MDI Prepolymers Extended With Amines A Reality!

Transcription

1 customized polyurethanes MDI Prepolymers Extended With Amines A Reality! Dr. Ashok M. Sarpeshkar

2 Overview Baytec MAC prepolymer product line Effect of free-monomer on properties Curing with MbOCA Curing with other chain extenders DMA, DSC, TMA Analysis Conclusions

3 Baytec MAC Prepolymers MAC = MDI-amine-cured Specialty MDI & free of TDI monomer Low-melting solids with excellent shelf life Diamine cure with MDI prepolymers now possible Processing profile comparable to TDI prepolymers End-use property benefits

4 Baytec MAC Product Line Baytec MAC Prepolymer Polyol %NCO 90 C Component (mpa.s) Desmodur VP.PU MS 40TF01 Polyester Desmodur VP.PU MS 40TF03 Polyester Desmodur VP.PU MS 58TF02 Polyester Desmodur VP.PU MS 78TF03 Polyester Desmodur VP.PU ME 40TF04 Polyether Desmodur VP.PU ME 60TF04 Polyether Desmodur VP.PU ME 80TF04 Polyether

5 Effect of free-monomer Property a Units MS 40TF01 TEC-41 b TS-35 c Hardness A/D 93/36 90/36 86/34 Comp.Set d % Graves Tear pli Ten. Strength psi Elongation % Abrasion mg loss a extended with XL-1604 ; b unstripped; c <0.5% monomer; d 24 hr./70 C Lowering free-monomer in TDI prepolymers Free-monomer in MDI prepolymers produces softer elastomer compromises tear properties better elastomeric properties

6 MbOCA cured polyester prepolymers - processing Process MS 40TF01 MS 40TF03 MS 58TF02 TDI/Polyester a Parameter %NCO Index Prepol Temp. 90 C 90 C 90 C 90 C Ext. Temp. 120 C 120 C 120 C 120 C Gel Time 3:20 4:30 1:15 6:00 Demold Time 25:00 25:00 25:00 25:00 Postcure 110 C/24 hr. 110 C/24 hr. 110 C/24 hr. 110 C/24 hr. a <0.1% free monomer

7 MbOCA cured polyester elastomers Properties MS 40TF01 MS 40TF03 MS 58TF02 TDI/Polyester a Hardness 92A/42D 91A/40D 98A/5D 90A/42D Ten. Strength 5609 psi Elongation 645% Die C Tear 562 pli Split Tear 440 pli Resilience 33% T. Abrasion 1.8 mg loss Comp. Set b 30% a <0.1% free-tdi prepolymer; 4% NCO b 22 hr./70 C

8 Processing & property benefits - polyesters Processing similar to TDI prepolymers Faster reactivity compared to free-monomer TDI prepolymers Reactivity suitable for producing large parts knittable Superior overall end-use properties Outstanding abrasion resistance Excellent tear resistance

9 MbOCA cured polyether prepolymers - processing Process ME 40TF04 ME 60TF04 ME 80TF04 TDI/Polyether a Parameter %NCO Index Prepol Temp. 90 C 90 C 90 C 66 C Ext. Temp. 120 C 120 C 120 C 116 C Gel Time 6:40 2:30 1:00 7:00 Demold Time 15:00 15:00 15:00 25:00 Postcure 110 C/16 hr. 110 C/16 hr. 110 C/16 hr. 110 C/16 hr. a <0.1% free monomer

10 MbOCA cured polyether elastomers Properties ME 40TF04 ME 60TF04 ME 80TF04 TDI/Polyether a Hardness 95A 98A/55D 65D 95-97A Ten. Strength 5652 psi Elongation 484% Die C Tear 662 pli Resilience 43% T. Abrasion 4.4 mg loss N/A Comp. Set 24hr./70 C 29% a <0.1% free monomer; NCO = 6.1%

11 Processing & property benefits - polyethers Faster reactivity compared to free-monomer TDI prepolymers Reactivity suitable for producing large parts knittable Superior overall end-use properties Good abrasion resistance Excellent tear resistance

12 Processing with non-mboca curatives Processing Baytec XL-1604 Lonzacure MbOCA Parameter MCDEA Prepol Temp C 80 C 90 C Extender Temp. 100 C 100 C 120 C Gel Time 15:00 2:30 2:00 0:15 4:30 1:00 Demold Time 15:00-30:00 15:00 30:00 25:00 Postcure Conditions 110 C/24 hr. 110 C/24 hr. 110 C/24 hr. Reactivity MCDEA > MbOCA > XL-1604 Gel times depend on %NCO Shorter demold period

13 Elastomer properties Polyester Systems Properties MS 40TF01 MS 40TF01 MS 40TF03 MS 40TF03 (MCDEA) (XL-1604) (MCDEA) (XL-1604) Hardness 95A/44D 91A/38D 96A/57D 90A/38D Ten. Strength 7652 psi Elongation 692% Die C Tear 627 pli Resilience 42% T. Abrasion 66mg loss Comp. Set 22 hr/70 C 30%

14 Elastomer properties - Polyether Systems Properties ME 40TF04 ME 40TF04 ME 60TF04 ME 60TF04 (MCDEA) (XL-1604) (MCDEA) (XL-1604) Hardness 97A/42D 91A/34D 99A/53D 97A/45d Ten. Strength 5362 psi Elongation 510% Die C Tear 560 pli Resilience 51% T. Abrasion 4.1 mg loss Comp. Set 22 hr/70 C 40%

15 Property trends with non-mboca curatives Property Polyester Polyether Shore Hardness >90A >90A Tensile Strength psi Elongation % Die C Tear pli Resilience 40 46% Comp. Set 25 32% Abrasion 23 82mg Benefits Higher hardness elastomers from MCDEA Excellent tensile, elongation & tear from polyesters Outstanding abrasion resistance from polyethers

16 DMA Analysis polyester systems DSC DMA TMA Prepolymer Tg ( C) MS 40TF01-27 (-28) MS 58TF02-21 (-22) MS 40TF03-34 (-31) TDI/Polyester -21 (-21) ΔCp (J/g C) 0.34 (0.42) 0.29 (0.31) 0.24 (0.39) 0.38 (0.44) Tm ( C) ΔHm (J/g) Tg** ( C) ( C) C (Pa) T onset ( C) x * x * x * x * *onset of major softening; **from peak in G curve; ()DSC reheat data

17 DMA, DSC & TMA Analysis Good agreement between soft segment Tg by DMA & DSC MS 58TF02 shows comparatively higher Tg (-21 C) Heat of fusion of MS 58TF02 (2.21J/g) shows low level of hard segment crystallinity Rubbery plateau similar for 4% NCO prepolymers ( C) MS 58TF02 has higher modulus due to higher NCO content Temperatures at which modulus is off by 20% of rubbery plateau correlate well with TMA values MS 58TF02 has highest softening temperature (204 C)

18 DSC Analysis polyester systems Normalized Heat Flow (W/g) Temperature ( C)

19 TMA Scans polyester systems Height % Temperature ( C)

20 G (Loss Modulus) polyester systems G" TDI / Polyester MS40TF01 MS40TF03 MS58TF02 G" ( ) [Pa] Temp [ C]

21 G (Elastic Modulus) polyester systems G' TDI / Polyester MS40TF01 MS40TF03 MS58TF02 G' ( ) [Pa] Temp [ C]

22 Tan Delta polyester systems Tan delta TDI / Polyester MS40TF01 MS40TF03 MS58TF02 tan( ) ( ) [ ] Temp [ C]

23 Conclusions New MDI prepolymers for the hot-cast elastomer industry Diamine curing now possible with TDI- free prepolymers Complements TDI prepolymer chemistry Beneficial effect of free-mdi monomer Gel times sufficiently long for casting big parts Polyester and polyether prepolymers Curatives other then MbOCA can be used to advantage Overall property profile equal to or superior to TDI prepolymers Outstanding abrasion and tear properties

24 Acknowledgements Michael Barnes, Jens Krause Frank Muschiol, Peter Plate Hartmut Nefzger Manfred Schmidt Gilbert Ellerbe Marylyn Donaldson Richard Rogers John D. Hodel John Liddle Marie Urick

25 Thank You for Your Attention! customized polyurethanes