DE102009028200A1 - Use of amorphous polyolefin to produce foam, where used polyolefin exhibits three of following conditions specified range of melting enthalpy, softening point, needle penetration, tensile strength and glass transition temperature - Google Patents

Abstract

The present invention relates to the use of amorphous polyolefins for the production of foams, corresponding foams and their use.

Description

The The present invention relates to the use of amorphous polyolefins for the production of foams, corresponding foams as well as their use.

polyolefin have opened up a wide range of applications. Especially win in comparison with other foamed plastics the polyolefins are becoming increasingly important. Most polyolefin foams today are made of low density polyethylene (LDPE), copolymers like Polyethylene-co-vinyl acetate) (EVA), high density polyethylene (HDPE), Linear Low Density Polyethylene (LLDPE), as well as isotactic polypropylene (iPP).

In EP 0 928 805 For example, a process for making foam parts from high melt strength propylene polymer materials is claimed. C ₂ -C ₃ -C ₄ terpolymers having very high propene contents of 85-96 m% and very low ethene contents of 1.5-5 m% and 1-butene contents of 2.5-10 m% and Polyolefin compositions of propene-rich copolymers and terpolymers used. The polymer materials are irradiated and then extruded together with a physical expander. Particularly emphasized are the better low-temperature strength and the higher flexibility compared to polyethylene-based systems. Compared to foams which are based on pure PP, the improved low-temperature resistance is emphasized above all. However, the polymers mentioned have poor low-temperature properties, in particular relatively high glass transition temperatures and poor low-temperature flexibilities.

In WO 00/15697 thermoplastic polymer foams are claimed which are said to have so-called. klangabtötende properties, a certain mechanical strength, economic manufacturability and hydrolytic stability. This is achieved essentially by thermoplastic polymer foams with average cell sizes ≥ 2 mm, of substantially open-cell structure, and by a mechanical perforation-enabled pore connection between the cells. In particular, polystyrene and polyolefin resins are mentioned as thermoplastic resins, including ethylene-styrene copolymer resins, their mixtures with polyethylene, polypropylene and / or polyethylene copolymer resins. Accordingly, particularly effective are mixtures of low-density polyethylene and so-called.

interpolymers consisting of olefins and aromat. Vinyl or vinylidene compounds. By focusing on these interpolymers but before claimed recyclability due to lack of variety purity of Monomers (mixture of aliphatic and aromatic monomers) abandoned again. In addition, the described necessary mechanical Perforation extremely complex and in their feasibility on foams of very limited Geometries (in particular thicknesses) and certain manufacturing methods limited.

In EP 0 761 750 are described low density plastic products, in particular pipes or pipe sections for the sanitary sector, which are obtained by crosslinking and foaming thermoplastic polymers. The thermoplastic polymers listed here are composed of polyethylene, isotactic polypropylene, poly (ethylene-co-vinyl acetate), polystyrene and acrylonitrile-butadiene-styrene polymers. The polymers mentioned exhibit poor low-temperature properties and / or lack of elasticity or flexibility.

In US 5,585,411 polymer foams are described which consist essentially of poly (1-butene), polybutylene, styrene block or styrene star polymers and or an olefinic rubber and a non-elastomeric polyolefin such. As low density polyethylene (LDPE) put together. The poly (1-butene) homo- or copolymer used can be isotactic, syndiotactic or elastomeric. The use of styrene block and / or star polymers causes a significant cost penalty of the specified mixture. According to their stated composition, the materials listed have a significant disadvantage in terms of their flexibility.

In EP 0 526 872 describes a process for the preparation of open-cell crosslinked polyolefin foams. The expansion of the foam is done using microwave radiation. As polyolefin resins are mentioned those which have a certain proportion of low density polyethylene. In order to ensure sufficient extensibility of the polyolefin material for foam production, plasticizers are used. According to their stated composition, the materials have a significant disadvantage in terms of their flexibility. The use of plasticizers (especially the phthalates mentioned) is of concern for ecological, but especially toxicological reasons and limits the range of application of the foams considerably.

In WO 92/16363 describes non-crosslinked polyolefin foams based on polyethylene or polypropylene for processing in sleeves and profiles. Preference is given to using low-density polyethylene and / or low molecular weight (LDPE / ULMWPE) as well as polyethylene polymers containing polar groups. According to their stated composition, the materials have a significant disadvantage in terms of their flexibility. The use of amino acids and / or ionomers leads to poor thermal stability of the products and a bad color.

In EP 0 019 021 polyolefin foams are described which contain one or more amino acids as nucleating agent. In particular, polyethylene polymers (HDPE, LDPE) and polypropylene polymers and so-called ionomers are mentioned as polyolefins. According to their stated composition, the materials have a significant disadvantage in terms of their flexibility. The use of amino acids and / or ionomers leads to a poor thermal stability and / or a poor color of the products, which significantly limits their field of application.

In GB 1595106 Essentially, closed-cell, foamed plastic films are described which preferably consist of a mixture of 90.5-95% LDPE and 9.5-5% HDPE. The mixture component is also called an ionomer. In order to improve the adhesion of the film, a (two-sided) corona treatment of the foamed films is proposed. According to their stated composition, the materials have a significant disadvantage in terms of their flexibility. The use of ionomers leads to poor thermal stability of the products and a bad color. The proposed corona treatment represents an additional expense that increases the cost of production.

In US 4,191,719 Foamed moldings are described from an orientable thermoplastic composition and an additive, wherein the additive from the group of Metallresinate and / or the (modified) rosin ester is selected. As thermoplastic materials, crystalline ethene or propene polymers are mentioned. According to their stated composition, the materials have a significant disadvantage in terms of their flexibility.

In US 4,020,025 describes foamable polymer compositions containing a polyolefin, a styrene polymer and a hydrogenated styrene-butadiene block copolymer. Polyolefins are polyethylene and ethylene copolymers having densities from 0.918 to 0.965 g / cm ³ . According to their stated composition, the materials have a significant disadvantage in terms of their flexibility.

EP 0 910 605 describes foamable crosslinkable compositions comprising a blend of polypropylene with a silane-grafted substantially linear polyolefin.

The foams or processes known from the prior art for their production have a number of disadvantages. Thus, many of the polymers used, for. As polyethylene low density (LDPE) and polystyrene (PS), not over 100 ° C, since they are at these temperatures melt or lack sufficient strength feature. Furthermore, polypropylene and poly (1-butene) alone no uniform foam structure with sufficient flexibility form. Especially in the field of low-temperature flexibility Many of the polymers mentioned have deficiencies by relatively high glass transition temperatures. Most The polymers mentioned have only a low adhesion, so that an additional expensive treatment (eg Corona) becomes necessary for the assembly of the foams. Continue to point many of the mentioned materials have a poor miscibility with the in all cases used polyolefin polymers. This leads to poor mechanical material properties in the foams. Finally, many lead the additives used (eg, amino acids, metal sensitates etc.) to an undesirable color or low thermal stability the foams.

task The present invention accordingly provides the device of polymer foams, which are the disadvantages of The prior art systems do not have and simple to be processed.

Surprisingly has been found that amorphous polyolefins with special Properties particularly suitable for the production of polymer foams are.

• – eine durch Differentialkalorimetrie in der zweiten Aufheizung bestimmte Schmelzenthalpie von mindestens 1 J/g und maximal 50 J/g,
• – einen Erweichungspunkt bestimmt durch Ring & Kugel-Methode von mindestens 60°C und maximal 170°C,
• – eine Nadelpenetration von mindestens 1·0,1 mm und maximal 70·0,1 mm,
• – eine Zugfestigkeit von mindestens 0,1 MPa und maximal 30 MPa,
• – eine durch Differentialkalorimetrie in der zweiten Aufheizung bestimmte Glasübergangstemperatur von maximal –8°C.

Accordingly, a first aspect of the present invention is the use of one or more amorphous polyolefins for producing foams, wherein at least one of the amorphous polyolefins used has at least three, preferably all, of the following material properties:

• A melting enthalpy of at least determined by differential calorimetry in the second heating at least 1 J / g and a maximum of 50 J / g,
• A softening point determined by ring & ball method of at least 60 ° C and at most 170 ° C,
• A needle penetration of at least 1 x 0.1 mm and a maximum of 70 x 0.1 mm,
• A tensile strength of at least 0.1 MPa and a maximum of 30 MPa,
• A maximum glass transition temperature of -8 ° C determined by differential scanning calorimetry in the second heating.

The Use of the specially selected polyolefins for the preparation of foams is so far unknown.

According to the present invention, the polyolefins may be used alone or used in combination with one or more other polymers become. The production of polymer foams can therefore either under exclusive use of the largely amorphous polyolefins or using polymer blends with the invention used amorphous polyolefins. For mixtures lies the proportion of largely amorphous polyolefin at 5-100 ma-%, preferably at least 10 m%, more preferably at at least 20mA%, and more preferably at more than 25mA%. For the production of polymer foams with very good adhesion to untreated polyolefin surfaces in particular mixtures with a proportion of min. 50 ma-% largely amorphous polyolefin are preferred, mixtures are particularly preferred with a share of at least 70 ma-%, most preferred is the exclusive use of largely amorphous polyolefins in the polymer portion.

mixtures, at least 50% by mass of at least one amorphous polyolefin have the advantage that their physical properties - in particular the adhesion properties - essentially of the invention amorphous polyolefins are dominated and such mixtures with can be produced very little effort.

on the other hand are in mixtures with a proportion of amorphous polyolefins of less than 50 ma-% of the material properties, in particular the Material cohesion in a much larger Dimensions variable, so that even such mixtures advantageous can be. For mixtures with a proportion of inventive amorphous polyolefin of <5 ma-% is no longer a positive influence of the amorphous polyolefin detect.

Become in the foams exclusively largely amorphous Used polyolefins, so either a single amorphous Polyolefin, or a mixture of several amorphous polyolefins be used.

At least one of the amorphous polyolefins used is not more than 25% by mass, preferably 0.1 to 20% by mass, more preferably 1-16% by mass Ethene, at most 98% by mass, preferably 0.1-90% by mass, especially preferably 1 to 80% by mass, and particularly preferably 4 to 70% by mass Propene and / or at most 100% by mass, preferably 5-100% by mass, more preferably 10-95mA% and especially preferred 15 to 90 ma-% of an α-olefin having 4 to 20 carbon atoms.

Especially At least one of the amorphous polyolefins used is selected poly (1-butene) homopolymer, poly (ethylene-co-propylene) copolymers with a maximum of 25 m% ethylene content, polyethylene-co-1-butene) copolymers with a maximum of 20% by mass of ethylene, poly (propylene-co-1-butene) copolymers, or Polyethylene-co-propylene-co-perylene) terpolymers with a maximum of 20 ma-% Ethylene content and a propylene content of 20-98 m%.

In a particular preferred embodiment is at least one of the amorphous polyolefins used a polyethylene-co-propylene-co-1-butene) terpolymer having a Ethylene content of 1 to 15 m%, preferably 2 to 12 m%, a Propylene content of 50 to 78 m%, preferably of 52 to 75 m% and a 1-butene content of 15 to 46 m%, preferably from 18 to 42% by mass.

In another particular preferred embodiment it is at least one of the amorphous polyolefins used a poly (ethylene-co-propylene-co-1-butene) terpolymer having an ethylene content from 1 to 10mA%, preferably 2 to 8mA%, of a propylene content from 15 to 46mA%, preferably from 18 to 42mA% and a 1-butene content from 50 to 78mA%, preferably from 55 to 75mA%.

In a further particular preferred embodiment, at least one of used amorphous polyolefins to a poly (1-butene) copolymer having a content of 1-butene of at least 85% by mass, preferably of at least 87% by mass, more preferably of at least 90% by mass and most preferably of at least 92 ma -%.

The by means of DSC in the 2nd heating certain melting enthalpy of Amorphous polyolefins used in the invention is between 1 and 50 J / g, preferably between 2 and 40 J / g, especially preferably between 3 and 35 J / g, and more preferably between 4 and 30 J / g, with further preferred ranges between 4 and 15 J / g, between 12 and 25 y / g, between 18 and 28 y / g and between 22 and 30 y / g lie. The DSC thermogram shows the 2nd heating at least one melting peak, preferably at least 2 and especially preferably 2 to 4 melting peaks, of which at least one peak maximum at a temperature of at least 20 ° C and a maximum of 100 ° C having.

Of the using ring & ball method determined softening point of the inventively used (unfoamed) Polyolefins is 60 to 170 ° C, preferably 70 to 155 ° C, more preferably 80 to 150 ° C and more preferably 85 to 148 ° C with further preferred ranges between 80 and 120 ° C, between 95 and 130 ° C and between 120 and 145 ° C lie. For applications, in which the polymer foam applied to temperature-sensitive substrates is to be, in particular the use of inventive amorphous polyolefins having a softening point of <120 ° C, in particular of <100 ° C exhibit. A special feature of the invention amorphous polyolefins it is that they with appropriate handling -. B. by Schneckenmaschinen- also below the softening point can still be processed molten. Softening points are only possible according to the "Ring & Ball Method" used in the present case then by definition determine if the influence the melt viscosity on the measured values is low. in the Case of the present invention is this requirement for Viscosity values (measured at 190 ° C) up to approx. 600,000 mPa · s given. For amorphous according to the invention Polyolefins having a melt viscosity of> 600,000 mPa · s Therefore, no softening points are determined or indicated.

The Needle penetration of the unfoamed polyolefins is 1-70 x 0.1 mm, preferably 4-60 x 0.1 mm, more preferably 8-50 x 0.1 mm and in particular preferably 10 to 45 x 0.1 mm, with further preferred ranges between 12 and 25 x 0.1 mm and between 20 and 35 x 0.1 mm lie. Amorphous polyolefins according to the invention, a lower needle penetration, in particular <15 · 0.1 mm, are particularly advantageous for polymer foams can be used, which has a slightly lower flexibility at the same time should have higher mechanical stability. Amorphous polyolefins of the invention containing a higher needle penetration, in particular of> 20 · 0.1 mm have, however, can be very advantageous for the production use of polymer foams with high flexibility, the latter additionally being a substantially closed one Have cell structure.

The Tensile strength of the invention used Polyolefins in the unfoamed state is 0.1 to 30 MPa, preferably 0.5 to 25 MPa, more preferably 1 to 22 MPa, and more preferably 2 to 20 MPa, with further preferred ranges between 4 and 12 MPa and between 10 and 18 MPa. Show the polyolefins of the invention having melt viscosities of <100,000 mPa · s (at 190 ° C), a tensile strength of not more than 15 MPa, preferably not more than 12 MPa, more preferably not more than 10 MPa. In a particular embodiment, in particular when a good balance between mechanical strength and flexibility the polymer foams is required, those for the production the polymer foams used according to the invention amorphous Polyolefins have a melt viscosity of <80,000 mPa · s (at 190 ° C) on, with their tensile strength at a maximum of 8 MPa, preferably at maximum 6 MPa, and more preferably between 2 and 5.5 MPa.

Furthermore, the polyolefins used according to the invention have a glass transition temperature of from -8 to -80 ° C., preferably from -10 to -65 ° C., particularly preferably from -12 to -55 ° C. and especially preferably -14, determined by differential calorimetry in the second heating to -48 ° C. In particular, amorphous polyolefins having a low glass transition temperature and used according to the invention have excellent low-temperature flexibility and are particularly suitable for insulating layers which are applied together with geomembranes or as part of a geomembrane. In a particular, preferred embodiment, in particular when polymer foams are to be produced which, in addition to high low-temperature flexibility, also have high mechanical strength and a rather low-volume cell structure, the amorphous polyolefins according to the invention used for producing the polymer foams contain a proportion of 1-butene of at least 50 ma-%, preferably at least 55mA%, more preferably at least 60mA% and more preferably more than 65mA% and have a glass transition temperature of <-35 ° C, preferably of <-38 ° C, more preferably of <-40 ° C and especially before zugt of <-42 ° C on.

The determined by Oszillationsrheometrie melt viscosity the unfoamed amorphous polyolefins is at 190 ° C 1,000-5,000,000 mPa · s, preferably 3,000 to 3,000,000 mPa · s, more preferably 5,000 to 2,000,000 mPa · s and in particular 7,500 to 1,500,000 mPa · s with further preferred ranges between 7,000 and 55,000 MPa · s, between 20,000 and 40,000 mPa · s, between 50,000 and 150,000 mPa · s, between 80,000 and 250,000 mPa · s, between 200,000 and 600,000 mPa · s and between 500,000 and 1,500,000 MPa · s lie. Special advantage of inventive amorphous polyolefins of low melt viscosity (<100,000 mPa · s at 190 ° C) is good flowability their polymer melts and the compositions containing them or formulations, as well as the proportionate simple expansion of the polymer melts by chemical and / or physical blowing agents. Amorphous according to the invention Polyolefins of low melt viscosity are particularly suitable for the production of foams a high Share of open cell structures. Another advantage of foams using the invention amorphous polyolefins (i.e., their polymer content wholly or partly from the invention amorphous polyolefins) is the specifically adjustable adhesion and / or surface tack that provides good adhesion the foams on numerous natural and / or synthetic materials, in particular wood, paper, polymer and plastic surfaces causes.

special Advantage of amorphous polyolefins according to the invention with high melt viscosity (> 100,000 mPa · s at 190 ° C) however, is the high stability of these polymers Polymer foams especially during the cooling process. Amorphous polyolefins of high melt viscosity according to the invention are particularly suitable for the production of foams which have a high proportion of closed cell structures. Another advantage of using inventive is high-viscosity amorphous polyolefins produced foams their high mechanical stability in both tensile and at pressure load.

In a further preferred particular embodiment, in particular when polymer foams with good plastic deformability and outstanding low-temperature flexibility and rather large-volume cell structure are to be produced, the amorphous polyolefins according to the invention used for producing the polymer foams contain a proportion of C ₄ -C ₁₀ α-olefins, particularly preferably 1 -Hexene and / or 1-octene of at least 20mA%, preferably of at least 25mA%, more preferably of at least 28mA% and more preferably of more than 30mA% and have a glass transition temperature of <-40 ° C, preferably of <-42 ° C, more preferably of <-45 ° C and particularly preferably of <-48 ° C on.

The Elongation at break of the invention used Polyolefins in the unfoamed state is 1 to 5,000%, preferably 10-4,000%, particularly preferably 50 to 3,500%, and more preferably 100 to 2,500%, with others Preferential ranges between 100 and 500%, between 250 and 750%, between 500 and 1250% and between 700 and 1500%. In a special, preferred embodiment, the inventive amorphous polyolefins in the unfoamed state a tensile strength of at least 2 MPa and a maximum of 18 MPa, with simultaneous the elongation at break also in the unfoamed state at more than 500%, preferably at more than 600%, more preferably more than 650%, and more preferably between 700 and 1500% lies.

The processes for preparing the amorphous polyolefins require the use of homogeneous or heterogeneous polymerization catalysts. As possible catalysts for the preparation of the polyolefins used in the present invention, metallocene catalysts (eg, zirconocene catalysts, lanthanocene catalysts, etc.), Cr catalysts, V catalysts, Ti catalysts, etc. can be used. Particularly preferred is the use of titanium-containing Ziegler-Natta catalysts, wherein both supported and unsupported catalyst systems can be used. The amorphous polyolefins are produced, for example, by the following process:
An amorphous polyolefin used according to the invention is obtainable, for example, by polymerization of α-olefin monomers with a TiCl ₃ · (AlCl ₃ ) _n mixed catalyst (n = 0.2 to 0.5), a trialkylaluminum compound (for example triethylaluminum, preferably triisopropylaluminum, particularly preferably triisobutylaluminum) is used as cocatalyst. The molar ratio of catalyst to cocatalyst is preferably between 1: 1 and 1:10. The activity of the catalyst used is preferably between 5,000 and 20,000 g of polymer / g of catalyst. The monomer ethene is used in gaseous form, while the monomers propene and 1-butene can be used both gaseous and liquid. Higher homologs are used liquid. If propene and / or 1-butene are used in liquid form, a pressure corresponding to the reaction conditions must be maintained in the reactor used, which has sufficient monomer concentrations ensured in the liquid phase. The molecular weight regulator used is gaseous hydrogen. The polymerization is carried out in an inert solvent, which z. B. is selected from the group of aliphatic hydrocarbons. The mass ratio of polymer to solvent in the stationary reaction state of the polymerization is between 1: 100 and 1: 0.01, preferably between 1:50 and 1: 0.1 and more preferably between 1:10 and 1: 0.2. In a specific embodiment, it is between 1: 1 and 1: 0.01. Polymerization in the monomer introduced is also possible, in which case the mass ratio of polymer to solvent is preferably between 1: 2 and 1: 0.75. The polymerization is carried out either in a stirred tank or in a stirred tank cascade; In a particular embodiment, a flow tube or a tubular reactor with forced delivery (eg a screw machine) can also be used. The use of the tubular reactor with forced delivery can be done either as a sole solution or in combination with a stirred tank or stirred tank cascade. Here, both a series and a parallel connection of the individual reactors are possible. The reaction temperature is between 30 and 200 ° C, preferably between 70 and 150 ° C and more preferably between 80 and 130 ° C.

catalyst and cocatalyst become suitable at the end of the reaction decomposed, wherein the decomposed catalyst components either remain in the polymer or via a washing step be removed. The polymer is characterized by in unreactive Ingredients transferred decomposed catalyst components not in the manufacturing process according to the invention inked. The polymers of the invention can be in the state of the art either in shape their reaction solution or at a later date chemically stabilized to protect it from the harmful Influence of higher temperatures, solar radiation, Humidity and oxygen to protect. It can for example stabilizers, the hindered amines (HALS stabilizers), hindered phenols, phosphites, UV absorbers such. B. hydroxybenzophenones, Contain hydroxyphenylbenzotriazoles and / or aromatic amines, be used. The effective amount of stabilizers is thereby normally in the range of 0.1 to 2% by weight, based on the polymer.

The Polymerization can be either batch, continuous or semi-continuous be carried out, particularly preferred is a continuous Method. To control the molecular weight, if desired, according to the prior art in the presence of hydrogen or another suitable regulator.

The Surface tack of the foams produced can be about the polymers used or the Targeted adjustment of polymer composition. For foams with low surface tackiness are particularly suitable Mixtures of largely amorphous polyolefins with isotactic Polypropylene or atactic polypropylene, by metallocene catalysis was produced. As amorphous polyolefin are preferred 1-butene homo- or copolymers with small amounts of ethene or propene for use.

For Foams with high surface tack are suitable particularly propylene- or butene-rich terpolymers having an ethene content from 1 to 25mA%, preferably 2 to 24mA%, especially preferably 4-23% by mass, and particularly preferably 5-22 % by mass. The highest surface tackiness will be achieved with amorphous polyolefins, those with supported Ziegler-Natta catalysts without the addition of tactic controllers (such as external donors). Good results one achieves here also by admixture of metallocene-based amorphous propene-1-butene copolymer.

In In a particular embodiment, mixtures of hard (i.e., needle penetration <10 x 0.1 mm) and soft (i.e., needle penetration> 20 x 0.1 mm) amorphous polyolefins used for a special ratio of strength and adjust elasticity. Preferably, the contain Mixtures 50-80% hard and 20-50% soft amorphous Polyolefins.

Hardness Foams are particularly well based on largely amorphous propene and / or 1-butene homopolymers, or 1-butene or propene-rich copolymers having a comonomer content of <30 m%, preferably <25 m%, especially preferably <20 m% and particularly preferably <18 m%. Preferably these are poly (ethylene-co-1-butene), polypropylene-co-1-butene), Poly (propylene-co-1hexene) or polypropylene co-1-octene).

switch Foams, on the other hand, are particularly well based on Ethene-propene-1-butene terpolymers obtained.

In a further particular embodiment, a plurality of amorphous polyolefins are distinguished melt viscosity used to obtain foams with the largest possible cell size distribution. Preferably, the melt viscosities (at 190 ° C) of the polyolefins used in this case a difference of at least 50,000 mPa · s, more preferably at least 75,000 mPa · s and particularly preferably of at least 100,000 mPa · s.

In Another particular embodiment is amorphous Polyolefins with different softening temperatures and / or Melting temperatures used to special temperature properties of To achieve foams. In this case, the foaming process also be controlled by the choice of mixing temperature that only one or a part of the mixture used melted another part but remains solid, creating inhomogeneous foam structures are accessible with special properties.

Become Mixtures of amorphous polyolefins with one or more others Polymers used to make the foams can the one or more further polymers may be selected from the group comprising isotactic polypropylene, syndiotactic Polypropylene, atactic polypropylene, high density polyethylene (HDPE), low density branched polyethylene (LDPE), linear low density Polyethylene (LLDPE), Ethylene Vinyl Acetate Copolymer (EVA), Ethylene Propene Rubber (EPR), ethylene-propene-diene-copolymers (EPDM), polybutadiene, polystyrene, syndiotactic polystyrene, acrylonitrile-butadiene-styrene terpolymers (ABS) and styrene-acrylonitrile copolymers (SAN).

In another embodiment of the present invention, the one or more amorphous polyolefins are modified with one or more silanes. Corresponding polyolefins are for example made DE 4000696 and US 5,241,014 known. In these silane-modified polyolefins, one or more silanes are grafted onto the aforesaid one or more amorphous polyolefins. The silane to be grafted preferably has olefinic double bonds and one to three directly connected to the silicon atom alkoxy groups. In particular, the one or more silanes are selected from the group consisting of vinyltrimethoxysilane (VTMO), vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-methacryloxypropyltrimethoxysilane (MEMO; H ₂ C =C (CH ₃ ) COO (CH ₂ ) ₃ -Si (OCH ₃ ) ₃ ), 3-methacryloxypropyltriethoxysilane, vinyldimethylmethoxysilane and / or vinylmethyldibutoxysilane. Most preferably, the silane is vinyltrimethoxysilane. The silane is usually used in the grafting in amounts of 0.1 to 10 wt .-%, preferably 0.5 to 5 wt .-%, based on the amorphous polyolefin. The one or more silanes can be grafted onto the polymer by any of the methods of the prior art, for example in solution or preferably in the melt, using a radical donor in sufficient quantity. A suitable mode of operation can be DE-OS 40 00 695 are taken, to which reference is expressly made. For example, the following radical donors can be used: diacyl peroxides such as. For example, dilauryl peroxide or didecanoyl peroxide, alkyl peresters such as. B. tert-butyl peroxy-2-ethylhexanoate, perketals such. For example, 1,1-di (tert-butylperoxy) -3,3,5-trimethylcyclohexane or 1,1-di (tert-butylperoxy) cyclohexane, dialkyl peroxides such. B. tert-Butylcumylperoxid, di (tert.butyl) peroxide or dicumyl peroxide, C-radical donors such. B. 3,4-dimethyl-3,4-diphenylhexane or 2,3-dimethyl-2,3-diphenylbutane and azo compounds such. B. 2,2'-azo-di (2-acetoxypropane). In a particular, preferred embodiment, the silane modification of the amorphous polyolefins according to the invention and / or the mixtures containing them takes place immediately before foaming (ie no further solidification or formulation takes place between the modification and the foaming). This has the advantage that a particularly homogeneous crosslinking, and thus the generation of a very uniform cell structure, is made possible by the introduced silane groups.

The polymer mixture used according to the invention or the polyolefin used according to the invention, and thus the foam according to the invention, may contain all polymer additives corresponding to the state of the art, which are advantageous for achieving the material properties according to the invention. In particular, stabilizers such. Hindered amines - so-called HALS stabilizers -, hindered phenols, phosphites, UV absorbers (eg, hydroxybenzophenones, hydroxyphenylbenzotriazoles and / or aromatic amines, etc. Furthermore, depending on the desired field of application, the use of lubricants, Halogenated and / or non-halogenated flame retardants are not preferred because of their toxicity, whereas preference is given to non-halogenated flame retardants, such as, for example, BaSO _4. Because of their toxicity, the use of plasticizers, such as, for example, is preferred Phthalates not preferred.

In the foams, the polyolefin used according to the invention or the polymer mixture used according to the invention may contain all fillers corresponding to the prior art. Examples of such fillers are mineral and / or synthetic and / or natural, organic and / or inorganic materials, such as. Calcium oxide, magnesium oxide, calcium carbonate, barium sulfate, silica, phyllosilicate, carbon black, bitumen, wood (eg, pulverized, granules, micro-granules, fibers, etc.), paper, natural and / or synthetic fibers, etc. In addition to the fillers, synthetic or non-synthetic dyes or pigments may be used simultaneously or alternatively, e.g. B. carbon black (black), iron oxide (yellow), effect pigments based on mica or synthetic carriers, etc.

method for producing foams comprising foaming one or more of the above amorphous polyolefins also the subject of the present invention. Especially preferred is a process for producing foams comprising foaming one or more amorphous polyolefins, wherein the processing temperature at least in a partial area the processing machine below the softening point at least one of the amorphous polyolefins used.

The Polymer foams of the present invention may produced by different techniques and procedures. Examples are - without relying on them restrict - semicontinuous and / or continuous Extrusion process, but also batch process. Also the use of discontinuous and continuous process steps during the production is possible. The use of a decomposing Propellant and crosslinking are included in the manufacturing process. The continuous extrusion process is preferred.

In an extrusion process, the cell size by various parameters that affect the type and amount of Propellant, the type of polymer, the geometry of the nozzle orifice, the shear rate at the nozzle, the amount of one (optional) nucleating agent, the (optional) use of a cell enlarging agent Include and the foaming temperature. For the remaining parameters, the type and amount of propellant the biggest effect on cell size.

The for the preparation of the invention Polymer foams suitable blowing agent for foaming include all types of known blowing agents, physical and / or chemical blowing agents, including inorganic ones Blowing agent, organic blowing agent and chemical blowing agent. In the event that used for foaming Mixture moisture-crosslinking groups (eg., Silane groups) contains the physical blowing agents used preferably with water or steam saturated to a fast and complete To achieve networking. Include suitable inorganic blowing agents Carbon dioxide, nitrogen, argon, water, air, oxygen and helium one. Organic leavening agents include aliphatic hydrocarbons with 1-6 carbon atoms, aliphatic alcohols with 1-3 Carbon atoms and fully or partially halogenated aliphatic hydrocarbons having 1-4 carbon atoms one. Aliphatic hydrocarbons include methane, Ethane, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, Hexane, isohexane, heptane, octane, methylpentane, dimethylpentane, butene, Pentene, 4-methylpentene, hexene, hedge, 2,2-dimethylbutane and petroleum ether one. Aliphatic alcohols include methanol, ethanol, n-propanol and isopropanol. Complete and partial halogenated aliphatic hydrocarbons Chlorinated hydrocarbons, fluorocarbons and chlorofluorocarbons one. Chlorinated hydrocarbons for use in this Invention includes methyl chloride, methylene chloride, ethyl chloride, Ethylene dichloride, 1,1,1-trichloroethane, trichloromethane and carbon tetrachloride one. Fluorohydrocarbons for use in this invention include methyl fluoride, methylene fluoride, ethyl fluoride, 1,1-difluoroethane (HFC-152a), 1,1,1-trifluoroethane (HFC-143a), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,2,2, tetrafluoroethane (HFC-134), pentafluoroethane, 2,2-difluoropropane, 1,1,1-trifluoropropane and 1,1,1,3,3-pentafluoropropane one. Partially hydrogenated chlorofluorocarbons for use in this invention include chlorofluoromethane, chlorodifluoromethane (HCFC-22), 1,1-dichloro-1-fluoroethane (HCFC-141b), 1-chloro-1,1-difluoroethane (HCFC-142b), 1,1-dichloro-2,2,2-trifluoroethane (HCFC-123), 1,2-dichloro-1,2,2-trifluoroethane (HCFC-123a) and 1-chloro-1,2,2,2-tetrafluoroethane (HCFC-124). Fully halogenated hydrocarbons can are also used but are for environmental reasons not preferred: fluorotrichloromethane (CFC-11), dichlorodifluoromethane (CFC-12), 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113), 1,2-dichloro-1,1,2,2-tetrafluoroethane (CFC-114), chloro-1,1,2,2,2-pentafluoroethane (CFC-115), trichlorofluoromethane.

Chemical blowing agents for use in this invention also include azodicarbonamide, azodiisobutyronitrile, benzenesulfonyl hydrazide, 4,4-oxybenzenesulfonyl semicarbazide, 4,4-oxybis (benzenesulfonylhydrazide), diphenylsulfone-3,3-disulfonylhydrazide, p-toluenesulfonyl semicarbazide, N, N-dimethyl-N , N-dinitrosoterephthalamide and trihydrazine triazine, N = N-dinitrosopentamethylenetetramine, dinitrosotrimethyltriamine, sodium bicarbonate, sodium bicarbonate, mixtures of sodium bicarbonate and citric acid, ammonium carbonate, ammonium bicarbonate, potassium bicarbonate, diazoaminobenzene, diazoaminotoluene, azodicarbonamide, hydrazodicarbonamide, diazoisobutyronitrile, barium azodicarboxylate and 5-hydroxytetrazole. Also, mixtures of all of these blowing agents are considered to be within the scope of this invention. Preferred blowing agents for the extrusion process and the batch process for producing meltable beads are physical blowing agents, with volatile organic blowing agents being preferred, especially preferred are cure hydrocarbons (eg propane and butane).

preferred Blowing agent for the production of crosslinked foams are decomposing propellants and nitrogen.

Propellants, the relatively high solubility in the polymer used and a small molecule size lead at low dosage to large cell sizes. Examples of such propellants are - without themselves limited to these - propane, n-butane, isobutane, n-pentane, methyl chloride, methylene chloride, ethyl chloride, methanol, Ethanol, dimethyl ether, water and / or a mixed propellant, containing one or more of said blowing agents. Examples of other control additives with respect The cell size are waxy materials with relatively low melting point. It also leads also a low shear rate at the nozzle opening to big cell sizes.

The Amount of blowing agent incorporated in the polymer melt material to make a foam-forming gel is varied so as required to achieve a predetermined density.

The Amount of the optional nucleating agent used to make the foams of the present invention, will be according to the desired cell size, the foam temperature and the composition of the nucleating agent varied. So little or no nucleating agent should be used when large cell sizes are desired are. As an optional nucleating agent, which is the foamable Mixture can be added, are suitable - without to limit these - calcium carbonate, polyolefin waxes (in particular polyethylene and polypropylene waxes, both pure as well as oxidized waxes are included), as well as Fischer-Tropsch waxes, Barium stearate, calcium stearate, talc, clay, titanium dioxide, silica, Diatomaceous earth and mixtures of citric acid and sodium bicarbonate. The amount of optionally used nucleating agent may vary from 0.01 to 5 parts by weight per 100 parts by weight of the polymer resin mixture pass.

In front mixing with the blowing agent, the polymer is at a temperature above its glass transition temperature or above its glass transition temperature Softening point or heated above its melting temperature. In the present case of largely amorphous polyolefins is doing at temperatures of 60-250 ° C, preferably at 70-230 ° C. and most preferably worked at 80-200 ° C, this temperature being of the polymer composition and the (part) crystallinity the used, largely amorphous polyolefin and possibly Blend partner depends. The propellant can be melted in the Polymer material by mechanical aids such. B. extruder, Melting kneader, mixers, etc. are incorporated. If an extruder is used, so can one-, two- as well as multi-screw extruder used in twin-screw extruders. as well as counter running operations of the screws possible are. For a better mixing is the concurrent Driving is preferred, while shear-sensitive polymers the opposite running is preferred. For multi-screw extruders In particular, those which contain a central spindle are preferred. because here the best mixing results with low polymer load to be obtained. Beside these "promotional" mixers For example, polymer melt and blowing agent can also be used in a tube reactor be mixed with mixing elements. In the latter case, the direct metering of the polymer melt into the tubular reactor by means of a gear pump, which has a corresponding pressure in the tubular reactor builds. If melt kneaders are used, they can be operated both continuously and discontinuously. In a particular embodiment of the manufacturing process becomes the largely amorphous polyolefin immediately after the polymerization chemically stabilized and then without packaging directly to a Foam processed. The processing can become a foam either at the point of polymerization or at another place, in the latter case, transport of the stabilized polymer melt z. B. by heated containers and / or a trace-heated melt line he follows. The blowing agent is mixed with the molten polymer material mixed at an elevated pressure sufficient to one to avoid substantial expansion of the molten polymer material and to disperse the blowing agent homogeneously. Optionally, too a nucleating agent is mixed into the polymer melt or dry with the polymer material before plasticizing or melting be mixed. The foamable gel typically becomes initially cooled to the physical characteristics to optimize the foam structure. The gel is then passed through a nozzle any shape in an area with reduced or lower Pressure extruded or promoted to the foam structure to build. The pressure present is lower than that, in which the foamable gel before being extruded through the Nozzle is held, and can be both larger, equal, as well as less than the atmospheric pressure lie. It is preferably between 1,200 and 0 mbar (abs.), Especially preferably between 1200 and 500 mbar (abs.), very particularly preferably between 1,100 and 800 mbar (abs.).

Around the permeability of the polymers used for reduce the blowing agent used and thus the dimensional stability The foam cells can increase before foaming Additives are incorporated into the polymer composition. Suitable for this purpose in particular fatty acid esters and fatty acid amides. Examples for such additives are, but are not limited to, Glycerol monostearate and stearylic acid amide.

The polymer foams of the present invention may be crosslinked or uncrosslinked. Process for the preparation of polymer foam structures and their processing are in CP Park, Polyolefin Foam (Chapter 8 of the Handbook of Polymer Foam and Foam Technology, edited by Daniel Klemper and Vahid Sendijarevic, Hanser Publishers, Munich (2004)) listed.

Not crosslinked foams can according to the invention z. B. in an intermeshing strand form by extrusion the thermoplastic polymer resin (i.e., the polymer material) produced by a nozzle with many openings become.

The The present foam structure can also be present in non-crosslinked foam beads be formed, which are suitable to in a further molding process to be melted in appropriate forms. The foam beads can be produced by an extrusion process or a batch process become. In the extrusion process, the foam strands by means of conventional foam extrusion apparatus, through a multi-hole nozzle promoted and then granulated to the To form foam globules. Be in a batch process individual polymer particles, such as. B. granulated resin pellets in a liquid medium in which they are essentially not are soluble, such. As water, suspended. These are with a propellant interspersed by the propellant in the liquid Medium at elevated pressure and elevated Temperature introduced in an autoclave or other pressure vessel will, and quickly into the atmosphere or area discharged under reduced pressure to expand, and so the foam beads to build.

crosslinked Foams of the present invention may be either by the cross-linked foam method using a decomposing propellant or by conventional extrusion processes getting produced.

In preparing crosslinked polymer foams using a decomposing blowing agent, the crosslinked foams can be made according to the invention by blending a thermoplastic polymer with a decomposing chemical blowing agent and heating it to form a foamable, plasticized or molten polymeric material. By extruding the foamable, molten polymeric material through a die, inducing cross-linking in the molten polymeric material and exposing the molten polymeric material to an elevated temperature to release the blowing agent, the foam structure is formed. In this case, polymer melt and blowing agent z. B. with an extruder, mixer, mixer or the like. If an extruder is used, it is possible to use single-, two- as well as multi-screw extruders, with twin-screw extruders enabling both identical and counter-rotating modes of operation of the screws. For a better mixing the concurrent driving is preferred, while in shear-sensitive polymers, the counter-running procedure is preferred. In the case of multi-screw extruders, preference is given in particular to those which contain a central spindle, since here the best mixing results are achieved with simultaneously low polymer loading. If melt kneaders are used, they can be operated both continuously and discontinuously. In a particular embodiment, the polymerization with the aid of polar decomposition agents such. For example, water or alcohols (e.g., methanol, ethanol, propanol, octanol, etc.), and optionally with the use of an oxidizing agent, are free of active catalyst / cocatalyst components, and then either without prior degassing or after only a portion of the solvent has been removed , optionally crosslinked and then foamed directly. In particular, liquid gases, in particular propane and n-butane, are preferred solvents for the polymerization. Before foaming in this case additional auxiliaries such. As stabilizers, plasticizers, lubricants, nucleating agents, crosslinking additives, etc. added. Chemical blowing agents are preferably dry-blended prior to heating the polymeric material, but may also be added to the melt. The cross-linking can be induced by addition of a cross-linking agent or by irradiation. The crosslinking agents preferably used in this invention are organic peroxides. Examples of organic peroxides include, but are not limited to, dicumyl peroxide, 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, 2 , 5-Dimethyl-2,5-di-tert-butylperoxyhexine, α, α'-bis (tert-butyl peroxy) diisopropylbenzene, tert-butyl peroxy ketone and tert-butyl peroxybenzoate. As an alternative to the use of chemical crosslinking agents, the crosslinking of the polymer or the used Po lymer mixture also be carried out by high-energy radiation. The exposure of the polymer material to the radiation can be carried out both before foaming and after foaming. In particular, electron radiation is suitable as high-energy radiation.

The cells formed by foaming can, depending on the intended application, open or closed be. Open cells can either be directly during the foaming step arise, or subsequently be generated by mechanical perforation of closed cells. A further possibility for the generation of open cell structures Represents the subsequent compression of closed cell structures which, tearing open the cells to an open cell Foam structure leads. For closed cells can the cells either empty, or still (partially) with propellant be filled. For foams filled with Cells are preferably inert propellants such. Argon, helium, Nitrogen and / or carbon dioxide used.

The Induction of cross-linking and exposure to an elevated temperature to foaming or The expansion can be done simultaneously or on top of each other happen following. If a cross-linking agent is used, it is incorporated into the polymer material in the same way as the chemical blowing agent. When using a cross-linking agent becomes the foamable molten polymer material a temperature of preferably less than 160 ° C, especially preferably less than 150 ° C and especially less exposed as 140 ° C, to decompose the cross-linking Agent and / or the propellant and / or premature crosslinking to prevent. Are irradiation techniques used for crosslinking, The foamable molten polymer material becomes a Temperature of preferably less than 170 ° C, more preferably less than 160 ° C, and more preferably less exposed as 150 ° C to a decomposing propellant to prevent. The foamable molten polymer becomes extruded through a die of desired shape or promoted. The foamable structure then becomes cross-linked and at a high temperature (160-250 ° C), z. B. in an oven, expanded. In a particular embodiment the mixture of the polymer with blowing agent and crosslinking aid at a temperature below the decomposition point of the propellant or crosslinking agent. In this case, the application of the Polymer-blowing agent-crosslinker mixture without prior crosslinking respectively. The expansion and / or networking then takes place in one separate temperature control step. This embodiment is suitable especially good for foaming cavities. If the crosslinking by irradiation, the foamable Irradiated structure to crosslink the polymer material, which then, as described above, expanded at an elevated temperature becomes.

Alternatively, or in addition to the use of a crosslinking agent or crosslinking by irradiation in a crosslinking foam process using a decomposing blowing agent, crosslinking may also be accomplished with the aid of silane crosslinks as described in U.S. Pat CP Park, Polyolefin Foam (Chapter 8 of the Handbook of Polymer Foam and Foam Technology, edited by Daniel Klemper and Vahid Sendijarevic, Hanser Publishers, Munich (2004)) to be achieved.

Crosslinked foams of the present invention can also be formed into crosslinked foam beads. To prepare the foam beads, isolated polymer particles, such. Granulated polymer pellets are suspended in a liquid medium in which they are substantially insoluble (e.g., water); impregnated with a cross-linking agent and a blowing agent at an elevated pressure and temperature in an autoclave or other pressure vessel, and rapidly released into the atmosphere or a reduced pressure region, thereby forming the foam beads. In another version of the process, the polymer beads are impregnated with the blowing agent, cooled down, discharged from the kettle and then expanded by heating or steam. In a variation of the above method, additional monomers can be incorporated into the suspended pellets simultaneously with the crosslinking agent to form a graft copolymer with the polymeric material. Examples of such additional monomers include but are not limited to: maleic anhydride, itaconic anhydride, styrene, methyl methacrylate, butyl methacrylate, vinyl alcohols, and vinyl silanes. These monomers may be used either alone or in admixture with free radical generators. Examples of free-radical formers include, but are not limited to, organic peroxides such as dicumyl peroxide, 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di-tert butylperoxyhexane, 2,5-dimethyl-2,5-di-tert-butylperoxyhexine, α, α'-bis (tert-butylperoxy) diisopropylbenzene, tert-butyl peroxyketone and tert-butyl peroxybenzoate. The propellant may be incorporated into the resin pellets while in suspension or, alternatively, in a non-aqueous state. The expandable beads are then heated by heating z. B. expanded with steam and formed by a conventional molding method. This can be z. B. by loading a mold with the foam beads, the subsequent Zusammenpres In order to compress the beads and a final heating of the mold or the beads (eg, with steam) to effect the merging and welding of the beads and to form the article, carried out the form. Optionally, the beads may be heated with air or other medium prior to filling the mold. Due to the good surface adhesion of the largely amorphous polyolefins used according to the invention, the shaping process can be carried out at far lower temperatures than hitherto possible. The molding temperatures are between 40 and 200 ° C, preferably between 45 and 150 ° C and more preferably between 50 and 140 ° C. To improve mold release, the use of a release agent (eg a low-melting polyolefin wax or a Fischer-Tropsch wax) makes sense. Descriptions of the above methods and methods are in CP Park, Polyolefin Foam (Chapter 8 of the Handbook of Polymer Foam and Foam Technology, edited by Daniel Klemper and Vahid Sendijarevic, Hanser Publishers, Munich (2004)) to find. The foam beads may also be prepared by preparing a mixture of the polymer, crosslinking agent and disintegrating agents in a suitable mixing apparatus or extruder and forming the mixture into pellets and then heating the pellets.

Of the Degree of crosslinking of the invention produced Foams are preferably between 30 and 100%, especially preferably between 50 and 100%, and more preferably between 80 and 100%.

One another process for the preparation of crosslinked foam beads, which are suitable for molding in articles is the polymeric material to melt and use it with a physical blowing agent in one conventional foam extrusion apparatus to mix a in the to form a substantial continuous foam strand, which gluing on granulated or pelleted. The foam beads are then cross-linked by irradiation. The cross-linked foam beads can then be fused and formed, to form different articles.

In addition, silane crosslinking technology can be used for the extrusion process. A description of this method is also in CP Park, Polyolefin Foam (Chapter 8 of the Handbook of Polymer Foam and Foam Technology, edited by Daniel Klemper and Vahid Sendijarevic, Hanser Publishers, Munich (2004)) to find. When silane crosslinking processes are used with conventional extrusion processes, a polymer is grafted with a vinyl-functional silane or an azido-functional silane and expanded to form foams. The extruded foams are then exposed to warm, moist air to start the cross-linking.

In a particular embodiment, an already silane-functionalized, largely amorphous polyolefin is used, which can be used either as a sole component or as a component of a mixture with other largely amorphous polyolefins and / or as mixtures with other polymers. Corresponding polyolefins have already been described above. The preparation of such a silane-functionalized largely amorphous polyolefin is z. In DE 4000696 and US 5,241,014 described.

Foams made by the method described above have densities of from 5 kg / m ³ to 500 kg / m ³ , with foams having densities of from 10 kg / m ³ to 400 kg / m ³ being preferred. The foams may be open or closed celled, preferred are foams that are substantially open or substantially closed-celled.

The foams of the invention are suitable for a variety of applications, in particular for sound absorption, Sound insulation, liquid absorption, filtration, for Padding of packaging or as upholstery elements in furniture, for vibration damping (eg in the automotive sector), as Packaging, as packaging, for thermal insulation, as volume elements with low density (eg in the clothing area and / or as a buoyant body z. B. in swimming elements), for cavity sealing, for the production of filter elements or sandwich structures or as insulation in the automotive sector. The said use is also an object of the present invention.

Especially is with the polymer foams produced according to the invention a joining by briefly heating the foam surface (eg with hot air, infrared radiation or similar) possible.

In a further particularly preferred embodiment, the foams according to the invention are a geomembrane or constituents of a floor covering, in particular a carpet backing, which is preferably a carpet backing for carpets whose studs and / or filaments at least partially made of polyolefins and / or with the help of egg nes polyolefin hot melt adhesive were fixed. In particular, the foaming of the polymer mixture applied to the carpet backing which contains at least one amorphous polyolefin according to the invention can take place in such a way that either the foam which has already been expanded is applied directly to the backing, or else the unfoamed mixture (particularly preferably molten) is applied to the backing and a subsequent thermal treatment (eg., By IR emitter, water vapor, microwave radiation, etc.) is subjected, which causes the expansion, or causally causes. Corresponding floor coverings are also the subject of the present invention.

A Another application is cavity sealing. Other applications, in which in addition to the material properties of the foam and a Bonding is desired, for example, filter elements or Sandwich structures z. B. of cardboard, paper, wood, glass, metal and / or Plastics, both similar and different Materials can be connected. Furthermore, are suitable the foams of the invention as insulation in the automotive sector (eg interior insulation, engine compartment insulation, etc.).

Structures containing foam and one, two or more film layers are also provided by the present invention. In this case, the film of all the prior art corresponding polymer materials, but in particular consist largely amorphous polyolefins. Examples of films of amorphous polyolefins are z. B. in the WO 2006/108747 to find. Also, the use for Schlagabsorbtion or shock absorption, z. B. in running shoes (especially in the area of the footbed) and the use in gymnastic mats and in the field of sports floors are possible. Foams of high density according to the invention can also be used in the field of cable filling compounds and / or for structural applications, for. B. in the automotive or architectural use.

The Foam parts have due to their surface tackiness a basic liability on the surfaces of particular PP, PE, metals, wood, paper / cardboard, glass, etc., what the assembly facilitated.

On The reason of their molecular structure according to the invention to Foam production, amorphous polyolefins used have good ductility, without this first with the help of artificial plasticizers (which ecologically and above all health are questionable) would have to be achieved.

The Amorphous polyolefins used in the invention have (depending on the polymer composition) already by itself good adhesion on many materials. The liability can by the common or alternative use with (silane) modified largely amorphous polyolefins are further improved. especially become very much with the modified largely amorphous polyolefins good adhesion to polymers (especially polypropylene, polyethylene, ABS, polycarbonate, PMMA, SAN, S / MSA, EVA, nylon) as well as on glass, Metals, wood and paper or cardboard.

Also without further explanation it is assumed that a person skilled in the art can make the most of the above description. The preferred embodiments and examples are therefore only as descriptive, in no way as limiting in any way To understand the revelation. Hereinafter, the present invention explained in more detail by way of examples. alternative Embodiments of the present invention are analogous Way available.

analytics:

a) high temperature ¹³ C NMR

• [1] S. Berger, S. Braun, H.-O. Kalinowski, 13C-NMR-Spektroskopie, Georg Thieme Verlag Stuttgart 1985
• [2] A. E. Tonelli, NMR Spectroscopy and Polymer Microstructure, Verlag Chemie Weinheim 1989
• [3] J. L. Koenig, Spectroscopy of Polymers, ACS Professional Reference Books, Washington 1992
• [4] J. C. Randall, Polymer Sequence Determination, Academic Press, New York 1977
• [5] A. Zambelli et al: Macomolecules, 8, 687 (1975)
• [6] A. Filho, G. Galland: J. Appl. Polym. Sci., 80, 1880 (2001)

The polymer composition of the polyolefins used is determined by means of high-temperature ¹³ C-NMR. The ¹³ C NMR spectroscopy of polymers is described, for example, in the following publications:

• [1] S. Berger, S. Braun, H.-O. Kalinowski, 13C-NMR spectroscopy, Georg Thieme Verlag Stuttgart 1985
• [2] AE Tonelli, NMR Spectroscopy and Polymer Microstructure, Verlag Chemie Weinheim 1989
• [3] JL Koenig, Spectroscopy of Polymers, ACS Professional Reference Books, Washington 1992
• [4] JC Randall, Polymer Sequence Determination, Academic Press, New York 1977
• [5] A. Zambelli et al: Macomolecules, 8, 687 (1975)
• [6] A. Filho, G. Galland: J. Appl. Polym. Sci., 80, 1880 (2001)

b) Rheology

The rheological measurements on the unfoamed polyolefins are carried out according to ASTM D 4440-01 ("Standard Test Method for Plastics: Dynamic Mechanical Properties Melt Rheology") using an Anton Paar rheometer MCR 501 with a plate-plate geometry (plate diameter: 50 mm) as oscillation measurement. The maximum sample deformation used is 1% in all measurements, the temperature-dependent measurements are carried out at a measuring frequency of 1 Hz and a cooling rate of 1.5 K / min. The maximum deformation of the sample is chosen so that the sample is in the linear viscoelastic region during the entire measurement period. The polymers according to the invention are thus distinguished inter alia by the fact that their melts show a viscoelastic behavior. Viscoelastic materials are characterized by their ability to dissipatively dissipate stresses resulting from a deformation over a certain time compared to Hook's solid bodies (relaxation). In contrast to Newtonian fluids, which undergo exclusively irreversible deformation under the effect of shear / strain, viscoelastic fluids can regain some of the deformation energy after the shear force has been removed (so-called "memory effect") [ NP Cheremisinoff, "An Introduction to Polymer Rheology and Processing"; CRC Press; London; 1993 ]. Another characteristic of the melts of the polymers according to the invention is the occurrence of a so-called intrinsic viscosity. As such, a behavior is described in which the shear stress as occurring force degrades the initial structure of the material as a function of the shear rate. Since this degradation process requires a minimum shear rate, the material flows below this shear rate like a Newtonian fluid. One explanation provides the principle of Le Chatelier, where the "dodging" of the pseudoplastic liquid (before the mechanical stress) in alignment along the thrust surfaces to reduce the frictional resistance consists. The latter leads to the degradation of the equilibrium structure of the initial state and to the construction of a thrust-oriented structure, which in turn has a facilitated flow (viscosity reduction) result. In polymer melts, the Newtonian range is perceptible only at very low shear rates or small shear amplitudes. Its determination is possible and necessary via rheometric test methods (amplitude "sweeps", ie measurement at a fixed frequency as a function of the shear amplitude), if the measurement is to be carried out in the reversible, ie reproducible range [ RS steering; "Rheology of plastics"; C. Hanser Verlag; Munich; 1971 ; J. Meissner; "Rheological behavior of plastic melts and solutions" in: "Practical rheology of plastics";VDI-Verlag; Dusseldorf, 1978 ; J.-F. Jansson; Proc. 8th. Int. Congr. Rheol .; 1980; Vol. 3 ]. The vibrational rheometry is due to their low force, their low deformation and thus low impact on the sample morphology particularly well suited for the investigation of materials that show pseudoplastic behavior. In the present case, the measurement of modified polymers is always carried out without further additions in the uncrosslinked state, whereby it is expedient to perform a coating with dry protective or inert gas (for example nitrogen, argon, etc.) during the measurement.

c) Needle penetration (PEN)

The needle penetration of the unfoamed polyolefins is determined according to DIN EN 1426 certainly. In the present case, the measurement of modified polymers is always carried out without further additions in the uncrosslinked state, whereby it is expedient to perform a coating with dry protective or inert gas (for example nitrogen, argon, etc.) during the measurement.

d) DSC

The melting enthalpy, the glass transition temperature and the melting range of the crystalline fraction of the unfoamed polyolefins are determined by differential scanning calorimetry (DSC) according to DIN 53 765 from the 2nd heating curve at a heating rate of 10 K / min. The inflection point of the heat flow curve is evaluated as the glass transition temperature. In the present case, the measurement of modified polymers is always carried out without further additions in the uncrosslinked state, meaning that during the measurement it is advisable to apply a dry protective or inert gas (eg nitrogen, argon, etc.).

e) tensile strength and elongation at break

The determination of the tensile strength and elongation at break of the unfoamed polyolefins is carried out after DIN EN ISO 527-3.

f) softening point (ring & ball)

The determination of the softening point of the unfoamed polyolefins by the ring and ball method is carried out according to DIN EN 1427 , The measurement of modified polymers is carried out in the present case always without further additions in the uncrosslinked state, meaningful way during the measurement Be with dry protective or inert gas (eg nitrogen, argon, etc.). Softening points can only be determined by definition according to the "Ring & Ball Method" used in this case if the influence of the melt viscosity on the measured values is low. In the case of the present invention, this requirement is given for viscosity values (measured at 190 ° C) to about 600,000 mPa · s. For amorphous polyolefins according to the invention having a melt viscosity of> 600,000 mPa · s, therefore, no softening points are determined or indicated.

g) adhesive shear strength

The determination of the adhesive shear strength of the unfoamed polyolefins takes place after DIN EN 1465 , All test specimens used are cleaned and dedusted before sample preparation. All plastic test specimens are additionally degreased before sample preparation with a suitable cleaning agent. The storage of all cleaned, dedusted and degreased test specimens before use in the climatic chamber at 20 ° C and 20% rel. Humidity. As a result, a uniform water content z. B. achieved in wood test specimens. Due to an increased moisture-related singular effects z. B. in hydrophilic or hydrolysis-sensitive polymers are excluded or minimized. In the measurement of foamed polyolefins, the foaming process usually takes place after joining the adhesive bond by thermal energy.

The The measuring methods described here refer to every survey in the context of the present invention, regardless whether it is the base polymer to be grafted or the invention Polyolefin acts.

Examples:

1. Preparation of inventively used amorphous polyolefins for the production of polymer foams:

• * im Polymer; bestimmt durch ¹³C-NMR-Spektroskopie

The preparation of amorphous polyolefins (. Ex. No. 1-8 of the present invention) is carried out using a mixed catalyst of a crystalline titanium trichloride in the form of a reduced aluminum TiCl ₄ (TiCl ₃ 0.33 AlCl ₃₎ and triisobutylaluminum (in the weight ratio 1: 4 ). The monomers listed in Table 1 are polymerized in the solvent n-butane at 70 ° C in a laboratory autoclave, depending on the target molecular weight different amounts of hydrogen are used as molecular weight regulator. There are pressures of 10 to 36 bar. The monomers ethene and propene are added continuously during the reaction time of 3 h, the monomer 1-butene is presented together with the solvent used. After 3 h, the reaction mixture is mixed with isopropanol, whereby the reaction is stopped. In an evaporator unreacted monomers and the solvent n-butane are evaporated. The polymer is melted and filled at a temperature of 190 ° C. attempt 1 2 3 4 C ₂ * [ma-%] 0 7.7 1 5 C ₃ * [ma-%] 73 55 35 4 C ₄ * (ma-%] 27 37.3 64 91 C _5-20 * [ma-%] - - - - η _{190 ° C} [mPa · s] 1900 68,000 32,000 15,000 PEN [0.1 mm] 8th 19 18 11 T _ad. [° C] 136 95 80 110 T _g [° C] -23 -38 -41 -45 ΔH _M [Y / g] 12.8 1.65 2.4 4.7 Tensile strength [MPa] 2.8 5.4 3.9 8.9 Elongation at break [%] 65 1104 424 58 attempt 5 6 7 8th C ₂ * [ma-%] 10 13 9 8th C ₃ * [ma-%] 61 70 46 62 C ₄ * [ma-%] 29 17 - - C _5-20 * [ma-%] - - 1-octene 45 C ₁₈ 30 η _{190 ° C} [mPa · s] 221000 529000 920000 2200000 PEN [0.1 mm] 22 16 38 29 T _ad. [° C] 158 125 nb nb T _g [° C] -34 -31 -38 -39 ΔH _M [Y / g] 1.2 7.1 3.2 2.1 Tensile strength [MPa] 2.1 nb nb nb Elongation at break [%] 753 nb nb nb Polymers used according to the invention

• * in the polymer; determined by ¹³ C NMR spectroscopy

2. Compositions of foamable mixtures:

a) Components used (product names):

• VESTOPLAST 704 (Evonik Degussa GmbH) Propenreiches Poly (1-olefin) copolymer having a melt viscosity (190 ° C) of 2,900 mPa · s.
• VESTOPLAST 206 (Evonik Degussa GmbH) silane-modified Poly (1-olefin) with a melt viscosity (190 ° C) of 6,300 mPa · s.
• Affinity GA 1900 (The Dow Chemical Company) metallocene based poly (ethylene-co-1-octene) polymer having a melt viscosity (190 ° C) of 6,000 mPa · s.
• SABIC PP520P (Saudi Basic Industries Corporation) propylene homopolymer having a melt flow rate MFR _{230 ° C / 2.16kg} of 10.5 g / 10 minutes.
• SABIC LDPE2101 (Saudi Basic Industries Corporation) Low density polyethylene (LDPE) with a melt flow rate MFR _{190 ° C / 2.16kg} of 0.85 g / 10 minutes.
• VESTOWAX A227 (Evonik Degussa GmbH) unfunctionalized Polyethylene hard paraffin with a dropping point of 102-110 ° C.
• IRGANOX 1010 (CIBA Specialty Chemicals) Pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate); Polymeric stabilizer.
• dicumylperoxide peroxide, bis (1-methyl-1phenylethyl); Initiator; SADT (Self-accelerating decomposition temperature) = 80 ° C.
• Dynasylan VTMO (Evonik Degussa GmbH) vinyltrimethoxysilane; Silane monomer.

• * Produkt der Evonik Degussa GmbH
• ** Produkt The Dow Chemical Company
• *** Produkt der Saudi Basic Industries Corporation (SABIC)
• **** Produkt der CIBA Specialty Chemicals

b) compositions attempt 9 10 11 12 13 Polymer. lt. Ex. 1 2 5 6 6 Proportion of polymer [% by mass] 20 35 58 28 22 VESTOPLAST ^® 704 * [ma-%] - - 5 - - VESTOPLAST ^® 206 * [ma-%] 20 - - 21.5 - AFFINITY ^® GA 1900 ** [ma-%] - - 10 - 5 SABIC ^® PP520P *** [% by mass] 54.5 - 25 49 - SABIC ^® LDPE2101 *** [% by mass] - 54 - - 63 VESTOWAX ^® A227 * [% by mass] 3 1 - 0.75 - IRGANOX ^® 1010 **** [ma-%] 1 0.5 0.5 0.75 0.5 Dicumyl peroxide [ma-%] - 3.5 - - 3.5 Dynasylan ^® VTMO * [% by mass] - 4.5 - - 4.5 2,2'-diethoxy-2,2'-azopropane [ma-%] - 1.5 - - - N, N'-di (tert-butyl) azodicarbonamide [ma-%] 1.5 - - - 1.5 Azodicarbonamide [ma-%] - - 1.5 - - attempt 14 15 16 17 18 Polymer. lt. Ex. 8th 6 2 5 5 Proportion of polymer [% by mass] 75 70 18 85 95 VESTOPLAST ^® 704 * [ma-%] - - 6 - - VESTOPLAST ^® 206 * [ma-%] 10 - - - - AFFINITY ^® GA 1900 ** [ma-%] - - - - 4.5 SABIC ^® PP520P *** [% by mass] 10 - 72 7.5 - SABIC ^® LDPE2101 *** [% by mass] - 20 - - - VESTOWAX ^® A227 * [% by mass] 2.5 1.5 2 5 - IRGANOX ^® 1010 **** [ma-%] 1 0.5 0.5 1 0.5 Dicumyl peroxide [ma-%] - 2.5 - - - Dynasylan ^® VTMO * [% by mass] - 4.0 - - - 2,2'-diethoxy-2,2'-azopropane [ma-%] - - 1.5 - - N, N'-di (tert-butyl) azodicarbonamide [ma-%] - -1.5 - - - Azodicarbonamide [ma-%] 1.5 - - 1.5 - Table 2: Composition of the foamable mixtures

• * Product of Evonik Degussa GmbH
• ** Product The Dow Chemical Company
• *** Product of Saudi Basic Industries Corporation (SABIC)
• **** Product of CIBA Specialty Chemicals

3. Implementation of Foam tests and foam properties

• *: Nach 2 Wochen Lagerung im Klimaschrank (20°C; 65% rel. Luftfeuchte)
• HWF: hart und wenig flexibel
• WF: weich und flexibel
• GM: Gleichmäßige Porenverteilung
• UG: Ungleichmäßige Porenverteilung
• OZ: Überwiegend offen-zellig
• GZ: Überwiegend geschlossen-zellig

The compositions (see Table 2) are mixed in a laboratory tumble mixer at room temperature for at least 30 minutes and then metered via a belt weigher into the first section of a single-screw extruder equipped with 5 sections (with independent temperature control units). If a physical expansion agent is used, this is in the third section via a High-pressure membrane pump added. The discharge from the extruder takes place through a 3 mm flat nozzle directly into a discharge bath through which the discharge direction flows (water, 20 ° C.). The foam sheets are cut and hung for further cooling and drying. After a cooling time of 3 h, specimens of 2 × 10 cm are cut to size using metal templates and transferred to the climatic chamber (20 ° C., 65% relative humidity) for further storage. attempt 19 20 21 22 23 Composition according to Table 2 9 10 11 12 13 Melt temperature extruder section 1 [° C] 135 100 140 140 110 Melt temperature extruder section 2 [° C] 150 115 160 160 140 Melt temperature extruder section 3 [° C] 155 120 175 160 155 Melt temperature extruder section 4 [° C] 170 130 190 155 170 Melt temperature extruder section 5 [° C] 180 155 215 160 180 Melt temperature discharge nozzle [° C] 185 165 225 180 185 Physical expansion medium - - - propane - Foam thickness * [mm] 11.3 9.7 8.6 8.0 8.8 Macroscope. Evaluation* HWF WF WF WF WF Pore size / distribution * big GM small GM small GM medium GM small GM Cell structure * OZ GZ OZ OZ GZ attempt 24 25 26 27 28 Composition according to Table 2 14 15 16 17 18 Melt temperature extruder section 1 [° C] 140 110 135 140 140 Melt temperature extruder section 2 [° C] 160 14 155 160 160 Melt temperature extruder section 3 [° C] 175 155 160 175 160 Melt temperature extruder section 4 [° C] 190 170 160 190 155 Melt temperature extruder section 5 [° C] 215 180 155 215 165 Melt temperature discharge nozzle [° C] 225 185 175 225 175 Physical expansion medium - - - - propane Foam thickness * [mm] 8.0 8.4 10.2 12.4 14.1 Macroscope. Evaluation* WF WF HWF WF WF Pore size / distribution * small GM medium GM medium GM big GM big GM Cell structure * GZ GZ GZ GZ OZ Table 3: Test conditions Foam tests and material behavior Polymer foams.

• *: After 2 weeks storage in a climatic chamber (20 ° C, 65% relative humidity)
• HWF: hard and not very flexible
• WF: soft and flexible
• GM: Uniform pore distribution
• UG: Uneven pore distribution
• OZ: Predominantly open-celled
• GZ: predominantly closed-celled

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

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Claims (17)

Use of one or more amorphous polyolefins for producing foams, characterized in that at least one of the amorphous polyolefins used has at least three of the following material properties: a melting enthalpy determined by differential calorimetry in the second heating of at least 1 J / g and at most 50 J / g , - a softening point determined by ring & ball method of at least 60 ° C and at most 170 ° C, - a needle penetration of at least 1 x 0.1 mm and a maximum of 70 x 0.1 mm, - a tensile strength of at least 0.1 MPa and a maximum of 30 MPa, - a maximum glass transition temperature determined by differential scanning calorimetry in the second heating at -8 ° C. Use according to claim 1, characterized in that at least one of the amorphous polyolefins used from a maximum of 25% by mass of ethylene, at most 98% by mass of propylene and / or from not more than 100% by mass of an α-olefin containing 4 to 20 carbon atoms is constructed. Use according to claim 1 or 2, characterized in that at least one of the used amorphous polyolefins is selected from poly (1-butene) homopolymer, Poly (ethylene-co-propylene) copolymers with a maximum of 25 m% ethylene content, Poly (ethylene-co-1-butene) copolymers with a maximum of 20 m% ethylene content, Poly (propylene-co-1-butene) copolymers, or poly (ethylene-co-propylene-co-butene) terpolymers with a maximum of 20% by mass of ethylene and a propylene content of 20-98 % by mass. Use according to one or more of claims 1 to 3, characterized in that the polyolefins alone or in combination with one or more other polymers be used. Use according to claim 4, characterized characterized in that the proportion of polyolefins 5-100 ma-%, based on the total amount of polymers. Use according to claim 4 or 5, characterized in that the one or more further polymers are selected from the group comprising isotactic Polypropylene, syndiotactic polypropylene, atactic polypropylene, high density polyethylene (HDPE), low density branched polyethylene (LDPE), linear low density polyethylene (LLDPE), ethylene-vinyl acetate copolymer (EVA), ethylene-propene-rubber (EPR), ethylene-propene-diene copolymers (EPDM), polybutadiene, polystyrene, syndiotactic polystyrene, acrylonitrile-butadiene-styrene terpolymers (ABS) and styrene-acrylonitrile copolymers (SAN). Use according to one or more of claims 1 to 6, characterized in that the one or more amorphous polyolefins with one or more silanes are modified. Foams containing amorphous polyolefins, characterized in that at least one of the contained amorphous Polyolefins at least three of the following material properties having: One by differential scanning calorimetry the second heating certain melting enthalpy of at least 1 J / g and a maximum of 50 J / g, - a softening point determined by ring & ball method of at least 60 ° C and a maximum of 170 ° C, - one Needle penetration of at least 1 x 0.1 mm and a maximum of 70 x 0.1 mm, A tensile strength of at least 0.1 MPa and maximum 30 MPa, - one by differential calorimetry in the second heating certain glass transition temperature from a maximum of -8 ° C. Foams according to claim 8, characterized in that the amorphous polyolefins in the Foaming in combination with one or more others Present polymers. Foams according to claim 8 or 9, characterized in that they additionally stabilizers, lubricants, Plasticizers, halogenated and / or non-halogenated flame retardants, Fillers or synthetic and / or non-synthetic Dyes or pigments included. Process for producing foams comprising foaming one or more amorphous polyolefins according to claim 1, wherein the processing temperature at least in a subarea of the processing machine below the softening point of at least one of the amorphous used Polyolefins lies. Process according to claim 11, characterized characterized in that semicontinuous and / or continuous Extrusion process or batch process can be used. A method according to claim 11 or 12, characterized in that for foaming physical and / or chemical blowing agents are used. Method according to one or more of claims 11 to 13, characterized in that before the Blend with the propellant the one or more amorphous polyolefins to a temperature above the glass transition temperature or heated above the softening point or above the melting temperature become. Use of foams according to a or more of claims 8 to 10 for sound absorption, Sound insulation, liquid absorption, filtration, for Padding of packaging or as upholstery elements in furniture, for vibration damping, as packaging, as packaging, for thermal insulation, as volume elements with lower Density, for cavity sealing, for the production of filter elements or sandwich structures or as insulators in the automotive sector. Use according to claim 15, characterized in that it is geomembranes or to Components of a floor covering. Floor covering containing foams according to claim 8th.