POSS STRUCTURE AND PROPERTY RELATIONSHIPS

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1 PSS STUCTUE AND PPETY ELATINSHIPS. Blaski, A. Bolf, M. Carr, K. Chaffee, E. Choe, A. Farris, F. Feher,. Gozales, D. Hilto, H. Jeo, P. Joes, A. Lee, J. Lelad, J. Lichteha,. Marshma, P. Mather, B. Moore, F. Nguye, Y. toari, H. viatt, S. Phillips, A. omo-uribe, P. uth, J. Schwab, E. Shockey,, Stapleto, S. Svejda, B. Viers, T. Walker, Timothy Haddad (voice) (fax)

2 Hybrid Iorgaic/rgaic Polymers U s e x i d a t i o Ceramics HYBID PPETIES SPACE Polymers Toughess, Lightweight & Ease of Processig Hybrid plastics ca bridge the barrier betwee ceramics ad polymers

3 PSS Macromers For Naocomposites H H H = Cl 3 Y cyclopetyl cyclohexyl cycloheptyl isobutyl Icorporated Y Fuctioalities Y Halides Alcohols Esters Bispheols Nitriles Amies Isocyaates Epoxides laes laols lylchlorides Styryls α-olefis Acrylics Norboreyls PSS-based macromers are ow available through either Gelest or Aldrich PSS techology is commercialized by Hybrid Plastics i Foutai Valley CA

4 PSS Polymer Icorporatio PSS Bead PSS Pedet PSS Crosslikig PSS Bledig ze & Shape

5 Structure-Property elatioships shape size solubility Cocerted esearch Effort: Maximizig property ehacemets through chages at the ao level Polymer miscibility vs. PSS/PSS iteractios

6 PSS laol Sythesis Cl 3 H 2 / Acetoe H Cl 3 1 H 2 / Acetoe H = clohexyl 2 H H = clohexyl clopetyl cloheptyl H Cl 3 Brow & Vogt: JACS, 1965, p Feher et al: JACS, 1989, p 1741; rgaometallics, 1991, p 2526

7 Bead ad Pedat PSS Architectures H H H H H Macromolecules, 1993, 26, 2141 J. Iorg. rgaomet. Polym., 1995, 5, 237 Chemistry of Materials, 1996, 8, m 4 Macromolecules, 1995, 28, 8435 Macromolecules, 1996, 29, 7302 J. Polym. Sci.,B. 1998, 36, 1857 Macromolecules, 1999, 32,

8 PSS BEAD CPLYMES Ph Ph Ph Ph PSS/Dimethylsiloxae PSS/Viylmethylsiloxae PSS/Tetrapheyldisiloxae Ph Ph Ph PSS/Dipheylsiloxae PSS/Allylpheylsiloxae PSS/ctamethyltetrasiloxae Ph PSS/Pheylmethylsiloxae PSS/Tetramethyldisiloxae PSS/ligodimethylsiloxae From the PSS-Diol a variety of bead copolymers have bee prepared

9 BEAD PLYME DSC ANALYSIS This DSC thermogram is typical for all of the PSS/loxae copolymers. Decompositio, which is idicated by the edothermic peak, begis at about 450 C. DSC shows o T g or T m. Ph 8 PSS/Pheylmethylsiloxae

10 TMA CHAACTEIZATIN Thermomechaical aalysis does reveal thermal trasitios i these copolymers. PSS/loxae copolymers with two or less siloxae uits betwee PSS groups softe i the decompositio temperature rage. The first heat reveals a complex thermal behavior. Ph 8 PSS/Pheylmethylsiloxae

11 TMA CHAACTEIZATIN The PSS/loxae copolymers with four or more - repeat uits i the siloxae segmet have softeig temperatures well below the decompositio temperatures PSS/ligodimethylsiloxae

12 DMA CHAACTEIZATIN The copolymers with low softeig temperatures ca also be molded ito bars for mechaical testig. Dyamic mechaical aalysis reveals a T g (64 C) ad the tail ed of a sub T g relaxatio (-20 C) PSS/ligodimethylsiloxae

13 Tg s F BEAD CPLYMES Glass Trasitio vs % loxae m Tg C % loxae

14 PSS Macromer Useful for Hydrosilatio I order to ivestigate siloxae polymers cotaiig pedet PSS macromers, we sythesized two allyl derivatives. It is the possible to icorporate these macromers ito a siloxae polymer cotaiig H bods via hydrosilatio. H H H Cl 3 3 NEt 3 / THF 3 HNEt 3 Cl 2a: = cyclohexyl 7a: = cyclohexyl This high yield reactio is virtually quatitative with isolated yields typically greater tha 95 %

15 PSS Hydrosilatio to a loxae Polymer H x y z y x x = 18.8 y = 9.3 7a: = cyclohexyl 7b: = cyclopetyl + Platium Catalyst = clohexyl z y x = 18.8 y + z = 9.3 z = # of PSS y = # of TMSallyl Wt % PSS = clopetyl z y 53 % % % % % % % A short chai poly(dimethyl-co-methylhydrido)siloxae copolymer is hydrosilated first with a PSS-allyl ad the the remaiig hydrides are redered iert with trimethylsilyl groups.

16 TMA of Pedet PSS-loxaes 0 Dimesio Chage (µm) Z = Z = 1.5 Z = 0, y = Z = 0, Y = Z = Temperature (ÞC) z y 18.8 z + y = 9.3

17 Space Fillig Model of a PSS Macromer = 5.4 Å Cp Cp = 15 Å = cyclopetyl

18 Coceptual Model for PSS Polymers

19 1 H NM Spectrum of a PSS Macromer -equitorial -axial -ipso = C 6 H PPM

20 29 NM Spectrum of a PSS Macromer -clopetyl -Styryl = C 5 H PPM

21 TGA Data for PSS-Styryl Polymers TGA WEIGHT (%) Mole % PSS 100 % 50 % 20 % 10 % 0 % x y Temp

22 DSC Data for PSS-Styryl Polymers 3 Heat Flow (W/g) Mole % PSS 50% 20 % 10% 0% x y Temp

23 TMA Plot PSS Polymers ( = clopetyl) x y Cp Cp Cp Cp Cp Cp Cp

24 TMA Plot PSS Polymers ( = clohexyl) x y

25 TMA Compariso for 2 PSS Copolymers = clohexyl = clopetyl Total TMA Dimesio Chage 3.5 mm Temp

26 TMA Plot Compariso For PSS-Styryl ad PSS-EthylStyryl Polymers ( = clohexyl ad clopetyl)

27 heology of a 16 Mole % PSS Polymer G'' (rad/s) w a T (rad/s) Cp Cp Cp Cp Cp Cp Cp = C 5 H 9 Tg = 126 C Tg = 199 C M = 42 K Dp = 160

28 heology of a 8 Mole % PSS Polymer Glassy egio ubbery egio G', G'' (Pa) w a T (rad/s) = C 6 H 11 Tg = 136 C M = 72 K Dp = 360

29 PSS Norboreyl Sythesis H H H 2a,b Cl 3 (EthylNorboreyl) 3 NEt 3-3 HNEt 3 Cl a: = cyclohexyl b: = cyclopetyl 6a,b This high yield reactio is virtually quatitative ad isolated yields are typically aroud 95 %. The orboreeylethyl trichlorosilae ca be sythesized from HCl 3 ad viylorboree

30 Polymerizatio of PSS Norborees x y 6a,b MP with Mo Catalysts a: = cyclohexyl b: = cyclopetyl Both block ad radom copolymers were sythesized. The wt. % PSS was varied from 0 to 50 wt. % PSS. A ideal polymerizatio would yield polymers with 500 moomer uits. 0 wt % PSS, 0 mole % PSS: x = 500, y = 0 10 wt % PSS, 1 mole % PSS: x = 495, y = 5 50 wt % PSS, 8 mole % PSS: x = 460, y = 40 7a,b

31 DSC Data for Block Copolymers Heat Flow (mw) Norb(0-50)-block 0% 10% 20% 30% 40% 50% Whe orboree ad PSS-orboree are sequetially polymerized to form block copolymers oly a sigle Tg is observed from the orboree block. The PSS orboree block does ot give rise to ay trasitio up to 350 C that ca be observed by DSC. Homo polymers of PSSstyryls ad acrylates show the same behavior Temp

32 DSC Data for adom Copolymers Norb(0-50)-radom 3 Heat Flow (mw) % 10% 20% 30% 40% Whe orboree ad PSSorboree are copolymerized radomly, a material is obtaied with a sigle Tg. This glass trasitio icreases with icreasig PSS cotet. This effect is stroger tha that observed for PSS-styryls but ot as large as see i PSSacrylics % Temp

33 Storage Modulus ad Loss Taget clohexyl elaxatio: 14.7 kcal/mol 10 9 (Pa) % 40% 30% 20% 10% 0% Temperature (ÞC) Temperature (ÞC) 50% 40% 30% 20% 10% 0% x y No Maximum for 50% PSS Various Wt % clohexyl PSS Polyorboree adom Copolymers

34 Glass Trasitio Temperature Variatio PSS-Tg CpPSS-Tg Weight Percet PSS

Naodstructure (Diameter ~ 6m) clohexylpss-rich domais

35 TEM of adom PSS Norborees 50PSS/PN 50CpPSS/PN Coarse lider Naostructure (Diameter ~ 12m) Fie lider Naodstructure (Diameter ~ 6m) clohexylpss-rich domais may etrai more uorieted polyorboree chais tha clopetylpss-rich domais.

36 TEM of Diblock PSS Norborees 10wt % of CpPSS 30wt% of CpPSS 60wt% of CpPSS 10wt% of PSS 30wt % of PSS 60wt% of PSS

37 Sythesis of PSS Kaptos NH 2 H 2 N NH 2 H 2 N H N H N H N H H H N H H + + N N N N m

39 DMTA of PSS Kaptos

40 New PSS Moomers H H H NEt 3 H 'Cl 3 ' 2 Cl 3 NEt 3 NEt 3 ' ' 2 Poor Solubility Excellet Solubility clodehydratio leads to very soluble moomer Fuctioalizatio readily forms soluble PSS macromers

isobutyl-pss Moomers 100 60 50 40 30 20 10 0 = isobutyl

41 isobutyl-pss Moomers = isobutyl Weight % PSS with orboree isobutylpss-norboree dissolves orboree!!!

42 Summary The successful icorporatio of ao-sized iorgaic clusters (PSS) ito a wide variety of polymers has bee demostrated. These PSS clusters have a remarkable effect o the thermal trasitios ad mechaical properties of the polymers they are copolymerized ito. The PSS effect o the properties of aalogous polymers shows a depedecy o the type of alkyl group o the PSS cluster. TEM images of both radomly ad diblock copolymerized polymers illustrate this depedecy, as the size of the PSS domais are alkylgroup depedet. TEM images also illustrate that withi the polymer matrix, the PSS cages ted to associate with themselves.

POSS Lubricants and Blends

POSS Lubricants and Blends PSS Lubricants and Blends usty L. Blanski, Shawn H. Phillips, Joe Lichtenhan, Joe Schwab, Andre Lee, Justin Leland, and Patrick uth AFL/PSM 10 E. Saturn Blvd. Edwards AFB CA 93524 661-525-5391 Edwards