Presented by Wally Chang, Ph.D. Coim USA Inc.

Transcription

1 Presented by Wally Chang, Ph.D. Coim USA Inc. 1

2 PU Applications 1. Foams a. Flexible Foams b. Rigid Foams 2. CASE a. Coatings b. Adhesives c. Sealants d. Elastomers 2

3 Polyester Foam CASE 3

4 Physical Properties of Polyurethane Comparison between Polyester and Polyether Wear resistance Load bearing Tensile strength Tear strength Heat resistance Solvent resistance xidative resistance Radiation stability + UV resistance Biodegradability + Weathering resistance Crystallization rate Adhesion to substrate Flame lamination + Energy absorption Hysteresis Resilience Low temperature flexibility Hydrolytic stability Fungus resistance Viscosity of prepolymer Ester + + Ether + + 4

5 Urethane NC + H N H C Polyurethane 5

6 Urea NC + H N 2 N H C Polyurea NH 6

7 Bubble Formation The Reaction of Isocyanates with Water NC + H 2 [ N H C H [ CN N H C N H + C Polyurea 7

8 Isocyanurate 3 NC N C N C N C Polyisocyanurate 8

9 Morphology Hard domains Soft matrix 9

10 Main Polyols for Polyurethane Application 1. Polyester Polyol a. PES (Diacid Based) b. PCL (Polycaprolactone) 2. Polyether Polyol a. PPG (Polypropylene Glycol) b. PEG (Polyethylene Glycol) c. PTMG (Polytetramethylene Glycol) 3. PCG (Polycarbonate Glycol) 10

11 Polyester Ester Group 11

12 Polyether Ether Group 12

13 Polycarbonate Carbonate Group 13

14 Polyesterification H-R-H + H- -(CH 2 ) x - C C -H ( C) H-R- [ C -(CH 2 ) x - C - -R- ] n H + H 2 DP = 2 x n

15 CH 2 CH 2 CH 2 CH 2 H H Diethylene Polyol (DEG) Raw Material Diols CH 2 CH 2 H H Ethylene Polyol (EG) CH 2 CH CH 3 H H Propylene Polyol (PG) CH 2 CH 2 CH 2 CH 2 H H 1,4-Butanediol (1,4BD) H CH 3 CH 2 C CH 2 CH 3 H Neopentyl Polyol (NPG) CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 H H 1,6-Hexanediol (1,6HD) 15

16 Raw Material Diacids H C (CH 2 ) 4 C H Adipic Acid (AA) CH CH CH CH Phthalic Anhydride (PA) Isophthalic Acid (IA) Terephthalic Acid (TA) 16

17 Raw Material Triols CH 2 -H CH 3 CH 2 C CH 2 -H CH 2 -H Trimethylolpropane (TMP) CH 2 CH CH 2 H H H Glycerin (GLY) 17

18 Functionality of Polyesters H-R-H + H- C -(CH 2 ) 4 - CH 2 H CH H CH 2 H Glycerin (GLY) C -H H H H 18

19 Functionality W.L. Chang's equation f = (n - 2)EW/Y f : functionality of prepolymer n : functionality of modifier (branched raw material) EW : equivalent weight of prepolymer Y : yield of prepolymer based on one mole of modifier Reference: W. L. Chang, J. Appl. Polym. Sci., 51, 1077 (1994) 19

20 Polyester formulation and calculated functionality grams EG TMP(n=3.0) AA 811 rganotin catalyst 0.04 Total weight 1,200 H2-200 Yield 1,000 H# 56.1 grams 1, (1 mole) 2, , , f Calculation of functionality EW = 56100/56.1 = 1000 Y = 3000 f = 2/[1-(3-2)1000/3000] =

21 MDI-prepolymer formulation and calculated functionality grams PEAG TMP(n=3.0) 30 MDI 350 Yield 1,320 NC% 3.78% grams 4, (1 mole) 1, , % f Calculation of functionality 2.46 EW = 4202/3.78 = Y = f = 2/[1-(3-2)1110.8/5896.0] =

22 Polyester Preparation I. Uncatalyzed polyesterification II. Catalyzed polyesterification 1. Tin compounds 2. Titanium compounds 3. thers 22

23 Side Reactions of Polyester Preparation Unsaturated End Group Formation CH -H CH CH 2 + H 2 CH 3 C CH 2 CH 2 C CH + CH 2 CH C 23

24 Side Reactions of Polyester Preparation Aldehyde Formation CH 2 CH 2 H H CH 3 C H + H 2 C CH CH 2 + HC C CH 3 CH C C CH 3 + C C H 24

25 Side Reactions of Polyester Preparation Polyene Formation C CH CH 2 + CH 3 C H ( CH CH ) n Polyene (Color formation) 25

26 Ingredients DEG-AA Polyesters M.W. 2,000 m.p., C State at 25 C liquid EG-AA 52 solid PG-AA 1,4BD-AA liquid 54 solid NPG-AA liquid solid 1,6HD-AA 56 solid 26

27 PDI (Polydispersity Index) Mw PDI = = 1 + P Mn P: extent of reaction (P=100%) Polyester Theoretical PDI 2.0 PEAG-2000 catalyzed PDI 2.8 uncatalyzed

28 EW (Equivalent Weight) Calculation EW of Glycol Material EW = 56,100 H # MW = EW x f MW: molecular weight f: functionality H # EW f MW

29 H# Polyester C Viscosity AN (acid number) Time, hours 29

30 Reaction Time and Acid Number PDEAG-2000 at 230 C Time, hours AN, catalyzed AN, uncatalyzed Reference: W.L. Chang, J. Polym. Sci.: Part A: 31, 493 (1993) 30

31 Hydrolytic Stability MDI Elastomers MDI/1,4BD/polyester (1,4BD/1,6HD-AA, H# 56) T.S. retention, % Acid number C water immersion, days 31

32 C H trace amount Acid Number of Polyols Acid number >> n M if present 3 Trimerization ( NC C ( M n trimerization catalyst ( C ( trimerization catalyst n M N C C N N C M = M M i where = i K, Na, Fe, etc. Poly isocyanurate 32

33 10,000 8,000 Polyester 60 C MDI 60 C 1,4-BD 60 C Pot Life Test Viscosity, cps 6,000 4,000 2, Time, seconds 33

34 Effect of Polyester Acid Number on Pot Life MDI/Uncatalyzed PBAG2000/1,4BD Pot life, minutes Acid number of polyester 34

35 60 EG/1,4BD-AA polyester m.p., C eutectic point EG mole% 35

36 Polyester 60C Glycol/Adipic Acid, MW 2,000 3,000 2,500 2,600 Viscosity, cps 2,000 1,500 1, ,100 1,100 1,400 1, DEG EG PG 1,4BD NPG 1,6HD 36

37 Effect of Polyester Acid Number on Polyester Viscosity 1,600 Vviscosity of polyester, cps 1,400 1,200 1, Acid number of polyester 37

38 70 1,4BD-AA polyester m.p., C ,000 2,000 3,000 4,000 5,000 6,000 M.W. 38

39 PBAG Sp. gravity Temperature, C 39

40 Hydrolytic Stability of PU/Polyester Elastomers PHDG (1,6HD/dodecanedioic acid) > > > > PHAG (1,6HD-AA) PBAG (1,4ND-AA) PEAG (EG-AA) PDEAG (DEG-AA) Reference: W.L. Chang, Polyurethanes World Congress, September 29 - ctober 1, 705 (1997) 40

41 Polyester Applications DEG-AA pigment carriers, soft elastomers, coatings, adhesives EG-AA cast elastomers PG-AA inks, radcure oligomers, coatings 1,4BD-AA TPU, adhesives, cast elastomers NPG-AA outdoor coatings, radcure oligomers 1,6HD-AA adhesives, coatings, TPU, cast elastomers Mixed Polyols-AA microcellular PU, TPU, cast elastomers, adhesives, coatings Polyols-AA/IA floor coatings, adhesives TMP/Polyols-AA foams, elastomers GLY/DEG-AA foams, elastomers 41

42 Polyester Foam Market Garment Industry Clothing innerliner - composites Fabric adhesive - automotive Reasons used over ethers flame lamination solvent resistance greater strength fine uniform cell structure Novelty / Industrial High strength High elongation Diecuttability Technical Foams Reticulated foams Cell size variations Post treated foams Low perm gasketing Hydrophilic foams Sponge foams 42

43 Polyester Flexible Foam for Shock Absorption Polyester Flexible Foam 43

44 Polyester Flexible Foam for Filter Application Polyester Flexible Foam 44

45 Polyester Flexible Foam for Packaging Application Polyester Flexible Foam 45

46 Polyester Flexible Foam for Bras Application Polyester Flexible Foam 46

47 Polyester Flexible Foam for Shoulder Pad Application Polyester Flexible Foam 47

48 Polyester Flexible Foam for Paint Brush Application Polyester Flexible Foam 48

49 Polyester Flexible Foam for Scrubbing Pad Polyester Flexible Foam 49

50 Comparison of Polyester vs. Polyether Foams Polyester Foam Positive good green strength less burn-off fine cell foam high tensile strength high tear strength high elongation pin-hole free solvent resistance - dry cleaning Negative hydrolytic instability poor compression sets higher price Polyether Foam Positive hydrolytic stability good compression sets better clickability lower price Negative coarser foam / cell size control lower tensile strength lower tear strength lower elongation swelling in dry cleaning solvents 50

51 Cellesters for Flexible Foam Solvent resistance Heat resistance Flame lamination Tensile strength Tear strength Wear resistance Load bearing Energy absorption 51

52 CH 2 CH 2 CH 2 CH 2 H Formation of Cyclic Structure from Diethylene Glycol (DEG) H + H C (CH 2 ) 4 C H Diethylene Glycol (DEG) Adipic Acid (AA) CH 2 CH 2 CH 2 CH 2 C (CH 2 ) C 4 lactone structure 13 - membered ring 1.00 wt% in PDEAG2000 8,13-Dioxo-1,4,7-Trioxacyclotridecane 1,4,7-Trioxacyclotridecane-8,13-Dione m.p C CAS#:

53 Cellesters for Low-Fogging Flexible Foam H# Viscosity, 25C, cps Applications ,000 Textile 20,000 Clickable 53

54 Elastomers I. CPU (Cast PU) slightly crosslinked I.I. (isocyanate index) II. TPU (Thermoplastic PU) linear structure I.I. (isocyanate index) III. Microcellular elastomer 54

55 TPU (Thermoplastic PU) Applications Film and sheet w w w w w w Hose w w Shoes w w conveyor belts welded hollow bodies textile lamination protective coverings sealing of foams abrasion resistant coatings inner liner of fire hoses inner layer of tubes outer materials of ski boot ice hockey boots Automotive w w w w w w exterior body parts bearing bushings gaskets tie rod shock absorbers tank bleeding tubes Mechanical goods w w w w toothed belts couplings screens cables Medical Adhesives 55

56 Very low APHA of polyester color Very low acid number of polyester No pink color of polyester Tailored polyester backbone for improving TPU physical properties Consistent reactivity for TPU manufacturing Low yellow index of PU product 56

57 TPU (Thermoplastic PU) continuous process - reaction extruder process MDI polyester chain extender additives catalyst feed zone mix zone extrusion zone twin screw extruder 90 C 150 C 200 C cutter water bath conveyer dryer pellets 57

58 Formation of Cyclic Structure Impurity in PBAG [Poly(butylene adipate) Glycol] CH 2 CH 2 CH 2 CH 2 H H + H C (CH 2 ) 4 C H 1,4-Butanediol (1,4BD) Adipic Acid (AA) CH 2 CH 2 CH 2 CH 2 lactone structure 12 - membered ring C (CH 2 ) 4 C 0.30 wt% in PBAG

59 Microcellular Elastomers MDI Isonate 2143L (optional) polyester polyester chain extender (EG, etc.) water amine catalysts (Dabco EG, etc.) surfactant (L5305, etc.) pigment (Ti2, etc.) additives NC% ~ 19.0% (quasi prepolymer) mold post cure shoe soles 59

60 Polyurethane Fibers Spandex Melt spinning H H + X CN CH 2 NC polyester MDI CN CH N H C C N H CH 2 2 NC + (X-2) CN CH 2 NC CH 2 CH 2 CH 2 CH 2 H H 1,4BD melt TPU spinnerets spinning Spandex 60

61 Polyester for Rigid Foam DEG/aromatic acid based polyester Phthalate Terephthalate 61

62 Chemical Structure of Main Raw Materials Glycol: DEG (diethylene glycol) H H 2,2'-xybis[ethanol] Diethylene Glycol (DEG)

63 Chemical Structure of Main Raw Materials Acid: PA (phthalic anhydride) TPA (terephthalic acid) H H Phthalic Anhydride (PA) Terephthalic Acid (TPA)

64 Chemical Equation of DEG/PA Polyester Preparation H H + DEG (diethylene glycol) PA (phthalic anhydride) o C catalyst - H 2 (under vacuum) H H n Poly(diethylene phthalate) glycol 25 o C: liquid + free DEG 10-15%

65 Chemical Equation of DEG/TPA Polyester Preparation H H H + DEG (diethylene glycol) H TPA (terephthalic acid) o C catalyst - H 2 (under vacuum) H H Poly(diethylene terephthalate) glycol 25 o C: solid n + free DEG 10-15%

66 Chemical Equation of DEG/TPA/PA Polyester Preparation H H H + + DEG (diethylene glycol) H TPA (terephthalic acid) PA (phthalic anhydride) o C catalyst - H 2 (under vacuum) DEG-TPA-DEG-PA-DEG + DEG-TPA-DEG + DEG-PA-DEG + free DEG state: 25 o C state: 25 o C state: 25 o C 10-15%

67 Shelf Life PA/DEG Polyester: 6 years TPA/PA/DEG Polyester: 1 year

68 Boardstock PIR foam Rigid Foam Ø Polyisocyanurate (Polyiso) is a closed-cell, rigid foam insulation board used in commercial roofing Ø Polyiso insulation is the best choice as a cost-effective, energy efficient and environmentally responsible insulation product 68

69 Rigid Foam Boardstock PIR foam 69

70 Rigid Foam Typical formulation of PIR boardstock rigid foam ingredients wt., phr wt% aromatic polyester (H# 240) 71 31% K octoate 3 1.5% K acetate % amine catalyst (PMDETA) % surfactant % n-pentane 15 6% water 0.3 flame retardant (TCPP) 9 B-side, total % Isocyanate (PMDI, f=3.0) % Isocyanate Index (I.I.) % 5% 70

71 Rigid Foam Bun stock PIR foam 71

72 Rigid Foam Spray Polyurethane Foam (SPF) 72

73 Rigid Foam Spray Polyurethane Foam (wall foam) (SPF) 73

74 Rigid Foam Spray Polyurethane Foam (roof foam) (SPF)

75 Rigid Foam Spray Polyurethane Foam (SPF) Currently foamers use 3 polyols mix for SPF Polyols wt% func. advantages disadvantages aromatic polyester Mannich polyether sucrose-initiated polyether ~ high aromaticity low func. ~ increase reactivity increase smoke ~ high func. increase smoke 75

76 Rigid Foam Spray Polyurethane Foam (SPF) Mannich Polyether Polyol H H H N N H C 9 H 19 H Mannich polyether polyol is an auto-catalytic polyether polyol used for SPF to increase SPF reactivity 76

77 Typical formulation of PUR spray rigid foam ingredients wt., phr wt%, B-side aromatic polyester Mannich polyether sucrose-polyether TCPP flame retardant Br flame retardant amine catalyst, amine catalyst, water blowing agent surfactant PMDI (f=2.7) 134 Index

78 Rigid Foam Pour-in-Place Foam designed to fill and insulate large voids and blind cavities 78

79 Aromaticity% Competitor, based on aromatic molecule 63% 61% 59% 57% 55% 53% 51% 49% 47% 45% 43% 41% 39% 37% 35% 33% 31% 29% 27% 25% 23% 21% 19% 17% y = x 10% 11% 12% 13% 14% 15% 16% 17% 18% 19% 20% 21% 22% 23% 24% 25% 26% 27% 28% 29% 30% 31% 32% 33% 34% 35% Coim USA, based on C6H4 (phenyl)

80 What are the advantages from TPA? Ø better flammability resistance than PA Ø higher compressive strength than PA

81 Thank you! Thank you! Thank you! Thank you! Thank you! Thank you! Thank you! Thank you! Thank you! Thank you! Thank you! Thank you! Thank you! Thank you! Thank you! 81