Thermoplastic elastomer composition having low density and good mechanical properties by using uncoated hollow glass microspheres

Abstract

The present invention relates to a thermoplastic elastomer composition having a styrene block copolymer (SBC), a polyolefin or copolyester thermoplastic elastomer and uncoated hollow glass microspheres, wherein the polyolefin or thermoplastic elastomer is functionalized by grafting reaction with vinyl alkoxysilane, vinyl acyloxysilane, methacryloxyalkylalkoxysilane or methacryloxyalkylacyloxysilane or grafting reaction with anhydride of an unsaturated organic acid. The present invention also relates to a method for preparing a thermoplastic elastomer using the thermoplastic elastomer composition and the thermoplastic elastomer obtained thereby. In addition, the present invention also relates to different uses of the thermoplastic elastomer, wherein a thermoplastic elastomer with low density but good mechanical properties is required.

Description

Technical Field

[0001] The present invention relates to a thermoplastic elastomer composition having a styrene block copolymer (SBC), a polyolefin or copolyester-based thermoplastic elastomer (TPC) and uncoated hollow glass microspheres, wherein the polyolefin or TPC is functionalized by grafting reaction with vinylalkoxysilane, vinylacyloxysilane, methacryloxyalkylalkoxysilane, methacryloxyalkylacyloxysilane or grafting reaction with anhydride of an unsaturated organic acid. The present invention also relates to a method for preparing a thermoplastic elastomer using the thermoplastic elastomer composition according to the present invention and the thermoplastic elastomer obtained thereby. In addition, the present invention also relates to various uses of thermoplastic elastomers, in which a thermoplastic elastomer having a low density but good mechanical properties is required. Background Art

[0002] In many applications or for the manufacture of various parts, thermoplastic elastomers are required. Here, weight reduction is generally desired, so the thermoplastic elastomers used should have a low density. However, the reduction in the density of the thermoplastic elastomer should not be at the expense of mechanical properties and processability. It is also desirable that, in order to prepare thermoplastic elastomers with low density, no foaming process is required and they can be processed by standard injection molding processes or standard extrusion processes.

[0003] It is well known that vinylalkoxysilanes, vinylacyloxysilanes, methacryloxyalkylacyloxysilanes and methacryloxyalkylalkoxysilanes are suitable for free radical grafting of polyolefins. These so-called organofunctional silanes are suitable for surface modification of mineral and metal surfaces, since almost all of these surfaces have hydroxyl groups which usually form covalent bonds with alkoxysilanes (Si-OR+HO-Y->Si-O-Y+HO-R) and thus make bonding between the surface and the silane possible. Since the surface of the hollow glass microspheres is covered with Si-OH groups which can be consumed by alkoxysilanes or acyloxysilanes, alkoxysilanes and acyloxysilanes are extremely suitable for attaching hollow glass microspheres to polymers.

[0004] In such production methods known to date, non-functionalized glass microspheres are linked to the elastomeric phase of a thermoplastic elastomer via a functionalized elastomer. This is done by using grafted SBCs instead of grafted polypropylene. However, the thermoplastic elastomers obtained generally do not have sufficiently good mechanical values.

[0005] In order to reduce the density of pure thermoplastic compositions without elastomers, such preparation methods are known, in which functional groups are first applied to the surface of hollow glass microspheres, on which thermoplastics are coupled by emulsion methods. The hollow glass microspheres first functionalized by the emulsion method and coated with thermoplastics must then be dried and separated, and can then be embedded in another thermoplastic whose density is desired to be reduced. This multi-stage process is not only technically complex, but also time-consuming and cost-intensive. In addition, the method for reducing the density of thermoplastics is not easy to transfer to thermoplastic elastomers, because the latter are composed of at least two phases.

[0006] Furthermore, the same applicant of the present invention has filed an invention patent, namely the currently unpublished application with the application number DE 10 2017122 314, which discloses a thermoplastic elastomer composition with low density and good mechanical properties, which has a styrene block copolymer (SBC), a polyolefin functionalized with an anhydride of an organic acid and hollow glass microspheres surface-treated or surface-coated with a silane-type agent. In this prior application, the applicant always considered that the surface coating of the hollow glass microspheres was necessary for connecting the hollow glass microspheres to the thermoplastic phase in order to provide a thermoplastic elastomer (TPE) that is both light and has good mechanical values. Comparative tests using functionalized SBCs instead of functionalized polyolefins also resulted in a reduction in the weight of the TPE obtained, but the evaluation was not satisfactory. It was therefore considered necessary to ensure that the hollow glass microspheres were connected to the polyolefin used. For this purpose, surface-coated hollow glass microspheres and functionalized polyolefins were used in the prior application, through which they could be connected to each other. Summary of the invention

[0007] The inventors of the present application have now surprisingly found that lightweight thermoplastic elastomers with similar mechanical properties can also be prepared without using surface-treated or surface-coated hollow glass microspheres if the polyolefin or TPC is still in the form of a functionalized polyolefin or functionalized TPC.

[0008] The present invention solves the problem of providing a thermoplastic elastomer or an alternative composition having a low density (preferably <0.9 g / cm 3 ), and in the case of the thermoplastic elastomer or alternative composition, the mechanical values ​​are in a suitable range for many desired applications. In addition, thermoplastic elastomers can be prepared in a simpler, cheaper and faster way than previously using surface-coated hollow glass microspheres.

[0009] The thermoplastic elastomer composition according to the present invention has a styrene block copolymer (SBC), a polyolefin or copolyester thermoplastic elastomer and uncoated hollow glass microspheres, wherein the polyolefin or copolyester thermoplastic elastomer is functionalized by grafting reaction with vinylalkoxysilane, vinylacyloxysilane, methacryloxyalkylalkoxysilane, methacryloxyalkylacyloxysilane or grafting reaction with anhydride of an organic acid (functionalized polyolefin or TPC). The thermoplastic elastomer composition according to the present invention can be processed into a thermoplastic elastomer as a simple mixture of its components, for example in an extruder. For this purpose, no complicated intermediate steps or separation of intermediate products are required.

[0010] According to the present application, a thermoplastic elastomer is understood to be a thermoplastic elastomer which consists of a polymer mixture (blend) which comprises an elastomer and a thermoplastic or a thermoplastic elastomer and which has properties similar to those of vulcanized rubber at its use temperature, but which can be processed and handled like a thermoplastic at elevated temperatures.

[0011] Since the thermoplastic elastomer composition according to the present invention has a styrene block copolymer (SBC) as an elastomer component, it is also referred to herein as a styrene block copolymer (TPS)-based thermoplastic elastomer composition. This also applies to the thermoplastic elastomer according to the present invention.

[0012] It is assumed that due to its composition, the thermoplastic elastomer prepared from the thermoplastic composition according to the invention has a thermoplastic phase and an elastomeric phase, wherein the elastomeric phase comprises an SBC and the thermoplastic phase comprises a functionalized polyolefin or a functionalized TPC. When a functionalized polyolefin or TPC is used, the uncoated hollow glass microspheres, like the coated hollow glass microspheres of DE 10 2017 122 314, appear to have an affinity for the thermoplastic phase and not for the elastomeric phase. Comparative tests in which the functionalization of the polyolefin or TPC is replaced by the functionalization of the elastomer show that the TPE has significantly weakened mechanical properties.

[0013] The hollow glass microspheres used for preparing the thermoplastic elastomer according to the present invention are uncoated, i.e. those hollow glass microspheres that do not have a coating on their surface. In the present invention, coating is understood as a subsequent functionalization step after the preparation of the hollow glass microspheres. Uncoated hollow glass microspheres are glass microspheres whose surface is formed by the glass of the hollow glass microspheres.

[0014] The present invention also relates in particular to an embodiment, wherein in the thermoplastic elastomer composition according to the present invention, the styrene block copolymer is a triblock copolymer, in which two end blocks are formed by polystyrene and the middle block is formed by a polymer different from polystyrene. In this case, it is preferred that the middle block of the triblock copolymer is formed by polyolefin. The styrene block copolymer is preferably one selected from the group consisting of SEBS, SEPS, SBS, SEEPS, SiBS, SIS, SIBS or a mixture thereof. It is also preferred that the styrene block copolymer is not functionalized by anhydride, vinyl alkoxysilane, vinyl acyloxysilane, methacryloxyalkyl alkoxysilane or methacryloxyalkyl acyloxysilane of an organic acid. More preferably, the styrene block copolymer is a styrene block copolymer not grafted with anhydride, vinyl alkoxysilane, vinyl acyloxysilane, methacryloxyalkyl alkoxysilane or methacryloxyalkyl acyloxysilane of an unsaturated organic acid. The styrene block copolymer is preferably an ungrafted styrene block copolymer. The styrene block copolymers are preferably unfunctionalized styrene block copolymers.Styrene block copolymers that can be used according to the invention are described in more detail below.

[0015] In a further embodiment of the present invention it is preferred that in the thermoplastic elastomer composition according to the invention the functionalization of the functionalized polyolefin or TPC is carried out by anhydrides of unsaturated organic dicarboxylic acids, preferably anhydrides of organic 1,2-dicarboxylic acids, or by vinylalkoxysilanes, vinylacyloxysilanes, methacryloxyalkylalkoxysilanes or methacryloxyalkylacyloxysilanes.

[0016] The anhydrides of unsaturated organic carboxylic acids or vinylalkoxysilanes, vinylacyloxysilanes, methacryloxyalkylalkoxysilanes or methacryloxyalkylacyloxysilanes are preferably bonded to the polyolefins or TPC by free radical grafting. For this purpose, the anhydrides of unsaturated organic carboxylic acids or vinylalkoxysilanes, vinylacyloxysilanes, methacryloxyalkylalkoxysilanes or methacryloxyalkylacyloxysilanes are "grafted" onto suitable polyolefins or TPCs (grafting treatment). For this purpose, it is preferred to use anhydrides of unsaturated organic acids or vinylalkoxysilanes, vinylacyloxysilanes, methacryloxyalkylalkoxysilanes or methacryloxyalkylacyloxysilanes having reactive double bonds, in the case of anhydrides, for example maleic anhydride, in the case of organosilanes, specifically vinyl-functionalized or methacrylic acid-functionalized organosilanes. Further details about the polyolefins or TPCs grafted with anhydrides or alkoxysilanes or acyloxysilanes of unsaturated organic carboxylic acids and the preparation by grafting reaction are described below and shown in Figure 1 and 2 middle. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 The grafting reaction of a polyolefin or TPC 1 with a vinylsilane or methacryloxysilane 2 in the presence of a free radical initiator 3 is shown, producing a vinylsilane or methacryloxysilane grafted polyolefin or TPC 4 .

[0018] Figure 2 Also shown is the grafting reaction of polyolefin or TPC 1 with maleic anhydride (MAH) 5 in the presence of free radical initiator 3 to produce MAH grafted polyolefin or TPC 6.

[0019] exist Figure 3 The hollow glass microspheres 7 are connected according to Figure 1 4. The functionalized polyolefin or TPC was prepared according to Eq. DETAILED DESCRIPTION

[0020] In another embodiment according to the invention, the functionalized polyolefin in the thermoplastic composition according to the invention is preferably a functionalized polypropylene. Very particularly preferably, the functionalized polyolefin is a polypropylene grafted with maleic anhydride (MAH-g-PP).

[0021] In another embodiment according to the invention, the thermoplastic elastomer composition can additionally have a polyolefin or TPC which is preferably not functionalized with an anhydride of an organic carboxylic acid (unfunctionalized polyolefin or TPC). Particularly preferably, the unfunctionalized polyolefin is polypropylene or polyethylene, more preferably polypropylene. The polyolefins which can be used according to the invention are described below. It is also preferred that the unfunctionalized polyolefin is added to the composition according to the invention in which a functionalized polyolefin is used. It is also preferred that the unfunctionalized TPC is used in the composition according to the invention in which a functionalized TPC is present.

[0022] In one embodiment it is preferred that in the composition according to the invention a polyolefin functionalized by grafting reaction with anhydrides of unsaturated organic acids is used. In this embodiment, the resulting thermoplastic elastomer is suitable for adhesion to polypropylene or polyamide.

[0023] In another embodiment, it is preferred to use polyolefins functionalized by grafting reaction with vinylalkoxysilanes, vinylacyloxysilanes, methacryloxyalkylalkoxysilanes or methacryloxyalkylacyloxysilanes in the composition according to the invention. In this embodiment, the resulting thermoplastic elastomer is particularly suitable for adhesion to polypropylene. If adhesion to polyamides is desired, this can be achieved by additionally adding polyolefins functionalized by grafting reaction with anhydrides of unsaturated organic acids.

[0024] In a further embodiment, it is preferred to use in the composition according to the invention a TPC which has been functionalized by grafting reaction with vinylalkoxysilanes, vinylacyloxysilanes, methacryloxyalkylalkoxysilanes or methacryloxyalkylacyloxysilanes or with anhydrides of unsaturated organic acids, preferably with anhydrides of unsaturated organic acids and more preferably with maleic anhydride. In this embodiment, the resulting thermoplastic elastomer is preferably used for bonding to polar thermoplastics, for example ABS, PC, PC / ABS, PA or SAN.

[0025] Furthermore, the thermoplastic elastomer composition may additionally contain a plasticizer. Corresponding plasticizers that can be used according to the invention are likewise described below.

[0026] Furthermore, the thermoplastic elastomer composition according to the invention may also contain further additives, such as stabilizers, auxiliaries, dyes, further fillers other than hollow glass microspheres and / or compatibilizers, which are likewise described in more detail below.

[0027] The present invention also relates to a process for preparing a thermoplastic elastomer of the styrene block copolymer type. In this case, the ingredients of the thermoplastic elastomer composition according to the invention are mixed with one another at a temperature in the range of 150° C. to 240° C., preferably in the range of 180° C. to 220° C. The process according to the invention is described in more detail below.

[0028] The invention also relates to a thermoplastic elastomer obtainable or obtained by the process according to the invention. The thermoplastic elastomer according to the invention is characterized by a hardness in the range of 40 Shore A hardness up to 30 Shore D hardness, a hardness in the range of 0.5 to 1.1 g / cm 3 Low density in the range of 2.0 MPa, tensile strength of at least 2.0 MPa, elongation at break of at least 100% and compression set of less than 70% after 72 hours at room temperature. All mentioned (preferred) features of the elastomer composition according to the invention should also apply to the thermoplastic elastomer according to the invention.

[0029] The present invention also relates to the use of a polyolefin or TPC for preparing a thermoplastic elastomer composition according to the invention or a thermoplastic elastomer according to the invention, wherein the polyolefin or TPC is functionalized by grafting reaction with a vinylalkoxysilane, vinylacyloxysilane, methacryloxyalkylalkoxysilane or methacryloxyalkylacyloxysilane or an anhydride of an unsaturated organic carboxylic acid.

[0030] Furthermore, the present invention also relates to the use of uncoated hollow glass microspheres for preparing the thermoplastic elastomer composition according to the invention or the thermoplastic elastomer according to the invention.

[0031] It is known that thermoplastic elastomers are not only suitable as the only material for the manufacture of any product or article. Rather, this class of materials is characterized by being combined with thermoplastics (hard plastics or hard components), more precisely without the use of additional adhesives, tackifiers or tackification methods, such as corona treatment. It is also known that the composition of the various TPEs (soft components) determines their ability and strength to combine with the selected hard component. Therefore, providing TPEs with suitable properties for compounding with other thermoplastics is almost always one of the tasks of TPE manufacturers.

[0032] The present invention therefore also relates to the use of the thermoplastic elastomer according to the invention for preparing a composite material with a thermoplastic (hard component), such as a polyolefin, a polyamide or another polar thermoplastic, or for bonding the thermoplastic elastomer composition according to the invention to one of these thermoplastics. In other words, the present invention also relates to a method for preparing a composite material, the composite material consisting of a thermoplastic elastomer according to the invention and a thermoplastic, such as a polyolefin, a polyamide or another polar thermoplastic, wherein the thermoplastic elastomer composition is compounded with the thermoplastic. In this case, the processing method used as the preparation of the article in the use according to the invention or in the method according to the invention is injection molding, multi-component injection molding, insert injection molding, extrusion, coextrusion or compression molding, wherein injection molding, multi-component injection molding, insert injection molding, extrusion and coextrusion and very particularly preferably multi-component injection molding are preferred. As described above, the use of functionalized polyolefins is particularly suitable for bonding to polypropylene or polyamide as the thermoplastic hard component. As also described above, the use of functionalized TPCs is particularly suitable for adhesion to polar thermoplastics.

[0033] The invention therefore also relates to a composite material consisting of a thermoplastic elastomer according to the invention and a thermoplastic, particularly preferably a polyamide, a polyolefin or another polar thermoplastic, such as ABS, PC, PC / ABS or SAN.

[0034] The invention also relates to the use of the thermoplastic elastomers according to the invention and / or the composite materials according to the invention as components or moldings for use in the interior and exterior areas of automobiles, in industrial plants, industrial tools, power tools for professional and / or personal use, household appliances, products in the consumer electronics sector, medical consumables and devices, containers for sports goods, hygiene products and cosmetics, sealing materials or consumable preparations.

[0035] The components mentioned above and used in the thermoplastic elastomer composition according to the invention or in the thermoplastic elastomer according to the invention and in the uses and methods according to the invention are described in more detail below:

[0036] A: Styrene block copolymer

[0037] B: Functionalized polyolefin or functionalized TPC

[0038] C: Hollow glass beads

[0039] D: Polyolefin or TPC (each unfunctionalized)

[0040] E: Plasticizer

[0041] F: Stabilizers, additives, dyes

[0042] Component A: Styrene block copolymer

[0043] According to the invention, the term "styrene block copolymer" (SBC) is understood to mean a multiblock copolymer in which at least one block is polystyrene. At least one of the other blocks is usually polybutadiene, polyisoprene or polyisobutylene. SBC can be a triblock copolymer of ABA structure, in which the A block is usually polystyrene and the B block is usually composed of polybutadiene, polyisoprene or polyisobutylene (SBS, SIS, SiBS). Alternatively, in the A block, the styrene monomer can be partially or completely replaced by a derivative of styrene, such as α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-tert-butylstyrene, 4-cyclohexylstyrene or vinylnaphthalene such as 1-vinylnaphthalene and 2-vinylnaphthalene. Alternatively, the B block can also contain a mixture of dienes such as SIBS (the B block consists of a mixture of butadiene and isoprene). In addition, it is also conceivable to use an SBC composed of styrene monomers and diene monomers as a hydrogenated derivative. In this case, the units of the B block are partially or completely present in hydrogenated form. Polystyrene block-poly(ethylene-co-butylene) block-polystyrene (SEBS), polystyrene block-poly(ethylene-co-propylene) block-polystyrene (SEPS) and polystyrene block-poly(ethylene-co-(ethylene-propylene)) block-polystyrene (SEEPS) are preferably mentioned here. In addition to triblock copolymers of the monomers mentioned below, diblock copolymers, tetrablock copolymers or multiblock copolymers of styrene, styrene derivatives (A blocks) and butadiene, isoprene, isobutylene and mixtures thereof (B blocks) with different A and B block sequences (e.g. BAB, ABAB, etc.) can also be used as an alternative. Preferred SBCs consist of the triblock copolymer ABA.

[0044] The SBC according to the invention preferably has a weight average molecular weight (Mw) of 50,000 to 1,000,000 g / mol, particularly preferably 100,000 to 500,000 g / mol.

[0045] The SBC is preferably present in the thermoplastic elastomer composition according to the present invention or in the thermoplastic elastomer according to the present invention in an amount ranging from 12 to 30 wt. %, more preferably ranging from 15 to 25 wt. % and most preferably ranging from 18 to 23 wt. %, based on the total weight of the thermoplastic elastomer composition or the thermoplastic elastomer.

[0046] Component B: Functionalized polyolefin or functionalized TPC

[0047] According to the invention, as described above, the polyolefin or TPC is functionalized with vinylalkoxysilane, vinylacyloxysilane, methacryloxyalkylalkoxysilane or methacryloxyalkylacyloxysilane or an anhydride of an unsaturated organic acid. Preferably, the functionalization is carried out by grafting, wherein vinylalkoxysilane, vinylacyloxysilane, methacryloxyalkylalkoxysilane or methacryloxyalkylacyloxysilane or an anhydride of an unsaturated organic acid is grafted onto a suitable polyolefin. After the grafting reaction with the vinylalkoxysilane, the polyolefin or TPC is present in the form of a 2-ethyl-alkoxysilane-modified polyolefin or TPC. After the grafting reaction with the vinylacyloxysilane, the polyolefin or TPC is present in the form of a 2-ethyl-acyloxysilane-modified polyolefin or TPC. After the grafting reaction with methacryloxyalkylalkoxysilane, the polyolefin or TPC is in the form of a 2-methyl-acryloyl-alkylalkoxysilane-modified polyolefin or TPC. After the grafting reaction with methacryloxyalkylacyloxysilane, the polyolefin or TPC is in the form of a 2-methyl-acryloyl-alkylacyloxysilane-modified polyolefin or TPC. After the grafting reaction with the anhydride of an unsaturated organic acid, the polyolefin or TPC is in the form of a 1,2-dicarboxylic acid-modified polyolefin or TPC. These are polyolefins or TPCs modified with vinylalkoxysilane, vinylacyloxysilane, methacryloxyalkylalkoxysilane or methacryloxyalkylacyloxysilane or anhydride of an unsaturated organic acid with the aid of a free radical initiator as described above. Figure 1 and 2 The reaction products of the reaction in the reaction equation.

[0048] "Grafting" is generally understood to mean that in the case of an already preformed molecular chain of a base polymer (here a polyolefin or TPC), further molecular components (here vinylalkoxysilane, vinylacyloxysilane, methacryloxyalkylalkoxysilane or methacryloxyalkylacyloxysilane or anhydride of an unsaturated organic carboxylic acid) are subsequently "grafted" onto it. Such functionalized polymers are also referred to as "grafted polymers". Grafted polymers can be prepared in different ways, for example after mixing the base polymer with the molecular components to be grafted in the desired ratio and then forming free radicals by decomposition of peroxides or by irradiation, preferably by peroxides. In this case, free radical sites are formed on the base polymer, to which the molecular components to be grafted are added. For this purpose, the anhydride of the organic carboxylic acid must have reactive sites that can be attacked by the free radical sites of the base polymer. Grafting can sometimes also occur if the mixture of the base polymer and the molecular components to be grafted is subjected to an intense mechanical heat treatment. The grafting reaction of the polymer is preferably carried out in a solid phase reactor, a mill, an extruder or in solution or emulsion in a reactor and is known to those skilled in the art in the field of thermoplastics. For polyolefins or TPCs, it is preferred to react in a solid phase reactor or extruder.

[0049] In the present invention, polyolefins are understood to be polymers which are prepared from olefins such as ethylene, propylene, 1-butene or isobutylene by chain polymerization. In this case, saturated polymers are preferably prepared by polymerization from unsaturated olefins.

[0050] In this case, the polyolefin according to the invention may be a homopolymer, a random copolymer or also a block copolymer, such as a polyolefin block copolymer (OBC), wherein preference is given according to the invention to homopolymers or random copolymers, which are preferably prepared from olefins, preferably aliphatic olefins.

[0051] Particularly preferably, the polyolefin is a non-elastomeric polyolefin, ie has no elastomeric properties. The polyolefin is more preferably a thermoplastic.

[0052] As grafting basis, commercially available polyolefins can be used, which are described below:

[0053] The polyolefin may be, for example, a homopolymer or a random copolymer consisting of olefins. Examples are: copolymers of polyethylene, such as HDPE (high density polyethylene), MDPE (medium density polyethylene), LDPE (low density polyethylene), LLDPE (linear low density polyethylene), VLDPE (very low density polyethylene); homopolymers of propylene (hPP); random copolymers of propylene and ethylene (rPP); and combinations thereof.

[0054] Polyolefins suitable for the invention as a basis for functionalization with anhydrides of dicarboxylic acids are in particular those which are suitable for processing by injection molding. Suitable polyolefins are those which have good flow properties and rigidity.

[0055] Homopolymers of propylene (hPP) are commercially available and any of these available hPP can be used according to the present invention. It is preferred to use hPP according to the present invention.

[0056] Commercially available hPP is, for example, a product of LyondellBasell, which is marketed under the trade name Available, such as HP500N, HP501L.

[0057] Random polypropylene copolymers (rPP) are likewise commercially available and any of these rPP may be used according to the present invention. As copolymer monomers, ethylene and / or butene are preferred.

[0058] Polyethylenes of different densities such as HDPE, MDPE, LDPE, LLDPE, VLDPE can be used according to the invention. These are commercially available in abundance.

[0059] However it is particularly preferred according to the present invention that the polyolefin is a polyolefin comprising propylene in its repeating units. Still more preferably, the polyolefin is hPP.

[0060] The OBC that can be used as a polyolefin according to the present invention is a block copolymer whose blocks are composed of olefin monomers as repeating units. In this case, the OBC according to the present invention has at least two different polymer blocks. These blocks can be composed of one olefin category or of two or more olefin categories. The olefin used to constitute the OBC that can be used according to the present invention is an aliphatic olefin, such as ethylene, propylene or butene, wherein ethylene and propylene are preferred according to the present invention. Particularly preferably, the OBC that can be used according to the present invention is composed only of aliphatic olefins as so-called repeating units. According to the present invention, the definition of OBC excludes those with aromatic groups (these are referred to as TPS (thermoplastic elastomers based on styrene) by those skilled in the art). For the applications described herein or for the compositions according to the present invention, it is particularly preferred that such OBC, whose blocks are composed of polypropylene, polyethylene or random ethylene / propylene copolymers or are composed of them. Commercially available is, for example, the OBC with the trade name Hifax CA 10 A of LyondellBasell. In addition, it is particularly preferred to be the polyolefin block copolymer described in detail in US 8,481,637 B2 (referred to there as "olefin block copolymer, OBC"), which is cited in full herein as a reference. Included here are polymers having alternating blocks of hard (very rigid) and soft (highly elastic) segments. These products are marketed by Dow Elastomers under the trade name INFUSE TM Particularly preferred are the types of TPE recommended for application (INFUSE TM 9010, 9007, 9107, 9807).

[0061] Further examples of OBCs which can be used according to the invention are so-called hydrogenated diene block copolymers. Such polymers preferably have polymer blocks consisting of hydrogenated polybutadiene or hydrogenated polyisoprene.

[0062] It is preferred according to the invention to use OBC together with a non-elastomeric polyolefin.

[0063] Preferably, TPCs (copolyester TPEs) suitable according to the invention are usually copolyesters in the form of copolymers, which have monomer components connected via ester groups (-C(=O)-O-) in the polymer backbone. Such thermoplastic copolyester elastomers can be prepared by polycondensation. Such copolyesters are preferably multiblock copolyesters, which usually have crystalline segments consisting of hard blocks (X) and amorphous segments consisting of soft blocks (Y). Suitable monomer components for constructing hard blocks (X) and soft blocks (Y) in multiblock copolyesters are known to those skilled in the art. Copolyesters preferably used according to the invention have a melting point or softening point in the range of 160°C to 300°C, preferably 165°C to 270°C, particularly preferably 170°C to 220°C. Preferred TPCs according to the invention are linear multiblock polyesters with randomly distributed high-melting hard polyester blocks and low-melting soft polyester blocks. In this case, the hard blocks form crystalline regions and the soft blocks form amorphous regions, which determine the elastic behavior at the application temperature of the TPC. The hard polyester blocks are preferably composed of short-chain dicarboxylic acids or aromatic dicarboxylic acids or mixtures of dicarboxylic acids having less than 4 C atoms. Preference is given to aromatic dicarboxylic acids, particularly preferably isophthalic acid or terephthalic acid. The alcohol component is likewise preferably difunctional and consists of short-chain alkyl diols or short-chain polyoxyalkylene diols having less than 3 repeating units or mixtures of different diols. Preference is given to short-chain diols such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol, particularly preferably 1,4-butanediol. The soft polyester blocks are preferably composed of aliphatic or aromatic dicarboxylic acids, preferably aromatic dicarboxylic acids, very particularly preferably isophthalic acid or terephthalic acid. In order to produce soft regions in the case of TPC, different diol types are used, polyether diols such as polyethylene glycol, polypropylene glycol, polyethylene-co-propylene glycol, polytetramethylene glycol or soft polyester diols composed of alkane dicarboxylic acids, such as adipic acid or sebacic acid, and alkane diols, or polycaprolactone diols or aliphatic polycarbonate diols. However, mixtures of diols can also be used. Preference is given to combining hard TPC regions, the hard TPC regions being composed of terephthalic acid and short-chain diols, particularly preferably of 1,4-butanediol, with soft regions, wherein the hard TPC regions are preferably composed of terephthalic acid and polyether diols, very particularly preferably of polytetramethylene glycol. Copolyesters suitable as component B in the composition according to the invention can be prepared according to methods known to those skilled in the art or are commercially available. Suitable commercially available copolyesters are, for example, TICONA- P.GROUP– DSM– Kolon– PTS– Ria-Polymers– LG Chem.– and DuPont–

[0064] If an anhydride of an unsaturated organic acid is used for the grafting reaction, maleic anhydride is particularly preferably used.

[0065] In the case where vinylalkoxysilane, vinylacyloxysilane, methacryloxyalkylalkoxysilane or methacryloxyalkylacyloxysilane is used for the grafting reaction, monoalkoxy or monoacyloxysilane, dialkoxy or diacyloxysilane, or trialkoxy or triacyloxysilane can be used, wherein trialkoxysilane or triacyloxysilane is preferred. In addition, the alkoxy group may be a substituted or unsubstituted alkoxy group. Preferably, it is C 1-8 -alkoxy groups, more preferably methoxy, ethoxy or propoxy groups and most preferably methoxy groups. The acyloxy groups may be C 1-8 -acyloxy groups, among which C 1-3 -acyloxy groups and most preferably acetoxy groups. The last-mentioned groups preferably remain bonded to the silicon atom of the silane after grafting. In order to be able to graft silanes, the alkoxysilane to be grafted has another group with a double bond or an epoxy group. This group can be, for example, a substituted or unsubstituted vinyl, epoxy or alkylacryloyl group (alkyl=C 1-5 -alkyl, preferably C 1-3 -alkyl and particularly preferably methyl), said group may also be represented by the following group -(CH2) n -O- or –(CH2) n - is bonded to the silicon atom of the silane, wherein n=1 to 5, more preferably 1 to 3, still more preferably 3, wherein n-propyl is most preferred. In the group -(CH2) n In the case of -O-, the oxygen atom is bonded to the silicon atom of the silane. Such silanes to be grafted are available, for example, under the trade name of Wacker Available.

[0066] Preferred vinyl silanes are: vinyl trialkoxysilane (especially vinyl trimethoxysilane, vinyl triethoxysilane), vinyl alkyl dialkoxysilane (especially vinyl dimethoxymethylsilane), vinyl tricarboxysilane (especially vinyl triacetoxysilane). These are shown in the following formulas (I) to (III):

[0067]

[0068] Wherein, R2 to R5 are each independently an alkyl group, preferably a methyl group or an ethyl group.

[0069] Preferred methacryloxyalkylalkoxysilanes and methacryloxyalkylacyloxysilanes are: 3-methacryloxypropyl-trialkoxysilane or methacryloxymethyl-trialkoxysilane (especially 3-methacryloxypropyl-trimethoxysilane, 3-methacryloxypropyl-triethoxysilane, methacryloxymethyl-trimethoxysilane, methacryloxymethyl-triethoxysilane), 3-methacryloxypropyl-alkyldialkoxysilane or methacryloxymethyl-alkyldialkoxysilane (especially methacryloxymethyl-dimethoxymethylsilane), 3-methacryloxypropyl-tricarboxysilane or methacryloxymethyl-tricarboxysilane (especially: 3-methacryloxypropyl-triacetoxysilane). These are shown in the following formulas (IV) to (VI):

[0070]

[0071] Among them, R1 is an alkylene group, preferably a methylene group or a propylene group; R2 to R5 are each independently an alkyl group, preferably a methyl group or an ethyl group.

[0072] The amount of anhydride of the unsaturated organic carboxylic acid in the grafted polyolefin is in the range of 0.1 to 5 wt %, still more preferably in the range of 0.5 to 2 wt %, based on the total weight of the polyolefin functionalized with the anhydride of the organic carboxylic acid.

[0073] The amount of vinylalkoxysilane, vinylacyloxysilane, methacryloxyalkylalkoxysilane or methacryloxyalkylacyloxysilane in the grafted polyolefin is in the range of 0.5% to 5% by weight, still more preferably in the range of 1% to 4% by weight, based on the total weight of the polyolefin functionalized with vinylalkoxysilane, vinylacyloxysilane, methacryloxyalkylalkoxysilane or methacryloxyalkylacyloxysilane.

[0074] According to the invention, polypropylene, particularly preferably hPP, is preferably used as polyolefin. Polypropylene grafted with maleic anhydride is also known in the art as MAH-g-PP. One such MAH-g-PP is marketed under the trade name “ "TPPP" is known and is known, for example, under the model " TPPP 2112GA" or " TPPP 8112GA” is available.

[0075] The amount of anhydride of the unsaturated organic carboxylic acid in the grafted TPC is in the range of 0.1 wt % to 5 wt %, still more preferably in the range of 0.5 wt % to 2 wt %, based on the total weight of the TPC functionalized with the anhydride of the organic carboxylic acid.

[0076] One such MAH-g-TPC is marketed under the trade name " TPHY" is known and is referred to, for example, as " TPHY45602PCX" is available.

[0077] In the thermoplastic elastomer composition according to the present invention or the thermoplastic elastomer according to the present invention, the weight ratio of the functionalized polyolefin or TPC to the SBC is preferably in the range of 15:100 to 140:100, more preferably in the range of 20:100 to 98:100.

[0078] Component C: Hollow glass microspheres

[0079] The hollow glass microspheres that can be used in the thermoplastic elastomer composition according to the present invention or the thermoplastic elastomer according to the present invention have a glass shell and a hollow core, and can be filled with a gas having an atmospheric pressure or a reduced pressure. The glass shell contains silicon dioxide as a main component, and can contain sodium oxide, magnesium oxide, calcium oxide, boron oxide, phosphorus oxide, etc. as additional components.

[0080] The hollow glass microspheres can be substantially circular, but can also deviate from this shape, for example have an elliptical shape, and / or have recesses or indentations in the surface. Preferably, the hollow glass microspheres have a ratio of the shortest axis to the longest axis of ≥0.85, more preferably 0.90 and most preferably 0.95.

[0081] Since high shear forces act during the mixing of the thermoplastic elastomer composition according to the invention, the hollow glass microspheres may break. This breakage must be avoided by a correctly selected isostatic rupture strength (isostatischen Bruchfestigkeit; English: collapse strength). The hollow glass microspheres preferably have an isostatic rupture strength (10% by volume) of 55 MPa or more, more preferably 69 MPa or more and most preferably 100 MPa or more. "Isostatic rupture strength (10% by volume)" is defined according to ASTM D-3102-78, in which an appropriate amount of hollow glass microspheres is introduced into glycerol and the pressure is increased until 10% by volume is broken.

[0082] The average diameter is preferably in the range of 10 μm to 70 μm, more preferably in the range of 10 μm to 35 μm. The average diameter can be measured using a commercially available laser diffraction particle size measurement instrument.

[0083] Hollow glass microspheres preferably have a thickness of 0.9 g / cm 3 or less, more preferably 0.6 g / cm 3 or less and 0.3g / cm 3The actual density of the hollow glass microspheres is determined using a pycnometer, for example the AccuPyc II 1340 pycnometer from Micromeritics.

[0084] Hollow glass microspheres that can be used according to the invention are available from 3M Company. According to the invention, preferably iM16K type hollow glass microspheres are used.

[0085] In the thermoplastic elastomer composition according to the present invention or the thermoplastic elastomer according to the present invention, the weight ratio of the hollow glass microspheres to the SBC is preferably in the range of 30:100 to 250:100, more preferably in the range of 50:100 to 150:100.

[0086] Component D: Polyolefin or TPC (unfunctionalized)

[0087] The same polyolefins or TPCs mentioned above for the functionalized polyolefins or functionalized TPCs can be used here (here, however, unfunctionalized).

[0088] In the thermoplastic elastomer composition according to the invention or the thermoplastic elastomer according to the invention, the weight ratio of polyolefin or TPC (each unfunctionalized) to SBC is preferably in the range of 0:100 to 105:100, more preferably at most 80:100.

[0089] It is also preferred that the weight ratio of the sum of the polyolefin or TPC (each unfunctionalized) and the functionalized polyolefin or functionalized TPC to the SBC is in the range of 15:100 to 140:100.

[0090] Component E: Plasticizer

[0091] Suitable plasticizers are known to those skilled in the art in principle. Suitable plasticizers for non-polar elastomers (e.g. SBC) are industrial or medical mineral oils or white oils, natural oils, such as soybean oil or rapeseed oil, as well as alkyl sulfonyl esters, especially alkyl sulfonyl phenyl esters, wherein the alkyl substituent contains a straight and / or branched alkyl chain with>5 C atoms. Also dialkyl or trialkyl esters of trimellitic acid, wherein the alkyl substituent preferably contains a straight and / or branched alkyl chain with>4 C atoms. In addition, alkyl esters of dicarboxylic acids, tricarboxylic acids and higher polycarboxylic acids are also used as corresponding plasticizers, wherein the alkyl substituent is preferably a straight and / or branched alkyl chain. As examples, list: di(2-ethylhexyl) adipate and tributyl-O-acetyl citrate. In addition, the carboxylic acid esters of monoalkylene glycol and / or polyalkylene glycol can also be used as plasticizers, such as ethylene glycol adipate. According to the present invention, industrial or medical mineral oils or white oils are preferably used here. Examples of industrial mineral oil include Shell Catenex T 145S.

[0092] As suitable plasticizers, it is also possible to use mixtures of the substance classes described.

[0093] In the thermoplastic elastomer composition according to the present invention or the thermoplastic elastomer according to the present invention, the weight ratio of the plasticizer to the SBC is preferably in the range of 50:100 to 300:100, more preferably in the range of 100:100 to 250:100.

[0094] Component F: Additives, such as stabilizers, auxiliaries and colorants

[0095] Suitable additives are, for example, but not limited to: processing aids, metal soaps, fatty acids and fatty acid derivatives, paraffin waxes, microcrystalline waxes, lubricants, mold release agents, flame retardants, smoke suppressants, tackifiers, tracers, minerals, crystallization accelerators and retarders, antifogging agents, antistatic agents, and biocides and fungicides.

[0096] As processing aids and stabilizers, for example, the following can be used: anti-aging agents or anti-ozonants, such as anti-ozon waxes, stabilizers, such as heat stabilizers, anti-weathering stabilizers; oxidation inhibitors, antioxidants, UV stabilizers, other light stabilizers, defoamers, lubricants, dispersants, release agents, anti-caking agents, free radical scavengers, metal deactivators, and also additives such as foaming aids, foaming agents, impact modifiers, adhesives and viscosity modifiers.

[0097] Furthermore, as additives, colorants such as masterbatches, pigments, dyes, for example, titanium dioxide, lithopone, zinc oxide, iron oxide, ultramarine blue, chromium oxide, antimony sulfite can be used.

[0098] In the thermoplastic elastomer composition according to the present invention or the thermoplastic elastomer according to the present invention, the weight ratio of the sum of all additives to SBC is preferably in the range of 0.1:100 to 50:100, more preferably in the range of 0.5:100 to 25:100.

[0099] Preparation of the composition according to the invention:

[0100] The thermoplastic elastomer composition according to the invention can be prepared by mixing components A, B, C, D, E and F, as long as they are present in the composition. Mixing can be carried out in the mixing systems known in rubber and plastics technology, such as kneaders, internal mixers (e.g. internal mixers with intermeshing or tangential rotor geometry) and also in continuous mixing devices such as mixing extruders, for example mixing extruders with 2 to 4 and more screws (e.g. twin-screw extruders).

[0101] When carrying out the preparation method according to the invention, it is important to ensure that the mixing temperature is high enough so that, if components B and D are used according to the invention, a transition to a plastic state is possible, but the plastic state is not impaired. This is ensured if a temperature above the highest melting temperature or softening temperature of components B and C (if used according to the invention) is selected. At the same time, sufficient energy input must be ensured, which is determined by the number of revolutions and the throughput in the extruder (see the examples).

[0102] Particularly preferably, the mixing of the components, insofar as they are present in the composition, is carried out at a temperature in the range from 150°C to 240°C and preferably from 180°C to 220°C.

[0103] The terms "including", "containing", and "having / involving" used in this application should also be intended to include the term "consisting of in each instance where they are used, such that these embodiments are also disclosed in this application.

[0104] Example:

[0105] Determination methods and definitions:

[0106] The density was determined in accordance with DIN EN ISO 1183-1.

[0107] The Shore hardness is determined in accordance with DIN EN ISO 868 and DIN ISO 7619-1.

[0108] The determination of tensile strength and elongation at break was carried out in accordance with DIN 53504 / ISO 37. In contrast to ISO 37, the test was carried out with a type S2 test bar at an application rate of 200 mm / min.

[0109] The compression set was determined in accordance with DIN ISO 815-1, method A.

[0110] The tear strength was determined according to ISO 34-1.

[0111] Determination of the adhesion of the thermoplastic elastomer composition on PA6 according to VDI2019: PA6 with the product name Frianyl B3 V2 NC1102 from Nilit Plastics was used as PA6. The adhesion of the thermoplastic elastomer composition on polypropylene (PP) (type: HP501L; Manufacturer: Basell Polyolefins).

[0112] The melt flow index was determined in accordance with DIN EN ISO 1133.

[0113] Extruder parameters and injection molding parameters:

[0114] The preparation of the thermoplastic elastomer of the present invention is carried out in a continuous process on a twin-screw extruder (48L / D). Hollow glass microspheres are added by side feeding. The extruder speed is 500 rpm and the production capacity is 20 kg / h. The set temperature profile runs from 170 to 190° C. The extrudate is granulated for subsequent injection molding or extrusion processing.

[0115] The test specimens were prepared by injection molding using a temperature profile from 180 to 200°C.

[0116] Preparation Example

[0117] Table 1 shows the abbreviations used for the components in the Examples and Comparative Examples:

[0118] Table 1:

[0119] Components raw material A SBC B1 Polyolefins functionalized with anhydrides of organic carboxylic acids B2 Polyolefins functionalized with alkoxysilanes or acyloxysilanes C Hollow glass beads D Polyolefins (unfunctionalized) E Plasticizers F additive G Silanized hollow glass microspheres H SBC functionalized with anhydrides of organic carboxylic acids

[0120] Embodiment and comparative example:

[0121] Preparation of Thermoplastic Elastomer Compositions and Elastomers (According to the Invention and Not According to the Invention):

[0122] Thermoplastic elastomers were produced according to the above-described production variants using the ingredients shown in Tables 3 and 4. The manufacturers and types of the components used are given in Table 2. Mechanical measurements and values ​​concerning processability are given in Tables 5 and 6.

[0123] Table 2:

[0124]

[0125] *Maleic anhydride grafted SEBS

[0126] Preparation of polyolefin B2:

[0127] Functionalized polyolefin B2 was prepared by Silane for HP501L GF 31 was grafted. For this purpose, 0.06 wt.% HXY-85W (85% in white oil) was dissolved in 5 wt% Geniosil GF 31 liquid and fed into a twin screw extruder at room temperature to form HP501L. The weight % values ​​are based on the amount of polypropylene used. In the mixing section, the mixture is first slowly heated to 160° C. for homogenization. The temperature is then raised to 200° C., in which case free radical grafting takes place. The volatile components are removed by vacuum degassing.

[0128] Table 3:

[0129]

[0130] Comparative Example 1: There are no interacting groups between the polyolefin and the hollow glass microspheres; Comparative Examples 2 and 3: There are interacting groups between the polyolefin and the hollow glass microspheres; Examples 1 and 2: There are functionalized olefins but uncoated hollow glass microspheres;

[0131] Table 4:

[0132]

[0133] Example 3: with functionalized polyolefin, but with uncoated hollow glass microspheres; Comparative Example 4: with functionalized SBC, but with uncoated hollow glass microspheres; Comparative Example 5: with unfunctionalized polyolefin, but with uncoated hollow glass microspheres;

[0134] Table 5: Mechanical values ​​of the examples from Table 3:

[0135]

[0136] The values ​​of density, hardness, tensile strength, elongation at break and tear strength were recorded at room temperature.

[0137] Table 6: Mechanical values ​​of the examples from Table 4:

[0138]

[0139] The values ​​of density, hardness, tensile strength, elongation at break and tear strength were recorded at room temperature.

Claims

1. A thermoplastic elastomer composition comprising a styrene block copolymer, a polyolefin or copolyester thermoplastic elastomer and uncoated hollow glass microspheres, in, The polyolefin or copolyester thermoplastic elastomer is functionalized by grafting reaction with anhydride of unsaturated organic acid or vinyl alkoxysilane or vinyl acyloxysilane or methacryloxyalkylalkoxysilane or methacryloxyalkylacyloxysilane, The thermoplastic elastomer composition may or may not additionally contain an unfunctionalized copolyester thermoplastic elastomer or an unfunctionalized polyolefin, The weight ratio of the sum of the unfunctionalized copolyester-based thermoplastic elastomer or unfunctionalized polyolefin and the functionalized copolyester-based thermoplastic elastomer or functionalized polyolefin to the styrene block copolymer is in the range of 15:100 to 140:

100.

2. The thermoplastic elastomer composition according to claim 1, wherein The styrene block copolymer is a triblock copolymer in which two terminal blocks are formed of polystyrene and a middle block is formed of a polymer different from polystyrene.

3. The thermoplastic elastomer composition according to claim 2, wherein The middle block of the triblock copolymer is formed from a polyolefin.

4. The thermoplastic elastomer composition according to any one of claims 1 to 3, wherein the styrene block copolymer is SEBS, SEPS, SBS, SEEPS, SIS or SIBS.

5. The thermoplastic elastomer composition according to any one of claims 1 to 3, wherein The styrene block copolymer is not grafted with anhydride of unsaturated organic acid or vinyl alkoxysilane or vinyl acyloxysilane or methacryloxyalkylalkoxysilane or methacryloxyalkylacyloxysilane.

6. The thermoplastic elastomer composition according to any one of claims 1 to 3, wherein The anhydride of the unsaturated organic acid is an anhydride of an organic unsaturated dicarboxylic acid.

7. The thermoplastic elastomer composition according to any one of claims 1 to 3, wherein The anhydride of the unsaturated organic acid is an anhydride of an organic unsaturated 1,2-dicarboxylic acid.

8. The thermoplastic elastomer composition according to any one of claims 1 to 3, further comprising a plasticizer.

9. A method for preparing a thermoplastic elastomer, comprising mixing the ingredients of the thermoplastic elastomer composition according to any one of claims 1 to 8 with each other at a temperature in the range of 150°C to 240°C.

10. A thermoplastic elastomer obtainable by the process according to claim 9.

11. Use of a polyolefin or copolyester thermoplastic elastomer for preparing the thermoplastic elastomer composition according to any one of claims 1 to 8 or the thermoplastic elastomer according to claim 10, wherein: The polyolefin or copolyester-based thermoplastic elastomer is functionalized with anhydride of an unsaturated organic carboxylic acid or vinyl alkoxysilane or vinyl acyloxysilane or methacryloxyalkylalkoxysilane or methacryloxyalkylacyloxysilane.

12. Use of uncoated hollow glass microspheres for preparing the thermoplastic elastomer composition according to any one of claims 1 to 8 or the thermoplastic elastomer according to claim 10.

13. Use of the thermoplastic elastomer according to claim 10 for preparing a composite material with thermoplastic plastics.

14. A composite material consisting of the thermoplastic elastomer according to claim 10 and a thermoplastic plastic.

15. Use of the thermoplastic elastomer according to claim 10 and / or the composite material according to claim 14 as components or moldings in the interior and exterior areas of automobiles, industrial equipment, industrial tools, power tools for professional and / or personal use, household appliances, products in the consumer electronics sector, medical consumables and equipment, sports goods, containers for hygiene products and cosmetics, sealing materials or consumable preparations.

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