WO2008037398A1

WO2008037398A1 - Peroxide-containing active ingredient composition for targeted scission or cross-linking reactions in plastics

Info

Publication number: WO2008037398A1
Application number: PCT/EP2007/008224
Authority: WO
Inventors: Eric Richter; Reinhold Kling
Original assignee: Clariant Finance (Bvi) Limited
Priority date: 2006-09-28
Filing date: 2007-09-21
Publication date: 2008-04-03
Also published as: DE102006045812A1

Abstract

The claimed peroxide-containing composition contains a high proportion of peroxides and several polyolefin waxes, the quantitatively greater fraction representing a metallocene polyolefin wax and the other waxes being polar or apolar non metallocene polyolefin waxes, such as EVA or montan wax. All of the polyolefin waxes make up at least 15 wt.% of the formula and melt at a temperature of between 80 and 170 °C. The claimed active ingredient composition has a reduced dust content and is used for modifying plastics by cross-linking or chain scission.

Description

description

Peroxide-containing active ingredient composition for targeted degradation or crosslinking reactions in plastics

The present invention relates to active ingredient compositions with which targeted degradation of polymer chains or crosslinking reactions in plastics can be triggered and thus a chemical change of the plastics is effected.

In order to adjust the molecular weight in the polymerization or in the extrusion of polypropylene, peroxides which lead to a reduced chain length of the polypropylene are deliberately used in the prior art. In the case of polyethylene (PE), polyvinyl chloride (PVC), polystyrene (PS), polymethyl methacrylates (PMMA), elastomers, rubbers and other polymers, crosslinking reactions are triggered by the addition of peroxide. It is common practice for these substances to be incorporated into a polymeric carrier, the amount of peroxide is usually well below 10 wt .-% and is usually added after the masterbatch technique.

High demands are placed on such peroxide-containing compositions:

These must be easy to distribute in the plastic to a uniform

To cause degradation or a uniform crosslinking of the polymer. The compositions must be compatible with the polymeric matrix as much as possible in order not to trigger a negative impact on the mechanical properties.

The following single-stage or multi-stage processes are currently known for the preparation of dust-free, granular and pulverulent peroxide-containing active ingredient compositions or preparations: For the peroxide mixture, all components are mixed cold and added to the plastic via the main feed of the extruder. Alternatively, the waxy or polymeric formulation moieties are fed via the main feed of the extruder while the peroxide addition is via sidefeeder.

In the preparation of peroxide preparations, the addition of the active substance via the sidefeeder is preferred. Subsequently, a melt blend can be made in a suitable extruder, kneader or compactor. This is followed by granulation, grinding or spraying.

A cold mix consists of suitable polymer supports such as polyethylene, polypropylene or ethylene vinyl acetate copolymer and the like. In addition, further dispersing aids such as waxes, fatty acid derivatives, stearates, etc. may be advantageous. However, the disadvantage of known polymer blends is always that the polymer compound quickly reaches the critical melt temperature of the peroxide mixture and that the decomposition reaction occurs. Higher loadings with peroxide are not possible. In addition, some peroxides are liquid, which significantly limits the percentage incorporation amount.

In EP 0 423 639, poly-epsilon-caprolactam is used as carrier for peroxide masterbatches.

KR 2000 055104 describes a peroxide masterbatch which has a peroxide content of 5 to 50% by weight and 50 to 95% by weight of a porous polyolefinic carrier. The masterbatch is prepared by dissolving the organic peroxide in an organic solvent, then introducing it into the porous carrier material while stirring, causing the solvent to evaporate. The peroxide is absorbed by the porous polyolefinic carrier material. IT 1 318 708 describes a masterbatch containing 40% by weight of peroxymon F, 5.5% by weight of 2-tert-amylhydroquinone, 10% by weight of triallycyanurate and 44.5% by weight of EPM.

All peroxide preparations hitherto used in practice, if they have a high active ingredient content, are produced with a special carrier material or with a combination of a special carrier and a complex process equipment. This leads to the end product becoming expensive or the end use being limited by the carrier used.

As a rule, larger production quantities are necessary for the processes mentioned, in order to arrive at economical production costs. Special, tailored to individual customer requirements peroxide compositions are complex in the production and storage and can usually not be realized under economic conditions.

In such preparations prepared on a conventional compounding line, an addition amount of 10 to 15% is an upper limit because the active ingredients are present as a liquid and can not be incorporated in greater amount or because the maximum polymeric uptake is achieved. The product accumulates increasingly on the strand surface. Strand granulation is state of the art at masterbatch companies. One way to improve this would be to use special plastics that flow easily, are processable at lower temperatures, and that would be well tolerated by different polymers. However, polymers that have this property pattern, in turn, have higher purchase costs.

The object of the present invention was to be able to load peroxide-containing compositions for polymer processing with the highest possible proportion of peroxides, so that the production of these

Preparations economically and ecologically advantageous can be accomplished and delivers products of high quality. Another object of the invention was to make a conventional polymeric support as unnecessary as possible, which on the one hand, the production of a peroxide-containing composition with a significantly higher active substance content is possible and, secondly, the preparation of the invention in significantly more polymers, elastomers or rubbers with different chemical Incorporation can be incorporated because fewer compatibility problems occur due to the high amount of active ingredient. The new carrier material should also allow easier incorporation and distribution into the polymers, resulting in a more uniform molecular or molecular weight distribution.

Surprisingly, it has now been found that polyolefin waxes, in particular polypropylene waxes, produced with the aid of metallocene catalysts are particularly advantageously suitable as carriers for peroxides, with a significantly higher loading than in polymers being possible.

The object is achieved by a peroxide-containing

Composition comprising i) one or more peroxides, ii) one or more metallocene polyolefin waxes, iii) optionally one or more waxes selected from polar and non-polar

Non-metallocene polyolefin optionally grows one or more montanic acid and / or one or more

Fatty acid derivatives and v) optionally one or more homopolymers and / or copolymers of

Ethylene and / or propylene, characterized in that the composition comprises one or more peroxides in an amount of at least 15 to 85% by weight and at least 15% by weight.

Wax, based in each case on the total weight of the composition. Preferably, the composition contains at least 50 wt .-% metallocene polyolefin waxes, in particular polypropylene Metailocenwachse, based on the total wax content. Metallocene waxes or metallocene polyolefin waxes are by definition waxes which are prepared in the presence of metallocenes as catalysts by polyaddition. The composition thus prepared is compounded by extrusion into the preparation according to the invention.

The metallocene waxes have a low dropping point, high transparency and low viscosity. The use of these waxes greatly facilitates the incorporation of the peroxides. The process temperatures can be kept low so that the peroxides do not start prematurely. In addition, a higher loading of the compositions with peroxides is possible than hitherto known, a higher compatibility with different polymeric plastics occurs and can be dispensed with a polymeric support.

The metallocene waxes have a melt viscosity measured at a

Temperature of 17O ⁰ C, in the range of 40 to 80 000 mPa-s, preferably from 45 to 35 000 mPa-s, more preferably from 50 to 10,000 mPa-s.

All waxy components of the composition and the homo- and / or copolymers of ethylene and / or propylene, ii), iii) iv) and v) melt in the temperature range between 80 and 17O ⁰ C.

According to preferred peroxide preparations contain 15 to 85 wt .-%, preferably 20 to 80 wt .-%, of one or more organic or inorganic peroxides, preferably organic peroxides, and 10 to 85% by weight, preferably 12 to 80 parts by weight. % of the metallocene polyolefin wax, 0 to 30 wt .-%, preferably 0.1 to 25 wt .-% of one or more non-metallocene waxes, such as polar and nonpolar polyolefin, EVA, or montan waxes.

In addition, the composition according to the invention may, if necessary, also contain fibers and reinforcing agents. Such fillers and reinforcing agents may be silicates, silicic acids, zeolites, talc, chalk, kaolin or additives such as phenols, Coagents such as triallyl cyanurate (TCA), EDMA and others. Propellants such as azodicarbonamide, citric acid and others, accelerators such as zinc oxides and stearic acids, between 0 to 25 wt .-%, based on the total weight of the composition may be advantageous. Also, additives such as phenols, phosphites, co-stabilizers, etc. may be contained in an amount of from 0 to 5% by weight, if necessary, based on the total weight of the composition.

The waxes prepared as catalyst in the presence of metallocene are in particular copolymer waxes of propylene and 0.1 to 50% of ethylene and / or 0.1 to 50% of at least one branched or unbranched 1-alkene having 4 to 20 C atoms with a dropping point ( Ring / ball) between 80 and 17O ⁰ C.

The metallocene waxes prepared as catalysts in the presence of metallocenes are largely or completely amorphous and can additionally be polar modified if required.

Non-metallocene polyolefin waxes which can be used according to the invention are, on the one hand, especially ethylene vinyl acetate (EVA) waxes having a dropping point between 90 and 120 ^° C., a vinyl acetate content of 1 to 30% and a viscosity of 50 to 3000 mPa.s. preferably from 50 to 1500 mPa.s, measured at a temperature of 140 ⁰ C, as well as nonpolar, but also polar non-metallocene waxes having a dropping point between 90 to 135 ° C and a viscosity of less than 30,000 mPa-s, preferably smaller than 15,000 mPa-s, measured at a temperature 140 ⁰ C, on the other hand can also

Montanwachse with a dropping point between 75 and 100 ⁰ C, an acid number of 6 to 35% and a viscosity of 20 to 800 mPa-s, preferably 25 to 600 mPa-s, measured at a temperature of 100 ⁰ C, be suitable.

Suitable non-metallocene polyolefin waxes are further homopolymers of ethylene or higher 1-olefins having 3 to 10 carbon atoms or copolymers thereof with one another. Preferably, the polyolefin waxes a weight average molecular weight M _w between 1000 and 20,000 g / mol and a number average molecular weight M _{n of} between 500 and 15,000 g / mol.

Metallocene compounds of the formula I are used for the preparation of the metallocene polyolefin waxes used according to the invention.

This formula also includes compounds of the formula Ia,

the formula Ib

and the formula Ic

In formulas I, Ia and Ib, M ^{1 is} a Group IVb, Vb or VIb metal of the Periodic Table, for example, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, preferably titanium, zirconium, hafnium.

R ¹ and R ² are identical or different and represent a hydrogen atom, a C ₁ -C 1 _0, preferably C ₁ -C ₃ alkyl, in particular methyl, a C1-C1 ₀ -, preferably Ci-C ₃ alkoxy group, a Cβ -Cio, preferably Cβ-Cβ-aryl group, a C ₆ -C ₁₀ -, preferably C ₆ -C ₈ -aryloxy, a C ₂ -C ₀ , preferably C ₂ -C ₄ -alkenyl, a C7-C ₄₀ -, preferably C7-Ci _O -arylalkyl, a C ₇ -C ₄₀ -, preferably C ₇ -C ₂ alkylaryl group, a C ₈ -C ₄₀ -, preferably C ₈ -C ₂ - arylalkenyl group or a halogen, preferably chlorine atom.

R ³ and R ⁴ are identical or different and denote a mono- or polynuclear hydrocarbon radical which can form a sandwich structure with the central atom M ¹ . R ³ and R ⁴ are preferably cyclopentadienyl, indenyl, tetrahydroindenyl, benzoindenyl or fluorenyl, it being possible for the basic units to carry additional substituents or to bridge them with one another. In addition, one of the radicals R ³ and R ^{4 may be} a substituted nitrogen atom, wherein R ^{24 has} the meaning of R ¹⁷ and is preferably methyl, tert-butyl or cyclohexyl.

R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are identical or different and denote a hydrogen atom, a halogen atom, preferably a fluorine, chlorine or bromine atom, a Ci-Ci ₀ -, preferably Ci-C ₄ alkyl group, a C ₆ -C _O -, preferably C ₆ -C ₈ -aryl group, a C ₁ -C 1 ₀ -, preferably Ci-C ₃ alkoxy group, a -NR ¹ V, -SR ¹⁶ -, -OSiR ¹ V, -SiR ¹ V or -PR ¹⁶ ₂ radical, wherein R ^{16 is} a C1-C10, preferably Ci-C ₃ alkyl group or C ₆ -Ci ₀ -, preferably C ₆ -C ₈ -Arγlgruppe or in the case Si or P-containing radicals is also a halogen atom, preferably chlorine atom or two adjacent radicals R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ or R ¹⁰ form a ring with the C atoms connecting them. Particularly preferred ligands are the substituted compounds of the parent compounds cyclopentadienyl, indenyl, tetrahydroindenyl, benzoindenyl or fluorenyl.

R is ¹³

IVP- - IvF-M ² -CR ¹⁹ ,, O-IvF-O-

RIB

R18 L. R18

= BR ¹⁷ , = AIR ¹⁷ , -Ge, -Sn-, -O-, -S-, = SO, = SO _2l = NR ¹⁷ , = CO, = PR ¹⁷ or = P (O) R ¹⁷ , where R ¹⁷ , R ¹⁸ and R ^{19 are the} same or different and a hydrogen atom, a halogen atom, preferably a fluorine, chlorine or bromine atom, a C ₁ -C ₃₀ , preferably Ci-C ₄ alkyl, especially methyl group, a Ci-Cio-fluoroalkyl, preferably CF ₃ group, a C ₆ -Cio-fluoroaryl, preferably pentafluorophenyl, a C ₆ -CiO, preferably Cε-Cs-aryl group, a C ₁ -Ci _O -, preferably Ci- C ₄ -alkoxy, in particular

Methoxy group, a _C2-C10, preferably C ₂ -C ₄ alkenyl group, a C ₇ -C 4 ₀ -, preferably C ₇ -Cio-aralkyl group, a C ₈ -C ₄ O-, preferably Cs-C ₁₂ - arylalkenyl or a C ₇ -C _4O, preferably C ₇ -C ₂ -alkylaryl group, or R ¹⁷ and R ¹⁸ or R ¹⁷ and R ¹⁹ in each case together with the atoms connecting them, a ring.

M ² is silicon, germanium or tin, preferably silicon and germanium. R ¹³ is preferably = CR ¹⁷ R ¹⁸ , = SiR ¹⁷ R ¹⁸ , = GeR ¹⁷ R ¹⁸ , -O-, -S-, = SO, = PR ¹⁷ or = P (O) R ¹⁷ .

R ¹¹ and R ¹² are the same or different and have the meaning given for R ¹⁷ , m and n are the same or different and are zero, 1 or 2, preferably zero or 1, where m plus n is zero, 1 or 2, preferably zero or 1.

R ¹⁴ and R ¹⁵ have the meaning of R ¹⁷ and R ¹⁸ .

Examples of suitable metallocenes are:

Bis-O-S-trimethylcyclopentadienylzirconium dichloride, Bis (1, 2,4-trimethylcyclopentadienyl) zirconium dichloride, bis (1, 2-dimethylcyclopentadienyl) zirconium dichloride, bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (1-methylindenyl) zirconium dichloride, bis (1-n-butyl) -3 -methyl-cyclopentadienyl) zirconium dichloride, bis (2-methyl-4,6-di-i-propyl-indenyl) zirconium dichloride, bis (2-methylindenyl) zirconium dichloride, bis (4-methylindenyl) zirconium dichloride, bis (5-methylindenyl) zirconium dichloride , bis (alkylcyclopentadienyl) zirconium dichloride, bis (alkylindenyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dichloride, bis (indenyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (octadecylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride , Bis-trimethylsilylcyclopentadienyljzirconium dichloride, biscyclopentadienylzirconiumdibenzyl, biscyclopentadienylzirconiumdimethyl, bistetrahydroindenylzirconiumdichloride, dimethylsilyl-θ-fluorenylcyclopentene adienylzirconium dichloride, dimethylsilyl-bis-1,1'-trimethylcyclopentadienylzirconium dichloride, dimethylsilyl-bis-1,1'-dimethyl-cyclopentadienylzirconium dichloride, dimethylsilyl-bis-1- (2-methyl-4,5-benzoindenyl) zirconium dichloride, dimethylsilyl bis- 1- (2-methyl-4-ethylindenyl) zirconium dichloride, dimethylsilylbis-1- (2-methyl-4-i-propylindenyl) zirconium dichloride, dimethylsilylbis-1- (2-methyl-4-phenylindenyl) zirconium dichloride, dimethylsilyl bis-1- (2-methyl-indenyl) zirconium dichloride, dimethylsilyl-bis-1- (2-methyltetrahydroindenyl) zirconium dichloride, dimethylsilyl-bis-1-indenylzirconium dichloride, dimethylsilyl-bis-1-indenylzirconium dimethyl, dimethylsilyl-bis-1-tetrahydroindenylzirconium dichloride . Diphenylmethylene-θ-fluorenylcyclopentadienylzirconium dichloride, diphenylsilyl-bis-1-indenylzirconium dichloride, ethylene-bis-1- (2-methyl-4,5-benzoindenyl) zirconium dichloride, ethylene-bis-1- (2-methyl-4-phenylindenyl) zirconium dichloride, Ethylene-bis-1- (2-methyl-tetrahydroindenyl) zirconium dichloride, ethylene-bis-1- (4,7-dimethyl-indenyl) zirconium dichloride, ethylene-bis-1-indenylzirconium dichloride, ethylene-bis-1-tetrahydroindenylzirconium dichloride, indenyl cyclopentadienyl zirconium dichloride, isopropylidene (1-indenyl) (cyclopentadienyl) zirconium dichloride, isopropylidene (9-fluorenyl) (cyclopentadienyl) zirconium dichloride, phenylmethylsilylbis-1- (2-methylindenyl) zirconium dichloride, and each of the alkyl or aryl derivatives of these metallocene dichlorides.

To activate the single-center catalyst systems are suitable

Cocatalysts used. Suitable cocatalysts for metallocenes of the formula I are organoaluminum compounds, in particular alumoxanes or else aluminum-free systems such as R ²⁰ _× NH ₄ -XBR ² VR ²⁰ χPH ₄ -BR ²¹ ₄ , R ²⁰ ₃ CBR ²¹ ₄ or BR ²¹ ₃ . In these formulas, x is a number from 1 to 4, the radicals R ²⁰ are identical or different, preferably identical, and are Ci-Cio-alkyl or Cβ-C-iβ-aryl or two radicals R ²⁰ form together with the connecting them Atom is a ring, and the radicals R ²¹ are the same or different, preferably the same, and are C ₆ -C ₈ -aryl which may be substituted by alkyl, haloalkyl or fluorine. In particular, R ^{20 is} ethyl, propyl, butyl or phenyl and R ^{21 is} phenyl, pentafluorophenyl, 3,5-bis-trifluoromethylphenyl, mesityl, xylyl or ToIyI.

In addition, a third component is often required to maintain protection of polar catalyst poisons. For this, organoaluminum compound, e.g. Triethylaluminum, tributylaluminum and others and mixtures suitable.

Depending on the process, supported single-center catalysts can also be used. Preference is given to catalyst systems in which the Residual contents of support material and cocatalyst should not exceed a concentration of 100 ppm in the product.

Here, the melt viscosities were determined according to DIN 53019 with a rotary viscometer, the dropping points according to DIN 51801/2, the softening points ring / ball according to DIN EN 1427. The drop point determination is carried out with a drop point device according to Ubbelohde according to DIN 51801/2, the softening point ring / ball according to DIN EN 1427.

Hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxyketals, peroxy (di) carbonates, peracids, peracid esters, ketone peroxides, and others are used according to the invention as peroxides. This can e.g. Di-tert-butyl peroxide, dicumyl peroxide and diacetyl peroxide.

The incorporation of the peroxides in the waxes is carried out according to the known prior art by mixing all components at elevated temperature to a homogeneous mass and then converted into a suitable final form. The preparation of such mixtures is usually carried out on an extruder or kneader, but there are also less commonly used other aggregates. The final form is usually the granules, which through

Strand granulation, hot break or underwater granulation is produced. Of the known methods, the extruder and underwater granulation are especially preferred.

The required proportion of metallocene wax in the inventive

Peroxide preparation is dependent on the additive-matrix interaction, the surface structure of the peroxide, the surface structure of the finished article, the desired crosslinking reaction, the desired degradation reaction, the reaction temperature (starting temperature) of the peroxide and the desired end product use amount. The present invention also relates to a process for producing the active ingredient composition according to the invention by combining the individual constituents and subsequent homogenization in the extruder or kneader. The premixing of the individual components is preferred in the preparation of the composition and can be carried out in a suitable mixing apparatus. Optionally, however, it is also possible to add the active compounds or further additives later via a side dosing in solid or liquid form

The raw materials used can be in various forms. The waxes, as well as the other additives and additives may e.g. as granules, dandruff, powder or ultrafine powder in the mixture, while the peroxides can also be present in liquid form.

The following single-stage or multi-stage processes are currently known for the production of dust-free, granular and powdery active substance compositions:

All components can be cold mixed and added via the main feed of an extruder, or the waxy / polymeric formulation portions are fed via the main feed of the extruder, the peroxides are introduced into the machine in powder or liquid via corresponding side feeds. Subsequently, a melt mixture can be carried out in a suitable extruder or in kneaders. This is followed by granulation, grinding or spraying.

The mixing can also be done by a gravimetric dosing (adding according to the weight) directly on the processing machine, a premix is then eliminated. If the formulation is to be used as a dust-free powder mixture, a mixing phase with higher mixing energy follows, advantageously heating in a first phase to about 15 K below the softening point of the metallocene wax and in a second phase to about 5 K below the softening point of the metallocene wax , The first phase lasts about 3 to 10 minutes, preferably 5 to 7 minutes, the second phase lasts about 1 to 5 minutes, preferably 2 to 3 minutes

The hot mixture can only be used if the starting temperature of the peroxide is at least 15 to 20 K above the softening temperature of the waxes used, otherwise premature, spontaneous reaction of the peroxide may occur.

When mixed at elevated temperature, the heat energy can be introduced via friction, via separate heating of the mixing trough or in both ways.

In the production of the composition on the extruder, it is preferable to work with a screw assembly which is tailored to the high active ingredient content. The temperature profile is preferably lower than indicated in the prior art. For the preparation of the compositions according to the invention, underwater granulation is advantageously used, but strand granulation or hot blasting can also be used.

In contrast to the peroxide-containing compositions described in the prior art, these can be added to a wide range of polymers. Examples include: polyolefins, ethylene-vinyl acetate copolymers (EVA), polyvinyl chloride (PVC), polystyrene (PS), styrene-acrylonitrile copolymers (SAN), acrylonitrile-butadiene-styrene copolymers (ABS), copolymers, the above plastics, elastomers, rubbers and various special polymers. After mixing with the polymer and achieving the required target concentration, the plastic mixtures can be processed to the desired end products.

embodiments

The polyolefins a) to c) used according to the invention, which have been listed in Table 1, were prepared by copolymerization of propylene with ethylene with the metallocene dimethylsilylbisindenylzirconium dichloride catalyst as described in EP-A-0 384 264 (general instructions Examples 1 to 16). The different softening points and viscosities were adjusted by varying the ethylene input and the polymerization temperature.

Table 1: Polyolefins used

Polyolefin a) Polyolefin b) Polyolefin c)

Softening / dripping point (° C) 92 ^η) 102 ^υ 135 ¹ '

Viscosity at 170 ^° C. (mPa.s) 7900 9800 100

¹⁾ drop point nonpolar & polar PE wax):

montan wax

The product characteristics were determined by the following methods:

Drop point: ISO 2176 / ASTM D 3954 [ ⁰ C]

Viscosity: DIN 53018 (mPa-s) Density: ISO 1183 (g / cm ³ )

Molar mass: according to GPZ method

The application takes place in the fine-grained state (sprayed or ground), but granulate form is also possible (with separate addition of the individual components to the machine).

The peroxide preparations according to the invention were prepared as described below:

As a mixture for extrusion (mixture of waxes): Mixer: Henschel mixer, content 5 liters

Approach: according to the examples given below Premixing: approx. 2 to 4 min. at U = 600 / min

Subsequently, the extrusion was carried out on a co-rotating twin screw with downstream strand pelletizing, partly also underwater pelletizing was used (Example 1 and 2). Granule size in diameter 0.8 to 3 mm.

Mixing time: 5 min to 10 min at U = 360 min ^"1

Production Examples 1 to 5:

In the following examples, the following peroxide-containing compositions were prepared by the methods described above. As metallocene waxes, the above-described wax a), b) or c) was used in each case: 1) 40 wt .-% di (2-tert-butyl-peroxyisoprpyl) benzene 40 wt .-% metallocene wax b)

20% by weight of metallocene wax c)

2) 60% by weight of di (2-tert-butylperoxyisopropyl) benzene 40% by weight of metallocene wax a)

3) 40% by weight of di (2-tert-butylperoxyisophenyl) benzene 35% by weight of metallocene wax a)

25% by weight of polar polyethylene wax

4) 40% by weight of di (2-tert-butylperoxyisopropyl) benzene 35% by weight of metallocene wax a) 25% by weight of nonpolar polyethylene wax

5) 40% by weight of di (2-tert-butylperoxyisopropyl) benzene 52.5% by weight of metallocene wax a)

7.5% by weight montan wax

Application examples:

In the peroxide preparations according to Preparation Examples 1 to 4, the waxes were mixed cold, the peroxide was added via a sidefeeder in an extruder with co-rotating twin screw with a special

Screw construction and with a low temperature image. The peroxide compositions prepared in this way can be used in PE, PP but also in other polymers in order to initiate a crosslinking reaction or to bring about a degradation of the polymer chain. Despite the high proportion of active ingredient, in other polymers which do not belong to the polyolefins, hardly any negative interactions have been observed, so that the use of the peroxide-containing compositions according to the invention also offers special technical advantages in other polymers.

Claims

claims:

1. Highly charged peroxide-containing composition for targeted degradation or for crosslinking reactions in plastics containing

i) one or more peroxides ii) one or more metallocene polyolefin waxes, iii) optionally one or more waxes selected from polar and non-polar

Non-metallocene polyolefin iv) optionally one or more montan waxes and / or one or more

Fatty acid derivatives iv) optionally one or more homo- and / or copolymers of ethylene and / or propylene, characterized in that it contains peroxides in an amount of 15 to 85 wt .-% and at least 15 wt .-% waxes, based on the respective

Total weight of the composition.

2. peroxide-containing composition according to claim 1, characterized in that the composition contains at least 50 wt .-% metallocene polyolefin wax.

3. peroxide-containing composition according to claim 1, characterized in that the waxes or the copolymers of ethylene of the components ii), iii), iv) and v) at temperatures in the range of 80 to 170 ⁰ C melt.

4. peroxide-containing composition according to claim 1, 2 or 3, characterized in that the metallocene polyolefin wax has a dropping point between 80 and 170 ⁰ C and a melt viscosity, measured at 170 ⁰ C between 40 and 80 000 nnPa-s, preferably between 45 to 35,000 mPa.s, in particular in the range of 50 to 10,000 mPa.s.

5. peroxide-containing composition according to one or more of claims 1 to 4, characterized in that these 15 to 85 wt .-%, preferably 20 to 80 wt .-% of one or more organic or inorganic, preferably organic, peroxides and 15 bis 85 wt .-%, preferably 20 to 80 wt .-% of the metallocene polyolefin wax, 0 to 30 wt .-%, preferably 0.1 to 25 wt .-% of one or more non-metallocene waxes, such as polar and non-polar polyolefins- , EVA or montan waxes.

6. peroxide-containing composition according to one or more of claims 1 to 5, characterized in that the peroxides are selected from organic products.

7. peroxide-containing composition according to one or more of claims 1 to 6, characterized in that these one or more

Contains peroxides selected from the group of suitable hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxyketals, peroxy (di) carbonates, peracids, peracid esters, ketone peroxides, and mixtures of these, preferably di-tert-butyl peroxide, dicumole peroxide or diacetyl peroxide.

8. peroxide-containing composition according to one or more of claims 1 to 7, characterized in that it contains one or more polar or nonpolar non-metallocene polyolefin waxes and EVA, or montan wax or fatty acid derivatives, the / a dropping point below 135 ⁰ C. and a viscosity of less than 30,000 mPa-s (measured at 140 ⁰ C) possess.

9. peroxide-containing composition according to one or more of claims 1 to 8, characterized in that this in addition to the metallocene polyolefin wax ii) one or more metallocene copolymer waxes of propylene and 0.1 to 50 wt .-% of one or more other monomers selected from ethylene and branched or unbranched 1-alkenes having 4 to 20 carbon atoms.

10. peroxide-containing composition according to one or more of claims 1 to 8, characterized in that these additionally fillers and reinforcing agents such as silicates, silicas, zeolites, talc, chalk, kaolin or additives such as phenols, coagents such as triallyl cyanurate (TCA), EDMA and others, blowing agents such as azodicarbonamide, citric acid, accelerators such as zinc oxides and stearic acids in an amount ranging from 0.1 to 25 wt .-%.

11. peroxide-containing composition according to one or more of claims 1 to 9, characterized in that this is a very good

Compatibility with polymers such as polyethylene or polypropylene, with copolymers of polyolefins, with polyvinyl chloride (PVC), with polystyrene (PS), with polymethamethyl acrylate (PMMA), and with ethylene-vinyl acetate copolymers (EVA), styrene-acrylonitrile copolymers (SAN ), Acrylonitrile-butadiene-styrene copolymers (ABS), mixed polymers containing the above plastics or with elastomers, with rubber and with other special polymers.

12. A method for producing a peroxide-containing composition according to one or more of claims 1 to 11, characterized in that alternatively

a) the individual components are mixed cold, or b) the addition is made via the main feed of an extruder or c) the waxy / polymeric formulation components are fed via the main feed of the extruder, the peroxides being introduced in powder form or liquid optionally via corresponding side feeds into the machine and subsequently the homogenization of the individual components takes place in the extruder.

13. The method according to claim 10, characterized in that subsequent to the homogenization granulation via strand and Kopfgranulierung or the spraying takes place.

14. Use of a peroxide-containing composition according to one or more of claims 1 to 11 for the preparation of crosslinked polymers or for the targeted degradation of the chain length of polymers to increase the melt flow.