NEW DEVELOPMENTS IN CATALYSIS

Transcription

1 You are now at HOME NEWS PUBLICATIONS LECTURES PATENTS DOWNLOADS NEW DEVELOPMENTS IN CATALYSIS Werner J. Blank King Industries Inc. Science Road Norwalk, CT USA

2 MARKET PLACE DRIVING FACTORS ENVIRONMENTAL REGULATIONS SAFETY- HEALTH ENERGY DELAYING FACTORS REGULATIONS FRAGMENTATION OF MARKETS UNCERTAINTY IN MARKET PLACE

3 COATING TECHNOLOGIES HIGH SOLIDS - SOLVENT FREE VISCOSITY/SOLIDS & POTLIFE/DRY TIME WATERBORNE COSOLVENT, APPLICATION CONDITIONS DRY-TIME ELECTROCOATING PRODUCTION VOLUME, SUBSTRATE CURE TEMPERATURE UV/EB COATING COMPLEX OBJECTS, PIGMENTS POWDER COATING LOW FILM THICKNESS, CURE TEMPERATURE FLOW AND LEVELING

4 CONDENSATION REACTIONS Amino resins, melamine, urea formaldehyde Blocked isocyanate Silane, siloxane FORMALDEHYDE, ALCOHOL, WATER KETOXIME, PYRAZOL, ALCOHOL ALCOHOL Hydroxyethyl amide -carboxyl WATER Methylol amide, glycoluril, cyclic urea WATER Hydroxyl-carboxyl WATER

5 Ring Opening and Addition Reaction Isocyanate, Uretdione, Carbodiimide Cyclic acylurea Epoxy, Glycidyl, Cycloaliphatic, Oxetane Cyclic Carbonate 2-Oxazoline Aziridine Michael Addition Azlactone

6 CATALYST NEEDS ISOCYANATE WATERBORNE 2K BLOCKED ISOCYANATE URETDIONE EPOXY POTLIFE-REACTIVITY WATER REACTION CURE TEMPERATURE Yellowing, Reactivity HYBRID SYSTEMS MELAMINE BLOCKED ISOCYANATE ISOCYANATE SILOXANE

7 CATALYSTS FOR ISOCYANATE SYSTEMS REQUIREMENTS ORGANOTIN FREE CATALYSE NCO OH POTLIFE REACTIVITY NO SIDE REACTION WATER REACTION WATER REACTION EXTERIOR DURABILITY

8 SCREENING OF CATALYSTS APPLICATION TESTS FORMULATION POTLIFE (2X VISC.) GEL TIME TACK FREE DRY-THROUGH MODEL SYSTEMS (ANALYTICAL) DISAPPEARANCE OF NCO FORMATION OF URETHANE / UREA MW

9 1A H 2A Catalyst for NCO Not a Catalyst 3A 4A 5A 6A 7A Li Be B C N O F Ne Na Mg Al Si P S Cl Ar 3 3B 4B 5B 6B 7B B K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn Fr Ra Ac Rf Db Sg Bh Hs Mt Periodic Table B 2B 8A He 6 Lanthanid es 7 Actinides Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr

10 Isocyanate Peak Decay Abs Wavenumber Time (sec)

11 FUNCTIONAL GROUPS USED n-butanol Isobutanol 2-Butanol OH OH OH 1 2-Butoxyethanol HE Ester HE Carbamate TPM O R O O O OH R OH N H O O O OH OH

12 CATALYSTS USED Dibutyltin dilaurate Zr dionate complex Bi 2-ethylhexanoate Zn 2-ethylhexanoate DBTDL Zr Chelate Bi Carboxyl Zn Carboxyl Reaction conditions Solvent Xylene Isocyanate HDI trimer Isocyanate concentration, mol/l 1.12 NCO/OH 1/1 Temperature, C 20

13 HDI-TRIMER DBTDL % Sn n-butanol Isobutanol 2-Butanol 2-Butoxyethanol1 HE Ester HE Carbamate TPM HALF LIFE, Sec.

14 HDI-TRIMER Zr Chelate % Zr n-butanol Isobutanol 2-Butanol 2-Butoxyethanol1 HE Ester HE Carbamate TPM HALF LIFE, Sec.

15 HDI-TRIMER Bi Carboxyl 0.14 % Bi n-butanol Isobutanol 2-Butanol 2-Butoxyethanol1 HE Ester HE Carbamate TPM HALF LIFE, Sec.

16 HDI-TRIMER Zn Carboxyl 0.27 % Zn n-butanol Isobutanol 2-Butanol 2-Butoxyethanol1 HE Ester HE Carbamate TPM HALF LIFE, Sec.

17 ZIRCONIUM CHELATE CATALYSIS +ROH (AcAc) Zr (AcAc) Zr 4 4 -ROH (fast) 0 R H +AcAc (slow) -AcAc (AcAc) Zr-OR 3 SL2203

18 ZIRCONIUM CHELATE CATALYSIS ROH O R NH-C-OR (AcAc) Zr-OR 3 3 O (AcAc) Zr-N-C-OR R R -NCO (AcAc) Zr-OR 3 R N=C=O SL2204

19 HYDROLYSIS OF Zr CHELATE Zr(AcAc) + H O (AcAc) ZrOH+AcAc (AcAc) ZrOH (AcAc) ZrOZr(AcAc) SL2205

20 [Bi 2 (CH 4 H 8 O 3 H) 3 (CH 4 H 8 O 3 H 2 )] )] 3+

21 Bismuth Catalysis Bi(L) X + R OH Bi(L) X-1 -OR + LH Bi(L) X-1 -OR + RNCO RNCOOR Bi(L) X-1 + LH + R OH Bi(L) X + RNHCOOR Bi(L) X-1 -OR + RNHCOOR

22 REACTION OF BLOCKED ISOCYANATE RNHCOO-BL RNCO + R OH k 1 k -1 k 2 k -2 RNCO + H-BL RNHCO-OR RNHCO-BL +R OH k 3 k -3 RNHCO-OR +HBL

23 CATALYST DEACTIVATION Me (L) x + H 2 O MeO (OH) + xl k 1 k -1 CATALYST REACTIVATION

24 POLYMERIC MDI BLOCKED Catalyst 0.25 % Me CATALYST C18 sarcosine C36 acid Isostearate Ethylhexanoate DBTDL No catalyst Bi MEK RUBS Temperature, C

25 BLOCKING AGENTS - CATALYSTS Malonate Uretdione Alcohol Phenol Caprolactam Dimethylpyrazole Ketoxime DBTDL Bi, DBN, DBU, DBTDL, Zn Bi, Co, DBTDL, Zn Bi, Ca, Cr, Mn, DBTDL, Zn Bi, Co, DBTDL, Zn Bi, Ca, Co, DBTDL, Zn Bi, Ca, Co, DBTDL, Zn CURE TEMPERATURE, C

26 AUTOMOTIVE CLEARCOATS Crosslinker Melamine-formaldehyde Isocyanate Siloxane Weakness Acid etch Scratch Cost MF BI Si

27 HYBRID CROSSLINKING Melamine RSO 3 H/A R-PO 4 A Zn-CH Bl. Isocyanate DBTDL R-PO 4 A RSO 3 R DBTDL Al-Ch Bi-Carb Siloxane

28 ACKNOWLEDGEMENT Alex He John Florio Dan Miller Marie Picci Ram Subrayan