Adhesion Mechanisms of Polyurethanes to Glass Surfaces I. Structure-Property Relationships in Polyurethanes and Their Effects on Adhesion to Glass

Polyurethanes were prepared from toluene diisocyanate (TDI), 1-4-butane diol (BDO) and polycaprolactone-based triols with varying molecular weights. Among each molecular weight triol-based urethane, hard segment content was varied from 20% to 70%. Differential scanning calorimetry, tensile testing, and Iosipescu shear testing were done on all the various urethanes prepared. Thermal characterization data revealed the dependence of phase separation on hard segment content as well as on the triol molecular weight. Tensile data and Iosipescu shear data further confirmed the observations made from the DSC data. The data further indicated that phase separation can greatly improve the modulus of cross-linked segmented urethanes. Adhesion of these urethanes to glass surface was evaluated using soda-lime float glass plate. Urethane samples were cast on the air side of the glass plates and adhesion was measured in shear mode. Adhesion data indicated that in addition to hard segment content, modulus, cross-link density, and molecular weight of the triols, phase separation seems to be a major factor in controlling adhesion. Surfaces of the failed adhesion samples were also analyzed and the failure mode was found to be cohesive, in varying degree, with the different urethane systems.     

Biconstituent fibers from segmented polyurethanes and nylon 6

The characteristics of Monvelle, a new biconstituent fiber from nylon 6 and a segmented polyurethane, are reviewed briefly, and some of the technical problems inherent in producing such a fiber are discussed. The characterization of two series of polyurethanes which can be melt spun is given in detail. The chemical composition of the hard segment was maintained constant, being derived from 4,4′-diphenylmethane diisocyanate (MDI) and 1,4-butanediol, in all polymers. In one series using poly(butylene adipate) of MW 2000 as the soft segment, the average hard segment content was varied from 33% to 54%. In the other series, the hard segment content was held at 43%, and three additional soft segments, each at MW 2000, were used: poly(ethylene adipate), polycaprolactone and poly-1,4-oxybutylene glycol (PBG). Characterizations include molecular weight distributions, thermal analysis, rheological studies, and selected small-angle and wide-angle x-ray diffraction and polarized light microscopy. Crystallinity, melt viscosity, and activation energy of flow increased with increasing hardsegment content. Changes in the polyester soft segments had little effect on the properties studied, but with PBG the crystalline melting point of the polymer, without annealing, was higher and the melt viscosity was slightly higher than corresponding polyester-based samples, in agreement with previous reports of sharper phase separation in polyether urethanes, compared to polyester urethanes.     

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.     

Degradation of crosslinked poly(ester‐urethanes) elastomers in distilled water: Influence of hard segment

Polyurethane elastomers are frequently used in wet conditions. Crosslinked polyurethanes based on poly(ethylene adipate) diol, 4,4′‐diphenylmethane diisocyanate, 1,6 hexane diisocyanate—with different hard‐segment compositions but with the same molecular weight soft segment—were degraded in distilled water at 37°C, in a specific environment; in the dark without exposure to enzymatic conditions and under the continuous circulation of water. The incubation of polymer samples took place over a period of maximum 30 days. The degradation process was evaluated by the changes in mechanical properties and surface relief observed by optical microscopy. The changes in hydrogen bonding were collected through attenuated total reflectance infrared (ATR‐FTIR) spectroscopy which indicated that aliphatic diisocyanates allow for a better formation of hydrogen bonds. The mechanical properties of the degraded films show that the crosslinked polyurethanes containing aromatic diisocyanate suffer a decrease in tensile strength between 33 and 56% depending on the chain extender and hard segment content. The hydrolytic degradation behavior of crosslinked polyurethanes was found to be dependent on the diisocyanate and chain extender structure, as well as on the hard segment content and chemical crosslinks. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Structure‐property relationships of degradable polyurethane elastomers containing an amino acid‐based chain extender

A series of degradable polyurethanes of variable soft segment chemistry and content were synthesized and characterized. An amino acid‐based diester chain extender was used to confer degradability and both polycaprolactone diol (PCL) and polyethylene oxide (PEO) were used as soft segments. In addition, the diisocyanate component was a potentially nontoxic diisocyanate (2,6‐diisocyanato methyl caproate, LDI). The physicochemical properties of these unique series of polyurethanes were investigated. It was found that the PEO containing polyurethanes were generally weak, tacky amorphous materials. In contrast, the PCL polyurethanes were relatively strong, elastomeric materials which ranged from completely amorphous to semicrystalline as noted by differential scanning calorimetry. The PCL containing polyurethanes exhibited increasing tensile strength, modulus, and ultimate strain with increasing PCL molecular weight because of increasing phase separation and increasing soft segment crystallinity. Fourier transform infrared analysis showed significant hard segment urea and urethane hydrogen bonding which increased with hard segment content, although interphase bonding is believed to be significant for the PCL polyurethanes. Surface characterization carried out by contact angle analysis and X‐ray photoelectron spectroscopy indicated soft segment surface enrichment for all of the polyurethanes. The PEO‐based polymers were very hydrophilic whereas the PCL‐based polymers displayed significantly higher contact angles, indicating greater surface hydrophobicity. The observed diversity in material properties suggests that these polyurethanes may be useful for a wide range of applications. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1522–1534, 2000     

Synthesis and properties of novel biodegradable polyurethanes containing fluorinated aliphatic side chains

This study used 5H–octafluoropentanoylfluoride and 2-amino-2-methyl-1,3-propanediol to synthesize a novel fluoro chain extender 2,2,3,3,4,4,5,5-octafluoro-N-(1,3-dihydroxy-2-methylpropan-2-yl) pentanamide (ODMP). Furthermore, 4,4′-diphenylmethane diisocyanate served as the hard segment, polycaprolactone diol (PCL) served as the soft segment, and ODMP served as the chain extender in the novel synthesized polyurethanes (ODMP/PUs). Gel permeation chromatography revealed that the molecular weight of the ODMP/PUs increased when the ODMP content was increased. ¹H and ¹⁹F nuclear magnetic resonance and Fourier transform infrared spectroscopy verified that the ODMP chain extenders were successfully synthesized and that the ODMP chain extenders were successfully incorporated into the backbone of the PUs. The interaction between the -NH (hydrogen bond) and CF₂ groups in the ODMP/PUs became stronger when the ODMP content was increased. Thermal analysis revealed that the initial decomposition temperature of the ODMP/PUs decreased and the second decomposition temperature increased when the polymers’ ODMP content was increased. Higher ODMP content also resulted in the ODMP/PUs’ higher glass transition and dynamic glass transition temperatures and lower ODMP maximum stress and Young’s modulus, causing a lower elongation at break. ODMP/PUs with higher ODMP content exhibited more protrusions and more rugged surfaces. The chemical resistance of the ODMP/PUs increased when the fluorine content was increased. Scanning electron microscopy revealed that ODMP/PUs with higher PCL content exhibited higher levels of hydrolytic degradation. Finally, in vitro erythrocyte tests revealed that increasing the ODMP chain extender content reduced the average number of erythrocytes adhering to the surface of the PUs.     

A facile method for the study of slow physical and chemical processes in polymeric systems

A method is described for continuously following a long-duration process in a complex polymeric system by isothermal calorimetry. Computerized models for slow physical or chemical processes have been applied to calorimetric runs under different conditions and these have given information in the form of thermodynamic and kinetic data. The method also gives a means of determining the relationship between molecular weight and functionality for one of the polymers used, the order of reaction, and the degree of conversion before the start of the measurements. An example is given of a kinetic study of the reaction of hydroxyl-terminated polybutadiene with two different diisocyanates. The temperature dependence of the formation of urethanes, the rate constants, and the degree of conversion before the start of the measurements were determined as well as the heat of reaction for the formation of urethanes using hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI) as curing agents. The results have been compared with other kinetic studies of these systems.     

Properties of crosslinked blends of pellethene and multiblock polyurethane containing poly(ethylene oxide) for biomaterials

A series of multiblock polyurethanes, containing various poly(ethylene oxide) (PEO; number‐average molecular weight = 400–3400) contents (0–80 wt %) and prepared from hexamethylene diisocyanate/PEO/poly(dimethylsiloxane) diol/polybutadiene diol/1,4‐butanediol, were used as modifying additives (30 wt %) to improve the properties of biomedical‐grade Pellethene. Different molecular weights of PEO were used to keep poly(ethylene glycol) at a fixed molar content, if possible, although the PEO content, related to the PEO block length in the multiblock polyurethanes, was varied from 0 to 80 wt %. The hydrophilic PEO component was introduced through the addition of PEO‐containing polyurethanes and dicumyl peroxide as a crosslinking agent in a Pellethene matrix. As the PEO content (PEO block length) increased, the hydrogen‐bonding fraction of the crosslinked Pellethene/multiblock polyurethane blends increased, and this indicated an increase in the phase separation with an increase in the PEO content in the crosslinked Pellethene/multiblock polyurethane blends. According to electron spectroscopy for chemical analysis, the ratio of ether carbon to alkyl carbon in the crosslinked Pellethene/multiblock polyurethane blends increased remarkably with increasing PEO content. The water contact angle of the crosslinked Pellethene/multiblock polyurethane blend film surfaces decreased with increasing PEO content. The water absorption and mechanical properties (tensile modulus, strength, and elongation at break) of the crosslinked Pellethene/multiblock polyurethane blend films increased with increasing PEO content. The platelet adhesion on the crosslinked Pellethene/multiblock polyurethane blend film surfaces decreased significantly with increasing PEO content. These results suggest that crosslinked Pellethene/multiblock polyurethane blends containing the hydrophilic component PEO may have potential for biomaterials that come into direct contact with blood. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2348–2357, 2004     

Synthesis and curing of millable polyurethanes based on castor oil

This paper presents the results of studies on the synthesis and curing of millable polyurethanes based on castor oil. To facilitate the preparation of millable urethanes, the hydroxy number of castor oil was modified to about two by acetylation. It was then used with tolylene diisocyanate (NCO/OH-ratios 1:0.9, 1:1 and 1:1.1, resp.) for polyurethane preparation. The dynamic curing of the synthesized polyurethanes was studied in a Brabender Plasticorder using various sulfur vulcanizing systems. The effect of stoichiometric ratio and choice of chain extenders on the dynamic curing behaviour was also studied. An NCO/OH ratio of 0.9 and 1,4-butanediol (30 wt.-%) as chain extender were found to favour the formation of a crosslinkable polyurethane. It was observed that a cure system containing sulfur, N-cyclohexyl-2-benzothiazole sulfenamide and mecraptobenzothiazole was a possible choice for the preparation of a sulfur-crosslinked polyurethane.     

Dielectric and viscoelastic properties of some meta-tetramethyl xylene diisocyanate-based polyurethanes as a function of sample composition

A series of linear segmented polyurethanes were synthesized, based on soft segments of polycaprolactone having an average number molecular weight of 2100, or hydroxy–terminated polybutadiene having an approximate molecular weight of 2800. Hara segments were made of meta–tetramethyl xylene diisocyanate and diethyl toluene diamine. The dynamic Young's modulus and loss tangent, relative permittivity, and dielectric loss, were found to be significantly affected by soft segment polarity and hard segment content. These results are discussed in terms of polymer morphology, such as degree of phase separation and soft segment phase state.     

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     

Properties of polyisobutylene polyurethane block copolymers: 3. Hard segments based on 4,4′-dicyclohexylmethane diisocyanate (H12MDI) and butane diol

A series of polyisobutylene (PIB) polyurethanes based on 4,4′-dicyclohexylmethane diisocyanate (H₁₂MDI) have been synthesized and their structure-property relationships have been investigated. The PIB glycol was synthesized by the ‘inifer’ technique. Sample compositions were designed for independent investigation of the effects on physical properties of hard segment content and soft segment molecular weight and for comparison with corresponding 4,4′-diphenylmethane diisocyanate (MDI) based PIB polyurethanes. Increasing hard segment content resulted in improved dynamic and tensile modulus while elongation at break was unaffected. Increasing soft segment molecular weight led to decreased mechanical properties attributed to larger domain sizes as indicated by small angle X-ray scattering (SAXS). Both the soft segment T_g and the extent of interfacial mixing as measured by SAXS were unaffected by hard segment content and soft segment molecular weight suggesting that the materials were highly phase separated. In comparison with corresponding MDI based materials the H₁₂MDI based polyurethanes exhibited less hard segment ordering, slightly less interfacial mixing, smaller domain sizes, and slightly better ultimate tensile properties.     

Crystallinity and morphology of segmented polyurethanes with different soft-segment length

A series of polycaprolactone/4,4′-diphenylmethane diisocyanate/1,4-butanediol (PCL/MDI/BDO) segmented polyurethanes of different compositions was synthesized by solution polymerization. The molecular weight of PCL diols used was in the range of 1600–7000. The crystallinity and morphology of these polymers were studied by using DSC, dynamic mechanical analysis, WAXD, and polarizing microscopy methods. It was found that the crystallinity of PCL prepolymers was depressed in segmented polyurethanes. A lower limit of PCL molecular weight was found, below which the PCL segments were not able to crystallize at the usual processing conditions. This limit of molecular weight is in the range of 2000–3000 and exhibits a slight increase with increasing hard-segment content of polyurethanes. The glass transition temperature related to the PCL segment regions in polyurethane specimens deviated from that of pure amorphous PCL prepolymer to a higher temperature. The deviation resulted from the crystallization of PCL segments and also the influence of hard segments. The formation of hard-segment domains becomes very difficult for polyurethanes having low hard-segment content and short hard-segment length. There is a lower limit of hard-segment content and segment length. Only above that limit do the polyurethanes have enough hard-segment domains acting as physical crosslinks at temperatures above the melting point of the PCL crystals. The structural characteristics of segmented polyurethanes which may exhibit a shape memory effect are also discussed. © 1996 John Wiley & Sons, Inc.     

Influence of the solids content on the properties of waterborne polyurethane dispersions obtained with polycarbonate of hexanediol

Waterborne polyurethane adhesives are an interesting alternative to the current solvent-borne polyurethane adhesives used in the industry. Different aliphatic waterborne polyurethane dispersions (PUDs) with different solids content were synthesised by reacting isophorone diisocyanate (IPDI) with a polycarbonate derived from hexanediol via the acetone method. The PUDs were characterised by Brookfield viscosity, pH, particle size, transmission electron microscopy (TEM) and solids content measurement. The dry polyurethane films were characterised by ATR-IR spectroscopy, plate–plate rheology, differential scanning calorimetry (DSC) and thermal gravimetry (TGA). Their adhesion was evaluated from T-peel tests of flexible PVC/waterborne polyurethane dispersion/flexible PVC joints and single lap-shear tests of aluminium/waterborne polyurethane dispersion/aluminium joints.The PUDs showed bimodal particle size distribution. The mean particle size of the PUDs decreased by increasing their solids content but the particle size distribution of the PUDs increased by decreasing their solids content. As the solids content increased the Brookfield viscosity of the PUDs increased due to lower mean particle size where particle crowding was favoured, the PUD having 44 wt% solids content was an exception (higher particle size but lower polydispersity). On the other hand, the increase in the solids content increased the hard segments content and the degree of phase separation of the polyurethanes. The greater the solids content of the polyurethanes, the lower their glass transition temperatures values and the lower the elastic moduli. Adhesive strength under peel stresses were not affected by the solids content in the polyurethanes but the single lap-shear strength values decreased by increasing the solid contents in the polyurethanes due to lower hard segments content.     

Effects of TDI and FA‐703 on physico‐mechanical properties of polyurethane dispersion

A series of water dispersion polyurethanes dispersions (PUDs) were prepared by polyaddition reaction using isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), poly(oxytetramethylene) glycol (PTMG), dimethylol propionic acid (DMPA), and triol (trade name FA‐703). Various formulations were designed to investigate the effects of process variables such as TDI and FA‐703 on the physico‐mechanical properties of PUD. IR spectroscopy was used to check the end of polymerization reaction and characterization of polymer. Evolution of the particle size distribution, contact angle, T_g, molecular weight, viscosity, and mechanical properties of the emulsion‐cast films were significantly affected by variable content of TDI and FA‐703. Average particle size of the prepared polyurethane emulsions and contact angle decrease with increase of content of FA‐703 and TDI. Molecular weight, T_g, tensile strength, tear strength, hardness, viscosity and elongation at break increase with increase of content of FA‐703 and TDI. The increase of molecular weight, tensile strength, tear strength and elongation at break properties are interpreted in terms of increasing hard segments, chain flexibility, and phase separation in high content of FA‐703 and TDI‐based polyurethane. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Structure–property relationships of thermoplastic polyurethane elastomers based on polycarbonate diols

The phase-separation behavior and morphology of polycarbonate-based polyurethanes were investigated as a function of the soft-segment molecular weight and chemical structure and the 4,4′-diphenylmethane diisocyanate/1,4-butanediol based hard-segment contents. Polarized optical microscopy and atomic force microscopy images showed that the surface morphologies changed as the soft-segment molecular weight and hard-segment content varied and also when the sample preparation conditions were modified. An increase in the soft- and hard-segment lengths led to increased phase separation with respect to the lower molecular weight soft segment, and this showed an interlocked and connected morphology of intermixed soft and hard domains. The surface morphology of phase-separated polyurethanes with hard segments composed of more than four to five 4,4′-diphenylmethane diisocyanate units contained globular hard-segment domains formed by spherulites, in which the size and connectivity between the branched lamellae changed with the hard-segment size. Interlamellar areas related to the soft segment were seen in the spherulites. Variations in the hard-segment spherulites were observed for polyurethanes based on soft segments of different molecular weights. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and properties of novel biodegradable poly(ε‐caprolactone)/ poly(ethylene glycol)‐based polyurethane elastomers

Elastomeric polyurethanes with tunable biodegradation properties and suitable for numerous biomedical applications were synthesized via reaction of epoxy‐terminated polyurethanes (EUPs) with 1,6‐hexamethylenediamine as curing agent. The EUPs themselves were prepared from glycidol and isocyanate‐terminated polyurethanes made from poly(ε‐caprolactone) (PCL) or poly(ethylene glycol) (PEG) and 1,6‐hexamethylene diisocyanate. All the polymers were characterized by conventional methods, and their physical, mechanical, thermal, and degradation properties were studied. The results showed that the degradation rate and mechanical properties of the final products can be controlled by the amount of PEG or PCL present in the EUP. Increasing the PEG content causes an increase of hydrolytic degradation rate, and increasing the PCL content improves the mechanical properties of the final products. Evaluation of cytotoxcicity showed nontoxic behavior of the prepared samples, but the cytocompatibility of these polymers needs to be improved. Copyright © 2006 Society of Chemical Industry     

Preparation and properties of urethane alkyd based on a castor oil/jatropha oil mixture

Castor oil is the only major natural vegetable oil that contains a hydroxyl group and so it is widely used in many chemical industries, especially in the production of polyurethanes. In this work, castor oil was interesterified with jatropha oil and the product was subsequently reacted with toluene diisocyanate to obtain urethane alkyd. The prepared urethane alkyd was characterized and its properties were determined and compared with those of the conventional (glycerol/jatropha oil) and commercial urethane alkyds. The castor oil/jatropha oil-based urethane alkyd had a lower molecular weight and viscosity, a slightly lower hardness and greatly longer drying time than the conventional and commercial urethane alkyds, but otherwise the film properties were broadly similar, including being very flexible, with an excellent adhesion and high impact resistance. In addition, they also exhibited excellent resistance to water and acid.     

Microdomain composition and properties differences of biodegradable polyurethanes based on MDI and HDI

The study of the effect of the diisocyanate structure on the microstructure and macroscopic properties of polyurethanes was the main aim of this work. Biodegradable segmented thermoplastic elastomeric polyurethanes based on a poly(hexamethylene carbonate‐co‐caprolactone)diol (PHM‐co‐PCL) as soft segment were synthesized using 1,4‐butanediol (BD) as chain extender and both 4,4′‐diphenylmethane diisocyanate (MDI) and 1,6‐hexamethylene diisocyanate (HDI) as components of the hard segment by the two shoot synthesis procedure. Microphase structure and properties were analyzed using Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC) as complementary techniques, used to characterize thermal transitions of the polyurethanes and to assign them to determinate functional groups interactions. Gaussian deconvolution technique was used to decompose carbonyl region in four peaks and to study the hydrogen bonding within the different polyurethanes. Both DSC and FTIR showed that MDI‐based biodegradable polyurethanes were less phase segregated than to those based on HDI, and thus that diisocyanate structure has an important role on microdomain composition and polyurethanes properties. Macroscopic properties as hardness and water‐polymer contact angles are related to polyurethanes microphase compositions. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers.     

聚硅氧烷聚氨酯的合成与性能

氨基硅油、甲苯二异氰酸酯与相对分子质量为1000和2000左右的聚氧化丙烯二醇在无溶剂条件下制备了相应的两类氨基硅油改性聚氨酯。测试结果表明,采用无环境污染的该法制备的改性聚氨酯与文献报道的溶剂法制备的改性聚氨酯具有类似的改性效果,改性后的聚氨酯兼有有机硅和聚氨酯的特性。w(氨基硅油)=3%～15%时,有较明显的改性效果,且在w(氨基硅油)=10%时,两类改性聚氨酯都具有最佳综合性能,其伸长率较未改性的分别提高28 05%,52 38%,其表面水接触角分别提高了23°,25°,耐热性也有较大提高。