Acetylene terminated

An interesting approach to thermosetting acetylene-terminated polyimides via the Michael addition reaction has appeared (38). Acetylene-terminated aspartimides are readily prepared ia high yield via two routes, shown ia Figure 7. 

Fig. 7. Acetylene-terminated aspartimides. (a) Reaction of aromatic diamine with A/-(3-ethynylphenyl)maleimide [105280-01-17 ia a 1 2 molar ratio yields a prepolymer of this general formula, (b) Bismaleimide reacts with 3-ethynylaniline [54060-30-9] ia a 1 2 molar ratio to yield a prepolymer of this general...

Many engineering thermoplastics (e.g., polysulfone, polycarbonate, etc.) have limited utility in applications that require exposure to chemical environments. Environmental stress cracking [13] occurs when a stressed polymer is exposed to solvents. Poly(aryl ether phenylquin-oxalines) [27] and poly(aryl ether benzoxazoles) [60] show poor resistance to environmental stress cracking in the presence of acetone, chloroform, etc. This is expected because these structures are amorphous, and there is no crystallinity or liquid crystalline type structure to give solvent resistance. Thus, these materials may have limited utility in processes or applications that require multiple solvent coatings or exposures, whereas acetylene terminated polyaryl ethers [13] exhibit excellent processability, high adhesive properties, and good resistance to hydraulic fluid. 

Cross-Linking and Isomerization Reactions of an Acetylene-Terminated Polyisoimide Prepolymer... 

Acetylene terminated polyimide prepolymers have many advantages over conventional polyimides in the areas of processing and solvent resistance. In addition, the presence of the isoimide structure further extends the the utility of these systems by modification of the solubility properties and glass transition temperature. 

This work discusses the thermal crosslinking and isomerization reactions occurring in the acetylene terminated isoimide prepolymer Thermid IP600. The techniques of Fourier Transform Infrared Spectrometry and Differential Scanning Calorimetry are used to determine the contribution of these two reactions during the thermal cure including their kinetics at 183° C. 

The goal of this work is to elucidate the relationship between the thermal isomerization and crosslinking reactions occurring in this acetylene terminated polyisoimide oligomer Thermid IP600. The... 

Structure of Thermid IP-600 Acetylene Terminated Isoimide Oligomer. 

Eddy, L. T. R. Lucarelli, A. M. Helminiak, T. Jones, W. Picklesimer, L. F. An Evaluation of An Acetylene Terminated Sulfone Oligomer. Internal Report, A FWAL/MLBC, January 1983. 

Landis, A. L. Chemistry of Procesible Acetylene-Terminated Imides, Pinal Report, AFWAL/ML Contract F33615-82-C-5016, August 1983. 

Lind, A. C. Saundreczki, T. C.j Levy, R. L. Characterization of Acetylene Terminated Resin Cures States. Interim Technical Report, AFWAL/ML Contract F33615-80-C-5170, August 1984. 

Acetylene-terminated oligomers, incorporation of isoimide functionality, 462 Acid functionalities, block copolymers, 258... 

The Fukuyama indole synthesis involving radical cyclization of 2-alkenylisocyanides was extended by the author to allow preparation of2,3-disubstituted derivatives <00S429>. In this process, radical cyclization of 2-isocyanocinnamate (119) yields the 2-stannylindole 120, which upon treatment with iodine is converted into the 2-iodoindole 121. These N-unprotected 2-iodoindoles can then undergo a variety of palladium-catalyzed coupling reactions such as reaction with terminal acetylenes, terminal olefins, carbonylation and Suzuki coupling with phenyl borate to furnish the corresponding 2,3-disubstituted indoles. 

In the energy domain, new and efficient uses in gas lines, electric cable ducts and the like, will promote surface stabilization and endurance as well as complex stress capability of various extruded or cast systems. Such reactants as acetylene terminated polymers have yielded cross-linked cured, networks of exceptional density and durability. A diimide dianhydride combined with (3) ethynylaniline yields an acetylene terminated tetraimide. On further polymerization at 250°C, the cross-linked structure derived can be used continuously at about 230°C. When this is combined with polymer carbon fibers or filaments, an exceedingly refractory and tough binder is produced. 

Other acetylene-terminated resins (ATR) similar to ATS as shown in Eq. 5 have also been prepared (13, 15). The cured... 

About 1970, research was initiated under Air Force funding on acetylene-terminated imide oligomers (ATI) which could be thermally chain extended through the acetylenic end-groups (33, 34). This effort resulted in the development of HR-600 (Eq. 9) and subsequent commercialization by Gulf Oil Chemicals Company in the form of Ther-mid -600. Neat resin properties of HR-600 are presented in Table IV while preliminary composite properties are given in Table V. 

Although HR-600/Thermid-600 provided promising neat resin and composite properties, major processing problems have plagued these as well as other acetylene-terminated oligomers. Resin flow and wetting is inhibited due to the reaction of the terminal ethynyl groups prior to the formation of a complete melt or soft state. This becomes even more severe due to heat transfer problems as... 

Table IV. Cured Acetylene-Terminated Imide (HR-600) Properties1 2...

To improve the processability of PPQ, appropriate phenylquinox-aline oligomers were end-capped with acetylenic groups using 3-(3,4-diaminophenoxy)phenylacetylene (43) or 4-(3- and 4-ethynyl-phenoxy)benzil (44, 45) (Eq. 10). The processability was improved but at the sacrifice of the thermooxidative stability. In general, cured acetylene-terminated heterocyclic polymers are less stable in a thermooxidative environment than the parent linear polymer. 

A thin molding of an acetylene-terminated phenylquinoxaline, fabricated by compression molding at 316°C for 26 hr and at 371°C for 5 hr, gave tensile strength of 103 MPa (15,000 psi), tensile modulus of 2.62 GPa (380,000 psi) and elongation of 5% (46). Preliminary unidirectional graphite fiber laminate properties are reported in Table VI. 

Table VI - Unidirectional HT-S Graphite Fiber Laminate Properties of Acetylene-Terminated Phenylquinoxaline Resin1 2...

In recent years acetylene terminated resins (AT-resins) have shown promise in the area of high temperature applications and are possible replacements for state-of-the-art epoxy resin systems where humidity exposure is expected. Acetylene terminated resins have two important advantages over previously developed systems ... 

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