Polymer Fundamentals for Coatings. Werner J. Blank

Transcription

1 You are now at HOME NEWS PUBLICATIONS LECTURES PATENTS DOWNLOADS Polymer Fundamentals for Coatings Werner J. Blank King Industries Inc Science Road Norwalk, CT

2 7000 RESIN CONSUMPTION % SPECIAL MM lbs % ARCHIT OEM Year SL2375

3 COATING FORMULATIONS POWDER SYSTEM UV CURE WATERBORNE HIGH SOLIDS LOW SOLIDS WATER SOLVENT PIGMENT RESIN WEIGHT, % SL2376

4 700 SOLVENT CONSUMPTION ACTUAL & PREDICTED GALLON MM THINNERS WATER BASED SOLV BASED 0 85 act 90 pred. 97 act 02 pred YEAR SL2374

5 OEM RESINS LBS APPLICATION Automotive Machinery Paper Can Furniture Wood Plastic Coil Electric Appliance Marine Transportation Miscellaneous RESIN, MM. lb. SL2367

6 RESINS OEM 2002 MM. LB POLYESTER RESIN TYPE ACRYLIC EPOXY ASPHALT PVC ALKYDS POLYURETHANE RESIN, MM. lb. SL2370

7 RESINS OEM 2002 MM. LB RESIN TYPE OTHER PVACET PVDC SILICONE CELLULOSICS POLYIMIDE ELASTOMER RESIN, MM. lb. SL2371

8 Specialty Coatings 2002 RESINS MM. LB APPLICATION Military Camouflage Aerosol Fire Retardant Traffic Paint Automotive Refinishing Industrial Maintenance RESIN, MM. lb. SL2369

9 RESINS SPECIALTY 2002 MM. LB RESIN TYPE ACRYLIC EPOXY ALKYDS POLYURETHANE OTHERS ISOCYANATE POLYESTER SILICONE PVACET NITROCELLULOSE PVC RESIN, MM. lb. SL2373

10 ARCHITECTURAL 2002 RESINS MM. LB APPLICATION Other Exterior SB Exterior WB Interior SB Interior WB RESIN, MM. lb. SL2368

11 RESINS ARCHITECTURAL 2002 MM. LB RESIN TYPE ASPHALT PV ACETATE ACRYLIC ALKYDS URETHANES OLEORESINS EPOXY NITROCELLULOSE SHELLAC SBR PVDC RESIN, MM. lb. SL2372

12 Architecture Linear

13 Branched

14 Highly branched

15 Dendrimer

16 Random Copolymer Flexible

17 Block Rigid - flexible

18 Homo polymer Rigid

19 Alternating

20 Flexible

21 Structure Glass Transition Temperature Mobility of polymer chains Free volume Molecular weight Functional groups Crosslinking Tg Viscosity Physical properties Chemical properties

22

23 Tg of copolymer 1 Tg = W 1 + Tg 1 Tg 2 + Tgn W n = weight fraction

24 WLF Equation log η T = (T-Tg) 51.6+(T-Tg) η = Poise T, Tg = K or C L.E.Nielsen, Polymer Rheology, Marcel Dekker, 1977, pp33,74,133

25 VISCOSITY, POISE 1E6 1E5 1E4 1E3 1E2 1E1 1E0 VISCOSITY as a FUNCTION OF Tg WILLIAMS,LANDEL,FERRY EQUATION Tg of polymer E TEMPERATURE C SL1513bw

26 k=25000 Tg vs MOLECULAR WEIGHT OF OLIGOMERS 200 Tg in K k= k= Tgo = Tg- K Mn MOLECULAR WEIGHT SL1504

27 VISCOSITY vs. HYDROXYL CONTENT NPG/TMP/DIBASIC ACID VISCOSITY (POISE) Tg HYDROXYL mol/ Visc. Tg

28 WLF Equation log η T = (T-Tg) 51.6+(T-Tg) Tg s =C o -C 1 xw s

29 VISCOSITY OF K-FLEX UD VISCOSITY, LOG POISE, 25 C Tgs = C 0 -C 1 xws C 0 = C 1 = 365 Methanol C 1 = 339 Water C 1 = 320 Acetone C 1 =239 Bu-acetate WEIGHT FRACTION OF SOLVENT SL1507 METHANOL WATER ACETONE BU ACETATE

30 Polyurethane polyol 100 1E1 1E2 1E3 1E4 MOLECULAR WEIGHT

31 Viscosity and MW log η = Α + C x Mw 1/2 Number average chain length P.J.Flory J.Am.Chem..Soc., 62, 1057 (1940)

32 4 VISCOSITY OF POLYESTER BLEND AT 109 C VISCOSITY (log POISE) TIME IN MINUTES at 109 C MEASURED DATA POINT SL2307

33 Solubility Parameter Interaction parameter Cohesive energy Hildebrand, Prausnitz Hansen parameter δ 2 = δ d 2 + δ p 2 + δ h 2

34 Interaction parameter Weak Poly.-Sol. Strong Poly.-Sol.

35 Solubility Parameter Solvent WATER METHANOL 2-METHOXYPROPYLENE GLYCOL N-BUTANOL 2-BUTOXYETHANOL ACETONE BUTYL ACETATE 2-METHOXYPROPYLACETATE METHYLISOBUTYLKETONE TRICHLOROETHYLENE m-xylene OCTANE cal 1/2 cm -3/2 Dispersion Polar Hydrogen SL2386

36 Solubility Parameter Resin EPOXY MW 1000 CELLULOSE ACETATE HMMM PV ACETATE NITROCELLULOSE PMMA ALKYD SHORT POLYISOBUTYLENE ALKYD LONG POLYSTYRENE cal 1/2 cm -3/2 Dispersion Polar Hydrogen SL2387

37 Waterborne Coatings Soluble Dispersion

38 Waterborne coatings Acid number Appearance Soluble Clear Colloid Turbid Dispersion 0-20 White

39 VISCOSITY OF DISPERSION 1E3 VISCOSITY 1E2 1E1 1E0 1E-1 Continous phase VOLUME FRACTION SPHERE SPH SW SPH FLOC SL2094

40 Mooney Equation k e V i log η =log η e (1- Vi/θ) η e = viscosity of medium k e = shape constant (2.5) θ = packing factor Vi = volume fraction

41 Coalescence

42 Crosslinking Creation of networks + solvent resistance hardness chemical resistance durability flexibility Tg - elongation flexibility

43

44 NETWORK FORMATION A4 + B2 DEGREE OF POLYMERIZATION Ws Mw Mn P(X4) P(X3) FRACTION CONVERSION

45 8000 STRESS-STRAIN FRONT FACTOR = 1 STRESS, PSI EXTENSION RATIO \ HILTON93\ NETWO RK3\ EXTENSION SL1707

46

47 SWELL RATIO

48 SWELL RATIO AND MWxl MW between X-LINKS LINEAR SWELL RATIO HILTON\ SWELCOM1 SL1757

49 POLYMERS CHAIN GROWTH FREE RADICALS ACRYLIC, VINYL STEP GROWTH CONDENSATION POLYESTER, ALKYD EPOXY MELAMINE

50 CHAIN GROWTH FREE RADICALS ACRYLIC, VINYL R O O R' n R= -H, -CH 2 CH 2 OH, C 1 -C 8

51 STEP GROWTH CONDENSATION Polyester R-OH + R COOH R-OCOR +H 2 O Epoxy O O O OH O O O

52 Acknowledgment King Industries Inc.