Oligomer or polymer, composition, use of the oligomer or polymer and intermediate

Abstract

This object is achieved by an oligomer or polymer, comprising a phosphorus-comprising structural element described herein, its composition comprising the aforementioned oligomer or polymer and an organic component to be stabilized, and by the possible uses of the oligomers or polymers according to the invention, relating to a molding compound or a molded part, and relating to an intermediate suitable for synthesizing the oligomers or polymers according to the invention. Advantageous developments thereof are also described.

Claims

1. 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; the oligomer or polymer further comprising the following repeating unit of Formula III ##STR00024## wherein D is the same or different at each occurrence and is a functionality derived A from an aliphatic or heterocyclic.

2. The oligomer or polymer according to claim 1, wherein R.sup.1 is defined according to Formula IIa ##STR00025##

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

4. The oligomer or polymer according to claim 3, where the functionality derived from a diol is a functionality derived from hydroxyethyl-4-hydroxytetramethylpiperidine, 1,4-dithiane-2,5-diol, or 2,3-dimethoxy-1,4-butanediol.

5. The oligomer or polymer according to claim 1, wherein the repeating unit is defined according to the repeating units of Formulas III and IIIa ##STR00027## 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.

6. The oligomer or polymer according to claim 5, wherein the molar ratio of the repeating units III to IIIa is from 0.1:99.9 to 50:50.

7. A composition comprising at least one organic component to be stabilized and at least one oligomer or polymer according to claim 1.

8. The composition according to claim 7, 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.

9. The composition according to claim 7, 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.

10. The composition according to claim 7, 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.

11. A method of stabilizing an organic material comprising incorporating into the organic material an effective amount of an oligomer or polymer according to claim 1.

12. The method according to claim 11, 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.

13. A molding compound or a molded part, produced from a plastic composition according to claim 7.

14. The molded part according to claim 13, 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.

Description

Methods for Stabilization

(1) The additive according to the invention, which can be present as a powder, liquid, oil, compacted, on a carrier material, as granulate, solution or flakes, is preferably mixed with the polymer to be stabilized; the polymer matrix is melted and then cooled. As an alternative to this, it is also possible to introduce the additive into a polymer melt in a molten state.

(2) If further components are added to the polymer composition, said components can be added to the polymers separately in the form of liquids, powders, granules or compacted products, or together with the additive composition according to the invention, as described above.

(3) The additive composition described above and optionally additional additives are incorporated into the plastic through conventional processing methods, wherein the polymer is melted and mixed with the additive composition according to the invention and the optionally further additives, preferably using mixers, kneaders and extruders. Extruders, such as e.g. single-screw extruders, twin-screw extruders, planetary roller extruders, ring extruders, co-kneaders, which are preferably equipped with vacuum degassing, are preferred as processing machines. The processing can take place under air or optionally under inert gas conditions.

(4) Furthermore, the additive compositions according to the invention can be produced and introduced in the form of so-called masterbatches or concentrates comprising, for example, 10-90% of the compositions according to the invention in a polymer.

(5) The present invention is described in more detail using the following embodiments, without restricting the subject matter of the present invention to the examples.

Synthesis Example 1: Synthesis of Tocopherol Phosphorus Dichloride

(6) 1 ml (11.4 mmol) of phosphorus trichloride, 4.9117 g (11.4 mmol) of -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 a-tocopherol phosphorus dichloride are determined by means of .sup.1H and .sup.31P NMR spectra. The purity of the product is >99%.

(7) ##STR00017##

Synthesis Example 2: Synthesis of a Polymeric Phosphite Having Isosorbide Units

(8) 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.

(9) ##STR00018##

Synthesis Example 3: Synthesis of a Copolymer Comprising Isosorbide and Piperidine Units

(10) 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.

(11) ##STR00019##

Synthesis Example 4: Synthesis of a Polymeric Phosphite Having Hydroquinone Units

(12) ##STR00020##

(13) 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

(14) 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.

Synthesis Example 6: Synthesis of a Polymeric Phosphite Having 1,4-Cyclohexanediol Units

(15) ##STR00021##

(16) 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

(17) A structure comparable to that in Example 1 was used. 1.5862 g (10.3 mmol) of vanillyl 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

(18) 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 1H and .sup.31P NMR spectra.

Synthesis Example 9: Synthesis of a Polyphosphite Having Hydroxyethyl-4-Hydroxytetramethylpiperidine Units

(19) 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

(20) 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.

(21) 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%

(22) 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

(23) 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.

(24) 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

(25) 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.

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

(27) 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

(28) 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.).