Effects of the incorporation of low‐molecular‐weight diurethanes on thermal and rheological properties of thermoplastic polyurethane

In this study, two low‐molecular‐weight diurethanes were synthesized and blended with thermoplastic polyurethane (TPU). The effects of the incorporation on the thermal and rheological properties of TPU were evaluated. The diurethanes were obtained from the reaction of 4,4′‐diphenylmethane‐diisocyanate (MDI) with 1‐butanol (Additive 1) or 1‐octanol (Additive 2). Blending of the additives with TPU was carried out in a torque rheometer, and the blends obtained were analyzed by differential scanning calorimetry (DSC), torque rheometry, and capillary rheometry. The torque rheometry showed that an increase in the amount of both additives displaced the charging peaks to longer times and reduced the torque values after melting. The DSC analysis showed that the incorporation of the additives did not affect the glass transition temperature (T_g) of the flexible phase of TPU. However, an increase in the amount of Additive 1 led to a reduction in the T_g of the rigid phase, while increasing the amount of Additive 2 caused an increase in the T_g of this phase. Capillary rheometry results showed that blends with up to 2 wt % of additive led to intrinsic viscosity and melt‐flow stability values higher than those of processed TPU. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

天然橡胶硫化胶的热氧老化性研究

用热分析法(TGA、DSC)和裂解气相色谱-质谱分析(PGC-MS)研究了天然橡胶硫化胶的耐老化性能及其机理。结果表明,天然橡胶硫化胶的热氧老化初期力学性能和交联密度增加,热失重起始温度上升,随着老化过程的进行,降解效应占优势,硬度和交联密度下降,热氧稳定性变差。其热解机理可能是主链中键的断裂,产物主要是异戊二烯单体和1,4-二甲基-4-乙烯基环己烯。     

Synthesis and characterization of block copolymers based on natural rubber and polypropylene oxide

Segmented block copolymers from different grades of hydroxyl terminated liquid natural rubber (HTNR) (M _n 3000, 8800, 10,000, and 17,000) and polypropylene oxide (PPO) (M _n 1000, 2000, 3000, and 4000) have been synthesized and characterized by spectral analysis, thermal analysis, scanning electron microscopy (SEM), and mechanical testing. The glass transition temperature of NR block was found to be at about ?64°C, which is independent of the PPO whose transition is around 15°C. The thermogravimetric analysis (TGA) shows that the thermal degradation of the samples proceeded in two steps characteristic of the immiscible components. The inability of PPO segments to provide physical crosslinking and the subsequent formation of hard domains is reflected in the low tensile properties and tear properties. The amorphous nature of the PPO phase and its immiscibility with NR phase are evidenced by the SEM studies. The effect of molecular weight of PPO as well as HTNR on the properties of the block copolymers has also been discussed. © 2006 Wiley Periodicals, Inc. JAppl Polym Sci 103: 909–916, 2007     

Synthesis and characterization of block copolymers from aromatic diols,fumaric acid,sebacic acid and PEG

The syntheses of two linear unsaturated aromatic oligoesters, poly(hydroquinone fumarate‐co‐sebacate) (PHFS) and poly(resorcinol fumarate‐co‐sebacate) (PRFS), are described. PHFS, PRFS and poly(ethylene glycol) (PEG) are then used to prepare di‐ and tri‐block copolymers. Products thus obtained are investigated in terms of molecular weight, composition, structure and thermal properties by gel permeation chromatography (GPC), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and NMR and FTIR spectroscopies. A number of design parameters including the molecular weights of PHFS, PRFS and PEG and the ratios of PEG to PPFS or to PEFS are varied in order to assess their effects on product yields and properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2358–2363, 2003     

Synthesis,characterization, and thermal properties of phosphorus‐containing,wholly aromatic thermotropic copolyesters

A series of phosphorus‐containing, wholly aromatic thermotropic copolyesters from acetylated 2‐(6‐oxide‐6H‐dibenz〈c,e〉〈1,2〉oxa phosphorin‐6‐yl)‐1,4‐dihydroxy phenylene, p‐acetoxybenzoic acid, terephthalic acid, and isophthalic acid were prepared by melting polycondensation. The structure and basic properties of the polymers, such as the glass‐transition temperature (T_g), melting temperature (T_m), thermal stability, crystallinity, and liquid crystallinity, were investigated with Fourier transform infrared, elemental analysis, differential scanning calorimetry (DSC), thermogravimetric analysis, wide‐angle X‐ray diffraction, and hot‐stage polarizing optical microscopy. The copolyesters had relatively high T_g values ranging from 183 to 192°C. The T_m values obtained from DSC curves for samples P‐20 and P‐25 were 290 and 287°C, respectively (where the number in the sample name indicates the molar fraction of the phosphorus‐containing monomer in the reactants). The initial flow temperatures of other samples observed with hot‐stage polarizing microscopy were 271–290°C. The 5% degradation temperatures in nitrogen ranged from 431 to 462°C, and the char yields at 640°C were 41–52%. All the copolyesters, except P‐40, were thermotropic and nematic. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1278–1284, 2002     

Development of polyurethanes with azo‐type chromophores for second‐order nonlinear optical applications

Active nonlinear optical nitro‐substituted thiazole, benzothiazole, and thiadiazole chromophores were prepared and condensed with tolylene‐2,4‐diisocyanate (TDI) and 4,4′‐methylenedi(phenyl isocyanate) (MDI) to yield a series of polyurethanes. The resulting polyurethanes were characterized with Fourier transform infrared, proton nuclear magnetic resonance, and ultraviolet–visible spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and gel permeation chromatography. The weight‐average molecular weights of the polyurethanes ranged between 19,500 and 28,000 (weight‐average molecular weight/number‐average molecular weight = 1.71–2.15). All the polyurethanes exhibited excellent solubility in most common organic solvents, and this indicated that these polyurethanes offered good processability. The glass‐transition temperatures (T_g's) of the polyurethanes were in the range of 166–204°C. Among the polyurethanes, chromophores containing the nitrothiazole moiety exhibited lower T_g values in comparison with those of chromophores containing nitrobenzothiazole and nitrothiadiazole moieties. This was attributed to the small size of the nitrothiazole moiety in the polyurethane matrix. The polyurethanes containing a TDI backbone demonstrated relatively high T_g values in comparison with those of the polyurethanes containing an MDI backbone. This was a result of an enhancement of the rigidity caused by the incorporation of a toluene ring into the polyurethane backbone. The second harmonic generation (SHG) coefficients of the poled polyurethane films ranged from 67.29 to 105.45 pm/V at 1064 nm. High thermal endurance of the poled dipoles was observed for all the polyurethanes. This was attributed to the formation of extensive hydrogen bonds between urethane linkages. Furthermore, none of the developed polyurethanes showed SHG decay below 150°C, and this signified their acceptability for nonlinear optical devices. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis,characterization, and thermal properties of copolymers of behenyl acrylate and behenyl fumarate

Radical copolymerization of behenyl (systematic IUPAC nomenclature: n‐docosyl) acrylate and behenyl fumarate has been carried out in toluene at 70°C using benzoyl peroxide as initiator. Gel permeation chromatography was used to determine molecular weights (MW) and molecular weight distribution (MWD) of behenyl acrylate–behenyl fumarate (BA‐BF) copolymers. ¹H NMR and carbon analysis was used to determine the composition of BA‐BF copolymers. Monomer reactivity ratios for high conversion polymerization were calculated by conversion‐extended Kelen‐Tudos plot. Differential scanning calorimetric (DSC) measurements shows sharp melting peaks at about 64°C. Thermal stability studies were performed with thermogravimetric analyzer (TGA). By using these DSC and TGA data in several nonisothermal methods, the activation energies were calculated. X‐ray diffraction studies show the linearity of the copolymers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2721–2726, 2003     

Improved mechanical and antibacterial properties of thermoplastic polyurethanes by efficient double functionalization of silver nanoparticles

When making nanocomposites, there is a big challenge to obtain both functional and mechanical enhancement. In this study, a new in situ polymerization methodology for the incorporation of surface modified silver nanoparticles (AgNPs) in a thermoplastic polyurethane matrix was developed. AgNPs with contents ranging from 0 to 1.5 wt % were used. A double functionalization of the nanoparticles with oleic acid was performed, which lead to a reaction of carboxylic acid groups in the nanoparticle's surface with isocyanate groups of the 4,4′‐methylene diphenyl diisocyanate monomer as corroborated from the Raman results. The successful incorporation of the nanoparticles was verified with EDS, TGA, and Raman measurements. Thermal properties of nanocomposites were investigated by DSC. AgNPs made positive impact in two ways: first, increased more than twice the elastic modulus, as studied via nanoindentation measurements and second, based on the inhibition zone method, great bactericidal effectiveness for nanocomposites containing 1.5 wt % AgNPs was observed for Escherichia coli. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46180.     

Thermal and mechanical properties of multiple‐component aliphatic degradable polyurethanes

Macroscopic thermal and mechanical properties of complex aliphatic polycarbonate‐based polyurethane (PU) films containing degradable ester units in PU backbone were studied by a combination of several experimental techniques. Differential scanning calorimetry (DSC) revealed that the synthesized oligomeric diol (DL‐L) contributes (in addition to polycarbonate diol) to the formation of soft‐segment domains, while the hard‐segment domains are formed from 1,6‐diisocyanatohexane (HDI) and butane‐1,4‐diol (BD). Three main phase transitions were detected by DSC and by dynamic mechanical thermal analysis. Thermogravimetric analysis (TGA) of two‐component PUs showed that the PU made from DL‐L and HDI is the least thermostable product, while the PU made from polycarbonate diol and HDI is the most stable one. The differences in the thermal stability of different four‐component PUs are not important. Tensile properties very sensitively reflect the changes in composition and in microstructure of PU samples; the best tensile properties exhibits the degradable sample containing the equimolar ratio of hydroxyl groups of macrodiol, oligomeric diol DL‐L and butane‐1,4‐diol. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41872.     

Biodegradable polymers. XI. Spectral,thermal, morphological,and biodegradability properties of environment‐friendly green plastics of soy protein modified with thiosemicarbazide

The demand for biodegradable polymers produced from renewable natural resources continues to grow as environmental concerns increase. Biodegradable plastics derived from agricultural feedstock are a new generation of materials capable of reducing the environmental impact in terms of energy consumption and greenhouse effect in specific applications to perform as traditional/conventional plastics when in use and are completely biodegradable within a composting cycle through the action of living/micro‐organisms. The objective of this study is to examine the potentiality and performance pattern of soy protein isolate (SPI) resin, modified with various concentrations of thiosemicarbazide (TSC), as a thermoplastic to substitute some conventional petroleum‐based plastics. The spectral, thermal, morphological properties and the biodegradability of the modified resin have been investigated. The spectral studies indicate that TSC is not crosslinked with the protein moiety; rather, it acts as a modifier. Thermogravimetric analysis of the modified material has been followed using a computer analysis method (LOTUS package) developed by us for assigning the degradation mechanism. A number of equations have been used to evaluate the kinetic parameters. The degradation mechanism has been ascertained on the basis of the kinetic parameters. It is expected that, this environment‐friendly, fully biodegradable and sustainable TSC‐modified SPI green plastic could be commercially used for making molded products. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3134–3142, 2007     

Synthesis and characterization of PMMA‐b‐PBMA block copolymers by atom transfer radical polymerization

The synthesis of diblock copolymers using atom transfer radical polymerization, ATRP, of n‐butyl methacrylate, BMA, and methyl methacrylate, MMA, is reported. These copolymers were prepared from 2‐bromoisobutyryl‐terminated macroinitiators of poly(MMA) and poly(BMA), using copper chloride, CuCl,/N,N,N′,N″,N″‐pentamethyldiethylenetretramine, PMDETA, as the catalyst system, at 100°C in bulk and in benzonitrile solution. The block copolymers were characterized by means of size‐exclusion chromatography, SEC, and ¹H‐NMR spectroscopy. The SEC analysis of the synthesized diblock copolymers confirmed important differences in the molecular weight control depending on the reaction medium (solvent effect) and the chemical structure of the macroinitiator used. In addition, differential scanning calorimetry, (DSC) measurements were performed, showing for all the copolymers a phase separation. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2683–2691, 2002     

Phase structure and thermal stability of crosslinked polyurethane elastomers based on well‐defined prepolymers

Taking advantage of the DSC method, general procedures were presented for qualitative and quantitative evaluation of the phase separation degree and the crystalline phase content in polyurethane elastomers with well‐defined structures. Those elastomers were obtained not only in a typical one‐step method but also in the prepolymer method with the use of urethane oligomers with controlled molecular weight distribution (MWD). Prepolymers with well defined chain structures and narrow distributions of their molecular weights (MWD) M _w/M _n = 1.1–1.3 were produced in a multistage method, i.e., in step‐by‐step polyaddition of 2,4‐ and 2,6‐TDI with polyoxyethylenediols or with polycaprolactonediols of varied molecular weights. Isocyanate oligomers obtained at individual stages were then crosslinked with triethanolamine, whereas hydroxyl‐terminated oligomers were crosslinked with 4,4′,4″‐triphenylmethane triisocyanate (Desmodur RE). The obtained polyurethane elastomers were found to be characterized by the presence of five phases: soft phase consisted of flexible polyol‐type segments, crystalline phase made of soft segments, crystalline and amorphous hard phase made of hard segments, and intermediate phase, which was a composition of the soft and hard segments. The polyurethanes obtained out of prepolymers with defined MWD were characterized by better phase separation of the soft segments and increased structural order inside the hard phase as well as by better thermal stability than polyurethanes obtained from the typical one‐step method. The structural effects were also discussed on the thermal properties of the synthesized elastomers as analyzed by the TG and DTA methods. © 2007 Wiley Periodicals, Inc. J Appl PolymSci 104: 1464–1474, 2007     

Synthesis and characterization of N‐acryloylcarbazole/methyl methacrylate copolymers

Copolymers of N‐acryloylcarbazole (A) and methyl methacrylate (M) were synthesized in different in‐feed ratios. The composition of the copolymer was determined by the help of ¹H NMR spectrum. The comonomer reactivity ratios determined by Kelen‐Tudos (KT) and nonlinear error‐in‐variables methods were r_A = 1.12 ± 0.16, r_M = 0.94 ± 0.14, and r_A = 1.05, r_M = 0.90, respectively. Complete spectral assignments of the ¹H and ¹³C ¹H NMR spectra of the copolymers were done by the help of distortionless enhancement by polarization transfer (DEPT) and two‐dimensional NMR techniques, such as heteronuclear single quantum coherence (HSQC), total correlation spectroscopy (TOCSY), and heteronuclear multiple bond correlation (HMBC). The methine, α‐methyl, and carbonyl carbon resonances were found to be sequence sensitive. The signals obtained were broad because of the restricted rotation of bulky carbazole group and the quadrupolar effect of nitrogen present in carbazole moiety. Glass transition temperatures (T_g) were determined by differential scanning calorimetry and were found to be characteristic of copolymer composition. As the N‐acryloylcarbazole content increases, the T_g increases from 378.3 K for poly(methyl methacrylate) to 430.4 K for poly(N‐acryloylcarbazole). Variation in T_g with the copolymer composition were found to be in good agreement with theoretical values obtained from Johnston and Barton equations. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2667–2676, 2006     

Synthesis and performance of phenolic polybutadiene‐bound stabilizers

An antioxidant derivative, 6‐sulfanylhexyl 3‐(3,5‐di‐tert‐butyl‐4‐hydroxyphenyl)propanoate, was synthesized and examined. With a radical initiator, the addition of this compound to pending vinyls of OH‐telechelic, low molecular weight liquid polybutadiene (LBH) was performed to various degrees of conversion to form polymeric antioxidants (PAOs) in which the phenolic moiety was separated from the main chain by a spacer [? CH₂CH₂? S? (CH₂)₆? O? CO? ]. Pure, unstabilized LBH was mixed in several ratios with PAOs, Irganox 1520, and Irganox 1076, and the oxidation stabilities of these mixtures, determined by thermogravimetric analysis and differential scanning calorimetry, were compared. Probably because of their good compatibility with LBH, PAOs exhibited equal or better effectiveness than commercial antioxidants of the Irganox type. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 885–889, 2003     

Degradation kinetics of poly(HDDA‐co‐MMA)

1,6‐hexanediol diacrylate (HDDA) and methyl methacrylate (MMA) were copolymerized in different weight ratios using UV light induced photo‐polymerization to give poly(HDDA‐co‐MMA). Differential scanning calorimetry shows that copolymer was formed. The thermogravimetric and differential scanning calorimetric studies with different heating rates were carried out on these copolymers to understand the nature of degradation and to determine its kinetics. Different kinetic models were adopted to evaluate various parameters like the activation energy, the order, and the frequency factor. These analyses are important to study the binder removal from 3D‐shaped ceramic objects made by techniques like Solid free form fabrication. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Study on the liquefied‐MDI‐based shape memory polyurethanes

A series of liquefied‐MDI‐based polyurethanes having shape memory behavior, with various soft segments, chain extenders, and micro‐phase separation promoters were synthesized. Their morphology and properties were investigated in terms of thermal properties, dynamic mechanical properties, and shape recovery behavior. The results indicate that the soft segment formed with longer chain segment incline to crystallize during the cooling scans and the resulting SMPU have the higher crystallinity. Meanwhile, the chain extenders, which can enhance the polarity of hard segment, incline to have excellent shape memory properties with bigger storage modulus in rubbery state too. It was also found that the micro‐phase separation promoters have great influence on the shape memory behavior due to the enhancement of micro‐phase separation of SMPU. Furthermore, it was proved again that SMPU with longer soft segment and lower hard segment contents usually showed good shape memory behavior. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Synthesis,characterization, and performance evaluation of the AM/AMPS/DMDAAC/SSS quadripolymer as a fluid loss additive for water‐based drilling fluid

According to the molecular structure design requirements of the fluid loss additive resistant to high temperature, 2‐acrylamide‐2‐methyl propane sulfonic acid (AMPS), acrylamide (AM), dimethyl diallyl ammonium chloride (DMDAAC) and sodium styrene sulfonate (SSS) are selected as the structure monomers. Using ammonium persulfate as initiator, a new quadripolymer is synthesized through free radical aqueous solution polymerization. According to the minimum filtration loss of the fresh water‐based drilling fluid with 0.5 wt % quadripolymer, The synthesis conditions are optimized by orthogonal test: the mole ratio of AMPS/AM/DMDAAC/SSS is 5/7/2/1, the monomer concentration is 30 wt %, the initiator concentration is 0.8 wt %, the reaction temperature is 75°C and the pH is 10. The structure of the quadripolymer is characterized by Fourier transform infrared spectroscopy and nuclear magnetic resonance hydrogen spectroscopy. The results show that the quadripolymer contains all the designed functional groups. The thermal stability of the quadripolymer is tested by thermogravimetry, differential thermogravimetry, and differential scanning calorimetry. The results show that the thermal degradation of the quadripolymer is not obvious before 272.3°C. The rheological performance and filtration loss of the quadripolymer are evaluated. The results indicate that the filtration loss decreases with the increasing dosage of the quadripolymer before and after thermal aging test at 180°C for 16 h, and the filtration loss before the thermal aging test is smaller than that after the thermal aging test. The high temperature high pressure filtration loss (FL_(HTHP)) experiment results also show that the quadripolymer fluid loss additive has excellent temperature‐resistant performance. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41762.     

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.     

Structural,thermal, morphological and dynamic mechanical characteristics of waste‐reinforced polypropylene composites: A novel approach for recycling electronic waste

An in‐depth investigation has been carried toward utilizing polymer‐rich nonmetallic fraction of printed circuit boards (PCBs) as reinforcing fillers in polypropylene (PP) composites. The influence of waste additions (up to 25 wt %) on structural, thermal, morphological, and dynamic mechanical behavior of PP composites was investigated using a range of analytical techniques. The incorporation of PCB waste was found to affect the crystalline morphology resulting in the formation of smaller spherulites. The presence of glass fibers in PCB waste promoted the formation of β‐crystal enhancing the mechanical properties of composites. Thermal analysis showed a maximum increase of ～15 °C in the crystallization onset temperature (T_co) suggesting the nucleating effect of the filler, a feature also supported by structural investigations. Polarized microscopy revealed a reduction in the spherulite size after 5 wt % PCB waste loading owing to the presence of large number of nucleation sites. The incorporation of waste also increased the thermal stability of composites increasing the final degradation temperature by up to 14 °C. Dynamic mechanical properties of PP/PCB waste composites were determined in the temperature range ?20 to 155 °C; a significant increase in the storage modulus further confirmed the reinforcing effect of waste additives. This investigation has shown that the nonmetallic fraction of PCB waste could be used as a cost‐effective reinforcing filler for PP, providing an environmental friendly route to utilize electronic waste in value‐added products. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43389.