400D-A NITRO-STRIILIZED PROTON ABSTRACTION DOPED mooel P COMPO4UDS RS PRECURSORS T.. (U) PENINSYLYRNIN STATE UWHY UNIVERSITY PARK DEPT OF

Transcription

1 400D-A NITRO-STRIILIZED PROTON ABSTRACTION DOPED mooel P COMPO4UDS RS PRECURSORS T.. (U) PENINSYLYRNIN STATE UWHY UNIVERSITY PARK DEPT OF MATERIRLS SCI.. UNCLASSIFIED S L HILKER ET AL. 01 AUG 97 TR-4 F/G 71'6 NL

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3 OFFICE OF NAVAL RESEARCH Contract N K-0899 a In MV 00 R&T Code 1513A:DHP Technical Report No. 4 Nitro-Stabilized Proton Abstraction Doped Model Compounds As Precursors To Conducting Polymers by Brian L. Hilker, John A. Hancock, Lawrence F. Hancock and Bernard Gordon III DTIC ELECTE Prepared for Publication S % 2 1 W, IAU in the ACS Division of Polymer Chemistry, Polymer Preprints Penn State University Polymer Science Section Materials Science and Engineering Department University Park, PA August 1, 1987 Reproduction in whole or part is permitted for any purpose of the United States Government This document has been approved for public release and sale; its distribution is unlimited. *

4 Unclassified SECURITY CLASSIFICATION OF THIS PAGE REPORT DOCUMENTATION PAGE Ia. REPORT SECURITY CLASSIFICATION lb. RESTRICTIVE MARKINGS Unclassified NONE 2a. SECURITY CLASSIFICATION AUTHORITY 3. DISTRIBUTION I AVAILABILITY OF REPORT 2b. DECLASSIFICATION IDOWNGRADING SCHEDULE Approach for public release; Distribution unlimited 4. PERFORMING ORGANIZATION REPORT NUMBER(S) S. MONITORING ORGANIZATION REPORT NUMBER(S) Technical Report Number: 4 5a. NAME OF PERFORMING ORGANIZATION 6b. OFFICE SYMBOL 7a. NAME OF MONITORING ORGANIZATION The Pennsylvania State (if applicable) OFFICE OF NAVAL RESEARCH University I 6c. ADDRESS (City, State, and ZIPCode) 7b. ADDRESS (City, State, and ZIP Code) University Park, PA Arlington, VA Ga. NAME OF FUNQING/SPONSORING 8b. OFFICE SYMBOL 9. PROCUREMENT INSTRUMENT IDENTIFICATION NUMBER ORGANIZATION (It applicable) OFFICE OF NAVAL RESEARCH O1_ NOOO14-85-K c. ADDRESS (City, State, and ZIP Code) 10 SOURCE OF FUNDING NUMBERS PROGRAM PROJECT TASK WORK UNIT ELEMENT NO. NO. NO. ACCESSION NO I1. TITLE (Include Security Classification) Nitro-Stabilized Proton Abstraction Doped Model Compounds as Precursors to Conducting Polymers (unclassified) 12. PERSONAL AUTHOR(S) B. L. Hilker, J. A. Hancock, L. F. Hancock and B. Gordon TTT 13a. TYPE OF REPORT 13b. TIME COVERED 14. DATE OF REPORT (Year, Month, Oay) 15. PAGE COUNT FROM TO /l/ SUPPLEMENTARY NOTATION 17. COSATI CODES 18. SUBJECT TERMS (Continue on reverse if necessary and identify by block number) FIELD GROUP SUB-GROUP Conductive Polymers Electronic Stabilization \ 19. ABSTRACT (Continue on reverse if necessary and identify by block number) NITRO-STABILIZED PROTON ABSTRACTION DOPED MODEL COMPOUNDS AS PRECURSORS TO CONDUCTING POLYMERS.,Departie-nt of Materials Science and Engineering, Polymer Science Program, Penn State. quite attention recently, but a few traditional need for toxic dopants, material intractabilities, and poor environmental and oxidative stabilities still exist that severely plague the field. Although most work on solving these problems has been based on electron transfer as a "doping" mechanism, we have defined a new mechanism based on Proton Abstraction Dopind (PAD), which has eliminated many of the above problems but has created several of its own. Our previous work has centered on abstraction of doubly benzylic and/or allylic protons with strong base, but both the use of strong base and the resulting reactive anion make this a difficult system to handle in the air. Preliminary results show that the incorporation of electron withdrawing nitro groups into these materials seems to overeolft rhia Drnht-m A11"haligh _tln.- Ir, Ja 1 IP "' the... - PAR (GEN Ae, MO, H10 A onducting polymers have problems such as the a 20. DISTRIBUTION " I AVAILABILITY OF ABSTRAC ABSTRACT SECU-R-TY CLAS*SFICATION "UNCLASSFIEO/UNLIMITEO 03 SAME AS T11. -OrTIC USERS Unclasstfi d 22a NAME OF RESPONSIBLE INDIVIDUAL 22b TELEPHONE (Include Area Code) 22c. OFFICE SYMIBOL Dr. Kenneth J. Wynne \( &10 ONR DO FORM 1473, 84 MAR 83 APR edition may be used unti exhausted. SECURITY CLASSIFICATION OF THIS PAGF All other edition% are obsolete.

5 nitro stabilized conductive anions offer much promise in overcoming many of the traditional problems plaguing the conductive polymer field. Acc sio~i Fo NTIS, CRA JUSI'l y--- A j. 4 ' *

6 NITRO-STABILZE PROTON4 ABSTRACTION DOPED We decided to examine thewe low molecular weight model MODEL COMPOUNDS AS PRECU.RSORS compounds since early work in our laboratory showed reasonable TO CONDUCTING POLYMERS conductivities with such materials. Since these low molecular weight species are easier to prepare, purify, and characterize than their high B. L Hilker. J. A. Hancock, L F. Hancock, and B. Gordon III molecular weight polymeric analogs, they make an ideal choice for Department of Materials Science and Engineering conductivity studies. Polymner ScienceProgram Pann Silo The model compounds in this work have all been produced via Lermess method of condensation of active hydrogens with aldehydes University Park, PA using ani ethylenedlunine catalyst. *VNCH!!. PhCHO Conducting polymers have poawe quite a bit of attention recently Usng2H2 this baicgonoi a rdcdf o (IadhVe)n with potential future end uses in lightweight batteries, electromagnetic UsnIhsbss opud( a rdcdfo ntroehne and ~itrence shieling. antistatic dvics and varius space apiations. bu nitropropane. compound (Ill) fromn 2-phenyl-l-irehn n afewpolensstilexisithatseveypliguiethefild. Tradlitionally.thete benzaldehyde, and compound (V) from 1-3-dinitropropane and problems include the need for toxic dopaes. due material invactabillities tha benzaldehyde. All were purified by either high pressure liquid hinder processing, and poor enviroinmental andl oxidative stblitis Mos chromatographty or vacuum distillation directly prior to doping via PAD. wokonslingte rolm ane basedi on electron muse a"oig The same preparation. purification, and charceiz~ation benefits are work on soing o uroory en ave dfndanwmcaimbdan seen with the anion PAD-produced species. They are prepared using a Proawn Abstraction Doping (PADI which has eliminated many of the rltvl ekbnptsimtnbtxd ssonblw above polers but has cre- - several of its own. Our previous work has %CH centeredf on abstrutllon of doubly bensylic &diii allylic pratons with strong JCCI base, but boith e ses of strang base and the resulting reative anion make this a difficult system to hande in the at. (TV2 This paper will outline one phase of our currant work in maing 01 nitro-stabilized PAD conducting model compoundis and other moieties for Preliminary conductivity tests show steady reasding~s of about 10-7 later inporation into polymers in orde t alleviate th abv rbes (cm Q)- 1 I in air for anion salt (VI). Mwe meaurements were constant over The PAD tchnique of removing protons froma doubly benzylic ani xsllyic each of the fiv days tested Longer dim-scale tests will be fun with results sites to obtain condtictive anins has shown promise in our laboratory. 2 it to follow. Although these conductivities are a few orders of magnitude also helps overcome the need for highly toxic dopants and even maeil lower than previous readinp we have taken, they offer much promise. The intractability problems before doping. Firs, a base is used to absa a lower readings are attributed to a "localited" anionic species nature that does pook toforma cndutinganin intea ofusin a ale eduingnot allow for the aromatic ring to be delocalized into the pi network. Future protn t fom aconuctng nio intea fusig atoxc rducngrm. efforts will examnine means of forcing the aromatic ring into the stabilized, Second, the precursor (i.e. 1) contains; an isolated methylene in each repeat dlclzd odcie noi ewr n hudtu aehge unit that is free to roat thus making the polymer soluble whereas the deoi.conductiv ii aronose e. w e r aend befoe. ths wthae her tnoariton to oally-conjud prcrspdpecursors tmoaml atm An thrd inntas I into a polymer backbone or attached to a polymer as a pendant inkomalo to totaly-conjubled. rcros ADpeusr side group to produce astabilized conductive polymeric system. likely~~~~~ tbe xdtvl )ob In conclusion, this work has shown that PAD is one good & Iallt, alternative methodl to die oft-problemnatic current methods of producing stable, conveniently-useful conductive polymers. The PAD technique eliminates the need for highly toxic dopants andl uses materials that are lest M intractable before doping, but produces a few problem of its own such as Another benefit of this propored investigation lies in trying to materriatl stability in air. With the incorporation of electron withdrawing inicres envifrnmental and oxidaotive stabilities of these model compounds. groups such as nitro groups into these materials, this problem seems to be Since nitro groups (anid other electron withdrawing groups) withdraw overcome a evidenced by the five-day constant conductivity finding. The electron density from the proposed anions (much as VI). these materials are cutrent preliminary reslts show that much work is still necessary, but PAD less likely toreact with puetc and electropilic species in the etnvironmenit nitro stabilized conductive anion offer much promise in overcoming many than nonsiabilised equivalents. Resting this, materials like (111), (IV). of the traditional problems plaguing the conductive polymer field. and (Y) have quite lowered Ias relative to equivalent materials without electron withdrawing groups. [Also a kinetic argument of Finkel'stein 3 ACKNOWLEDGEMENT: 'The support of the Office Of Naval Research i seem so show that these nitro materials may have increased oxidative gritefully acknowledged. stabilities for similar reasona.i Compound (111) has an estimated pi~a of about 19 based on a simple extrapolation method sing standard pka REFERENCES table. By this method, the Ia of compound (IV) is estimated to be B. Gordon Ill and L F. Hancock. Polyns. Prep. 26(1), andl that of compoundl (V) about 14. (1985). 2 L F Hancock.. "Studies in Conducting Polymers: Oxidation of Polyacetylene. Proto Abstraction Polymers" (Masters: thesis. The 2 Pennsylvania State University, 1986), p E. 1. Fankelatein, S. M. Doloro, andl E. 1. Kozlov, Zhurnal C1y1aO2 (Cyy<3 Organkheskol Khi. 14(3) (1973).A 0 1Y J.Marc, A~wcjD~uL~bmj=3rd Ed. (New York: John 00 N2 140 Wiley and Sons, 1995), pp. 22D-222. (TV)0. M.O.M er, Journal1 of Applied Chemistry of USSR, (19"11).

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