USE OF ORGANIC OXYIMIDES AS RADICAL GENERATORS IN PLASTICS, METHOD FOR GENERATING RADICALS IN PLASTICS AND USE OF SAID METHOD

Abstract

The present invention relates to the use of phosphorus-containing organic oxyimides according to the general formula I described below as flame retardant for plastic materials, as radical generators in plastic materials and/or as stabilisers for plastic materials. The present invention relates in addition to a flame-retardant plastic material moulding compound in which the previously described phosphorus-containing organic oxyimides are integrated, and also to a method for the production of the previously mentioned plastic material composition. Furthermore, the present invention relates to a moulded part, a paint or a coating made of the previously mentioned flame-retardant plastic material composition.

Claims

1-18. (canceled)

19. A method of incorporating a radical generator into a plastic material comprising incorporating into said plastic material an organic oxyimide having the structural element of formula I ##STR00031##

20. The method according to claim 19, wherein the oxyimide is selected from the group consisting of a) oxyimides comprising at least one structural element of formula II ##STR00032## wherein R.sup.1 is hydrogen or an optionally substituted alkyl-, cycloalkyl-, aryl-, heteroaryl- or acyl-radical, and b) bridged oxyimides comprising at least one structural element of formula III, ##STR00033## wherein R.sup.2 is an optionally substituted akylene-, cycloalkylene-, arylene-, heteroarylene- or bridging acyl-radical.

21. The method according to claim 20, wherein R.sup.2 is selected from the group consisting of (CH.sub.2).sub.n with n=1 to 18, CH(CH.sub.3), C(CH.sub.3).sub.2, O, S, SO.sub.2, NHCO, CO ##STR00034## wherein the cycloaliphatic or aromatic ring systems contained in the above groups is unsubstituted or substituted by one or more alkyl- and/or alkoxy-groups, Q upon each occurrence, is the same or different and is selected from the group consisting of a chemical bond, (CH.sub.2).sub.n with n=1 to 18, CH(CH.sub.3), C(CH.sub.3).sub.2, O, S, SO.sub.2, NHCO, CO, OC(O)O and m is 0 or 1 to 18.

22. The method according to claim 19, wherein the organic oxyimide has one of the following formulae, ##STR00035## ##STR00036## R.sup.1 and R.sup.2 having respectively the above-indicated meaning.

23. The method according to claim 20, wherein R.sup.1H, R.sup.1=alkyl or R.sup.1=acyl.

24. The method according to claim 19, which further includes incorporating at least one chain transfer agent.

25. The method according to claim 19, which further includes incorporating at least one multifunctional compound selected from the group consisting of a) repeatedly unsaturated oligomers and polymers based on polybutadiene or polyisoprene, b) di- and polyvinyl compounds, c) di- and polyallyl compounds, d) di- and polymaleimides, e) di- and poly(meth)acrylesters of di- and polyalcohols, and f) organofunctional silanes, and combinations thereof.

26. The method according to claim 19, which further includes incorporating at least one nitroxyl radical.

27. The method according to claim 19, which further includes incorporating at least one catalytic compound.

28. The method according to claim 19, which includes incorporating at least one further radical former.

29. The method according to claim 28, wherein the further radical former is selected from the group consisting of N-alkoxyamines, CC radical formers, radical formers with azo groups (NN), radical formers with hydrazine groups (NHHN), radical formers with hydrazone groups (CNNH), radical formers with azine groups (>CNNC<), radical formers with triazene groups (NNN<), radical formers with disulfide- or polysulfide groups (SS), radical formers with thiol groups (SH), thiuram sulfide, dithiocarbamates, mercaptobenzothiazole, and sulphenamides.

30. The method according to claim 29, wherein the further radical former is selected from the group consisting of a) N-alkoxyamines according to the structural formula ##STR00037## wherein R.sup.3 is hydrogen or an optionally substituted alkyl-, cycloalkyl-, aryl-, heteroaryl- or acyl-radical, R.sup.4 is an alkoxy-, aryloxy-, cycloalkoxy-, aralkoxy- or acyloxy-radical, Z is hydrogen or an optionally substituted alkyl-, cycloalkyl-, aryl-, heteroaryl- or acyl-radical, or two Z radicals form a closed ring which is optionally substituted with an ester-, ether-, amine-, amide-, carboxy- or urethane-group, b) azo compounds according to the structural formulae
R.sup.5NNR.sup.5 or ##STR00038## wherein R.sup.5 is an alkyl-, cycloalkyl- or aryl-radical, R.sup.6 upon each occurrence, is the same or different and is a linear or branched alkyl-radical, R.sup.7 upon each occurrence, is the same or different and is hydrogen or a linear or branched alkyl-radical, and R.sup.8 upon each occurrence, is the same or different and is an alkyl-, alkoxy-, aryloxy-, cycloalkyloxy-, aralkoxy or acyloxy-radical, c) dicumylenes according to the structural formula ##STR00039## wherein R.sup.7 has the previously indicated meaning, and d) polycumylenes according to the structural formula ##STR00040## wherein R.sup.7 has the previously indicated meaning and 2<n<100.

31. The method according to claim 19, wherein the plastic materials are thermoplastic, elastomeric or duroplastic polymers.

32. The method according to claim 31, wherein the plastic materials are thermoplastic polymers.

33. The method according to claim 32, wherein the thermoplastic polymers are selected from the group consisting of a) polymers made of olefins or diolefins, b) polystyrene, polymethylstyrene, polyvinyl naphthalene, styrene-butadiene (SB), styrene-butadiene-styrene (SBS), styrene-ethylene-butylene-styrene (SEBS), styrene-ethylene-propylene-styrene, styrene-isoprene, styrene-isoprene-styrene (SIS), styrene-butadiene-acrylonitrile (ABS), styrene-acrylonitrile-acrylate (ASA), styrene-ethylene, and styrene-maleic anhydride polymers, c) halogen-containing polymers, d) polymers of unsaturated esters, e) polymers made of unsaturated alcohols and derivatives, f) polyacetals, g) polyphenylene oxides and blends with polystyrene or polyamides, h) polymers of cyclic ethers, i) polyurethanes made of hydroxy-terminated polyethers or polyesters and aromatic or aliphatic isocyanates, j) polyamides, k) polyimides, polyamide imides, polyether imides, polyester imides, poly(ether)ketones, polysulphones, polyethersulphones, polyarylsulphones, polyphenylene sulphide, polybenzimidazoles, and polyhydantoins, l) polyesters made of aliphatic or aromatic dicarboxylic acids and diols or made of hydroxycarboxylic acids, m) polycarbonates, polyester carbonates, and blends thereof, n) cellulose derivatives, o) non-thermoplastic or duroplastic plastic materials, and p) mixtures, combinations, or blends thereof.

34. The method according to claim 19, wherein the organic oxyimide is incorporated at a concentration of 0.01 to 30% by weight, relative to the plastic material.

35. The method according to claim 19, which results in modification of the plastic material, wherein the result is increasing the molecular weight of the plastic material, branching or crosslinking of the plastic material, molecular weight decrease of the plastic material, influencing a molecular weight distribution of the plastic material, and/or grafting of unsaturated monomers onto the plastic material.

36. The method according to claim 19, wherein the radical generator is activated thermally or by irradiation.

37. The method according to claim 36, wherein the activation is effected during shaping of the plastic material or shaping of a moulding compound comprising the plastic material.

38. The method according to claim 37, wherein the shaping is carried out by injection moulding or by extrusion.

Description

EXAMPLE 1

Molecular Weight Decrease of Polypropylene

[0166] The extrusions of the polypropylene samples (Moplen HP 500N) with addition of the radical generators are effected at the indicated temperature and with a screw speed of rotation of 400 rpm on an 11 mm twin-screw extruder (Process 11 of Thermo Scientific). The desired ratio of polymer and additives is firstly homogenised by mixing and supplied for extrusion via volumetric metering. The MVR (melt volume rate) of the granulated extruded samples was determined subsequently at 230 C./2.16 kg according to ISO 1133 and the average weight of the molecular weight was determined by means of high-temperature gel permeation chromatography.

TABLE-US-00001 TABLE 1 Compositions in polypropylene and results of the analyses of the melt volume flow rates and of the molecular weight Test Extrusion number Additive temperature [] MVR Mw Comparative Without 240 14 400,000 example 1 Comparative Without 260 15 381,000 example 2 Comparative Without 280 22 362,000 example 3 Comparative Without 300 25 n.d. example 4 Example 1 0.1% oxyimide 1 280 45 n.d. according to the invention Example 2 0.2% oxyimide 1 280 61 244,000 Example 3 0.5% oxyimide 1 280 84 n.d. Example 4 0.2% oxyimide 1 240 25 346,000 Example 5 0.2% oxyimide 1 260 30 317,000 Example 6 0.2% oxyimide 1 300 >200 n.d. Example 7 0.1% oxyimide 2 280 27 n.d. n.d. = not determined

[0167] Oxyimide 1=N-hydroxyphthalimide

##STR00029##

[0168] Oxyimide 2 (produced according to WO 2014154636)

##STR00030##

[0169] Surprisingly, it is shown that the compositions with the oxyimides according to the invention have a higher MVR (=lower molecular weight) and, likewise, in the GPC measurement, a lower molecular weight than the comparative examples. With increasing concentration of oxyimide and increasing processing temperature, the molecular weight reduces furthermore.

EXAMPLE 2

Molecular Weight Increase of Polyethylene

[0170] The molecular weight increase of the PE types (obtainable at ExxonMobil) via reactive extrusion with N-hydroxyphthalimide (NHPI) was effected at 200 C., with a screw speed of rotation of 300 rpm on an 11 mm twin-screw extruder (Process 11 of Thermo Scientific). The analyses of the melt volume flow rates (MVR) were effected according to ISO 1133 at a temperature of 190 C. and a weight of 5 kg or 10 kg.

TABLE-US-00002 TABLE 2 Compositions in polyethylene and results of the analyses of the melt volume flow rates MVR MVR (5 kg, 190 C.)/ (10 kg, 190 C.)/ Example Composition cm.sup.3 * min.sup.1 cm.sup.3 * min.sup.1 Comparative example 1 LDPE (LD 185 BW) 100% 10.2 31.7 NHPI 0% Example 1 according LDPE (LD 185 BW) 99.80% 9.9 to the invention NHPI 0.20% Example 2 according LDPE (LD 185 BW) 99.60% 9.7 to the invention NHPI 0.40% Example 3 according LDPE (LD 185 BW) 99.20% 9.0 31.2 to the invention NHPI 0.80% Comparative example 2 HDPE (HTA 108) 100% 12.9 NHPI 0% Example 4 according HDPE (HTA 108) 99.20% 12.5 to the invention NHPI 0.80%

[0171] With reference to the significant reduction in MVR values of the examples according to the invention relative to the comparative examples, an increase in melt viscosity is shown, which can be attributed to an increase in the molecular weight. Hence, a controlled increase in the molecular weight by means of the method described within the present application can be established.