OLIGOMER OR POLYMER, COMPOSITION, USE OF THE OLIGOMER OR POLYMER AND INTERMEDIATE

Abstract

The present invention relates to an oligomer or polymer, or to a composition comprising said oligomer or polymer, which are particularly useful as a stabiliser for organic materials. The present invention also relates to an intermediate for the synthesis of the above-mentioned oligomers or polymers.

Claims

1-16. (canceled)

17. An oligomer or polymer, comprising, as a structural element, a structure according to the general Formula I ##STR00022## wherein R.sup.1 is defined according to Formula II ##STR00023## wherein R is the same or different at each occurrence and is selected from the group consisting of hydrogen or linear or branched alkyl radicals having from 1 to 36 carbon atoms, and x is 0 or 1.

18. The oligomer or polymer according to claim 17, wherein R.sup.1 is defined according to Formula IIa ##STR00024##

19. The oligomer or polymer according to claim 17, which comprises the following repeating unit according to Formula III ##STR00025## wherein D is the same or different at each occurrence and is a functionality derived from a diol.

20. The oligomer or polymer according to claim 19, wherein the functionality derived from a diol is a functionality derived from an aliphatic, aromatic, or heterocyclic diol.

21. The oligomer or polymer according to claim 19, wherein the functionality derived from a diol is a) a functionality derived from an aliphatic diol; b) a functionality derived from an aromatic diol; c) a functionality derived from a heterocyclic diol; or d) a functionality derived from one of the following diols: 2,3-dimethoxy-1,4-butanediol, ##STR00026##

22. The oligomer or polymer according to claim 21, wherein the functionality derived from a diol is a functionality derived from: hydroxyethyl-4-hydroxytetramethylpiperidine, 1,4-dithiane-2,5-diol, hydroquinone, resorcinol, 1,5-, 2,6- or 2,7-dihydroxynaphthalene, or vanillyl alcohol, or a functionality derived from one of the following diols: ##STR00027## wherein, respectively independent of one another, A means a direct bond, —O—, —SO.sub.2—, —C(O)—, —CH(CH.sub.3)— or —C(CH.sub.3).sub.2—, and R′ and R″ are the same or different at each occurrence and are selected from the group consisting of linear or branched alkyl moieties having 1 to 36 carbon atoms, or a functionality derived from hydroxyethyl-4-hydroxytetramethylpiperidine, 1,4-dithiane-2,5-diol, or 2,3-dimethoxy-1,4-butanediol.

23. The oligomer or polymer according to claim 19, wherein the repeating unit is defined according to the repeating units of Formulas III and IIIa ##STR00028## and these are comprised in the oligomer or polymer, wherein D′ corresponds to the definition of D, with the proviso that D and D′ are derived from different diols.

24. The oligomer or polymer according to claim 23, wherein the molar ratio of the repeating units III to IIIa is from 0.1:99.9 to 50:50.

25. The oligomer or polymer according to claim 17, wherein x is 0 for all repeating units according to Formula I, or the oligomer or polymer comprises both repeating units according to Formula I, in which x=0, and repeating units according to Formula I, in which x=1, wherein the molar ratio of the repeating units according to Formula I, in which x=0, to the repeating units according to Formula I, in which x=1, is from 50:50 to <100:>0.

26. A composition comprising at least one organic component to be stabilized and at least one oligomer or polymer according to claim 17.

27. The composition according to claim 26, wherein the at least one oligomer or polymer is present in a proportion by weight, based on the total composition, of 0.01 to 5.0 parts by weight.

28. The composition according to claim 26, wherein the at least one organic component to be stabilized is selected from the group consisting of plastics, at least one oil, fat or wax, and polymerizable monomers.

29. The composition according to claim 26, comprising at least one additive selected from the group consisting of primary antioxidants, secondary antioxidants, UV absorbers, light stabilizers, metal deactivators, filler deactivators, antiozonants, nucleating agents, antinucleating agents, impact modifiers, plasticizers, lubricants, rheology modifiers, thixotropic agents, chain extenders, processing aids, mold release agents, flame retardants, pigments, dyes, optical brighteners, antimicrobial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, crosslinking agents, anticrosslinking agents, hydrophilic agents, hydrophobic agents, adhesion promoters, dispersants, compatibilizers, oxygen scavengers, acid scavengers, blowing agents, degradation additives, defoaming aids, odor scavengers, marking agents, anti-fogging agents, fillers and reinforcements.

30. A method of stabilizing an organic material comprising incorporating into the organic material an effective amount of an oligomer or polymer according to claim 17.

31. The method according to claim 30, wherein the oligomer or polymer: provides protection against thermal, actinic or oxidative degradation of plastics, provides flame retardancy to plastics, provides protection against thermal, actinic or oxidative degradation of lacquers, paints and coatings, provides protection against thermal, actinic or oxidative degradation of oils, fats or waxes, provides protection against thermal, actinic or oxidative degradation of mineral or synthetic lubricants, hydraulic oils, engine oils, turbine oils, gear oils, metalworking fluids or lubricating greases, or provides protection against premature polymerization and/or oxidation of polymerizable monomers.

32. A molding compound or a molded part, produced from a plastic composition according to claim 26.

33. The molded part according to claim 32, which is an injection molded part, a foil, a film, a foam, a fiber, a cable, a pipe, a profile, a hollow body, a ribbon, a membrane and/or an adhesive.

34. An intermediate according to claim 19, which is of the following general formula IV ##STR00029## wherein R.sup.1 and x are as already defined, and X is the same or different at each occurrence and represents a leaving group.

35. The intermediate according to claim 34, wherein the leaving group is selected from the group consisting of Cl, Br, and I.

36. The intermediate according to claim 34, wherein the diol from which a functionality is derived from is selected from the group consisting of ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,3-cyclohexanediol and 1,4-cyclohexanedimethanol.

Description

SYNTHESIS EXAMPLE 1

Synthesis of Tocopherol Phosphorus Dichloride

[0164] 1 ml (11.4 mmol) of phosphorus trichloride, 4.9117 g (11.4 mmol) of α-tocopherol and 40 ml of chloroform are placed in a 250 ml three-necked flask having a reflux condenser and magnetic stirrer. The reaction mixture is heated at 70° C. for 10 hours. The purity and conversion of the α-tocopherol phosphorus dichloride are determined by means of .sup.1H and .sup.31P NMR spectra. The purity of the product is >99%.

##STR00017##

SYNTHESIS EXAMPLE 2

Synthesis of a Polymeric Phosphite having Isosorbide Units

[0165] A structure comparable to that in Example 1 was used. 1.5015 g (10.3 mmol) of isosorbide, 8 ml (36.1 mmol) of triethylamine and 20 ml of acetonitrile are added to the tocopherol phosphorus dichloride. 2 ml (49.3 mmol) of methanol are added after one hour at room temperature. The product is purified in toluene. The purity of the polyphosphite is determined by means of .sup.1H and .sup.31P NMR spectra.

##STR00018##

SYNTHESIS EXAMPLE 3

Synthesis of a Copolymer Comprising Isosorbide and Piperidine Units

[0166] A structure comparable to that in Example 1 was used. 0.2063 g (1.0 mmol) of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-ethanol, 4 ml (28.9 mmol) of triethylamine and 20 ml of chloroform are added to the tocopherol phosphorus dichloride. After one hour, 1.3467 g (9.2 mmol) of isosorbide, 5.5 ml (39.7 mmol) of triethylamine and 20 ml of acetonitrile are added to the reaction mixture. 2 ml (49.3 mmol) of methanol are added after one hour at room temperature. The product is purified in toluene. The purity of the polyphosphite is determined by means of .sup.1H and .sup.31P NMR spectra.

##STR00019##

SYNTHESIS EXAMPLE 4

Synthesis of a Polymeric Phosphite having Hydroquinone Units

[0167] ##STR00020##

[0168] A structure comparable to that in Example 1 was used. 1.1290 g (10.3 mmol) of hydroquinone, 8 ml (36.1 mmol) of triethylamine and 20 ml of acetonitrile are added to the tocopherol phosphorus dichloride. 2 ml (49.3 mmol) of methanol are added after one hour at room temperature. The product is purified in toluene. The purity of the polyphosphite is determined by means of .sup.1H and .sup.31P NMR spectra.

SYNTHESIS EXAMPLE 5

Synthesis of a Copolymer Comprising Hydroquinone and Piperidine Units

[0169] A structure comparable to that in Example 1 was used. 0.2065 g (1.0 mmol) of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-ethanol, 4 ml (28.9 mmol) of triethylamine and 20 ml of chloroform are added to the tocopherol phosphorus dichloride. After one hour, 1.0189 g (9.2 mmol) of hydroquinone, 5.5 ml (39.7 mmol) of triethylamine and 20 ml of acetonitrile are added to the reaction mixture. 2 ml (49.3 mmol) of methanol are added after one hour at room temperature. The product is purified in toluene. The purity of the polyphosphite is determined by means of .sup.1H and .sup.31P NMR spectra.

##STR00021##

SYNTHESIS EXAMPLE 6

Synthesis of a Polymeric Phosphite having 1,4-Cyclohexanediol Units

[0170] A structure comparable to that in Example 1 was used. 1.1952 g (10.3 mmol) of 1,4-cyclohexanediol, 8 ml (36.1 mmol) of triethylamine and 20 ml of acetonitrile are added to the tocopherol phosphorus dichloride. 2 ml (49.3 mmol) of methanol are added after one hour at room temperature. The product is purified in toluene. The purity of the polyphosphite is determined by means of .sup.1H and .sup.31P NMR spectra.

SYNTHESIS EXAMPLE 7

Synthesis of a Polyphosphite having Vanillyl Alcohol Units

[0171] A structure comparable to that in Example 1 was used. 1.5862 g (10.3 mmol) of yanillyl alcohol, 8 ml (36.1 mmol) of triethylamine and 20 ml of acetonitrile are added to the tocopherol phosphorus dichloride. 2 ml (49.3 mmol) of methanol are added after one hour at room temperature. The product is purified in toluene. The purity of the polyphosphite is determined by means of .sup.1H and .sup.31P NMR spectra.

SYNTHESIS EXAMPLE 8

Synthesis of a Polyphosphite having 1,6-Hexanediol Units

[0172] A structure comparable to that in Example 1 was used. 1.2158 g (10.3 mmol) of 1,6-hexanediol, 8 ml (36.1 mmol) of triethylamine and 20 ml of acetonitrile are added to the tocopherol phosphorus dichloride. 2 ml (49.3 mmol) of methanol are added after one hour at room temperature. The product is purified in toluene. The purity of the polyphosphite is determined by means of .sup.1H and .sup.31P NMR spectra.

SYNTHESIS EXAMPLE 9

Synthesis of a Polyphosphite having Hydroxyethyl-4-Hydroxytetramethylpiperidine Units

[0173] A structure comparable to that in Example 1 was used. 2.0713 g (10.3 mmol) of hydroxyethyl-4-hydroxytetramethylpiperidine, 8 ml (36.1 mmol) of triethylamine and 20 ml of acetonitrile are added to the tocopherol phosphorus dichloride. 2 ml (49.3 mmol) of methanol are added after one hour at room temperature. The product is purified in toluene. The purity of the polyphosphite is determined by means of .sup.1H and .sup.31P NMR spectra.

EXAMPLE 1

Long-Term Extrusions

[0174] The compounds of Examples 2, 3, 4, 6, 7, 8 and 9 and the commercial phosphites ADK STAB 2112 (tris(2,4-di-tert-butylphenol) phosphite) and Doverphos S-9228 (bis(2,4-dicumylphenyl)pentaerythritol diphosphite) were incorporated into polypropylene (Moplen HP 500 N) on a Micro Sec Model 2009. The compounds were processed at 200° C. for 30 minutes and the loss of force was measured.

TABLE-US-00001 Polypropylenes 100.0% 99.8% 99.8% 99.8% 99.8% 99.8% 99.8% 99.8% 99.8% 99.8% ADK STAB 2112  0.2% Doverphos S-9228  0.2% Example 2  0.2% Example 3  0.2% Example 4  0.2% Example 6  0.2% Example 7  0.2% Example 8  0.2% Example 9  0.2% Residual force    47%   65%   78%   97%   94%   96%   95%   94%   93%   94% Polypropylenes 99.8% 99.6% 99.6% 99.6% 99.6% 99.6% Calcium stearate  0.2%  0.2%  0.2%  0.2%  0.2%  0.2% (Comparison) ADK STAB 2112  0.2% (Comparison) Example 2  0.2% Example 3  0.2% Example 4  0.2% Example 5  0.2% Residual force   36%   44%   59%   57%   75%   60%

[0175] The polymers according to the invention have a higher residual force than the comparative examples, which results in a greater stabilizing effect.

EXAMPLE 2

Multiple Extrusions

[0176] For further testing, the phosphites were processed with and without a phenolic stabilizer (ADK STAB AO 60, pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)) using a Thermo Scientific Process 11 5 times at 230° C. The MFR (melt flow rate) was determined to analyze the compounds.

TABLE-US-00002 Polypropylene 99.8% 99.6% 99.6% 99.6% 99.6% 99.6% Calcium stearate (Comparison)  0.2% Example 2  0.2% Example 3  0.2% Example 4  0.2% Example 5  0.2% MFI extrusion @ 230° C. 1 Extrusion 17 17 16 15 16 15 2 Extrusion 18 17 16 16 16 15 3 Extrusion 19 16 16 16 16 15 4 Extrusion 19 17 16 16 16 16 5 Extrusion 20 17 16 15 16 16 Polypropylene 99.6% 99.4% 99.4% 99.4% 99.4% 99.4% Calcium stearate  0.2%  0.2%  0.2%  0.2%  0.2%  0.2% ADK STAB AO60 (Comparison)  0.2%  0.2%  0.2%  0.2%  0.2%  0.2% ADK STAB 2112 (Comparison)  0.2% Example 2 00.2% Example 3  0.2% Example 4  0.2% Example 5  0.2% MFI extrusion @ 230° C. 1 Extrusion 17 16 16 16 15 15 2 Extrusion 18 16 16 16 16 16 3 Extrusion 19 16 16 16 15 15 4 Extrusion 19 16 16 15 16 16 5 Extrusion 20 16 16 16 15 15

[0177] For multiple extrusion, the lowest MFR value, i.e. the best stabilizer effect, is obtained with the stabilizers according to the invention.

EXAMPLE 3

Multiple Extrusions at 260° C.

[0178] For further testing, the phosphites were processed without a phenolic stabilizer using a Thermo ScientificProcess 11 5 times at 260° C. The MFR (melt flow rate) was determined to analyze the compounds.

TABLE-US-00003 Polypropylenes 99.8% 99.6% 99.6% 99.6% 99.6% 99.6% 99.6% 99.6% 99.6% Calcium stearate  0.2%  0.2%  0.2%  0.2%  0.2%  0.2%  0.2%  0.2%  0.2% ADK STAB 2112  0.2% Doverphos S-9228  0.2% Example 2  0.2% Example 3  0.2% Example 4  0.2% Example 6  0.2% Example 8  0.2% Example 9  0.2% MFI extrusion @ 260° C. 1. Extrusion  30 23 18 19 17 19 17 17 17 2. Extrusion  43 27 20 19 18 19 18 18 18 3. Extrusion  79 34 21 19 18 20 18 19 18 4. Extrusion 128 43 23 20 18 20 19 20 18 5. Extrusion 209 60 25 20 19 21 20 22 19

[0179] For multiple extrusion, the lowest MFR value, i.e. the best stabilizing effect, is obtained with the stabilizers according to the invention, even at high temperatures (260° C.).