DE102006017346A1 - Migration-stable masterbatch for production of duroplastics, comprises a homogeneous mixture of bi- and-or poly-functional crosslinking monomer and masterbatch polymer - Google Patents

Abstract

A migration-stable masterbatch (I) comprising 1-45 wt% bi- and/or poly-functional crosslinkable monomers (II) and 55-99 wt% masterbatch polymer (III). Independent claims are included for (1) a masterbatch (I) in which the polymer is a mixture of two or more polymers as given below (2) a method (M1) for the production of (I) by melting the polymer (III), adding monomers (II), mixing to give the above composition, cooling and optionally pulverising the product (3) a method (M2) for the production of final polymers by mixing (I) with crosslinkable crude polymers and/or monomers thereof and then polymerising the mixture (4) moulded parts comprising (I) .

Description

The The invention relates to a migration stable masterbatch comprising a masterbatch polymer and a crosslinkable bifunctional and / or polyfunctional monomer from the series of allyl compounds and / or the acrylate compounds. The masterbatch is made with crosslinkable raw polymers mixed, and preferably by irradiation, reacted, producing a final polymer which has better heat and aging properties having. The invention further relates to a process for the preparation of the migration stable masterbatch, a method of preparation of the final polymer and a molding comprising the masterbatch.

Technical Polymers such as polyamides and / or polyesters have been in the past proven as versatile construction materials. Are now Various technical polymers are known that have very different properties have. For example, polyamides and / or polyesters used as standard construction materials. Furthermore, there are products with relatively high softening and continuous service temperature in the automotive industry in use, especially in the engine area of automobiles, or in electrical and Electronics area, in use.

In spite of this diverse applications however, there are applications of polyamides and / or polyesters, which the current formulations do not meet, so the properties the polyamide and / or polyester formulations by additives accordingly need to be improved. For example, the thermal long-term stability of these is problematic Polymers.

As well are the requirements of polyurethanes, polyolefins, polyester ester elastomers, ether elastomers, ether ester elastomers and polycaprolactones elevated. Here are higher ones Chemical resistance, insolubility in conventional solvents, Improvement of the abrasion behavior, improvement of the mechanical and electrical properties, as well as the aging behavior desired. Often the polymers mentioned with stabilizers, fillers and Reinforcing materials, and processing aids. however Often the disadvantage of aging, as well as poor chemical resistance consist.

The EP 0671 434 A1 describes the crosslinking of fluorosilicone with vinylidene fluoride by diallyl phthalate or triallyl isocyanurate. These are reacted by means of free radical initiators by means of irradiation of gamma rays or temperature ranges from 80 ° C to 165 ° C. Due to the high volatility of diallyl phthalate and triallyl isocyanurate, the reaction can not be carried out at higher temperatures. Furthermore, these crosslinking agents tend to form crystals even at temperatures above the melting point.

The DE 100 16 120 A1 describes the use of diallyl phthalate (DAP), triallyl isocyanurate (TAIC) and / or triallyl cyanurate (TAC) as a crosslinking aid in the case of rubbers on silicon dioxide as carrier substance with organic peroxides. However, this is disadvantageous because silica greatly affects the impact strengths of the polymers. Another disadvantage is the Abrassivität of silica. Silica and other porous fillers also have a negative impact on processing semicrystalline polymers as the elongation at break is reduced, which has a negative impact on elasticity.

Out the prior art are other numerous compositions and manufacturing process for Crosslinking and the use of microporous carriers known. However own they have the disadvantage that they are not suitable for further processing Injection molding pre-dried can be since the crosslinking monomer is from the series of cyanuric triallyl esters (TAC), isocyanuric triallyl ester (TAIC), Isocyanuric acid trimethylallyl ester (TMAIC), trimellitic allyl ester (TAM), diallyl phthalate (DAP) and / or trimethylpropane triallyl acrylate (TMPTA) evaporated or degassed. As a result, a sufficient degree of crosslinking does not become reached. For cost reasons and from the point of view of environmental protection is the high volatility the crosslinkable monomers unacceptable.

Further Disadvantages of these systems are that when processing microporous masterbatches, which is a microporous carrier and a crosslinking agent, it will cause squeezing of the crosslinking monomers that comes to smear effects and to drastic deterioration at the material supply lead to the processing devices.

The DE 4020 797 A1 describes the preparation of rubber blends with hydrogenated acetyl nitrile copolymer with triallyl isocyanurates, organic sulfur compounds and organic peroxides for better adhesion to metals. In this case, very large amounts of 5 to 30 wt .-% triallyl cyanurates in the end product, ie needed in the final polymer.

Of the The present invention is based on the object, a masterbatch for polymers to provide the preparation of, preferably radiation-crosslinked, Polymers with improved chemical resistance, insolubility in conventional solvents, Improvement of the abrasion behavior as well as improvement of the mechanical and electrical properties and aging behavior.

Further The present invention is based on the object, a masterbatch for polymers to provide an improvement in processability allows the produced polymers and / or masterbatches.

Farther The present invention is based on the object, a masterbatch to provide, which alone or optionally together with the raw polymers to be processed mixed, dried.

This task is solved by
migration stable masterbatch comprising
From 1 to 45% by weight of bi- and / or polyfunctionally crosslinkable monomers; and 55 to 99% by weight of masterbatch polymer,
wherein the wt .-% is based on the total amount of bi- and / or polyfunctional crosslinkable monomers and the masterbatch polymers in the migration-stable masterbatch.

preferred Further developments of the masterbatch according to the invention are in the subclaims 2 to 20 indicated.

Under the term "masterbatch" within the meaning of the invention is a plastic additive to understand, which in particular as Granules to be crosslinked crude polymer and / or monomers thereof is added to improve the properties and / or an improved processability of the final polymer to be produced to reach.

Under the term "migration-stable Masterbatch "im Meaning of the invention is to be understood as a masterbatch, in which the crosslinkable bifunctional and / or polyfunctional monomers preferably in a solution in the masterbatch polymer. Under solution is preferably understood a physical solution, in particular no chemical reaction of the bifunctional and / or polyfunctional Monomers with the masterbatch polymer takes place. Under solution becomes in particular understood a homogeneous mixture of substances, which also the smallest partial volume of the solution have a similar composition.

Preferably is the proportion of physically undissolved crosslinkable bifunctional and / or polyfunctional monomers in the masterbatch less than 5 Wt .-%, more preferably less than 1 wt .-%, particularly preferably less than 0.1 wt .-% based on the total amount of migration stable Masterbatches. Most preferably, the proportion of physical not solved crosslinkable bifunctional and / or polyfunctional monomer 0 % By weight, based on the total amount of the migration-stable masterbatch.

Preferably the masterbatch is in comminuted form. The masterbatch can be used as granules, pellets, sausages, Briquettes or in the form of tablets.

Under the term "end polymer" in the context of the invention are polymers to be understood from the masterbatch of the invention and further crosslinkable crude polymers can be produced. The final polymers may be, for example by injection molding, Blowing, deep drawing or extrusion are processed.

Under the term "crude polymer" within the meaning of the invention is a mass understood to be the crosslinkable polymers, oligomers and / or crosslinkable monomers thereof. The crude polymer is added to the migration stable masterbatch and to the final polymer, preferably by irradiation, for example by UV rays, accelerated electron beams or γ-rays, crosslinked.

It can be found extremely advantageously that in the production of moldings when extruding a composition which comprises the masterbatch according to the invention and a crude polymer, there are no lubricating effects and the composition exhibits excellent behavior in the supply of material to the materials having pending devices. In contrast to crosslinkable bifunctional and / or polyfunctional monomers, which are applied to a microporous support, such as silicon dioxide, there are no Auspress effects of the monomers to be crosslinked during processing, for example during extrusion. This also prevents contamination of the machines and / or the environment, since no volatile substances are released from the masterbatch according to the invention.

Further can the masterbatch according to the invention advantageous with further crosslinkable crude polymers or monomers thereof are processed, with the resulting end polymers an excellent elongation at break and elasticity exhibit. Preferably, these are radiation-crosslinkable crude polymers or monomers thereof.

Further allows the masterbatch according to the invention the production of preferably radiation-crosslinkable polymers with a reduced abrasion on the processing device, for example an extruder, since the masterbatch preferably without a carrier is used. The carriers used in the prior art, are common mineral type, such as porous silica, and can the Damage processing device.

Further can the masterbatch according to the invention or a dry blend of masterbatch and others cross-linkable, preferably radiation-crosslinkable, raw polymers are pre-dried, without it leads to outgassing of the monomers to be crosslinked. Therefore, can the masterbatch according to the invention as a dry mix with all possible Modifications of filled and unfilled polymers be used. Under filled Polymers are preferably polymers which are mineral fibers, Glass fibers, polymer fibers and / or particles thereof.

In the masterbatch according to the invention are the bi- and / or polyfunctional crosslinkable monomers in a physical solution which reduces outgassing during processing. this makes possible a precise dosage of the crosslinkable monomers and is also out Cost reasons and ecological establish advantageous. Due to the exact Dosierbarkeit the production of final polymers with a defined cross-linking and quality. Furthermore, the networkable bi- and / or polyfunctional crosslinkable monomers also not on the environment.

Of the inventive masterbatch allows the production of a variety of different polymers the basis of a single masterbatch recipe. This will be significant Costs saved, not for each raw polymer has been formulated into a special crosslinkable blend must become.

The The above advantages are based on the fact that the bi- and / or polyfunctional crosslinkable monomers in the masterbatch according to the invention in a physical solution available. When using crosslinkable monomers based on a porous one carrier are processed, the crosslinkable monomers are not dissolved, but only sucked up and therefore have a higher vapor pressure and are therefore pressed or discharged during processing, so that the masterbatch or the end products made therefrom have no defined quality.

Under Use of the masterbatches according to the invention can polymers be produced with a definable degree of crosslinking, since in the masterbatch according to the invention contained crosslinkable bi- and / or polyfunctional monomers less than 5% by weight, preferably less than 2% by weight, most preferably less than 0.5% by weight, based on the total amount evaporate on migration stable masterbatch. Due to the low Evaporation is possible Process polymers with smaller amounts of crosslinking agent.

The Inventive masterbatch as well as the end polymers produced therewith are also excellent by extruding, injection molding or blowing process.

at an embodiment the crosslinkable bifunctional and / or polyfunctional monomers are radiation-crosslinkable. Preferably, the migration-stable masterbatch polymer comprises bifunctional and / or polyfunctionally crosslinkable monomers which preferably UV, β, γ and / or Electron radiation are crosslinkable.

The polyfunctional crosslinkable monomers are preferably trifunctional monomers. In one embodiment, the crosslinkable bifunctional and / or polyfunctional monomers are allyl esters and / or acrylates. The acrylates may also be methacrylates. Especially The masterbatch according to the invention preferably comprises isocyanuric triallyl tri-functional monomers.

Preferably are the crosslinkable bifunctional and / or polyfunctional monomers from the group consisting of cyanuric triallyl ester (TAC), isocyanuric triallyl ester (TAIC), Isocyanuric acid trimethylallyl ester (TMAIC), trimellitic allyl ester (TAM), diallyl phthalate (DAP), trimethylolpropane triallyl acrylate (TMPTA), trimethylolpropane trimethacrylate (TRIM) and mixtures thereof.

at an embodiment comprises the migration-stable according to the invention Masterbatch crosslinkable bifunctional and / or polyfunctional monomers in a concentration of 5 to 40 wt .-% and 95 to 60 wt .-% Masterbatchpolymer, preferably bifunctional and / or polyfunctional Monomers in a concentration of 20 to 30 wt .-% and 80 bis 70 wt .-% masterbatch polymer, wherein the wt .-% on the Total amount of bi- and / or polyfunctionally crosslinkable monomers and the masterbatch polymer in the migration stable masterbatch refers.

Preferably contains the masterbatch polymer is less than 1% by weight, more preferably less as 0.5 wt%, more preferably less than 0.1 wt%, most preferably less than 0.05% by weight of water, based on the total amount to masterbatch.

at an embodiment For example, the migration stable masterbatch comprises masterbatch polymers selected from the group consisting of polyurethanes, polyamides, polyvinyls, polyalkenes, Polyterephthalates, polyesters, polyethers, polyester-elastomers, polyether-elastomers, Polyester ether elastomers, polyacrylates, polymethacrylates, polyvinylidene fluoride, Ionomers thereof, copolymers thereof and mixtures thereof. For the copolymers These may be alternating copolymers, block polymers, graft polymers and statistical copolymers.

at an embodiment are the polyalkenes of the group consisting of high-density polyethylene (HDPE), low density polyethylene (LDPE), low linear density polyethylene (LLDPE), polypropylene copolymers (PP copolymer), and / or PP homopolymer, selected.

Under Ionomers are metal salts of polymers, in particular of polymethacrylates, Understood. As ionomer, for example, zinc ionomer methyl methacrylate be used.

Preferably includes the migration-stable masterbatch polyamide (PA). Preferably these are PA 6, PA 6.6, PA 6.9, PA 6.12, PA 12, and / or PA 11.

In one embodiment, the migration stable masterbatch comprises polymers selected from the group consisting of poly (C ₁ -C ₄ ) alkylene terephthalate, polynaphthylic acid amide, polyisophthalic acid amide, polyterephthalic acid amide, polyterephthalic acid hexamethylenediamide, copolymers thereof, and mixtures thereof.

at an embodiment For example, the migration stable masterbatch comprises masterbatch polymers selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, Copolymers thereof and mixtures thereof.

at an embodiment For example, the migration stable masterbatch comprises masterbatch polymers selected from the group consisting of polyhexamethylene adipamide, Polycaprolactam, polylaurolactam, polytetramethyleneadipamide, Copolymers thereof and mixtures thereof.

at an embodiment For example, the migration stable masterbatch comprises masterbatch polymers selected from the group consisting of polyurethane ether ester elastomers, polyurethane ester elastomers, Polyurethane ether elastomers, polyetheresteramide elastomers, polyether elastomers, polyetherester elastomers, Copolymers thereof and mixtures thereof. For example, a polyurethane tetramethylene ether used.

at an embodiment For example, the migration stable masterbatch comprises masterbatch polymers selected from the group consisting of polyethylene, polypropylene, copolymers and mixtures thereof.

In one embodiment, the migration stable masterbatch comprises masterbatch polymers selected from the group consisting of alkyl methacrylates, especially methyl methacrylates, ethylme thacrylates, their metal salts and mixtures thereof.

at an embodiment For example, the masterbatch polymer includes other polymers selected from the group consisting of polyesters, polyesteramides, polyphenylene ethers, Polyphenylene sulfides, aromatic polyetheramides, polyamides, polylactams and mixtures thereof.

at another embodiment For example, the masterbatch polymer includes other polymers selected from the group consisting of polydiaminobutane diadipidamide, polydiamonohexamethylene sebaciddiamide, polydiaminohexamethylene dodecane diamide, Polyaminoundecanamide, polylaurolactam, polyarylamide or mixtures from that.

In one embodiment, this includes
migration-stable masterbatch,
From 1 to 45% by weight of bi and / or polyfunctionally crosslinkable monomers; and 99 to 55% by weight of a masterbatch polymer
the formula I H - [- XR ¹ -X-] _n - [- YR ¹ -Y-] _m -OH (I) and / or the formula II H - [- XR ¹ -Y-] _n -OH (II) and / or the formula III H - [- XR ¹ -] _n --OH (III) wherein R ¹ is (CH ₂ ) ₁ , and / or phenyl, cyclohexyl, cyclopentenyl, cyclooctyl, cyclohexenyl, naphthyl, diphenyldimethylmethane or a C ₁ -C ₄ alkyl substituted derivative thereof, provided that when R ^{1 is the} same Phenyl is that XY groups are ortho, meta or para to each other,
and l is 1 to 12 and m and n is an integer, preferably 10 to 1000;
wherein X is O, S or NR ² , where R ² is H or C ₁ -C ₄ alkyl,
wherein Y is CO, COO, CONR ³ , where R ³ is H or C ₁ -C ₄ alkyl,
wherein the wt .-% is based on the total amount of bi- and / or polyfunctional crosslinkable monomers and the masterbatch polymers in the migration-stable masterbatch.

In one embodiment the masterbatch polymers that preferably polymers of formula I are, polyamides, polymers from the group of poly (C ₁ -C ₄₎ alkylene terephthalates, polyurethanes, copolymers and / or mixtures thereof.

at an embodiment are the masterbatch polymers, which are preferably polymers of Formula I are, from the group consisting of polydiaminohexamethylene adipic diamide, Polydiaminobutane diadipidamide, polydiaminohexamethylene azelaine diamide, Polydiaminohexa methylensebazindiamid, polydiaminohexamethylenedodecandiamide, Polydiaminodecansebazinediamide, poly-m-diaminoxylylene adipamide, Polydiaminoisophthalsäurediamid, Polydiaminohexamethylenedodecanediamide, polydiaminodicyclohexamethylenedodecanediamide, Polydiaminohexamethylene terephthalamide, polyethylene terephthalate, Copolymers thereof and mixtures thereof, selected.

In a further embodiment, the masterbatch polymers, which are preferably polymers of the formula II, are selected from the group consisting of polyamides, such as, for example, polycaprolactam, polylaurolactam, polyaminoundecanamide,
Polyurethanes, polycaprolactone, copolymers and mixtures thereof.

at another embodiment are the masterbatch polymers, which are preferably polymers of the formula III are, from the group of polyethers, such as polytetrahydrofuran, Polyethylene glycol, polypropylene glycol, polyether elastomers, polyphenylene ethers, Polyphenylene sulfide, copolymers and mixtures thereof.

Likewise, masterbatch polymers, which are preferably polymers of the formula I, formula II and / or formula III, can be selected from the group of polyurethane ester ether elastomers, polyetherester elastomers, and polyester ester elastomers. These masterbatch polymers can be blended together in any manner as well as with other polymers. For this purpose, it is possible to use polymers from the group consisting of polyesters, polyesteramides, aromatic polyetheramides, polyarylamides or mixtures thereof, and in particular all of the abovementioned masterbatch polymers or those specified in the claims.

Preferably are in the masterbatch polymer according to the invention as crosslinkable monomers Triallylisocyanurate in combination with Masterbatch polymers selected from the group consisting of polyamides, especially polyamide 6, 11, 12, 6.6, polyurethanes, in particular thermoplastic polyurethane ether elastomers, Polybutylene terephthalate, polyethylene terephthalate and / or polyolefins, used.

Furthermore, in the DE 38 28 690 A1 on page 4 and 5 modifier described as component C are used as additives, which are described below (the percentages by weight always refer to the modifier composition itself):
By way of example, these are graft polymers which are obtained by graft polymerization of from 5 to 90% by weight, preferably from 10 to 70% by weight, in particular from 15 to 50% by weight. at least one vinyl monomer mixture of methyl methacrylate and an acrylic acid ester of a C ₂ to C ₁₀ primary or secondary monohydric aliphatic alcohol, such as n-butyl acrylate, to from 10 to 95, preferably from 30 to 90, in particular from 50 to 85,% by weight. a particulate crosslinked diene rubber.

In addition, as Graft monomers still 0.1 to 10 wt .-%. of the acrylic or methacrylic ester of tertiary Butanols and / or 0.1-30 wt .-% of a mixture of styrene or α-methyl styrene and acrylonitrile, methacrylonitrile or maleic anhydride on the rubber base be grafted.

Especially preferred graft monomers are mixtures of methyl acrylate and n-butyl acrylate in the quantitative ratio from 85:15 to 98: 2 and mixtures thereof with tertiary butyl acrylate and / or styrene and acrylonitrile.

Preferred diene rubbers are crosslinked homo- and / or copolymers of conjugated C ₄ to C ₆ dienes. A particularly preferred diene is butadiene-1,3.

The diene copolymers in addition to the diene radicals up to 20 wt .-%, based on the diene copolymer, residues of other ethylenically unsaturated monomers such as styrene, acrylonitrile, esters of acrylic or methacrylic acid with monohydric C ₁ to C ₄ alcohols, such as methyl acrylate, ethyl acrylate , Methyl methacrylate and ethyl methacrylate or their metal salts such as zinc, sodium in copolymerized form. The preparation of the diene rubber graft base and the graft polymers prepared therefrom is described, for example, in Methods of Organic Chemistry (Houben-Weyl), Vol. 14/1, Georg Thieme Verlag, Stuttgart 1961, pp. 383 to 406 and in Ullmanns Encyclopedia of Industrial Chemistry ", 4th Edition, Vol. 19, Verlag Chemie, Weinheim 1981, pp. 279 to 284.

As further additives for the composition according to the invention, conventional modifiers of the prior art can be used. In particular, may be mentioned:
The in the DE 38 41 183 A1 These include, for example, graft polymers of acrylate rubber having a glass transition temperature below -20 ° C as a graft and polymerizable ethylenically unsaturated monomers having a glass transition temperature above 25 ° C as grafting monomers and with styrene and / or acrylonitrile and / or (Meth) acrylic acid alkyl esters grafted polybutadienes, butadiene / styrene copolymers and acrylate rubbers.

Likewise, silicone rubbers having graft-active sites that in the DE 37 04 657 A1 . DE 37 04 655 A1 . DE 36 31 540 A1 and DE 36 31 539 A1 described are used. Similar modifiers based on silicone rubber are also disclosed in the prior art of the publications DE 37 25 576 A1 . EP 0 235 690 A1 . DE 38 00 603 A1 and EP 0319 290 A1 described.

In the EP 0 233 473 A1 elastomeric components such as acrylic acid derivatives with monomers containing epoxy groups are described as a graft. The EP 0 319 581 A1 describes modifiers of ethylene copolymer with α, β-unsaturated carboxylic acid alkyl esters and maleic anhydride, EP 0 256 461 A1 describes on pages 5 and 6 a number of ethylene-propylene rubbers (EPM rubber) and ethylene-propylene-diene rubbers (EPDM rubbers) and their combination with other modifiers. The rubbers have a ratio of ethylene to propylene units of 20:80 preferably 65:35. Similarly constructed polymers are also used as impact modifiers in EP 0 320 651 A1 and EP 0 320 647 A1 be wrote. Also the EP 0 484 737 A1 describes end group-stabilized polyoxymethylene polymers, EPM and EPDM rubbers grafted with acrylic acid derivatives, epoxides, dicarboxylic acids and dicarboxylic acid anhydrides, polymers of styrene derivatives, acrylic acid derivatives, acrylonitrile and polyenes. Suitable graftlinking monomers are described in US Pat US 4,148,846 described.

The EP 0 313 862 A1 describes the use of ethylene vinyl alcohol together with grafted hydrogenated styrene-ethylene-butylene block copolymer modified with an unsaturated dicarboxylic acid or an unsaturated dicarboxylic anhydride. In the EP 0 389 055 A1 the use of epoxy- and oxazoline-containing aromatic vinyl-diene-vinyl-cyanide copolymers or aromatic polyesters as copolymers is described.

As a further modifier and polyurethane can be used as in the EP 0 115 846 A1 . EP 0 115 847 A1 . EP 0 116 456 A1 . EP 0 117 664 A1 and EP 0 327 384 A1 mentioned. Commercially available commercially such products under the name Desmopan ^® (manufacturer: Bayer AG, Leverkusen) and Elastollan ^® (manufacturer: Elastogran Polyurethane GmbH, lemförde, Germany).

The WO 93/08234 describes the use of ethyl copolymer ionomers and copolyesterurethanes which are also suitable as modifiers.

The Modifiers can in the masterbatch according to the invention in an amount of from 0 to 90% by weight, in particular from 0 to 70% by weight, preferably from 0 to 40% by weight, based on the total polymer content be included.

The Production of polyamides according to formula I and formula II is in the Kunststoffhandbuch Bd. 3/4 by Becker / Braun published by Dr. med. Bottenbruch and dr. Binsack, Carl Hanser Verlag, Munich 1998, described.

preferred Use find polyamide 6, polyamide 6.6, polyamide 11, polyamide 12, polyamide 6.9, polyamide 6.10, polyamide 6.12, polyamide 10.10, aromatic polyamides of terephthalic acid, isophthalic acid and phthalic acid, or meta-xylylenediamine, para-xylylenediamine and adipic acid, Derivatives of diaminodicyclohexylmethane or 3,3-dimethyl-p-diaminocyclohexylmethane with dodecanedioic acid or other diacids, or Mixtures thereof. Likewise, copolymers thereof are in use.

The Preparation of polyesters is described in the Kunststoffhandbuch, Vol. VIII, Polyester, from Dr. med. L. Goerden, Carl Hanser Verlag, Munich 1971 described.

polybutylene terephthalate is prepared, for example, from dimethyl terephthalate and 1,4-butanediol; polyethylene terephthalate is prepared, for example, from dimethyl terephthalate and 1,2-ethanediol.

The Preparation of polyurethanes according to formula I, formula II and / or Formula III is in Holden / Kricheldorf / Quirk, Thermoplastic Elastomers, 3rd Ed. Carl Hanser Verlag, Munich 2004 described. For example, they are made up of aromatic substances or aliphatic diisocyanurates, examples being 4,4'-diphenylmethane diisocyanurate and hexamethylene diisocyanurate, condensed with α, ω-diols, such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, polytetrahydrofurandiol, Polypropylene glycol, polyethylene glycol, adipate ester, caprolactone, Carbodiimides and / or ether esters.

Polyether ester elastomers, polyetheresteramide elastomers, polyether elastomers in the context of the invention are based, for example, on the combination of the formula I and / or formula II and / or formula III. Examples of these are commercially available as Hytrel ^® (Dupont), Arnitel ^® (DSM) or Pibiflex ^® (P Group) available.

The Migration-stable masterbatch becomes the raw polymer to be processed given and subsequently processed together with this to a shaped body, which in the second step is preferably crosslinked by radiation crosslinking. Radiation crosslinking is preferably carried out by UV, β, γ and / or electron radiation. For example, the radiation is transmitted through an electron accelerator generated. Preferably, this becomes bifunctional and / or polyfunctional crosslinkable monomer from the masterbatch by heating, preferably Melting of the masterbatch polymer, homogeneously mixed.

In one embodiment, the crude polymers further comprise fillers and / or reinforcing agents. Preferably, the crude polymers comprise fillers and / or reinforcing agents in amounts of from 3 to 60% by weight, based on the amount of the crude polymer. The filling and / or reinforcing materials can also the Final polymer and / or the masterbatch polymer are added directly.

at an embodiment comprises the migration-stable masterbatch and / or the crude polymer and / or Final polymer colorant, Stabilizers, modifiers, processing aids, flame retardants, plasticizers or mixtures thereof.

at an embodiment comprises the migration-stable masterbatch and / or the crude polymer and / or Final polymer further talc, mineral, carbon fiber, aramid fiber, boron nitride, Aluminum nitrite, magnesium hydrate, aluminum trihydrate, nanotubes, conductive carbon blacks, Metal powder, glass beads, glass fiber or mixtures thereof.

nanotubes are tubes whose diameter is smaller than 100 nm. Preferably exist the nanotubes made of materials that can form layers, such as for example graphite.

Preferably includes the migration-stable masterbatch and / or the crude polymer no porous materials. Under the term "no porous Materials "im Sense of the present invention are preferably porosities of less than 5%, more preferably less than 1%. % Porosity means open volume based on the volume of the solid structure. The sum of the open cavities is in% relative to the outer volume indicated, which corresponds to 100%.

It was surprisingly found that with the migration stable masterbatch invention excellent processing with the raw polymers selected from the group consisting of polyurethane, polyamide, polyvinyls, polyalkenes, Polyterephthalates, polyesters, polyethers, polyester elastomers, polyether elastomers, Polyester ether elastomers, polyacrylates, polymethacrylates, polyvinylidene fluoride, ionomers thereof, copolymers thereof and mixtures thereof. Especially it was surprising that by the application of the migration-stable masterbatch according to the invention Raw polymers from the group of olefins, preferably polyethylene and / or Polypropylene, with and without fillers to radiantly crosslink in a dry mix Have parts processed with all the advantages. It was the same also surprising that by applying the masterbatch according to the invention further raw polymers from the group of methyl methacrylates, ethyl methyl acrylates and / or their metal salts with and without fillers to be radiantly crosslinked in a dry-blend Process parts, profiles and / or foils with all the advantages to let.

It was still surprising that by applying the masterbatch according to the invention further raw polymers from the group of polyamides, polyurethanes, polybutylene terephthalates, and polyethylene terephthalates with and without fillers are in excellent Manner in a dry mix with radiation cross-linked parts all advantages.

in the migration stable according to the invention Masterbatch, the crosslinking monomers are so good in the masterbatch polymer solved, that during drying and / or during processing of the masterbatch or the masterbatch with the raw polymers in the machines, in particular injection molding machines and extruders that are networkable Do not degas or flooding monomers, which is the surface of the Parts very strongly adversely affected. This will make the production of dried comminuted masterbatch, especially in the form of granules, allows wherein the crushed masterbatch is not glued and free-flowing. It will be the provision of an optimally dosed masterbatch allows. Furthermore, contamination of the machines with the migration stable according to the invention Masterbatch polymer avoided.

The property values of the final product are improved by this method, since not with high concentrations of silica as in DE 100 16 120 A1 described, must be worked. Silica dioxide greatly affects the physical properties of the finished product. Here are the impact resistance and notched impact strength called. When processed with silica, the radiation-crosslinking monomers are squeezed out and there are smearing effects and drastic deterioration of the feed behavior during processing. The end polymers prepared by crosslinking, preferably by radiation crosslinking, with the masterbatch according to the invention have in particular a higher resistance to chemicals, insolubility in conventional solvents, improvement of the abrasion behavior, improvement of the mechanical and electrical properties, as well as the aging behavior.

Preferably is the migration-stable masterbatch a granulate. The granules preferably has a granule size of 0.1 mm. up to 10 mm, further preferably from 1 to 4 mm, on.

Based on the final polymer, the proportions of
migration-stable masterbatch and crude polymer 1 to 50% by weight of masterbatch with 99 to 50% by weight of crude polymer, preferably 10 to 40% by weight of masterbatch with 90 to 60% by weight of crude polymer,
wherein the wt .-% is based on the total amount of bi- and / or polyfunctional crosslinkable monomers and the masterbatch polymers in the migration-stable masterbatch.

• (a) Schmelzen eines Masterbatchpolymers;
• (b) Einbringen von bi- und/oder polyfunktional vernetzbaren Monomeren in die Schmelze des Masterbatchpolymers aus Schritt (a);
• (c) Mischen der Masse aus Schritt (b) und Bereitstellen einer Mischung aus 1 bis 45 Gew.-% bi- und/oder polyfunktional vernetzbaren Monomeren; und 55 bis 99 Gew.-% Masterbatchpolymer, wobei sich die Angabe Gew.-% auf die Gesamtmenge der bi- und/oder polyfunktional vernetzbaren Monomeren und der Masterbatchpolymere in dem migrationsstabilen Masterbatch bezieht.
• (d) Abkühlen der Mischung aus Schritt (c),
• (e) optional Zerkleinern der Mischung aus Schritt (d).

The object is further achieved by a method for producing the masterbatch comprising the steps:

• (a) melting a masterbatch polymer;
• (b) introducing bi- and / or polyfunctionally crosslinkable monomers into the melt of the masterbatch polymer from step (a);
• (c) mixing the composition of step (b) and providing a mixture of 1 to 45% by weight of bi- and / or polyfunctionally crosslinkable monomers; and 55 to 99% by weight of the masterbatch polymer, wherein the wt% is based on the total amount of the bi- and / or polyfunctionally crosslinkable monomers and the masterbatch polymers in the migration-stable masterbatch.
• (d) cooling the mixture from step (c),
• (e) optionally comminuting the mixture of step (d).

preferred Further developments of the method according to the invention for the preparation of the masterbatch are given in subclaims 22 to 33.

at an embodiment if the mixture in step (e) becomes granules, pellets, sausages, Crushed briquettes or tablets.

Preferably the masterbatch is at temperatures 20 to 40 ° C above the melting point of the masterbatch polymer melted.

at an embodiment the granules are dried after step (d) or (e). The drying is preferably carried out at temperatures in a range of 30 ° C to 120 ° C. Especially Preferably, the granules are dried in a range of 70 ° C to 110 ° C.

The Mixture is, for example, in a single-shaft or twin-screw extruder at 140 to 280 ° C melted and extruded. The homogeneous, molten extrudate is then withdrawn as a strand through a water bath and in a Granulator crushed and dried.

Surprisingly, evaporate the dissolved in the masterbatch invention and / or polyfunctionally crosslinkable monomers not during drying.

at an embodiment in step (a), (b), (c), (d) and / or (e) of the masterbatch also colorants, Stabilizers, plasticizers, flame retardants or mixtures of it admitted.

at an embodiment in step (a), (b), (c), (d) and / or (e) of the masterbatch talc, mineral, glass fibers, carbon fiber, aramid fiber, boron nitride, Aluminum nitrite, metal powder, nanotubes and conductive carbon black or Mixtures of it added.

Preferably become the migration-stable masterbatch no porous materials added.

at an embodiment The migration-stable masterbatch will not be filled and filled reinforcing materials added.

• (a) Mischen des Masterbatches wie vorstehend definiert mit vernetzungsfähigen Rohpolymeren und/oder Monomeren davon,
• (b) Polymerisieren der Mischung aus Schritt (a) zum Endpolymer.

The object is further achieved by a process for the preparation of the end polymers, comprising the steps:

• (a) mixing the masterbatch as defined above with crosslinkable crude polymers and / or monomers thereof,
• (b) polymerizing the mixture of step (a) to the final polymer.

preferred Further developments of the method according to the invention for the preparation of the final polymer are given in subclaims 29 to 32.

In principle, all types of polymers which are compatible with the components of the masterbatch polymer can be used as crude polymers. To the compatible raw polymers belong vorzugswei polymers which, with the masterbatch, achieve a degree of crosslinking of more than 70%, preferably more than 90%, particularly preferably more than 95%, based on the potential crosslinking sites.

at an embodiment the polymerization takes place by radiation crosslinking. The radiation crosslinking can by means of UV, β, γ-rays and / or electron beams, carried out become.

at an embodiment become the masterbatch polymers used in the masterbatch also used as crude polymers, the crude polymers in difference have crosslinkable sites to the masterbatch polymers and / or exist as oligomers and / or monomers. Preferably it is the masterbatch polymers and the crude polymers are polymers, which are composed of the same monomers.

at an embodiment in step (a) 1 to 50 wt .-%, preferably 10 to 40 wt. % Masterbatch based on the total final polymer added.

The The object is also achieved by a molding which contains the masterbatch according to the invention includes. The moldings can For example, have thermoset properties. The molding For example, it can be molded by extrusion, injection molding, blowing or deep drawing will and will be afterwards preferably crosslinked by radiation.

figure

1 shows a thermo-mechanical cross-linker The following examples are intended to illustrate but not limit the invention.

Description of the thermomechanical Networking tester:

To determine the degree of crosslinking also mechanically, a thermomechanical crosslinking tester was used as described below (see also 1 ).

Description of the thermomechanical Networking tester:

• 1 PTS-Vernetzungstester X 30.00
• 1 Prismenauflage X 10.10
• 1 Digitale mikroprozessorgeregelte X 30.20
• Lötstation ERSA DIGITAL 2000A
• incl. Bedienungsanleitung von ERSA
• 1 Auflagetisch für Messproben X 10.11
• Durchmesser 63 mm
• 1 Standardprüfspitze 2 mm X 10.02
• 1 Zusatzgewicht 1 kg X 10.12
• Durchmesser 80 mm

The PTS crosslinking tester available from the company Plastic Technology Service (Hautschenmühle, Germany) consists of

• 1 PTS crosslinking tester X 30.00
• 1 prism support X 10.10
• 1 Digital microprocessor-controlled X 30.20
• Soldering station ERSA DIGITAL 2000A
• incl. manual of ERSA
• 1 support table for measurement samples X 10.11
• Diameter 63 mm
• 1 standard probe 2 mm X 10.02
• 1 additional weight 1 kg X 10.12
• Diameter 80 mm

Equipment:

• 1 probe 1 mm X 10.01
• 1 probe 3 mm X 10.03
• 1 probe 4 mm X 10.04
• 1 probe 6 mm X 10.06

Service:

• – Vulkanisaten
• – strahlenvernetzten Polyolefinen
• – strahlenvernetzten Elastomeren, wie PTS-GAMMAFLEX
• – strahlenvernetztem TPU
• – strahlenvernetzten technischen Teilen z.B. aus Polyamid

The PTS crosslinking tester is a device for rapid quality testing or determination of the crosslinking density or determination of the melting point of

• - Vulcanizates
• - radiation crosslinked polyolefins
• - Radiation crosslinked elastomers, such as PTS-GAMMAFLEX
• - radiation crosslinked TPU
• - Radiation-crosslinked technical parts, eg made of polyamide

Testing of soft materials:

ever after Shore hardness you use the probes 4 mm or 6 mm and the standard test load 1 kg (without additional weight).

Testing of rigid materials e.g. PA / GV:

you used depending on the stiffness of the polymer and molding geometry probes from 1-3 mm and 1-2 kg test load.

Carrying out the test:

turn on a device and wait about 1 minute for the probe to warm is completed. Too early Placing the probe Otherwise measure the thermal expansion the probe and not the thermal behavior of the molding.

With the left hand, the locking screw is released while holding the adjusting wheel, which over the rack the probe arbitrarily positioned.

Then you bring the probe with the adjusting wheel to the sample, the device clamps with the Locking screw firmly and examines the behavior of the plastic sample on the dial gauge.

• – sofortiges schnelles Eindringen der Spitze bei nicht vernetzter Probe
• – langsames Eindringen der Prüfspitze bei schlechter Vernetzung
• – kein Eindringen bzw. Feststellung der Wärmedehnung der Probe bei hochvernetztem Prüfkörper

The following test results are possible;

• - Immediate rapid penetration of the tip in non-crosslinked sample
• - slow penetration of the probe in poor networking
• - No penetration or determination of the thermal expansion of the sample in highly cross-linked test specimen

gel value

Of the Gelwert indicates how much weight percent of the final polymer after the Crosslinking reaction and after extraction with a solvent remain. The gel value is a measure of the degree of crosslinking of the The final polymer.

viscosity

The viscosity was measured with a capillary viscometer. The measurement was carried out with an Ubbelohde viscometer at 25 ° C.

Example 1 (preparation Masterbatch)

A polyamide 6 having a relative viscosity (η _rel ) of 2.7 is melt extruded with 25 wt% triallyl isocyanurate (TAIC) in a twin-screw extruder at 240 to 265 ° C. The homogeneous, molten extrudate is withdrawn as a strand through a water bath and comminuted in a granulator and dried at 90 ° C for 4 h. In further examples, this masterbatch is mixed with various polymers and injection-molded into shaped parts via an injection molding machine. In a further step, the moldings are irradiated in an irradiation chamber with β or γ rays. With a temperature measuring device, the crosslinked moldings are tested for the degree of crosslinking or wet-chemically determined in boiling solvents gel values. (Polyolefins with xylene, polyamides with sulfuric or formic acid, polyurethanes with THF). The remaining gel value is a measure of crosslinking.

Example 2 to 6 and 8 to 13

In Examples 2 to 13, the masterbatch of Example 1 with mixed polyamides and an injection molding machine to moldings at 265 to 280 ° C injection molded. Subsequently become the moldings in a radiation chamber with β-rays irradiated. Become a thermomechanical crosslinker the crosslinked moldings tested for the degree of crosslinking (penetration test). The gel value is determined in concentrated formic acid.

Example 7

in the Example 7, 15 wt .-% masterbatch from Example 1 with 85 wt .-% Polyamide 6.6 (relative viscosity 2,7) mixed and over an injection molding machine to moldings at 280 to 295 ° C. injection molded. Subsequently become the moldings in a radiation chamber with β-rays irradiated. Become a thermomechanical crosslinker the crosslinked moldings tested for the degree of crosslinking (penetration test). The gel value is determined in concentrated formic acid.

Comparative Example 7a

94.6 % By weight of polyamide 6.6 (relative viscosity 2.7) is 5.4% by weight BETALINK IC / W70 based on the total amount of polyamide 6.6 and BETALINK mixed (PTS, Adelshofen). BETALINK IC / W70 consists of 30% by weight Silica support (Silica) and 70% by weight of TAIC based on the total weight of BETALINK, which have been compounded. The mixture is over one Injection molding machine injection molded into molded parts or in an extruder to hoses or profiles processed. In a further step, the Shaped parts irradiated in a radiation chamber with β-rays at 100 kGy. With a thermomechanical crosslinking tester, the networked Moldings tested for the degree of crosslinking (penetration test). Of the Gel value is determined in concentrated formic acid.

Comparative Example 7b

94.2 % By weight of polyamide 6.6 (relative viscosity 2.7) is 5.8% by weight BETALINK IC / W65PA6 based on the total amount of polyamide 6.6 and BETALINK mixed. BETALINK IC / W65PA6 consists of 35% by weight PA6 carrier and 65 wt .-% TAIC based on the total weight of the mixture, wherein BETALINK IC / W65PA6 is not compounded (that is, not solved), but the TAIC is blown warm on the microporous PA6 support. The mixture is over an injection molding machine injection molded into molded parts or in one Extruder to hoses or profiles processed. In a further step, the Shaped parts irradiated in a radiation chamber with β or γ rays at 100 kGy.

Result from example 7 and Comparative Examples 7a and 7b:

Theoretically the content of TAIC in the finished compound is 3.77% by weight. In the finished injection molded parts of Example 7 could be 3.75 wt .-%. TAIC are detected, which an amount of almost 100%. In the finished injection molded parts from Example 7a only 1.6% by weight of TAIC could be detected, i.e. more than the half TAIC is lost. After irradiation with 100 gGy (electron beam) only 39% gel was achieved, which was not available for most applications is sufficient. In the finished injection molded parts from Example 7b could only 2.3% by weight of TAIC are detected, i. it still works lost significant amounts of TAIC. After irradiation with 100 gGy (electron beam) was only achieved a gel value of 48%, the for most applications is insufficient.

Description to table 1:

Of the Crosslinking tester is set to a temperature of 350 ° C. A test tip of 2 mm diameter is attached and one Load of 1 kg. Test time: 20 sec.

• PA = Polyamid

These test conditions are far above the melting points of all polyamides. Table 1

• PA = polyamide

Example 14

One Polyamide 12 is mixed with 25 wt .-% triallyl isocyanurate (TAIC) in one Twin-screw extruder in the melt at 220 ° C extruded. The homogeneous, molten Extrudate is withdrawn as a strand through a water bath and in a Granulator crushed and at 80 ° C. dried. This masterbatch will be described in more examples with different Mixed polyamides and over an injection molding machine injection molded into molded parts or in one Extruder to hoses or profiles processed. In a further step, the Shaped parts irradiated in a radiation chamber with β or γ rays at 100 kGy.

Example 15 to 22

• PA = Polyamid
• Bei den Glasfasern und Kohlefasern handelt es sich um kompakte nicht-poröse Strukturen

In Examples 15 to 22, the masterbatch of Example 14 is ge with various polyamides ge mixed and injection-molded on an injection molding machine to form parts at 220 ° C. Subsequently, the moldings are exposed in an irradiation chamber with β-rays. With a thermo-mechanical cross-linking tester, the cross-linked molded parts are tested for the degree of cross-linking. Table 2

• PA = polyamide
• The glass fibers and carbon fibers are compact non-porous structures

Example 23

One Polyurethane C4 ether (polyurethane tetramethylene ether) is used with 30 Wt% triallyl cyanurate (TAC) in a twin-screw extruder in the Melt at 200 ° C extruded. The homogeneous, molten extrudate is stranded withdrawn through a water bath and crushed in a granulator and at 80 ° C dried. This masterbatch is used in further examples with polyurethane and / or mixed with different polyamides and over one injection molding machine injection molded into moldings. In a further step, the moldings in an irradiation chamber with β-rays applied.

Example 24 to 31

• PA = Polyamid
• TPU = thermoplastische PUR-Elastomere
• PUR = Polyurethan

In Examples 24 to 31, the masterbatch from Example 23 is mixed with polyurethane and / or various polyamides and injection-molded via an injection molding machine into moldings at 200 ° C. At closing the moldings are exposed in an irradiation chamber with β-rays. With a thermo-mechanical cross-linking tester, the cross-linked molded parts are tested for the degree of cross-linking. Table 3

• PA = polyamide
• TPU = thermoplastic polyurethane elastomers
• PUR = polyurethane

Example 32

One Zinc-ionomer-methyl methacrylate is mixed with 30% by weight of triallyl cyanurate (TAC) in a twin-screw extruder in the melt at 220 ° C extruded. The homogeneous, molten one Extrudate is withdrawn as a strand through a water bath and in a Granulator crushed and dried. This masterbatch will be in more Examples mixed with different polyamides and polyesters and over an injection molding machine injection-molded into moldings. In another Step the moldings in an irradiation chamber with β-rays applied.

Example 33 to 44

• A = Polyamid
• PBT = Polybutylentherephthalat
• PET = Polyethylenterephthalat

• a) Da keine ungiftigen Lösungsmittel bekannt sind, beschränkt man sich bei PBT und PET auf den Penetrationstest.

In Examples 33 to 44, the masterbatch from Example 32 is mixed with various polyamides and polyesters and injected via an injection molding machine at 240 ° C to 270 ° C to form parts. Subsequently, the moldings are exposed in an irradiation chamber with β-rays. With a ther momechanical crosslinking tester, the crosslinked moldings are tested for the degree of crosslinking. Table 4

• A = polyamide
• PBT = polybutylene terephthalate
• PET = polyethylene terephthalate

• a) Since no non-toxic solvents are known, the PBT and PET are limited to the penetration test.

Example 45

One LLDPE with an MFI of 3-4 g / 10 min. (190 ° C, 2.16 kg) is 25 wt .-% Trimethylpropane triallyl acrylate (TMPTA) in a single-screw extruder in the melt at 180 ° C. extruded. The homogeneous, molten extrudate is stranded withdrawn through a water bath and crushed in a granulator and at 80 ° C dried. This masterbatch will be described in more examples with different Polyolefins mixed and over an injection molding machine injection-molded into moldings. In another Step the moldings in an irradiation chamber with β-rays applied. The gel value determination is carried out in hot xylene.

Example 46 to 53

• HDPE = high density Polyethylen
• LDPE = low density Polyethylen
• PP = Polypropylen
• MFI = Melt flow index (Schmelzflußindex)
• * MFI g/10 min. (190°C, 2,16 kg)
• ** MFI g/10 min. (230°C, 16 kg)

In Examples 46 to 53, the masterbatch from Example 45 is mixed with various polyolefins and injection molded into moldings via an injection molding machine. Subsequently, the moldings are exposed in an irradiation chamber with β-rays. With a thermo-mechanical cross-linking tester, the cross-linked molded parts are tested for the degree of cross-linking. Table 5

• HDPE = high density polyethylene
• LDPE = low density polyethylene
• PP = polypropylene
• MFI = melt flow index
• * MFI g / 10 min. (190 ° C, 2.16 kg)
• ** MFI g / 10 min. (230 ° C, 16 kg)

Claims (35)

Migration stable masterbatch, comprising 1 up to 45% by weight of bi- and / or polyfunctionally crosslinkable monomers; and 55 to 99% by weight of masterbatch polymer, where the indication Wt .-% of the total amount of bi- and / or polyfunctional crosslinkable Monomers and the masterbatch polymers in the migration stable masterbatch refers. Migration-stable masterbatch according to claim 1, comprising crosslinkable bifunctional and / or poly functionally crosslinkable monomers selected from the group consisting of cyanuric triallyl ester, isocyanuric triallyl ester, isocyanuric trimethylallyl ester, trimellitic acid allyl ester, diallyl phthalate, trimethylolpropane triallyl acrylate, trimethylolpropane trimethacrylate, and mixtures thereof. A migration stable masterbatch according to claim 1 or 2, wherein the masterbatch polymer is selected from the group consisting of polyurethane, Polyamide, polyvinyls, polyalkenes, polyterephthalates, polyesters, Polyethers, polyester elastomers, polyether elastomers, polyester ether elastomers, polyacrylates, Polymethacrylates, polyvinylidene fluoride, ionomers thereof, copolymers and mixtures thereof is. The migration stable masterbatch of any one of claims 1 to 3, wherein the masterbatch polymer is selected from the group consisting of poly (C ₁ -C ₄ ) alkylene terephthalate, polynaphthylic acid amide, polyisophthalic acid amide, polyterephthalic acid amide, polyterephthalic acid hexamethylenediamide, copolymers thereof, and mixtures thereof. Migration-stable masterbatch according to one of claims 1 to 4, wherein the masterbatch polymer is selected from the group consisting of polyethylene terephthalate, Polybutylene terephthalate, copolymers thereof and mixtures thereof, selected is. Migration-stable masterbatch according to one of claims 1 to 5, wherein the masterbatch polymer is selected from the group consisting of polyhexamethylene adipamide, Polycaprolactam, polylaurolactam, polytetramethyleneadipamide, Copolymers thereof and mixtures thereof. Migration-stable masterbatch according to one of claims 1 to 6, wherein the masterbatch polymer is selected from the group consisting of polyurethane ether ester elastomers, Polyurethane ester elastomers, polyurethane ether elastomers, polyetheresteramide elastomers, Polyether elastomers, polyetherester elastomers, copolymers thereof and mixtures thereof is. Migration-stable masterbatch according to one of claims 1 to 7, wherein the masterbatch polymer is selected from the group consisting of polyethylene, polypropylene, Copolymers thereof and mixtures thereof. Migration-stable masterbatch according to one of claims 1 to 8, wherein the masterbatch polymer is selected from the group consisting of alkyl methacrylates, in particular methyl methacrylates, ethyl methacrylates, their metal salts and mixtures thereof is. Migration-stable masterbatch according to one of claims 1 to 9, wherein the masterbatch polymer further polymers selected from the group consisting of polyesters, polyesteramides, polyphenylene ethers, Polyphenylene sulfides, aromatic polyetheramides, polyamides, polylactams and mixtures thereof. Migration-stable masterbatch according to one of claims 1 to 10, wherein the masterbatch polymer further polymers selected from the group consisting of polydiaminobutadipidamide, polyaminoundecanamide, Polylaurolactam, polyarylamide, polydiaminohexamethylene adipamide, Polydiaminohexamethylene azelaine diamide, polydiaminohexamethylene sebacamide diamide, Polydiaminohexamethylenedodecanediamide, Polydiaminodecansebazinediamide, Poly-m-diaminoxylylene adipamide, polydiaminoisophthalic acid diamide, Polydiaminohexamethylenedodecanediamide, polydiaminodicyclohexamethylenedodecanediamide, Polydiaminohexamethylene terephthalamide, copolymers thereof and mixtures of which contains. Migration stable masterbatch, wherein the masterbatch polymer a mixture is two or more of those in claims 2 to Contains 11 specified polymers. Migration-stable masterbatch according to one of claims 1 to 12, comprising 5 to 40 wt .-% bi- and / or polyfunctional crosslinkable Monomers and 95 to 60 wt .-% masterbatch polymer, wherein the Indicating wt .-% on the total amount of bi- and / or polyfunctional crosslinkable monomers and the masterbatch polymers in the migration stable Masterbatch relates. Migration-stable masterbatch according to Claim 13, comprising 20 to 30 wt .-% bi- and / or polyfunctional crosslinkable Monomers and 80 to 70 wt .-% masterbatch polymer, wherein the Indicating wt .-% on the total amount of bi- and / or polyfunctional crosslinkable monomers and the masterbatch polymers in the migration stable Masterbatch relates. Migration-stable masterbatch according to one of claims 1 to 14, further comprising colorants, stabilizers, Plasticizers, flame retardants or mixtures thereof. Migration-stable masterbatch according to one of claims 1 to 15, further comprising talc, mineral, glass fibers, carbon fiber, Aramid fiber, boron nitride, aluminum nitrite, metal powder, nanotubes and Leitruße or mixtures thereof. Migration-stable masterbatch according to one of claims 1 to 16, which is not porous Materials includes. Migration-stable masterbatch according to one of claims 1 to 15, which does not fill and reinforcing materials includes. Migration-stable masterbatch according to one of claims 1 to 18, wherein the migration stable masterbatch is a granulate, the preferably a granule size of 0.1 mm to 10 mm. Migration-stable masterbatch according to one of claims 1 to 19, wherein the crosslinkable bifunctional and / or polyfunctional crosslinkable monomer is a radiation-crosslinkable, preferably a UV, electron beam, β or γ radiation crosslinkable Monomer is. Process for the preparation of a migration stable Masterbatch according to one of the claims 1 to 20, comprising the steps: (a) melting a masterbatch polymer; (B) Introduction of bi- and / or polyfunctional crosslinkable monomers into the melt of the masterbatch polymer of step (a); (C) Mixing the mass from step (b) and providing a mixture from 1 to 45% by weight of bi- and / or polyfunctionally crosslinkable monomers; and 55 to 99% by weight of masterbatch polymer, where the indication Wt .-% of the total amount of bi- and / or polyfunctional crosslinkable Monomers and the masterbatch polymers in the migration stable Masterbatch relates. (d) cooling the mixture from step (C) (e) optionally comminuting the mixture of step (d). Process for the preparation of migration stable Masterbatches according to claim 21, wherein in step (e) the mixture from step (d) is granulated. Process for the preparation of migration stable Masterbatches according to claim 21 or 22, further comprising after step (d) or (e) a drying step. Process for the preparation of migration stable Masterbatch according to one of the claims 21 to 23, wherein a migration stable masterbatch polymer as in one of the claims 3 to 14 defined and / or the bi- and / or polyfunctional crosslinkable Monomers as defined in claim 2 or 20 can be used. Process for the preparation of migration stable Masterbatch according to one of the claims 21 to 24, wherein in step (a), (b), (c), (d) and / or (e) further Additives, in particular colorants, Stabilizers, plasticizers, flame retardants or mixtures be admitted. Process for the preparation of migration stable Masterbatch according to one of the claims 21 to 25, wherein in step (a), (b), (c), (d) and / or (e) further Talcum, mineral, glass fibers, carbon fiber, aramid fiber, boron nitride, Aluminum nitrite, metal powder, nanotubes and conductive carbon black or Mixtures of which are added. Process for the preparation of migration stable Masterbatch according to one of the claims 21 to 26, wherein the migration stable masterbatch no porous materials includes. Process for the preparation of migration stable Masterbatch according to one of the claims 21 to 27, wherein the migration stable masterbatch no fill and reinforcing materials includes. Process for preparing the final polymers comprising the steps: (a) mixing the masterbatch as in one of the claims 1 to 20 defined with crosslinkable crude polymers and / or Monomers thereof, (b) polymerizing the mixture of step (a) to the final polymer. Process for the preparation of the end polymers according to claim 29, wherein in step (b) the polymerization of the mixture by irradiation, preferably with β- or γ radiation, he follows. Process for the preparation of the end polymers according to claim 29 or 30, characterized in that in step (a) 1 to 50 Wt .-% masterbatch based on the total final polymer added become. Process for the preparation of the end polymers according to claim 31, wherein in step (a) 10 to 40 wt .-% masterbatch based on the entire final polymer is added. Process for the preparation of the end polymers according to a the claims 29 to 32, wherein the crosslinkable crude polymers and / or Monomers thereof, from the group of polyurethanes, polyamides, polyvinyls, Polyalkenes, polyterephthalates, polyesters, polyethers, polyester elastomers, Polyether elastomers, polyester ether elastomers, polyacrylates, polymethacrylates, Polyvinylidene fluoride, ionomers thereof, copolymers thereof and mixtures and monomers thereof are selected. Molding comprising a masterbatch as in one the claims 1 to 20 defined. Use of a polymer based on a masterbatch as in any of the claims 1 to 20 defined for the production of a thermoset.