Polyurethane cationomers with pendant trialkylammonium groups: Effects of ion content,alkyl group,and neutralizing anion

Diphenylmethane-4,4′-diisocyanate based polyether polyurethane cationomers were synthesized using 3-trialkylammonium-(1,2-propanediol)iodide (TAPI) as the chain extender. The ionic content was varied by substituting up to 100% of 3-dialkylamino-1,2-propanediol (DAP) for TAPI. Cationomers with bromine and chlorine ions were prepared from the iodine-based polymer via ion exchange. The morphology and properties of the cationomers were studied as a function of alkyl group, ion content, and anion type using small-angle x-ray scattering, tensile testing, dynamic mechanical thermal analysis, and differential scanning calorimetry. The bulky side groups of DAP and TAPI prevented crystallization in the hard domains, and consequently little or no phase separation was evident in the unionized materials. Polyurethanes with cationic functionality showed dramatic improvements in phase separation and tensile properties. Results suggest tht while ionic interactions are the primary driving force for phase separation, they produce a morphology not typical of ionomers, but rather akin to that of a conventional polyurethane with semicrystalline hard segments. © 1994 John Wiley & Sons, Inc.     

Synthesis and surface properties of polyurethane modified by polysiloxane

A series of polyurethanes modified by polysiloxane (Si-PU) were synthesized based on 2,4-toluene diisocyanate (TDI), dihydroxybutyl-terminated polydimethylsiloxane (DHPDMS), polytetramethylene glycol (PTMG) and 1,4-butanediol (BDO). Fourier transform infrared spectroscopy analysis showed that DHPDMS had been incorporated into the polyurethane chains. With the increase of DHPDMS content, the water contact angle increased while the surface tension decreased. As the DHPDMS content increases above 5%, both the contact angle and the surface tension tend to approach a constant. The contact angle increases with increasing temperature, and it tends to approach a constant when the temperature is higher than 50°C. The result indicates that Si-PU exhibits good surface and mechanical properties when the DHPDMS content is 5%. __________ Translated from Polymer Materials Science and Engineering, 2007, 23(3): 47–50 [译自: 高分子科学与工程]     

Polyurethane cationomers III: Oxygen permeation

Dynamic oxygen permeation measurements at 20–70°C on films cast from solutions and emulsions of three series of polyurethane (PU) cationomers based on MDI, HDI, and TDI that are the subject of Parts I and II of this series were made by Barrer's vacuum technique. For the MDI system, films cast from solutions of ionized PU exhibit permeation coefficients P that are higher at 20–40°C (below the glass transition temperature T_gh of the hard domains) than at 50–70°C (above T_gh) by factors of about 5 and 40. This is the opposite of what is observed for normal homopolymers and un-ionized PU. This phenomenon is attributed to the continuous/dispersed morphology of these films. At the low temperature, oxygen molecules diffuse through the continuous phase (soft domains) only. But at the high temperature, oxygen molecules diffuse through soft domains and subsequently through hard domains, leading to an increase in diffusion pathlength. For films cast from the PU emulsions, such a drop in P was not observed because the hard domains were partially inverted from the dispersed phase to a continuous phase that gives an interwoven morphology. Such morphology allows oxygen molecules to diffuse through soft and phase-inverted hard domains simultaneously. For the HDI and TDI systems, P and D vs. 1/T plots show no zone of discontinuity. This is attributed to a T_gh that is lower than or close to the permeation temperature. © 1995 John Wiley & Sons, Inc.     

Synthesis and optical properties of new polyurethane cationomers with anchored stilbene chromophores

An ionic diol bearing a one‐sided urethane‐stilbene group located on the ammonium quaternary structure was prepared and proposed as an intermediate for polyurethane ionomer synthesis. Polyurethane cationomers with stilbene ionic groups based on poly(tetramethylene oxide) diols, 4,4′‐diphenylmethane diisocyanate and the aforementioned ionic diol, were synthesized and characterized. Some aspects of the trans–cis photoisomerism and fluorescent emission of the stilbene chromophore in polyurethane cationomers were studied comparatively with the urethane‐stilbene diol. The stilbene polycations absorbed at λ_A = 316 nm and emitted violet‐blue light with an emission maxima at λ_F = 444 nm (dimethylformamide solution) and λ_F = 465 nm (film). These polymers are known for their elastomeric properties and are assumed to be of great interest for some future applications. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1918–1928, 2002     

氨乙基氨丙基聚二甲基硅氧烷改性水性聚酯型聚氨酯的研究

由聚酯二元醇、异佛尔酮二异氰酸酯和二羟甲基丙酸合成聚氨酯预聚体，以氨乙基氨丙基聚二甲基硅氧(AEAPS)为扩链剂，制备了AEAPS改性聚氨酯水分散液。与未改性的聚氨酯水分散液相比，AEAPS改性聚氨酯水分散液的粒径增大，但粒径分布和表面张力基本不变，说明疏水的聚二甲基硅氧烷侧链被包裹于分散颗粒的内部；此外，改性聚氨酯水分散液的冻融稳定性显著增强。AEAPS改性聚氨酯水分散液成膜后，吸水率明显下降，水在膜表面的接触角增加，400℃时热失重下降，具有良好的疏水性和耐热性。     

Novel Polyurethane Gels: The Effect of Structure on Gelation

Novel polyurethane gels have been reported in common solvent like dimethyl formamide (DMF). Polyurethanes have been synthesized from diisocyanates, diols and rigid chain extenders. We have illustrated the influence of chemical structure of the chain extenders on gelation rate, thermal property and morphology of the gels in DMF. Gelation rate increases significantly with the rigidity of the chain extender. Introduction of more rigid chain extender molecules in polyurethane prepolymer enhanced the thermal stability of the pure polymer. On the contrary, the solvent retention power of the gels gradually decreases with increasing rigidity of chain extender presumably because of the poor dispersion/greater aggregation of the hard segments in the soft segment matrix. Morphology and formation of gelation have been discussed.     

Synthesis and characterization of novel thermosetting polyphosphazene‐urethanes

Polyphosphazenes are ready to move from the level of a mere scientific curiosity to the rank of industrially and commercially important macromolecules because they have experienced an explosive development during the last 10 years. In this paper, novel linear poly [bis‐(phenoxy) _1.8 (4‐hydroxybutaneoxy) _0.2 phosphazene] (PPHBP) was synthesized and characterized by FTIR, NMR, and GPC. Then, a series of new thermosetting polyphosphazene‐urethanes (PPU)s were prepared by using PPHBP polyol via a two‐step method. The FTIR spectra have showed the PPUs were successfully prepared. Compared to conventional polyurethane, the results of differential scanning calorimetry (DSC) and thermogravimetric analysis (TG) have indicated that the PPUs exhibited better thermal stability and flame resistance. The study on water contact angle showed that PPUs were more hydrophobic than conventional polyurethane. This may widen the opportunities for producing a new class of polyurethanes with broad range of uses. Copyright © 2009 John Wiley & Sons, Ltd.     

四甲基苯二甲基二异氰酸酯基水性聚氨酯的合成和性能

采用四甲基苯二甲基二异氰酸酯、聚酯二元醇和二羟甲基丙酸为原料,合成了一系列具有不同异氰酸根与羟基摩尔比（n(-NCO)/n(-OH)）的聚氨酯乳液。 研究了n(-NCO)/n(-OH)对水性聚氨酯性能的影响。 结果表明,当该比值增加时,乳液的粒径增大,分布变宽,结晶性降低,耐热性下降,耐水性能呈现降低的趋势。 当异氰酸根与羟基摩尔比为3时,四甲基苯二甲基二异氰酸酯基水性聚氨酯的乳液粒径为10～30 nm,膜的分解温度达到275 ℃,24 h吸水率低于10%。     

Chlorine-Functional Silsesquioxanes (POSS-Cl) as Effective Flame Retardants and Reinforcing Additives for Rigid Polyurethane Foams

The subject of the research was the production of silsesquioxane modified rigid polyurethane (PUR) foams (POSS-Cl) with chlorine functional groups (chlorobenzyl, chloropropyl, chlorobenzylethyl) characterized by reduced flammability. The foams were prepared in a one-step additive polymerization reaction of isocyanates with polyols, and the POSS modifier was added to the reaction system in an amount of 2 wt.% polyol. The influence of POSS was analyzed by performing a series of tests, such as determination of the kinetics of foam growth, determination of apparent density, and structure analysis. Compressive strength, three-point bending strength, hardness, and shape stability at reduced and elevated temperatures were tested, and the hydrophobicity of the surface was determined. The most important measurement was the determination of the thermal stability (TGA) and the flammability of the modified systems using a cone calorimeter. The obtained results, after comparing with the results for unmodified foam, showed a large influence of POSS modifiers on the functional properties, especially thermal and fire-retardant, of the obtained PUR-POSS-Cl systems.     

Study on siloxane‐modified polyurethane dispersions from various polydimethylsiloxanes

In this work, various polydimethylsiloxanes (PDMS) are incorporated with isophorone diisocyanate (IPDI), 2,2‐bis(hydroxymethyl)propionic acid (DMPA), and poly(tetramethylene oxide) (PTMO) by the prepolymer process to synthesize a series of siloxane‐modified polyurethane dispersions (PUDs) with 35 wt % solid content, viscosities of 20–100 cps, and particle sizes of 40–130 nm. Hydrophobic PDMS was introduced into the PU chain either based on random distribution or through the block segment arrangement. We also establish the composition‐property relationship of PDMS‐PUD, which includes PDMS's type and molecular weight and PDMS‐PUD film's contact angle and mechanical property. The tensile strength of PDMS‐PUD film is decreased with increasing amount of PDMS. Scanning electron microscopy for chemical element analysis indicated that PDMS migrated to the surface much more easily in the block arrangement than in the random distribution. Also, some PDMS‐PUD films show a peau‐like surface, so their PUDs are considered promising to be used in processes for textiles. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3482–3490, 2005     

Effect of a Nanoclay on the Mechanical,Thermal and Flame Retardant Properties of Rigid Polyurethane Foam

Water blown rigid polyurethane foams (PUF) with organoclay/organically modified nanoclay (ONC) were prepared and their properties such as density, mechanical, morphological, insulation, thermal and flame retardant properties were studied. In this investigation, the ONC content was varied from 1 to 10 parts per hundred of polyol (php) by weight. It was observed that the compressive strength of ONC filled PUF increased up to 3 php of ONC loading and then it decreased. Wide angle X-ray diffraction and transmission electron microscopy studies indicated the exfoliated dispersion of ONC in PUF. The thermal conductivity of ONC filled PUF decreases up to 5 php and then increases. The glass transition temperature (Tg) of PUF decreases on loading of ONC. The TGA analysis shows that there is slight increase in degradation temperature with increase in ONC loading. The flame retardant properties (LOI and flame spread rate) are improved slightly on addition (3 php) of ONC filled PUF.     

Basic structure–property behavior of polyurethane cationomers

Polyurethane (PU) cationomers were synthesized from polytetramethylene adipate glycol (PTAd), isophorone diisocyanate (IPDI), and N-methyl diethanolamine (MDEA) according to a prepolymer mixing process. Basic structure-property behavior of the emulsion (obtained by adding water to the ionomer solution) and emulsion cast film was studied with regard to the molecular weight (M_n) of PTAd, MDEA content, degree of neutralization, and extender functionality. Particle size decreased asymptotically with increasing M_n of PTAd due to the increased chain flexibility, and with the degree of neutralization due to the increased hydrophilicity of the PU. Emulsion viscosity generally showed the opposite tendency with particle size dependence. The major transition temperature, corresponding to the glass transition (T_g) of phase mixed PU or hard segment-rich phase of the PU monotonically increased with MDEA content, degree of neutralization, and with increasing extender functionality. However, with increasing M_n of PTAd, T_g first decreased (M_n = 1000) and then increased (M_n = 1500, 2000), due respectively to the increased hard fraction of phase mixed PU, and soft segment crystallization. Tensile strength increased and elongation at break decreased with MDEA content, degree of neutralization, and extender functionality. © 1994 John Wiley & Sons, Inc.     

Preparation and Characterization of Optically Active Polyurethane from Rotatory Binaphthol Monomer and Polyurethane Prepolymer

Optically active polymers are promising multifunctional materials with great application potentials. Herein, environmentally friendly optically active polyurethanes (OPUs) were obtained by introducing rotatory binaphthol monomer to polyurethane. The influence of binaphthol monomer content on the structure, mechanical properties, infrared emissivity, and thermal insulation of OPUs was studied intensively. Structure characterization indicated that the optically active polyurethanes have been successfully synthesized. The OPU synthesized with BIMOL and BDO at the mole ratio of 1:1 presented better thermal resistance. In addition, OPUs showed enhanced tensile strength and stretchability with the increase of BINOL content to a certain extent due to its rigid structural features and high molecular weight. The optically active polyurethanes showed lower infrared emissivity values (8–14 μm) than waterborne polyurethane (WPU), and the infrared emissivity decreased from 0.850 to 0.572 as the content of the BINOL monomer increased. Moreover, OPU4 exhibited the best heat insulation and cooling ability with about a 7 °C temperature difference. The thus-synthesized optically active polyurethanes provide an effective solution for developing highly effective thermal insulation materials.     

Studies on the Particle Morphology of Waterborne Cationic Polyurethane/Polyacrylate Microemulsions

Polyurethane containing tertiary nitrogen atoms was synthesized from polyol, diphenylmethane diisoccyanate (MDI) and N‐methyl diethanolamine. The polymer was converted into cationomers by quarternizing with methacrylic acid (MAA) and then dispersed in water. In this reaction, methyl methacrylate (MMA) was used to decrease viscosity; at the same time, it was the monomer in the later reaction. Finally the cationic polyurethane dispersions were further polymerized with an oil‐soluble initiator, azobisisobutyronitrile (AIBN), water‐soluble initiator, K₂S₂O₈ (KPS) and the mixture of AIBN and KPS. The different emulsion particles with shell‐core structure, “invert” shell‐core structure and “irregular” sandwich structure were obtained; the morphological structures were characterized by TEM observation, FT‐IR and particle size analysis.     

Hydration characterization of hydrophobically modified polymers by dielectric measurements in the millimeter range

Bound water molecules, the fraction of water molecules that are present in the hydration shells of polymers, lose their rotational mobility in the time scale of 10-50 ps, leading to additional ordering compared with unperturbed water. The amount of bound water per number of carbons in the nonpolar groups as measured by the method of waveguide dielectric resonance increased in the following order: hydrophobically modified chitosan < globular protein < hydrophobically modified polyacrylamide. The hydrophobic modification of acrylamide and chitosan polymers gave smaller variation in hydration than did both the coil-to-globule transition of poly(N-isopropylacrylamide) and the masking of nonpolar groups within the protein globule.     

Polyurethane elastomers based on amphiphilic poly(caprolactone)‐b‐poly(butadiene)‐b‐poly(caprolactone) triblockcopolyols

Hydroxyl‐terminated poly(butadiene) (HTPB; M_n = 2100 g mol⁻¹) was capped with 30 and 60 wt % of ɛ‐caprolactone to reach amphiphilic triblock copolymers in form of capped poly(butadiene) CPB. The former (CPB30; M_n = 3300 g/mol) is amorphous with a glass temperature of −56 °C. CPB60 (M_n = 4000 g mol⁻¹) is semi‐crystalline with a melting point of 50 °C and a glass transition at −47 °C. The CPBs, HTPB and polycaprolactone diol (M_n = 2000 g mol⁻¹) were used as soft segment components in the preparation of polyurethane elastomers (PUE), using a 1/1 mixture of an MDI prepolymer and uretonimine modified MDI, and hard phase components in form of 1,3‐propane diol, 1,4‐butane diol, and 1,5‐pentane diol. CPB‐based elastomers with 1,4 butane diol (8 wt %) show hard domains as fringed aggregates with a better connection to the continuous phase than the HTPB‐based PUE. The soft segment glass transition temperature (T_g) is at −28 °C for HTPB‐based PUE and at −43 °C for those of CPB. The tensile strength of the CPB30&60‐based PUE is found between 20 and 30 MPa at an elongation at break of 400% and 550%, respectively. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1162–1172     

Rigid-rod polymers with polysiloxane side chains. 2. Synthesis and characterization of aromatic polybenzobisoxazoles with polysiloxane side chains and composite formation with polysiloxane matrices

Aromatic polybenzobisoxazoles, having polydimethylsiloxane side chains (SCPBOs), were prepared using terephthaloyl chloride-terminated polydimethylsiloxane macromonomers and 3,3′-bis(trimethylsiloxy)-4,4′-bis(trimethylsilylamino)biphenyl for the purpose of dispersing rigid-rod molecules in silicone matrices for molecular reinforcement. The degree of polymerization of the side chain was varied from 7.8 to 45.4, and a small amount of (3-butenyloxy)terephthaloyl chloride was copolymerized to give the polymers a functionality that can be linked to the matrices. For all the SCPBOs, the WAXD pattern showed only diffuse reflections, suggesting limited structural regularity, although the polymers were optically anisotropic. No melting transition was observed below the side chain decomposition temperature, 350°C. A polydimethylsiloxane/polybenzobisoxazole composite elastomer was obtained first curing the polysiloxane matrix containing the prepolymer of the SCPBO, followed by in situ thermal ring closure of the prepolymer. Some reinforcement was observed, but the presence of plasticizing effect by the unbound SCPBO was suggested at the same time. © 1995 John Wiley & Sons, Inc.     

一种新型的侧链型聚氨酯高分子钌聚合物的合成

通过分子设计,将带有-OH端基的钌(Ⅱ)联吡啶配合物[Ru(bpy)2L]PF6{L=希夫碱4-[(N甲-基-N羟-乙基)氨基]苯甲醛缩肼基硫代甲酸甲酯}与甲苯-2,4异-氰酸酯、丙烯酸羟乙酯发生共聚合反应,合成了新的侧链型聚氨酯高分子钌聚合物(4)。4的结构经红外光谱和差热分析表征。