Method of making thermoplastic vulcanizates and thermoplastic vulcanizates made therefrom
Provided are methods of making thermoplastic vulcanizates and thermoplastic vulcanizates made therefrom. The methods can comprise adding vulcanizable elastomer to a reactor; adding a masterbatch comprising a thermoplastic resin and a metal oxide to the reactor; adding a curative to the reactor; and dynamically vulcanizing the elastomer.
1. A method of making a thermoplastic vulcanizate, the method comprising the steps of:
adding vulcanizable elastomer comprising a poly(ethylene-propylene-diene)copolymer to a reactor;
adding a masterbatch comprising a thermoplastic resin and a metal oxide comprising zinc oxide to the reactor, wherein the thermoplastic resin comprises a polypropylene;
adding a phenolic resin curative to the reactor; and
dynamically vulcanizing the elastomer with the curative in the presence of the metal oxide.
2. The method of claim 1 , further comprising the step of mixing the vulcanizable elastomer and the masterbatch above the melt temperature of the thermoplastic resin.
3. The method of claim 1 , further comprising the step of adding to the reactor a thermoplastic resin substantially devoid of the metal oxide.
4. The method of claim 3 , wherein the thermoplastic resin in the masterbatch is the same as the thermoplastic resin substantially devoid of the metal oxide.
5. A method of making a thermoplastic vulcanizate, the method comprising the steps of:
a. mixing a vulcanizable elastomer comprising a poly(ethylene-propylene-diene)copolymer and at least one first thermoplastic resin comprising a first polypropylene above the melt temperature of the first thermoplastic resin to form a molten mass;
b. adding a masterbatch consisting essentially of a second thermoplastic resin comprising a second polypropylene and a metal oxide comprising zinc oxide to the molten mass;
c. melting the second thermoplastic resin to disperse the metal oxide within the molten mass;
d. adding a phenolic resin curative to the molten mass; and
e. dynamically vulcanizing the elastomer with the curative in the presence of the metal oxide.
6. The method of claim 5 , wherein the first thermoplastic resin is substantially devoid of metal oxide.
7. The method of claim 5 , wherein the metal oxide is at least one oxide of a zinc, calcium, magnesium, aluminum, and ferrite.
8. The method of claim 5 , wherein the zinc oxide has a mean particle diameter of from about 0.01 μm to about 0.5 μm.
9. The method of claim 5 , wherein the masterbatch comprises from about 25 wt % to about 75 wt % of the metal oxide based on the weight of the masterbatch.
10. The method of claim 5 , wherein the masterbatch comprises about 40 wt % to about 60 wt % of the metal oxide based on the weight of the masterbatch.
11. The method of claim 5 , wherein the masterbatch contains less than 25 wt % of material other than the metal oxide or the thermoplastic resin based on the weight of the masterbatch.
12. The method of claim 5 , wherein the masterbatch contains less than 5 wt % of material other than the metal oxide or the thermoplastic resin based on the weight of the masterbatch.
13. The method of claim 5 , wherein the masterbatch contains consists essentially of the metal oxide and the thermoplastic resin.
14. The method of claim 5 , wherein the masterbatch is added to the reactor in form of pellets.
15. The method of claim 5 , wherein the thermoplastic resin in the masterbatch has a melt flow rate, as determined according to ASTM D-1238 at 230° C., 2.16 kg, of from about 0.1 g/10 min to about 50.0 g/10 min.
16. The method of claim 5 , wherein the metal oxide in the masterbatch is added in an amount from about 0.25 to about 5.0 parts by weight per 100 parts by weight elastomer.
17. The method of claim 5 , wherein the metal oxide in the masterbatch is added in an amount from about 0.5 to about 4.0 parts by weight per 100 parts by weight elastomer.
18. A method of making a thermoplastic vulcanizate, the method comprising the steps of:
adding a poly(ethylene-propylene-diene)copolymer to a twin-screw extruder through the feed throat of the extruder;
adding a polypropylene to the twin-screw extruder through the feed throat of the extruder;
mixing, within an initial mix zone, the poly(ethylene-propylene-diene)copolymer and the polypropylene at a temperature above the melt temperature of the polypropylene to form a molten mass;
adding a masterbatch consisting essentially of a polypropylene and a zinc oxide to the twin-screw extruder through an inlet in a barrel downstream of the initial mix zone;
melting the polypropylene in the masterbatch and mixing the molten polypropylene with the molten mass;
adding a phenolic resin curative to the twin-extruder through an inlet in a barrel downstream of the barrel where the masterbatch is added;
mixing the phenolic resin curative with the molten mass while transferring the molten mass through a cure zone where dynamic vulcanization of the poly(ethylene-propylene-diene)copolymer takes place to form a thermoplastic vulcanizate; and
removing the thermoplastic vulcanizate from the twin-screw extruder.
19. A thermoplastic vulcanizate made by the method of claim 5 .
20. The method of claim 1 , wherein the zinc oxide has a mean particle diameter of from about 0.01 μm to about 0.5 μm.
21. The method of claim 18 , wherein the zinc oxide has a mean particle diameter of from about 0.01 μm to about 0.5 μm.