DE102006017346B4 - Migration-stable masterbatch with improved crosslinking properties, process for its preparation and use thereof - Google Patents

Abstract

Migration stable masterbatch, comprising
From 15 to 45% by weight of bi- and / or polyfunctionally crosslinkable monomers; and
55 to 85% by weight of masterbatch polymer selected from PA 6, PA 6.6, PA 6.9, PA 6.10, PA 6.12, PA 10.10, PA 11 and / or PA 12,
wherein the wt .-% is based on the total amount of bi- and / or polyfunctionally crosslinkable monomers and the masterbatch polymers in the migration-stable masterbatch and wherein the masterbatch is a granulate,
wherein the bifunctional and / or polyfunctional crosslinkable monomers are electron-beam, β or γ radiation crosslinkable monomers and from the group,
consisting of cyanuric triallyl ester, isocyanuric triallyl ester, isocyanuric trimethylallyl ester, trimellitic acid allyl ester, diallyl phthalate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, and mixtures thereof.

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 0 671 434 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.

The DE 691 13 841 T2 discloses the provision of a masterbatch containing polyamide and conjugated diolefin polymer.

The CH 663 621 A5 discloses a silane-containing masterbatch.

The GB 1 463 900 discloses a photosensitive polyamide composition for the production of printing plates.

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.

These Task is solved by a migration-stable masterbatch according to claim 1.

preferred Further developments of the masterbatch according to the invention are in the dependent claims 2 to 4 indicated.

Under the term "masterbatch" in the sense The invention is a plastic additive to understand, which in particular as granules to be crosslinked crude polymer and / or monomers of which 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.

The Masterbatch is available as granules.

Under the term "end polymer" in the sense The invention relates to polymers comprising the masterbatch according to 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" in the sense the invention is to be understood as a composition comprising crosslinkable polymers, Oligomeric 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 to be extremely advantageous that in the production of moldings in extrusion ren a mass comprising the masterbatch according to the invention and a raw polymer, there is no smearing effects and the mass has an excellent behavior in the material supply to the processing 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.

The crosslinkable bifunctional and / or polyfunctional monomers are β-, γ- and / or electron radiation crosslinkable.

The crosslinkable bifunctional and / or polyfunctional monomers are selected from the group consisting of cyanuric triallyl ester (TAC), isocyanuric triallyl ester (TAIC), isocyanuric tri-methylallylester (TMAIC), trimellitic allylester (TAM), diallyl phthalate (DAP), trimethylolpropane triacrylate (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 20 to 30% by weight and 80 to 70% by weight Masterbatchpolymer, whereby the indication Gew .-% on the total quantity bi- and / or polyfunctionally crosslinkable monomers and masterbatch polymers in the migration stable masterbatch relates.

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.

The Migration-stable masterbatch contains polyamides (PA), where it PA 6, PA 6.6, PA 6.9, PA 6.10, PA 6.12, PA 10.10, PA 11 and / or PA 12 is.

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 and / or 6.6 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 grafted onto the rubber base. Especially preferred Grafting monomers are mixtures of methyl acrylate and n-butyl acrylate in quantity 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 z. In "Methods of Organic Chemistry" (Houben-Weyl), Vol. 14/1, Georg Thieme Verlag, Stuttgart 1961, pp. 383 to 406 and in "Ullmanns Encyclopadie der technischen Chemie", 4th Edition, Vol. 19 , Verlag Chemie, Weinheim 1981, pp. 279-284.

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 are elastomeric components such as acrylic acid derivatives with epoxy groups ent holding monomers 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 described. 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 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. The radiation crosslinking is effected by β, γ and / or electron radiation. For example the radiation is generated by an electron accelerator. Preferably, the bifunctional and / or polyfunctional crosslinkable Monomer from the masterbatch by heating, preferably melting of the masterbatch polymer, homogeneously mixed.

at an embodiment The crude polymers further include fillers and / or reinforcing agents. Preferably For example, the raw polymers include fillers and / or reinforcing materials in amounts of 3 to 60 wt .-% based on the amount of the crude polymer. The filling and / or reinforcing materials can also added directly to the final polymer and / or the masterbatch polymer become.

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 has surprisingly been found that with the migration-stable masterbatch according to the invention excellent processing with the crude polymers selected from the group consisting 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. In particular, it was surprising that, by using the migration-stable masterbatch according to the invention, crude polymers from the group of olefins, preferably polyethylene and / or polypropylene, with and without fillers can be processed in an outstanding manner in a dry mixture to give radiation-crosslinked parts with all advantages. Likewise, it was also surprising that by using the masterbatch according to the invention further raw polymers from the group of methyl methacrylates, ethylmethyl acrylates and / or their metal salts with and without fillers in an excellent manner in a dry blend to radiation-crosslinking parts, profiles and / or films with all advantages.

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 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 chemical resistance, insolubility in conventional solvents, improvement of the abrasion behavior, improvement of the mechanical and electrical properties and of the aging behavior.

The Migration-stable masterbatch is a granulate. The granules point preferably a granule size of 0.1 mm. to 10 mm, more preferably from 1 to 4 mm.

Based on the final polymer, the proportions of migration-stable masterbatch and crude polymer are 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.

The Task is further solved by a method according to claim 5 for the preparation of the masterbatch.

preferred Further developments of the method according to the invention for the preparation of the masterbatch are given in the subclaims 6 to 8.

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 masterbatch of the invention may be used in a process for the preparation of the final polymers, the process comprising the steps of:

• (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.

Basically, as Raw polymers are used with all types of polymers the components of the masterbatch polymer are compatible. To the tolerable Include crude polymers preferably polymers which have a degree of crosslinking with the masterbatch more than 70%, preferably more than 90%, more preferably reach more than 95% of the potential crosslinks.

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 a process variant in step (a) 1 to 50 wt .-%, preferably 10 to 40 wt .-% masterbatch based on the total Final polymer added.

The Masterbatch can be used in the production of molded parts. The moldings can, for example Have thermoset properties. The molding can, for example by extrusion, injection molding, Blowing or deep drawing are formed and then preferably crosslinked by rays.

figure

1 shows a thermo-mechanical crosslinking knife

The The following examples are intended to illustrate but not limit the invention.

Description of the thermomechanical crosslinking 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 crosslinking tester:

The PTS crosslinking tester available from the company Plastic Technology Service (Hautschenmühle, Germany) consists of
1 PTS networking tester × 30.00
1 prism support × 10.10
1 Digital Microprocessor Controlled × 30.20
Soldering station ERSA DIGITAL 2000A
incl. manual of ERSA
1 support table for test samples × 10.11
Diameter 63 mm
1 standard probe 2 mm × 10.02
1 additional weight 1 kg × 10.12
Diameter 80 mm

Equipment:

• 1 probe 1 mm × 10.01
• 1 probe 3 mm × 10.03
• 1 probe 4 mm × 10.04
• 1 probe 6 mm × 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 z. B. of polyamide

exam 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).

exam rigid materials z. B. PA / GM:

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

execution The examination:

turn on a device and wait about 1 minute for the probe to warm is completed. Too early Placing the probe otherwise you 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 of masterbatch)

A polyamide 6 having a relative viscosity (η _rel ) of 2.7 is melt extruded with 25% by weight 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 molded parts 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 were compounded through. The mixture is poured over an injection molding machine injection molded into moldings or in an extruder to hoses or Profiles processed. In a further step, the moldings in an irradiation chamber with β-rays irradiated with 100 kGy. With a thermomechanical crosslinking tester The crosslinked moldings are tested for the degree of crosslinking (Penetration Test). 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 / W65PA 6 based on the total amount of polyamide 6.6 and BETALINK mixed. BETALINK IC / W65PA 6 consists of 35% by weight of PA 6-support and 65% by weight TAIC based on the total weight of the mixture, wherein BETALINK IC / W65PA 6 is not compounded (ie not dissolved), but the TAIC is blown warm on the microporous PA 6 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 3.75 wt .-%. TAIC are detected, which corresponds to an amount of almost 100%. In the finished injection molded parts from Example 7a only 1.6 wt .-% TAIC could be detected, ie more than half TAIC is lost. After irradiation with 100 gGy (electron beam) was only achieved a gel value of 39%, which is not sufficient for most applications. In the finished injection molded parts from example 7b, only 2.3% by weight of TAIC could be detected, ie significant amounts of TAIC are still lost. After irradiation with 100 gGy (electron beam), only a gel value of 48% was achieved, which is insufficient for most applications.

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 example Master batch Ex. Polymer / irradiation dose Masterbatch / polymer injection molding machine (wt .-%) Gel weight% Result under test conditions 350 ° C / 2 mm / 1 kg load / 20 sec. 2 1 PA 6/100 kGy 0/100 0 complete penetration 3 1 PA 6/100 kGy 15/85 70 no intrusion measurable 4 1 PA 6, 30% fiberglass / 100 kGy 0/100 0 complete penetration 5 1 PA 6, 30% fiberglass / 100 kGy 13/87 71 no intrusion measurable 6 1 PA 6.6 / 100 kGy 0/100 0 complete penetration 7 1 PA 6.6 / 100 kGy 15/85 72 no intrusion measurable Comp. 7a 7a PA 6.6 / 100 kGy 5.4 / 94.5 39 1 mm penetration depth Comp. 7b 7b PA 6.6 / 100 kGy 5.8 / 91.2 48 1 mm penetration depth 8th 1 PA 6.6, 35% fiberglass / 100 kGy 0/100 0 complete penetration 9 1 PA 6.6, 35% fiberglass / 100 kGy 13/87 78 no intrusion measurable 10 1 PA 6.9 / 100 kGy 0/100 0 complete penetration 11 1 PA 6.9 / 100 kGy 15/85 68 no intrusion measurable 12 1 PA 6.12 / 66 kGy 0/100 0 complete penetration 13 1 PA 6.12 / 66 kGy 15/85 75 no intrusion measurable

• PA = polyamide

Example 14

A polyamide 12 is extruded in the melt at 220 ° C. with 25% by weight of triallyl isocyanurate (TAIC) in a twin-screw extruder. The homogeneous, molten extrudate is withdrawn as a strand through a water bath and comminuted in a granulator and dried at 80 ° C. In other examples, this masterbatch is mixed with various polyamides and injected into shaped parts via an injection molding machine cast or processed in an extruder into hoses or profiles. In a further step, the moldings are irradiated in an irradiation 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 mixed with various polyamides and injection molded via an injection molding machine into moldings 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 example Masterbatch Example Nr. Polymer / irradiation _dose Masterbatch / polymer injection molding machine (% by weight) _Gel weight% Result under test conditions 350 ° C / 2 mm / 1 kg load / 20 sec. 15 fourteen PA 12/66 kGy 0/100 0 complete penetration 16 fourteen PA 12/66 kGy 15/85 75 no intrusion measurable 17 fourteen PA 12, 30% fiberglass / 66 kGy 0/100 0 complete penetration 18 fourteen PA 12, 30% fiberglass / 66 kGy 15/85 80 no intrusion measurable 19 fourteen PA 11/66 kG 0/100 0 complete penetration 20 fourteen PA 11/66 kGy 18/82 85 no intrusion measurable 21 fourteen PA 11, 30% carbon fiber 66 kGy 0/100 0 complete penetration 22 fourteen PA 11, 30% carbon fiber 66 kGy 18/82 87 no intrusion measurable

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

Non-inventive 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.

Noninventive 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. 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 3 example Masterbatch Example Nr. Polymer / irradiation _dose Masterbatch / polymer injection molding machine (% by weight) _Gel weight% Result under test conditions 350 ° C / 2 mm / 1 kg load / 20 sec. 24 23 PA 12/66 kGy 0/100 0 complete penetration 25 23 PA 12/66 kGy 15/85 75 no intrusion measurable 26 23 PA 12, 30% fiberglass / 66 kGy 0/100 0 complete penetration 27 23 PA 12, 30% fiberglass / 66 kGy 15/85 80 no intrusion measurable 28 23 PA 11/66 kGy 0/100 0 complete penetration 29 23 PA 11/66 kGy 18/82 78 no intrusion measurable 30 23 TPU 150 kG 0/100 0 complete penetration 31 23 TPU / 150 kGy 22/78 65 no intrusion measurable

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

Non-inventive 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.

Noninventive Example 33-44

• PA = 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 thermo-mechanical cross-linking tester, the cross-linked molded parts are tested for the degree of cross-linking. Table 4 example Masterbatch Example Nr. Polymer / irradiation _dose Masterbatch / polymer injection molding machine (% by weight) _Gel weight% Result under test conditions 350 ° C / 2 mm / 1 kg load / 20 sec. 33 32 PA 6, 30% fiberglass / 150 kGy 15/85 78 no intrusion measurable 34 23 PA 6.6, 30% glass fiber / 150 kGy 20/80 78 no intrusion measurable 35 32 PA 6/150 kGy 18/82 70 no intrusion measurable 36 32 PA 6, 30% mineral 150 kGy 20/80 72 no intrusion measurable 37 32 PBT / 150 kGy 0/100 a) complete penetration 38 32 PBT / 150 kGy 22/78 a) no intrusion measurable 39 32 PBT, 20% boron nitride / 150 kGy 20/80 a) no intrusion measurable 40 32 PBT, 30% glass fiber / 150 kGy 15/85 a) no intrusion measurable 41 32 PA 6.6, 30% carbon fiber / 120 kGy 20/80 76 no intrusion measurable 42 32 PA 11/66 kGy 18/82 80 no intrusion measurable 43 32 PET / 150 kGy 0/100 a) complete penetration 44 32 PET / 150 kGy 22/78 a) no intrusion measurable

• PA = 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 reacted with 25% by weight of trimethylpropane triallyl acrylate (TMPTA) extruded in a single-screw extruder in the melt at 180 ° C. The homogeneous, molten one 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 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 example Masterbatch Example Nr. Polymer / irradiation _dose Masterbatch / polymer injection molding machine (% by weight) _Gel weight% Result under test conditions 350 ° C / 2 mm / 1 kg load / 20 sec. Penetration depth in [mm] 46 47 HDPE, MFI 5 * / 100 kGy 0/100 55 0.05 47 47 HDPE, MFI 5 * / 100 kGy 15/85 70 0.02 48 47 LDPE, MFI 4.5 * / 100 kGy 0/100 57 0.06 49 47 LDPE, MFI 4.5 * / 100 kGy 15/85 73 0.04 50 47 Homo PP, MFI 15 ** / 20 kGy 0/100 0 2 complete penetration 51 47 Homo PP, MFI 15 ** / 20 kGy 18/82 70 0.04 52 47 Homo PP, MFI 15 **, 40% talc / 20 kGy 0/100 0 2 complete penetration 53 47 Homo PP, MFI 15 **, 40% talc / 20 kGy 22/78 75 0.02

• 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 (9)

Migration stable masterbatch, comprising 15 up to 45% by weight of bi- and / or polyfunctionally crosslinkable monomers; and 55 to 85% by weight of masterbatch polymer selected from PA 6, PA 6.6, PA 6.9, PA 6.10, PA 6.12, PA 10.10, PA 11 and / or PA 12, where the indication wt .-% on the total amount of bi- and / or polyfunctionally crosslinkable monomers and the masterbatch polymers in the migration stable masterbatch, and wherein the masterbatch is a granulate, being the bifunctional and / or polyfunctional crosslinkable monomers with electron beams, β- or γ-radiation crosslinkable monomers are and from the group, consisting of cyanuric triallyl ester, Isocyanursäuretriallylester, Isocyanursäuretrimethylallylester, Trimellithsäureallylester, diallyl phthalate, Trimethylolpropane triacrylate, trimethylolpropane trimethacrylate and mixtures thereof, selected become. A migration stable masterbatch according to claim 1, further comprising colorants, Stabilizers, plasticizers, flame retardants or mixtures from that. Migration-stable masterbatch according to one of the preceding Claims, further comprising talc, mineral, glass fibers, carbon fiber, aramid fiber, Boron nitride, aluminum nitride, metal powder, nanotubes and Leitruße or Mixtures thereof. Migration-stable masterbatch according to one of the preceding Claims, wherein the migration stable masterbatch has a granule size of 0.1 mm to 10 mm. Process for the preparation of a migration stable Masterbatch according to one of the claims 1 to 4, comprising the steps: (a) melting a masterbatch polymer, selected from PA 6, PA 6.6, PA 6.9, PA 6.10, PA 6.12, PA 10.10, PA 11 and / or PA 12; (B) introduction of bi- and / or polyfunctional crosslinkable Monomers in the melt of the masterbatch polymer of step (a), wherein the bifunctional and / or polyfunctional crosslinkable monomers with electron beams, β- or γ-radiation are crosslinkable monomers and from the group, consisting of triallyl cyanurate, Isocyanursäuretriallylester, Isocyanursäuretrimethylallylester, Trimellithsäureallylester, diallyl phthalate, Trimethylolpropane triacrylate, trimethylolpropane trimethacrylate and mixtures thereof, selected become; (c) mixing the mass from step (b) and providing a mixture of 15 to 45 wt .-% bi- and / or polyfunctional crosslinkable monomers; and 55 to 85% by weight of masterbatch polymer, in which the indication wt .-% on 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) granulating the mixture from step (d). Process for the preparation of migration stable Masterbatches according to claim 5, further comprising after step (d) or (e) a drying step. Process for the preparation of migration stable A masterbatch according to claim 5 or 6, wherein in step (a), (b), (c), (d) and / or (e) further additives, in particular colorants, stabilizers, Plasticizers, flame retardants or mixtures thereof added become. Process for the preparation of migration stable Masterbatch according to one of the claims 5 to 7, wherein in step (a), (b), (c), (d) and / or (e) further Talc, mineral, glass fibers, carbon fibers, aramid fibers, boron nitride, Aluminum nitride, metal powder, nanotubes and conductive carbon black or Mixtures of which are added. Use of a masterbatch according to one of claims 1 to 4 and networkable Raw polymers for the preparation of a dry blend.

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