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Glenn Research Center Cleveland, Ohio 44135

Technical Support Package
Better End-Cap Processing for Oxidation-Resistant Polyimides
NASA Tech Briefs LEW-17429-1

National Aeronautics and Space Administration

by the National Aeronautics and Space Administration.nasa. .gov NOTICE: This document was prepared under the sponsorship of the National Aeronautics and Space Administration. E-mail: help@sti. It is provided under the Commercial Technology Program of the National Aeronautics and Space Administration to make available the results of aerospace-related developments considered having wider technological. either expressed or implied. it is for identification only. MD 21076-1320 Telephone: (301) 621-0390.nasa.Technical Support Package for BETTER END-CAP PROCESSING FOR OXIDATION-RESISTANT POLYIMIDES LEW-17429-1 NASA Tech Briefs The information in this Technical Support Package comprises the documentation referenced in LEW-17429-1 of NASA Tech Briefs. Further assistance is available from sources listed in NASA Tech Briefs on the page entitled “NASA Commercial Technology Team.sti.” Additional information regarding research and technology in this general area may be found in a variety of publications available from the NASA Scientific and Technical Information (STI) Program Office. scientific. You can access the STI Program Office via http://www. or commercial applications.gov or as follows: NASA STI Help Desk NASA Center for AeroSpace Information 7121 Standard Drive Hanover. This usage does not constitute an official endorsement. Fax: (301) 621-0134. Neither the United States Government nor any person acting on behalf of the United States Government assumes any liability resulting from the use of the information contained in this document or warrants that such use will be free from privately owned rights. If trade names or manufacturers’ names are used in this report.

NE is the oxidative weak link in addition to polymers used in composite applications. From prior art. the endcap crosslinks through the double bond into a tough heat-resistant part. and prolong the lifetime of the material. benzocyclobutenes and biphenylenes. following imidization. For example. High-temperature polyimide matrix composites are used in the cooler parts of aircraft engines because of their high specific strength and lower density compared to metals. -1- LEW-17429-1 . Hence. thereby allowing flow and improving processability. the use temperature can be raised and/or lifetimes can be prolonged. This invention describes an improved processing protocol for a series of replacement endcaps that preserve the desired processability of NE. [Known examples are Cycap. for a recent review. allows the production of void-free composite parts. the new endcaps predominantly undergo crosslinking in an inert atmosphere. this crosslinked system subsequently air oxidizes and aromatizes in a controlled fashion to increase the long-term stability over that of the NE. However. It is this very endcap. NE is important to processability of high-temperature resins because it does not give off volatile byproducts during final cure and. that accounts for much of the weight loss in the polymer on aging in air at elevated temperatures. at elevated temperatures. A. Understanding this degradation provides clues for designing new endcaps to slow down degradation. crosslinks to form a stable network structure. Thus. see: M. 1998. NE serves to control molecular weight during oligomerization and. are generally capped at each end by a norbornenyl endcap which serves a double function: (1) it limits the average molecular weight of the polymer chains (oligomers). the endcap limits the use of PMR polyimides to lower temperature parts of the engine and/or shorter lifetimes. Thus. (2) Upon further treatment (curing). so important to processing. Section I  Description of the Problem A polyimide is a polymer composed of alternating units of diamine and dianhydride. Meador. linked to each other via imide bonds (Scheme 1). but most prominently by utilizing structures with more aromatic character. it limits the use of norbornene endcapped polyimide matrices to 315 °C use temperatures for lifetimes up to 1. acetylene terminated imides (ATI). therefore. Annual Reviews in Material Sciences. Researchers have tried to improve the stability by a variety of means.Better End-Cap Processing for Oxidation-Resistant Polyimides Brief Abstract New latent reactive endcaps are replacements for the norbornene-endcap (NE) utilized extensively in high-temperature polymers for composite applications. the poor thermo-oxidative stability of the endcap is a known problem. PMR polyimides. 28:599-630]. commonly used in the aerospace industry.000 hours. PEPA. V-cap.

2001] discusses the use of 1. Jones. crosslinking is the predominant. However. Meador. As a result. Path A oxidation products like 2 are cleavage products that are most likely formed concomitant with large amounts of weight loss in the polymer system. The present invention is a class of new endcaps of structure 7 shown. M. Path A degradation proceeds through initial scission and oxidative opening of the norbornyl ring to form a 2-hydroxy substituted maleimide 2. The prior art [M. which exclusively or primarily follow path B degradation.. In these structures.6-tetrahydrophthalic anhydride as the endcap are frangible and lack the desirable tensile strength. the endcap is a 1. Cycap). and result in less shrinkage and cracking in the oxidation layer. St. There can also be sizable increases in cost (e. Therefore. 22. Clair Polym. 3 and 4 and related secondary degradation products. P.744 Bl. the endcap is -2- LEW-17429-1 .B.6-Tetrahydrophthalic anhydride was considered as an endcap for polyimide adhesives [A. Section II  Technical Description The purpose of the present invention is to lower the amount of weight loss and the thermooxidative aging of PMR-polymers over their lifetime that results from the facile degradation of the nadic endcap. Tg are considerably lower).2001. 1982. US 6. Final Report . Eng. structures like 3 and 4 from path B are more oxidatively stable and form with very little weight loss. J. each modification results in changes in the nature of the crosslinking and undesirable changes in processability (e. pathway. 9-14] but the crosslinking temperature was too high (>415 °C). Unfortunately. Meador.3. Aug. and/or mechanical behavior (e.A.K. in Scheme 3. and A. the endcap contains no bridging methylene.2.699 Bl. Path B degradation proceeds through oxidation of the bridging methylene of the norbornene moieties followed by carbon monoxide extrusion. 1. and therefore does not give the same type of crosslinked structure.g. Oxygen-bridged analogues (X=O) of the norbornene endcap have been considered [E. V-cap and ATI both crosslink at a considerably lower temperature-during imidization-and cause early gelation). new endcap structures which more strongly favor path B degradation will lead to lower weight loss in addition polyimides. 16.L. this structure favors retro-Diels-Alder reaction over crosslinking through the double bond.3. St. and W. Under air the endcap subsequently aromatizes in competition with cross-linking — which is undesirable.g.2. Patent No.A. if not exclusive. Oct.6tetrahydrophthalic anhydrides as endcaps. A. Our previous work on the aging of PMR-15 revealed that the degradation of the nadic endcap can occur (as shown in Scheme 2) via two primary pathways. 1970].274. 14.A. Sci. Aromatization of the resulting biradical leads to substituted phthalimides.303. R. Burns. Rather.3.However.g.2. NASA CR-72633.. Patent No. under inert atmosphere. US 6. Following crosslinking. Primer. In contrast.6-tetrahydrophthalic anhydride that maintains its stability during imidization (200 °C). but is totally unaware that when crosslinking is carried out in air.3. it is accompanied by substantial amounts of aromatization. in the case of PEPA. Clair and T.2..B. Kendrick. composites made with 1.

as others have tried in the past. In addition. could substantially increase the lifetime and use temperatures of polymer matrix composites. trialkylsilyloxy etc. the payoff for developing polymer composites that can -3- LEW-17429-1 . Hence. This competition is undesirable since it leads to composites that are frangible and lack the desirable tensile strength. The replacement endcaps. As previously stated. In the present invention. The main advantage of preserving the same crosslinking scheme and physical properties as nadic while controlling the degradation is faster industry acceptance of the resulting new polymer as a matrix material for composites applications where higher use temperatures or longer lifetimes are desired. 4. In the present invention.3. we also carefully consider how the substitution affects initial crosslinking. under inert atmosphere. the aging endcap spontaneously aromatizes in air and is thereby converted to a thermally stable capping group. we carefully control the conditions under which crosslinking occurs. following imidization. carbomethoxy. crosslinking is the predominant. pathway.3-butadiene as shown in Scheme 3. Section III  Unique or Novel Features The unique feature of the present invention is not. when properly processed.2. this does not work because the nature of the crosslinking changes in ways that either hurt the processabilily or detrimentally change the mechanical properties of the resulting polymer. However. the endcaps are easily synthesized in one step from readily available. aryl. Examples of 7 are derivatives of 1. alkoxy. Ultimately. flouro. inexpensive starting materials. if not exclusive. 5 and/or 6position with groups like alkyl. Following crosslinking. allowing for use in engine parts such as inlets.spontaneously converted upon aging in air to a thermally stable capping group. chloro. crosslinking proceeds through the double bond the same as nadic. by differential scanning calorimetry. nitro. Tg and other physical properties are similar to polymers containing NE. Section IV  Potential Commercial Applications The commercial potential of this invention is quite high.6-tetrahydrophthalic anhydride variously substituted in the 3. giving an identical crosslink skeleton. Examples given have crosslinking exotherms. to design an endcap that will be inherently more stable than the nadic endcap. fan ducts and exit flaps for high-speed aircraft. In addition. Many of the above compounds can be easily derived from Diels-Alder reaction between maleic anhydride and the appropriately substituted or polysubstituted 2. similar to the nadic endcap. Rather the present invention controls the known degradation of the nadic endcap thermo-oxidative aging by designing derivatives that strongly favor degradation through path B — aromatization to more oxidatively stable substituted phthalimides — which occurs with very little weight loss. Under air. the endcap aromatizes in competition with cross-linking.

which is easily accomplished in an autoclave — no unconventional methods and or new equipment will be needed to utilize the invention. since the new endcaps preserve the desired processability as NE — with the minor variation of inert atmosphere for crossslinking. -4- LEW-17429-1 . In addition.operate in higher temperature environments is weight savings — 10-20% over the engine part made with conventional materials like titanium.

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