exposure) was 6.6 which is a permissible level for exterior applications. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Properties of UV-curable polyurethane acrylates for primary optical fiber coating

Studies have been made on the effects of the chemical structure of reactive urethane acrylate prepolymers and diluents (reactive monomers) and overall composition of the prepolymer/diluent on the properties of the UV-curable polyurethane acrylates for primary optical fiber coating. We prepared several urethane acrylate prepolymers from two different isocyanates, 4,4′-dicyclohexylmethane diisocyanate (HMDI) or isophorone diisocyanate (IPDI), and two different polyols, polybutadiene diol (PBD) or polypropylene oxide diol (PPG), and 2-hydroxyethyl acrylate (HEA) with dibutyl tin dilaurate as a photoinitiator. UV-curable coating materials were formulated from the prepolymers and 2,2-dimethyl 2-phenyl acetophenone as a photoinitiator with one of four different diluents such as 1-vinyl 2-pyrrolidone (VP), lauryl methacrylate (LMA), acrylic acid 2-ethyl hexyl ester (AEHE), and acrylic acid n-butyl ester (ABE). It was found that AEHE is the desirable diluent in the formulation of the primary fiber-coating material. The desirable composition of PBD, when mixed PBD/PPG diols are used, should be about 50 wt % for optimum formulation. Most of the urethane acrylate prepolymers prepared in this study could be applied in the formulation of primary optical fiber coating and exhibited good properties of buffer functions, including low glass transition temperature, low modulus even at low temperature, say, below ?40°C, high refractive index, and low viscosity. © 1992 John Wiley & Sons, Inc.     

Total replacement of solvent in polyurethane synthesis using carbon dioxide soluble 1,3‐dichlorodistannoxane catalysts

This work demonstrates catalytic synthesis of polyurethanes using 1,3‐dichlorodistannoxane catalysts ( 1 ) in carbon dioxide (CO₂) and carbon dioxide expanded liquids (CXL). Catalytic polyurethane synthesis was also performed in pure organic solvent (dimethylformamide) for comparison. In this study, mainly, 4, 4′‐methylene‐bis‐(phenyl isocyanate) (MDI) as the diisocyanate precursor and ethylene glycol (EG) as the diol precursor were used for polyurethane synthesis. In addition to MDI, hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), and p‐isocyanatobenzylisocyanate (PIBI) were also used for polyurethane synthesis with different diols or triol in CO₂. Polyurethanes with a molecular weight ranging from 3000 to 70,000 were synthesized depending upon the combination of diisocyanate and diol used. Comparable yields of polyurethanes were obtained using an all butyl group substituted ( 1a ) catalyst in CO₂ (55 bars, 50°C) and in DMF (50°C). Additionally, the yield and polydispersity index (PDI) of polymer formed in neat CO₂ was comparable with those synthesized in the largely used organic solvent DMF. Interestingly, catalyst 1a in CXL (55 bars, 50°C) gave higher yields, and polymers with lower PDI (1.19). Reactions carried out in scCO₂ at 145 bars using PIBI and EG were found to be about three times faster than the reaction carried out in DMF. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Engineering plastics from lignin. VII. Structure property relationships of poly(butadiene glycol)-containing polyurethane networks

Hydroxypropyl lignin-based thermosetting polyurethanes containing polybutadiene (PBD) glycol soft segments (M_n of 2800 g M^?1) were synthesized with excess hexamethylene diisocyanate (HDI) and tolylene diisocyanate (TDI) by solution casting. Miscibility of the glycol with the lignin derivative was found to be poor as expected, and phase separation between the two polyol components in polyurethanes was detected by thermal and mechanical analysis, and by electron microscopy. This study examines the effect of concentration of polybutadiene glycol on the thermal and mechanical properties of the polyurethanes. The two-phase network system displayed significantly different properties than either the poly(ethylene glycol)-containing polyurethanes or their soft segment-free counterparts described previously. Macrophase separation was observed at nearly all degrees of mixing and was found to affect thermal and mechanical properties. The glass transition temperature (T_g) of the lignin phase in the TDI-based networks increased with poly(butadiene glycol) content rising from 3.6 to 71.4% of polyurethane, and this was attributed to the employment of a constant diisocyanate weight fraction which gave rise to a variable NCO/OH ratio and crosslink density. Distinct phase separation was evidenced by scanning electron microscopy (SEM) at above 3.6 and 7.1% glycol content for HDI- and TDI-based films, respectively. The polyurethane films behaved like rubber-toughened lignin networks when PBD was the discrete phase, and like lignin-reinforced rubber when the lignin derivative was discrete. This behavior was evidenced by the Young's modulus decreasing from 2000 to 50 MPa and ultimate strain rising from 6 to greater than 150%, with soft segment content increasing from 0 to 71.4%.     

阴离子型水性聚氨酯乳液的合成研究

以甲苯二异氰酸酯(TDI)、聚丙二醇(PPG)、二羟甲基丙酸(DMPA)为原料,制备了阴离子型水性聚氨酯乳液。探讨了温度、DMPA用量、异氰酸基团和羟基的物质的量比、PPG的相对分子质量对其乳液合成的影响,从而得出制备阴离子型水性聚氨酯乳液的较佳配方。     

Synthesis and characterization of aqueous cationomeric polyurethanes and their use as adhesives

Aqueous cationomeric polyurethanes (ACPU) were synthesized by a multistep reaction process. The alipathic diisocyanate, e.g., hexamethylene diisocyanate (HDI), was reacted with polyol, e.g., polypropylene glycol (PPG400) to form a prepolymer and it was chain-extended by reacting it with N-methyldietanolamine (N-MEDA). Quarternization was then carried out by using dimethyl sulfate (DMS), acetic acid (HAc), or hydrochloric acid (HCI). The resultant cationomers were self-emulsified with deionized water. The effect of different percentages of N-MEDA in the polymer backbone on the structure and properties of ACPU were studied. Viscosity, thermal properties, electrolytic stability, and pH stability of the cationomeric polyurethanes were also studied along with the adhesion strengths between flexible and rigid surfaces. © 1996 John Wiley & Sons, Inc.     

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     

Hydrophilicity,crystallinity and electrostatic dissipating properties of poly(oxyethylene)-segmented polyurethanes

Plaques of poly(oxyethylene)-segmented polyurethanes prepared from isophorone diisocyanate (IPDI) and polyethylene glycol (PEG) were used to probe the structure/property relationships with regard to hydrophilicity, crystallinity and electrostatic dissipating (ESD) ability. The prepared urethane polymers or oligomers consistently exhibited lower surface resistivities than their corresponding PEG-1000, 2000 and 8000 starting materials. The magnitude of the decrease in surface resistivity (ohm/sq) was correlated with heat of crystallinity, measured by differential scanning calorimetry. Surface resistivity as low as 10^7.5 ohm/sq for PEG-1000/IPDI polyurethane, a decrease by 2.5 orders of magnitude from pure PEG-1000, was observed and attributed to the differences in crystallinity. Polyurethanes containing PEG, polypropylene glycol (PPG) and mixed PEG/PPG were also prepared for comparison. The mixed PEG/MDEA (N -methyl diethanolamine) polyurethanes further demonstrated the importance of the nature and mobility of the hydrophilic groups for lowering the polymer surface resistivity. To account for these observations, an electron conducting mechanism via association and mobility of the hydrogen-bonded water molecules with hydrophilic poly(oxyethylene) groups is suggested. © 1999 Society of Chemical Industry     

New poly (urethane-methacrylate)s obtained by adjusting the structure of the polyols moieties: synthesis, transparent, thermal and mechanical properties

A series of novel cross-linked poly (urethane-methacrylate)s (PUAs) were synthesized in a three-step process: Four kinds of low number average molecular weight aromatic polyesters (PEs) with terminal hydroxyl groups were obtained by phthalic anhydride (PA) reacted with 1,2-propanediol (PDO), 1,4-butanediol (BDO), 1,6-hexanediol (HDO), and diethylene glycol (DEG), respectively. Then, a series of urethane-methacrylate macromonomers(UMAs), which have double bonds at the end of the chain, were prepared from isophorone diisocyanate (IPDI), the PEs obtained in first step, poly(ethylene glycol) 600 (PEG600) and ß-hydroxyethyl methacrylate(HEMA). Dibutytin dilaurate (DBTL) was used as catalyst. Finally, a series of thermosetting PUAs were synthesized by the polymerization of novel functional UMAs using 2,2'-azobis(isobutyronitrile) (AIBN) as catalyst. The compositions of the PEs and UMAs were determined by ¹H-NMR and fourier transform infrared (FT-IR). The properties of PUAs were measured by dynamic mechanical analysis (DMA), thermogravimetric analysis (TGA), wide-angle X-ray diffraction (WAXD), water uptake and optical properties testing, and mechanical performance measurements. The results revealed that the mechanical and degradation properties of PUAs were influenced by the kinds of PE or polyether polyols in the PUAs remarkably. The obtained PUAs present the good thermal and mechanical properties, low water uptake (below 1%) and high transparence (above 90%). The diversity of properties suggests that these PUAs can be used in a wide range of excellent optical polymer applications.     

Thermal decomposition of polyurethane pressure-sensitive adhesives dispersions

The thermal degradation of polyurethane pressure-sensitive adhesives (PSAs) at temperature 600 °C was investigated by the application of pyrolysis-gas chromatography technique. The present study was undertaken in order to determine the key thermal degradation products of polyurethane PSA based on isophorone diisocyanate (IPDI), polypropylene glycol (PPG), hydroxylated polybutadiene (HTPB), dimethylolpropionic acid (DMPA) and to elucidate the mechanism of the polyurethane PSAs pyrolysis.