Cross-linking polyimide materials

The most important polymeric matrices are linear and cross-linked polyesters, epoxy resins and linear and cross-linked polyimides the most important reinforcements are high-performance polymeric fibres and filaments (for polymeric composites), filaments of refractory metals and inorganic materials (E-glass, A12C>3, B, BN, SiC and Carbon) and whiskers (fibrillar single crystals of A1203, B4C, WC, SiC and C, exclusively for reinforcement of metals). 

Triazine Ring Cross-linked Polyimides and Refractory Materials Derived from Them... 

The graphite fiber reinforced triaryl-s-triazine ring (TSTR) cross-linked polyimides with ring-chain structures have good mechanical properties at elevated temperatures. On pyrolysis, the TSTR cross-linked polyimides were converted to refractory type materials which are believed to be graphitic type ladder polymers containing some nitrogen in their cyclic structures. 

Pyrolysis of TSTR cross-linked polyimides converts them to refractory type materials which show promise as matrix materials for carbon fibers. 

Recently, the polymer science field has focused on the role of polymers as membrane materials with precise, well-ordered structures through the development of defined synthesis and analysis of polymers. Among these well-ordered polymers are the hyperbranched polymers (e.g. hyperbranched polyimides). Part of the interest in such polymers is due to the expectation that they could have different properties as compared to common linear polymers. Also, cross-linked polyimides have attracted much attention from researchers, as can be judged by a high number of publications. 

Section I (Novel Membrane Materials and Transport in Them) focuses on the most recent advances in development of new membrane materials and considers the transport parameters and free volume of polymeric and even inorganic membranes. Kanehashi et al. (Chapter 1) present a detailed review of hyperbranched polyimides, which are compared with more common cross-linked polyimides. These polymers with unusual architecture were studied in the hope that they would show weaker tendency to plasticization than conventional linear polymers. However, many representatives of this new class of polymers reveal relatively poor film forming properties due to absence of chain entanglement. Nonetheless, some promising results obtained can show directions of further studies. 

Other Polymers. Besides polycarbonates, poly(methyl methacrylate)s, cycfic polyolefins, and uv-curable cross-linked polymers, a host of other polymers have been examined for their suitabiUty as substrate materials for optical data storage, preferably compact disks, in the last years. These polymers have not gained commercial importance polystyrene (PS), poly(vinyl chloride) (PVC), cellulose acetobutyrate (CAB), bis(diallylpolycarbonate) (BDPC), poly(ethylene terephthalate) (PET), styrene—acrylonitrile copolymers (SAN), poly(vinyl acetate) (PVAC), and for substrates with high resistance to heat softening, polysulfones (PSU) and polyimides (PI). 

Polymer-matrix materials include a wide range of specific materials. Perhaps the most commonly used polymer is epoxy. Other polymers include vinyl ester and polyester. Polymers can be either of the thermoset type, where cross-linking of polymer chains is irreversible, or of the thermoplastic type, where cross-linking does not take place but the matrix only hardens and can be softened and hardened repeatedly. For example, thermoplastics can be heated and reheated, as is essential to any injection-molding process. In contrast, thermosets do not melt upon reheating, so they cannot be injection molded. Polyimides have a higher temperature limit than epoxies (650°F versus 250°F or 350°F) (343°C versus 121°C or 177°C), but are much more brittle and considerably harder to process. 

In 1988 Heinze and Burton reported a facile synthesis of various a,p,P-trifluorostyrenes.15 These trifluorostyrene compounds were reported to be unstable to cyclodimerization at room temperature when stored neat, especially the compounds that were /lura-substituted with electron-donating substituents. They described the preparation of one compound, l,4-bis(trifluorovinyl)benzene with the observation that the material gelled when allowed to stand neat overnight. They offered the explanation that the gel was a polymer network connected with flnorinated cyclobutanes. Burton later went on to utilize this dimerization reaction for the cross-linking of polyimide thermoplastics.16... 

Direct Patterning of Photosensitive Polyimides. Photosensitive polyi-mides (PSPIs) are recently developed materials that can be directly photo-patterned like a negative photoresist (80,85,88,146-148). The most common PSPIs are polyamic acids that have been esterified with photoreactive alcohols and combined with photoinitiators to form a polymer that will crosslink under exposure to UV radiation and become insoluble. The unexposed material is selectively dissolved in a developer solution, and the patterned film is then cured to convert the cross-linked polyamic acid to a polyimide and drive off the cross-linking groups. 

Because PBI is expensive, other thermostable polymers were explored and tested as catalysts (246). A cross-linked version of a polyimide (PI) support with incorporated triazole rings (12b) gave better results than PBI for the epoxidation of cyclohexene. Moreover, it can be reused in the cyclohexene epoxidation at least 10 times without any loss of activity (247). Even less expensive, but thermooxidatively stable materials include polysiloxane-based resins, which have also been used for incorporation of Ti (see Section II,A). In this case, the synthesis comprises the polymerization of TEOS and an oligomeric dimethyl silanol with the addition of functional trialkoxysilanes such as trimethoxysilyl-2-ethylpyridine instead of Ti(OiPr)4 (248). Preliminary results show that the activity per Mo atom is higher than that of PBI-Mo. Furthermore, the degree of leaching of Mo is very low. Thus, it is expected that the polysiloxane-based systems may soon find wide application in oxidation chemistry. 

BPA/DC was compounded with high-temperature resistant ladder and semi-ladder polymers. A composition, which contained BPA/DC, a polyimide resin, organic Zn salt and benzyldimethylamine in A -methylpyrrolidone solution was described. The binder was destined for the manufacture of copper clad laminates. Tg of the cross-linked material was 265 °C [50]. Another example is a binder obtained from BPA/DC and polyphenylquinoxaline in chloroform [51]. 

Thermal compatibility — To increase electrical robustness, many commonly studied dielectric materials, including the polyimides and PVP above are annealed after printing. The purpose of this anneal is varied. In some materials, it serves to cause the evaporation of residual solvent. In other materials (for example, the polyimide and PVP above), it is used to cause a chemical conversion such as a cross-linking event. In every case, it is important that the requisite thermal process be compatible with the substrate and all layers that have already been printed at the time of annealing. 

A polymer s properties control the characteristics of the part made from it however, the polymer is only one of several constituents. Polymers are compounded with an array of other materials. The polyimides and polyetheretherketones discussed here use reinforcing fillers and curing agents. Curing agents are used to form the network of cross-links that guarantee elasticity rather than flow [3],... 

The polyimide class of polymers are known to possess a high degree of thermal stability. They decompose in an inert atmosphere around 500°C and in air about 400°C as indicated by thermo-gravimetric analysis (1). Because of the great thermal stability of 2,4,6-triphenyltriazine (2J (decomposes above 486°C), copolymerization of this compound with imides should lead to enhanced heat resistant materials in the form of triaryl-s-triazine ring (TSTR) cross-linked (XL) polyimides. 

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