ADDITIVE MIXTURE

Abstract

An additive mixture comprising (I) a copolymer having a number average molecular weight of 800 g/mol to 50 000 g/mol and containing recurring units of the formula (la) and (Ila) or recurring units of the formula (la) and (IIb), wherein the recurring units (la) and (Ila) can have a random, alternating or block distribution and the molar ratio of (la) to (Ila) is 1:10 to 10:1, the recurring units (la) and (lIb) can have a random, alternating or block distribution and the molar ratio of (la) to (lIb) is 1:10 to 10:1, the radicals R.sub.1 independently of one another are C.sub.10-C.sub.30alkyl and the radicals R.sub.2 independently of one another are hydrogen or C.sub.1-C.sub.30acyl, (II) a metal salt, preferably a transition metal salt, and (III) an oxidizable substrate, with the proviso that components (I) and (III) are different.

##STR00001##

Claims

1. An additive mixture comprising (I) a copolymer having a number average molecular weight of 800 g/mol to 50 000 g/mol and containing recurring units of the formula (Ia) and (IIa) or recurring units of the formula (Ia) and (IIb), ##STR00007## wherein the recurring units (Ia) and (IIa) can have a random, alternating or block distribution and the molar ratio of (Ia) to (IIa) is 1:10 to 10:1, the recurring units (Ia) and (IIb) can have a random, alternating or block distribution and the molar ratio of (Ia) to (IIb) is 1:10 to 10:1, the radicals R.sub.1 independently of one another are C.sub.10-C.sub.30alkyl and the radicals R.sub.2 independently of one another are hydrogen or C.sub.1-C.sub.30acyl, (II) a metal salt, preferably a transition metal salt, and (III) an oxidizable substrate, with the proviso that components (I) and (III) are different.

2. The additive mixture according to claim 1, wherein R.sub.2 is hydrogen, C.sub.10-C.sub.30alkanoyl or C.sub.10-C.sub.30alkenoyl, preferably hydrogen or C.sub.16-C.sub.24alkanoyl, in particular hydrogen or stearoyl.

3. The additive mixture according to claim 1, wherein component (II) is an organic salt of Fe, Co, Ce, Mn, Cu, Ni or Vd, preferably of Cu, Co or Mn, in particular Mn.

4. The additive mixture according to claim 1, wherein component (II) is a metal salt of a C.sub.6-C.sub.36carboxylic acid.

5. The additive mixture according to claim 1, wherein component (III) is selected from the group consisting of polybutadiene, polyester, squalane, squalene, polystyrene, poly-limonene, poly alpha pinene, poly beta pinene, poly-norbornene, polylactic acid and a mixture of linear and branched alkyl chain C.sub.6-C.sub.30alcohols.

6. The additive mixture according to claim 1, wherein component (III) is a polyterpene resin, preferably a polyterpene based on an alpha-pinene or a beta-pinene, in particular a polyterpene based on beta-pinene.

7. A composition containing components (A), (B) and optionally (C), wherein (A) is a polymeric resin, preferably a thermoplastic polymeric resin, (B) is the additive mixture according to claim 1, and (C) is a further additive, preferably an additive selected from the group consisting of nucleating agents, clarifiers, fillers, reinforcing agents, pigments, dyestuffs, light stabilizers, antioxidants, antifogging agents, antislip or antiblock additives, plasticizers, flame retardants, optical brighteners, photoinitiators, antistatic agents and blowing agents, with the proviso that the additives of components (B) and (C) are different.

8. The composition according to claim 7, wherein component (A) is selected from the group consisting of homo- or copolymers of olefin monomers, copolymers of olefin monomers with diolefin monomers, cyclic olefins, copolymers of one or more 1-olefins and diolefins with carbon monoxide, polyvinyl alcohol, polyamide, polybutylene terephthalate, polyethylene terephthalate, poly(butylene adipate-co-terephthalate) and polybutylene succinate.

9. The composition according to claim 7, wherein component (A) is selected from the group consisting of acrylates, urethanes, epoxies, polyesters, polystyrenics, polybutadiene, polyisoprene and their copolymers.

10. The composition according to claim 7, wherein the pigment is titanium dioxide and the clarifier is a sorbitol, an organic phosphate salt or a trisamide.

11. The composition according to claim 7, wherein component (B) is present in an amount of 0.001 to 20%, preferably 0.01 to 10%, in particular 1 to 5%, relative to the weight of component (A).

12. A shaped polymer article made of the composition according to claim 7.

13. The shaped polymer article according to claim 12, which is a film, a tape, a sheet, a laminate, an injection molded article, a blow molded article, a thermoformed article, a particle (powder) or a fiber.

14. The shaped polymer article according to claim 12, which is an extruded film or a coextruded multilayer film.

15. The shaped polymer article according to claim 12, which is a food packaging.

16. The use of the additive mixture according to claim 1 as oxygen scavenger, dispersant, compatibilizer, coupling agent, antistatic additive, oxygen barrier additive, water vapor barrier additive, pour-point depressant, flow modifier for crude oil, dish-washing detergent, antifouling agent in water systems, binder, metal deactivator or thermal stabilizer, preferably as oxygen scavenger.

17. A copolymer having a number average molecular weight of 800 g/mol to 50 000 g/mol and containing recurring units of the formula (Ia) and (IIa) or recurring units of the formula (Ia) and (IIb), ##STR00008## wherein the recurring units (Ia) and (IIa) can have a random, alternating or block distribution and the molar ratio of (Ia) to (IIa) is 1:10 to 10:1, the recurring units (Ia) and (IIb) can have a random, alternating or block distribution and the molar ratio of (Ia) to (IIb) is 1:10 to 10:1, the radicals R.sub.1 independently of one another are C.sub.10-C.sub.30alkyl and the radicals R.sub.2 independently of one another are hydrogen or C.sub.1-C.sub.30acyl, with the proviso, that R.sub.2 is not hydrogen in the recurring unit of formula (IIa).

Description

EXAMPLE 2: PREPARATION OF 1:1 N-STEAROYLOXY-MALEIMIDE/C.SUB.18.-C.SUB.22.ALK-1-ENE COPOLYMER

[0167] (Product 2)

[0168] 170 g of Product 1 according to Example 1 are dissolved in 1000 ml of tetrahydrofuran. Then 49.0 g of triethylamine are added. Subsequently 122.1 g of stearoyl chloride dissolved in 20 ml of tetrahydrofuran are added dropwise over 30 minutes. The mixture is stirred at room temperature over night. The obtained product is filtered and concentrated in a Rotavapor to give 240 g of a powdery solid product.

[0169] 1H-NMR (CDCl3, 300 MHz, [ppm]): 0.87-0.93 (CH3, taken as reference signal, peak surface=66 a.u.), 1.27-1.45 (CH2- and CH, peak surface=531 a.u.). The signal at shift between 1.27 and 1.45 ppm is clearly higher than for the starting products and corresponds to the expected value due to the addition of the stearyl chain.

[0170] Weight average molecular Mw: 53 400 g/mol

[0171] Number average molecular weight Mn: 2 000 g/mol.

[0172] Melting point: 49.9 C.

EXAMPLE A

[0173] The polymer used is low density polyethylene (LDPE) of melt flow index of 8 g/10 min (190 C., 2.16 kg) and density of 0.919 g/cm.sup.3. It is used in powder form, without pre-drying step. The additives indicated in the tables below are mixed to the LDPE powder and the mixture is compounded in a lab scale twin-screw mini-extruder (Xplore Instruments B.V.) with co-rotating screws and volume of 15 cm.sup.3 in a loop system during three minutes at constant screw rotating speed (100 rpm) under Nitrogen blanket. The percentages given below are weight percent. The melt temperature is 174 C.+2 C. After three minutes the by-pass is opened so that the melt can be collected. The melt is left at room temperature to cool down. The compounded LDPE is then cut to a bit of 2.5 g, placed in a hot press between two Teflon sheets and compression molded at 180 C. (press temperature) during a total duration of three minutes, with pressure of 0 bar during 1 minute, then 5 bar during 1 minute, then 45 bar during 1 minute. Then the compression molded sample is taken out and cooled at room temperature. This method enables to obtain a compression molded sample with thickness of roughly 150 micron.

[0174] Then the compression molded sample is cut to the quantity as indicated in the below tables and placed in a glass bottle of volume as indicated in the below tables, with an oxygen sensor, and hermetically closed. The amount of oxygen scavenged by the test samples is determined from the change in the oxygen concentration in the head space of the glass container. The glass containers with test samples are stored at 23 C. At known time intervals, as indicated in the below corresponding tables, the oxygen concentration is measured by applying the OpTech O.sub.2 apparatus (Mocon GmbH) onto the bottle at the position of the sensor. The oxygen concentration has an initial value close to 21%, the typical oxygen concentration in air, and then decreases over time (measurements typically performed up to 28 days) due to the scavenging action of the additives incorporated into the LDPE compounds. Knowing the bottle volume in ml and the concentration of the additives in the LDPE sample, the quantity of scavenged oxygen into ml O.sub.2 scavenged per gram scavenger can be determined according to the following equation:

Scavenged oxygen (ml/g)={(% O.sub.2).sub.i(% O.sub.2).sub.f}*0.01*V.sub.j/(W.sub.F*0.01*C.sub.S)

[0175] where:

[0176] (% O.sub.2).sub.i Initial oxygen concentration in the glass container (%);

[0177] (% O.sub.2).sub.f Oxygen concentration in the glass container at time of test (%)

[0178] 0.01: Conversion factor

[0179] V.sub.j: Free air volume of the glass container (ml)

[0180] W.sub.E: Weight of film placed into the glass container (g)

[0181] C.sub.s: Concentration of oxygen scavenger in film (%)

[0182] In addition, the L*, a* and b* color features of the samples are measured (apparatus Micro Color II from Dr. Bruno Lange GmbH), with a white background. In order to obtain the intrinsic color features of the samples, with as little possible influence from the white background, a total of 8 layers of each samples are measured. This stapling ensures that the transparency is reduced close to zero. L*, a* and b* are as defined in EN ISO 11664-4:2008 (ColorimetryPart 4: CIE 1976 L*a*b* Colour space).

[0183] The Transmittance and Haze are measured on one layer of the sample, with an apparatus haze-gard plus from BYK-Gardner GmbH, according to ASTM D 1003.

[0184] The recipes and results are given in the following tables.

TABLE-US-00001 TABLE 1 *.sup.) ml O.sub.2/g scavenger ml/g Number of days 0 3 7 14 28 Oxygen scavenger 0.2% of Product 1 + 0 7.4 12.3 13.6 24.9 0.2% of Mn stearate + 2% of Polyterpene 1 0.4% of Product 1 + 0 6.9 13.3 16.1 40.8 0.2% of Mn stearate + 2% of Polyterpene 1 0.2% of Product 2 + 0 8.9 15.5 19.3 34.8 0.2% of Mn stearate + 2% of Polyterpene 1 0.4% of Product 2 + 0 5.6 13.6 33.3 77.2 0.2% of Mn stearate + 2% of Polyterpene 1 *.sup.) High values are desired. Polyterpene 1: Polyterpene (softening point of 125 C.) based on beta-pinene. Amount of polymer film: 5 g. Volume of glass bottle: 100 ml.

TABLE-US-00002 TABLE 2 *.sup.) ml O.sub.2/g scavenger [ml/g] Number of days Additives 0 2 5 7 14 21 0.2% of Product 1 + 0 40.0 88.7 113.0 148.7 171.3 0.1% of Mn stearate + 2% of Polyterpene 2 0.2% of Product 1 + 0 36.3 85.4 120.0 170.0 181.7 0.2% of Mn stearate + 2% of Polyterpene 2 0.2% of Product 2 + 0 40.0 93.9 124.8 165.2 181.7 0.1% of Mn stearate + 2% of Polyterpene 2 0.2% of Product 2 + 0 51.3 111.3 141.7 181.7 181.7 0.2% of Mn stearate + 2% of Polyterpene 2 *.sup.) High values are desired. Polyterpene 2: Polyterpene (softening point of 115 C.) based on alpha-pinene. Amount of polymer film: 5 g. Volume of glass bottle: 100 ml.

TABLE-US-00003 TABLE 3 .sup.1)Transmittance .sup.2)Haze Additives [%] [%] L* a* b* 0.2% of Product 1 + 92.2 42.6 75.2 0.3 2.8 0.1% of Mn stearate + 2% of Polyterpene 2 0.2% of Product 1 + 92.4 38.1 74.7 0.8 4.4 0.2% of Mn stearate + 2% of Polyterpene 2 0.2% of Product 2 + 92.2 42.4 75.0 0.0 3.4 0.1% of Mn stearate + 2% of Polyterpene 2 0.2% of Product 2 + 91.7 33.4 74.9 0.8 4.1 0.2% of Mn stearate + 2% of Polyterpene 2 .sup.1)High values are desired. .sup.2)Low values are desired.