Temperature Imides

The authors [1] studied kinetics of poly (amic acid) (PAA) solid-state imidization both in the presence of nanofiller (layered silicate Na+-montmorillonite) and without it. It was found, that temperature imidization 1] raising in range 423-523 K and nanofiller contents Wc increase in range 0-7 phr result to essential imidization kinetics changes expressed by two aspects by essential increase of reaction rate (reaction rate constant of first order k increases about on two order) and by raising of conversion (imidization) limiting degree Q im from about 0,25 for imidization reaction without filler at 7 i=423 K up to 1,0 at Na -montmorillonite content 7... 

Methoxypolyethylene glycol maleimide has been prepared at ambient temperature by reacting the corresponding polyethylene oxide with A-methoxycarbonyl- maleimide. Since malimide derivatives are ordinarily prepared at 140°C, this ambient temperature imidization procedure dramatically broadens the scope and utilization of this reaction. 

Polymerization, Properties, and Applications. Acrylamide is polymerized free-radically in aqueous acid solution. At too high a polymerization temperature, imide structures, and hence cross-linking, occur. When the... 

Chemical imidization is not widely used because it employs additional reagents. However, it has the advantage of low temperature imidization and can he nsed to directly form fine polyimide molding powder (16,50). A t5 ical chemical imidization reaction employs a 20-30% solids polyamic acid in an amide solvent with a slight molar excess of acetic anhydride and a molar equivalent of a triamine (triethyl amine, pyridine, or -picoline) (51-54). The percent conversion for chemical imidization is a function of polyimide solnhiUty. If the polymer crystallizes and/or precipitates from the reaction medium, imidization will he incomplete (16,50). Those systems that remain soluble must imdergo thermal treatment to convert any isoimide, and remove residual solvent. The mechanistic routes of chemical imidization are shown in Figure 4, and involve the use of a triamine... 

Polymers in Solution. Polyacrylamide is soluble in water at all concentrations, temperatures, and pH values. An extrapolated theta temperature in water is approximately —40° C (17). Insoluble gel fractions are sometimes obtained owing to cross-link formation between chains or to the formation of imide groups along the polymer chains (18). In very dilute solution, polyacrylamide exists as unassociated coils which can have an eUipsoidal or beanlike stmcture (19). Large aggregates of polymer chains have been observed in hydrolyzed polyacrylamides (20) and in copolymers containing a small amount of hydrophobic groups (21). 

A cross-linked and crystalline copoly(ester—imide) containing an alkene function was made by reaction of an unsaturated diacid chloride containing a cychc imido group with ethylene glycol at low temperature (27). 

There are two types of deposited films known as siUcon nitride. One is deposited via plasma-enhanced CVD at temperatures <350° C (18). In this process silane and ammonia react in an argon plasma to form siUcon imide [14515-04-9] SiNH. 

Polymers based on trimellitic anhydride are widely used in premium electromagnetic wire enamels requiring high temperature performance. Several types of trimellitic anhydride-derived polymers are used as wire enamels poly(amide—imide)s (133), poly(ester—imide)s (134), and poly(amide—imide— ester)s (135). Excellent performance characteristics are imparted by trimellitic anhydride-based polymers for wire enamel requirements of flexibiUty, snap, burnout, scrap resistance, heat shock, and dielectric strength. 

I itro-DisplacementPolymerization. The facile nucleophilic displacement of a nitro group on a phthalimide by an oxyanion has been used to prepare polyetherimides by heating bisphenoxides with bisnitrophthalimides (91). For example with 4,4 -dinitro monomers, a polymer with the Ultem backbone is prepared as follows (92). Because of the high reactivity of the nitro phthalimides, the polymerkation can be carried out at temperatures below 75°C. Relative reactivities are nitro compounds over halogens, Ai-aryl imides over A/-alkyl imides, and 3-substituents over 4-substituents. Solvents are usually dipolar aprotic Hquids such as dimethyl sulfoxide, and sometimes an aromatic Hquid is used, in addition. 

Virtually all of the organo derivatives of CA are produced by reactions characteristic of a cycHc imide, wherein isocyanurate nitrogen (frequendy as the anion) nucleophilically attacks a positively polarized carbon of the second reactant. Cyanuric acid and ethylene oxide react neady quantitatively at 100°C to form tris(2-hydroxyethyl)isocyanurate [839-90-7] (THEIC) (48—52). Substitution of propylene oxide yields the hydroxypropyl analogue (48,49). At elevated temperatures (- 200° C). CA and alkylene oxides react in inert solvent to give A/-hydroxyalkyloxazohdones in approximately 70% yield (53). Alternatively, THEIC can be prepared by reaction of CA and 2-chloroethanol in aqueous caustic (52). THEIC can react further via its hydroxyl fiinctionahty to form esters, ethers, urethanes, phosphites, etc (54). Reaction of CA with epichlorohydrin in alkaline dioxane solution gives... 

Post-Curing. Whenever production techniques or economics permit, it is recommended that compounds based on terpolymer grades be post-cured. Relatively short press cures can be continued with an oven cure in order to develop full physical properties and maximum resistance to compression set. Various combinations of time and temperature may be used, but a cycle of 4 h at 175°C is the most common. The post-cure increases modulus, gready improves compresson set performance, and stabilizes the initial stress/strain properties, as chemically the polymer goes from an amide formation to a more stable imide formation. Peroxide-cured dipolymer compounds need not be post-cured. 

Other Polyimides. In 1979, Rohm Haas introduced Kamax resin, which was thought to be an /V-methylamine imidization product of poly(methyl methacrylate) (118). The product was then withdrawn, but was reintroduced in the late 1980s. The partly imidized resins are similar to poly(methyl methacrylate) but have a higher glass-transition temperature. 

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