Entwicklung und Anwendung von Polymer -Nanokompositmaterialien

Transkript

1 . In te rdiszi pli när. In te gral. Inno vativ. Entwicklung und Anwendung von Polymer-Nanokompositmaterialien Surfaces and Interfaces - Engineering at the Nanoscale GV/DEHEMA, Frankfurt, 09. März 2005 Ihr Partner für Projekte in der chemischen und pharmazeutischen Industrie Gliederung Nanotechnologie bei Bayer Technology Services Einführung Technologieplattform Beispiele zu F&E-Aktivitäten im Gebiet der Nanokomposite bei Bayer arbon Nanotubes arbosilan-vernetzer Ausgewählte Polymer-Nanokompositmaterialien von Bayer MaterialScience Dispercoll S Bayblend 1

2 Strategische Management-Holding Holding Bayer AG Konzernvorstand orporate enter Arbeitsgebiete Servicegebiete Bayer Healthare Bayer ropscience Bayer MaterialScience 1 Bayer hemicals 1 Bayer Business Services Bayer Technology Services Bayer Industry Services Lanxess 1 D040 3A 1 Vorstand und Aufsichtsrat der Bayer AG haben beschlossen, die hemieaktivitäten (mit Ausnahme von Wolff Walsrode und H.. Starck) sowie Teile des Polymergesc hä fts bis Anfang unter einem gemeinsamen Dach und unter dem Namen Lanxess an die Börse zu bringen. Stand: Bayer innovation fields: Science for a better life Nucleic acid diagnostics / personalized medicine Health are Innovative drugs Medical technology Therapeutic proteins rop Science Material Science Intelligent materials Industrial biotechnology / nutrition New energies Functional surfaces (e.g. nano-applications) 2

3 Nanotechnology areas at Bayer: Science for a better Life Nanoparticles/nanoadditives/ nanocomposites e.g. Bayblend FR with nano additives to improve flame retardancy 200 nm Functionalized coatings and surfaces e.g. Surfacemodified plastics: scratch resistance, UV protection, self-cleaning surfaces, etc. Nanoelectronics Nanobiotechnology e.g. Nanostructured surfaces for tantalum capacitor materials e.g. Nanophosphors for diagnostics Nanoencapsulation/ Drug delivery 10 0 nm ~ 7 nm DNA BTS Technology platforms Processing a talysis Synthesis Biotechnology Product De sign Bayer Technology Services Process Synthesis In silico- Technology Process Management Technology Na notechnology Nanotechnology 3

4 BTS Nanotechnology platform Interdisciplinary Technology for Material Science and Life Science Synthesis Recovery and purification Modification and processing Applications development Precipitation, crystallization, pyrolysis Scale-up, technical process (Re-)dispersion Deagglomeration Phase transfer Drying Separation Purification olloidal and chemical stabilization ompounding Dispersing haracterization Bionanotechnology (biochips, medical diagnostic assays) Nanocomposites New developments: nanocomposites Material Science: Polymer / Nanoparticle omposites Supercapacitors, electrodes for highperformance batteries Fiber-reinforced components e.g. on the basis of carbon nanotubes: hybrids with outstanding mechanical, electrical and physico-chemical properties Development of a process for the inexpensive manufacture of carbon nanotubes for mass applications Tires with low roll resistance omponents for electrostatic coati ng : 1 B028202RE nm 200 nm 4

5 B096501RE Low-ost Production of Multi-Walled arbon Nanotubes (MWNT) BTS Multi-Walled arbon Nanotubes (MWNT), diameter 5-50 nm, mean diameter approx nm compared to ideal SWNT higher number of defects but higher aspect ratio and easier processing already employed in polymer composite materials, mainly for enhancing the conductivity functionalization possible Main restraints for broad commercialization pricing and large scale availabity quality and reproducibility Development of a process for large scale NTproduction and polymer processing : 1 4 µm 20 n m 20 n m 25 n m 1µm BTS BTS Bayer process development for NT synthesis and polymers processing baytubes He l lfeldabbildung hydrocarbons, inert gas catalyst highly highly efficient process for for MWNT production melt impregnation in situ polymeri zation impregnation in solution H 2, inert gas, small amounts of hydrocarbons agglomerates of NT (> 98% -purity) optional high purification disentangling surface modification and chemical functionalization 5

6 NT Processing in various polymers Dispersion in-situ polymerization melt impregnation impregnation in solution 0,05 wt.-% NT 0,01 wt.-% NT omplete dispersion of MWNTs from their initial agglomerates achieved via intense mixing in e.g. a twin-screw extruder : nm NT in different polymers 20 0 nm 20 0 nm arbosilane cross-linkers for coating applications 6

7 ommercial (organo-) silanes I tetraalkoxysilanes for inorganic networks Me Me Me Me Tetr amethox ysi lane Et Et Et Et Tetr aethoxys il ane - high cross-linking density - high weight loss (~ 72 %) - complete condensation > only applicable for thin layers < 1 µm ommercial (organo-) silanes II non-functionalized organosilanes for organically modified inorganic networks Me Me M e Methyltrimethoxysilane Me Me M e Phenyltrimethoxysilane Me Me Me ctyltrimethoxysilane - reduced cross-linking density - reduced weight loss - preparation of thick layers possible 7

8 ommercial (organo-) silanes III functional organosilanes for organic-inorganic networks Me Me M e NH 2 Me Me Me SH Me Me Me N 3-Amino... 3-Mercapto... (3-Isocyanatopropyl-)Trimethoxysilane Me Me Me Me Me Me (3-Glycidyloxypropyl-)Trimethoxysilane (3-Methacr yloxypropyl-) Trimethoxysilane arbosilane cross-linkers requirements for new sol-gel precusor molecules flexible segments for modifying the inorganic network organic, non uv-absorbing groups but: simultaneously hard segments -- precondensed groups high functionality (high amount of -- forming groups) commercially available raw materials for production 8

9 arbosilane cross-linkers New polyfunctional sol-gel precursors D4-Diethoxide D4-lanol Et Et Et Et H H Et Et Et Et H H arbosilane cross-linkers ondensation product from sol-gel precursors Et Et Et Et Et Et Et Et H 3 Et Et Et Et Et n Et Et Et Et Et Et Et chemically integrated organic group, inorganic cross-linking mechanism, photochemically stable, no hazardous material 9

10 arbosilane cross-linkers - summary novel uv-stable sol-gel precursors could be synthesized coatings based on those novel precursors led to excellent weathering stability high scratch resistancy highly improved solvent and acid resistancy potential applications are seen as automotive clear coats hard coats for plastics anti-graffiti coatings biocide free fouling release coatings M e Et Et Et Et Me Me Me Me Me M e Et Et Me Et Et Polychloroprene dispersions with nanoparticle silica sol 10

11 Dispercoll + Dispercoll S Polychloroprene (R) dispersions Rapidly growing in areas such as foam to foam bonding countertop lamination insole bonding Adhesive performace similar to solvent-borne adhesives How can the 1K-properties be further improved? Development of the Dispercoll S product line for compounding with Dispercoll Dispercoll + Dispercoll S Modification of adhesive raw materials with nanoparticles Technical requirements for adhesives easier processi bi lity better adhesion options for further formulations high bonding strength Modification with nanoscale 2 New application fields for adhesives replacement of solvent based systems new chances for R- and PU-based systems Health, safety, environment working place hygiene environment protection safety for the user Focus on solvent free technologies 11

12 Production of amorphous nanoscaled silica Monomer and polymer silicic acid after kation exchange of waterglass particle condensation gelation nucleation 5 nm 10 nm particle increase, al kaline 3d - network 30 nm H H sol particle conditioning Dispercoll S nanoparticle silica sol Na + Na + H amorphous silica with surface silanol groups Na + ( - ) ( - ) 2 ( - ) ( - ) H H Na + alkaline stabilized particle size nm 12

13 Dispercoll S XP XP 5005 Dispercoll S Dispercoll S Dispercoll S XP XP 4510 Dispercoll S range of nano-thickeners XP XP available gradesxp 3030 Dispercoll + Dispercoll S TEM micrograph of a Dispercoll particle / Dispercoll S particle dispersion R latex particle Dispercoll S : nm 13

14 Dispercoll + Dispercoll S Rheology Viscosity [mpas] Recipe solids (%) pbw Dispercoll antioxidant 20 2 Dispercoll S metal oxide dispersion Shear rate [1/s] Dispercoll S acts as a shear thinning thickener Dispercoll + Dispercoll S Initial peel strength (wet bonding) on leather 1,4 1,2 (drying at RT, pressure 4 bar/10 s) adhesive based on Dispercoll [N/mm] 1 0,8 0,6 0,4 0,2 with resin 1* with resin 2 * with Dispercoll S pen time after application of adhesive [min.] *Terpene-phenole resin Dispercoll S improves the initial peel strength 14

15 Dispercoll + Dispercoll S Softening point (SBR rubber) Temperature [ ] resin* (Stand ard ) Dispercoll S larger particles Dispercoll S smaller particles Dispercoll S improves the softening point of Dispercoll formulations *Terpene-phenole resin Dispercoll + Dispercoll S Improvement of softening point with Dispercoll Dispercoll Dispercoll S l H l H H H H H-functionality: 1-2% Nanoparticle silica sol Network 15

16 Dispercoll + Dispercoll S Summary lica sol improves R dispersion adhesives rheology: viscosity regulation allows short production cycles due to higher initial wet-bonding strength higher heat resistance and thermal stability of the bonding (patented by Bayer MaterialScience) Bayblend FR: Eco sets the Market Trend Unique Market Position: Bayblend FR combines very safe flame retardancy, excellent mechanical properties and compliance with the most important eco labels 16

17 Bayblend FR is made of... Transmission Electron Micrograph, TEM (sample stained with s 4 ) Polycarbonate Heat distortion temperature Ductility Inherent flame resistance SAN* Good flowability *) Styrene / Acry lonitrile opolymer ABS* Toughness *) Acrylonitrile Butadiene Styrene Graft copolymer hemical resistance 2µm rganophosphate Flame retardancy Flowability Additives Teflon for antidripping Thermal stabilizer Nanoparticles in Bayblend FR Transmission Electron Micrograph (TEM) (sample not stained) Polycarbonate Nanoparticles ABS Specific inorganic nanoparticles are highly dispersable and help to improve nm 17

18 ... flame retardancy xygen Thermal Feedback Burning Gases Decomposition Zone Heat Smoke har formation P-ABS / Phosphate / nanoparticles Nanoparticles help to catalyze char formation at the surface Typical desired characteristics of polymer nanocomposites mechanical properties scratch resistance resistance towards chemicals flame retardancy hydrophobicity / hydrophilicity gas barrier properties / permeation UV-/ IR absorption properties... the original polymer properties, e.g. transparency, should not be affected by the additional component(s) 18

19 Preparation of polymer nanocomposites: Engineering at the nanoscale Synthesis Producer or supplier of nanoparticles agglomerates as powders, eventually surface modified well dispersed nanoparticles as suspension in solvent, eventually surface modified Adaptation of particle surfaces, general questions Shielding of adhesion forces? Deagglomeration of nanoparticles? Physical compatibility with polymer? Bonding behavior with polymer matrix? How to suppress reactivity or catalytic activity (including photocatalytic behavior in final composite) of particles towards polymer melt? How to avoid agglomeration during modification? How to obtain a thermally stable surface modification? Application Polymer producer Polymer synthesis Expertise in compounding System expertise and market knowledge (polymer) Summary and onclusion Increasing interest in nanotechnology for new and better products with higher value; polymer nanocomposites important class of materials Possible strategies: i) building up organic/inorganic networks, ii) combining different networks, iii) combining particles and polymers Value-added chain of nanomaterials: Know-how: Synthesis: Processing: hemistry Physics Analytics Materials Science Biology omputer Science NAN- MATERIALS Lacquers Emulsions Dispersions Plastics Foils End product: Automotive industry Films UV- protection Displays 19

20 Acknowledgements Dr. Herbert Blankenheim Dr. Steffen Hofacker Dr. Harald Pielartzik Dr. Martin Vollmer Dr. Eckard Wenz Dr. Matthias Voetz Dr. Arno Nennemann Dr. gurd Buchholz. Interdiszi pli när. Integral. Innovativ. Kontakt: Dr. hristoph Schild Bayer Technology Services GmbH Physics and hemistry of Interfaces Leverkusen, Gebäude E 41 Tel.: LEV FAX: LEV hristoph.schild@bayertechnology.com Ihr Partner für Projekte in der chemischen und pharmazeutischen Industrie 20