Effect of isocyanates on the crystallinity and thermal stability of polyurethanes

Polyurethanes were synthesized from polyester and butanediol with three different diisocyanates, i.e., 4,4´-diphenylmethane diisocyanate (MDI), m-xylene diisocyanate (XDI), and 2,4-toluene diiscynate (TDI). The effect of chemical structures of diisocyate compounds on the degree of crystallinity and the thermal stability were observed. Differential scanning calorimetry (DSC) and small-angle X-ray scattering (SAXS) were used to determine the degree of crystallinity of the hard segment. The thermal degradation of polyurethanes was studied by the thermogravimetric method. It has been shown that the polyurethane hard-segment crystallinity decreases in the following order: MDI> XDI> TDI>. The experimental results also indicated that polyurethanes with aralkyl diisocyanates, i.e., XDI, had the best thermal stability. The polyurethanes synthesized from aromatic diisocyanates, i.e., MDI and TDI, had worse thermal stability than from XDI. However, owing to the higher degree of hard-segment crystallinity for polyurethanes from MDI, these polyurethanes had a better thermal stability than those based on TDI. © 1996 John Wiley & Sons, Inc.     

Preparation and properties of polycarbodiimides

A series of polycarbodiimides was prepared from isocyanates using 1-phenyl-3-methyl-2-phospholene-1 oxide as catalyst. The molecular weight of the series was varied by employing controlled amounts of phenyl isocyanate as a terminating agent. The resultant polymers showed improved processing over very high molecular weight unterminated polymer, while still maintaining good thermal stability and equivalent mechanical properties. A study of the viscoelastic properties of these polymers using modulus–temperature plots showed that the materials underwent a crosslinking reaction at elevated temperatures (200–250°C). These reactions could be explained on the basis of a model, diphenylarbodiimide, and most likely include the formation of carbodiimide dimers and trimers.     

Synthesis,characterization and thermal dissociation of 2‐butoxyethanol‐blocked diisocyanates and their use in the synthesis of isocyanate‐terminated prepolymers

A series of blocked diisocyanates has been synthesized from toluene diisocyante (TDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 4,4′‐diphenylmethane diisocyanate (MDI) and 2‐butoxyethanol. The synthesis of blocked diisocyanate adducts was confirmed by Fourier transform infrared, ¹H NMR, electron impact mass spectrometry and nitrogen analysis. Differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA) and carbon dioxide evolution were used to determine the minimum de‐blocking temperatures. De‐blocking temperatures determined by these three techniques were found to be in the order DSC > TGA > CO₂ evolution. The effect of different metal catalysts on thermal de‐blocking reaction of the blocked diisocyanates was studied, using the carbon dioxide evolution method. It was found that iron(III) oxide has the maximum catalytic activity on de‐blocking. The solubility of the blocked diisocyanate adducts was determined in different solvents. The study revealed that at 30 °C blocked IPDI and HDI adducts show better solubility than adducts based on TDI and MDI. Isocyanate‐terminated prepolymers of blocked diisocyanates and hydroxyl‐terminated polybutadiene (HTPB) were prepared. The storage stability and gelation times of the prepolymers were studied. Results showed that all the diisocyanate‐HTPB compositions are stable at 50 °C for more than three months. However, aliphatic diisocyanate‐HTPB compositions require greater gelation time than aromatic diisocyanate‐HTPB compositions at their respective de‐blocking temperatures. Copyright © 2007 Society of Chemical Industry     

Synthesis and characterization of radiation curable polyurethanes containing pendant acrylate groups

A series of radiation sensitive and relatively high molecular weight poly(tetramethylene adipate) polyurethanes containing pendant acryfate functionality was synthesized. These radiation curable materials possess good mechanical properties and behave like common thermoplastic elastomers prior to chemical crosslinking which further enhances their strength and insolublizes them. Both the precursor and the cured materials were characterized by stress-strain, differential scanning calorimetry. and dynamic mechanical testing. It was found that the poly-(tetramethylene adipate) soft segments with molecular weight of 2000 or higher were crystallizable in the cross-linked network. The soft segment molecular weight and the diisocyanate type were found to be important in determining the tensile and thermal properties of these male-rials. The crosslinking process was found to depress crystallization of the soft segments and to improve tensile properties. Increasing the soft segment molecular weight resulted in an Increased elongation al break bill a decreased ultimate stress for both the precursor linear polymers and the crosslinked materials.     

Synthesis and properties of polyurethane resins based on liquefied wood

Three polyurethane resins were synthesized from liquefied wood and three diisocyanates, i.e., TDI, IPDI, and HDI. The liquefied wood was obtained by the liquefaction of benzylated wood wastes using Dibasic esters (DBE) as solvent with hydrochloric acid as catalyst for 3 h, at 80°C. The thermal stability and microphase morphology of polyurethane films were investigated by TG, DSC, WAXD, and SEM methods. The experimental results indicated that polyurethane resins from liquefied wood had higher thermal stability than traditional ones, and the special structure and the difference of chemical structure of diisocyanates resulted in the crytallinity and microphase separation of obtained polyurethanes. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 351–356, 2004     

Examining the thermal degradation behaviour of a series of cyanate ester homopolymers

A series of thermally stable dicyanate monomers was prepared containing different thermally stable structural units, namely 2,2′‐bis(4‐cyanatophenyl)propane, bis‐4‐cyanato‐biphenyl, bis‐4‐cyanato naphthalene, 3,3′‐bis(4‐cyanatophenyl)sulfide and 3,3′‐bis(4‐cyanatophenyl)sulfone, was prepared and the identity of the products was confirmed by Fourier transform infrared and NMR spectral methods. The corresponding cyanate homopolymers were prepared and their properties were evaluated and compared. The composites were analysed for their thermal stability and thermal degradation kinetics. The series of homopolymers exhibit excellent thermal characteristics, e.g. relatively high glass transition temperatures of at least 215 °C, which were inversely proportional to the molecular weight between the crosslinks, high thermal decomposition temperature and high activation energies for the decomposition of cured resins. Determination of their limiting oxygen indices indicates that all the homopolymers are characterized as ‘self‐extinguishing’ materials. © 2019 Society of Chemical Industry     

Thermal stability of polyurethanes based on vegetable oils

A series of polyurethanes from polyols derived from soybean, corn, safflower, sunflower, peanut, olive, canola, and castor oil were prepared, and their thermal stability in air and nitrogen assessed by thermogravimetric analysis, FTIR, and GC/MS. Oil‐based polyurethanes generally had better initial thermal stability (below 10% weight loss) in air than the polypropylene oxide‐based polyurethane, while the latter was more stable in nitrogen at the initial stage of degradation. If weight loss at a higher conversion is taken as the criterion of stability, then oil polyurethanes have better thermal stability both in air and in nitrogen. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1723–1734, 2000     

Effect of segment size and polydispersity on the properties of polyurethane block polymers

The dynamic-mechanical and thermal scanning behaviour of a series of specially synthesized linear segmented polyurethanes is presented. These materials possess a well defined segment molecular weight and molecular weight distribution and no possibility of intermolecular hydrogen bonding. The dynamic-mechanical transitions observed are assigned to specific molecular motions and the effect of segment size and molecular weight distribution is described. The results are explained in terms of hard segment domain perfection. Differential scanning calorimetry (d.s.c.) curves of annealed samples indicate that domain morphology may be affected by thermal treatment. A comparison of dynamic mechanical and d.s.c. results to hydrogen-bonded polyurethanes is made.     

Smoke and toxicant production during thermal degradation

A series of materials were tested in a radiant furnace for their production of toxicants (carbon monoxide and hydrogen chloride) while concurrently measuring the weight remaining of the test specimen. In addition, the effect of sample form on toxicant production was considered for Douglas fir and polyvinyl chloride. The smoke-exposure profile was found to be dependent on the material's form. The specimen-irradiation time and the incident heat flux. The calculation of exposure using a Ct product based on the area under the production curve was found useful for smoke and toxicants. Concentrations of toxic gases produced were not linearly related to sample-weight loss throughout the experiments. The influence of sample form on smoke and toxicant production was greater for Douglas fir than for polyvinyl chloride. The results indicate that in toxicity tests samples should be tested in their end-use form and that a material's thermal properties may influence toxicity-value calculations.     

Thermal and mechanical properties of linear segmented polyurethanes with butadiene soft segments

A series of segmented polyurethanes based on a hydroxyl terminated polybutadiene soft segment (HTPBD) have been prepared with varying hard segment content between 20 and 60 weight percent. These materials are linear and amorphous and have no potential for hydrogen bonding between the “hard” and “soft” segments. The existence of two-phase morphology was deduced from dynamic mechanical behavior and thermal analysis. Both techniques showed a soft segment glass transition temperature, T_gs, at ?56°C and hard segment transitions between 20 and 100°C, depending on the urethane content. The low value of T_g, only 8° higher than the T_g of free HTPBD and independent of hard segment concentration indicated nearly complete phase segregation. Depending on the nature of the continuous and dispersed phases, the urethanes behaved as elastomers below 40 weight percent hard segment or as glasslike materials at higher hard segment contents. The effect of thermal history on transitions of the HTPBDurethanes was also investigated and the results suggest that the absence of hydrogen bonding to the soft segment must account for the extraordinary insensitivity to thermal history in dynamic mechanical, thermal and stress-strain behavior. Comparisons are made to the more common polyurethanes containing polyether and polyester soft segments.     

以生物基二聚脂肪酸制备聚氨酯丙烯酸酯树脂及其性能研究

为了减缓石油资源消耗,利用可再生二聚酸制备聚氨酯丙烯酸酯。将二聚脂肪酸(DA)与乙二醇(EG)以不同的物质的量比缩合制得3种不同羟值的聚酯二元醇(A-1、A-2、A-3),再依次通过与甲苯二异氰酸酯(TDI)、丙烯酸羟乙酯(HEA)反应引入丙烯酸酯基团,从而制得3种可光固化的聚氨酯丙烯酸酯树脂(B-1、B-2、B-3)。利用傅立叶变换红外光谱(FT-IR)对原料及合成产物进行了结构表征;采用实时红外分析(RT-IR)研究了不同条件下树脂的光固化性能;采用万能试验机、差示扫描量热仪(DSC)、热重分析仪(TGA)分析测试了固化膜的力学性能、玻璃化转变温度和热稳定性;同时测试了固化膜的接触角及铅笔硬度等。结果表明:随着二聚酸含量的升高,所制得的聚酯二元醇黏度和数均相对分子质量增大,羟值降低。最终所制备的聚氨酯丙烯酸酯树脂固化膜的热稳定性和附着力基本相同,但随着羟值含量的降低,软段部分增加,双键含量降低,交联密度下降,导致固化膜铅笔硬度、吸水率降低,柔韧性增加。     

Effect of fiber content and type,compatibilizer, and heating rate on thermogravimetric properties of natural fiber high density polyethylene composites

Natural fiber polyethylene composites containing kenaf fibers, wood flour, newsprint, and rice hulls at 25 and 50% (by weight) fiber content were sampled and studied using thermogravimetric analysis (TGA). The effects of fiber type and content, compatibilizer and heating rate on the thermal stability and degradation of the composites were evaluated. Among different natural fibers, kenef fibers were found to be the least thermally stable ones whereas newsprint fibers proved to be the most stable fibers in composite formulations. Composites containing higher amounts of natural fiber degraded at a higher rate and exhibited higher weight loss. The presence of the compatibilizer resulted in composites with slower thermal degradation. Heating rate increased both temperature and rate of main degradation peaks. FTIR and DSC results are also presented to discuss phenomena leading to thermal degradation. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers.     

聚碳酸酯二醇型水性聚氨酯胶粘剂的研究

采用预聚体分散法制备了一系列聚碳酸酯二醇(PCDL)型水性聚氨酯(WPU)胶粘剂,并借助傅里叶变换红外光谱(FT-IR)法来跟踪预聚体的合成过程,同时还考察了该WPU胶粘剂的粘度、热稳定性和初粘强度等性能。实验结果表明,PCDL的结构和相对分子质量对该WPU胶粘剂的性能影响很大;以PCDLT-6002为原料制备的WPU胶粘剂,其粘度最低(175 mPa.s)、热稳定性最好、软链段玻璃化转变温度(Tg)最低(-33.97℃)、有软段结晶熔融峰且初粘强度最高(81N/25 mm,此时活化温度为70℃)。     

On the Stability of Selected Monomeric and Polymeric Aryl Sulfonic Acids on Heating in Water (Part 1)

A number of low molecular weight sulfonated aromatic compounds: carboxamides, imides, sulfonamides, as well as sulfonated polymers; aramides and poly(styrene‐p‐sulfonic acid), were tested for their stability on heating in water and dilute acid to temperatures ranging from 130–200 °C. Desulfonation was observed with some compounds. Sulfonamide linkages were found to be stable, while carboxamide linkages and phthalimides were not.     

Compatibilization of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)–poly(lactic acid) blends with diisocyanates

Poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) was blended with poly(lactic acid) (PLA) with various reactive processing agents to decrease its brittleness and enhance its processability. Three diisocyanates, namely, hexamethylene diisocyanate, poly(hexamethylene diisocyanate), and 1,4‐phenylene diisocyanate, were used as compatibilizing agents. The morphology, thermomechanical properties, and rheological behavior were investigated with scanning electron microscopy, thermogravimetric analysis, differential scanning calorimetry, tensile testing, dynamomechanical thermal analysis in torsion mode (dynamic mechanical analysis), and oscillatory rheometry with a parallel‐plate setup. The presence of the diisocyanates resulted in an enhanced polymer blend compatibility; this led to an improvement in the overall mechanical performance but did not affect the thermal stability of the system. A slight reduction in the PHBV crystallinity was observed with the incorporation of the diisocyanates. The addition of diisocyanates to the PHBV–PLA blend resulted in a notable increase in the final complex viscosity at low frequencies when compared with the same system without compatibilizers. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44806.     

Study on thermal stability of typical carbon fiber epoxy composites after airworthiness fire protection test

The thermal stability of the T700 carbon fiber epoxy composites, which had been tested under different conditions (nonvibration plus nonscrubbing airflow, vibration, scrubbing airflow, and vibration plus scrubbing airflow), were investigated according to the obtained weight loss behavior, integral program decomposition temperature (IPDF), and activation energies (E) by using thermogravietry-differential thermal analyzer. The results indicate that the weight loss ratio, IPDF, and E of T700 carbon fiber epoxy and its residues in the third and fourth layers are similar under the nonvibration plus nonscrubbing airflow and vibration, and the thermal stability under the vibration condition is slightly stronger. In addition, the weight loss ratio, IPDF, and E of the epoxy and its residues in materials are also similar under scrubbing airflow and vibration plus scrubbing airflow, and the thermal stability under vibration plus scrubbing airflow is better. However, it is significantly less than the thermal stability of materials under nonvibration plus nonscrubbing airflow and vibration. Therefore, it can be found that the vibration exacerbates the flame severity and the scrubbing airflow has a significant cooling effect on the material during the airworthiness fire protection test, which have guiding significance on the airworthiness fire prevention items formulation of carbon fiber composite.     

Hexafluoroisopropyl Carbamates as Selective MAGL and Dual MAGL/FAAH Inhibitors: Biochemical and Physicochemical Properties

A series of hexafluoroisopropyl carbamates with indolylalkyl- and azaindolylalkyl-substituents at the carbamate nitrogen was synthesized and evaluated for inhibition of the endocannabinoid degrading enzymes fatty acid amide hydrolase (FAAH) and monoacylglycerol lipase (MAGL). The synthesized derivatives with butyl to heptyl spacers between the heteroaryl and the carbamate moiety were inhibitors of both enzymes. For investigated compounds in which the alkyl chain was partially incorporated into a piperidine ring, different results were obtained. Compounds with a methylene spacer between the piperidine ring and the heteroaromatic system were found to be selective MAGL inhibitors, while an extension of the alkyl spacer to two to four atoms resulted in dual inhibition of FAAH/MAGL. The only small change in enzyme inhibitory activity with variation of the heteroaromatic system indicates that the reactive hexafluoroisopropyl carbamate group is mainly responsible for the strength of the inhibitory effect of the compounds. Selected derivatives were also tested for hydrolytic stability in aqueous solution, liver homogenate and blood plasma as well as for aqueous solubility and for permeability in a Caco-2 cell model. Some compounds showed a slightly higher MAGL inhibitory effect than the known selective MAGL inhibitor ABX-1431 and also partly surpassed this substance with regard to certain physicochemical and biochemical properties such as water solubility and cell permeability.     

Thermal stability of chemically crosslinked moisture‐cured polyurethane coatings

Polyurethane prepolymers are widely used in reactive hot melt adhesives and moisture‐cured coatings. The segmented moisture‐cured formulations, based on polytetramethylene glycol (PTMG‐1000)/trimethylol propane (TMP)/isophorone diisocyanate (IPDI) and PTMG/TMP/toluene diisocyanate (TDI), were prepared with NCO/OH ratio of 1.6 : 1.0. The excess isocyanate groups of the prepolymers were chain extended in the ratio of 2 : 1 (NCO/OH) with different aliphatic diols and 4 : 1 with different aromatic diamines. The surplus isocyanate groups of the formulations were completely reacted with atmospheric moisture, and the thermal stability of the postcured materials obtained as cast films were evaluated by thermogravimetric (TG) analysis. It was observed that initial degradation temperatures were above 270°C, with two‐ or three‐step degradation profiles. The degradation parameters were evaluated using the Broido and Coats–Redfern methods. The thermal resistance of moisture‐cured formulations using diisocyanates with the cycloaliphatic structures (IPDI) and the aromatic TDI, at the same NCO/OH ratio (1.6), and TMP content were compared from the isothermal TG experiments at different temperatures and dynamic TG experiments at different heating rates in nitrogen and oxygen environments. The observation suggests that polyurethane‐containing sulfone groups and straight‐chain diol chain extenders were more stable. It was also observed that at lower temperature polyurethane, prepared from aliphatic diisocyanates (IPDI), was more stable than the aromatic diisocyanate (TDI) containing polyurethanes. At high temperature, the stability order follows the reverse trend. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1509–1518, 2005     

Synthesis and characterization of new soluble and thermostable polyimides via novel diisocyanates

A facile synthesis of two novel diisocyanates containing methylene groups and preformed imide structure is described. Furthermore, six thermally stable and soluble polyimides were synthesized by polycondensation of these two diisocyanates with pyromellitic dianhydride (PMDA), 3, 3 ′,4, 4 ′‐benzophenonetetracarboxylic dianhydride (BTDA) and hexafluoroisopropylidene‐2,2‐bis‐(phthalic anhydride) (6FDA) in N,N ‐dimethyl acetamide. All monomers and polymers were characterized by conventional methods and their physical properties such as solution viscosity, solubility properties, thermal stability and thermal behaviour were studied. © 1999 Society of Chemical Industry     

Variation of Poisson's ratio of refractory materials with thermal shocks

Investigations into the changes of Poisson's ratio as well as other mechanical properties of selected types of refractories subjected to thermal shocks have been carried out. The investigations included several types of porous refractory materials e.g. magnesia, magnesia–spinel, magnesia–chrome, chrome–magnesia, mullite, silica and low cement chamotte castable. The Poisson's ratio value of the examined materials decreased after each thermal shock. Decreasing of Poisson ratio caused by a stronger drop in Young's modulus than that for shear modulus was explained.It was found that some tested materials were characterized by low values of Poisson's ratio, which after series of severe thermal shocks decreased even to negative values. In order to explain the observed phenomenon, an attempt to correlate the obtained results with the microstructure of materials before and after a series of thermal shocks was undertaken. A hypothetical model of the microstructure of a porous ceramic material with negative Poisson ratio was proposed.