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Rubber Division, ACS Fall 2009 Meeting Pittsburgh

Rubber Division, ACS Fall 2009 Meeting Pittsburgh. An Original Anti-Reversion Nitrosamine-Free Curing Agent as an Alternative to TMTD. An Original NR Anti-Reversion Nitrosamine-free Curing Agent. CONTENTS. Company introduction 2) Reference compound 3) Experimental design 4) Conclusion.

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Rubber Division, ACS Fall 2009 Meeting Pittsburgh

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  1. Rubber Division, ACS Fall 2009 Meeting Pittsburgh

  2. An Original Anti-Reversion Nitrosamine-Free Curing Agent as an Alternative to TMTD

  3. An Original NR Anti-Reversion Nitrosamine-free Curing Agent CONTENTS • Company introduction • 2) Reference compound • 3) Experimental design • 4) Conclusion

  4. An Original NR Anti-Reversion Nitrosamine-free Curing Agent CONTENTS • Company introduction • 2) Reference compound • 3) Experimental design • 4) Conclusion

  5. Discover MLPC International MLPC International is located in France, in the southwest, near by Bordeaux. MLPC supplies various curing agents either in powder form or in Mixland form (pellets or slabs). MLPC is a world leader for predispersed curing agents (Mixland+)

  6. Discover MLPC International MLPC belongs to the french chemical group MLPC ‘s facilities

  7. An Original NR Anti-Reversion Nitrosamine-free Curing Agent Why this survey? -To save curing energy, it is important to reduce energy consumption by cured part: for instance, by shortening the cure time. -NR is a renewable material, but its heat resistance needs to be improved MLPC’s goal is to offer answers to these challenges

  8. An Original NR Anti-Reversion Nitrosamine-free Curing Agent CONTENTS • Company introduction • 2) Reference compound • 3) Experimental design • 4) Improved recipe • 5) Conclusion

  9. An Original NR Anti-Reversion Nitrosamine-free Curing Agent NR reference compound The main goal is to replace TMTD *= included stearic acid **= nitrosamine generator

  10. An Original NR Anti-Reversion Nitrosamine-free Curing Agent RHEOMETRIC FEATURES of reference compound T (with TMTD) at VARIOUS curing temperatures. t 3 scorch time @ 125°C = 9.38 min Note: To increase cure temperature from 160 to 180°C cuts the cure time by 2 roughly

  11. An Original NR Anti-Reversion Nitrosamine-free Curing Agent CONTENTS • Company introduction • 2) Reference compound • 3) Experimental design • 4) Conclusion

  12. An Original NR Anti-Reversion Nitrosamine-free Curing Agent NR reference compound *= included stearic acid **= nitrosamine generator

  13. An Original NR Anti-Reversion Nitrosamine-free Curing Agent Structure of Mixland TBP 75 GA It is based on a modified poly-ter-butyl-phenol disulfide No Nitrogen=> cannot generate Nitrosamine X average= 2.1, Y average= 5

  14. An Original NR Anti-Reversion Nitrosamine-free Curing Agent 3X3 experimental cubic volume design How to proceed? (-1,+1,+1) (+1,+1,+1) (-1,+1,-1) (0,0,0) (+1,-1,+1) (-1,-1,-1) (+1,-1,-1) Rubber Chem Conference, Birmingham - 08 & 09 Nov. 2004 14

  15. An Original NR Anti-Reversion Nitrosamine-free Curing Agent 3X3 experimental design

  16. An Original NR Anti-Reversion Nitrosamine-free Curing Agent Curing systems of the 9 recipes WEIGHT DETERMINATION GRID

  17. An Original NR Anti-Reversion Nitrosamine-free Curing Agent The 3 first compound rheometric curves @ 160°C (MDR) Torque dN.m Torque dN.m Strong reversion of reference T, low torque of A, B & C; C reverses

  18. An Original NR Anti-Reversion Nitrosamine-free Curing Agent The 3 middle compound rheometric curves @ 160°C (MDR) Torque dN.m Higher torque of D, E and F; D reverses

  19. An Original NR Anti-Reversion Nitrosamine-free Curing Agent The 3 last compound rheometric curves @ 160°C (MDR) Torque dN.m No reversion for G & I, reversion for H

  20. An Original NR Anti-Reversion Nitrosamine-free Curing Agent Compound rheometric data

  21. An Original NR Anti-Reversion Nitrosamine-free Curing Agent

  22. An Original NR Anti-Reversion Nitrosamine-free Curing Agent Mechanical properties 160°C cured sheets. => Similar properties, except B, with lower pontal density

  23. An Original NR Anti-Reversion Nitrosamine-free Curing Agent Mechanical properties, 160°C cured sheets => Variable according to the recipe.

  24. An Original NR Anti-Reversion Nitrosamine-free Curing Agent Next step of the survey -We carried out cure tests @ 160°C -We decided to go forward by carying out curing tests at higher temperature: 170°C and 180°C Possible to maintain mechanical properties?

  25. An Original NR Anti-Reversion Nitrosamine-free Curing Agent Next step of the survey • To clarify the lecture, we focused onto only • 4 experimental compounds (B, F, G & H) to compare • their properties @ 160, 170 & 180°C to reference compound T. Reversion index Slope @ Tc 50 T 90 Mh-Ml

  26. An Original NR Anti-Reversion Nitrosamine-free Curing Agent => Dramatic reduction of reversion vs higher temperature

  27. An Original NR Anti-Reversion Nitrosamine-free Curing Agent • The rate of curing is lower than TMTD, that makes the compound easier to handle.

  28. An Original NR Anti-Reversion Nitrosamine-free Curing Agent • The cure time @ 180°C is similar to 160°C reference compound cure time.

  29. An Original NR Anti-Reversion Nitrosamine-free Curing Agent => Both 170 & 180 °C torques are similar to reference.

  30. An Original NR Anti-Reversion Nitrosamine-free Curing Agent Possible origin of reversion resistance Lab survey carried out in ARKEMA Research Center of Lacq (France). Experimental test of cross-linking of TME (2, 3 dimethyl-2-butene) with both TBP and CBS. How?

  31. Model compound vulcanization (MCV) approach:characterization of possible hybrid bonds An Original NR Anti-Reversion Nitrosamine-free Curing Agent • Experiments: • Model compound used: • 2,3-dimethyl 2-butene (TME) • Experimental conditions : cure 30 and 60 min @ 145°C under nitrogen atmosphere

  32. An Original NR Anti-Reversion Nitrosamine-free Curing Agent Conventional Sulfur bonds Hybrid bonds 3 different mechanisms detected by HPLC/MS Hypothesis: the hybrid bonds bring reversion resistance. Sulfoxide bonds

  33. An Original NR Anti-Reversion Nitrosamine-free Curing Agent Hybrid bonds: Monosulfidic bond Dissociation energy: to be evaluated Mono and disulfidic bond Disulfidic bond

  34. An Original NR Anti-Reversion Nitrosamine-free Curing Agent Cost effect *: this overcost could easily be compensated by using higher level of suitable fillers, by the reduction of the time of curing, by an easier handle of a less scorchy compound.

  35. An Original NR Anti-Reversion Nitrosamine-free Curing Agent CONTENTS • Company introduction • 2) Reference compound • 3) Experimental design • 4) Conclusion

  36. An Original NR Anti-Reversion Nitrosamine-free Curing Agent 2 examples of behavior of both compound T @ 160°C and compound G @180°C

  37. An Original NR Anti-Reversion Nitrosamine-free Curing Agent GENERAL CONCLUSIONS Comparatively to TMTD, TBP 75, combined with CBS, brings: - Improvment of reversion resistance - Better curing efficiency at high temperature -Better scorch safety -Curing cycle reduction time - No nitrosamine contamination

  38. thank you for your attention. 38

  39. An Original NR Anti-Reversion Nitrosamine-free Curing Agent Thermal stability of crosslinks

  40. An Original NR Anti-Reversion Nitrosamine-free Curing Agent Examples of T90 of the 9 compounds of the design @ 160°C (ref compound T=1.33 min Reference: TS= 16.7 MPa

  41. An Original NR Anti-Reversion Nitrosamine-free Curing Agent Examples of delta torque of the 9 compounds of the design @ 160°C (reference compound T = 8.65 dN.m) Reference: TS= 16.7 MPa

  42. An Original NR Anti-Reversion Nitrosamine-free Curing Agent Examples of reversion index response of the 9 compounds of the design at 160°C (reference compound T= 0.205 ) Reference: TS= 16.7 MPa

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