阅读说明：本技术 具有改善机械性能的聚合物组合物 (Polymer compositions with improved mechanical properties ) 是由 R·罗斯卡普 D·坤泽勒 P·许布舍尔 R·茨罗特兹 H·阿克曼 F·霍夫林 于 2018-08-03 设计创作，主要内容包括：本发明涉及一种组合物,其包含至少一种热塑性弹性体(TPE)和至少一种非交联的弹性体和任选的至少一种用于催化至少一种非交联的弹性体扩链和/或交联和/或偶联反应的催化剂的熔融共混物。本发明还涉及用于制备一种聚合物组合物的方法,一种包含由该组合物组成的基材层的成型制品,制备成型制品的方法,和使用本发明的成型制品覆盖屋顶的方法。(The present invention relates to a composition comprising a melt blend of at least one thermoplastic elastomer (TPE) and at least one non-crosslinked elastomer and optionally at least one catalyst for catalyzing at least one non-crosslinked elastomer chain extension and/or crosslinking and/or coupling reaction. The invention also relates to a process for preparing a polymer composition, a shaped article comprising a substrate layer consisting of the composition, a process for preparing a shaped article, and a process for covering a roof using the shaped article of the invention.)

1. A composition comprising a melt blend of:

a)15-95 wt% of at least one thermoplastic elastomer,

b)5 to 50 wt% of at least one non-crosslinked elastomer, based on the total weight of the blend, wherein the melt blend is obtained by melt processing the blend components.

2. The composition according to claim 1, wherein the blend further comprises:

c)0.1 to 5.0 wt% of at least one catalyst based on the total weight of the blend.

3. The composition according to claim 2, wherein the at least one non-crosslinked elastomer is crosslinked during melt processing to a degree of crosslinking of not more than 10.0 wt.%, more preferably not more than 5 wt.%, even more preferably not more than 2.5 wt.%, most preferably not more than 1.5 wt.%, measured using the method as defined in the ISO 10147 standard.

4. Composition according to claim 2 or 3, wherein the at least one catalyst is chosen from ZnO, CaO, MgO, Al₂O₃，CrO₃，FeO，Fe₂O₃NiO, zinc salts of fatty acids having at least 6 carbon atoms, preferably at least 13 carbon atoms, and zinc borate.

5. The composition according to any one of claims 2 to 4, wherein the blend further comprises at least one metal salt of a fatty acid different from the at least one catalyst and/or one or more fatty acids.

6. The composition according to any one of claims 2 to 5, wherein the at least one catalyst is ZnO, a zinc salt of a fatty acid having at least 6 carbon atoms, preferably at least 13 carbon atoms, or zinc borate or a mixture of ZnO and at least one other metal oxide selected from CaO, MgO, Al₂O₃、CrO₃、FeO、Fe₂O₃And NiO.

7. The composition according to any one of the preceding claims, wherein the at least one non-crosslinked elastomer has a mole percent unsaturation of not more than 5.0, preferably not more than 2.5, prior to melt processing.

8. Composition according to any one of the preceding claims, in which the at least one non-crosslinked elastomer is chosen from butyl rubbers and halogenated butyl rubbers, preferably halogenated butyl rubbers and/or at least one thermoplastic elastomer is a thermoplastic polyolefin elastomer (TPE-O).

9. A composition according to any one of the preceding claims wherein in the composition the thermoplastic elastomer and the elastomer form a co-continuous phase.

10. The composition according to any of the preceding claims, wherein the blend further comprises 0.1 to 10.0 wt%, preferably 0.1 to 5.0 wt%, based on the total weight of the blend, of at least one alkoxyamine hindered amine light stabilizer (NOR-HALS).

11. The composition according to any one of the preceding claims, comprising at least 75 wt%, preferably at least 85 wt% of the melt blend, based on the total weight of the composition.

12. A composition according to any preceding claim having a blocking value of no more than 5.0N/15mm, preferably no more than 2.5N/15mm, most preferably no more than 1.5N/15mm, as determined by the method cited in the specification.

13. Composition according to any one of the preceding claims, having a thickness of not more than 50N/mm measured at a temperature of 23 ℃ using the method as defined in ISO 527-2 standard²Preferably not more than 25N/mm²Most preferably not more than 15N/mm²And/or at least 5N/mm measured by using the method as defined in ISO 527-2 standard²Preferably at least 7.5N/mm²Most preferably at least 10N/mm²And/or an elongation at break of at least 500%, preferably at least 600%, most preferably at least 650%, determined by using the method as defined in ISO 527-2 standard.

14. Composition according to any one of the preceding claims, having an impact resistance measured by using a method as defined in the EN12691 type a standard of at least 1000mm, preferably at least 1250mm and/or an impact resistance measured by using a method as defined in the EN12691 type B standard of at least 1750mm, preferably at least 2000mm, wherein both impact resistances are measured using a layer consisting of the composition and having a thickness of 0.8 mm.

15. A method of preparing a polymer composition, the method comprising the steps of:

i) introducing the blend components as defined in one of claims 1 to 14 into a mixing device,

ii) melt processing the blend components in a mixing device at a temperature above the melting point of the at least one thermoplastic elastomer.

16. The process according to claim 15, wherein the mixing device is a continuous extrusion device comprising an extruder and a die and the process comprises the further step iii): extruding the melt-processed mixture obtained in step ii) through a die.

17. A polymer composition obtainable by using the method according to claim 15 or 16.

18. A shaped article comprising a substrate layer having a thickness of at least 0.1mm, said substrate layer consisting of a composition according to any one of claims 1 to 14 or a polymer composition according to claim 17.

19. A method of making a shaped article comprising the steps of:

i) introducing the blend components as defined in one of claims 1 to 14 into a continuous extrusion apparatus comprising an extruder and a flat die,

ii) melt processing the blend components in an extruder to obtain a melt processed mixture of the blend components, and

iii) extruding the melt-processed mixture through a flat die to form a substrate layer, and optionally

iv) using spaced apart calender cooling rolls through which the formed substrate layer is stretched immediately after step iii).

20. A method of covering a roof comprising the steps of:

i) applying a shaped article according to claim 18 to the surface of a roof to be covered,

ii) overlapping adjacent edges of the article,

iii) heating the adjacent edges of the article in the overlap region slightly above the melting temperature of the thermoplastic elastomer and joining the overlap region under sufficient pressure to provide acceptable seam strength without the use of adhesive.

Technical Field

The present invention relates to polymer compositions and their use for the preparation of industrial liners such as waterproofing membranes.

Background

Waterproofing membranes are used in the construction industry to seal foundations, underground surfaces or roof structures against water penetration.

Summary of The Invention

It is an object of the present invention to provide a polymer composition having a low modulus of elasticity, high impact resistance, low adhesion and good weldability.

It is another object of the present invention to provide a polymer composition which can be produced at a lower cost than thermoplastic vulcanizates (TPVs) of the prior art.

It has surprisingly been found that a polymer composition solving the problems associated with the prior art polymer compositions for use as waterproofing and roofing membranes, obtainable as a melt blend of at least one thermoplastic polymer and at least one non-crosslinked elastomer and optionally at least one catalyst, is obtained.

The subject of the present invention is a composition as defined in claim 1.

One of the advantages of the composition according to the invention is that it is more flexible than typical TPO-and dynamically crosslinked TPV-materials and as flexible as typical PVC-materials containing 20 to 50 wt.% of plasticizer.

Although a relatively large amount of elastomer component is required to obtain high flexibility, the compositions of the present invention exhibit only minor blocking behavior. Depending on the embodiment of the composition, blocking may also be completely eliminated.

In addition, the compositions of the present invention exhibit excellent mechanical properties, in particular high impact resistance and shear strength, which are comparable to or higher than those of the TPO materials of the prior art. Finally, shaped articles consisting of the composition of the invention can be joined to each other and to other thermoplastic articles, such as roofing membranes, by heat welding.

Other aspects of the invention are presented in the other independent claims. Preferred aspects of the invention are shown in the dependent claims.

Detailed Description

The subject of the present invention is a composition comprising a melt blend of:

a)15-95 wt% of at least one thermoplastic elastomer,

b)5 to 50 wt% of at least one non-crosslinked elastomer, based on the total weight of the blend, wherein the melt blend is obtained by melt processing the blend components.

In this context, the term "poly" means a substance which formally contains two or more functional groups present in its name per molecule. For example, a polyol refers to a compound having at least two hydroxyl groups. Polyether refers to a compound having at least two ether groups.

The term thermoplastic elastomer (TPE) refers to a polymeric material having elastomer-like properties and thermoplastic processability.

The term "thermoplastic olefin (TPO)" refers to a thermoplastic elastomer (TPE) consisting of only olefin monomer units. The term "thermoplastic olefin" as also used herein may be used interchangeably with the terms "thermoplastic polyolefin" and "olefinic thermoplastic elastomer" (TPE-O).

The term "elastomer" refers to any polymer or combination of polymers that is capable of recovering from large deformations and may or has been modified to a state that is substantially insoluble (but may swell) in boiling solvents. As used herein, the term "elastomer" may be used interchangeably with the term "rubber".

The term "molecular weight" refers to the molar mass (g/mol) of a molecule or a portion of a molecule (also referred to as a "group"). The term "average molecular weight" refers to the number average molecular weight (M) of an oligomer or polymer mixture of molecules or groups_n). The molecular weight can be determined by Gel Permeation Chromatography (GPC) with polystyrene standards.

The term "glass transition temperature" refers to the temperature, as measured by Differential Scanning Calorimetry (DSC) method according to ISO 11357, above which the polymer composition becomes soft and flexible, and below which it becomes hard and glassy. Can be used forMeasurements were made using a Mettler Toledo 822e instrument with a heating rate of 2 degrees Celsius/min. T is_gValues can be determined from the measured DSC curves by means of DSC software.

The term "crosslinked" denotes a polymer matrix in which polymer chains are interconnected by a plurality of covalent bonds that are stable both mechanically and thermally. Other possible forms of crosslinked polymers, such as physically crosslinked polymers, are not considered "crosslinked" in the context of the present disclosure. The terms "cure" and "cure" may be used interchangeably with the term "crosslink".

The term "degree of crosslinking" refers to the proportion of components that are insoluble in boiling xylene. The percentage of insoluble fraction can be determined by refluxing the sample in boiling xylene, weighing the dried residue, and making appropriate corrections for other soluble and insoluble components present in the tested composition. Preferably, the degree of crosslinking is measured by using the method defined by the ISO 10147 standard.

The term "continuous" when used to describe a process or process steps refers to any process in which reagents and reaction products are continuously supplied and removed while steady state or stable reaction conditions are achieved.

The "amount or content of at least one component X" in the composition, for example "amount of at least one thermoplastic polymer" means the sum of the individual contents of all thermoplastic polymers contained in the combination. For example, in the case where the composition comprises at least 20 wt% of at least one thermoplastic polymer, the sum of the amounts of all thermoplastic polymers comprised in the composition is equal to 20 wt%.

The melt blend is obtained by melt processing the blend components. The term "melt processing" in this context refers to a process wherein at least one molten polymeric component is intimately mixed with at least one other component, which may be another molten polymeric component or a solid component, such as a catalyst. The term "melt processing" is used interchangeably with the terms "melt mixing" and "melt blending".

The term "blend component" refers to the components a) and b) and optionally other components of the blend, which are melt processed to obtain a melt blend. The ingredients of the blend and melt-blend may differ from each other due to reactions that may occur during melt processing, such as chain extension and/or crosslinking and/or coupling reactions.

According to one or more embodiments, the blend further comprises:

c)0.1 to 5.0 wt% of at least one catalyst, based on the total weight of the blend.

The melt processing is preferably carried out at a temperature above the melting point of the thermoplastic elastomer or, if the blend comprises more than one thermoplastic elastomer, above the melting point of the thermoplastic elastomer with the highest melting point. Melt processing can be carried out in a batch process using any conventional mixer, such as a Brabender, Banbury, or roll mixer, or can be carried out in a continuous process using a continuous type mixer, preferably an extrusion apparatus comprising an extruder, preferably a single or twin screw extruder and a die.

The maximum temperature of the blend during melt processing is preferably not less than 150 deg.C, more preferably not less than 160 deg.C, and most preferably not less than 180 deg.C. The maximum temperature of the blend during melt processing may be in the range of 150-250 deg.C, particularly 160-220 deg.C, such as 180-200 deg.C.

If the melt processing is carried out batchwise, the ingredients of the blend (i.e. the at least one thermoplastic elastomer, the at least one non-crosslinked elastomer and optionally the ingredients) are introduced into a batch mixing device and melt processed to give a homogeneous blend. In embodiments where the blend includes at least one catalyst, the temperature of the blend is increased during mixing until the chain extension and/or crosslinking and/or coupling reactions of the at least one non-crosslinked elastomer are initiated. This is usually marked by an increase in the torque value of the motor of the hybrid device. In the case of a continuous production process, the blend components (i.e., the at least one thermoplastic elastomer, the at least one non-crosslinked elastomer, and optional components) are melt processed in a continuous-type melt mixer, preferably a single-screw extruder or a twin-screw extruder, and the resulting molten blend is then extruded through an extruder die.

The preferred amount of the at least one thermoplastic elastomer depends on the intended application of the composition. If the composition is used to make a roofing membrane, the amount of the at least one thermoplastic elastomer is potentially reduced due to the large amount of additives (e.g., flame retardants). Preferably, at least one thermoplastic elastomer is present in the blend in a total amount of at least 15 wt%, more preferably at least 20 wt%, even more preferably at least 30 wt%, and most preferably at least 35 wt%, based on the total weight of the blend. In particular, the at least one thermoplastic elastomer may be present in the blend in a total amount of 15 to 95 wt%, preferably 20 to 95 wt%, more preferably 25 to 90 wt%, even more preferably 30 to 90 wt%, most preferably 35 to 85 wt%, based on the total weight of the blend. It may be preferred that the total amount of the at least one thermoplastic elastomer in the blend is from 15 to 70 wt%, preferably from 20 to 65 wt%, more preferably from 25 to 60 wt%, even more preferably from 30 to 55 wt%, most preferably from 35 to 55 wt%, based on the total weight of the blend. On the other hand, the total amount of at least one thermoplastic elastomer present in the blend is advantageously from 40 to 95phr (parts by weight per 100 parts by weight of at least one non-crosslinked elastomer), more preferably from 50 to 90phr, even more preferably from 55 to 85phr and most preferably from 60 to 85 phr.

The amount of the at least one non-crosslinked elastomer contained in the blend is not particularly limited. Increasing the proportion of non-crosslinked elastomer in the blend improves the flexibility of the resulting composition. However, it has also been found that blends containing more than 50 wt% of non-crosslinked elastomer are difficult to melt process due to the increased viscosity of the blend. Furthermore, it has been found that compositions containing a high amount of elastomer tend to exhibit increased blocking due to the large fraction of amorphous polymer. However, a certain amount of non-crosslinked elastomer is required to increase the flexibility of the composition over prior art TPV materials.

Preferably, the at least one non-crosslinked elastomer is present in the blend in a total amount of at least 5 wt%, more preferably at least 7.5 wt%, even more preferably at least 10 wt%, based on the total weight of the blend. In particular, it may be preferred that the at least one non-crosslinked elastomer is present in the blend in a total amount of from 5 to 50 wt%, more preferably from 10 to 45 wt%, even more preferably from 12.5 to 40 wt%, in particular from 15 to 35 wt%, most preferably from 15 to 30 wt%, based on the total weight of the blend.

At least one catalyst may be added to the blend during and/or after melt processing of the blend components to catalyze the chain extension and/or crosslinking and/or coupling reactions of the polymer components. At least the amount of catalyst is adjusted to prevent significant crosslinking of the at least one non-crosslinked elastomer during melt processing. By "substantially crosslinked" is meant crosslinking at least one non-crosslinked elastomer to a degree of crosslinking of at least 10 wt%, such as at least 15 wt%, in particular at least 20%, measured using a method as defined in ISO 10147 standard.

Significant crosslinking of the at least one non-crosslinked elastomer during melt processing is not preferred, as it has been found that this results in increased energy consumption during melt processing without having a significant positive effect on the blocking behavior of the resulting composition. The increase in energy consumption is a result of the higher viscosity of the crosslinked elastomer. Crosslinking of the at least one non-crosslinked elastomer to a significant degree of crosslinking during melt blending will also result in a dynamically crosslinked thermoplastic vulcanizate (TPE-V) in which the crosslinked elastomer is present as dispersed particles in a continuous thermoplastic matrix.

Preferably, the at least one elastomer is crosslinked during melt processing to a degree of crosslinking of no more than 10.0 wt%, more preferably no more than 5.0 wt%, even more preferably no more than 2.5 wt%, most preferably no more than 1.5 wt%, measured by using the method defined in the ISO 10147 standard. It may be preferred that the composition comprises 5 to 50 wt. -%, more preferably 10 to 45 wt. -%, even more preferably 12.5 to 40 wt. -%, in particular 15 to 35 wt. -%, most preferably 15 to 30 wt. -% of at least one elastomer having a degree of crosslinking of not more than 5 wt. -%, more preferably not more than 2.5 wt. -%, even more preferably not more than 2.0 wt. -%, most preferably not more than 1.5 wt. -%, based on the total weight of the blend. It may also be preferred that the at least one elastomer is not crosslinked during melt processing.

Preferably, the at least one catalyst is present in the blend in a total amount of no more than 5 wt%, more preferably no more than 4 wt%, most preferably no more than 2.5 wt%, based on the total weight of the blend. It may be preferred that the at least one catalyst is present in the blend in a total amount of from 0.1 to 5.0 wt%, more preferably from 0.1 to 2.5 wt%, even more preferably from 0.1 to 2.0 wt%, most preferably from 0.5 to 1.5 wt%, based on the total weight of the blend.

Suitable catalysts for use in the blend include metal oxides, metal salts of fatty acids and boric acid, sulfur, phenolic resin catalysts, fatty acids, and mixtures thereof.

Suitable metal oxide catalysts and fatty acid metal salts include, for example, ZnO, CaO, MgO, Al₂O₃、CrO₃、FeO、Fe₂O₃And NiO and zinc salts of fatty acids having at least 6 carbon atoms.

Suitable sulfur catalysts include, for example, powdered sulfur, precipitated sulfur, highly dispersed sulfur, surface treated sulfur, insoluble sulfur, dimorpholinodisulphide, alkylphenol disulphide and mixtures thereof. Such catalysts are present in the blend in a total amount of 0.5 to 5.0phr (parts by weight per 100 parts by weight of the at least one non-crosslinked elastomer).

Suitable phenolic resin catalysts include, for example, bromides of alkylphenol resins or mixed catalysts containing stannous chloride, chloroprene or another halogen donor and alkylphenol resins, and mixtures thereof. Such catalysts may be present in the blend in an amount of from 0.5 to 20.0 phr.

The at least one catalyst may also be used in combination with at least one accelerator selected from the group consisting of guanidine compounds, aldehyde amine compounds, aldehyde ammonium compounds, thiazole compounds, sulfonamide compounds, thiourea compounds, thiuram compounds, xanthane compounds, and dithiocarbamate compounds. Such accelerators are present in the blend in a total amount of 0.1 to 5.0 phr.

The at least one catalyst is preferably chosen from ZnO, CaO, MgO, Al₂O₃、CrO₃、FeO、Fe₂O₃NiO, zinc salts of fatty acids having at least 6 carbon atoms, preferably at least 13 carbon atoms, zinc borate, and mixtures thereof.

It has been demonstrated that metal oxide based catalysts and zinc salts of fatty acids having at least 6 carbon atoms, preferably at least 13 carbon atoms, and zinc borate can be used to prepare shaped articles composed of the composition, such as roofing membranes having a desirable white color. White roofing membranes absorb only a small amount of solar energy and therefore convert the impinging electromagnetic spectrum of a small amount of sunlight into heat and are therefore less susceptible to thermal degradation in hot weather outdoor applications. In contrast, a dark film absorbs most of the sunlight energy impinging on it, resulting in a rapid temperature rise of the surface.

According to one or more embodiments, at least one catalyst is ZnO, zinc salts of fatty acids having at least 6 carbon atoms, preferably at least 13 carbon atoms, or zinc borate, or a mixture of ZnO and another metal oxide selected from CaO, MgO, Al₂O₃、CrO₃、FeO、Fe₂O₃And NiO. Preferably, the at least one catalyst is chosen from ZnO, zinc salts of fatty acids having at least 6 carbon atoms, preferably at least 13 carbon atoms, even more preferably zinc stearate or borate.

The blend may further comprise one or more metal salts of fatty acids different from the at least one catalyst and/or the one or more fatty acids. Preferably, the metal in the metal salt of a fatty acid different from the at least one catalyst is selected from Zn, Ca, Mg, Al, Cr, Fe and Ni. Preferably, the fatty acid has at least 6 carbon atoms, more preferably at least 13 carbon atoms. Saturated fatty acids having at least 6 carbon atoms, in particular at least 13 carbon atoms, have been found to be particularly suitable.

According to one or more embodiments, the at least one catalyst is ZnO and the blend further comprises at least 0.05 wt%, preferably 0.1 to 0.5 wt%, based on the total weight of the blend, of a zinc salt of at least one fatty acid, preferably zinc stearate, and/or at least 0.05 wt%, preferably 0.1 to 0.5 wt%, based on the total weight of the blend, of at least one saturated fatty acid having at least 6 carbon atoms, preferably at least 13 carbon atoms.

According to one or more embodiments, the at least one catalyst is ZnO and the blend further comprises at least 0.05 wt%, preferably 0.1 to 0.5 wt%, based on the total weight of the blend, of zinc stearate and/or at least 0.05 wt%, preferably 0.1 to 0.5 wt%, based on the total weight of the blend, of a fatty acid selected from stearic acid and montanic acid.

It is also possible that a portion of the at least one catalyst present in the blend is not consumed in the chain extension and/or crosslinking and/or coupling reaction of the at least one non-crosslinked elastomer during the melt processing and extrusion steps. It may therefore be preferred that at least the catalyst is also present in the composition. The amount of the at least one catalyst in the composition is preferably significantly lower than the amount in the blend. It may be preferred that the composition comprises not more than 1.0 wt%, more preferably not more than 0.5 wt%, most preferably not more than 0.25 wt% of at least one catalyst based on the total weight of the composition.

The at least one non-crosslinked elastomer may be selected from the group consisting of butyl rubber, halogenated butyl rubber, ethylene propylene diene rubber (EPDM), natural rubber, neoprene, synthetic 1, 4-cis polyisoprene, polybutadiene, ethylene propylene rubber, styrene-butadiene copolymers, isoprene-butadiene copolymers, styrene-isoprene-butadiene rubber, methyl methacrylate-butadiene copolymers, methyl methacrylate-isoprene copolymers, acrylonitrile-isoprene copolymers, and acrylonitrile-butadiene copolymers.

Preferred non-crosslinked elastomers include isobutylene-based homopolymers and copolymers. These polymers may be described as C₄To C₇A random copolymer of an isomonoolefin derived unit, such as an isobutylene derived unit, and at least one other polymerizable unit.

In case the composition of the invention is used to prepare a waterproofing membrane, in particular for roofing applications, the at least one non-crosslinked elastomer should have a relatively low unsaturation. The term "unsaturation" refers herein to the ratio of the number of unsaturated carbon-carbon bonds to the number of atoms in the linear chain of an average theoretical linear elastomer molecule. Low unsaturation is critical in roofing applications where the polymer film must be able to withstand permanent exposure to various environmental factors, particularly ultraviolet radiation. On the other hand, a certain degree of unsaturation may also be preferred to allow chain extension and/or crosslinking and/or coupling reactions to occur during melt processing. Preferably, the at least one non-crosslinked elastomer has a mole percent unsaturation of no greater than 5.0, preferably no greater than 2.5, prior to melt processing.

It has been found that the viscosity of the at least one non-crosslinked elastomer has a significant effect on extrusion head pressure prior to melt processing. Preferably, the at least one non-crosslinked elastomer has a mooney viscosity (ML 1+8 at 125 ℃) of no greater than 100 prior to melt processing, more preferably no greater than 75, and most preferably no greater than 50. It is advantageous that the at least one non-crosslinked elastomer has a Mooney viscosity (ML 1+8 at 125 ℃) of from 10 to 75, more preferably from 20 to 50, prior to melt processing.

The at least one non-crosslinked elastomer is preferably selected from butyl rubber and halogenated butyl rubber, preferably halogenated butyl rubber. The term "halogenated rubber" refers herein to a rubber having a halogen content of at least 0.1 mol%, wherein the halogen is preferably selected from the group consisting of bromine, chlorine and iodine. Preferred halogenated butyl rubbers have a halogen content of from 0.1 to 10 wt.%, more preferably from 0.5 to 8 wt.%, most preferably from 0.5 to 5.0 wt.%, based on the total weight of the butyl rubber.

According to one or more embodiments, the at least one non-crosslinked elastomer is a halogenated butyl rubber, preferably a bromobutyl rubber or a chlorobutyl rubber, preferably having a halogen content of from 0.1 to 10 wt.%, more preferably from 0.5 to 8 wt.%, most preferably from 0.5 to 5.0 wt.%, based on the total weight of the halogenated rubber.

According to one or more embodiments, the at least one non-crosslinked elastomer is bromobutyl rubber, at least the catalyst is ZnO, and the blend further comprises at least 0.05 wt%, preferably from 0.1 to 0.5 wt%, based on the total weight of the blend, of at least one zinc salt of a fatty acid, preferably zinc stearate, and/or at least 0.05 wt%, preferably from 0.1 to 0.5 wt%, based on the total weight of the blend, of at least one saturated fatty acid having 6 carbon atoms, preferably at least 13 carbon atoms. The at least one saturated fatty acid may be selected from stearic acid and montanic acid.

According to one or more embodiments, the at least one non-crosslinked elastomer is bromobutyl rubber, at least the catalyst is selected from the group consisting of zinc salts of fatty acids, preferably zinc stearate, and zinc borate, and the at least one catalyst is present in the blend in a total amount ranging from 0.1 to 5.0 wt.%, more preferably from 0.1 to 2.5 wt.%, even more preferably from 0.1 to 2.0 wt.%, most preferably from 0.5 to 1.5 wt.%, based on the total weight of the blend.

According to one or more embodiments, the thermoplastic elastomer and the elastomer are present in the composition as a co-continuous phase, i.e., after melt processing. The term "co-continuous phase" refers herein to a morphology in which a continuous boundary line is formed between two phases, rather than an island-like dispersion of the first phase in the second continuous phase or an island-like dispersion of the second phase in the first continuous phase. The term "continuous phase" refers herein to a phase that contains at least one connecting pathway of a point of matter located entirely within the phase and that is macroscopically crossed over a sample of matter ("percolation").

Preferably, the at least one thermoplastic elastomer and the at least one non-crosslinked elastomer are compatible. The polymer components "compatible" in the present disclosure mean that the properties of the blends composed of at least one thermoplastic elastomer and at least one non-crosslinked elastomer are comparable to those of the individual polymer components. It may also be preferred that the at least one thermoplastic elastomer and the at least one non-crosslinked elastomer are partially miscible, but not necessarily completely miscible with each other. In the present disclosure, the polymer components are "miscible" meaning that the polymer blend consisting of at least one thermoplastic elastomer and at least one non-crosslinked elastomer has a negative gibbs free energy and heat of mixing. Polymer blends composed of completely miscible polymer components tend to have a single glass transition point, which can be measured using Dynamic Mechanical Thermal Analysis (DMTA). The glass transition point can be determined as, for example, the peak value (ratio of storage modulus and loss modulus) of the measured tan δ curve.

According to one or more embodiments, the at least one thermoplastic elastomer is a thermoplastic olefin (TPE-O). Thermoplastic olefins based on polymer blends as well as thermoplastic olefins of the block copolymer type, for example polyolefin elastomers (POE), are suitable as at least one thermoplastic elastomer in the composition of the invention.

Suitable elastomeric elastomers (POE) include propylene-based elastomers, such as metallocene-polymerized semi-crystalline propylene-ethylene copolymer elastomers having a total ethylene content in the range of 10 to 20 wt.%. These are commercially available, for example, under the trade name

(from Exxon Mobil), e.g.

6102 and6202. other suitable propylene-based elastomers include propylene-ethylene copolymer elastomers having a propylene monomer content of greater than 70 wt%, for example greater than 80 wt%, and an ethylene monomer content of greater than 5 wt%. These are commercially available, for example, under the trade name

(from the Dow Chemical Company), e.g.

4301 and

4200。

metallocene polymerized copolymers of ethylene and α -olefins having a total ethylene content in the range of 85-98 wt.%, e.g. ethylene with C₄-C₈α -copolymers of olefin comonomers are also suitable these copolymer compositions are sometimes referred to as "plastomers" and they are commercially available, for example under the trade name(from Exxon Mobil) and

(from Dow Chemicals).

Suitable thermoplastic olefins also include polypropylene impact copolymers and heterophasic polypropylene copolymers. These types of thermoplastic polyolefins typically include propylene polymers and elastomers, typically Olefin Copolymer Elastomers (OCE). The propylene polymer may be a propylene homopolymer or a random copolymer of propylene having a propylene content of, for example, at least 95 wt%. Suitable random copolymers include propylene with ethylene or with C₄-C₆α -olefin comonomer, typically a copolymer of ethylene suitable Olefin Copolymer Elastomers (OCE) include ethylene-propylene rubbers/elastomers having an ethylene content of, for example, 20 to 70 wt%.

Heterophasic polypropylene copolymers can be prepared as a reactor mixture, wherein the propylene homopolymer or random propylene copolymer and the Olefin Copolymer Elastomer (OCE) component are formed simultaneously by polymerizing propylene with another suitable olefin comonomer. Alternatively, they may be formed by melt processing of a propylene polymer with an olefin copolymer elastomer, each of which is formed separately prior to blending the ingredients. The preparation of heterophasic polypropylene copolymers as reactor blends is sometimes referred to as "reactor TPO". The amount of elastomeric component in polypropylene impact copolymers is typically significantly less than the amount in reactor TPO.

Suitable reactor TPO and heterophasic polypropylene copolymers are commercially available, for example under the trade name

(from LyondellBasell), e.g.

CA 10A and

CA12A, and tradename

For example

SD233 CF.

According to one or more embodiments, the at least one thermoplastic elastomer is selected from heterophasic polypropylene copolymers and metallocene-polymerized semi-crystalline propylene-ethylene copolymer elastomers, and mixtures thereof.

It may be preferred that the blend comprises at least one heterophasic polypropylene copolymer and at least one metallocene-polymerized semi-crystalline propylene-ethylene copolymer elastomer. The weight ratio of the amount of the at least one heterophasic polypropylene copolymer to the at least one metallocene-polymerized semi-crystalline propylene-ethylene copolymer elastomer may be in the range of 0.1 to 1.5, preferably 0.2 to 1.25, most preferably 0.3 to 0.75. The at least one heterophasic polypropylene copolymer may be selected from heterophasic polypropylene copolymers comprising isotactic polypropylene as matrix phase and ethylene propylene rubber as dispersed phase and heterophasic polypropylene copolymers comprising polypropylene-ethylene random copolymer as matrix phase and ethylene propylene rubber as dispersed phase.

The blend may further comprise at least one Hindered Amine Light Stabilizer (HALS). These compounds are typically added to polymer blends as stabilizers to prevent light-induced polymer degradation. Such stabilizers are particularly desirable where the composition is used in roofing applications, such as for providing a roofing membrane comprising one or more layers comprised of the composition of the present invention.

Preferably, no HALS type having a strong basicity is added to the blend, especially if the at least one catalyst comprises or consists of one or more metal oxides, zinc salts of fatty acids, zinc borate or mixtures thereof. The at least one hindered amine light stabilizer is preferably an alkoxyamine hindered amine light stabilizer (NOR-HALS), especially in the case where the at least one catalyst comprises or consists of at least one metal oxide, zinc salt of a fatty acid, zinc borate or a mixture thereof, especially ZnO. These HALS types are generally very low in basicity and pk_aThe value is about 4 to 5.

According to one or more embodiments, the blend further comprises 0.1 to 10.0 wt%, preferably 0.1 to 5.0 wt%, based on the total weight of the blend, of at least one alkoxyamine hindered amine light stabilizer (NOR-HALS). Suitable commercially available alkoxyamine hindered amine light stabilizers (NOR-HALS) include:

bis- (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) sebacate, e.g. as

NOR123 (from Ciba Chemicals, CAS number 129757-67-1) is commercially available; derivatives of N-butyl-2, 2,6, 6-tetramethyl-4-piperidinamine, e.g. as

NOR 152 (from Ciba Chemicals) is commercially available; reaction products of 3-bromo-1-propene, N-butyl-1-butylamine and N-butyl-2, 2,6, 6-tetramethyl-4-piperidinamine, in oxidized form, hydrogenated form, e.g. as Tinuvin

371 (from Ciba Chemicals) is commercially available; the reaction product of N, N' -ethane-1, 2-diylbis (1, 3-propanediamine), cyclohexane, peroxidized 4-butylamino-2, 2,6, 6-tetramethylpiperidine and 2,4, 6-trichloro-1, 3, 5-triazine is commercially available as Flamestab NOR 116 (from BASF); and HostavinNOW ex (from Clariant).

The blend may further comprise at least one flame retardant. These are particularly desirable where the composition is used in roofing applications, for example, to provide a roofing membrane comprising one or more layers comprised of the composition of the present invention.

According to one or more embodiments, the blend further comprises from 1 to 50 wt%, preferably from 5 to 40 wt%, based on the total weight of the blend, of at least one flame retardant selected from the group consisting of magnesium hydroxide, aluminum trihydroxide, antimony trioxide, ammonium polyphosphate and melamine-, melamine resin-, melamine derivative-, melamine formaldehyde-, silane-, siloxane-and polystyrene-coated ammonium polyphosphates.

Other suitable flame retardants include, for example, 1,3, 5-triazine compounds, such as melamine, melam, melem, melon, ammeline, ammelide, 2-ureidomelamine, acetoguanamine, benzoguanamine, diaminophenyltriazine, melamine salts and adducts, melamine cyanurate, melamine borate, melamine orthophosphate, melamine pyrophosphate, dimelamine pyrophosphate and melamine polyphosphate, polyphosphates of oligomeric and polymeric 1,3, 5-triazine compounds and 1,3, 5-triazine compounds, guanine, piperazine phosphate, piperazine polyphosphate, ethylenediamine phosphate, pentaerythritol, borophosphate, 1,3, 5-trishydroxyethyl isocyanurate, 1,3, 5-triglycidyl isocyanurate, triallyl isocyanurate and derivatives of the above compounds.

Suitable flame retardants are commercially available, for example under the trade name

And

(both from Albemarle) and under the trade name(from Clariant),

(from Phos-Check) and FR(from Budenheim).

The blend may further comprise at least one UV-absorber selected from the group consisting of hydroxybenzophenones, hydroxybenzotriazoles, triazines, anilines, benzoates, cyanoacrylates, phenylformamidines and mixtures thereof.

According to one or more embodiments, the blend further comprises 0.1 to 10.0 wt%, preferably 0.5 to 5.0 wt%, of at least one UV-absorber, based on the total weight of the blend. Suitable UV absorbers are commercially available, for example as commercial productsName (name)

(from Ciba Specialty Chemicals), e.g.

213、234、320、326-329、350、360、571。

The blend may also contain other additives such as fillers, heat stabilizers, plasticizers, blowing agents, dyes, colorants, pigments, delusterants, antistatic agents, impact modifiers, and processing aids such as lubricants, slip agents, antiblock agents, and drying aids (jest aids). Suitable fillers include, for example, inert mineral fillers such as sand, granite, calcium carbonate, clay, expanded clay, diatomaceous earth, pumice, mica, kaolin, talc, dolomite, xonotlite, perlite, vermiculite, wollastonite, barite, magnesium carbonate, calcium hydroxide, calcium aluminate, silica, fumed silica, fused silica, aerogels, glass beads, hollow glass spheres, ceramic spheres, bauxite, crushed concrete and zeolites.

According to one or more embodiments, the composition comprises at least 50 wt%, preferably at least 75 wt%, more preferably at least 85 wt%, most preferably at least 95 wt% of the melt blend, based on the total weight of the composition. According to one or more other embodiments, the composition consists of a molten mixture.

One of the advantages of the composition of the invention is that it exhibits low blocking behaviour, which enables problem-free post-treatment of the composition, such as cutting, welding, stacking and unwinding of rolls of film or foil made from shaped articles, such as from the composition. In particular, the composition may exhibit a blocking value of not more than 5N/15mm, preferably not more than 2.5N/15mm, most preferably not more than 1.5N/15mm, as determined by the method cited in the specification.

In the context of the present invention, the "blocking value" of a composition refers to the peel force required to separate two layers of the composition from each other, which is determined by using the measurement method described below.

Measurement of blocking value

The blocking value of the composition is determined on the basis of the measurement method as defined in the DIN 53366 standard. The measurement was performed at a temperature of 23 ℃ using a peel mode instead of a shear mode, i.e., sheets of the composition were separated from each other by using a peel force. The blocking value is determined by using 0.5kg/cm at a temperature of 50 DEG C²The force in N/15mm sheet width required to separate the two sheets from each other after pressing them together for 72 hours.

Another advantage of the composition of the present invention is that it has high flexibility, particularly as compared to prior art TPO materials. In particular, the composition has an elastic modulus not exceeding 50N/mm, measured at a temperature of 23 ℃ and with a crosshead speed of 5mm/min, by using the method defined in ISO 527-2 standard²Preferably not more than 25N/mm²Most preferably not more than 15N/mm²。

Another advantage of the composition of the invention is its high impact resistance. In particular, the impact resistance of the composition measured using the method defined in the standard type EN12691 a is at least 1000mm, preferably at least 1250mm, and/or the impact strength measured according to the method defined in the standard type EN 12691B is at least 1750mm, preferably at least 2000 mm. The impact resistance was measured using a layer consisting of the composition of the invention having a thickness of 0.8 mm.

The composition may have at least 7.5N/mm measured using a method as defined in ISO 527-2 standard at a temperature of 23 ℃ using a 100mm/min crosshead speed²Preferably at least 10N/mm²Tensile strength at break of (1).

The composition may have an elongation at break of at least 500%, preferably at least 600%, most preferably at least 650%, measured using a method as defined in ISO 527-2 standard at a temperature of 23 ℃ using a crosshead speed of 100 mm/min.

Another subject of the invention is a process for preparing a polymer composition, comprising the following steps:

I) introducing the blend components of the composition of the present invention into a mixing apparatus, and

II) melt processing the blend components in a mixing device at a temperature greater than the melting point of the at least one thermoplastic elastomer.

Where the blend components comprise more than one thermoplastic elastomer, melt processing is preferably carried out at a temperature above the melting point of the thermoplastic elastomer with the highest melting point.

The mixing apparatus may be a batch mixer, preferably a Brabender, Banbury or roll mixer. The maximum temperature of the blend during melt processing in the batch mixer is preferably not less than 150 deg.C, more preferably not less than 160 deg.C, and most preferably not less than 180 deg.C. The maximum temperature of the blend during melt processing can be in the range of 150-250 deg.C, particularly 160-220 deg.C, such as 180-200 deg.C.

In embodiments where the blend components comprise at least one catalyst, the temperature of the blend is preferably increased during mixing until the chain extension and/or crosslinking and/or coupling reactions of the at least one non-crosslinked elastomer are initiated. This is usually marked by an increase in the torque value of the motor of the hybrid device. Melt mixing may be continued until the torque value of the motor of the mixing device reaches a value, for example, 1-20%, preferably 1-15% higher than the lowest value measured at the beginning of melt mixing, i.e., before initiation of the chain extension and/or crosslinking and/or coupling reactions, after which mixing is not continued. The mixture thus obtained may be cooled to room temperature.

The catalyst and accelerator (if used) may be dispersed in the non-crosslinked elastomer in a separate processing step prior to melt mixing with the thermoplastic elastomer. Any conventional mixing device (e.g., a two-roll rubber mill, Bradender, or Banbury mixer) or continuous melt mixer (e.g., a single or twin-screw extruder) can be used to disperse the catalyst and optional accelerator in the non-crosslinked elastomer. In any case, the catalyst, optional accelerator, and at least one non-crosslinked elastomer are intimately melt mixed with the thermoplastic elastomer prior to initiating the chain extension and/or crosslinking and/or coupling reactions.

The mixing apparatus is preferably a continuous type mixer, more preferably an extrusion apparatus comprising an extruder such as a single or twin screw extruder and an extruder die. The ingredients of the blend are preferably melt processed in an extruder until a homogeneous blend is obtained. According to one or more embodiments, the mixing device is a continuous type extrusion device comprising an extruder and a die, and the process comprises the further step iii): extruding the melt-processed mixture obtained in step ii) through an extruder die.

Suitable extruders include a barrel and a screw unit contained in the barrel or ram. Any conventional extruder may be used, such as a ram extruder, a single screw extruder, or a twin screw extruder. Preferably, the extruder is a screw extruder, more preferably a twin screw extruder. The screw unit of a conventional screw extruder is generally considered to comprise feed, transition and metering zones. In the feed zone, the thermoplastic composition enters the path of the rotating screw and is conveyed to the transition zone where the composition is compressed and melted. The composition should be completely melted as it leaves the transition zone. The function of the metering zone is to homogenize the molten composition and to meter or pump it at a constant rate. The extruder apparatus further comprises a die, preferably a flat die, which consists of a manifold, a pathway and a lip region.

The extruder barrel contains a feed opening through which the material to be extruded is fed into the extruder and a discharge opening through which the material leaves the barrel. The discharge port is coupled to the die through a gate or adapter. The mixing device may be positioned between the barrel and the die. The feed port is typically connected to a hopper into which the material to be extruded is added. The screen assembly and breaker plate are preferably positioned at the end of the barrel to avoid clogging the nozzles. The extruder further comprises heating elements, cooling elements, temperature sensors and temperature control elements to provide temperature control zones along the barrel, also referred to as barrel zones. The extruder may comprise, for example, from 3 to 8 barrel zones, preferably at least 5 barrel zones, by means of which a temperature profile can be achieved in the barrel.

The extrusion process can be carried out by using different temperature profiles, such as a temperature increase profile (where the temperature increases downstream of the barrel), a temperature decrease profile (where the temperature decreases downstream of the barrel), and a hump temperature profile (where the temperature increases from the feed port to a certain set point, e.g., toward the middle of the barrel).

It may be preferred that the size of the extruder and the extrusion process parameters, in particular the temperature profile and the extrusion pressure, are selected/adjusted such that the degree of crosslinking of the at least one elastomer in the melt-processed mixture obtained in step ii) does not exceed 10.0 wt. -%, more preferably does not exceed 5.0 wt. -%, even more preferably does not exceed 2.5 wt. -%, most preferably does not exceed 2.0 wt. -%. In other words, it may be preferred that the dimensions of the extruder and the extrusion process parameters are selected/adjusted such that the at least one non-crosslinked elastomer is crosslinked to a degree of crosslinking of no more than 10.0 wt.%, more preferably no more than 5.0 wt.%, even more preferably no more than 2.5 wt.%, most preferably no more than 2.0 wt.% in the screw portion of the extruder.

The maximum temperature of the blend during melt processing in the screw zone of the extruder, i.e. the temperature at the end of the screw zone, is preferably not less than 150 c, more preferably not less than 160 c, most preferably not less than 180 c. The maximum temperature of the blend during melt processing in the screw zone of the extruder may be in the range of 150-.

The at least one thermoplastic elastomer, the at least one non-crosslinked elastomer and the catalyst (if used) may be fed to the extruder as separate streams, as a premix, a dry blend or as a masterbatch.

The at least one thermoplastic elastomer and the at least one non-crosslinked elastomer may be fed into the extruder through a feed port, and the at least one catalyst (if used) may be fed into the extruder through another port located downstream of the feed port. The term "downstream" refers herein to the direction to the outlet. The at least one non-crosslinked elastomer may also be mixed with the at least one catalyst (if used) to obtain a premix, which is then added to the extruder through the feed throat. The premixing may be carried out using blending equipment known to those skilled in the art. Preferably, the pre-mixing of the at least one non-crosslinked elastomer and the catalyst is carried out at a temperature above the melting point of the non-crosslinked elastomer and below the activation temperature of the catalyst, i.e. the temperature at which the chain extension and/or crosslinking and/or coupling reaction of the non-crosslinked elastomer is initiated. Alternatively, at least the thermoplastic elastomer and the at least one non-crosslinked elastomer may be processed into pellets or granules in a compounding extruder, which are then dry blended with the at least one catalyst (if used), and the resulting dry blend is then fed into the extruder through the feedthroat.

The at least one aminoalkoxy (NOR) Hindered Amine Light Stabilizer (HALS), as well as other additives, such as UV-and heat stabilizers, if used, may be fed into the extruder through the feed throat or through another port located downstream of the feed throat. It is also preferred to feed these additives into the extruder as a dry blend with at least one catalyst.

Another subject of the invention is a polymer composition obtainable by using the process for preparing the polymer composition of the invention.

Another subject of the invention is a shaped article comprising a substrate layer having a thickness of at least 0.1mm, said substrate layer consisting of a composition according to the invention or of a polymer composition according to the invention. Preferably, the substrate layer has a thickness of 0.1 to 5.0mm, more preferably 0.25 to 4.0mm, most preferably 0.3 to 3.0mm, as measured by the method defined in DIN EN 1849-2 standard. An optical microscope, for example of the Keyence VHX-600 type with a magnification of 30, can be used to measure the thickness of the layer section.

One of the advantages of the shaped articles according to the invention is the low blocking behavior, which enables problem-free post-processing of the shaped articles, such as cutting, welding, stacking and unwinding from a reel. In particular, the shaped article may exhibit a blocking value of not more than 5N/15mm, preferably not more than 2.5N/15mm, most preferably not more than 1.5N/15mm, as determined by the method cited in the specification.

Another advantage of the shaped article of the present invention is its high flexibility, particularly as compared to prior art waterproof and roofing membranes constructed of TPO materials. In particular, the shaped article may have a thickness of 5mm/mi at a temperature of 23 ℃ by using the method as defined in ISO 527-2 standardN measured at crosshead speed not exceeding 50N/mm²Preferably not more than 25N/mm²Most preferably not more than 15N/mm²The modulus of elasticity of (a).

Another advantage of the shaped articles of the invention is that they have a high impact resistance. In particular, the shaped article may have an impact resistance of at least 1000mm, preferably at least 1250mm, measured using the method defined in the standard type EN12691 a, and/or an impact resistance of at least 1750mm, preferably at least 2000mm, measured according to the method defined in the standard type EN 12691B. The impact resistance was measured with a molded article composed of a substrate layer having a thickness of 0.8 mm.

The shaped article may have a cross-head speed of 100mm/min of at least 7.5N/mm measured using the method defined in ISO 527-2 standard at a temperature of 23 ℃²Preferably at least 10N/mm²Tensile strength at break of (1).

The shaped article may have an elongation at break of at least 500%, preferably at least 600%, most preferably at least 650%, measured by using the method defined in ISO 527-2 standard, at a temperature of 23 ℃ using a crosshead speed of 100 mm/min.

The shaped article may further comprise a layer of reinforcing scrim (scrim) embedded in the substrate layer or a layer of reinforcing fibers bonded directly to one of its surfaces. Suitable reinforcing scrim layers may comprise a web of interwoven filaments of thermoplastic or metal having a tensile strength sufficient to resist tearing when exposed to typical tensile loads experienced by the roofing membrane from all directions. Preferred materials for reinforcing the scrim layer include polypropylene and polyethylene terephthalate (PET). The reinforcing fiber layer may be in the form of a fiber mat, a fiber fabric, or a fiber weave. Particularly suitable materials for the reinforcing fiber layer include inorganic fibers such as glass fibers, aramid fibers, wollastonite fibers, and carbon fibers, and synthetic organic fibers such as polyester fibers, ethylene and propylene homopolymer fibers, ethylene propylene copolymer fibers, viscose fibers, polyamide fibers, and nylon fibers.

Another subject of the invention is a process for the preparation of a shaped article comprising the following steps:

I) the blend components of the composition of the present invention are introduced into a continuous type extrusion apparatus comprising an extruder and a flat die,

II) melt-processing the blend components in an extruder to obtain a melt-processed mixture of the blend components, and

III) extruding the obtained melt-processed mixture through a flat die to form a substrate layer.

The extruder used in the process may be any conventional type of extruder, such as a single or twin screw extruder.

Preferably, the process for the preparation of a shaped article comprises the further steps of:

IV) using spaced apart calender cooling rolls through which the formed substrate layer is stretched immediately after step III).

Another subject of the invention is a method for covering a roof, comprising the following steps:

I) the shaped article of the invention is applied to the surface of the roof to be covered,

II) overlapping the adjacent edges of the shaped article,

III) heating the adjacent edges of the shaped article in the overlap region at slightly above the melting temperature of the at least one thermoplastic elastomer and joining the overlap region under sufficient pressure to provide acceptable seam strength without the use of adhesives.

Examples

The materials shown in table 1 were used in the examples.

TABLE 1 materials used in the experiments

Preparation of exemplary sheet

An exemplary sheet was produced using a laboratory scale extrusion-calendering apparatus consisting of a twin screw extruder (Berstorff GmbH), a flat die and a set of water cooled calendering rolls. The extrusion temperatures and pressures are listed in table 2.

In the preparation of the exemplary sheet, the thermoplastic elastomer and the non-crosslinked elastomer are fed into the extruder hopper. The blend is melt processed in a first of four zones of the extruder and an additive package comprising a mixture of a catalyst, a hindered amine light stabilizer (NOR-HALS), and a flame retardant is added to the partially melt processed blend at the beginning of a second zone of the extruder. The melt processed blend was then extruded through a flat die into a single layer sheet having a thickness of about 0.8 mm.

Test pieces were cut from the exemplary sheet to test the mechanical properties of the compositions. Table 2 and table 3 show the ingredients of the blends and the measured properties of the exemplary sheets.

Tensile strength, elongation at break and E-modulus

The tensile strength at break, elongation at break and E-modulus were measured at 100%, 300% and at break using a crosshead speed of 100mm/min for tensile strength and elongation at break and a speed of 5mm/min for E-modulus at a temperature of 23 ℃ according to ISO 527-2 standard. The values given in table 3 were obtained with test samples cut from the example sheet in the length direction.

Adhesion behavior

The blocking values of the compositions of the examples were determined at a temperature of 23 ℃ based on the measurement method defined in the DIN 53366 standard. The measurement was performed using a peeling mode instead of a shearing mode, i.e., sheets were separated from each other by peeling. The blocking value is 0.5kg/cm²Is determined by the force, in N/15mm sheet width, required to separate two sheets of the test composition from each other after the sheets have been pressed together at a temperature of 50 c for 72 hours. The blocking value was measured using the same equipment as used for measuring tensile strength.

Impact resistance

The impact resistance was measured by using the method defined in EN12691 type a standard and EN12691 type B standard.

Molecular weight

Number average (M)_n) And weight average (M)_w) The molecular weight and the polydispersity index (PDI) were determined by HT-GPC (gel permeation chromatography) measurements carried out under the following conditions:

system Agilent 1100

Concentration detector, refractive index detector

PSS polyolefin lin xl (0.8cm x 5cm,10 μm)

Column 4 XPSS polyolefin lin xl (0.8cm X30 cm,10 μm)

Eluent 1,2, 4-trichlorobenzene

Flow rate 1mL/min

Injection volume of 200. mu.L

The temperature is 160 DEG C

Calibration with respect to polystyrene

Standard sample polystyrene 266-

Sample preparation 27mg of each sample was dissolved in 9ml of 1,2, 4-trichlorobenzene at 160 ℃ for 2 hours.

Weldability

The weldability of the exemplary sheets was tested using a welding temperature of 240 ℃ and a welding speed of 3.5 m/min. A Sarnamatic 661 automatic welder was used when welding the sheets. Weldability was considered satisfactory when, in the tear test, a fracture occurred outside the weld between the connecting tabs (OK).

TABLE 2

Composition [ phr]	Ex-1	Ex-2	Ex-3	Ex-4	Ex-5	Ex-6	aRef-1
								Hifax CA 10	20	20	20	20	20	20	20
Vistamaxx 6202	49	49	49	49	49	49	49
								BB2030	31	31	31	31	-	-	31
RB100	-	-	-	-	31	-	-
								RB301	-	-	-	-	-	31	-
SiloxActif E80	-	1.38	1.38	1.38	1.38	1.38	1.38
								Stearic acid	0.35	0.35	0.35	0.35	0.35	0.35	0.35
Heat stabilizer	0.1	0.1	0.1	0.1	0.1	0.1	0.1
								NOR-HALS 1	0.45	0.45	0.45	0.45	0.45	0.45	0.45
NOR-HALS 2	0.3	0.3	0.3	0.3	0.3	0.3	0.3
								Alumina trihydrate	42	42	42	42	42	42	42
Titanium dioxide	3	3	3	3	3	3	3
								Extruder conditions
Extrusion temperature [ deg.C]	185	185	195	205	185	185	185
								Head pressure [ bar ]]	69	70	71	69	72	81	70

^aExtruding Ex-2 into sheetCuring the material in an oven at 190 ℃ in a nitrogen atmosphere