DE102008041281A1 - Modified polyolefin based on a base polyolefin, which has specific content of propylene and isotactic poly(propylene)-triad and is grafted with silane e.g. vinyltrimethoxy silane, useful as or in molding composition and adhesives - Google Patents

Abstract

Modified polyolefin based on at least one base polyolefin, is claimed, where the base polyolefin: has a propylene content of 50-90 wt.%, calculated by 1>3>C-NMR-spectroscopy, an isotactic poly(propylene)-triad content of 40-80 wt.%, relative to the total detected propylene triad and calculated by 1>3>C-NMR-spectroscopy; exhibits a solubility in xylene, at room temperature, of less than 96 wt.% and a solubility in tetrahydrofuran, at room temperature, of at least 10 wt.% and maximum of 62 wt.%; and is grafted with one or more silane. Independent claims are included for: (1) a method for preparing the modified polyolefin comprising contacting the silane with at least one radical starter, where a grafting reaction of the silane takes place on the base polyolefin; and (2) a molding composition, protective composition, adhesive, sealant, marking composition, coating composition, sealing strips, roofing membranes, primer, primer formulation, adhesive formulation, dispersion, suspension and/or emulsion comprising the modified polyolefin.

Description

The The present invention relates to modified high molecular weight polyolefins Softening point and plastic deformability in uncrosslinked Condition based on partially crystalline polyolefin polymers, the a certain proportion of isotactic poly (propylene) chain elements contain, wherein the polymer or polymers one or more Silanes are grafted, a process for the preparation of polyolefins and their use, in particular in or as an adhesive.

amorphous Poly-alpha-olefins are often used as adhesive raw materials for a wide range of applications. The application area extends from the hygiene sector to laminations and packaging adhesives until constructive bonding and uses in wood processing. Unmodified amorphous poly-alpha olefins (so-called APAOs) characterized by a purely physical curing, the due to its thermoplastic character any reversible is. However, they have only limited tensile and adhesive shear strengths and a relatively low heat resistance. Furthermore no covalent incorporation becomes more reactive with them Reach surface groups (such as -OH) in a bond.

The described disadvantages of unmodified APAOs can be overcome rectify a subsequent functionalization (modification), especially carboxylic acids or carboxylic acid derivatives and / or silanes for modification.

The preparation of silane-modified polyolefins by reacting polyethylene with unsaturated silanes has long been known. Already in EP 0 004 034 B1 describes a method for crosslinking poly (α-olefins) with the aid of silane compounds, the highest possible degree of crosslinking should be achieved. The crosslinking takes place immediately after grafting and leads to stiff, high-strength materials with low embrittlement temperature, as z. B used for the production of cable sheathing and or moldings. As adhesives, the described polymers can not be used. In the US 4,412,042 describes a process for the preparation of silane linkages crosslinked polyolefins whose crosslinked products are said to have high mechanical strength, improved ductility and reduced permanent percent elongation. The polyolefins used are low density ethylene copolymers prepared by gas phase polymerization. The polymers of the invention are used as coating materials for the production of wires or cables and for the production of moldings, pipes, plates or films. As adhesives, the described polymers can not be used.

In the DE 196 35 71 , of the DE 23 53 783 and the DE 24 06 844 are described methods for crosslinking polyethylene polymers or ethylene copolymers containing small amounts of propene and / or 1-butene. Target products are cross-linked polyethylene-based moldings. In the DE 25 54 525 and the DE 26 42 927 describes processes for the production of extruded products, including the silane functionalization of a polymer, the incorporation of a silanol condensation catalyst and the shaping and crosslinking of the polymer, in one operation, by using an extruder. End applications include cables, pipes and hoses. With the polymers produced in this way, no adhesions are possible, and the entire further processing is possible only to a very limited extent due to the crosslinking carried out immediately after the modification.

Also known for a long time, the possibility of introducing silane groups in polyolefins adhesion to functional surfaces such. B. glass to improve. So be already in the US 3,075,948 Graft polymers consisting of unsaturated silane monomers and solid poly (alpha-olefins) having 2 to 6 carbon atoms which are said to have improved heat resistance and good adhesion to glass. The modification described is either a pure surface modification of solid polymer particles, polymer disks or polymer moldings, or particularly preferably a solution modification in which the polymer is at least partially dissolved, or a melt modification which is, however, not preferred. The resulting modified polymers are used for the production of moldings and containers and as a coating of glass containers, for use as hot melt adhesives they are not due to the completely different requirements profile (melt viscosity, material stiffness in the uncrosslinked state, etc.).

The use of amorphous polyalpha-olefins) for the silane crosslinking is already known. For example, in the EP 0 260 103 B1 described amorphous silane-modified polymers with saturated carbon skeleton and low molecular weight, which are used as coating agents for protection against weathering. Examples of such polymers are copolymers of ethylene and / or α-olefins, in particular EPM and EPDM. The base polymers described are amorphous and rubbery and have a high elasticity. Due to their amorphous character, the heat resistance in the uncrosslinked state is poor. For the intended applications in the present application in the adhesive and sealant area, the products are not suitable.

In the DE 40 00 695 describes the use of substantially amorphous poly (alpha olefins) in a process in which the APAOs are reacted with a free radical donor and optionally additionally graftable monomers (eg, vinyl silanes) with simultaneous shear stress. The resulting products are suitable for use as carpet coating compounds or as hot melt adhesives. The polymers are characterized by a relatively low softening point of 70 to 140 ° C. The heat of the uncrosslinked adhesive bond is poor due to the low softening point, a plastic deformability below the softening point in the uncrosslinked state is not given, so that they application areas, eg. As in the automotive sector, where a high initial heat is required and in the field of structural bonding and sealants, in which a plastic deformability is required immediately after the joining / cooling process, remain closed.

In the JP 2003-002930A For example, graft polymers are prepared from amorphous poly (α-olefin) s, unsaturated carboxylic acids, and optionally additionally unsaturated aromatic substances (eg, styrene). The polyolefins used are amorphous and have no crystallinity> 1 J / g in DSC measurements. Moisture-curing monomer systems such. As vinyl silanes are not discussed, the grafted polyolefins do not have the desired material parameters due to the properties of their base polymer and the graft monomers used, in particular they are too soft and have too low a tensile strength. In the WO 03/070786 discloses a process for producing modified poly (1-butene) polymers, the modified poly (1-butene) polymers obtainable therefrom, and an adhesive composition containing the modified poly (1-butene) polymers. Here, the poly (1-butene) base polymer used for the modification has a melting point in the range of 0 to 100 ° C, an isotactic index of <20% and a polydispersity of <4.0. As graft monomers are unsaturated carboxylic acids, carboxylic anhydrides or corresponding derivatives such as amides, esters, etc. mentioned. Vinyl silanes are not described. The modified polymers produced are relatively soft and rather waxy in nature due to their low crystallinity, the low polydispersity leads to difficulties in processing. The low melting point causes poor heat resistance of the adhesive bonds. The polymers are not suitable for the applications intended in the present application.

In the WO 2006/069205 modified polyolefins are described based on low-viscosity polypropylene polymers having a propylene content of> 50 ma-% and high proportion of isotactic propylene sequences, which can be prepared, inter alia, via a radical graft polymerization. Due to the material properties of the base polymers used, the products obtained are not suitable for the intended use in the present application.

In the WO 2007/067243 are described by carboxylic acids functionalized polypropylene polymers with high to very high propylene content. Moisture-curing systems such. B. based on silanes are not described. Due to the base polymers used and the grafting monomers used, the products described are not suitable for the intended use in the present application.

In the WO 91/06580 silane-modified unsaturated amorphous polymers are described which in the crosslinked state z. B. can be used as a shaped body. Other application examples of the silane-modified polymers include adhesive compositions, including hotmelt adhesives. As examples of unsaturated base polymers are rubbery polymers such. Styrene-butadiene block copolymers (SBS), styrene-isoprene block copolymers (SIS), styrene-butadiene rubber (SBR), nitrile rubber, polychloroprene rubber and butyl rubber. All of the above base polymers have rubber elasticity (ie, poor processability) or other negative material properties (such as poor thermal endurance) that make them unsuitable for hot melt adhesive applications.

The use of silane-modified polymers in hot-melt adhesives is also known. For example, in the WO 89/11513 describes an adhesive composition containing at least one silane-modified or silane-grafted semi-crystalline polymer. Homopolymers, copolymers and terpolymers of C _2-6 α-olefins and also isotactic polypropylene polymers and blends of polypropylenes, in particular if they also contain atactic polypropylene, are mentioned as base polymers. When grafting isotactic polypropylene (iPP), the molecular structure of iPP makes it extremely difficult rapid and complete polymer degradation, with only very low Pfropfraten can be achieved. The graft products also have a strong waxy character and no plastic deformability in the uncrosslinked state. By contrast, atactic polypropylene has a very low softening point by itself [see, for example, US Pat. B .: H.-G. Elias; Macromolecules; Vol. III; Wiley-VCH: Weinheim; 2001 ]. The in the WO 89/11513 The procedure described leads to an addition of these disadvantages, and to a very poor product performance. The adjustment of viscosity, melting behavior and tack of the adhesive composition is attributed to the use of longer-chain (≥3 bond atoms between Si atom and the polymer chain) silane monomers, which should lead to a "more open structure". The use of longer chain silane monomers is disadvantageous insofar as it leads to a weaker crosslinking due to a higher degree of polymerization of the network chains (ie the monomeric repeat units between two crosslinking points), which additionally has an adverse effect on the material properties of the graft polymer.

In the DE 195 16 457 describes a crosslinkable adhesive composition consisting of at least 50 m% of a silane-grafted polyolefin and additionally a carboxylic acid-grafted polyolefin. As the base polymers for the grafting, there are mentioned poly (ethylene-co-vinyl acetate), polypropylene, polyethylene, polyethylene-co-methacrylate) and poly (ethylene-co-methacrylic acid). Due to the base polymers used and the graft monomers used, the products described are not suitable for the desired fields of use.

In the EP 1 508 579 are described (silane) modified crystalline polyolefin waxes. The waxes used are prepared by metallocene catalysis and have a high propylene content. Due to their waxy properties and the resulting poor adhesive properties, the described polymers are not suitable for the intended fields of use. A plastic deformability below the softening point in the uncrosslinked state according to the present requirement conditions is not available.

In the WO 2007/001694 For example, adhesive compositions containing functionalized polymers (e.g., silane-grafted or maleic anhydride-grafted propylene polymers) are described. The base polymers are prepared with metallocene catalysts. The base polymers are made with metallocene catalysts and do not have the requisite material properties needed, for example, to achieve high rates of functionalization.

In the WO 2007/002177 describes adhesive compositions based on poly (propylene) -random copolymers and functionalized polyolefin copolymers and non-functionalized adhesive resins, wherein the poly (propylene) -random copolymers have a melting enthalpy of 0.5 to 70 J / g and a proportion of isotactic Propylentriaden of at least 75% (more preferably> 90%), and the functionalized (syndiotactic) polymers used have a content of functional monomer units of at least 0.1%. The described poly (propylene) random copolymers are preferably prepared by metallocene catalysis, the polydispersity being given on the one hand as 1.5 to 40, on the other hand as 1.8 to 5. The former range has an unusually wide range for metallocene-catalyzed polymers which indicate a multimodal molecular weight distribution and the simultaneous presence of several catalyst species. In the same direction, the indicated melting range of 25 to 105 ° C which has several melting peaks of different intensities, wherein the specified limit of 105 ° C has an unusually low value for polypropylene polymers, in particular for isotactic polypropylene polymers. The functionalized polyolefin copolymers include functionalized poly (propylene) random copolymers, syndiotactic polypropylene copolymers, and so-called isotactic atactic polypropylene graft polymers. As functional monomer units in particular maleic anhydride and glycidyl methacrylates but also various other functional groups such. As vinyl silanes called. Base polymers with low to moderate proportions of isotactic propylene segments are not described. Due to the sometimes very high proportion of isotactic polypropylene units (with strong radical polymer degradation), a poor ratio of grafting / functionalization to chain scission sets in. The mentioned upper limit for the melting range ensures a low heat resistance of the corresponding bonds. The described syndiotactic polypropylene polymers are also expensive and barely available on the market.

In the WO 2007008765 the use of low-viscosity silane-grafted polyethylene-co-1-olefin) polymers as adhesive raw material is described. The polymers which are used for the modification have an ethylene content of at least 50 mol% of ethylene and preferably a polydispersity of 1 to 3.5, the total range being given as 1 to 5. They show a low melt viscosity of at least 2,000 and a maximum of 50,000 cP at 177 ° C. As 1-olefin comonomers are many higher 1-Ole fin like B. 1-hexene and 1-octene but also some branched 1-olefins such. B. 3-methyl-1-pentene and various other monomers, such as. As dienes, styrene, etc., which do not meet the previous requirement "1-olefin", and thus lead to polymers with completely different material properties. Diene polymers, in particular, tend to crosslink and form gel particles when used in peroxidic processes. This is enhanced by the presence according to the invention of vinyl end groups in the base polymers. The silane-grafted polymers have very low failure temperatures of only> 43 ° C. (PAFT)) or> 60 ° C. (SAFT). The use of high ethylene content polyolefins inevitably implies the presence of long ethylene blocks in the polymer. This in turn leads to poor wetting and adhesion properties on many plastic surfaces, so that many bonding problems can not be solved optimally. The ungrafted base polymers have a relatively low molecular weight and melt viscosity of at most 50,000 cP at 177 ° C. Known manner, the molecular weight (and thus also the melt viscosity) degraded in a peroxidically induced grafting reaction by chain scission. Polymers according to the invention with high functionalization rates therefore inevitably have very low molecular weights / melt viscosities, and are unsuitable for many fields of application. As is known, the polydispersity of the polymers used is further reduced by peroxide-induced grafting reactions. Consequently, the modified polymers have a polydispersity of significantly less than 3.5, which leads to various disadvantages, especially in terms of processing properties. The use of relatively low molecular weight base polymers generally leads to rather low rates of functionalization. Also described are resin compositions containing already crosslinked poly (ethylene-co-1-olefin) polymers. Such compositions containing rubbery constituents are not suitable for optically demanding applications (poor surface structure) and, moreover, can not be processed on many application systems customary in the adhesive sector (eg melt spraying) (blockage of the application nozzles). The hot melt adhesives described as application mainly have low melt viscosities. Also described is the use of crystalline and partially crystalline poly (propylene-co-1-olefin) polymers, which should also be suitable for the grafting. These have a propylene content of at least 50 mol% and preferably also a melt viscosity of at most 50,000 cP at 177 ° C (before grafting and after grafting) and a polydispersity of 1 to 3.5. The crystallinity is specified with a maximum of 2 to 60% (ie 3 to 100 J / g) and is thus substantially in the range of high crystallinity. This in turn causes a poor wetting of, or a poor adhesion to Polyolefinoberflächen and excludes many fields of application.

In the EP 0 827 994 the use of silane-grafted amorphous polyalpha-olefins) is described as a moisture-crosslinking adhesive raw material or adhesive. Atactic polypropylene (aPP), atactic poly (1-butene) or preferably co- or terpolymers of C ₄ -C ₁₀ alpha-olefins (0 to 95 m%), propene (5 to 100 m%) are used as the base polymers. and ethylene (0 to 20mA%). The silane-modified APAO shown in the examples has a very low softening point of 98 ° C, a needle penetration of 15 x 0.1 mm and a melt viscosity of 6,000 mPa · s. The atactic polyolefins and low crystallinity APAOs used in the modification result in products which, when uncrosslinked, have a low softening temperature and therefore are unsuitable for many applications. A plastic deformability below the softening point in the uncrosslinked state is not given.

In terms of the solubility of polypropylene polymers in aromatic Solvents and ethers, there are numerous publications in the scientific literature.

The proportion of xylene-soluble constituents is isotactic poly (propylene) homopolymer, which was obtained by metallocene catalysis, usually significantly <1 ma-%, in random copolymers with ethylene xylene-soluble proportions of not more than 5 m% are found depending on the ethylene content ( W. Spaleck in: "Metallocenes Based Polyolefins"; J. Scheirs, W. Kaminsky (ed.); J. Wiley &Sons;Weinheim; 1999 ).

Since the solubility of polypropylene depends both on the molecular weight and on its crystallinity, appropriate fractionation can be carried out by solution experiments [ A. Lehtinen; Macromol. Chem. Phys .; 195 (1994); 1539ff ].

It has long been known that by extraction with ether amorphous atactic moieties [ J. Boor; "Ziegler-Natta Catalysts and Polymerization"; Academic Press; New York; 1979 ] and low molecular weight low crystallinity constituents [ G. Natta, I. Pasquon, A. Zambelli, G. Gatti; Makromol. Chem .; 70 (1964); 191ff ] obtained from polypropylene polymers. Highly crystalline isotactic polymers, on the other hand, have a very low solubility, both in aliphatic solvents and in ethers, even at elevated temperature [ BA Krentsel, YV Kissin, VI Kleiner, LL Stotskaya; "Polymers and Copolymers of higher 1-Ole fins "; P. 19/20; Hanser Publ .; Munich; 1997 ]. The soluble polymer components generally have no or only a very low crystallinity, and show no melting point YV Kissin; "Isospecific polymerization of olefins"; Springer Verlag; New York; 1985 ]. Tetrahydrofuran-soluble polypropylene oligomers have very low number-average molecular weights of significantly less than 1500 g / mol [ H. El Mansouri, N. Yagoubi, D. Scholler, A. Feigenbaum, D. Ferrier; J. Appl. Polym. Sci .; 71 (1999); 371ff ].

It Thus, there was a need for functionalized polyolefins, with improved material properties, especially on such polyolefins, in the uncrosslinked state a high softening point, good adhesive properties, especially on glass, wood, untreated polyethylene and untreated Polypropylene and (in the uncrosslinked state) a high plastic Have deformability below their softening point, and by a high degree of functionalization after crosslinking have a very good material cohesion (tensile strength). Surprisingly has been found that polyolefins according to the present Invention fulfill the complex requirement profile and thus particularly suitable for use in or as an adhesive.

Accordingly, a first aspect of the present invention are modified polyolefins based on at least one base polyolefin, which is preferably selected from polyethylene-co-propylene), poly (propylene-co-1-butene) and polyethylene-co-propylene-co-1 butene), with a propylene content determined by ¹³ C-NMR spectroscopy of between 50 and 90% by mass and with a content of isotactic poly (propylene) triads of at least 40% by mass, determined by ¹³ C-NMR spectroscopy not more than 80% by mass, based on the total of detected propylene triads, the base polyolefin having a solubility in xylene (ie the proportion of the polymer sample which dissolves in xylene in a standardized solution test) at room temperature of less than 96% by mass and a solubility in THF (ie the proportion of the polymer sample which dissolves in a standardized solution in tetrahydrofuran) at room temperature of at least 10 and up to 62% by mass, based on the base polyol efine (resp. the base polyolefin) one or more silanes are grafted. In a further embodiment, the modified polyolefins according to the invention can be based on mixtures of the abovementioned base polyolefins with crystalline or partially crystalline poly (propylene) polymers, that is, onto the abovementioned base polyolefins and the crystalline or partially crystalline poly (propylene) polymers, the one or more silanes are grafted ,

The according to the invention, specially selected Polyolefins are particularly suitable and preferred for the preparation of bonding and show there compared to the known ones Polymers decisive advantages. Thus, the polyolefins according to the present invention in the application both in the uncrosslinked as also in the networked state higher softening points and thus a higher heat resistance as well as below its softening point a plastic deformability in the uncrosslinked state. By a high grafting is after the networking achieved a high material cohesion, what for the first time a combination of plastic deformability in the cold uncrosslinked state and high cohesion value in the cold networked state allows. Due to the fact that the invention Polymers already in the uncrosslinked state a high softening temperature can be used in bonds that already immediately after physical hardening (cooling) withstand high thermal loads - d. H. a high one Heat level must have -. The height Functionalization also allows an improved Connection to functional surfaces (eg OH groups of glass, wood, etc.).

Essential for the positive properties of the polyolefins according to the invention is / are the special composition or the specific material properties of the base polymer used and / or the base polymer mixture used. This (S) contains between 50 and 90% by mass of propylene, preferably 52-85% by mass, particularly preferably 55 to 80% by mass, and particularly preferably 57-75% by mass, wherein the determined by ¹³ C NMR spectroscopy content of isotactic poly (propylene) triads at least 40mA%, preferably at least 50mA%, more preferably between 52 and 80mA% and most preferably between 53 and 75mA% based on the total detected propylene triads. The (also determined by ¹³ C NMR spectroscopy) total content of propylene triads in the novel base polymer (or the base polymer mixture) is at least 40% by mass, preferably at least 43% by mass, more preferably between 45 and 80 m% and in particular preferably between 47 and 78 m%, based on the detected propylene content of the polymer.

The use of a polymer mixture of one or more polyolefins according to the invention and / or other partially crystalline and / or crystalline propylene polymers is advantageous if, for performance reasons, a fine adjustment of certain material properties of the base polymer such. As the needle penetration is necessary, or special packaging forms (eg powder) are desired. For example, the needle penetration of the base polymer can be achieved by adding a crystalline Reduce polyolefin wax. In general, when polymer blends are used for modification, the crystalline polypropylene polymers are limited to a proportion of not more than 20% by mass, preferably not more than 18% by mass, more preferably not more than 16% by mass and especially preferably not more than 15% by mass Material properties of the unmodified and the modified polymer blend causally correlate with the material properties of the inventive used tecrystalline polypropylene polymer. Suitable blend components are generally all propylene-based polyolefins, all polyolefin waxes and all other polyolefin polymers which are macroscopically miscible with the partially crystalline unmodified polypropylene polymers (base polymers) according to the invention. An important feature of the base polymers according to the invention is that, regardless of whether a single polymer or a polymer mixture is used, the molecular weight distribution curve of the base polymer (s) determined by high-temperature gel permeation chromatography (ht-GPC) particularly preferably shows a monomodal course. This is particularly advantageous because it enables the production of products with defined melting and setting behavior.

By the proportion of isotactic according to the invention Polypropylene chain elements will have the high softening temperature both the base polymer and the uncrosslinked graft polymer achieved by the proportion of the invention Propylene trihydrate is used during the graft polymerization "in situ "a polymeric plasticizer is formed, which the plastic deformability of the invention Polymers or polymer blends also below the softening temperature in the uncrosslinked state. At the same time is over limiting the propylene content of a polymer available which is sufficiently resistant to β-Scission (chain cleavage after hydrogen abstraction) is, and so to a graft polymer having sufficient molecular weight and high Pfropfraten leads.

Of the Content of comonomer results for the inventive Polymers as 100% by mass minus propylene content, with both a also two comonomers can be used. Preferably contain the polymers of the invention as olefin monomers In addition to propylene and ethylene and / or 1-butene.

In a particularly preferred embodiment is the base polymer is a poly (ethylene-co-propylene) having a Ethylene content of at least 10mA%, preferably of at least 12mA%, more preferably from 14 to 20% by mass and especially preferred from 15 to 19 ma-%. This monomer combination has the advantage that on the ethylene content, the material properties of used base polymer particularly good control, there already low ethylene content leads to an effective disturbance of the Cause crystallinity of the propylene chain elements, which is the production of base polymers with greater flexibility allows.

In a further, particularly preferred embodiment it is in the base polymer to a poly (propylene-co-1-butene) with a 1-butene content of at least 15mA% preferably of at least 17 m%, more preferably from 17 to 50% by mass, and especially preferred from 18 to 40 ma-%. This monomer combination has the advantage that over the 1-butene content of the base polymer used is a very effective Control of the low temperature properties of the modified polymer can be done, in particular, are deep glass transition temperatures to realize only by a specific 1-butene content. Come in addition, that also other material properties such. B. the elongation at break in the uncrosslinked state is positively influenced by the comonomer 1-butene can be. In a particular preferred embodiment For example, the base polymer is a poly (ethylene-co-propylene-co-1-butene) terpolymer.

In Another particularly preferred embodiment the base polymer is a poly (ethylene-co-propylene-co-1-butene) with a combined content of ethylene and 1-butene of at least 10% by mass, preferably at least 12% by mass, more preferably between 15 and 50 m%, and more preferably between 17 and 45 m%, wherein further particularly preferred embodiments combined Content of ethylene and 1-butene of 22 to 37 m% and 37 to 43, respectively ma-%. The used unmodified (ungrafted) Base polymers or their mixtures with semicrystalline and / or crystalline propylene polymers are characterized in that their Solubility in xylene (i.e., the proportion of the polymer sample, which in a standardized solution in xylene soluble) at room temperature at less than 96mA%, preferably at a maximum of 95.5% by mass, more preferably at maximum 95% by mass, and more preferably at a maximum of 94.5% by mass. This has the advantage that the inventive Polymers or polymer blends a balance from crystalline, semi-crystalline and non-crystalline polymer fractions containing the special material properties of the invention allow modified polymer first.

The used unmodified (ungrafted) base polymers or their mixtures with teilkristal Linen and / or crystalline propylene polymers are characterized in that their solubility in tetrahydrofuran (THF) (ie the proportion of the polymer sample which is soluble in a standardized solution in tetrahydrofuran) at room temperature at least 10% by mass, preferably at least 11 ma %, more preferably between 12 and 62% by mass, and particularly preferably between 13 and 60% by mass, with further particular embodiments having a THF-soluble polymer content of between 10 and 18% by mass and between 22 and 38% by mass. % exhibit. This has the advantage that the polymers or polymer mixtures according to the invention contain a sufficient amount of atactic polymer fractions as well as polymer molecules of low to medium chain length, which is important for the flexibility of the modified polymer according to the invention and its adhesion to many polymer substrates.

The drawing unmodified (ungrafted) base polymers characterized by the fact that their by Oszillationsrheometrie in a Shear rate of 1 Hz and a maximum deformation 1% certain melt viscosity at 190 ° C 50,000 to 3,000,000 mPa.s, preferably 75,000 to 1,500,000 mPa.s, particularly preferably 90,000 to 1,000,000 mPa · s, and in particular preferably 100,000 to 750,000 mPa · s, wherein furthermore the ranges of 100,000 to 200,000 mPa · s, from 175,000 to 290,000 mPa · s, from 300,000 to 450,000 mPa · s and from 400,000 to 720,000 mPa · s in particular are preferred.

Of the Softening point of unmodified (ungrafted) base polymers, measured by ring & ball method, is 140 to 170 ° C, preferably 143 to 168 ° C, more preferably 145 to 166 ° C and especially preferred from 148 to 165 ° C.

The Needle penetration of unmodified (ungrafted) base polymers is at least 10 x 0.1 mm, preferably at least 13 x 0.1 mm, more preferably between 13 and 35 x 0.1 mm and more preferably between 14 and 33 x 0.1 mm, further, the ranges of 15 to 19 x 0.1 mm, of 17 to 25 x 0.1 mm and 21 to 35 x 0.1 mm in particular are preferred.

The glass transition temperature, determined by DSC, of the unmodified (ungrafted) base polymers is at most -20.degree. C., preferably at most -23.degree. C., particularly preferably at most -25.degree. C. and particularly preferably less than -30.degree. Accordingly, the polymers according to the invention are also suitable for use at very low temperatures and have, in particular, good low-temperature flexibility, what they can, for. B. of corresponding polymers with high to very high propylene content (T _g > -10 ° C) differs.

In the above-mentioned base polymers or mixtures of the novel base polymers and other partially crystalline or crystalline propylene polymers, one or more silanes are grafted in the polyolefins according to the invention. The grafted silane 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. Through the use of different silane monomers, the material properties of the modified polyolefins according to the invention can be adapted exactly to the respective requirements of the present application. So can be z. For example, the rate of crosslinking and compatibility with other polymers (such as formulation ingredients) may vary.

The polymers modified with the silanes have special properties which, when used, lead to the abovementioned advantages. Thus, the melt viscosity of the modified (grafted) polyolefin according to the invention or the inventively modified polyolefin mixture in the uncrosslinked state, determined with Oszillationsrheometrie at 1 Hz and a maximum deformation of 1% at 190 ° C 1 000 to 50 000 mPa · s, preferably 2,000 to 45,000 mPa.s, more preferably 2,500 to 40,000 mPa.s, and particularly preferably 3,000 to 30,000 mPa.s. Modified polyolefins are thus made available which, owing to their variable melt viscosity in the uncrosslinked state, are suitable for a very wide variety of application methods and accordingly can also be used in a very wide variety of applications (eg hotmelt adhesives, sealants, molding compounds, primers, etc.) , The softening point of the uncrosslinked modified (grafted) polyolefin of the invention, as measured by ring & ball method, is 140-170 ° C, preferably 145-168 ° C, more preferably 147-166 ° C and most preferably 150-165 ° C. Thus, modified polyolefins are provided which have a high softening point in comparison with the previously known modified polymers, and thus lead to a high heat resistance of a bond produced using the modified polyolefins according to the invention even in the uncrosslinked state. The needle penetration of the un crosslinked modified polyolefin according to the invention is at least 18 x 0.1 mm, preferably at least 20 x 0.1 mm, more preferably between 22 and 40 x 0.1 mm and particularly preferably between 24 and 38 x 0.1 mm. Thus, modified polyolefins are provided which, in the uncrosslinked state, provide the material-side prerequisites for plastic deformation. The tensile strength of the modified polyolefins according to the invention is (without further additives) in the uncrosslinked state at a maximum of 2 MPa, preferably not more than 1.9 MPa, more preferably not more than 1.8 MPa and particularly preferably between 0.5 and 1.75 MPa. This ensures, in particular, a basic cohesion as well as the plastic deformability in the uncrosslinked state. The tensile elongation at break of the modified polyolefins according to the invention is (without further additives) in the uncrosslinked state at least 75%, and preferably at most 600%, preferably at most 575%, more preferably at most 550% and particularly preferably between 75 and 525 %. As a result, modified polyolefins are provided which have a sufficient degree of flexibility, but at the same time dominate the plastic material properties in the uncrosslinked state.

Without further additives and after a storage period of the standard test specimens 40 days in a climatic chamber at 20 ° C and 65% relative Humidity is the tensile strength of the invention modified polyolefins in the crosslinked state by at least 50% higher than in the uncrosslinked state, preferably at least 100%, more preferably at least 125% and especially preferred by at least 150%, whereby as tensile strength a value of at least 1.75 MPa, preferably of at least 2.0 MPa, more preferably of at least 2.25 MPa, and more preferably at least 2.35 MPa is achieved. In a further particularly preferred embodiment is the tensile strength of the invention modified polyolefins (without further additives) in the crosslinked Condition after a storage period of the standard test specimen 40 days in a climatic chamber at 20 ° C and 65% relative Humidity at least 3.5 MPa. It will thus be modified Polyolefins provided by virtue of their specific material characteristics (such as a very high Grafting degree) in the uncrosslinked state also below its softening point plastically deformable, and at the same time by networking the curing reactive groups to compounds with very high strength can. Without further additives and after a storage period 40 days in a climatic chamber at 20 ° C and 65% relative Humidity is the tensile strain determined in the tensile test the modified polyolefins according to the invention (Standard test specimen) in the crosslinked state at maximum 700%, preferably at most 600%, more preferably between 75 and 550%, and more preferably between 100 and 500%, wherein other particularly preferred ranges between 125 and 325%, between 330 and 400% and between 410 and 490%. The invention Polymers thus have, despite the occurring during storage networking and the associated increase in material cohesion (see tensile strength) also after crosslinking a high flexibility on. A special feature of the polymers according to the invention is that the elongation at break depends on the polymer composition of the semicrystalline used according to the invention Polyolefins or depending on the used grafting monomer with increasing Networking can both increase and decrease, so here is one individual adaptation to the technical application conditions is possible. The modified invention Polyolefins have (after complete separation of unreacted residual monomer) one by RFA spectroscopy (X-ray fluorescence spectroscopy) certain silicon content of at least 0.3 m%, preferably from at least 0.35mA%, more preferably at least 0.4mA% and more preferably from 0.45 to 2mA%, with others particularly preferred ranges between 0.4 and 0.85 m%, between 0.7 and 1.25mA%, between 0.95 and 1.55mA% and between 1.35 and 1.85mA%.

polyolefins with the mentioned preferred properties are suitable throughout special way for bonding, especially for use as or in hot melt adhesives and show advantageous properties over known systems. This is especially true for their excellent adhesion on untreated polyolefins, especially on untreated polypropylene and paper / cardboard, wood, glass and or metals, in particular aluminum.

Another object of the present invention are methods for preparing a modified polyolefin according to the invention, wherein at least one base polyolefin having a determined by ¹³ C-NMR spectroscopy content of propylene of at least 50% by mass and not more than 90% by mass and with a by ¹³ C -NMR spectroscopy determined content of isotactic poly (propylene) triads of at least 40% by mass and not more than 80% by mass, based on the total detected propylene triads and a solubility in xylene (ie the proportion of the polymer sample, which in a standardized solution in Xylene is soluble) at room temperature of less than 96% by mass and in THF (ie the proportion of the polymer sample which is soluble in a standardized solution in tetrahydrofuran) at room temperature of at least 10% by mass and at most 62% by mass, with at least a radical initiator and one or more silanes is brought into contact, whereupon a grafting reaction of the one or more n silanes on the at least one base polyo In order to prepare the alternative embodiment comprising mixtures of the at least one above-mentioned base polyolefins with crystalline or partially crystalline poly (propylene) polymers, the said mixtures are used in the same way as the same.

The Preparation of the base polymer according to the invention is carried out by polymerization of the monomers mentioned in the above Amounts.

The polymers of the invention are obtainable for example by polymerization of propylene optionally with ethylene and / or 1-butene with a TiCl ₃ • (AlCl _{3) n} -Mischkatalysator (n = 0.2 to 0.5), wherein a trialkylaluminum compound is used as cocatalyst , The monomer ethene is used in gaseous form, while the monomers propene and 1-butene can be used both gaseous and liquid. As a molecular weight regulator, for example, gaseous hydrogen can be used. The polymerization is preferably carried out in an inert solvent, which z. B. is selected from the group of aliphatic hydrocarbons. Polymerization in the initially charged monomer is also possible. The polymerization is carried out either in a stirred tank or in a stirred tank cascade. The polymers according to the invention can be chemically stabilized according to the prior art, either in the form of their reaction solution or at a later time to protect them from the damaging influence z. B. of sunlight, humidity and oxygen to protect. Stabilizers which contain hindered amines (HALS stabilizers), hindered phenols, phosphites and / or aromatic amines (such as eg tetrakis (methylene- (3,5-di-tert-butyl-4-hydroxy) hydrocinnamate) and / or 2 , 4,8,10-tetraoxa-3,9-diphosphaspiro-3,9.bis (octadecyloxy) [5,5] undecane) are used. Particular preference is given to using those stabilizers which contain only one hydrolytically active end group. The effective amount of stabilizers is in the range of 0.1 to 2 wt .-%, based on the polymer.

suitable Silanes for grafting are in advance in the description of olefins called, preferably are those from the group comprising Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, Vinyldimethylethoxysilane and / or vinylmethyldibutoxysilane, in particular Vinyltrimethoxysilane. The silane becomes common in grafting in amounts of from 0.1 to 20% by weight, preferably 0.5 to 17% by weight, more preferably from 0.75 to 15% by weight and especially preferred from 1 to 14 wt .-%, based on the base polymer used, wherein further particularly preferred ranges between 0.75 and 3.5% by weight, between 3.0 and 8.5% by weight, between 7.5 and 10.75% by weight and between 10.0 and 13.75 wt .-% are.

The one or more silanes can be grafted onto the base polymer by any of the methods of the prior art, for example in solution or preferably in the melt, wherein one or more radical donors are used 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). The grafting takes place in particular at a temperature of 30 to 250 ° C.

In a particular embodiment is a Solution process, wherein aliphatic and / or aromatic Hydrocarbons and cyclic ethers as solvents can be used. Particularly preferred is as Solvent at least one aromatic hydrocarbon used. Suitable aromatic hydrocarbons are in particular Trichlorobenzene, dichlorobenzene, toluene and xylene, particularly preferred xylene is used. Particularly preferred aliphatic hydrocarbons For example, propane, n-butane, hexane, heptane, cyclohexane and Octane. Particularly preferred cyclic ether is tetrahydrofuran (THF).

Become Ether, especially cyclic ethers used as solvent, so must the initiator used and the reaction conditions be selected with special care to the education of explosive peroxides of the ethers used to prevent or to control. In particular, the additional use special inhibitors (eg IONOL).

In the case of a grafting process in solution, the concentration of the base polymer used is at least 10mA%, preferably at least 15mA%, more preferably at least 20mA% and most preferably at least 22.5mA%. The reaction temperature of the grafting process in solution is at 30 to 200 ° C, preferably at 40 to 190 ° C, more preferably at 50 to 180 ° C and particularly preferably at 55 to 140 ° C. The solution grafting is carried out either batchwise or continuously. In the case of a discontinuous reaction procedure, the solid polymer (eg as granules, powder, etc.) is first dissolved in the solvent used. Alternatively, a conditioned polymerization solution from the preparation process of the base polymer is used directly and brought to the reaction temperature. This is followed by the addition of the monomer (s) and radical initiator (s). In a particularly preferred embodiment, solvent base polymers (e) and monomer (s) are initially charged and brought to the reaction temperature while the radical initiator (s) are continuously metered in over a defined period of time. This has the advantage that the steady-state radical concentration is low and therefore the ratio of grafting reaction to chain scission is particularly favorable (ie more grafting reaction and less chain scission). In a further particularly preferred embodiment, solvent and base polymer (s) are initially charged and brought to reaction temperature, while monomer (s) and free radical initiator are metered in continuously (for example in the form of a mixture) or separated over a defined period of time. This has the advantage that both the stationary radical concentration and the monomer concentration at the reaction site are low, which suppresses both the chain scission and the formation of homopolymers. This is particularly important when using monomers that are highly prone to thermally initiated (homo) polymerization at the reaction temperature. Very particular preference is given to adding a further amount of radical initiator (s) after the different defined addition periods in order to minimize the content of residual monomers in the reaction solution. As a reactor, a stirred tank is preferably used, the use of alternative reaction vessel is also possible. In the case of a continuous reaction, the solid polymer is first dissolved in at least one solvent in one or more feed tanks (eg stirred tanks) and then metered continuously into the reaction tank (s). In an alternative, also particularly preferred embodiment, a conditioned polymer solution from a preparation process of the base polymer is used directly. In a further likewise particularly preferred embodiment, the solid polymer (for example in the form of powder, granules, pellets, etc.) is metered continuously together with at least one solvent into a (single- or multi-shaft) screw machine or a Kontikneter, under the action of Temperature and shear dissolved, and then metered continuously into the / the reaction vessel. Suitable reaction vessels or reactors for carrying out the continuous grafting reaction in solution are continuous stirred tanks, stirred tank cascades, flow tubes, forced flow flow tubes (eg screw machines), reaction kneaders and any desired combinations thereof. If flow tubes with forced delivery are used, they are preferably extruders, with one-, two- as well as multi-shaft extruders being used. Two- and / or more-shaft extruders are particularly preferably used. Particularly preferred for the continuous preparation of the modified polymers according to the invention in solution is the use of a reactor combination of flow tube, flow tube with forced delivery and continuous stirred tank in any order, preferably either in the flow tube with forced delivery or in the continuous stirred tank and the removal of residual monomers and volatile Neben- / Degradation products takes place. Alternatively, it is preferably a melt process, wherein at least one free radical initiator is metered directly into the melt. In particular, in this process variant, the temperature of the polymer composition at the time of addition of at least one radical initiator above the SADT (Self accelerating decomposition temperature = temperature above a self-accelerating decomposition can use) at least one of the added radical initiator. The reaction temperature of the grafting process in the melt is 160 to 250 ° C, preferably 165 to 240 ° C, more preferably 168 to 235 ° C and most preferably 170 to 230 ° C.

The Melt-grafting takes place either in discontinuous or in continuous driving style. In the case of a discontinuous reaction For example, the solid polymer (eg, as granules, powders, pellets, etc.) is first melted and optionally homogenized. Alternatively it will directly a conditioned polymer melt from a polymerization process used and brought to reaction temperature. It follows the addition of monomers and radical initiators.

In In a particular embodiment, monomer (s) and Polymer melt homogeneously mixed and to reaction temperature brought while the radical starter over be dosed continuously over a defined period of time. This has the advantage that the stationary radical concentration is low, and therefore the ratio of grafting reaction to chain scission particularly favorable (i.e., more grafting reaction and less chain scission) precipitates.

In a further particularly preferred embodiment, the polymer melt is introduced and homogenized, while monomer (e) and free-radical initiator are metered in together (for example in the form of a mixture) or separately over a defined period of time. This has the advantage that both the stationary radical concentration, as well as the monomer concentration remains low at the reaction site, which suppresses both the chain scission and the formation of homopolymer. The latter is particularly important in the use of monomers which tend to thermal (homo) polymerization at the present reaction temperature. The reactor used is preferably a stirred tank with stirring agitator or a reaction kneader.

in the Case of continuous reaction is first in one or more storage containers (eg stirred kettles) the solid polymer is melted and then continuously dosed into the reaction vessel (s). In an alternative, also particularly preferred embodiment, is direct a conditioned polymer melt from a polymerization process used. In a further likewise particularly preferred embodiment becomes the solid polymer (eg in the form of powder, granules, pellets etc.) continuously in a (single or multi-shaft) screw machine or a Kontikneter dosed, under the action of temperature and shear melted, and then continuously dosed into the reaction vessel (s). As a reaction vessel or reactors for the implementation of continuous Grafting reaction in the melt are continuous stirred tank, Stirred tank cascades, flow tubes, flow tubes with forced conveying (eg screw machines), reaction kneader as well as their enclosed combinations in question. Be flow pipes used with forced promotion, that's how it is preferably extruders, with one-, two- as well as multi-well Extruders are used. Particularly preferred are two and / or multi-shaft extruder used. Especially preferred for continuous Preparation of the modified invention Polymers in the melt is the use of a reactor combination from flow tube, flow tube with forced delivery and continuous stirred tank in any order, preferably either in the flow tube with forced delivery or in the continuous stirred tank also the distance of residual monomers and volatile by-products / degradation products he follows.

The Modified polymers according to the invention are suitable in the networked or uncrosslinked state for use in or as molding compounds, protective compounds, adhesives, sealants, Marking compounds, coating compounds, geomembranes or roofing membranes, Primers, primer formulations, primer formulations, dispersions, Suspensions and / or emulsions. Accordingly, the use the modified polyolefins according to the invention in the stated fields of application and corresponding molding compounds, protective compounds, Adhesives, sealants, marking compounds, coating compounds, Geomembranes or roof membranes, primers or primer formulations, Adhesion promoter formulations, dispersions, suspensions and / or Emulsions containing the polyolefins according to the invention also the subject of the present invention.

The Polyolefins according to the invention are particularly suitable Way of use as and / or in molding compounds. About that In addition, the molding compositions may contain other ingredients. The other ingredients may in particular other polymers include, wherein these other polymers to a or several ethylene polymers, and / or isotactic propylene polymers and / or syndiotactic propylene polymers and / or isotactic Poly-1-butene polymers and / or syndiotactic poly-1-butene polymers can act. Preferably, these are molding compositions which except at least one invention Polymer another modified and / or unmodified polyolefin, in particular polypropylene and / or fillers and / or Reinforcement materials such. B. contain glass fibers.

The Modified polyolefins according to the invention are suitable especially for use as and / or in protective materials. Preferably, these are protective compounds except at least one polymer of the invention another modified and / or unmodified polyolefin, in particular Polypropylene and / or fillers and / or reinforcing materials such as B. contain glass fibers. In particular, it is with the protective compositions according to the invention are those which are used in the automotive sector. Very particularly preferred are underbody protection compounds (PVC plastisol replacement).

The Modified polyolefins according to the invention are suitable especially for use as and / or in adhesives.

To adjust the necessary adhesive properties for the adhesive user, initial adhesion, crosslinking rate, crosslinking density, viscosity, hardness, elasticity, temperature and oxidation stability, etc., further substances can be added to the polyolefins according to the invention, which are usually used to adjust the desired adhesive properties. Of course, care must be taken to ensure that the water contained in the aggregates the rate of crosslinking of he can increase adhesive according to the invention. It is particularly characteristic of the present invention that via the silane groups of the polymers according to the invention, a reactive attachment to the additives used can take place. In particular, fillers and / or reinforcing materials (eg fibers) used are reactively bound to the polymer matrix by the silane groups present in the polymers according to the invention, which leads to particularly advantageous material properties, in particular a high material cohesion (tensile strength) and a very high tear resistance in fiber reinforcements ,

One another essential characteristic of the invention modified polyolefins is that in addition to fillers, too a chemical connection of the adhesive / adhesive component the surfaces to be bonded can take place. this leads to to a particularly good adhesion and adhesion to surfaces that over corresponding reactive groups (eg -OH). Next The reactive bond is still a particularly high bond strength to achieve surfaces that have a similar Surface polarity as the invention modified polyolefins (eg poly (1-butene), Polypropylene, polyethylene, etc.).

In the adhesive formulations according to the invention can in addition to the modified invention Polyolefins contain other ingredients. At the others Ingredients may be especially in solution formulations cyclic and / or linear aliphatic and / or aromatic Hydrocarbons with or without heteroatoms act, including corresponding halogenated hydrocarbons. Preferably, but none halogenated hydrocarbons used. In the liquid at room temperature Adhesive formulations have the hydrocarbons mentioned Formulation proportion of not more than 90% by mass, preferably not more than 80% by mass, more preferably at most 75mA%, and especially preferred of max. 50 ma-%.

All it is particularly preferable for the inventive Adhesive formulation around a hot melt adhesive formulation, for all known to the expert types of bonds can be used.

The Hot melt adhesive formulation according to the invention may contain other ingredients necessary to achieve special Properties such. B. deformability, adhesion, Processability, cure speed, crosslink density, (Melt or solution) viscosity, strength, Crystallization rate, tackiness, storage stability etc. are necessary. The proportion of other components is in a particular embodiment of the present invention particularly preferably at a maximum of 10 ma-%. This has the advantage that the material properties of the adhesive formulation substantially that of the polymer of the invention used are. Such an adhesive formulation can be combined with produce very little effort.

alternative may in a further embodiment of the present Invention, the proportion of other ingredients> 10 ma-% amount. In this case do the other ingredients maximum 80% by mass of the total formulation, preferably not more than 60% by mass, more preferably not more than 50% by mass, in particular preferably not more than 40% by mass.

at the other components may be crosslinking accelerators, in particular to silanol condensation catalysts to inorganic and / or organic fillers, optionally electric may be conductive or insulating, inorganic and / or organic pigments which are optionally electrically conductive or may be insulating, synthetic and / or natural Resins, in particular adhesive resins, synthetic and / or natural oils, inorganic and / or organic, synthetic and / or natural Polymers that are either electrically conductive or insulating may be inorganic and / or organic, synthetic and / or natural fibers which are optionally electrically conductive or may be insulating, inorganic and / or organic Stabilizers and / or inorganic and / or organic flame retardants act.

In particular, the other constituents comprise resins, the resins being used to adapt certain properties of the adhesive layer, in particular the tackiness and / or adhesion, the flow and creep behavior of the adhesive layer and / or the adhesive viscosity, to particular requirements. These may be natural resins and / or synthetic resins. In the case of natural resins, these natural resins contain abietic acid as the main component (eg rosin). Furthermore, the resins may be terpene or polyterpene resins, petroleum resins and / or kumarone-indene resins, in particular so-called C ₅ resins and / or C ₉ resins and / or copolymers of C ₅ - / C ₉ resins acts. The proportion of the resins in the hot melt adhesive formulation according to the invention is in particular at most 45% by mass, preferably between 1 and 40% by mass, more preferably between 2 and 30% by mass, and in particular Preferably, between 3 and 20 ma-%, based on the total formulation.

Farther can in the hot melt adhesive formulations of the invention classic amorphous (or semi-crystalline) poly (α-olefins) (so-called APAOs) may be included as further constituents. In the mentioned amorphous (or semi-crystalline) poly (α-olefins) can it is homo- / co- and / or terpolymers of ethylene, propylene, 1-butene or linear and / or branched 1-olefins having 5-20 carbon atoms act, which z. B. by classical Ziegler-Natta catalysis or Metallocene catalysis are available. The proportion of amorphous Poly (α-olefins) is in particular at most 50% by mass preferably at a maximum of 40% by mass and more preferably at maximum 30% by mass, based on the total formulation. Preferably it is the other ingredients to crystalline or partially crystalline polyolefins, in particular isotactic polypropylene, syndiotactic polypropylene, polyethylene (HOPE, LDPE and / or LLDPE), isotactic poly (1-butene), syndiotactic poly (1-butene) their copolymers and / or their copolymers with linear and / or branched 1-olefins having 5 to 10 carbon atoms. Furthermore is preferred that it is the crystalline or semi-crystalline Polyolefins are chemically modified polyolefins, wherein the chemical modification, especially of maleic anhydride, Itaconic anhydride, acrylic acid, acrylates, methacrylates, unsaturated epoxy compounds, silane acrylates, silanes and Hydroxyalkylsilane includes.

Farther the other constituents can be polymers with polar groups include. Polymers with polar groups include polystyrene copolymers (eg with maleic anhydride, acrylonitrile, etc.), polyacrylates, Polymethacrylates, (co) polyesters, polyurethanes, (co) polyamides, polyether ketones, Polyacrylic acid, polycarbonates and chemically modified Polyolefins (such as poly (propylene-graft-maleic anhydride) or poly (propylene-graft-alkoxyvinylsilane). It can be at the Mixing of the polymers of the invention with the polar group-containing polymers to an immediate and / or delayed reactive bonding of the polymer chains, which preferably leads to an improved compatibility occurs between the two polymer phases, which is for example in a shift in the glass transition temperatures of the used Polymers can be seen. Particularly preferably the leads reactive binding to the polymer phases a common Glass transition temperature show, so a macroscopic Have miscibility.

Farther the other constituents can be homopolymers and / or copolymers (or oligomers) based on ethylene, propylene, acrylonitrile, a diene and / or a cyclic diene, butadiene, styrene and / or isoprene in particular, these polymers are block copolymers, especially to rubbers such. Example, natural and synthetic rubber, Poly (butadiene), poly (isoprene), styrene-butadiene rubber, styrene-isoprene rubber and nitrile rubber. The proportion of polymers based on butadiene, Styrene, and / or isoprene is at most 20% by mass, preferably 1 to 15% by mass, more preferably 1.5 to 10% by mass, and especially 2 to 9% by mass, based on the hot melt adhesive formulations. Oligomers are preferably butadiene oligomers.

Farther For example, the other ingredients may include elastomeric polymers Based on ethylene, propylene, a diene and / or cis, cis-1,5-cyclooctadiene, exo-dicyclopentadiene, endo-dicyclopentadiene, 1,4-hexadiene and 5-ethylidene-2-norbornene include, in particular, this is ethylene-propylene rubber, EPM (double bond free, ethylene content 40 to 75 m%) and / or EPDM. The proportion of polymers based on ethylene, propylene, a diene and / or cis, cis-1,5-cyclohexadiene, exo-dicyclopentadiene, endo-dicyclopentadiene, 1,4-hexadiene and 5-ethylidene-2-norbornene is usually not more than 20% by mass, preferably 1 to 15% by mass, more preferably 1.5 to 10% by mass, and especially 2 to 9% by mass, based on the hot melt adhesive formulations.

alternative For example, the other ingredients may include waxes, in particular modified and unmodified waxes, these being preferably crystalline, semi-crystalline and / or amorphous polyolefin waxes based on polyethylene, polypropylene and / or poly (1-butene), Paraffin waxes, metallocene waxes, microwaxes, polyamide waxes, polytetrafluoroethylene waxes and / or Fischer-Tropsch waxes. The proportion of waxes is not more than 50% by mass, preferably from 1 to 40% by mass, more preferably from 2 to 30% by mass, and particularly preferably 3 to 20% by mass, based on the Hot melt adhesive formulations.

Furthermore, the further constituents may include fillers, wherein the fillers are used to specific property profiles of the adhesive layer, such. As the temperature application range, the strength, the shrinkage, the electrical conductivity, the magnetism and / or the thermal conductivity specifically adapted to specific requirements. In general, the fillers are inorganic and / or organic fillers. The inorganic fillers are in particular selected from silicic acids (including hydrophobized silicic acids), quartz flour, chalks, titanium dioxide, zinc oxide, zirconium oxide (the latter three preferably in the form of nanoscale particles), barite, glass particles (in particular spherical particles to increase the light reflection), glass fibers, carbon fibers , Asbestos particles, asbestos fibers and / or metal powders. Organic fillers are, for example, carbon black, bitumen, crosslinked polyethylene, crosslinked rubber or rubber mixtures, synthetic fibers such. As polyethylene fibers, polypropylene fibers, polyester fibers, polyamide fibers, aramid fibers, saran fibers, MP fibers or natural fibers such as straw, wood, wool, cotton, silk, flax, hemp, jute, and / or sisal. The proportion of fillers is at most 80% by mass, preferably 1 to 60% by mass, more preferably 5 to 40% by mass, and particularly preferably 7 to 30% by mass, based on the hot-melt adhesive formulations.

Also the other ingredients can be crosslinking accelerators include. This is particularly preferred when the inventive Polymers are used in a bonding process in a short time after the addition to reach their maximum capacity. As crosslinking accelerators are a variety of chemical Compounds, in particular Brönstedt and / or Lewis acids such as Acetic acid, itaconic acid, zinc (II) acetate, Cadmium acetate, zinc oxide, zinc stearate, zinc (II) chloride, tin (IV) chloride, Dibutyltin oxide, dibutyltin dilaurate, bismuth citrate, bismuth (III) oxide, Bismuth titanate, tetrabutylgermanium, tetrabutyltin, titanium boride, Titanium (IV) oxide, titanium acetylacetonate, tributyl titanate, sodium chloride, Magnesium (II) chloride, zinc acetylacetonate, zinc methacrylate, zinc niobate, Tin (II) oxide, tin (IV) oxide, zirconium (IV) acetylacetonate, zirconium (IV) oxide and / or zirconium (IV) silicate.

Also the other constituents may comprise stabilizers, these are used to prepare the adhesive formulation external influences such. The influence of (processing) heat, shear stress, Sunlight, humidity and oxygen to protect. Suitable stabilizers are, for example, hindered amines (HALS stabilizers), hindered phenols, phosphites and / or aromatic amines, as they are z. Under the product names IRGANOX, KINOX, DOVERNOX, WESTON, IRGAPHOS, DOVERPHOS and / or IONOL are commercially available. Especially preferably contain the inventively used Stabilizers only one hydrolytically active group per molecule. In the formulations mentioned, the proportion of Stabilizers not more than 3% by mass, preferably between 0.05 and 2.5% by mass and more preferably between 0.1 and 2 m%, based on the Hot melt adhesive formulations. In a special Embodiment takes place a reactive connection of the / Stabilizers / stabilizers modified according to the invention Polymer, causing a stabilizer migration from the adhesive bond is prevented.

About that In addition, the other ingredients may include one or more oils include, which are natural and / or synthetic oils can act. These one or more oils preferably at the processing temperature, a viscosity of 0.1 to 1 000 mPa · s, preferably from 1 to 750 mPa · s, most preferably from 2 to 500 mPa · s. Suitable oils are, for example, mineral oils, (medicinal) white oils, Isobutene oils, butadiene oils, hydrogenated butadiene oils and / or paraffin oils. The proportion of one or more oils is at most 50% by mass, preferably 1 to 45% by mass, especially preferably 3 to 40% by mass and in particular 5 to 38% by mass on the hot melt adhesive formulations.

Farther can in the hot melt adhesive formulations inorganic and / or organic pigments, UV-active substances, organic and / or inorganic nucleating agents that promote the crystallization of Polymer accelerate and thus the open time of bonding reduce, be included.

In a further preferred form of the invention Hot melt adhesive formulations are the formulations described above to multiphase blends.

One Another object of the present invention are adhesions containing one or more modified polyolefins of the present invention Invention. In particular, the bonds are packaging bonds, Bonding of hygiene articles, wood bonds, adhesions and / or sealing glass surfaces, label bonds Laminating bonds, carpet or artificial turf bonding, Shoe gluing, pressure sensitive gluing, book gluing or textile adhesives.

Particularly characteristic of the present invention is that when using the modified polyolefins according to the invention for bonding to or from Polyolefin surfaces and / or glass surfaces on an energetic and / or chemical pretreatment of Polyolefinoberflächen and / or glass surfaces, eg. By flame treatment, plasma treatment, corona treatment, sulfonation, etching, priming contract, etc., and yet a very good adhesion is achieved on these surfaces.

In the case of packaging bonds, the packaging materials may include the materials wood, cardboard, paper, plastic, metal, ceramics, glass, synthetic and / or natural fibers and / or textiles. The packaging materials are preferably non-polar plastics, in particular polyethylene, polypropylene, poly (1-butene) or their copolymers with linear and / or branched C _2-20 1-olefins, for example uncrosslinked polyethylene such as. As LDPE, LLDPE and / or HDPE, and / or to (eg silane) crosslinked polyolefin, in particular silane-crosslinked polyethylene. Furthermore, it may be in the non-polar plastics in particular polystyrene, polybutadiene, polyisoprene homo- and / or copolymers, and / or their copolymers with linear and / or branched C _2-20 1-olefins or dienes, such as. As EPDM, EPM or EPR, and / or synthetic or natural rubber.

The modified polymers according to the invention are characterized in that they (without further additives) after a storage period of at least 14 days in a climate-controlled cabinet in a pure polypropylene (material: untreated isotactic polypropylene) a Klebscherfestigkeit of at least 0.75 N / mm ² , preferably from at least 1 N / mm ^2, and more preferably at least 1.25 N / mm ² . After a storage period of 42 days, (without further additives) adhesive shear strengths on untreated polypropylene of at least 1 N / mm ² , preferably at least 1.25 N / mm ² , more preferably at least 1.5 N / mm ^2, and particularly preferably at least Reached 1.75 N / mm ² .

in the Traps of polar plastics are in particular polyacrylates, in particular polyalkyl methacrylates, to polyvinyl acetate to polyester and / or copolyesters, in particular polyethylene terephthalate and / or Polybutylene terephthalate to polyamides and / or (co) polyamides to Acrylonitrile copolymers, in particular acyl nitrile / butadiene / styrene copolymers and / or styrene / acrylonitrile copolymers to form maleic anhydride copolymers, in particular, S / MSA copolymers and / or MSA-grafted polyolefins such as As polypropylene and / or polyethylene to polyvinyl chloride and / or polycarbonates.

As a general rule the packaging materials can be used as a box, box, container, Sheet, disc, film and / or foil present. For example, you can corresponding plastic films via extrusion, calender, blow molding, Casting technique, solution drawing, thermoforming or one Combination of several of these techniques are produced. For example If the plastic films are single-layer films, the oriented or not oriented. In case of orientation the monolayer film can have a one, two or multi-axis orientation be present, with the orientation axes at any angle to Slide-off direction can stand.

alternative the plastic films may be multilayer films, the film layers being of the same as well as different ones Material can be made. The modified invention Polymers are particularly suitable for adhesion To improve polyolefin films. Here is both the improvement the adhesion between two polyolefin layers as well as the improvement the adhesion of the uppermost polyolefin layer (eg for a Coating / painting, etc.) by the invention modified polymers in particular possible. Multilayer films can be oriented or not oriented. In the event of orientation of the multilayer plastic films can be a one, two- or multi-axial orientation, with the orientation axes can be at any angle to the film take-off direction. In a particular embodiment, it is the multilayer plastic film around a composite film. The invention modified polymers are outstandingly suitable for adhesion between polymer film and composite material and / or to improve. In particular, excellent adhesion properties in polyolefin-aluminum, polyolefin-glass, polyolefin-paper / cardboard, and Polyolefin / natural fiber composites to realize. When bonding of composite films may include one or more of the film layers consist of composite material, wherein the composite materials in continuous form (eg paper, aluminum foil or the like) and / or discontinuous Form (eg., Particles and / or fibers) may be present.

Especially are in the bonding of plastic packaging materials according to the present invention generally no chemical and / or energetic Pretreatments of the plastic surfaces (eg plasma, Corona treatment, etching, sulfonation, etc.) for the achievement of liability necessary.

In the case of gluing wood packaging materials, the wood packaging may be solid wood, real wood laminates, plastic laminates, MDF boards and / or similar woody materials. Both resin and oil-poor woods such. B. beech, oak, etc., but resin or oil rich woods such as teak, pine, etc. are used. In particular, adhesions are not significantly weakened by the diffusion of oils and / or resins or their components from the wood to the adhesive boundary layer to the polymer of the invention, so even after a long storage time still high adhesive shear values. The natural moisture contained in most common types of wood (depending on the thickness of the adhesive layer) achieves rapid and complete crosslinking of the adhesive layer, which leads to particularly high adhesive shear strengths in wood bonds using the polymers according to the invention.

at The bonding of toiletries is basically no restrictions, for example, it can be here to act on diapers, bandages, etc. As a rule, by the invention Bonding built a multi-layered structure, the different Materials such. As polymer films and nonwoven covers. About that In addition, moisture-absorbing substances, such as z. B. polyacrylic acid particles (especially uncrosslinked or partially crosslinked), contained in the bond by the modified polyolefins according to the invention can also be connected to the adhesive layer reactive. In particular, the invention are suitable modified polyolefins also as matrix and or base layer for Absorber layers.

One further field of application of the invention Bondings are structural wood bonds, especially edge banding and / or Dekorpapierummantelungen and / or Dekorfolienlamaminierungen and / or Montageverklebungen (eg in furniture). there are due to the crosslinking of the invention Polymers, in contrast to unmodified polyolefins, include those Bonding possible, which is a high temperature load have to resist (eg laminated work surfaces in the kitchen area). In the case of Holzverklebungen it can the wood types used are massive real wood, real wood laminates, plastic laminates, MDF boards and / or similar act woody substances. Both resin and oil can be used Woods such. B. beech, oak, etc., but also resin or oil rich Woods such as teak, pine etc. can be used. Especially become adhesions by the diffusion of oils and / or Resins or their components from the wood to the adhesive boundary layer for polymer of the invention is not significantly weakened, So even after a long storage time still high Klebscherwerte on. Due to the naturally existing in wood moisture succeeds in the bonding with the participation of wood a special full networking, which is too extreme leads to resistant bonds.

The modified polymers of the invention are characterized in that they (without further additions) in a pure wood bond (wood type: untreated beech) after at least 14 days storage a Klebscherfestigkeit of at least 0.75 N / mm ² , preferably of at least 1 N / mm ² , more preferably at least 1.25 N / mm ^2, and more preferably at least 1.5 N / mm ² . After a storage period of 42 days (without further additives) Klebscherfestigkeiten on untreated wood test specimens (beech) of at least 1 N / mm ² , preferably at least 1.25 N / mm ² , more preferably at least 1.5 N / mm ² and in particular preferably reached of at least 2 N / mm ² .

One another essential field of application of the invention Shifts are shifts involving a glass surface. The bond can moisture-absorbing substances such as As silica gel, molecular sieve, polyacrylic acid particles, etc. contain. This is preferably a multi-pane insulating glass composite. Suitable for this purpose are all types of multi-pane insulating glass composites known to the person skilled in the art, regardless of the individual structure, for example with or without additional spacer.

Farther can in Verkiebungen invention under Involvement of a glass surface performed a lamination become.

About that In addition, the glass surface may be around the surface act of glass fibers, for example, the surface of a Fiber optic cable, as z. B. for data and / or telephone lines is used.

by virtue of their plastic deformability in the unvemetzt state can be the modified polyolefins according to the invention particularly good in or used as sealants, in particular in such sealants, in whole or in part on a glass surface be applied.

In a further embodiment of the present invention, the object to be bonded is a label. The label can be made of a paper, plastic, metal and / or more consist layer film and in particular for the marking of painted, coated, anodized and / or otherwise surface-treated metal tinplate boxes in particular, and glass or plastic (especially PET) - bottles are used. In particular, the adhesive for label bonds may be a so-called "pressure-sensitive" adhesive (PSA).

In another embodiment of the present invention when the bonds are a lamination, wherein it is the surface to be laminated around the surface an inorganic and / or organic substance, preferably of metals (eg steel, aluminum, brass, copper, Tin, zinc, enamel), of glass, of ceramics and / or inorganic Building materials, such. B. open or closed-pored concrete. About that In addition, the surface may be wood, paper, Cardboard and / or plastics act. The surface can itself a composite of inorganic and organic materials (eg glass fiber composites). This can be counter-laminated Laminating material of inorganic and / or organic nature. Examples of counter-laminated inorganic laminating materials are ultra-thin glass panes, ceramic membranes and / or metal foils (eg aluminum foil). Corresponding examples gegenkaschierter Organic laminating materials are paper, cardboard, wood veneer, plastics (eg as a film), natural and / or synthetic textiles, Nonwoven, artificial leather and / or natural leather.

Especially these are the bonds according to the invention for gluing in the vehicle interior (eg screens, roof lining, Luggage compartment cover, interior trim, etc.).

In another particular embodiment of the present invention Invention are adhesives for the production of carpets and / or artificial turf. In particular, the bonding to the nubs and Filamenteinbindung used. It can be included in the Fibers or fiber composites around natural and / or synthetic Fibers act. Examples of natural fibers or fiber composites are wool, cotton, sisal, jute, straw, hemp, flax, silk and / or Blends of these fibers.

Examples synthetic fibers or fiber composites to be incorporated are (co) polyamide fibers, Polyethylene fibers, Co (polyester fibers), polypropylene fibers and / or Blends of these fibers. In the case of artificial turf bonding the filaments bound by the bonding are selected of polypropylene filaments, polyethylene filaments, polyamide filaments, Polyester filaments or mixed filaments of the listed Plastics. Particularly preferred are polyethylene filaments. In the field of artificial turf bonding is in particular the good adhesion the modified polyolefins according to the invention on untreated polyethylene and / or polypropylene together with a high tear strength of the filaments even at low Order weight and high flexibility of both the uncrosslinked as well as the crosslinked polymers as a particular advantage to call.

Preferably as the bond used for carpet backing. In addition, a textile substrate can additionally be counter laminated. A particular characteristic of the modified polyolefins according to the invention is a combination of low melt viscosity and high flexibility. The carpet elements obtained are, for example, so-called yard goods, carpet tiles or a subsequently deformable car carpet. In the mentioned applications for nubbed and filament incorporation, the modified polyolefin according to the invention contained has a melt viscosity at 190 ° C. of not more than 10,000 mPa.s, preferably not more than 8,000 mPa.s, more preferably from 1,000 to 7,000 mPa.s and particularly preferably from 1 250 to 6 500 mPa · s. The application weight is in particular 20 to 1500 g / m ² . The order of the melt adhesive composition is preferably carried out as a spray, doctor blade and / or roller application, particularly preferably as a roller application. Other examples are within the skill of one of ordinary skill in the art.

Farther it may be in the bonds according to the invention to act shoe bonding, for example, in the field of Sport shoes and / or for the production of so-called split leather used can be.

Also adhesions according to the invention are so-called "pressure-sensitive adhesions" (PSA). It is advantageous if at least one of the polymers and / or formulation constituents contained has a "cold flow" (ie no melting point or a melting point below room temperature). Cold flow formulation ingredients include, for example, poly (1-hexene), poly (1-octene), poly (1-hexene-co-1-octene), polyacrylates, etc. Crosslinking of the modified polyolefins of this invention within the corresponding pressure-sensitive adhesive formulations becomes particularly desirable made elastic adhesive bonds. A special feature of the modes according to the invention Fied polyolefins is that due to their high flexibility and the plastic deformability, the proportion of additional formulation components with "cold flow" can be chosen very low. In a particular, preferred embodiment, the proportion of other formulation constituents is <25% by mass, more preferably <15% by mass, and particularly preferably <10% by mass.

in the The case of book gluing is usually a gluing which is done in the process of bookbinding.

In the case of textile adhesives, a plurality of textile layers can be connected to one another selectively or in a planar manner, wherein textile elements to be bonded can comprise natural or synthetic materials. In particular, the natural textile elements are wool, horsehair, cotton, linen fabric, hemp, jute, sisal, flax, straw and / or leather. Preferred synthetic textile elements as constituents polypropylene, polyethylene, (co) polyamides, (co) polyester, nylon, perlon and / or Kevlar ^®. In particular, one or more of the elements to be bonded may be an insert. In a particular embodiment, the adhesive formulation according to the invention is introduced in the form of a powder between the textile layers to be bonded and activated by thermal energy (eg with the aid of an ironing press).

In an embodiment of the invention also of the present invention, the inventive modified polyolefins in marking compositions, coating compositions, Sealing membranes or roofing membranes are used.

The marking compositions according to the invention can already in the description of the molding compositions or adhesive formulations contain listed further ingredients. For example, you can the marking compositions of the invention as road marking compounds be used.

in the Case of coating compositions may be, for example, a Coating mass for cardboard or paper coating act as well a coating of a paperboard or paper-containing composite material, which as further components z. B. metal foils or metal layers (eg based on aluminum) and / or plastic films.

Farther the polymers of the invention are suitable for Use in geomembranes. In addition to the invention Polymers can be further constituents in the geomembranes be included, in particular, it is the other ingredients to other polymers, fillers and bitumen. In case of Geomembranes is the proportion of the invention modified polymers at a maximum of 30% by mass, preferably at maximum 27% by mass, more preferably at a maximum of 25% by mass and in particular preferably at a maximum of 22% by mass, based on the geomembrane. Especially If the geomembranes are roofing membranes.

Farther the modified invention are suitable Polyolefins for use as primers, adhesion promoters or in primer formulations and / or in primer formulations, in particular the absence halogenated organic constituents is advantageous. Especially are primer and adhesion promoter formulations which are the inventive Polymers contain used to provide adhesion of organic coatings and / or adhesives on untreated polyolefin surfaces, especially on untreated polyethylene, untreated polypropylene as well as on glass surfaces. In a special Case, the primer and / or primer formulations as Primer on polypropylene moldings such. B. car bumpers and / or trim panels applied to better adhesion to achieve the subsequent painting.

In the primers or primer formulations according to the invention can in addition to the modified invention Polyolefins contain other ingredients. In particular are in the room temperature liquid primer / primer formulations cyclic and / or linear aliphatic and / or aromatic hydrocarbons with or without heteroatoms, including the use of the corresponding halogenated hydrocarbons is possible. Preferably but no halogenated hydrocarbons are used. In the liquid at room temperature primers / primer formulations the said hydrocarbons have a formulation content of not more than 95% by mass, preferably not more than 93% by mass, more preferably not more than 90% by mass, and more preferably not more than 85% by mass.

Furthermore, the modified polyolefins according to the invention are suitable for use in dispersions, suspensions and / or emulsions. In the dispersions, suspensions and / or emulsions mentioned NEN the proportion of polyolefins according to the invention is preferably more than 10% by mass, based on the total formulation.

Of the Order of the modified polyolefin according to the invention occurs as a pure substance or in the form of the above-mentioned formulations (in the case of formulations that are solid at room temperature) on the substrates to be bonded, preferably in the form of a melt at temperatures between 50 ° C and 300 ° C, preferably between 100 ° C and 200 ° C, more preferred between 130 ° C and 180 ° C. During the Heating or melting is recommended overlay / Beschleierung with inert gas (eg nitrogen, argon, etc.) for the formation of To prevent gel particles on the surface. You can do that various application techniques such. B. roller or roller application, Slot die, squeegee coating, dot coating, multiline coating, Rototherm application, spray application in the swirling process or wide area with melt blow or air assisted spray process serve. When using the inventive modified polymers in the spray application is in particular the use of shielding gases (eg nitrogen, argon etc.) as Spraying medium preferred. The substrates are subsequently within the so-called "open time" whose Duration depends on the composition of the applied mixture is, put together. Is the applied adhesive through preheated substrates, rollers etc. or radiation at the application temperature held, so stands for the merger of Substrates naturally a longer time to disposal.

The Networking of the system is done by water; this happens depending on Requirements of the user and properties of the substrates by means of water vapor from the ambient air, by steam or hot water treatment or by water, which in the formulation components and / or Substrates is included.

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.

following The present invention will become more apparent by way of example explained. Alternative embodiments of the present invention Invention are available in an analogous manner.

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, the (co) monomer tacticity, and the number and nature of the (co) monomer blocks are determined by 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)

c) rheology

The melt viscosity is determined by Oszillationsrheometrie, working at a shear rate of 1 Hz. 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 recover 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. Because this degradation process is 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; Vo1. 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.

d) Needle penetration (PEN)

The needle penetration is according to DIN EN 1426 certainly.

e) DSC

The determination of the enthalpy of fusion, the glass transition temperature and the melting range of the crystalline portion is carried out 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.

h) tensile strength and elongation at break

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

i) softening point (ring & ball)

The determination of the softening point according to the ring and ball method is carried out according to DIN EN 1427 ,

j) adhesive shear strength

The determination of the adhesive shear strength is carried out according to DIN EN 1465 ,

k) RFA spectroscopy

The cast in aluminum shells and hardened Samples are punched out with a punching iron (diameter 30 mm). The determination is made as a double determination. The layer thickness of Polymer samples is> 5 mm. The samples are placed in the sample holder and measured (measuring instrument: PANalytical PW 2404). The quantitative determination is made against an external calibration of Si in borax tablets.

l) xylene solubility

It is a mixture of xylene isomers used, wherein the polymer under Dissolved backflow and then the solution is cooled to room temperature. 2 g of polyolefin in 250 ml of xylene with stirring and heating to the boiling point solved by xylene. After 20 min under reflux was boiled, leaves the polymer solution on Cool to 25 ° C. Unsolved or failed Polyolefin is filtered off (15 cm suction filter, Sartorius 390 filter paper) and dried. The remaining polymer solution is in a 5-fold excess of methanol (with a 37% aqueous HCl added) precipitated. The resulting precipitate is filtered off and at 80 ° C. dried in a drying oven (vacuum).

m) solubility in THF

The solubility in THF is a characteristic of partially crystalline polyolefins. The procedure is analogous to the solution attempts in xylene.

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. Inventive Base polymers and comparative examples not according to the invention

The preparation of the base polymers (.. Ex invention No. 3 to 6) is performed 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.

2. Inventive modified polymers:

Preparation of the invention modified polyolefins in the melt:

A semicrystalline polyolefin (composition and material parameters see Table 1) is in a twin-screw extruder (Berstorff ZE40) with the monomer vinyltrimethoxysilane and the initiator dicumyl peroxide (amount see Table 2) at a certain reaction temperature (see Table 2) for about 90 seconds the (VWZ) mixed. The excess monomer is evaporated in the last zone of the extruder at a vacuum of about 20 mbar. This is followed by stabilization by about 0.3 m% IRGANOX 1076.

Preparation of the invention modified polyolefins in solution

• *: Im unvernetzten Zustand ohne Lagerung.
• **: Im vernetzten Zustand nach 40 Tagen Lagerung (20°C/65% rel. Luftfeuchte).

150 g of a partially crystalline polyolefin (composition and material parameters, see Table 1) are dissolved in a laboratory reactor in 750 g of a solvent (see Table 3 for type) and brought to a specific reaction temperature (Table 3). Subsequently, 1.85 g of dicumyl peroxide and 18.75 g of vinyltrimethoxysilane are metered in continuously for a reaction time of 120 minutes. Following the addition, a 30-minute post-reaction phase follows. Solvent and residual monomers are separated via an evaporator. Ex. 15 Ex. 16 Base polymer It. Ex. 3 4 solvent xylene toluene Reaction Temp. [° C] 130 130 η _{190 ° C} [mPa · s] 54,000 46,000 PEN [0.1 mm] 21 27 Terw. [° C] 159 160 Si [ma-%] 0.33 0.38 Tensile strength "0" [MPa] * 1.85 1.7 Tensile strength "40" [MPa] ** 2.9 3.1 Elongation at break "0" [%] * 370 550 Elongation at break "40" [%] ** 310 460

• *: In uncrosslinked condition without storage.
• **: In cross-linked state after 40 days of storage (20 ° C / 65% relative humidity).

3. bonds:

a) wood gluing

The inventively modified polyolefins are melted at 190 ° C in a drying oven under a protective gas atmosphere (eg nitrogen, argon, etc.) for one hour and then at a temperature of 170 ° C (using a thermocouple) on a wood test specimen (wood: beech massive ) applied. Within 20 seconds, it is simply overlapped with another wood test specimen (wood species: solid beech) in an area of 4 cm ² and pressed together for 5 minutes with a weight of 2 kg. Supernatant adhesive polymer is removed. Subsequently, the bond pattern stores a certain number of days at 20 ° C / 65% rel. Humidity in the climatic chamber and is then tested by tensile test for its mechanical properties.

b) polypropylene bonds:

The inventively modified polyolefins are melted at 190 ° C in a drying oven under a protective gas atmosphere (eg., Nitrogen, argon, etc.) for one hour and then at a temperature of 170 ° C (using a thermocouple) on a Polypropylenprüfkörper (isotactic polypropylene, " PP-DWST / manufacturer: Simona AG). Within a period of 20 seconds, it is simply overlapped with another polypropylene test specimen (isotactic polypropylene, "PP-DWST / manufacturer: Simona AG) in an area of 4 cm ² and pressed together for 5 minutes with a weight of 2 kg. Supernatant adhesive polymer is removed. Subsequently, the bond pattern stores a certain number of days at 20 ° C / 65% rel. Humidity in the climatic chamber and is then tested by tensile test for its mechanical properties.

1 and 2 show results of corresponding adhesive shear tests on different samples.

The results show that adhesions of higher stability can be achieved when using the polyolefins according to the invention. Thus, bonds according to the invention show a higher adhesive shear strength than bonds with polymers known from the prior art. This is especially true for gluing with a storage period of more than 10 days. Thus, adhesions using the polymers according to the invention show greater long-term stability.

6. Example formulations for Adhesives / sealants with inventive Polymers.

Method:

To Melting of the modified invention Polyolefins at 190 ° C in a drying oven under a protective gas atmosphere (eg, nitrogen, argon, etc.) for one hour are the Formulation ingredients added, optionally melted and then with a suitable mixing apparatus (eg on a hotplate homogeneously mixed with an IKA stirrer with kneader):

Unreinforced molding compound

• 54.8 parts by weight according to the invention modified polyolefin according to Ex. 11
• 5 parts by weight of DBTL masterbatch (98% by mass VESTOPLAST ^® 708, 2% by mass of dibutyltin dilaurate)
• 40 parts by weight of isotactic polypropylene (eg SABIC PP 520 P)
• 0.2 part by weight IRGANOX 1076 (octadecyl-3,5-di (tert-butyl) -4-hydroxyhydrocinnamate)

Fiber-reinforced molding compound

• 49.8 parts by weight according to the invention modified polyolefin according to Ex. 11
• 5 parts by weight of glass fibers (eg Owen Corning CS429YZ)
• 5 parts by weight of DBTL masterbatch (98% by mass VESTOPLAST ^® 708, 2% by mass of dibutyltin dilaurate)
• 40 parts by weight of isotactic polypropylene (eg SABIC PP 520 P)
• 0.2 part by weight IRGANOX 1076 (octadecyl-3,5-di (tert-butyl) -4-hydroxyhydrocinnamate)

The Glass fibers are oven-baked at 550 ° C prior to use desized pyrolytically for one hour.

Protective compound (automotive underbody protection)

• 40 parts by weight modified according to the invention Polyolefin according to Ex. 3
• 44.3 parts by weight of partially crystalline polyolefin (for example VESTOPLAST 708)
• 5 parts by weight of DBTL masterbatch (98% by mass VESTOPLAST ^® 708, 2% by mass of dibutyltin dilaurate)
• 5 parts by weight of low viscosity polybutadiene oil (e.g. B. Polyol 110)
• 5 parts by weight of glass fibers (eg Owen Corning CS429YZ)
• 0.5 parts by weight of carbon black (eg Printex 60)
• 0.2 part by weight IRGANOX 1076 (octadecyl-3,5-di (tert-butyl) -4-hydroxyhydrocinnamate)

Sealant insulating glass

• 41.3 parts by weight modified according to the invention Polyolefin according to Ex. 11
• 5 parts by weight of DBTL masterbatch (98% by mass VESTOPLAST ^® 708, 2% by mass of dibutyltin dilaurate)
• 20 parts by weight of butylrubber
• 20 parts by weight of zeolite, 3A
• 10 parts by weight semi-crystalline polyolefin (z. B. VESTOPLAST ^® 750)
• 3 parts by weight carbon black (eg Printex 60)
• 0.5 part by weight of organic silane (eg Dynasilan GLYMO)
• 0.2 part by weight IRGANOX 1076 (octadecyl-3,5-di (tert-butyl) -4-hydroxyhydrocinnamate)

Hot melt adhesive for automotive interior

• 72.8 parts by weight modified according to the invention Polyolefin according to Ex. 4
• 5 parts by weight of DBTL masterbatch (98% by mass VESTOPLAST ^® 708, 2% by mass of dibutyltin dilaurate)
• 15 parts by weight of hydrocarbon resin (eg: ESCOREZ 5300)
• 2 parts by weight of rosin ester (eg FORAL 105)
• 5 parts by weight of poly (ethylene-co-vinyl acetate) (eg ESCORENE MV02514)
• 0.2 part by weight IRGANOX 1076 (octadecyl-3,5-di (tert-butyl) -4-hydroxyhydrocinnamate)

Hot melt adhesive for shoe bonding

• 39.8 parts by weight modified according to the invention Polyolefin according to Ex. 3
• 5 parts by weight of DBTL masterbatch (98% by mass VESTOPLAST ^® 708, 2% by mass of dibutyltin dilaurate)
• 35 parts by weight semi-crystalline polyolefin (z. B. VESTOPLAST ^® 408)
• 10 parts by weight of hydrocarbon resin (eg: ESCOREZ 5300)
• 5 parts by weight of poly (ethylene-co-vinyl acetate) (eg ESCORENE UL15028)
• 2 parts by weight polyethylene wax (z. B. VESTOWAX ^® A227)
• 3 parts by weight calcite
• 0.2 part by weight IRGANOX 1076 (octadecyl-3,5-di (tert-butyl) -4-hydroxyhydrocinnamate)

Hot melt adhesive for book bonding

• 45.7 parts by weight VESTOPLAST 408 ^®
• 30 parts by weight modified according to the invention Polyolefin according to Ex. 9
• 5 parts by weight of DBTL masterbatch (98% by mass VESTOPLAST ^® 708, 2% by mass of dibutyltin dilaurate)
• 10 parts by weight of saturated hydrocarbon resin (eg ARKON P90)
• 7 parts by weight of polyolefin wax (eg LICOWAX PP230)
• 2 parts by weight MSA-grafted polypropylene wax (eg LICOMONT TPAR504)
• 0.3 part by weight of IRGANOX 1076 (octadecyl-3,5-di (tert-butyl) -4-hydroxyhydrocinnamate)

Hot melt adhesive for packaging (Material: polypropylene)

• 54.7 parts by weight of partially crystalline polyolefin (z. B. VESTOPLAST ^® 828)
• 30 parts by weight modified according to the invention Polyolefin according to Ex. 11
• 5 parts by weight of DBTL masterbatch (98% by mass VESTOPLAST ^® 708, 2% by mass of dibutyltin dilaurate)
• 10 parts by weight hydrocarbon resin (eg: ESCOREZ 1102)
• 0.3 part by weight of IRGANOX 1076 (octadecyl-3,5-di (tert-butyl) -4-hydroxyhydrocinnamate)

Universal hot melt adhesive with a wide application profile

• 84.7 parts by weight modified according to the invention Polyolefin according to Ex. 14
• 5 parts by weight of DBTL masterbatch (98% by mass VESTOPLAST ^® 708, 2% by mass of dibutyltin dilaurate)
• 2 parts by weight of MSA-grafted polypropylene copolymer (e.g. Eg EXXELOR PO1015)
• 3 parts by weight of polyolefin wax (eg VESTOWAX A616)
• 5 parts by weight of hydrocarbon resin (eg: ESCOREZ 1102)
• 0.3 part by weight of IRGANOX 1076 (octadecyl-3,5-di (tert-butyl) -4-hydroxyhydrocinnamate)

Hot melt adhesive for edge banding

• 20.7 parts by weight modified according to the invention Polyolefin according to Ex. 9
• 5 parts by weight of DBTL masterbatch (98% by mass VESTOPLAST ^® 708, 2% by mass of dibutyltin dilaurate)
• 19 parts by weight of partially crystalline polyolefin VESTOPLAST ^® 891
• 10 parts by weight semi-crystalline polyolefin VESTOPLAST ^® 792
• 3 parts by weight of isotactic polypropylene (eg SABIC PP 579S)
• 2 parts by weight MSA-grafted polypropylene wax (eg LICOMONT TPAR504)
• 12 parts by weight hydrogenated aliphatic hydrocarbon resin (eg EASTOTAC H-130)
• 4 parts by weight of aromatic hydrocarbon resin (eg. NOVARES TN150)
• 12 parts by weight of poly (ethylene-co-vinyl acetate) copolymer (e.g. B. ELVAX210) 12 parts by weight calcite
• 0.3 part by weight of IRGANOX 1076 (octadecyl-3,5-di (tert-butyl) -4-hydroxyhydrocinnamate)

Primer for polypropylene / polyethylene (Recipe 1)

• 80 parts by weight of xylene
• 20 parts by weight modified according to the invention Polyolefin according to Ex. 10

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

• - EP 0004034 B1 [0004]
• US 4412042 [0004]
• - DE 1963571 [0005]
• - DE 2353783 [0005]
• - DE 2406844 [0005]
• - DE 2554525 [0005]
• - DE 2642927 [0005]
• US 3,075,948 [0006]
• - EP 0260103 B1 [0007]
• - DE 4000695 [0008, 0047]
• JP 2003-002930 A [0009]
• WO 03/070786 [0009]
• WO 2006/069205 [0010]
• WO 2007/067243 [0011]
• WO 91/06580 [0012]
• WO 89/11513 [0013, 0013]
• - DE 19516457 [0014]
• - EP 1508579 [0015]
• WO 2007/001694 [0016]
• WO 2007/002177 [0017]
• WO 2007008765 [0018]
• - EP 0827994 [0019]

Cited non-patent literature

• - H.-G. Elias; Macromolecules; Vol. III; Wiley-VCH: Weinheim; 2001 [0013]
• - W. Spaleck in: "Metallocenes based Polyolefins"; J. Scheirs, W. Kaminsky (ed.); J. Wiley &Sons;Weinheim; 1999 [0021]
• - A. Lehtinen; Macromol. Chem. Phys .; 195 (1994); 1539ff [0022]
• - J. Boor; "Ziegler-Natta Catalysts and Polymerization"; Academic Press; New York; 1979 [0023]
• G. Natta, I. Pasquon, A. Zambelli, G. Gatti; Makromol. Chem .; 70 (1964); 191ff [0023]
• BA Krentsel, YV Kissin, VI Kleiner, LL Stotskaya; "Polymers and Copolymers of higher 1-olefins"; P. 19/20; Hanser Publ .; Munich; 1997 [0023]
• - YV Kissin; "Isospecific polymerization of olefins"; Springer Verlag; New York; 1985 [0023]
• H. El Mansouri, N. Yagoubi, D. Scholler, A. Feigenbaum, D. Ferrier; J. Appl. Polym. Sci .; 71 (1999); 371ff [0023]
• - S. Berger, S. Braun, H. -O. Kalinowski, 13C NMR Spectroscopy, Georg Thieme Verlag Stuttgart 1985 [0115]
• AE Tonelli, NMR Spectroscopy and Polymer Microstructure, Verlag Chemie Weinheim 1989 [0115]
• - JL Koenig, Spectroscopy of Polymers, ACS Professional Reference Books, Washington 1992 [0115]
• JC Randall, Polymer Sequence Determination, Academic Press, New York 1977 [0115]
• A. Zambelli et al: Macomolecules, 8, 687 (1975) [0115]
• A. Filho, G. Galland: J. Appl. Polym. Sci., 80, 1880 (2001) [0115]
• - NP Cheremisinoff; "An Introduction to Polymer Rheology and Processing"; CRC Press; London; 1993 [0116]
• - 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; Vo1. 3 [0116]
• - DIN EN 1426 [0117]
• - DIN 53 765 [0118]
• - DIN EN ISO 527-3 [0119]
• - DIN EN 1427 [0120]
• - DIN EN 1465 [0121]

Claims (37)

Modified polyolefins based on at least one base polyolefin with a determined by ¹³ C-NMR spectroscopy content of propylene between 50 and 90% by mass and with a determined by ¹³ C-NMR spectroscopy content of isotactic poly (propylene) triads of at least 40 ma-% and at most 80 m%, based on the total detected propylene triads, wherein the base polyolefin has a solubility in xylene at room temperature of less than 96% by mass and a solubility in THF at room temperature of at least 10% by mass and at most 62% -%, wherein one or more silanes are grafted onto the base polyolefins. Modified polyolefins according to claim 1, characterized in that it is based on mixtures of at least a base polyolefin according to claim 1 with crystalline or semi-crystalline poly (propylene) polymers. Modified polyolefin according to claim 1 or 2, characterized in that in addition to propylene as Olefinmonomere Contains ethylene and / or 1-butene. Polyolefin according to one or more of claims 1 to 3, characterized in that the melt viscosity of unmodified (ungrafted) polyolefin 190 ° C 50 000 to 3,000,000 mPa · s. Polyolefin according to one or more of claims 1 to 4, characterized in that the Softening point, measured by ring & ball method, of the unmodified (ungrafted) polyolefin 140 to 170 ° C. Polyolefin according to one or more of claims 1 to 5, characterized in that the Needle penetration of the unmodified (ungrafted) polyolefin at least 10 x 0.1 mm. Polyolefin according to one or more of claims 1 to 6, characterized in that the by DSC certain glass transition temperature of the unmodified (ungrafted) polyolefins at a maximum of -20 ° C lies. Polyolefin according to one or more of claims 1 to 7, characterized in that it is selected from polyethylene-co-propylene), poly (propylene-co-1-butene) and poly (ethylene-co-propylene-co-1-butene). Polyolefin according to one or more of claims 1 to 8, characterized in that the melt viscosity of the modified (grafted) uncrosslinked polyolefin at 190 ° C 1 000 to 50 000 mPa · s. Polyolefin according to one or more of claims 1 to 9, characterized in that the Softening point, measured by ring & ball method, of the modified (grafted) uncrosslinked polyolefin 140 to 170 ° C. Polyolefin according to one or more of claims 1 to 10, characterized in that the Needle penetration of the modified (grafted) uncrosslinked polyolefin at least 18 x 0.1 mm. Polyolefin according to one or more of claims 1 to 11, characterized in that the tensile strength of the modified (grafted) polyolefin in the uncrosslinked state at a maximum of 2 MPa. Polyolefin according to one or more of claims 1 to 12, characterized in that the Tensile elongation of the modified (grafted) tensile test Polyolefins in the uncrosslinked state is at least 75%. Polyolefin according to one or more of claims 1 to 13, characterized in that the One or more silanes are selected from the group comprising vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, Vinyldimethylethoxysilane and / or vinylmethyldibutoxysilane. Polyolefin according to one or more of claims 1 to 14, characterized in that the by X-ray fluorescence spectroscopy certain silicon content is at least 0.3mA%. Process for the preparation of a modified polyolefin according to claim 1, characterized in that at least one base polyolefin having a determined by ¹³ C-NMR spectroscopy content of propylene of at least 50% by mass and at most 90% by mass and with a by ¹³ C-NMR Spectroscopic content of isotactic poly (propylene) triads of at least 40% by mass and not more than 80% by mass, based on the total detected propylene triads and a solubility in xylene at room temperature of less than 96% by mass and in THF at room temperature of at least 10mA% and at most 62mA%, is contacted with at least one free radical initiator and one or more silanes, whereupon a grafting reaction of the one or more silanes onto the at least one base polyolefin occurs. A method according to claim 16, characterized characterized in that the one or more silanes selected are from the group comprising vinyltrimethoxysilane, vinyltriethoxysilane, Vinyltris (2-methoxyethoxy) silane, 3-methacryloxypropyltrimethoxysilane, 3-Methacryloxypropyltriethoxysilane, vinyldimethylethoxysilane and / or Vinylmethyldibutoxysilan. A method according to claim 16 or 17, characterized in that the grafting of the one or more Silanes in solution or in the melt takes place. Method according to one or more of claims 16 to 18, characterized in that the grafting at a temperature of 30 to 250 ° C. Method according to one or more of claims 16 to 19, characterized in that it is is a solution process, and as a solvent at least one aromatic hydrocarbon is used. Method according to one or more of claims 16 to 19, characterized in that it is is a melt process, wherein at least one radical initiator is metered directly into the melt. A method according to claim 21, characterized characterized in that the temperature of the at least one base polyolefin containing melt at the time of addition of at least one Free radical initiators above the SADT (Self accelerating decompositon temperature) of the added radical initiator. Use of modified polyolefins according to one or more of claims 1 to 15 as or in molding compounds, in protective materials, as or in adhesives, in sealants, in Marking compounds, coating compounds, geomembranes or roofing membranes, as primer or in primer formulations and / or adhesion promoter formulations and / or in dispersions, suspensions or emulsions. Molding compounds, protective compounds, adhesives, sealants, Marking compounds, coating compounds, geomembranes or roofing membranes, Primers, primer formulations, primer formulations, dispersions, Suspensions and / or emulsions containing one or more modified Polyolefins according to one or more of the claims 1 to 15. Molding compositions according to claim 24, characterized in that it additionally comprises one or more ethylene polymers, and / or isotactic propylene polymers and / or syndiotactic Propylene polymers and / or isotactic poly-1-butene polymers and / or syndiotactic poly-1-butene polymers. Adhesives according to claim 24, characterized in that they are hot melt adhesive formulations is. Adhesives according to claim 24 or 26, characterized in that it additionally crosslinking accelerator, inorganic and / or organic fillers, inorganic and / or organic pigments, synthetic and / or natural Resins, inorganic and / or organic, synthetic and / or natural Polymers, inorganic and / or organic, synthetic and / or natural fibers, inorganic and / or organic stabilizers, inorganic and / or organic flame retardants, resins, amorphous Poly (α-olefins), polymers with polar groups, polymers based on ethylene, butadiene, styrene and / or isoprene, elastomers Polymers based on ethylene, propylene, acrylonitrile, a diene and / or a cyclic diene, styrene, waxes, one or more synthetic or natural oils and / or UV-active Contain substances. Geomembranes according to claim 24, characterized in that they additionally other Contain polymers, fillers and / or bitumen. Geomembranes according to claim 24 or 28, characterized in that the proportion of polyolefins according to one or more of the claims 1 to 15 maximum 30 ma-%, based on the geomembrane is. Adhesives containing one or more modified Polyolefins according to one or more of the claims 1 to 15. Adhesive bonds according to claim 30, characterized in that the bonds are packaging bonds, Bonding of hygiene articles, wood bonds, adhesions of glass surfaces, label sticking, lamination bonds, Carpet or artificial turf gluing, shoe gluing, pressure-sensitive Bonding, book bonding or Textilverklebungen acts. Adhesive bonds according to claim 30, characterized in that it is adhesive bonds in the vehicle interior is. Packaging bonds according to claim 30, characterized in that the packaging materials the Materials Wood, cardboard, paper, plastic, metal, ceramics, glass, Artificial and / or natural fibers and / or textiles include. Carpet bonding for nap and filament binding according to claim 30, characterized in that an application weight of 20 to 1500 g / m ² is used. Artificial grass bonding according to claim 30 characterized in that the integrated by the bonding Filaments are selected from polypropylene filaments, polyethylene filaments, Polyamide filaments, polyester filaments or mixed filaments of listed plastics. Primer and / or primer formulation according to Claim 24, containing one or more polyolefins according to one or more of claims 1 to 15 characterized that they are used to treat a polyolefin surface becomes. Dispersions, suspensions and / or emulsions according to Claim 24 containing one or more polyolefins according to one or more of claims 1 to 15, characterized the proportion of polymer is more than 10% by mass, based on the total formulation, is.