Functionality determination of hydroxyl–terminated butadiene prepolymers

Functionality of hydroxyl–terminated butadiene prepolymers (HTPB) was determined from gel point measurements as described by Strecker and French.² Commercial HTPB samples had functionalities ranging from 1.9 to 2.6, with most of the material close to 2.0. In order to calculate functionality from gel point measurements, the hydroxyl content of the HTPB must be known. A method was developed which gave reproducible results. Curing agents used in the gel studies were viscous liquid poly-functional isocyanates with functionalities of 2.00 and 2.50. An extensive study showed that no side reactions were occuring with the isocyanates at the temperatures employed. It is estimated that the precision of the method is ±0.80%. Functionality calculated by dividing molecular weight by equivalent weight results in lower values in all cases when compared to gel point measurements.     

Burning‐rate enhancement of a high‐energy rocket composite solid propellant based on ferrocene‐grafted hydroxyl‐terminated polybutadiene binder

Four different samples of ferrocene‐grafted hydroxyl‐terminated polybutadiene (Fc‐HTPB), containing 0.20, 0.52, 0.90, and 1.50 wt % iron, were synthesized by the Friedel–Crafts alkylation of ferrocene with hydroxyl‐terminated polybutadiene (HTPB) in the presence of AlCl₃ as a (Lewis acid) catalyst. The effects of the reaction conditions on the extent of ferrocene substitution were investigated. The Fc‐HTPBs were characterized by IR, ultraviolet–visible, ¹H‐NMR, and ¹³C‐NMR spectra. The iron content and number of hydroxyl groups were estimated, and the properties, including thermal degradation, viscosity, and propellant burning rates (BRs), were also studied. The thermogravimetric data indicated two major weight loss stages around 395 and 500°C. These two weight losses were due to the depolymerization and decomposition of the cyclized product, respectively, with increasing temperature. The Fc‐HTPB was cured with toluene diisocyanate and isophorone diisocyanate separately with butanediol–trimethylolpropane crosslinker to study their mechanical properties. Better mechanical properties were obtained for the gumstock of Fc‐HTPB polyurethanes with higher NCO/OH ratios. The BRs of the ammonium perchlorate (AP)‐based propellant compositions having these Fc‐HTPBs (without dilution) as a binder were much higher (8.66 mm/s) than those achieved with the HTPB/AP propellant (5.4 mm/s). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The effect of hydroxyl‐terminated polybutadiene‐grafted carbon fiber on the impact performance of carbon fiber–epoxy resin composites

Carbon fiber (CF) containing 1.4 and 2.1 mmol/g of —COOH and —OH groups, respectively, was functionalized by using an excess of tolylene‐2,4‐diisocyanate. The NCO‐modified CF was submitted to a graft reaction with hydroxyl‐terminated polybutadiene (HTPB). The HTPB‐grafted carbon fiber was employed as reinforcing agent for epoxy resin‐based composites. The presence of the flexible HTPB at the interface between the fiber and the matrix resulted in a substantial improvement on impact strength. Additional improvement on toughness was achieved by using epoxy matrix containing dispersed phase of HTPB. The composite morphology was also studied by scanning electron microscopy. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1424–1431, 1999     

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     

Functionality distribution and crosslink density of hydroxyl-terminated polybutadiene

A novel approach is proposed for estimating the average molecular weight between crosslinks (M?_c) from the functionality distribution of hydroxyl-terminated polybutadiene ( HTPB ). The functionality distribution of four free-radically polymerised HTPB prepolymers of varying hydroxyl content and molecular weight was determined by a combination of preparative and analytical gel permeation chromatography. The gumstock properties of the samples cured with stoichiometric amounts of toluene diisocyanate were not correlatable with the relative amounts of difunctional chain extender and multifunctional crosslinker present, unlike the case of HTPB with similar hydroxyl content and molecular weight. However, the mechanical properties and sol content could be correlated with the average molecular weight between crosslink sites, M?_c, of the cured polymer. The M?_c values derived by our method compare well with those of classical methods, and the observed differences are attributed to segmental entanglement. These M?_c values give consistently good correlation with all the gumstock properties, confirming the validity of our approach and the soundness of the techniques developed for the determination of the functionality distribution of HTPB .     

Thermomechanical and Morphological Characteristics of Cross‐Linked GAP and GAP–HTPB Networks with Different Diisocyanates

This paper describes the mechanical and thermal characterisation of cross‐linked glycidyl azide polymer (GAP) and GAP–hydroxyl terminated polybutadiene (HTPB) networks. Cross‐linked GAP and GAP–HTPB networks were prepared by reacting GAP diol and GAP–HTPB diol mixture with different diisocyanates. The physical and mechanical characteristics were found to be influenced by the type of isocyanate curing agents, [NCO]/[OH] equivalent ratios and concentration of GAP. For all the three types of curing agents, GAP–HTPB blends of 50 : 50 to 30 : 70 ratios show higher mechanical strength over the virgin networks of GAP or HTPB. Thermal decomposition of cross‐linked GAP–HTPB networks was evaluated by thermogravimetric analysis (TGA). The kinetic parameters for the decomposition of GAP–HTPB blends were found to be dependant on the concentration of GAP and HTPB in the blend. The cross‐linked GAP–HTPB blends were subjected to dynamic mechanical analysis (DMA). The glass transition characteristics of the blends were evaluated by DMA and it was found that blends prepared with GAP content up to 30% showed single transition in the loss tangent trace indicating no phase separation in the cured network.     

Anionic waterborne polyurethane dispersions based on hydroxyl‐terminated polybutadiene and poly(propylene glycol): Synthesis and characterization

Nonpolluting systems based on anionic polyurethane aqueous dispersions were obtained. The prepolymer based on hydroxyl‐terminated polybutadiene (HTPB), isophorone diisocyanate (IPDI), poly(propylene glycol) (PPG), and dimethylolpropionic acid (DMPA) were synthesized in bulk. After neutralization with triethylamine (TEA), the anionomer prepolymer was dispersed in water, followed by a chain‐extension reaction with ethylenediamine (EDA). The prepolymers were characterized by Fourier transform infrared spectrometry (FTIR) and the average particle size of the aqueous dispersions was determined by laser light scattering (LLS). The mechanical behavior of polyurethane‐cast films and the adhesive properties of the aqueous dispersions as coatings for wood were evaluated. It was observed that an increase in the HTPB content provoked an increase in the viscosity and in the particle size of the dispersions. The tensile strength and the modulus values of the films and the adhesiveness of the coatings in wood were also increased by increasing the HTPB content. On the other hand, the elongation of the polyurethane‐cast films and the tackness of the surface coatings decreased as the HTPB was increased. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 566–572, 2001     

预聚体法制备聚醚聚氨酯胶粘剂

以四氢呋喃-环氧丙烷共聚醚三醇、甲苯二异氰酸酯、1，4-丁二醇、白炭黑为原料，合成了聚醚预聚体，以四氢呋喃-环氧丙烷共聚醚三醇为固化剂，制备了双组分无溶剂聚氨酯胶粘剂。研究了硬段比例，NCO质量分数、白炭黑用量、预聚体贮存时间等因素对预聚体和胶粘剂性能的影响，测试了预聚体的粘度和NCO质量分数，以及胶粘剂固化物的力学性能，粘接强度。测试结果表明，将1，4-丁二醇（BG）和四氢呋喃-环氧丙烷共聚醚三醇（JF）的羟基摩尔比值控制在1.5，NCO质量分数控制在5.6%左右，白炭黑用量为10g，可以获得工艺性能和贮存性能良好的聚醚预聚体，与聚醚固化剂配制，可以获得比较高而且稳定的力学性能和粘接强度。     

Synthesis and Thermo-Oxidative Aging Resistance of Hydroxyl Terminated Polybutadiene Bound 2,2-Thiobis(4-methyl-6-tert-butylphenol)

A novel polymeric antioxidant HTPB-IPDI-TPH was synthesized by the reaction between 2,2-thiobis (4-methyl-6-tert-butylphenol) (TPH) and an adduct (HTPB-IPDI) from hydroxyl terminated polybutadiene (HTPB) and isophorone diisocyanate (IPDI). The effects of raw materials ratio and the reaction condition were investigated by measuring the content of the residual –NCO groups of the reactants during the reaction. The structure of HTPB-IPDI-TPH was characterized by FTIR and ¹H NMR. Thermo-oxidative aging resistance of HTPB-IPDI-TPH was evaluated by oxidation induction time (OIT) from DSC of natural rubber vulcanizates. The optimal reaction conditions between IPDI and HTPB were that the amount of dibutyltin dilaurate (DBTDL) was 0.6 wt% based on IPDI, and the temperature and time were 40°C and 270 min, respectively. The reaction conditions between TPH and HTPB-IPDI were that the molar ratio of TPH to –NCO in HTPB-IPDI was 3:1, and the amount of DBTDL was 1.6 wt% based on the total of reactants, and the temperature and time were 75°C and 360 min, respectively. Thermo-oxidative aging resistance of HTPB-IPDI-TPH was obviously superior to the corresponding low molecular counterpart (TPH) for natural rubber vulcanizates.     

Structure-property relationship of HTPB-based propellants. II. Formulation tailoring for better mechanical properties

There has been a constant endeavor to improve the mechanical properties of hydroxylterminated polybutadiene (HTPB) -based composite solid propellants. A systematic study has been conducted on different batches of HTPB resins with varying molecular weights and hydroxyl values. Propellant formulation experiments were conducted wherein the ratio of chain extender to crosslinker was systematically varied, with a view to achieve the maximum possible strain capability and moderately high tensile strength, keeping all other parameters constant. The influence of increasing hydroxyl content from trimethylolpropane at the expense of hydroxyl content from butanediol, on the mechanical properties of the finished propellant, has been depicted on 3-dimensional graphs. The isoproperty lines, plotted as a triangular chart with the percentage hydroxyl contents from the three constituents, can be used to arrive at the suitable formulation for a specified application depending upon the OH value of the resin. HTPB resins with high molecular weight, low functionality, and low hydroxyl value require higher levels of trifunctional curing agent and higher NCO / OH ratios to obtain outstanding mechanical properties, especially elastic properties, compared to low molecular weight, high functionality resins. The impact of hard and soft segment domain structure on the mechanical behavior of the cured systems is more pronounced in the low molecular weight resin formulations due to the higher hard segment content compared to those attainable in high molecular weight resin formulations. © 1993 John Wiley & Sons, Inc.     

Eco-Friendly Ether and Ester-Urethane Prepolymer: Structure,Processing and Properties

This study concerns bio-based urethane prepolymers. The relationship between the chemical structure and the thermal and processing parameters of bio-based isocyanate-terminated ether and ester-urethane prepolymers was investigated. Bio-based prepolymers were obtained with the use of bio-monomers such as bio-based diisocyanate, bio-based polyether polyol or polyester polyols. In addition to their composition, the bio-based prepolymers were different in the content of iso-cyanate groups content (ca. 6 and 8%). The process of pre-polymerization and the obtained bio-based prepolymers were analyzed by determining the content of unreacted NCO groups, Fourier transform infrared spectroscopy, proton nuclear magnetic resonance, thermogravimetry, and rheological measurements. The research conducted facilitated the evaluation of the properties and processability of urethane prepolymers based on natural components. The results indicate that a significant impact on the processability has the origin the polyol ingredient as well as the NCO content. The thermal stability of all of the prepolymers is similar. A prepolymer based on a poly-ether polyol is characterized by a lower viscosity at a lower temperature than the prepolymer based on a polyester polyol. The viscosity value depends on the NCO content.     

Structure–property relationship of HTPB-based propellants. III. Optimization trials with varying levels of diol–triol contents

A systematic study has been conducted on a composite solid propellant formulation using hydroxyl-terminated polybutadiene (HTPB) prepolymer with varying molecular weights and hydroxyl values. Fairly extensive regions of resin parameters have been studied. Contours of important propellant properties have been laid down. In this set of experiments, varying levels of diol and triol contents were used at two different NCO/OH ratios to arrive at the optimum level needed for different grades of HTPB resin. It is seen that different grades of HTPB resin require varying levels of diol–triol contents to give similar properties for the end product. Also, for the best performance, varying the diol–triol ratio at the optimum level of the diol–triol content is necessary. © 1994 John Wiley & Sons, Inc.     

Modification of unsaturated polyester resin by polyurethane prepolymers

Unsaturated polyester resins (UPRs) are extensively used by the fiber‐reinforced plastic (FRPs) industry. These resins have the disadvantages of brittleness and poor resistance to crack propagation. In this study, UPRs were chemically modified by reactive blending with polyurethane prepolymers having terminal isocyanate groups. Hybrid networks were formed by copolymerisation of unsaturated polyesters with styrene and simultaneous reaction between terminal hydroxyl groups of unsaturated polyester and isocyanate groups of polyurethane prepolymer. The prepolymers were based on toluene diisocyanate (TDI) and each of hydroxy‐terminated natural rubber (HTNR), hydroxy‐terminated polybutadiene (HTPB), polyethylene glycol (PEG), and castor oil. Properties like tensile strength, toughness, impact resistance, and elongation‐at‐break of the modified UPRs show considerable improvement by this modification. The thermal stability of the copolymer is also marginally better. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 449–456, 2006     

The kinetics of the reaction of isophorone di-isocyanate with mono-alcohols

Isophorone di-isocyanate (IPDI) is used to react with hydroxyl containing prepolymers in the preparation of polyurethane elastomers, particularly with hydroxy-terminated polybutadiene (HTPB) in composite propellant systems. In the present work, the kinetics of the reaction of IPDI with monoalcohols are studied, as a model for the polyurethane systems. A gas chromatography method is used to follow the reaction, which allows direct measurement of the reaction of individual isocyanate groups. The rates of individual isocyanate groups are described by a second order equation modified to include catalysis by the urethane products. The rates of primary and secondary isocyanate groups in the two isomers of IPDI are compared. Differences between the various isocyanate groups are relatively small, and are offset by the urethane catalysis effect, so that the overall disappearance of isocyanate is roughly second order. The reaction rate of IPDI with HTPB is faster than with the model compounds, and it is suggested that this arises because there is tendency for the isocyanate to complex with the hydroxyl end groups of the polymer.     

Aging of HTPB/AP‐based composite solid propellants,depending on the NCO/OH and triol/diol ratios

Aging behavior of hydroxyl‐terminated polybutadiene/ammonium perchlorate (HTPB/AP)‐based composite solid propellants was studied as a function of crosslink density, which is predominantly determined by the molar ratio of diisocyanate to total hydroxyl (NCO/OH ratio) and the molar ratio of triol to diol (triol/diol ratio). For this purpose, 16 propellant samples with different compositions were prepared by changing the NCO/OH ratio as 0.81, 0.82, 0.83, and 0.85 for each triol/diol ratio of 0.07, 0.09, 0.11, and 0.13, and subjected to an accelerated aging at 65°C. The changes in the mechanical properties were monitored throughout the aging period. In the initial part of the aging period, a sharp increase in stress, modulus, and hardness values and a sharp decrease in strain values were observed for all the propellants. At further stages of aging, only slight changes were observed in the mechanical properties. Concerning the aging criterion as reduction in the strain capability more than the half of the initial value, the propellants with respective NCO/OH‐triol/diol ratios of 0.81–0.09, 0.85–0.09, 0.81–0.13, 0.83–0.13, and 0.85–0.13 can be considered to be aged with time. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 959–964, 2001     

Synthesis and characterization of triazole rich polyether polyols using click chemistry for highly branched polyurethanes

The present work describes development of moisture cured polyurethane–urea coatings based on 1,2,3-triazole rich polyether polyols. In this paper, two polyether polyols were synthesized by using 1,3-dipolar azide–alkyne cycloaddition reaction and they were named as PL-1 and PL-2 where PL-1 is 9 terminal hydroxyl groups and PL-2 is 6 terminal hydroxyl groups. These polyols were reacted with 4, 4′-diisocyanatodicyclohexylmethane (H₁₂MDI) at OH:NCO ratio of 1:1.2 in order to obtain isocyanate terminated polyurethane prepolymers. The resulted prepolymers were casted on tin foil and cured under atmospheric moisture in order to get completely cured polyurethane–urea free films. The free films were characterized by using Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA) and dynamic mechanical thermal analysis (DMTA) techniques. The TGA and DMTA results showed that these films have good thermal and mechanical stability. Anti-microbial studies proved that these polyurethane films show good resistance towards different bacterial and fungal attacks. These polymers were also coated on mild steel panels in order to evaluate corrosion resistance properties by using salt spray and electro chemical polarization studies.     

端羟基液体聚丁二烯橡胶微观结构及其力学性能

通过FT—IR,HNMR,CNMR,GPC等方法,对相同牌号HTPB样品A和B的主链微观结构、羟基类型、环氧基团、官能度分布和固化物力学性能进行了对比,2个样品的主链微观结构、羟基类型、环氧基团含量基本一致,而官能度分布存在较大差异,由结果可得,HTPB官能度分布对其力学性能影响较大,二官能度为84．2％的样品A具有较好的力学性能,二官能度为676％的样品B具有相对较差的力学性能。     

Characterization of the network structure of hydroxyl terminated poly(butadiene) elastomers prepared by different reactive systems

Three types of hydroxyl terminated poly(butadiene) (HTPB) networks having different NCO/OH reactive group ratios were prepared using three different reactive systems (i.e., Desmodur N-100 pluriisocyanate, isophorone diisocyanate (IPDI)/trimethylol propane (TMP), and hexamethylene diisocyanate (HMDI)/TMP). Desmodur N-100 and TMP were used as polyfunctional reactants. The polymer–solvent interaction parameters (χ₁) for HTPB–tetrahydrofuran (THF) and HTPB–chloroform systems at 45°C were determined, using a vapor pressure osmometer (VPO), as 0.31 and 0.24, respectively. Equilibrium swelling values of the networks in THF and chloroform and the data obtained by osmometry were further used for the calculation of the mean number-average molecular weight between junction points (M _c) of HTPB networks through the Flory-Rehner equation. The M _c values of each network, which were calculated from the swelling data obtained in THF and chloroform using the corresponding χ₁ parameters for polymer–solvent systems, were found to be nearly the same. The changes in the mechanical, swelling, and the solubility properties of the networks prepared by three different reactive systems were followed. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 1129–1135, 1998     

互穿聚合物网络技术对丁羟推进剂粘合剂体系性能的改善

通过互穿聚合物网络(IPN)技术,在原有丁羟推进剂粘合剂体系中添加甲基丙烯酸B酯作为塑料相,合成了3个系列的胶片。测定了预聚物的动态黏度,发现改性的预聚物黏度在反应初期明显低于原有预聚物黏度,丙烯酸酯的加入明显改善了其加工工艺性能;对胶片力学性能的测试则表明,拉伸强度可达到1.432 MPa,断裂伸长率达到576.614%。可见,丙烯酸酯对胶片力学性能的改善起到了显著的作用。玻璃化转变温度的测定表征了IPN体系的相分离程度。     

Synthesis and characterization of polyurethane/bentonite nanoclay based nanocomposites using toluene diisocyanate

Polyurethanes (PUs) prepolymers blended with bentonite nanoclay and without bentonite nanoclay were prepared by the reaction of toluene-2,4-diisocyanate (TDI) and hydroxyl terminated polybutadiene (HTPB), and the chain was further extended with 1,4-butane diol (1,4-BDO) to get final polyurethane nanocomposites (PUNC). A mixture of polymer and bentonite clay enriched in montmorillonite (MMT) was formed in solution polymerization, in which MMT dispersed depending on interaction of MMT with polymer chains. The molecular structure of the monomers and the prepared PU nanocomposites was confirmed by FTIR. A series of PUNCs were prepared by varying the percent compositions of bentonite nanoclay into the PU matrix. The existence of the clay in to the PU was confirmed by scanning electron microscope (SEM). SEM images verified the good dispersion of the bentonite nanoclay in PU matrix.