DE102008041277A1 - Modified polyolefin comprising 1-butene, and an isotactic poly(1-butene)-triad useful e.g. as or in molding composition and adhesive, in protective composition, sealants, marking composition, coating composition and sealing strips - Google Patents

Abstract

Modified polyolefin comprising 1-butene at least 80 wt.%, calculated by 1>3>C-NMR-spectroscopy, and an isotactic poly(1-butene)-triad at least 60 wt.%, relative to the total detected 1-butene triad and calculated by 1>3>C-NMR-spectroscopy, is claimed, where the polyolefin 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 present invention relates to modified polyolefins having a determined by ¹³ C-NMR spectroscopy content of 1-butene of at least 80% by mass and with a determined by ¹³ C-NMR spectroscopy content of isotactic poly (1-butene) of triads at least 60% by mass, based on the total detected 1-butene triads, wherein one or more silanes are grafted onto the polymer, process for the preparation of the 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), in particular, carboxylic acids and silanes for modification be used.

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 cross-linked by silane linkages polyolefins whose crosslinked products should have a high mechanical strength, an improved ductility and a 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 polyalpha-olefins) having 2 to 6 carbon atoms which are said to have improved heat resistance and good adhesion to glass.

at the modification described is either one pure surface modification of solid polymer particles, Polymer discs or polymer moldings, or particularly preferred a solution modification in which the polymer is at least partially dissolved, or a melt modification which is not preferred. The obtained modified Polymers are used for the production of molded parts and Containers and as a coating of glass containers used, suitable for use as hot melt adhesives based on the completely different requirement profile (Melt viscosity, material stiffness in uncrosslinked Condition, etc.) not.

The use of amorphous poly (alpha-olefins) for silane crosslinking is already known. For example, in the EP 0 260 103 B1 amorphous silane-modified polymers with saturated carbons low molecular weight fabric scaffold described, which are used as a coating agent 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 polypropylene copolymers used have a low to moderate proportion of higher 1-olefins and a low crystallinity, and are very soft with a needle penetration of up to 50 · 0.1 mm. The tensile strength of such polyolefins in the uncrosslinked state is relatively low, so that they remain closed to numerous applications in which a high initial cohesion is required.

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 (Idemitsu Kosan) describe a process for preparing 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 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 polypropylenes and blends of polypropylenes, in particular if they contain atactic polypropylene, are mentioned as base polymers. The grafting of blends containing isotactic polypropylene results in extremely rapid and complete polymer degradation due to the molecular structure of the iPP, whereby only very low grafting rates can be achieved. Atakti On the other hand, beautiful polypropylene already has a very low tensile strength of its own [see, for example, US Pat. B .: H.-G. Elias; Macromolecules; Vol. III; Wiley-VCH: Weinheim; 2001 ], which is further reduced in the grafting reaction due to the inevitable polymer degradation. 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 in the crosslinked state adversely affects the material properties of the graft polymer, in particular its tensile strength / Cohesion.

The As a result, end products have poor material properties, in particular, the degree of functionalization is low and the tensile strength low.

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, poly (ethylene-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 polymers described are not suitable for the intended use in the present application.

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 made with metallocene catalysts and do not have the required material properties.

In the WO 2007/002177 describes adhesive compositions based on poly (propylene) random copolymers (at least 50% m propylene fraction) and functionalized polyolefin copolymers and nonfunctionalized adhesive resins, the poly (propylene) random copolymers having a melting enthalpy of 0.5 to 70 J / g and a proportion of isotactic propylene triads of at least 75% (particularly 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 high 1-butene content 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 described syndiotactic polypropylene polymers are also expensive and barely available on the market.

In the WO 2007008765 describes the use of low-viscosity silane-grafted poly (ethylene-co-1-olefin) polymers as adhesive raw material. 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 2000 and a maximum of 50,000 cP at 177 ° C. As 1-olefin comonomers numerous higher 1-olefin such. 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 chen. 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. Polymers with very high 1-butene levels as described in the present application are not described.

In the EP 0 827 994 describes the use of silane-grafted amorphous poly (alpha-olefins) as a moisture-curing 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 softening point of 98 ° C, a needle penetration of 15 x 0.1 mm and a melt viscosity of 6000 mPa · s. Tensile shear strengths of up to 3.5 N / mm ^{2 are} achieved on wood test specimens. The atactic polyolefins and low crystallinity APAOs used in the modification result in products which, when uncrosslinked, have a low softening temperature, relatively high needle penetration, and low tensile strength or material cohesion, and are therefore unsuitable for many applications.

It Thus, there was a need for functionalized polyolefins, with improved material properties, especially on such polyolefins, the high functionalization rate as well as already in the uncrosslinked Condition a high material cohesion (tensile strength) at sufficient flexibility (elongation at break), good adhesive properties, especially on wood and untreated polypropylene and a have low plastic deformability (needle penetration).

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 is a modified polyolefin containing isotactic structural elements, which is especially selected from poly (1-butene), poly (ethylene-co-1-butene), poly (propylene-co-1-butene ) and poly (ethylene-co-propylene-co-1-butene), characterized in that the determined by ¹³ C-NMR spectroscopy content of 1-butene at least 80% by mass and by ¹³ C-NMR spectroscopy certain content of isotactic poly (1-butene) triads is at least 60mA%, based on the total detected 1-butene triads, and wherein one or more silanes are grafted onto the polyolefin. The polyolefins of the invention, especially selected, are particularly and preferably suitable for the production of bonds and there show decisive advantages over the known polymers. Thus, the polyolefins according to the present invention, when applied both in the uncrosslinked and in the crosslinked state, have higher tensile strengths, higher adhesive shear strengths and lower needle penetration. Due to the denser formed network, the use of the polyolefins according to the invention for higher-stressed bonds is possible, what with the well-known systems in this way was not possible. As a result of the fact that the polymers according to the invention, even in the uncrosslinked state, have high material cohesion, high adhesive shear strength and lower needle penetration, they can be used in bonds which already have to endure high stresses immediately after physical hardening (cooling). Furthermore, the crosslinking of the polyolefins occurs more quickly in the case of adhesions, so that even a very high stress of the bonding can take place more quickly. This leads to higher processing numbers among the users and thus lowers the production costs. Due to the high degree of functionalization of the polymers according to the invention, a very dense polymer network can be formed by subsequent crosslinking, which allows a significantly higher stress than the previously known unmodified or modified APAO systems. The high degree of functionalization also allows an improved connection to functional surfaces (eg OH groups of glass, wood, etc.). Furthermore, due to the higher degree of functionalization in adhesive formulations, significantly lower quantities can be used, which entails economic and production-related advantages.

Essential for the positive properties of the polyolefins according to the invention is the special composition of the base polymer used. This contains at least 80 m% of 1-butene, preferably at least 83% by mass, more preferably at least 85% by mass, and most preferably at least 95% by mass, the content of isotactic poly (1) determined by ¹³ C-NMR spectroscopy at least 60% by mass, preferably at least 62% by mass, more preferably between 65 and 99% by mass, and particularly preferably between 67 and 90% by mass, based on the total of 1-butene triads detected, with further Preferred ranges are between 70 and 77 and between 73 and 87 m%.

By the high proportion of 1-butene will significantly material properties adjusted the modified polymer of the invention, so z. B. a particularly advantageous setting behavior with pronounced time-delayed recrystallization. Furthermore, the show polymers according to the invention have a particularly low glass transition temperature, which leads to excellent low temperature properties of the polymers. The high proportion of isotactic 1-butene triads requires a lot high cohesion and a particularly high hardness the cured polymers of the invention both in the uncrosslinked and in the crosslinked state.

Of the Content of comonomer results for the inventive Polymers as 100mA% minus 1-butene content, with both a also two comonomers can be used.

In a particular preferred embodiment is the base polymer Poly (1-butene) homopolymer.

In Another particularly preferred embodiment the base polymer is a polyethylene-co-1-butene) an ethylene content of at most 12 m%, preferably of not more than 10 m%, more preferably of at most 8% by mass, and especially preferred of max. 4 ma-%.

A particular advantage of this monomer combination lies in the very precisely dosed disturbance of the crystallinity of the 1-butene units by the ethylene units as z. B. already known from the literature Turner-Jones; Polymer; 7 (1966); 23 ff ]. This leads to significant changes in the material properties being achieved by means of low additions of ethylene, in particular a control of the material hardness (needle penetration), the softening point, the material cohesion and the adhesiveness.

In Another preferred embodiment is in the base polymer, a poly (propylene-co-1-butene) having a Propylene content of not more than 20% by mass, preferably not more than 17% by mass, especially preferably at most 14% by mass, and especially preferably at most 10 % by mass.

In Another particularly preferred embodiment the base polymer is a poly (ethylene-co-propylene-co-1-butene) with a combined content of ethylene and propylene of maximum 20% by mass preferably at most 15% by mass, particularly preferably at most 11 ma-% and especially preferably at most 7 ma-%.

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, especially preferably 90,000 to 1,000,000 mPa · s, and especially preferred 100,000 to 750,000 mPa · s, wherein the further the ranges from 110000 to 550000, from 120000 to 450000, from 150000 to 300,000 and from 400,000 to 980000 mPa · s in particular are preferred.

Of the Softening point of unmodified (ungrafted) base polymers, measured by ring & ball method, is 100 to 145 ° C, preferably 107 to 143 ° C, more preferably 109 to 142 ° C, and particularly preferably from 112 to 137 ° C.

The Needle penetration of unmodified (ungrafted) base polymers is at most 16 x 0.1 mm, preferably at most 15 x 0.1 mm, more preferably at most 14 x 0.1 mm and in particular preferably 1 to 13 x 0.1 mm.

The determined by DSC glass transition temperature of the unmodified (ungrafted) base polymers are at most -20 ° C, preferably at most -25 ° C, more preferably at most -30 ° C and more preferably less than -35 ° C.

One or more silanes are grafted onto the abovementioned base polymers in the case of 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.

The polymers modified with the silanes have special properties which, when used, lead to the above-mentioned advantages. Thus, the melt viscosity of the invention modified (grafted) polyolefins in the uncrosslinked state determined with oscillatory rheometry at 1 Hz and a deformation of not more than 1% at 190 ° C 1000 to 50 000 mPa · s, preferably 2,000 to 20,000 mPa · s, more preferably 2500 to 18000 mPa · s and particularly preferably 3000 to 16000 mPa · s. There are thus modified polyolefins for Provided due to their variable Melt viscosity in the uncrosslinked state for the most diverse application methods are suitable, and accordingly in a wide variety of applications (eg hotmelt adhesives, Sealants, molding compounds, primers, etc.) can be used. The softening point of the uncrosslinked invention modified (grafted) polyolefins, measured by ring & ball method, is 80 to 135 ° C, preferably 82 to 132 ° C, more preferably 85 to 130 ° C and especially preferred 87 to 128 ° C. There are thus modified polyolefins provided a medium softening point have, d. H. even in the uncrosslinked state to a sufficient Heat resistance of a using the inventive lead to modified adhesions produced modified polyolefins, but also a processing (especially in the melt) at moderate Allow processing and application temperatures, and thus also suitable for temperature-sensitive applications. The needle penetration of the uncrosslinked modified invention Polyolefin is at most 17 x 0.1 mm, preferably a maximum of 15 x 0.1 mm, more preferably a maximum of 13 x 0.1 mm and more preferably 2 to 12 x 0.1 mm. It will thus provided modified polyolefins, which have a high to medium hardness, resulting in compounds (eg, adhesive bonds) with high material cohesion leads.

As a result, is the tensile strength of the invention modified polyolefins (without further additives) in the uncrosslinked Condition at least 2 MPa, preferably at least 2.5 MPa, especially preferably at least 3 MPa, and more preferably at least 3.5 MPa. Without further additives and after a storage period 40 days in a climatic chamber at 25 ° C is the tensile strength the modified polyolefins according to the invention in the crosslinked state at least 4 MPa, preferably at least 6 MPa, more preferably at least 8 MPa and especially preferably at least 10 MPa. The elongation at break of the invention modified polyolefins are present (without further additives) in the uncrosslinked state at least 50%, preferably at least 100%, more preferably at least 200% and especially preferred at least 300%. Without further additions and after one Storage period of 40 days in a climatic chamber at 25 ° C is the elongation at break of the invention modified polyolefins in the crosslinked state at least 100%, preferably at least 150%, more preferably at least 200%, and more preferably at least 250%, d. H. that the modified polymers according to the invention despite the occurring during storage networking and the associated Increase of material cohesion (see tensile strength) retain a high degree of flexibility. The invention modified polyolefins have (after complete separation unreacted residual monomer) by RFA spectroscopy (X-ray fluorescence spectroscopy) certain silicon content of at least 0.3 m%, preferably from at least 0.4mA%, more preferably at least 0.5mA% and more preferably from 0.6 to 2mA%, with others particularly preferred ranges between 0.5 and 0.9 m%, between 0.8 and 1.3 m% and between 1.15 and 1.75 m%.

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 polyethylene, 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, characterized in that a polyolefin having a determined by ¹³ C-NMR spectroscopy content of 1-butene of at least 80% by mass and with a by ¹³ C-NMR Spectroscopy content of isotactic poly (1-butene) triads of at least 60mA%, based on the total detected 1-butene triads, is contacted with at least one free radical initiator and one or more silanes, followed by a grafting reaction of the or several silanes on the polyolefin takes place.

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 _n -Mischkatalysator (n = 0.2 to 0.5) obtained for example by polymerizing butene-1 optionally with ethylene and / or propylene with a TiCl ₃ • (AlCl _3), 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. 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 reaction temperature is between 30 and 200 ° C. 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, for example, tetrakis (methylene- (3,5-di-tert-butyl-4-hydroxy) hydrocinnamate) and / or 2,4,8,10-tetraoxa-3,9-diphosphaspiro-3,9-bis (octadecyl) [5,5] undecane). 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 15% by weight, more preferably from 0.75 to 13% by weight and especially preferred from 1 to 12.5% by weight, based on the base polymer, used, with further particularly preferred ranges between 0.75 and 3.5 Wt .-%, between 2 and 5.75 wt .-%, between 5 and 8.5 wt .-% and between 7.5 and 11.75 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, one or more radical donors being 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, it is a solution process, wherein aliphatic and / or aromatic hydrocarbons and cyclic ethers can be used as a solvent. Particular preference is given to using at least one aromatic hydrocarbon as the solvent. Suitable aromatic hydrocarbons are in particular trichlorobenzene, dichlorobenzene, toluene and xylene, particularly preferably xylene is used. Particularly preferred aliphatic hydrocarbons are, 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 is the concentration of the base polymer used is at least 10% by mass, preferably at least 15mA%, more preferably at least 20mA% and more preferably at least 22.5mA%. The reaction temperature 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 more preferably 55 to 140 ° C. The solution grafting takes place either in discontinuous or in a continuous manner. In the case of a discontinuous Reaction is first the solid polymer (For example, as granules, powder, etc.) in the solvent used solved. Alternatively, it is directly conditioned Polymerization solution from the preparation process of the base polymer used and brought to reaction temperature. It follows the addition the monomer (s) and the radical initiator (s). In a Particularly preferred embodiments are solvents Base polymer (s) and monomer (e) are initially charged and at reaction temperature brought while the radical starter over is / are continuously added 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 another Particularly preferred embodiments are solvents and base polymer (s) and brought to reaction temperature, while monomer (s) and free radical initiator together (e.g. in the form of a mixture) or separated from each other be dosed continuously 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, what both the chain scission and the formation of homopolymers pushes back. This is especially true when using Of monomers important at the reaction temperature strong to the thermal initiated (homo) polymerisation tend. Very particularly preferred following the different defined dosing periods an additional amount of free radical initiator (s) is added to the content to minimize residual monomers in the reaction solution. As the reactor, a stirred tank is preferably used, the Use of alternative reaction vessels is also possible.

in the Case of continuous reaction is first in one or more storage containers (eg stirred kettles) the solid polymer dissolved in at least one solvent and then continuously into the reaction vessel (s) dosed. In an alternative, also particularly preferred Embodiment, directly becomes a conditioned polymer solution used from a manufacturing process of the base polymer. In a another embodiment which is also particularly preferred becomes the solid polymer (eg in the form of powder, granules, pellets etc.) together with at least one solvent continuously in a (single or multi-shaft) screw machine or a Kontikneter metered, dissolved under the action of temperature and shear, and then continuously into the reaction vessel (s) dosed. As a reaction vessel or reactors for carrying out the continuous grafting reaction in Solution come continuous stirred tank, stirred tank cascades, Flow tubes, flow tubes with forced delivery (eg screw machines), reaction kneaders and any of them Combinations in question. Be flow tubes with forced delivery used, it is preferably extruder, wherein Both single-, two- as well as multi-shaft extruders are used. Two- and / or more-shaft extruders are particularly preferably used. Especially preferred for the continuous production of the invention modified polymers in solution is the use of a Reactor combination of flow tube, flow tube with forced conveying and continuous stirred tank in any order, preferably either in the flow tube with forced conveying or in a continuous stirred tank also the removal of residual monomers and volatile by-products / degradation products he follows. Alternatively, it is preferably a melt process, wherein at least one free-radical initiator is metered directly into the melt becomes. In particular, the temperature is in this process variant the polymer composition at the time of addition of at least one radical initiator above the SADT (Self accelerating decomposition temperature = Temperature above which use a self-accelerating decomposition can) at least one of the added radical starter.

The Reaction temperature of the grafting process in the melt is included 160 to 250 ° C, preferably 165 to 240 ° C, especially preferably at 168 to 235 ° C and especially preferred at 170 to 230 ° C.

Melt-grafting takes place either in discontinuous or continuous mode. In the case of a discontinuous reaction, the solid polymer (for example, as granules, powders, pellets, etc.) first melted and optionally homogenized. Alternatively, a conditioned polymer melt from a polymerization process is used directly and brought to the reaction temperature. This is followed by the addition of monomers (s) and free 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 Another particularly preferred embodiment submitted the polymer melt and homogenized while Monomer (s) and radical initiators together (for example, in the form of a Mixture) or separately over a defined period of time be metered in continuously. This has the advantage that both the stationary radical concentration, as well as the monomer concentration remains low at the reaction site, which is both the chain scission as also suppresses the formation of homopolymer.

The latter is particularly important in the use of monomers that are present in the the present reaction temperature for thermal (homo) polymerization tend. As a reactor is preferably a stirred tank with wandgängigem Stirring or a reaction kneader used.

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, marking compounds, Coating materials, geomembranes or roofing membranes, primers, primer formulations, Adhesion promoter formulations, dispersions, suspensions and / or Emulsions. Accordingly, the use of the invention modified polyolefins in the stated fields of use and corresponding Molding compounds, protective compounds, adhesives, 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, poly (1-butene) and / or fillers and / or reinforcing materials such. B. contain glass fibers.

The modified polyolefins according to the invention are particularly suitable for use as and / or in protective compositions. Preferably, these are protective compounds other than at least a polymer according to the invention, a further modified and / or unmodified polyolefin, in particular polypropylene and / or poly (1-butene) and / or fillers and / or reinforcing materials such. B. contain glass fibers. In particular, the protective compositions according to the invention are those used in the automotive sector. Very particularly preferably it is underbody protection compounds (PVC plastisol replacement).

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

to Adjustment of the properties required for the adhesive user such as bond strength, initial adhesion, crosslinking speed, crosslink density, Viscosity, hardness, elasticity, temperature and oxidation stability, etc. can the inventive Polyolefins are added to other substances, usually for setting the desired adhesive properties be used. It is naturally on it to ensure that the water contained in the aggregates, the rate of crosslinking increase the adhesive according to the invention can. Especially characteristic of the present invention is that on the silane groups of the invention Polymers a reactive attachment to the additives used can be done. In particular, fillers used are used and / or reinforcing materials (eg, fibers) through the contained in the polymers of the invention Silane groups are reactively attached to the polymer matrix, resulting in particular advantageous material properties, in particular a high material cohesion (Tensile strength) and a very high pull-out strength leads to 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.

The other constituents may be crosslinking accelerators, in particular silanol condensation catalysts, inorganic and / or organic fillers, which may optionally be electrically conductive or insulating, inorganic and / or organic pigments, which may optionally be electrically conductive or insulating, synthetic and / or or natural resins, in particular adhesive resins, syntheti and / or natural oils, inorganic and / or organic, synthetic and / or natural polymers, which may optionally be electrically conductive or insulating, inorganic and / or organic, synthetic and / or natural fibers, which may optionally be electrically conductive or insulating , inorganic and / or organic stabilizers, inorganic and / or organic flame retardants.

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 particularly preferably between 3 and 20% by mass, 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 with 5-20 Carbon atoms which z. B. by classical Ziegler-Natta catalysis or metallocene catalysis are available. The share of amorphous poly (α-olefins) is especially at maximum 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 (HDPE, 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, it is preferred that it is the crystalline or semi-crystalline polyolefins to chemically modified polyolefins the chemical modification in particular those by Maleic anhydride, itaconic anhydride, acrylic acid, Acrylates, methacrylates, unsaturated epoxy compounds, Silane acrylates, silanes and hydroxyalkylsilanes 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 miscibility exhibit.

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.

Further, the other ingredients may be 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 in particular, these are ethylene-propylene rubber, EPM (double bond-free, ethylene content 40-75 m%) and / or EPDM. The proportion of the 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 is usually not more than 20 ma-%, preferably 1 to 15 m%, particularly preferably 1.5 to 10 m% and in particular 2 to 9 m%, 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.

Farther the further constituents may comprise fillers, where the fillers are used to give specific property profiles the adhesive layer, such. B. the temperature application area, the Strength, shrinkage, electrical conductivity, the magnetism and / or the thermal conductivity specifically adapted to specific requirements.

Generally if the fillers are inorganic and / or organic fillers. The inorganic fillers are especially selected from silicic acids (including hydrophobic silicas), quartz flour, chalks, Titanium dioxide, zinc oxide, zirconium oxide (the latter three preferably in 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, cross-linked polyethylene, cross-linked rubber or rubber compounds, synthetic fibers such. 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 amount the filler is not more than 80% by mass, preferably 1 to 60% by mass, more preferably 5 to 40% by mass, and especially 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) acetyacetonate, 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 1000 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 hot melt adhesive formulations according to the invention the formulations described above are 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 of glass surfaces, label laminating laminating, Carpet or artificial turf gluing, shoe gluing, pressure-sensitive Gluing, book gluing or textile gluing.

Especially characteristic of the present invention is that when using the modified invention Polyolefins for bonding to or from polyolefin surfaces and or glass surfaces on an energetic and / or chemical pretreatment of the polyolefin surfaces and / or Glass surfaces, z. B. by flaming, plasma treatment, Corona treatment, sulfonation, etching, primer application, etc. can be dispensed with, 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 of the invention are characterized in that they (without further additions) after a storage period of at least 14 days in a climatic chamber at 20 ° C / 65% rel. Humidity in a pure Polypropylenverklebung (material: untreated isotactic polypropylene) have a Klebscherfestigkeit of at least 1 N / mm ² , preferably of at least 1.2 N / mm ² and more preferably of at least 1.3 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 Copolymamide 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. Generally, the packaging materials as a box, box, container, sheet, disc, film and / or foil available. For example, corresponding plastic films over Extrusion, calender, blow molding, casting technique, solution drawing, Deep drawing or a combination of several of these techniques getting produced. For example, it is the plastic films single-layer films that are oriented or not oriented. In the case of orientation of the monolayer film, a single, two- or multi-axial orientation, with the orientation axes can be at any angle to the film take-off direction.

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 invention modified polymers are particularly suitable for the To improve adhesion to polyolefin films. It is both the Improvement of adhesion between two polyolefin layers as well the improvement of the adhesion of the uppermost polyolefin layer (e.g. B. 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 Trapping of wood packaging materials may occur in the wood packaging to solid real wood, to 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 not significant to the polymer of the invention weakened, so even after a long storage period still high Klebscherwerte on. By the most common Wood species contained natural moisture is (depending of the thickness of the adhesive layer) a fast and complete Crosslinking of the adhesive layer is achieved, resulting in particularly high adhesive shear strengths in Holzverklebungen using the invention Polymers leads.

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 inventively modified are suitable Polyolefins also as a matrix 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 For example, if the wood used is massive real wood, to real wood laminates, to plastic laminates, to 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 not significant to the polymer of the invention weakened, so even after a long storage period still high Klebscherwerte on. By the nature in Wood existing moisture succeeds in the bonding below Involvement of wood a particularly complete networking, which leads to extremely resistant bonds leads.

The modified polymers of the invention are characterized in that they (without further additives) in a pure wood bonding (wood: untreated beech) after at least 14 days storage in a climatic chamber at 20 ° C / 65% relative humidity, a Klebscherfestigkeit of at least 2 N / mm ² , preferably of at least 2.5 N / mm ² , more preferably of at least 3 N / mm ² and particularly preferably of at least 4 N / mm ² .

After storage for 42 days in a climatic chamber at 20 ° C / 65% relative humidity (without further additives) Klebscherfestigkeiten on untreated wood test specimens (wood: beech) of at least 3.5 N / mm ² , preferably of at least 4 N / mm ² , more preferably at least 4.5 N / mm ² and especially preferably more than 5 N / mm ² .

One another essential field of application of the invention Bondings are bonds 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 bonding according to the 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.

In another embodiment of the present invention it is the object to be bonded to a label. The label may consist of a paper, plastic, metal and / or multilayer film and in particular for the marking of painted, coated, anodized and / or otherwise surface-treated metal, in particular Tinplate boxes and glass or plastic (in particular PET bottles) are used. In particular, it may be at the Adhesive for label gluing around a so-called "pressure-sensitive" adhesive (PSA) act.

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 in the form of a film), natural and / or synthetic Textiles, nonwoven, imitation 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 are in particular the good adhesion the modified polyolefins according to the invention on untreated polyolefin surfaces, in particular on Polyethylene, together with the high strength of the bond (also at low application weights), sufficient flexibility both the uncrosslinked and the crosslinked polymers to call special advantage.

Preferably the bond is used for carpet backing. In addition, in addition, a textile substrate be laminated against.

The carpet elements obtained are, for example, so-called yard goods, carpet tiles or a subsequently deformable car carpet. In the mentioned applications for nubbin 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 1250 up to 6500 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. A particular characteristic of the polymers modified according to the invention is a combination of low melt viscosity and high tensile strength (material cohesion).

Furthermore, the adhesions according to the invention can be shoe adhesions which are used, for example, in the field of sports shoes and / or for the production of so-called split leather you can.

Also Adhesions according to the invention are so-called "pressure-sensitive Bonding "(PSA). It is advantageous if at least one of the included polymers and / or formulation ingredients a "cold river" (that means no Melting point or a melting point below room temperature) having. For example, cold flow formulation ingredients are Poly (1-hexene), poly (1-octene), poly (1-hexene-co-1-octene), polyacrylates etc. By networking the invention modified polyolefins within the corresponding adhesive formulation can be particularly elastic adhesive bonds produce.

in the Traps of book bindings are usually one Bonding made in the process of bookbinding.

at Textile bonding can be several layers of textile or be connected to each other, wherein to be bonded Textile elements natural or synthetic materials may include. In particular, it is the natural Textile elements such as wool, horsehair, cotton, linen, 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-containing composite material, which as further components z. B. metal foils / metal layers (z. B. based on aluminum) and / or plastic films can.

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. A special Characteristic of the modified invention Polymers is their very good miscibility with bitumen, which u. a. also expresses that only very low amounts of polymer required for a phase inversion of the polymer / bitumen mixture become. In the case of geomembranes, the proportion of the invention is 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 polypropylene, untreated polyethylene 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 addition to the modified polyolefins according to the invention, further constituents may be present in the primers or primer formulations according to the invention. In particular, in the liquid at room temperature primers / primer formulations cyclic and / or linear aliphatic and / or aromatic Contain hydrocarbons with or without heteroatoms, also the use of the corresponding halogenated hydrocarbons is possible. Preferably, however, no halogenated hydrocarbons are used. In the primers / primer formulations which are liquid at room temperature, the hydrocarbons mentioned have a formulation proportion of not more than 95% by mass, preferably not more than 93% by mass, more preferably not more than 90% by mass, and particularly preferably not more than 85% by mass.

Farther the modified invention are suitable Polyolefins for use in dispersions, suspensions and / or Emulsions. In the dispersions, suspensions and / or Emulsions is the proportion of the invention Polyolefins 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) monomertacticity, 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 the ability to out of a Defor relaxation resulting dissipative dissipation over a certain time (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. Since this degradation process requires a minimum shear rate, the material flows below this shear rate like a Newtonian fluid. One explanation provides the principle of Le Chatelier, where the "dodging" of the pseudoplastic liquid (before the mechanical stress) in alignment along the thrust surfaces to reduce the frictional resistance consists. The latter leads to the degradation of the equilibrium structure of the initial state and to the construction of a thrust-oriented structure, which in turn has a facilitated flow (viscosity reduction) result. In polymer melts, the Newtonian range is perceptible only at very low shear rates or small shear amplitudes. Its determination is possible and necessary via rheometric test methods (amplitude "sweeps", ie measurement at a fixed frequency as a function of the shear amplitude), if the measurement is to be carried out in the reversible, ie reproducible range [ RS steering; "Rheology of plastics"; C. Hanser Verlag; Munich; 1971 ; J. Meissner; "Rheological behavior of plastic melts and solutions" in: "Practical rheology of plastics", VDI-Verlag; Dusseldorf; 1978 ; J.-F. Jansson; Proc. 8th. Int. Congr. Rheol .; 1980; Vol. 3 ]. The vibrational rheometry is due to their low force, their low deformation and thus low impact on the sample morphology particularly well suited for the investigation of materials that show pseudoplastic behavior.

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 in aluminum bowls cast and cured samples punched out with a punching iron (diameter 30 mm). The determination takes place as a double determination. The layer thickness of the polymer samples is> 5 mm. The samples will be placed in the sample holder and measured (measuring instrument: PANalytical PW 2404). The quantitative determination is made against an external one Calibration of Si in borax tablets.

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:

Inventive base polymers and comparative examples according to the invention

The preparation of the base polymers (inventive Ex. No. 3-6) is carried out using a mixed contact of a crystalline titanium trichloride in the form of an aluminum-reduced TiCl ₄ (TiCl ₃ x 0.33AlCl ₃ ) and aluminum triisobutyl (in a weight ratio of 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:

One semi-crystalline 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 (VWZ) mixed. The excess monomer is in the last Zone of the extruder evaporated at a vacuum of about 20 mbar. Subsequently stabilization takes place by about 0.3 m-% IRGANOX 1076.

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.

With the modified polyolefins according to the invention, it is possible on very untreated wooden surfaces to achieve very high adhesive shear values which are up to 10 times higher than the values known in the prior art lie (see 1 ).

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.

With the modified polyolefins according to the invention can be on untreated polypropylene Klebscherfestigkeiten as known from the prior art (see 2 ).

Example formulations for adhesives / sealants with polymers of the invention.

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

• 74.8 parts by weight according to the invention modified polyolefin according to Ex. 14
• 5 parts by weight of DBTL masterbatch (98% by mass VESTOPLAST ^® 708, 2% by mass of dibutyltin dilaurate)
• 20 parts by weight of isotactic poly (1-butene)
• 0.2 part by weight of IRGANOX 1076 (octadecyl-3,5-di- (tert-butyl) -4-hydroxy-hydrocinnamate)

Fiber-reinforced molding compound

• 59.8 parts by weight according to the invention modified polyolefin according to Ex. 14
• 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)
• 30 parts by weight of isotactic poly (1-butene)
• 0.2 part by weight of 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. 13
• 39.3 parts by weight of partially crystalline polyolefin (z. B. VESTOPLAST 708) 5 parts by weight of DBTL masterbatch (98% by mass VESTOPLAST ^® 708, 2% by mass of dibutyltin dilaurate)
• 10 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 of IRGANOX 1076 (octadecyl-3,5-di- (tert-butyl) -4-hydroxy-hydrocinnamate)

Sealant insulating glass

• 46.3 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)
• 20 parts by weight of butylrubber
• 20 parts by weight of zeolite, 3A
• 5 parts by weight of partially 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 of IRGANOX 1076 (octadecyl-3,5-di- (tert-butyl) -4-hydroxy-hydrocinnamate)

Hot melt adhesive for automotive interior

• 72.8 parts by weight modified according to the invention Polyolefin according to Ex. 12
• 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 of IRGANOX 1076 (octadecyl-3,5-di- (tert-butyl) -4-hydroxy-hydrocinnamate)

Hot melt adhesive for shoe bonding

• 49.8 parts by weight modified according to the invention Polyolefin according to Ex. 13
• 5 parts by weight of DBTL masterbatch (98% by mass VESTOPLAST ^® 708, 2% by mass of dibutyltin dilaurate)
• 20 parts by weight semi-crystalline polyolefin (z. B. VESTOPLAST ^® 408)
• 15 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 of IRGANOX 1076 (octadecyl-3,5-di- (tert-butyl) -4-hydroxy-hydrocinnamate)

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. 13
• 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-hydroxy-hydrocinnamate)

Hot melt adhesive for packaging (Material: polypropylene)

• 64.7 parts by weight of partially crystalline polyolefin (z. B. VESTOPLAST ^® 828)
• 20 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)
• 10 parts by weight hydrocarbon resin (eg: ESCOREZ 1102)
• 0.3 part by weight of IRGANOX 1076 (octadecyl-3,5-di- (tert-butyl) -4-hydroxy-hydrocinnamate)

Universal hot melt adhesive with a wide application profile

84.7 Weight fractions modified according to the invention Polyolefin according to Ex. 13

5 parts by weight of DBTL masterbatch (98% by mass VESTOPLAST ^® 708, 2% by mass of dibutyltin dilaurate)

3 Parts by weight of polyolefin wax (eg VESTOWAX A616)

7 Parts by weight of hydrocarbon resin (eg: ESCOREZ 1102)

0.3 Parts by weight IRGANOX 1076 (octadecyl-3,5-di- (tert-butyl) -4-hydroxy-hydrocinnamate)

Hot melt adhesive for edge banding

• 24.7 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)
• 15 parts by weight semi-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-hydroxy-hydrocinnamate)

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. 12

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]
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• US 3,075,948 [0006]
• - EP 0260103 B1 [0008]
• - DE 4000695 [0009]
• - JP 2003-002930 A [0010]
• WO 03/070786 [0011]
• - WO 2006/069205 [0012]
• WO 2007/067243 [0013]
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Cited non-patent literature

• - H.-G. Elias; Macromolecules; Vol. III; Wiley-VCH: Weinheim; 2001 [0014]
• - A. Turner-Jones; Polymer; 7 (1966); 23 ff [0030]
• - S. Berger, S. Braun, H.-O. Kalinowski, 13C-NMR spectroscopy, Georg Thieme Verlag Stuttgart 1985 [0119]
• AE Tonelli, NMR Spectroscopy and Polymer Microstructure, Verlag Chemie Weinheim 1989 [0119]
• - JL Koenig, Spectroscopy of Polymers, ACS Professional Reference Books, Washington 1992 [0119]
• JC Randall, Polymer Sequence Determination, Academic Press, New York 1977 [0119]
• A. Zambelli et al: Macomolecules, 8, 687 (1975) [0119]
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• - NP Cheremisinoff; "An Introduction to Polymer Rheology and Processing"; CRC Press; London; 1993 [0120]
• - RS steering; "Rheology of plastics"; C. Hanser Verlag; Munich; 1971 [0120]
• - J. Meissner; "Rheological behavior of plastic melts and solutions" in: "Practical rheology of plastics", VDI-Verlag; Dusseldorf; 1978 [0120]
• - J.-F. Jansson; Proc. 8th. Int. Congr. Rheol .; 1980; Vol. 3 [0120]
• - DIN EN 1426 [0121]
• - DIN 53 765 [0122]
• - DIN EN ISO 527-3 [0123]
• - DIN EN 1427 [0124]
• - DIN EN 1465 [0125]

Claims (35)

Modified polyolefin having a determined by ¹³ C-NMR spectroscopy content of 1-butene of at least 80% by mass and with a determined by ¹³ C-NMR spectroscopy content of isotactic poly (1-butene) triads of at least 60 mA %, based on the total detected 1-butene triads, and wherein one or more silanes are grafted onto the polyolefin. Polyolefin according to claim 1, characterized characterized in that the melt viscosity of the unmodified (ungrafted) Polyolefins at 190 ° C 50,000 to 3,000,000 mPa · s is. A polyolefin according to claim 1 or 2, characterized in that the softening point, measured by means of Ring & ball method, of unmodified (ungrafted) polyolefin 100-145 ° C is. Polyolefin according to one or more of claims 1 to 3, characterized in that the Needle penetration of the unmodified (ungrafted) polyolefin maximum 16 x 0.1 mm. Polyolefin according to one or more of claims 1 to 4, 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 5, characterized in that it is selected from poly (1-butene), poly (ethylene-co-1-butene), Poly (propylene-co-1-butene) and polyethylene-co-propylene-co-1-butene). Polyolefin according to one or more of claims 1 to 6, characterized in that the melt viscosity of the modified (grafted) uncrosslinked polyolefin at 190 ° C 1000 to 50,000 mPa · s. Polyolefin according to one or more of claims 1 to 7, characterized in that the Softening point, measured by ring & ball method, of the modified (grafted) uncrosslinked polyolefin is 80 to 135 ° C. Polyolefin according to one or more of claims 1 to 8, characterized in that the Needle penetration of the modified (grafted) uncrosslinked polyolefin maximum 17 x 0.1 mm. Polyolefin according to one or more of claims 1 to 9, characterized in that the Tensile strength in the uncrosslinked state is at least 2 MPa. Polyolefin according to one or more of claims 1 to 10, characterized in that the In the tensile test certain elongation at break in the uncrosslinked state at least 50%. Polyolefin according to one or more of claims 1 to 9, 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 10, characterized in that the by X-ray fluorescence spectroscopy certain silicon content is at least 0.3mA%. A process for the preparation of a modified polyolefin according to claim 1, characterized in that a polyolefin having a determined by ¹³ C-NMR spectroscopy content of 1-butene of at least 80% by mass and with a determined by ¹³ C-NMR spectroscopy content Isotactic poly (1-butene) triads of at least 60mA%, based on the total detected 1-butene triads, is contacted with at least one free radical initiator and one or more silanes, followed by a grafting reaction of the one or more silanes onto the polyolefin takes place. A method according to claim 14, 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 14 or 15, 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 14 to 16, characterized in that the grafting at a temperature of 80 to 250 ° C. Method according to one or more of claims 14 to 17, 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 14 to, characterized in that it is a melt process, wherein at least one radical initiator is metered directly into the melt. Method according to one or more of claims 14 to 19, characterized in that the temperature the polymer composition at the time of metering 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 13 as or in molding compounds, in protective compounds, as or in adhesives, in marking compounds, Coating materials, geomembranes or roofing membranes, as a primer or in primer formulations and / or primer formulations and / or in dispersions, suspensions or emulsions. Molding compounds, protective compounds, adhesives, marking compounds, Coating materials, geomembranes or roofing membranes, primers, primer formulations, Adhesion promoter formulations, dispersions, suspensions and / or Emulsions containing one or more modified polyolefins according to one or more of the claims 1 to 13. Molding compositions according to claim 22, 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 22, characterized in that they are hot melt adhesive formulations is. Adhesives according to claim 22 or 24, 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 22, characterized in that they additionally other Contain polymers, fillers and / or bitumen. Geomembranes according to claim 22 or 26, characterized in that the proportion of polyolefins according to one of claims 1 to 13 maximum 30 ma-%, based on the geomembrane. Adhesives containing one or more modified Polyolefins according to one or more of the claims 1 to 13. Adhesions according to claim 28, 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. Bonding according to claim 29, characterized in that it is adhesive bonds in the motor vehicle space acts. Packaging bonds according to claim 29, 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 29, characterized in that a coating weight of 20 to 1500 g / m ² is used. Artificial grass bonding according to claim 29 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 22, containing one or more polyolefins according to one or more of claims 1 to 13 characterized that they are used to treat a polyolefin surface becomes. Dispersions, suspensions and / or emulsions according to Claim 22 containing one or more polyolefins according to a or more of claims 1 to 13, characterized the proportion of polymer is more than 10% by mass, based on the total formulation, is.