阅读说明：本技术 通过使用未涂覆的中空玻璃微珠而具有低密度和良好机械性能的热塑性弹性体组合物 (Thermoplastic elastomer composition having low density and good mechanical properties by using uncoated hollow glass microspheres ) 是由 F·维尔萨克 M·黑特里希 于 2020-03-13 设计创作，主要内容包括：本发明涉及具有苯乙烯嵌段共聚物(SBC)、聚烯烃或共聚酯类热塑性弹性体和未涂覆的中空玻璃微珠的热塑性弹性体组合物,其中该聚烯烃或热塑性弹性体通过与乙烯基烷氧基硅烷、乙烯基酰氧基硅烷、甲基丙烯酰氧基烷基烷氧基硅烷或甲基丙烯酰氧基烷基酰氧基硅烷的接枝反应或与不饱和有机酸的酸酐的接枝反应被官能化。本发明同样涉及使用该热塑性弹性体组合物制备热塑性弹性体的方法以及由此获得的热塑性弹性体。此外,本发明还涉及该热塑性弹性体的不同用途,其中需要具有低密度但具有良好机械性能的热塑性弹性体。(The invention relates to a thermoplastic elastomer composition with Styrene Block Copolymers (SBC), a thermoplastic elastomer of the polyolefin or copolyester type and uncoated hollow glass microbeads, wherein the polyolefin or thermoplastic elastomer is functionalized by a grafting reaction with a vinylalkoxysilane, a vinylacyloxysilane, a methacryloxyalkylalkoxysilane or with an anhydride of an unsaturated organic acid. The invention also relates to a method for preparing a thermoplastic elastomer by using the thermoplastic elastomer composition and the thermoplastic elastomer obtained by the method. Furthermore, the present invention also relates to different uses of the thermoplastic elastomer, wherein a thermoplastic elastomer with a low density but good mechanical properties is desired.)

1. A thermoplastic elastomer composition comprising a styrene block copolymer, a polyolefin or copolyester-based thermoplastic elastomer and uncoated hollow glass microspheres,

wherein the polyolefin or copolyester thermoplastic elastomer is functionalized by a grafting reaction with an anhydride of an unsaturated organic acid or a vinylalkoxysilane or a vinylacyloxysilane or a methacryloxyalkylalkoxysilane or a methacryloxyalkylsilyl.

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

3. The thermoplastic elastomer composition of claim 2, wherein the midblock of the triblock copolymer is formed from a polyolefin.

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

5. Thermoplastic elastomer composition according to any one of claims 1 to 4, wherein the styrenic block copolymer is not grafted with an anhydride of an unsaturated organic acid or a vinylalkoxysilane or a vinylacyloxysilane or a methacryloxyalkylalkoxysilane.

6. Thermoplastic elastomer composition according to any of claims 1 to 5, wherein the anhydride of an unsaturated organic acid is preferably an anhydride of an organic unsaturated dicarboxylic acid, preferably an anhydride of an organic unsaturated 1, 2-dicarboxylic acid.

7. The thermoplastic elastomer composition according to any one of claims 1 to 6, which further contains a plasticizer.

8. A process for producing a thermoplastic elastomer by mixing the ingredients of the thermoplastic elastomer composition according to any one of claims 1 to 7 with each other at a temperature in the range of 150 ℃ to 240 ℃.

9. A thermoplastic elastomer obtainable by the process of claim 8.

10. Use of a polyolefin or TPC for the preparation of the thermoplastic elastomer composition of any one of claims 1 to 7 or the thermoplastic elastomer of claim 9, wherein the polyolefin or TPC is functionalized with an anhydride of an organic carboxylic acid or a vinyl alkoxysilane or a vinyl acyloxy silane or a methacryloxy alkyl alkoxysilane or a methacryloxy alkyl acyloxy silane.

11. Use of uncoated hollow glass microspheres for the preparation of the thermoplastic elastomer composition of any one of claims 1 to 7 or the thermoplastic elastomer of claim 9.

12. Use of the thermoplastic elastomer according to claim 9 for the preparation of a composite with a thermoplastic.

13. A composite material consisting of the thermoplastic elastomer and thermoplastic of claim 9.

14. Use of the thermoplastic elastomer of claim 9 and/or the composite material of claim 13 as a part or moulding for containers, sealing materials or consumable formulations for automotive interior and exterior areas, industrial equipment, industrial tools, professional and/or personal use power tools, household appliances, products in the consumer electronics field, medical consumables and equipment, sporting goods, hygiene goods and cosmetics.

Technical Field

The invention relates to thermoplastic elastomer compositions having Styrene Block Copolymers (SBC), thermoplastic elastomers (TPC) of the polyolefin or copolyester type and uncoated hollow glass microbeads, wherein the polyolefin or TPC is functionalized by a grafting reaction with vinylalkoxysilanes, vinylacyloxysilanes, methacryloxyalkylalkoxysilanes or with anhydrides of unsaturated organic acids. The invention likewise relates to a process for preparing thermoplastic elastomers using the thermoplastic elastomer compositions according to the invention and to the thermoplastic elastomers obtained thereby. Furthermore, the present invention relates to various uses of thermoplastic elastomers, wherein thermoplastic elastomers having low density but good mechanical properties are desired.

Background

Thermoplastic elastomers are required in many applications or for the manufacture of various parts. Weight reduction is generally desired here, and the thermoplastic elastomers used should therefore have a low density. However, the reduction in density of the thermoplastic elastomer should not be at the expense of mechanical properties and processability. It is furthermore desirable that in order to prepare thermoplastic elastomers having a low density, no foaming process is required and that they can be processed by standard injection moulding processes or standard extrusion processes.

It is well known that vinylalkoxysilanes, vinylacyloxysilanes, methacryloxyalkylacyloxysilanes and methacryloxyalkylalkoxysilanes are suitable for the 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 (Si-OR + HO-Y- > Si-O-Y + HO-R) with alkoxysilanes and thus make possible a bond between the surface and the silane. Since the surfaces of the hollow glass microspheres are covered with Si-OH groups that can be consumed by alkoxysilane or acyloxysilane, alkoxysilane and acyloxysilane are excellently suitable for attaching the hollow glass microspheres to the polymer.

Hitherto known in such manufacturing methods are non-functionalized glass microbeads linked to the elastomer phase of the thermoplastic elastomer by means of a functionalized elastomer. This was done by using grafted SBC instead of grafted polypropylene. However, the thermoplastic elastomers obtained do not generally have sufficiently good mechanical values.

In order to reduce the density of the pure elastomer-free thermoplastic compositions, production processes are known in which first functional groups are applied to the surface of hollow glass microbeads, onto which thermoplastics are coupled in the emulsion process. Hollow glass microspheres that are first functionalized by the emulsion process and coated with a thermoplastic must subsequently be dried and isolated, and can then be embedded in additional thermoplastics where a reduction in density is desired. This multi-stage process is not only technically complex, but also time-consuming and costly. Furthermore, the process for reducing the density of thermoplastics is not easily transferable to thermoplastic elastomers, since the latter consist of at least two phases.

Furthermore, the same applicant of the present invention has already filed an invention patent, a so far unpublished application with application number DE 102017122314, which discloses a thermoplastic elastomer composition with low density and good mechanical properties having a Styrene Block Copolymer (SBC), a polyolefin functionalized with an acid anhydride of an organic acid, and hollow glass microspheres surface-treated or surface-coated with a silane-based agent. In this prior application, the applicant has always considered that a surface coating of the hollow glass microspheres is necessary for attaching the hollow glass microspheres to the thermoplastic phase, in order to be able to provide a thermoplastic elastomer (TPE) that is both lightweight and has good mechanical values. Comparative tests using functionalized SBC instead of functionalized polyolefin also resulted in a weight reduction of the TPE obtained, but the evaluation was not satisfactory. It is therefore considered necessary to ensure that the hollow glass microspheres are bonded to the polyolefin used. For this purpose, surface-coated hollow glass microspheres and functionalized polyolefins are used in this prior application, by means of which they can be linked to one another.

Disclosure of Invention

The inventors of the present application have now surprisingly found that it is also possible to prepare lightweight thermoplastic elastomers with similar mechanical properties without using surface treated or surface coated hollow glass microspheres, if the polyolefin or TPC is still present in the form of a functionalized polyolefin or functionalized TPC.

The present invention herein solves the problem of providing thermoplastic elastomers or alternative compositions having low density (preferably<0.9g/cm³) And in the case of the thermoplastic elastomer or alternative composition, the mechanical values are in a suitable range for many desired applications. Furthermore, the thermoplastic elastomer can be prepared in a simpler, cheaper and faster manner than previously using surface-coated hollow glass microspheres.

The thermoplastic elastomer composition according to the present invention has a Styrene Block Copolymer (SBC), a polyolefin or copolyester based thermoplastic elastomer and uncoated hollow glass beads, wherein the polyolefin or copolyester based thermoplastic elastomer is functionalized (functionalized polyolefin or TPC) by a grafting reaction with a vinyl alkoxysilane, a vinyl acyloxy silane, a methacryloxy alkyl alkoxysilane, a methacryloxy alkyl acyloxy silane or a grafting reaction with an acid anhydride of an organic acid. The thermoplastic elastomer composition according to the invention can be processed as a simple mixture of its components, for example in an extruder, to a thermoplastic elastomer. No complicated intermediate steps or isolation of intermediates are required for this purpose.

According to the present application, a thermoplastic elastomer is understood to be a thermoplastic elastomer consisting of a polymer mixture (blend) comprising an elastomer and a thermoplastic or thermoplastic elastomer and having similar properties at its use temperature as vulcanized rubber, however it can be processed and treated at elevated temperatures as a thermoplastic (aufbereitet).

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 invention.

It is hypothesized that due to its ingredients, the thermoplastic elastomer prepared from the thermoplastic composition according to the present invention has a thermoplastic phase comprising the SBC and an elastomeric phase comprising the functionalized polyolefin or functionalized TPC. When functionalized polyolefins or TPCs are used, the uncoated hollow glass microspheres, like the coated hollow glass microspheres of DE 102017122314, appear to have an affinity for the thermoplastic phase but not for the elastomeric phase. Comparative tests with functionalization of the elastomer instead of functionalization of the polyolefin or TPC show that TPEs have significantly impaired mechanical properties.

The hollow glass microspheres used to prepare the thermoplastic elastomer according to the present invention are uncoated, i.e. those hollow glass microspheres which do not have a coating on their surface. In the present invention, coating is understood to be a subsequent functionalization step after the preparation of the hollow glass microspheres. The uncoated hollow glass beads are glass beads whose surfaces are formed of glass of the hollow glass beads.

The present invention also relates to an embodiment in which, in the thermoplastic elastomer composition according to the invention, the styrene block copolymer is a triblock copolymer in which the two end blocks are formed of polystyrene and the middle block is formed of a polymer different from polystyrene. In this case it is preferred that the mid-block of the triblock copolymer is formed from a 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 styrenic block copolymer is not functionalized with an anhydride of an organic acid, a vinyl alkoxysilane, a vinyl acyloxy silane, a methacryloxyalkyl alkoxysilane or a methacryloxyalkyl acyloxy silane. More preferably, the styrene block copolymer is a styrene block copolymer which is not grafted with an acid anhydride of an unsaturated organic acid, a vinyl alkoxysilane, a vinyl acyloxy silane, a methacryloxyalkyl alkoxysilane or a methacryloxyalkyl acyloxy silane. The styrene block copolymer is preferably an ungrafted styrene block copolymer. The styrenic block copolymer is preferably an unfunctionalized styrenic block copolymer. The styrenic block copolymers that can be used according to the present invention are described in more detail below.

In a further embodiment of the present invention it is preferred that in the thermoplastic elastomer composition according to the present invention the functionalization of the functionalized polyolefin or TPC is carried out by an anhydride of an unsaturated organic dicarboxylic acid, preferably an anhydride of an organic 1, 2-dicarboxylic acid, or by a vinyl alkoxysilane, a vinyl acyloxy silane, a methacryloxy alkylalkoxysilane or a methacryloxy alkylalkoxysilane.

The anhydride of an unsaturated organic carboxylic acid or a vinylalkoxysilane, vinylacyloxysilane, methacryloxyalkylalkoxysilane or methacryloxyalkylalkoxysilane is preferably bonded to the polyolefin or TPC by free radical grafting. To this end, anhydrides of unsaturated organic carboxylic acids or vinylalkoxysilanes, vinylacyloxysilanes, methacryloxyalkylalkoxysilanes or methacryloxyalkylalkoxysilanes are "grafted" onto suitable polyolefins or TPCs (grafting treatment). For this purpose, preference is given to using anhydrides of unsaturated organic acids having reactive double bonds, such as maleic anhydride in the case of anhydrides, or else vinylalkoxysilanes, vinylacyloxysilanes, methacryloxyalkylalkoxysilanes or methacryloxyalkylalkoxysilanes, specifically vinyl-or methacrylic-functionalized organosilanes in the case of organosilanes. Additional details regarding polyolefins or TPCs grafted with anhydrides of unsaturated organic carboxylic acids or alkoxysilanes or acyloxysilanes, as well as the preparation by grafting reactions, are described below and shown in FIGS. 1 and 2.

Drawings

Figure 1 shows the grafting reaction of a polyolefin or TPC 1 with a vinyl silane or methacryloxy silane 2 in the presence of a free radical initiator 3 to produce a vinyl silane or methacryloxy silane grafted polyolefin or TPC 4.

Figure 2 also shows the grafting reaction of polyolefin or TPC 1 with Maleic Anhydride (MAH)5 in the presence of a free radical initiator 3, resulting in MAH-grafted polyolefin or TPC 6.

In fig. 3, hollow glass microspheres 7 are shown attached to the functionalized polyolefin or TPC 4 prepared according to the equation of fig. 1.

Detailed Description

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

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

In one embodiment it is preferred to use a polyolefin functionalized by a grafting reaction with an anhydride of an unsaturated organic acid in the composition according to the invention. In this embodiment, the resulting thermoplastic elastomer is suitable for adhering to polypropylene or polyamide.

In a further embodiment it is preferred to use polyolefins which are functionalized by grafting reactions with vinylalkoxysilanes, vinylacyloxysilanes, methacryloxyalkylalkoxysilanes or methacryloxyalkylalkoxysilanes in the compositions according to the invention. In this embodiment, the resulting thermoplastic elastomer is particularly suitable for adhesion to polypropylene. If adhesion to the polyamide is desired, this can be achieved by the additional addition of a polyolefin functionalized by a grafting reaction with an anhydride of an unsaturated organic acid.

In a further embodiment it is preferred to use in the composition according to the invention a TPC functionalized by a grafting reaction with a vinyl alkoxysilane, a vinyl acyloxy silane, a methacryloxy alkyl alkoxysilane or a methacryloxy alkyl acyloxy silane or with an anhydride of an unsaturated organic acid, preferably an anhydride of an unsaturated organic acid and still more preferably a TPC functionalized with maleic anhydride. In this embodiment, the resulting thermoplastic elastomer is preferably used for adhesion to polar thermoplastics, such as ABS, PC/ABS, PA or SAN.

Further, the thermoplastic elastomer composition may additionally contain a plasticizer. Corresponding plasticizers which can be used according to the invention are also described below.

Furthermore, the thermoplastic elastomer composition according to the invention may also contain further additives, such as stabilizers, auxiliaries, dyes, further fillers which are not hollow glass microspheres and/or compatibilizers. These are also described in more detail below.

The invention also relates to a method for preparing the styrene block copolymer thermoplastic elastomer. In this case, the ingredients of the thermoplastic elastomer composition according to the invention are mixed with each other at a temperature in the range of 150 ℃ to 240 ℃, preferably in the range of 180 ℃ to 220 ℃. The process according to the invention is described in more detail below.

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 up to 30 Shore D, in the range of 0.5 to 1.1g/cm³A low density in the range, a tensile strength of at least 2.0MPa, an elongation at break of at least 100% and a compression set (DruckverformingRest) of less than 70% after 72 hours at room temperature. All mentioned (preferred) features of the elastomer composition according to the invention should here also apply to the thermoplastic elastomer according to the invention.

The invention also relates to the use of a polyolefin or a TPC, which is functionalized by a grafting reaction with a vinylalkoxysilane, a vinylacyloxysilane, a methacryloxyalkylalkoxysilane or an anhydride of an unsaturated organic carboxylic acid, for the preparation of a thermoplastic elastomer composition according to the invention or a thermoplastic elastomer according to the invention.

Furthermore, the present invention relates to the use of uncoated hollow glass microspheres for the preparation of the thermoplastic elastomer composition according to the invention or the thermoplastic elastomer according to the invention.

It is known that thermoplastic elastomers are not only suitable as the only material used to manufacture any products and articles. In contrast, such materials are characterized by bonding to thermoplastics (hard plastics or hard components), more precisely without the use of additional adhesives, tackifiers or tackifying methods, such as corona treatment. It is also known that the composition of the various TPEs (soft components) determines their binding capacity and strength with the hard component chosen. Therefore, it is almost always a task of TPE manufacturers to provide TPEs with suitable properties to be compounded with other thermoplastics.

The invention therefore also relates to the use of the thermoplastic elastomer according to the invention for the preparation of a composite material with a thermoplastic (hard component), for example a polyolefin, a polyamide or another polar thermoplastic, or for adhering the thermoplastic elastomer composition according to the invention to one of these thermoplastics. In other words, the invention also relates to a process for the preparation of a 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 a thermoplastic elastomer composition is compounded with the thermoplastic. In this case, injection molding, multicomponent injection molding, insert injection molding (Spritzguss-Einlegeverfahren), extrusion, coextrusion or compression molding are used as processing methods for producing articles in the use according to the invention or in the process according to the invention, preference being given to injection molding, multicomponent injection molding, insert injection molding, extrusion and coextrusion and very particular preference to multicomponent injection molding. As described above, the use of functionalized polyolefins is particularly suitable for adhesion to polypropylene or polyamide as the thermoplastic hard component. As also described above, the use of functionalized TPC is particularly suitable for adhesion to polar thermoplastics.

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/ABS or SAN.

The invention also relates to the use of the thermoplastic elastomers according to the invention and/or the use of the composites according to the invention as components or moldings for use in the interior and exterior regions of automobiles, in industrial equipment, in industrial tools, in electric tools for professional and/or personal use, in household appliances, in products in the consumer electronics field, in medical consumables and devices, in sporting goods, in hygiene products and in containers for cosmetics, in sealing materials or in consumable formulations.

The components mentioned hereinbefore and used in the thermoplastic elastomer composition according to the invention or in the thermoplastic elastomer according to the invention and in the use and process according to the invention are described in more detail as follows:

a: styrene block copolymer

B: functionalized polyolefins or functionalized TPCs

C: hollow glass bead

D: polyolefins or TPCs (each unfunctionalized)

E: plasticizer

F: stabilizers, auxiliaries, dyes

And (2) component A: styrene block copolymer

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 further blocks is usually polybutadiene, polyisoprene or polyisobutylene. SBCs can be triblock copolymers of the a-B-a structure, where the a block is typically polystyrene and the B block is typically composed of polybutadiene, polyisoprene, or polyisobutylene (SBS, SIS, SiBS). Alternatively, in the A block, the styrene monomer may be partially or fully replaced by derivatives of styrene, such as alpha-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-tert-butylstyrene, 4-cyclohexylstyrene or vinylnaphthalenes, such as 1-vinylnaphthalene and 2-vinylnaphthalene. Or the B block may also contain a mixture of dienes such as SIBS (B block consists of a mixture of butadiene and isoprene). Further, it is also conceivable to use SBC composed of styrene monomer and diene monomer as the hydrogenated derivative. In this case, the units of the B block are present partly or completely in hydrogenated form. Preference is given here to 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). In addition to triblock copolymers of the monomers mentioned below, diblock, tetrablock or multiblock copolymers of different A-block and B-block sequences thereof (e.g., B-A-B, A-B-A-B, etc.) may alternatively be used: styrene, styrene derivatives (A block) and butadiene, isoprene, isobutylene and mixtures thereof (B block). Preferred SBCs are composed of triblock copolymers A-B-A.

SBC's according to the invention preferably have a weight-average molecular weight (Mw) of from 50,000 to 1,000,000g/mol, particularly preferably from 100,000 to 500,000 g/mol.

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

And (B) component: functionalized polyolefins or functionalized TPCs

According to the invention, the polyolefin or TPC is functionalized with a vinyl alkoxysilane, a vinyl acyloxy silane, a methacryloxy alkyl alkoxy silane or a methacryloxy alkyl acyloxy silane or an anhydride of an unsaturated organic acid, as described above. Preferably, the functionalization is carried out by means of Grafting (Grafting-azess), in which a vinylalkoxysilane, a vinylacyloxysilane, a methacryloxyalkylalkoxysilane 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 vinyl acyloxy silane, the polyolefin or TPC is present in the form of a 2-ethyl-acyloxy silane modified polyolefin or TPC. After the grafting reaction with methacryloxyalkylalkoxysilane, the polyolefin or TPC is present in the form of a 2-methyl-acryloyl-alkylalkoxysilane modified polyolefin or TPC. After the grafting reaction with methacryloxyalkyl acyloxy silane, the polyolefin or TPC is present in the form of a 2-methyl-acryloyl-alkyl acyloxy silane modified polyolefin or TPC. After the grafting reaction with the anhydride of the unsaturated organic acid, the polyolefin or TPC exists in the form of a 1, 2-dicarboxylic acid modified polyolefin or TPC. These are the reaction products of polyolefins or TPCs with vinylalkoxysilanes, vinylacyloxysilanes, methacryloxyalkylalkoxysilanes or anhydrides of unsaturated organic acids with the aid of free radical initiators according to the reaction equations in FIGS. 1 and 2 described above.

"grafting" is generally understood to mean the subsequent "grafting" of further molecular constituents (here vinylalkoxysilanes, vinylacyloxysilanes, methacryloxyalkylalkoxysilanes or anhydrides of unsaturated organic carboxylic acids) onto the already preformed molecular chains of the base polymer (here polyolefin or TPC). Such functionalized polymers are also referred to as "graft polymers". The graft polymers can be prepared in different ways, for example after mixing the base polymer with the molecular constituents to be grafted in the desired ratio, and then free radicals are formed by decomposition of peroxides or by irradiation, preferably by peroxides. In this case, free-radical sites are formed on the base polymer, to which sites the molecular constituents to be grafted are added. For this reason, the anhydrides of the organic carboxylic acids must have reactive sites which can be attacked by the free radical sites of the base polymer. Grafting can sometimes also occur if the mixture of base polymer and molecular constituents to be grafted is subjected to intensive mechanical heat treatment. The grafting reaction of the polymer is preferably carried out in a solid phase reactor, a rolling 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. It is preferred for the polyolefin or TPC to be reacted in a solid phase reactor or extruder.

In the context of the present invention, polyolefins are understood as meaning polymers which are prepared from olefins, such as ethylene, propylene, 1-butene or isobutene, by chain polymerization. In this case, saturated polymers are preferably prepared from unsaturated olefins by polymerization.

In this case, the polyolefin may according to the invention be a homopolymer, a random copolymer, but also a block copolymer, for example a polyolefin block copolymer (OBC), wherein according to the invention preferably a homopolymer or a random copolymer is produced, preferably from an olefin, preferably an aliphatic olefin.

Particularly preferably, the polyolefin is a non-elastomeric polyolefin, i.e. without elastomeric properties. The polyolefin is more preferably a thermoplastic.

As a basis for grafting, it is possible to use commercially available polyolefins, which are described below:

the polyolefin may for example be 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.

Polyolefins suitable for the invention on the basis of functionalization with anhydrides of dicarboxylic acids are in particular those which are suitable for processing in injection molding. Suitable polyolefins are those having good flow properties and rigidity.

Homopolymers of propylene (hPP) are commercially available and any of these available hpps may be used in accordance with the present invention. Preferably hPP is used according to the invention.

Commercially available hPP is for example the product of LyondellBasell, under the trade nameCan be obtained, e.g. asHP500N、HP501L。

Random polypropylene copolymers (rpps) are also commercially available and any of these rpps may be used in accordance with the present invention. As the copolymer monomer, ethylene and/or butene is preferable.

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

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

The OBC which can be used as the polyolefin according to the present invention is a block copolymer whose blocks are composed of an olefin monomer as a repeating unit. In this case, the OBC according to the invention has at least two different polymer blocks. These blocks may be composed of one olefin class or of two or more olefin classes. The olefins used to make up the OBC that can be used according to the present invention are aliphatic olefins such as ethylene, propylene or butylene, with ethylene and propylene being preferred according to the present invention. Particularly preferably, the OBC usable according to the invention consists exclusively of aliphatic olefins as so-called repeating units. According to the invention, the definition of OBC excludes those having aromatic groups (these are known to the person skilled in the art as TPS (styrene-based thermoplastic elastomer)). Particularly preferred for the applications described herein or for the compositions according to the invention are OBCs whose blocks consist of or consist of polypropylene, polyethylene or random ethylene/propylene copolymers. Commercially available are OBCs, for example from LyondellBasell under the trade name Hifax CA 10A. Also particularly preferred are the polyolefin block copolymers (referred to herein as "olefin block copolymers," OBCs ") described in detail in US 8,481,637B 2, which is incorporated herein by reference in its entirety. Here a polymer with alternating blocks of hard (very rigid) and soft (highly elastic) segments. These products are sold under the trade name INFUSE by Dow Elastomers^TMAnd (5) selling. Particularly preferred is the type of recommended application for TPE (INFUSE)^TM9010、9007、9107、9807)。

A further example of an OBC that can be used according to the invention is a so-called hydrogenated diene block copolymer. Such polymers preferably have a polymer block composed of hydrogenated polybutadiene or hydrogenated polyisoprene.

It is preferred according to the present invention that the OBC is used together with a non-elastomeric polyolefin.

TPC (copolyester TPE) suitable according to the invention are preferably copolyesters, generally in the form of copolymers, having in the polymer main chain a copolymerA monomeric moiety linked through an ester group (-C (═ O) -O-). Such thermoplastic copolyester elastomers may be prepared by polycondensation. Such copolyesters are preferably multiblock copolyesters, which generally have crystalline segments composed of hard blocks (X) and amorphous segments composed of soft blocks (Y). Suitable monomer components for constructing the hard blocks (X) and the soft blocks (Y) in the multiblock copolyesters are known to the person skilled in the art. The copolyesters preferably used according to the invention have a melting or softening point in the range from 160 ℃ to 300 ℃, preferably from 165 ℃ to 270 ℃, particularly preferably from 170 ℃ to 220 ℃. The preferred TPC of the present invention is a linear multi-block polyester having randomly distributed high melting hard polyester blocks and low melting soft polyester blocks. In this case, the hard blocks form crystalline domains and the soft blocks form amorphous domains, 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 4C 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-propanediol, 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 of aromatic dicarboxylic acids, very particularly preferably of 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 alkanedicarboxylic acids, for example adipic acid or sebacic acid, and alkanediols, or polycaprolactone diols or aliphatic polycarbonate diols. However, mixtures of diols may also be used. Preferably, the hard TPC areas are combined with soft areas, wherein the hard TPC areas are composed of terephthalic acid and short-chain diols, particularly preferably 1, 4-butanediol, and the soft areas are composed of terephthalic acid and polyether diols, very particularly preferably polytetramethylene glycol. Is suitable as the basisThe copolyesters of component B in the compositions of the invention may be prepared according to methods known to those skilled in the art or may be commercially available. Suitable commercially available copolyesters are, for example, TICONA-P.GROUP–DSM–Kolon–PTS–Ria-Polymers–LG Chem.–And DuPont-

If anhydrides of unsaturated organic acids are used for the grafting reaction, maleic anhydride is particularly preferably used.

In the case of vinylalkoxysilanes, vinylacyloxysilanes, methacryloxyalkylalkoxysilanes or methacryloxyalkylalkoxysilanes for the grafting reaction, monoalkoxy or monoacyloxy silanes, dialkoxy or diacyloxy silanes or trialkoxy or triacyloxy silanes can be used, of which trialkoxysilanes or triacyloxy silanes are preferred. Further, the alkoxy group may be a substituted or unsubstituted alkoxy group. Preferably, it is C_1-8Alkoxy groups, more preferably methoxy, ethoxy or propoxy groups and most preferably methoxy groups. The acyloxy group may be C_1-8-acyloxy groups, of which C is more preferred_1-3-acyloxy groups and most preferred are acetoxy groups. The last-mentioned group preferably remains bonded to the silicon atom of the silane after grafting. In order to be able to graft silanes, the alkoxysilanes to be grafted have a further group with double bonds or epoxy groups. The group may be, for example, a substituted or unsubstituted vinyl, epoxy or alkylacryloyl group (alkyl ═ C)_1-5Alkyl, where C is preferred_1-3-alkyl and particularly preferably methyl), which can also be substituted by the following group- (CH)₂)_n-O-or- (CH)₂)_nOne of which is bonded to a silicon atom of the silane, wherein n ═ 1 to 5, more preferably 1 to 3, still more preferably 3, and most preferably n-propyl. In the group- (CH)₂)_nIn the case of-O-, the oxygen atom is bonded to the silicon atom of the silane. Such silanes to be grafted are, for example, those known under the name WackerCan be obtained.

Preferred vinylsilanes are: vinyltrialkoxysilanes (especially vinyltrimethoxysilane, vinyltriethoxysilane), vinylalkyldialkoxysilanes (especially vinyldimethoxymethylsilane), vinyltricarboxyloxysilanes (especially vinyltriacetoxysilane). These are shown in the following formulae (I) to (III):

wherein R2 to R5 are each, independently of one another, an alkyl group, preferably a methyl group or an ethyl group.

Preferred methacryloxyalkylalkoxysilanes and methacryloxyalkylalkoxysilanes are: 3-methacryloxypropyl-trialkoxysilane or methacryloxymethyl-trialkoxysilane (in particular 3-methacryloxypropyl-trimethoxysilane, 3-methacryloxypropyl-triethoxysilane, methacryloxymethyl-trimethoxysilane, methacryloxymethyl-triethoxysilane), 3-methacryloxypropyl-alkyldialkoxysilane or methacryloxymethyl-alkyldialkoxysilane (in particular methacryloxymethyl-dimethoxymethylsilane), 3-methacryloxypropyl-tricarboxysilane or methacryloxymethyl-tricarboxysilane (in particular: 3-methacryloxypropyl-triacetoxysilane). These are shown in the following formulae (IV) to (VI):

wherein R1 is an alkylene group, preferably a methylene or propylene group; r2 to R5 are each, independently of one another, an alkyl group, preferably a methyl group or an ethyl group.

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

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

According to the invention, polypropylene, particularly preferably hPP, is preferably used as polyolefin. The maleic anhydride grafted polypropylene is also known in the art as MAH-g-PP. One such MAH-g-PP is under the trade name "TPPP "is known and is for example of the type"TPPP 2112GA "or"TPPP 8112GA "is available.

The amount of anhydride of an unsaturated organic carboxylic acid in the grafted TPC 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 TPC functionalized with an anhydride of an organic carboxylic acid.

One such MAH-g-TPC is under the trade name "TPHY "is known and is for example in"TPHY 45602PCX "is available.

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

And (3) component C: hollow glass bead

The hollow glass microspheres useful for 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 may be filled with a gas having an atmospheric pressure or a reduced pressure. The glass shell contains silica as a main component, and may contain sodium oxide, magnesium oxide, calcium oxide, boron oxide, phosphorus oxide, or the like as additional components.

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

Since a high shearing force acts during mixing of the thermoplastic elastomer composition according to the present invention, the hollow glass microspheres may be broken. This rupture must be avoided by a correctly selected isostatic fracture strength (isostatischen Bruchfestigkeit; English: crush strength (collapse Strength)). The hollow glass microspheres preferably have an isostatic fracture strength (10 vol%) of 55MPa or more, more preferably 69MPa or more and most preferably 100MPa or more. "isostatic fracture strength (10 vol%)" was defined according to ASTM D-3102-78, wherein an appropriate amount of hollow glass microspheres were introduced into glycerol and the pressure was increased until 10% by volume was ruptured.

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 determined using a commercially available laser diffraction particle size meter.

The hollow glass beads preferably have a density of 0.9g/cm³Or less, more preferably 0.6g/cm³Or less and 0.3g/cm³Or a greater density. The actual density of the hollow glass microspheres is referred to herein and not the bulk density. The actual density of the hollow glass microspheres was determined using a pycnometer, such as an AccuPyc II 1340 pycnometer from Micromeritics.

Hollow glass microspheres useful according to the present invention are available from 3M company. It is preferable to use iM16K type hollow glass microspheres according to the present invention.

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

And (3) component D: polyolefins or TPCs (unfunctionalized)

The same polyolefins or TPCs mentioned above for the functionalized polyolefins or functionalized TPCs (however unfunctionalized here) may be used here.

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 from 0:100 to 105:100, more preferably at most 80: 100.

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

And (3) component E: plasticizer

Suitable plasticizers are known in principle to the person skilled in the art. Suitable plasticizers for nonpolar elastomers (e.g. SBC) are industrial or medical mineral or white oils, natural oils, such as soybean oil or rapeseed oil, and also alkylsulfonyl esters, in particular alkylsulfonylphenyl esters, in which the alkyl substituents contain straight and/or branched alkyl chains having > 5C atoms. Also dialkyl or trialkyl esters of trimellitic acid, where the alkyl substituents preferably contain linear and/or branched alkyl chains with > 4C atoms. Furthermore, alkyl esters of dicarboxylic acids, tricarboxylic acids and higher polycarboxylic acids are also used as corresponding plasticizers, the alkyl substituents preferably being straight and/or branched alkyl chains. Listed as examples: di (2-ethylhexyl) adipate and tributyl-O-acetyl citrate. Furthermore, it is also possible to use carboxylic acid esters of monoalkylene glycols and/or polyalkylene glycols as plasticizers, for example ethylene adipate. According to the invention, mineral or white oils are preferably used here, either industrially or medically. As the industrial mineral oil, Shell Catenex T145S can be mentioned.

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

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.

And (3) component F: additives, e.g. stabilisers, auxiliaries and colorants

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

As processing aids and stabilizers, the following can be used, for example: anti-ageing or anti-ozonant agents, such as anti-ozone waxes, stabilizers, such as heat stabilizers, stabilizers against weathering; oxidation inhibitors, antioxidants, UV stabilizers, further light stabilizers, defoamers, lubricants, dispersants, mold release agents, antiblocking agents, free-radical scavengers, metal deactivators, and, in addition, additives such as blowing aids, blowing agents, impact modifiers, tackifiers and viscosity modifiers.

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

In the thermoplastic elastomer composition according to the invention or the thermoplastic elastomer according to the 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.

Preparation of the composition according to the invention:

the thermoplastic elastomer composition according to the present 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 here using mixing systems known from rubber technology and plastics technology, such as kneaders, internal mixers (for example internal mixers with intermeshing or tangential rotor geometry) and also in continuous mixing devices, such as mixing extruders, for example mixing extruders having 2 to 4 and more screws (for example twin-screw extruders).

It is important to note when carrying out the preparation process according to the invention that the mixing temperature is sufficiently high that it can be converted into the plastic state if components B and D are used according to the invention, but is not impaired here. This is ensured if a temperature above the highest melting or softening temperature of components B and C (if used according to the invention) is selected. At the same time, care must be taken to ensure sufficient energy input, which is determined by the number of revolutions and throughput in the extruder (see examples).

It is particularly preferred that the mixing of the components (as long as they are present in the composition) is carried out at a temperature in the range of from 150 ℃ to 240 ℃ and preferably from 180 ℃ to 220 ℃.

The terms "comprising," "including," and "having" as used in this application should also be intended to include the term "consisting of … …" in each instance in which they are used, such that these embodiments are also disclosed in this application.

Example (b):

assay methods and definitions:

the density measurement was carried out in accordance with DIN EN ISO 1183-1.

The Shore hardness was determined according to DIN EN ISO 868 and DIN ISO 7619-1.

The tensile strength and elongation at break were determined in accordance with DIN 53504/ISO 37. Unlike ISO 37, test bars of type S2 were tested at an application rate of 200 mm/min.

The compression set is determined in accordance with DIN ISO 815-1, method A.

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

The adhesion of the thermoplastic elastomer composition on PA6 was determined according to VDI 2019: PA6 under the product name Frianyl B3V 2 NC1102 of Nilit Plastics was used as PA 6. The thermoplastic elastomer composition was also determined according to VDI2019 on polypropylene (PP) (type:HP 501L; the manufacturer: basell polyofins).

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

Extruder parameters and injection molding parameters:

the preparation of the thermoplastic elastomers of the present invention is carried out in a continuous process on a twin-screw extruder (48L/D). Hollow glass microspheres were added by side feeding. The extruder speed was 500 rpm and the throughput was 20 kg/h. The set temperature profile was run from 170 to 190 ℃. The extrudate is pelletized for subsequent injection molding or extrusion processing.

The preparation of the test specimens was carried out by injection molding with a temperature profile of 180 to 200 ℃.

Preparation example

Table 1 gives the abbreviations used for the components in the examples and comparative examples:

table 1:

components	Raw materials
		A	SBC
B1	Polyolefins functionalized with anhydrides of organic carboxylic acids
		B2	Polyolefins functionalized with alkoxysilanes or acyloxysilanes
C	Hollow glass bead
		D	Polyolefin (unfunctionalized)
E	Plasticizer
		F	Additive agent
G	Silanized hollow glass beads
		H	SBC functionalized with anhydrides of organic carboxylic acids

Examples and comparative examples:

preparation of thermoplastic elastomer compositions and elastomers (according to the invention and not according to the invention):

thermoplastic elastomers were prepared according to the preparation variant described above using the ingredients shown in tables 3 and 4. Table 2 gives the manufacturer and model number of the components used. The mechanical measurements and the values relating to the processability are given in tables 5 and 6.

Table 2:

maleic anhydride grafted SEBS

Preparation of polyolefin B2:

functionalized polyolefin B2 was prepared by reacting polypropyleneHP501L silaneGF 31 grafting. To this end 0.06% by weightHXY-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 formHP 501L. The weight% values are based on the amount of polypropylene used. The mixture was first slowly heated to 160 ℃ in the mixing section to mix. The temperature is then increased to 200 ℃ and the free-radical grafting is carried out in this case. Volatile constituents were removed by means of vacuum degassing.

Table 3:

comparative example 1: the polyolefin and the hollow glass micro-beads have no interactive groups; comparative examples 2 and 3: the polyolefin and the hollow glass bead have interactive groups; examples 1 and 2: with functionalized olefins but uncoated hollow glass microspheres;

table 4:

example 3: with functionalized polyolefins but uncoated hollow glass microspheres; comparative example 4: SBC with functionalization, but uncoated hollow glass beads; comparative example 5: with unfunctionalized polyolefin, but with uncoated hollow glass microspheres;

table 5: mechanical values from the examples of table 3:

the values for density, hardness, tensile strength, elongation at break and tear strength were recorded at room temperature.

Table 6: mechanical values from the examples of table 4:

the values for density, hardness, tensile strength, elongation at break and tear strength were recorded at room temperature.