Thermally stable polyester, process for its preparation and its use
View Patent ↗A polyester with a carbon black content of up to 20% by weight, based on the polyester, is condensed, after transesterification of DMT with diol, or after esterification of terephthalic acid with diol, with the aid of a titanium-based catalyst. The carbon black is added in the form of a carbon black dispersion together with the polycondensation catalyst to the transesterification product or esterification product. The carbon black dispersion comprises gas black or furnace black and a dispersing agent, and these are dispersed in diol. The diameter of the carbon black particles is below that of carbon black particles in a polyester using an antimony compound as catalyst.
1. A thermally stable polyester resin comprising: polyester; from 1 to 100 ppm of titanium, in the form of a titanium compound, as a polycondensation catalyst, based on the amount of polyester; from 0.01 to 20% by weight of agglomerated carbon black, based on the weight of the polyester; and from 0 to 200 ppm of phosphorous, in the form of a phosphorous compound, based on the amount of polyester.
2. The polyester as claimed in claim 1 , which comprises from 0.01 to 5% by weight of agglomerated carbon black, based on the weight of the polyester.
3. The polyester as claimed in claim 1 , which comprises from 0.1 to 2% by weight of agglomerated carbon black, based on the weight of the polyester.
4. The polyester as claimed in claim 1 , which comprises from 0.4 to 1.6% by weight of agglomerated carbon black, based on the weight of the polyester.
5. The polyester as claimed in claim 1 , wherein the polycondensation catalyst is selected from the group consisting of soluble and dispersible titanium compounds.
6. The polyester as claimed in claim 5 , wherein the polycondensation catalyst is composed of an ethylene-glycol-soluble titanium compound.
7. The polyester as claimed in claim 6 , wherein the titanium compound is a titanium potassium oxalate.
8. The polyester as claimed in claim 6 , wherein the titanium compound is a titanium alkoxide.
9. The polyester as claimed in claim 5 , wherein the polycondensation catalyst is composed of an ethylene-glycol-dispersible mixture made from titanium dioxide and silicon dioxide or metal oxide-titanium dioxide hydrate.
10. The polyester as claimed in claim 9 , wherein the polycondensation catalyst is a co-precipitate of TiO 2 :SiO 2 .
11. The polyester as claimed in claim 1 , wherein the amount of titanium is 5 to 50 ppm, based on the amount of the polyester.
12. The polyester as claimed in claim 1 , wherein the agglomerated carbon black is added in the form of a carbon black dispersion after the esterification, and wherein primary carbon black particles are dispersed in a lower-aliphatic diol, with admixture of a dispersing agent.
13. The polyester as claimed in claim 12 , wherein the carbon black dispersion is composed of primary carbon black particles with an average primary particle size below 100 nm and of a dispersing agent and ethylene glycol.
14. The polyester as claimed in claim 12 , wherein the dispersing agent is ionic and has been selected from the group consisting of polyacrylate, modified polyacrylate, naphthalenesulfonic acid-formaldehyde resin, and poly(vinylpyrrolidone-co-3-methyl-1-vinylimidazolium methyl sulfate).
15. The polyester as claimed in claim 12 , wherein the dispersing agent is nonionic and has been selected from the group consisting of polyvinylpyrrolidone, poly(vinylpyrrolidone-co-vinyl acetate), polyvinylcaprolactam, poly(viinylpyrrolidone-co-vinylcaprolactam), ethoxylated novolak, tristyrylphenol ethoxylate, and tri-sec-butylphenyl ethoxylate.
16. The polyester as claimed in claim 12 , wherein the carbon black is a gas black whose pH is below 7.
17. The polyester as claimed in claim 16 , wherein the dibutyl phthalate absorption rate, given by the ratio of dibutyl phthalate in ml to 100 g of carbon black powder, is in the range from above 50 to below 150.
18. The polyester as claimed in claim 17 , wherein the dibutyl phthalate absorption is in the range from above 90 to below 130.
19. The polyester as claimed in claim 12 , wherein the carbon black is a furnace black (flame black) whose pH is above 7.
20. The polyester as claimed in claim 12 , wherein the proportion of the dispersing agent is from 1 to 60% by weight, based on the dispersed carbon black.
21. The polyester as claimed in claim 12 , wherein the carbon black content of the dispersion is from 0.1 to 50% by weight, based on the dispersion.
22. The polyester as claimed in claim 21 , wherein the carbon black content of the dispersion is from 5 to 15% by weight, based on the dispersion.
23. The polyester as claimed in claim 12 , wherein the carbon black dispersion is composed of primary carbon black particles with an average primary particle size from 13 to 50 nm and of a dispersing agent and ethylene glycol.
24. The polyester as claimed in claim 1 , wherein 95% of the total number of agglomerated carbon black particles in the polyester have a diameter below 10 μm.
25. The polyester as claimed in claim 1 , wherein the polyester is incorporated into at least one of a textile filament and a technical filaments for use in safety belts, nets, staple fibers, BCF fibers, and monofilaments.
26. The polyester as claimed in claim 1 , wherein the polyester is incorporated into a fiber-nonwoven structures.
27. The polyester as claimed in claim 1 , wherein the polyester is incorporated into a film and provides the film with at least one of high-strength coloring, shading, and UV protection.
28. The polyester as claimed in claim 1 , wherein the polyester is incorporated into a master batch for use as an additive to polymer components.
29. The polyester as claimed in claim 1 , wherein the polyester is incorporated into an injection-molded articles.
30. A process for preparing a polyester comprising: reacting dimethyl terephthalate and a lower-aliphatic diol or, respectively, terephthalic acid and a lower-aliphatic diol to produce a prepolymer blend; polycondensing said prepolymer blend with the aid of a Ti compound as polycondensation catalyst, admixing from 0.01 to 20% by weight of carbon black, based on the weight of the polyester, which has been dispersed in a lower-aliphatic diol together with a dispersing agent, and optionally mixing phosphorus-containing compounds as additives with the other components of the reaction.
31. The process as claimed in claim 30 , wherein the polycondensation is carried out at a temperature of from 200 to 300° C. and at a subatniospheric pressure of from 0.2 to 0.5 mbar, until a desired IV of from 0.4 to 0.9 dl/g, measured in dichloroacetic acid at 25° C., has been achieved.
32. The process as claimed in claim 30 , wherein for the carbon black dispersion from 0.1 to 50% by weight of gas black or furnace black, based on the total weight of the carbon black dispersion, in the form of primary particles with an average particle size of from 13 to 50 nm, and from 1 to 60% by weight of dispersing agent, based on the carbon black, are dispersed in ethylene glycol.