ADDITIVE COMPOSITION AND USE THEREOF, CONDENSATION POLYMER COMPOSITION, MOLDING COMPOUND AND MOLDING COMPOUNDS PRODUCED THEREFROM, AND MOLDED PARTS AND USE THEREOF

Abstract

The invention relates to an additive composition with inorganic sulfites, organic derivatives of sulfurous acid and/or thiosulfates, and organic phosphorus compounds, said composition being capable of accelerating the hydrolytic decomposition of a thermoplastic condensation polymer upon working said additive composition into the condensation polymer. The invention additionally relates to a condensation polymer composition which is additivized with an additive composition according to the invention. The invention additionally relates to a method for the hydrolytic decomposition of a thermoplastic condensation polymer and to uses of the additive composition according to the invention and the thermoplastic condensation polymer composition.

Claims

1-23. (canceled)

24. An additive composition comprising: (a) at least one inorganic substance, at least one organic derivative of sulfurous acid or sulfinic acid, and/or at least one thiosulfate, and (b) at least one organic phosphorus compound.

25. The additive composition in accordance with claim 24, wherein the inorganic substance is a sulfite, a disulfite, or a hydrogen sulfite of a monovalent, bivalent, trivalent, or tetravalent metal.

26. The additive composition in accordance with claim 24, wherein the organic derivative of sulfurous acid or sulfinic acid is an organic ester of sulfurous acid or the sulfinic acid.

27. The additive composition in accordance with claim 24, wherein the inorganic thiosulfate is a thiosulfate of a monovalent, bivalent, trivalent, or tetravalent metal.

28. The additive composition in accordance with claim 24, wherein the organic phosphorous compound is hydrolyzable.

29. The additive composition in accordance with claim 24, wherein the organic phosphorus compound is selected from the group consisting of phosphites having one, two, or 3 linear or branched alkoxy groups, phosphites of the formulas: ##STR00017## wherein R.sup.1 is the same or different on every occurrence and is selected from the group consisting of linear or branched alkyl residues having 1 to 36 carbon atoms and aryl residues, compounds of the formula P(OR.sup.1).sub.3, where R.sup.1 is selected from the group consisting of linear or branched alkyl residues having 4 to 32 carbon atoms, and phosphates, diphosphates, metaphosphates, and polyphosphates that are derived from said phosphites.

30. The additive composition of claim 29, wherein the compound of formula the formula P(OR.sup.1).sub.3 is selected from the group consisting of trilauryl phosphite, triisodecyl phosphite, tridecyl phosphite, trihexadecyl phosphite, trioctadecyl phosphite, tribehenyl phosphite, triarachidyl phosphite, triceryl phosphite, trioleyl phosphite, trioleyl phosphite, and tris(2-ethylhexyl) phosphite, diphosphites and their higher molecular homologs, polyphosphites, partially esterified phosphonic acid compounds, tautomer form monostearyl phosphonate, distearyl phosphite and their alkali, alkaline earth salts, aluminum, or zinc salts, and phosphonites.

31. The additive composition in accordance with claim 24, wherein the organic phosphorus compound is a phosphite selected from the group consisting of ##STR00018## ##STR00019## where n is from 3 to 100, ##STR00020## where n is from 3 to 100, ##STR00021##

32. The additive composition in accordance with claim 24, wherein the organic phosphorus compound is a phosphonite.

33. The additive composition in accordance with claim 24, wherein the organic phosphorous compound is a phosphate.

34. The additive composition in accordance with claim 24, wherein the totality of the at least one sulfite, of the at least one organic derivative of the sulfurous acid, and/or of the at least one thiosulfate and the totality of the at least one organic phosphorus compound is present at a weight ratio of 20:1 to 1:20.

35. A condensation polymer composition comprising (A) at least one condensation polymer, and (B) an additive composition in accordance with claim 24.

36. The condensation polymer composition in accordance with claim 35, wherein the condensation polymer is selected from the group consisting of polyesters of aliphatic or aromatic dicarboxylic acids and diols, polyesters of hydroxylic carbon acids, and copolymers and mixtures or blends of two or more thereof; polyamides; semiaromatic polyamides; polycarbonates or polyester carbonates; and mixtures, combinations, or blends of two or more thereof.

37. The condensation polymer composition in accordance with claim 35, wherein the condensation polymer is selected from the group consisting of PLA, PBA, and copolymers thereof.

38. The condensation polymer composition in accordance with claim 35, wherein the additive composition is present in an amount of 0.01 to 10.00 wt % with respect to the total condensation polymer composition.

39. The condensation polymer composition in accordance with claim 35, further including at least one additive selected from the group consisting of primary antioxidants, secondary antioxidants, UV absorbers, light stabilizers, metal deactivators, filler deactivators, antiozonants, nucleation agents, anti-nucleation agents, toughening agents, mold lubricants, rheological modifiers, thixotropic agents, chain extenders, processing aids, mold removal aids, flame retardant agents, pigments dyes, optical brighteners, antimicrobial active agents, antistatic agents, slip agents, anti-blocking agents, coupling agents, crosslinking agents, anti-cross-linking agents, hydrophilization agents, hydrophobing agents, hydrolysis stabilizers, bonding agents, dispersing agents, compatibilizers, oxygen scavengers, acid scavengers, expanding agents, degradation additives, defoaming agents, odor scavengers, marking agents, and anti-fogging agents.

40. The condensation polymer composition in accordance with claim 39, wherein the at least one additive is contained in the condensation polymer composition in an amount of 0.01 to 5.00 wt % with respect to the total condensation polymer composition.

41. The condensation polymer composition in accordance with claim 39, wherein up to 80 parts by weight of at least one plasticizer, filler, and/or reinforcing material is/are contained with respect to 100 parts by weight of components (A) and (B).

42. The condensation polymer composition in accordance with claim 39, wherein (i) the degradation additives are selected from organic transition metal compounds; (ii) the plasticizers are selected from the group consisting of tributyl acetylcitrate, tributyl citrate, triethyl acetylcitrate, triethylcitrate, glycerol triacetate, epoxidized soy bean oil, and epoxidized linseed oil; (iii) the nucleation agents are selected from the group consisting of talcum, alkaline salts or alkaline earth salts of monofunctional and polyfunctional carboxylic acids, zinc glycerolate, 2,2′-methylene-bis-(4,6-di-tert-butylphenyl) phosphate, trisamides, and diamides; (iv) the chain extenders are selected from the group consisting of diepoxides, bis-oxazolines, bisoxazolones, bis-oxazines, diisocyanates, dianhydrides, bis-allyllactams, bis-maleimides, dicyanates, carbodiimides, and polymer chain extenders, and (v) the fillers and/or reinforcement materials are selected from the group consisting of calcium carbonates, silicates, talcum, mica, kaolins, metal oxides, metal hydroxides, black carbon, graphite, wood flour, fibers of natural products, fiberglass, carbon fibers, polyaramide fibers, and other synthetic polymer fibers, hydrotalcites, zeolites, and/or phyllosilicates.

43. The condensation polymer composition in accordance with claim 39, wherein the condensation polymer composition comprises: (A) 85.00 to 99.98 parts by weight, of the at least one condensation polymer, (B) 0.01 to 10.00 parts by weight, of the additive composition, and (C) 0.01 to 5.00 parts by weight of the at least one additive.

44. A molding compound or a molded part made from a condensation polymer composition in accordance with claim 35.

45. A method for hydrolytically decomposing a condensation polymer comprising combining an additive composition in accordance with claim 24 to the condensation polymer and the resulting composition is exposed to a hydrolyzing condition.

46. The method of claim 44, wherein the rate of hydrolysis is higher than that of a condensation polymer not combined with the additive composition.

Description

EMBODIMENTS

[0126] Luminy L 175 (≤0.5% D-lactic acid in accordance with the certificate, MVR=4.7 cm.sup.3/10 min, measured at 190° C./2.16 kg stamped weight) of the company of Corbion was used as PLA. The polymers were dried at 80° C. in a vacuum drying cabinet for at least 16 h before processing.

[0127] The manufacture of the examples in accordance with the invention and of the comparison examples took place by extrusion using a parallel twin screw extruder Process 11 of the company Thermo Scientific, having a screw diameter of 11 mm and a length to diameter ratio (/D) of 40.

[0128] The additives were manually mixed with the matrix polymer in a plastic bag and were volumetrically metered. The phosphate that is fluid at room temperature was diluted in ethyl acetate, was mixed with the polymer already derived at 80° C. in the vacuum furnace for 16 h, and was subsequently dried at 60° C. in the vacuum furnace for at least 16 h. The processing took place at a throughput of 1 kg/h and a screw speed of 200 r.p.m. at 200° C.

[0129] The polymer was stored as pellets in deionized water at 58° C. and the MVR was determined after different times.

[0130] The measurement of the MVR took place on a melt index test unit Ml-2 of the company Göttfert at a test temperature of 190° C. and a stamped weight of 2.16 kg. The samples were dried for approximately 16 h in the vacuum furnace at 80° C. before the measurement. The preheating time amounted to 4 minutes. The MVR is indicated in cm.sup.3/10 min.

TABLE-US-00001 MVR after MVR after MVR after 168 h MVR after 48 h water 96 h water water Example Additive extrusion storage storage storage Comparison Without 5.4 13.7 26  66 example 1 additive Example 1 in 0.4% sodium 5.2 21 48 152 accordance with sulfite + 0.1% the invention phosphite Example 2 in 0.25% sodium 6.3 32 81 306 accordance with sulfite + 0.25% the invention phosphite Example 3 in 0.1% sodium 6.2 46 132 >>300  accordance with sulfite + 0.4% the invention phosphite Example 4 in 0.5% sodium 7.2 42 124 280 accordance with sulfite + 0.5% the invention phosphite Example 5 in 0.25% sodium 8.0 60 202 >300  accordance with sulfite + 0.5% the invention phosphite Example 6 in 0.1% sodium 9.4 59 155 >300  accordance with sulfite + 0.5% the invention phosphite Example 7 in 0.25% sodium 4.4 11.6 28  79 accordance with sulfite + 0.25% the invention phosphate Example 8 in 0.1% sodium 4.8 16.2 45 138 accordance with sulfite + 0.4% the invention phosphate

[0131] Weston 618F (manufacturer: SI Group) of the following structure was used as the phosphite:

##STR00015##

[0132] Trioctylphosphate (Alfa Aesar) of the following structure was used as the phosphate:

##STR00016##

[0133] The combination of sulfite and phosphite or of sulfite and phosphate (examples in accordance with the invention) demonstrate a very much faster hydrolysis over the comparison example since a higher MVR is obtained in the same time of the water storage. The hydrolysis resistance of the polycondensation polymer can be controlled by a tailored additive recipe with a set ratio of sulfite to phosphite or phosphate.