Biobased polyurethanes from polyether polyols obtained by ionic‐coordinative polymerization of epoxidized methyl oleate

A series of poly(ether urethane) networks were synthesized from polyether polyols obtained by ionic‐coordinative polymerization of epoxidized methyl oleate (EMO) using 4,4′‐methylenebis(phenyl isocyanate) or l ‐lysine diisocyanate as coupling agents. Moreover, a variety of segmented poly(ether urethane) networks with different hard segment contents were obtained using 1,3‐propanediol as the chain extender. The materials were characterized by differential scanning calorimetry, thermogravimetric analysis, dynamic mechanical thermal analysis, and tensile properties. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Reduction of Epoxidized Vegetable Oils: A Novel Method to Prepare Bio‐Based Polyols for Polyurethanes

A novel method, epoxidation/reduction of vegetable oils, is developed to prepare bio‐based polyols for the manufacture of polyurethanes (PUs). These polyols are synthesized from castor oil (CO), epoxidized soybean oil, and epoxidized linseed oil and their molecular structures are characterized. They are used to prepare a variety of PUs, and their thermomechanical properties are compared to those of PU made with petroleum‐based polyol (P‐450). It is shown that PUs made with polyols from soybean and linseed oil exhibit higher glass transition temperatures, tensile strength, and Young's modulus and PU made with polyol from CO exhibits higher elongation at break and toughness than PU made with P‐450. However, PU made with P‐450 displays better thermal resistance because of tri‐ester structure and terminal functional groups. The method provides a versatile way to prepare bio‐polyols from vegetable oils, and it is expected to partially or completely replace petroleum‐based polyols in PUs manufacture.

     

Synthesis of poly(2‐oxazoline)s with side chain methyl ester functionalities: Detailed understanding of living copolymerization behavior of methyl ester containing monomers with 2‐alkyl‐2‐oxazolines

Poly(2‐oxazoline)s with methyl ester functionalized side chains are interesting as they can undergo a direct amidation reaction or can be hydrolyzed to the carboxylic acid, making them versatile functional polymers for conjugation. In this work, detailed studies on the homo‐ and copolymerization kinetics of two methyl ester functionalized 2‐oxazoline monomers with 2‐methyl‐2‐oxazoline, 2‐ethyl‐2‐oxazoline, and 2‐n‐propyl‐2‐oxazoline are reported. The homopolymerization of the methyl ester functionalized monomers is found to be faster compared to the alkyl monomers, while copolymerization unexpectedly reveals that the methyl ester containing monomers significantly accelerate the polymerization. A computational study confirms that methyl ester groups increase the electrophilicity of the living chain end, even if they are not directly attached to the terminal residue. Moreover, the electrophilicity of the living chain end is found to be more important than the nucleophilicity of the monomer in determining the rate of propagation. However, the monomer nucleophilicity can be correlated with the different rates of incorporation when two monomers compete for the same chain end, that is, in copolymerizations. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2649–2661     

Novel long chain unsaturated diisocyanate from fatty acid: Synthesis,characterization, and application in bio‐based polyurethane

A novel long chain linear unsaturated terminal diisocyanate, 1,16‐diisocyanatohexadec‐8‐ene (HDEDI) was synthesized from oleic acid via Curtius rearrangement. Its chemical structure was identified by FTIR, ¹H NMR, ¹³C NMR, and HRMS. This diisocyanate was used as a starting material for the preparation of entirely bio‐based polyurethanes (PUs) by reacting it with canola diol and canola polyol, respectively. The physical properties and crystalline structure of the PUs prepared from this diisocyanate were compared to their counterparts prepared from similar fatty acid‐derived diisocyanate, 1,7‐heptamethylene diisocyanate (HPMDI). The HDEDI based PUs demonstrated various different properties compared to those of HPMDI based PUs. For example, HDEDI based PUs exhibited a triclinic crystal form; whereas HPMDI based PUs exhibited a hexagonal crystal lattice. In addition, canola polyol‐HDEDI PU demonstrated a higher tensile strength at break than that of canola polyol‐HPMDI, attributed to the higher degree of hydrogen bonding associated with the former sample. Nevertheless, lower Young's modulus and higher elongation in canola polyol‐HDEDI PU were obtained because of the flexibility of the long chain introduced by the HDEDI diisocyanate. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3302–3310, 2010     

Thermoplastic elastomers based on poly(l‐Lysine)‐Poly(ε‐Caprolactone) multi‐block copolymers

Novel thermoplastic elastomers based on multi‐block copolymers of poly(l ‐lysine) (PLL), poly(N‐ε‐carbobenzyloxyl‐l ‐lysine) (PZLL), poly(ε‐caprolactone) (PCL), and poly(ethylene glycol) (PEG) were synthesized by combination of ring‐opening polymerization (ROP) and chain extension via l ‐lysine diisocyanate (LDI). SEC and ¹H NMR were used to characterize the multi‐block copolymers, with number‐average molecular weights between 38,900 and 73,400 g/mol. Multi‐block copolymers were proved to be good thermoplastic elastomers with Young's modulus between 5 and 60 MPa and tensile strain up to 1300%. The PLL‐containing multi‐block copolymers were electrospun into non‐woven mats that exhibited high surface hydrophilicity and wettability. The polypeptide–polyester materials were biocompatible, bio‐based and environment‐friendly for promising wide applications. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3012–3018     

Combining cationic ring‐opening polymerization and click chemistry for the design of functionalized polyurethanes

A straightforward strategy for the synthesis and functionalization of polyurethanes (PUs) via the use of alkyne‐functionalized polytetrahydrofuran (PTHF) diols is described. The alkyne groups have been introduced into the PTHF chains by the cationic ring‐opening copolymerization of tetrahydrofuran and glycidyl propargyl ether. These PTHF prepolymers were combined with 1,4‐butanediol and hexamethylene diisocyanate for the synthesis of linear PUs with latent functionalization sites. The polyether segments of the PUs have then been coupled with several types of functionalized azides by the copper‐catalyzed azide‐alkyne “click” chemistry, for example with phosphonium containing azides for their antibacterial properties. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Soft Matter Nanoparticles with Reactive Coronal Pentafluorophenyl Methacrylate Residues via Non‐Polar RAFT Dispersion Polymerization and Polymerization‐Induced Self‐Assembly

Soft matter nanoparticles exhibiting rich polymorphism with reactive pentafluorophenyl methacrylate (PFPMA) units in their coronae were prepared via non‐polar reversible addition‐fragmentation chain transfer dispersion polymerization and polymerization‐induced self‐assembly. Poly(stearyl methacrylate‐stat‐PFPMA) macro‐CTAs, containing up to 12 mol % PFPMA, were used in n‐octane and n‐tetradecane for the subsequent copolymerization of 3‐phenylpropyl methacrylate. Both formulations gave the full, common family of nanoparticles (spheres, worms, and vesicles) as determined by transmission electron microscopy. Reaction of the PFP ester repeating units in the coronal layer of spherical nanoparticles with benzylamine, tetrahydrofurfurylamine, N,N‐dimethylethylenediamine, and an amine functional methyl red dye yielded a new library of functional spherical nano‐objects. The success of the nucleophilic acyl substitution reactions was confirmed using a combination of ¹H/¹⁹F NMR and Fourier transform infrared spectroscopies as well as dynamic light scattering. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2326–2335     

Synthesis and characterization of polyurethanes from epoxidized methyl oleate based polyether polyols as renewable resources

Oligomeric polyether polyols were obtained through the acid‐catalyzed ring‐opening polymerization of epoxidized methyl oleate and the subsequent partial reduction of ester groups to give primary alcohols. The oligomers were characterized with titration, spectroscopic techniques (Fourier transform infrared and nuclear magnetic resonance), matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry, size exclusion chromatography, and differential scanning calorimetry. Depending on the degree of reduction, polyols of different hydroxyl content values were obtained and were reacted with 4,4′‐methylenebis(phenyl isocyanate) to yield polyurethanes. These materials, which were characterized by differential scanning calorimetry, thermogravimetric analysis, and dynamic mechanical thermal analysis, could behave as hard rubbers or rigid plastics. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 634–645, 2006     

Synthesis and deblocking of cardanol‐ and anacardate‐blocked toluene diisocyanates

Methyl anacardate and secondary butyl anacardate were prepared from anacardic acid and corresponding alcohols and were used, in addition to cardanol, as blocking agents for 2,4‐toluene diisocyanate (TDI). Blocked diisocyanate adducts were characterized via nitrogen estimation, Fourier transform infrared spectroscopy, and proton nuclear magnetic resonance spectroscopy. The deblocking temperatures of the adducts were determined using an FTIR spectrophotometer in conjunction with the carbon dioxide evolution method. The gel times of hydroxyl‐terminated polybutadiene–TDI adducts also were determined. Deblocking temperature and gel time analyses revealed that cardanol‐blocked 2,4‐TDI deblocks at a lower temperature and at a higher rate compared with anacardate‐blocked adducts. In addition, it was found that the electron‐withdrawing ester group reduces the deblocking temperature of the adduct only when it is in solvated form. All adducts were waxy solids that were found to be soluble in polyether polyol, polyester polyol, and polyhydrocarbon polyols. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4047–4055, 2004     

Degradable poly(ester triazole)s based on renewable resources

The copper(I)‐catalyzed alkyne‐azide cycloaddition (CuAAC) click polymerization has been used to obtain novel linear poly(ester triazole)s by reaction of bis‐alkyne having ester linkage and bis‐azido monomers, most of them derived from carbohydrates, such as glucose, arabinose, and erythrose, and therefore coming from natural renewable resources. The resulting polyesters had weight‐average molecular weights in the 11,500–148,000 range and were characterized by GPC, IR, and NMR spectroscopies. Thermal studies revealed them to be amorphous and stable up to 200 °C under nitrogen. Degradation studies showed that they were hydrolytically degradable. These studies were carried out at 50 °C in phosphate buffer solution at pH 7.4, and were monitored by GPC, and NMR spectroscopy. Finally, novel network hydrogels were obtained by crosslinking reaction of the poly(ester triazole) chains with hexamethylene diisocyanate. The water absorption and the kinetic parameters of the networks were studied. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2481–2493     

Novel hyperbranched polymers synthesized via A3 + B(B′) approach by radical addition‐coupling polymerization

In this study, a novel application of radical addition‐coupling polymerization (RACP) for synthesis of hyperbranched polymers is reported. By Cu/PMDETA‐mediated RACP of 2‐methyl‐2‐nitrosopropane with trimethylolpropane tris(2‐bromopropionate) or a bromo‐ended 3‐arm PS macromonomer, two types of hyperbranched polymers with high degree of polymerization are synthesized under mild conditions, respectively. The chemical structures of the hyperbranched polymers are carefully characterized. By selective degradations of the ester groups and weak bonds of NO? C in the polymers, high degree of alternative connection of the two monomers in the synthesized polymers have been identified. Based on the experimental results, mechanism of formation of the hyperbranched polymer is proposed, which includes formation of carbon radicals from the tribromo monomer through single electron transfer, its capture by 2‐methyl‐2‐nitrosopropane that results in nitroxide radical, and cross‐coupling reaction of the nitroxide radical with other carbon radicals. Hyperbranched polymer can be formed in a step‐growth mode after multiple steps of such reactions. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 904–913     

Synthesis and properties of bio‐based polyurethanes bearing hydroxy groups derived from alditols

Four kinds of bio‐based polyurethanes bearing hydroxy groups in the pendants were synthesized by the polyaddition of D ‐mannitol‐ and D,L ‐erythritol‐derived diols (1,2:5,6‐di‐O‐isopropylidene‐D ‐mannitol and 1,2‐O‐isopropylidene‐D,L ‐erythritol) with hexamethylene diisocyanate and methyl (S)‐2,6‐diisocyanatohexanoate and the subsequent deprotection of the isopropylidene groups. They were hydrolyzed much more quickly than the corresponding protected polyurethanes at 50 °C and pH 7.0, although their hydrolytic degradation rate was lower than that of polyurethanes with saccharic and glucuronic lactone groups, which had been reported in our previous articles. The introduction of D ‐mannitol units to the polyether‐polyurethanes containing poly(oxytetramethylene) glycol units also enhanced their hydrolyzibility. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis,characterization, and molecular modeling studies of novel polyurethanes based on 2,2′‐[ethane‐1,2‐diylbis(nitrilomethylylidene)]diphenol and 2,2′‐[hexane‐1,6‐diylbis(nitrilomethylylidene)] diphenol hard segments

Novel polyurethanes (PUs) based on 2,2′‐[ethane‐1,2‐diylbis(nitrilomethylylidene)]diphenol and 2,2′‐[hexane‐1,6‐diylbis(nitrilomethylylidene)]diphenol as hard segments containing four aromatic diisocyanates (4,4′‐diphenylmethane diisocyanate, toluene 2,4‐diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate) have been prepared. Fourier transform infrared, UV spectrophotometry, fluorescence spectroscopy, ¹H NMR and ¹³C NMR spectroscopy, thermogravimetric analysis, and differential thermal analysis have been used to determine the structural characterization and thermal properties of the segmented PUs. All the PUs contain domains of both semicrystalline and amorphous structures, as indicated by X‐ray diffraction. The acoustic properties have been calculated with the group contribution method. Molecular dynamics simulations have been performed on all the PUs to estimate the cohesive energy density and solubility parameter values, which compare well with the values calculated with the group contribution method. Furthermore, the simulation protocols have been applied to the PUs to produce X‐ray diffraction plots to determine the phase morphology of the PUs. The surface properties of the PUs have been estimated from the simulation protocols. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6032–6046, 2006     

Synthesis and evaluation of an ester‐functional alkoxyamine for nitroxide‐mediated polymerization

The ester‐functional alkoxyamine 2,2‐dimethyl‐3‐(1‐(4‐(methoxycarbonyl)phenyl)ethoxy)‐4‐(4‐(methoxycarbonyl)phenyl)‐3‐azapentane ( 2 ) was efficiently synthesized for use as a functional initiator in nitroxide‐mediated polymerization. Two equivalents of 1‐(4‐(methoxycarbonyl)phenyl)ethyl radical were added across the double bond of 2‐methyl‐2‐nitrosopropane to form alkoxyamine 2 , which was found to control the polymerization of styrene, isoprene, and n‐butyl acrylate. The ester moieties were hydrolyzed for subsequent esterification with 1‐pyrenebutanol to form a dipyrene‐labeled initiator that was used to probe nitroxide end‐group fidelity after styrene polymerization. High retention of nitroxide was confirmed by UV‐vis studies over a range of monomer conversions. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6342–6352, 2009     

Synthesis of poly(vinyl ether)‐based,ABA triblock‐type thermoplastic elastomers with functionalized soft segments and their gas permeability

The ABA‐type triblock copolymers consisting of poly(2‐adamantyl vinyl ether) [poly(2‐AdVE)] as outer hard segments and poly(6‐acetoxyhexyl vinyl ether) [poly(AcHVE)], poly(6‐hydroxyhexyl vinyl ether) [poly(HHVE)], or poly(2‐(2‐methoxyethoxy)ethyl vinyl ether) [poly(MOEOVE)] as inner soft segments were synthesized by sequential living cationic polymerization. Despite the presence of polar functional groups such as ester, hydroxyl, and oxyethylene units in their soft segments, the block copolymers formed elastomeric films. The thermal and mechanical properties and morphology of the block copolymers showed that the two polymer segments of these triblock copolymers were segregated into microphase‐separated structure. Effect of the functional groups in the soft segments on gas permeability was investigated as one of the characteristics of the new functional thermoplastic elastomers composed solely of poly(vinyl ether) backbones. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1114–1124     

Heteroarm H‐shaped terpolymers through the combination of the Diels–Alder reaction and controlled/living radical polymerization techniques

Heteroarm H‐shaped terpolymers (PS)(PtBA)–PEO–(PtBA)(PS) and (PS)(PtBA)–PPO–(PtBA)(PS) [where PS is polystyrene, PtBA is poly(tert‐butyl acrylate), PEO is poly(ethylene oxide), and PPO is poly(propylene oxide)], containing PEO or PPO as a backbone and PS and PtBA as side arms, were prepared via the combination of the Diels–Alder reaction and atom transfer radical and nitroxide‐mediated radical polymerization routes. Commercially available PEO or PPO containing bismaleimide end groups was reacted with a compound having an anthracene functionality, succinic acid anthracen‐9‐yl methyl ester 3‐(2‐bromo‐2‐methylpropionyloxy)‐2‐methyl‐2‐[2‐phenyl‐2‐(2,2,6,6‐tetramethylpiperidin‐1‐yloxy)ethoxycarbonyl]propyl ester, with a Diels–Alder reaction strategy. The obtained macroinitiator with tertiary bromide and 2,2,6,6‐tetramethylpiperidin‐1‐oxy functional end groups was used subsequently in the atom transfer radical polymerization of tert‐butyl acrylate and in the nitroxide‐mediated free‐radical polymerization of styrene to produce heteroarm H‐shaped terpolymers with moderately low molecular weight distributions (<1.31). The polymers were characterized with ¹H NMR, ultraviolet, gel permeation chromatography, and differential scanning calorimetry. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3947–3957, 2006     

Synthesis and reaction of β‐hydroxyaspartic acid‐based polymethacrylate

O‐Methacryloyl‐N‐(tert‐butoxycarbonyl)‐β‐hydroxyaspartic acid dimethyl ester was synthesized by methyl esterification of β‐hydroxyaspartic acid, followed by protection of the amino group with the tert‐butoxycarbonyl group and then the reaction of the hydroxyl group with methacryloyl chloride. The monomer efficiently underwent radical polymerization to afford the corresponding polymer with a number‐average molecular weight of 42,000 in good yields. The alkaline hydrolysis of the polymer occurred not only at the methyl ester but also at the ester moiety between the main and side chains of the polymer. The methyl ester‐free polymer gradually released β‐hydroxyaspartic acid moiety in a phosphate buffer solution with pH = 7.3 and 7.8. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2782–2788, 2002     

Donor–acceptor semiconducting polymers based on pyromellitic diimide

Three donor–acceptor copolymers P1 , P2 , and P3 with N,N′‐dodecylpyromellitic diimide as the electron‐acceptor unit with three diethynyl‐substituted donor monomers: 1,4‐diethynyl‐2,5‐bis(octyloxy)benzene, 2,7‐diethynyl‐9,9‐dioctyl‐9H‐fluorene, and 3,3′‐didodecyl‐5,5′‐diethynyl‐2,2′‐bithiophene have been synthesized by Sonogashira crosscoupling polymerization. The synthesized polymers showed deep highest occupied molecular orbital energy levels and larger band gaps (>2.5 eV). Polymers P1 , P2 , and P3 underwent fluorescence quenching with [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM), indicating the intermolecular photo‐induced charge transfer between the donor polymers and the PCBM acceptor. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1617–1622     

Synthesis of dual‐functional poly(6‐azidohexylmethacrylate) brushes by a RAFT agent carrying carboxylic acid end groups

Novel types of dual‐functional surface‐attached polymer brushes were developed by interface‐mediated reversible addition‐fragmentation chain transfer (RAFT) polymerization of 6‐azidohexylmethacrylate using the surface‐immobilized RAFT agent and the free initiator. The interface‐mediated RAFT polymerization produced silicon substrate coated with dual‐functional (azido groups from monomer and carboxylic acid groups from RAFT agent) poly(6‐azidohexylmethacrylate) [poly (AHMA)] with a grafting density as high as 0.59 chains/nm². Dual‐functional polymer brushes can represent an attractive chemical platform to deliberately introduce other molecular units at specific sites. The azido groups of the poly(AHMA) brushes can be modified with alkyl groups via click reaction, known for their DNA hybridization, while the carboxylic acid end groups can be reacted with amine groups via amide reaction, known for their antifouling properties. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1696–1706     

Novel active ester‐bridged copolynorbornene materials containing terminal functional hydroxyl,amino, methacryloyl,or ammonium groups via ring‐opening metathesis polymerization

Several random and block copolynorbornenes with side chains containing terminal hydroxyl, amino, methacryloyl or ammonium groups were derived from the functional alkyl ester‐containing norbornenes by ring‐opening metathesis polymerization (ROMP). The main chain of ROMP‐type polynorbornene had a more important role for glass‐transition temperature in comparison with vinyl addition polymerization. There is little effect on glass‐transition temperature (about ?39 °C) of polynorbornenes with different length of alkyl side chain. The organosoluble copolynorbornenes with active crosslinkable methylacryloyl side chains derived from functional hydroxyl group were prepared to improve the thermal stability of poly(methyl methacrylate) [decomposition temperature (T_d)^10% = 325 °C in nitrogen] by forming networked AB crosslinked polymer (T = 367 °C in nitrogen). The sizes of nanometer‐scale polymeric micelles of block copolymers having hydrophobic alkyl ester and hydrophilic ammonium groups were measured in the range of 11–25 nm by scanning electron microscopy. These polymeric materials with various functional groups or amphiphilic architectures are accessible by ROMP, whose topology makes them particularly attractive for application potential such as biomedical and photoelectric materials. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4233–4247, 2005