阅读说明：本技术 包含增容剂的循环聚乙烯-聚丙烯共混物 (Recycled polyethylene-polypropylene blends comprising compatibilizers ) 是由 苏珊娜·卡伦 赫尔曼·布劳恩 刘毅 马库斯·加莱特纳 格哈德·哈布纳 于 2020-03-27 设计创作，主要内容包括：本发明涉及一种包含共混物(A)和增容剂(B)的聚乙烯-聚丙烯组合物,共混物(A)为循环材料,所述共混物包含聚丙烯和聚乙烯,增容剂(B)为1-丁烯和乙烯的共聚物。此外,本发明涉及一种包含所述聚乙烯-聚丙烯组合物的制品和一种用于制备所述聚乙烯-聚丙烯组合物的方法。本发明还涉及增容剂(B)用于改善共混物(A)的抗冲性-刚度平衡和形态的用途,增容剂(B)为1-丁烯和乙烯的共聚物。(The invention relates to a polyethylene-polypropylene composition comprising a blend (A) which is a recycled material and a compatibilizer (B) which is a copolymer of 1-butene and ethylene. Furthermore, the present invention relates to an article comprising said polyethylene-polypropylene composition and to a process for preparing said polyethylene-polypropylene composition. The invention also relates to the use of a compatibilizer (B), which is a copolymer of 1-butene and ethylene, for improving the impact-stiffness balance and morphology of the blend (A).)

1. A polyethylene-polypropylene composition obtainable by blending a)75.0 to 94.0 wt. -%, based on the total weight of the polyethylene-polypropylene composition, of a blend (A) comprising

i) Polypropylene, and

ii) a Polyethylene (PE),

wherein the weight ratio of polypropylene to polyethylene is 3: 7 to 7: 3, and

wherein blend (a) is recycled material recovered from waste plastic material derived from post-consumer waste and/or industrial waste;

and

b)6.0 to 25.0 wt. -%, based on the total weight of the polyethylene-polypropylene composition, of a compatibilizer (B) which is a copolymer of 1-butene and ethylene.

2. Polyethylene-polypropylene composition according to claim 1, wherein the copolymer of 1-butene and ethylene has a density determined according to ISO 1183 equal to or lower than 930kg/m³Preferably 860 to 925kg/m³More preferably in the range of 880 to 920kg/m³Still more preferably from 890 to 915kg/m³Within the range of (1).

3. The polyethylene-polypropylene composition according to claim 1, wherein the copolymer of 1-butene and ethylene has a melt flow rate MFR determined according to ISO 1133₂(190 ℃, 2.16kg) is in the range of 1.0 to 20.0g/10min, preferably in the range of 1.5 to 15.0g/10min, more preferably in the range of 2.0 to 12.0g/10min, still more preferably in the range of 3.0 to 10.0g/10 min.

4. The polyethylene-polypropylene composition according to any one of the preceding claims, wherein the copolymer of 1-butene and ethylene has a content of 1-butene of at least 70.0 wt. -%, preferably in the range of from 70.0 to 92.0 wt. -%, more preferably in the range of from 75.0 to 90.0 wt. -%, still more preferably in the range of from 80.0 to 88.0 wt. -%, based on the total weight of the copolymer of 1-butene and ethylene.

5. The polyethylene-polypropylene composition according to any of the preceding claims, wherein the copolymer of 1-butene and ethylene has a melting temperature Tm determined according to ISO 11357 below 130 ℃, preferably in the range of from 90 to below 130 ℃, more preferably in the range of from 100 to 125 ℃, still more preferably in the range of from 105 to 115 ℃.

6. The polyethylene-polypropylene composition according to any one of the preceding claims, wherein the limonene content of blend (a) determined by using solid phase microextraction (HS-SPME-GC-MS) is

i) From 1ppm to 100ppm, preferably from 1ppm to 50ppm, more preferably from 2ppm to 50ppm, most preferably from 3ppm to 35 ppm;

ii) from 0.10ppm to less than 1ppm, preferably from 0.10ppm to less than 0.85ppm, most preferably from 0.10ppm to less than 0.60 ppm.

7. Polyethylene-polypropylene composition according to any one of the preceding claims, wherein the relative amount of units derived from ethylene in blend (a) is more than 20 wt. -%, preferably more than 27 wt. -%, more preferably more than 30 wt. -%, still more preferably more than 35 wt. -%, most preferably more than 40 wt. -%, based on the total weight of blend (a).

8. Polyethylene-polypropylene composition according to any one of the preceding claims, wherein blend (A) contains based on the total weight of blend (A)

i) Up to 6.0% by weight, preferably less than 0.1 to 6.0% by weight, of polystyrene, and/or

ii) up to 3% by weight, preferably from 0.1 to 3% by weight, of talc, and/or

iii) up to 5.0% by weight, preferably from 0.2 to 5.0% by weight, of a polyamide, and/or

iv) chalk in an amount of up to 3% by weight, preferably 0.1 to 3% by weight.

9. Polyethylene-polypropylene composition according to any one of the preceding claims, having a melt flow rate MFR determined according to ISO 1133 in the range of from 0.1 to 50.0g/10min, preferably in the range of from 1.0 to 20.0g/10min, more preferably in the range of from 2.0 to 15.0g/10min, still more preferably in the range of from 4.0 to 10.0g/10min₂(2.16kg，230℃)。

10. According to the preceding claimThe polyethylene-polypropylene composition of any one of claims, having at least 6.0kJ/m²Preferably from 6.0 to 15.0kJ/m²More preferably in the range of 7.0 to 10.0kJ/m²Still more preferably in the range of 7.0 to 9.0kJ/m²Simple beam notched impact strength measured at 23 ℃ according to ISO 179/1 eA.

11. Polyethylene-polypropylene composition according to any one of the preceding claims, having a tensile modulus determined according to ISO 527-2 of at least 600MPa, preferably in the range of 600 to 830MPa, more preferably in the range of 620 to 820MPa, still more preferably in the range of 640 to 770 MPa.

12. An article comprising the polyethylene-polypropylene composition according to any one of claims 1 to 11.

13. A process for preparing a polyethylene-polypropylene composition according to any one of claims 1 to 11, comprising the steps of:

a) the blend (A) is provided in an amount of 75.0 to 94.0 wt. -%, based on the total weight of the polyethylene-polypropylene composition,

b) the compatibilizer (B) is provided in an amount of 6.0 to 25.0 weight percent based on the total weight of the polyethylene-polypropylene composition,

c) melting and mixing the blend of blend (A) and compatibilizer (B), optionally in the presence of 0 to 1.0 weight percent of a stabilizer or stabilizer mixture, and

d) optionally granulating.

14. Use of a compatibilizer (B) which is a copolymer of 1-butene and ethylene and has a balance of impact resistance and stiffness for improving the blend (A)

i) 930kg/m or less³Preferably 860 to 925kg/m³More preferably in the range of 880 to 920kg/m³Still more preferably from 890 to 915kg/m³In accordance with ISO 1183And/or a density of

ii) a melt flow rate MFR determined according to ISO 1133 in the range from 1.0 to 20.0g/10min, preferably in the range from 1.5 to 15.0g/10min, more preferably in the range from 2.0 to 12.0g/10min, still more preferably in the range from 3.0 to 10.0g/10min₂(230℃，2.16kg)，

The blend (A) comprises

a) Polypropylene, and

b) the Polyethylene (PE) is added to the polyethylene,

wherein the weight ratio of polypropylene to polyethylene is 3: 7 to 7: 3, and

wherein blend (a) is recycled material recovered from waste plastic material derived from post-consumer waste and/or industrial waste.

Technical Field

The invention relates to a polyethylene-polypropylene composition comprising a blend (A) which is a recycled material and a compatibilizer (B) which is a copolymer of 1-butene and ethylene. Furthermore, the present invention relates to an article comprising said polyethylene-polypropylene composition and to a process for preparing said polyethylene-polypropylene composition. The invention also relates to the use of a compatibilizer (B), which is a copolymer of 1-butene and ethylene, for improving the impact-stiffness balance and morphology of the blend (A).

Background

Mechanical recycling of polymer waste from various collection systems is a major goal of current developments in this field. Mixing cycles of chemically similar polymers (e.g. styrene homopolymers and copolymers or polyamides) are often seen as a way to get rid of the classification dilemma that limits the process. Polypropylene and polyethylene are certainly candidate materials for such blends, but their inherent limited compatibility and miscibility often forces the application of some compatibilization in order to obtain compositions with good mechanical properties.

It is well known in the art that higher impact strength can be achieved by adding an elastomer (e.g., ethylene propylene rubber) as a compatibilizer, but this limits the stiffness of the resulting composition. Furthermore, many such elastomers are only provided in higher molecular weight forms or non-particulate forms, the latter requiring specific mixing equipment. WO 2015/169690 provides an alternative method by using a heterophasic ethylene-propylene copolymer as compatibilizer. The heterophasic copolymer comprises a crystalline matrix and an elastomeric component, which limits the stiffness loss but at the same time requires the addition of considerable amounts.

Disclosure of Invention

It is therefore an object of the present invention to provide a composition comprising recycled polypropylene and polyethylene, which composition is characterized by a high impact strength while the stiffness is also kept at a high level.

The present invention therefore relates to a polyethylene-polypropylene composition obtainable by blending

a)75.0 to 94.0 wt. -%, based on the total weight of the polyethylene-polypropylene composition, of a blend (A) comprising

i) Polypropylene, and

ii) a Polyethylene (PE),

wherein the weight ratio of polypropylene to polyethylene is 3: 7 to 7: 3, and

wherein blend (a) is recycled material recovered from waste plastic material derived from post-consumer waste and/or industrial waste;

and

b)6.0 to 25.0 wt. -%, based on the total weight of the polyethylene-polypropylene composition, of a compatibilizer (B) which is a copolymer of 1-butene and ethylene.

According to one embodiment of the invention, the copolymer of 1-butene and ethylene has a density, determined according to ISO 1183, equal to or lower than 930kg/m³Preferably 860 to 925kg/m³More preferably in the range of 880 to 920kg/m³Still more preferably from 890 to 915kg/m³Within the range of (1).

According to another embodiment of the invention, the melt flow rate MFR, determined according to ISO 1133, of a copolymer of 1-butene and ethylene₂(190 ℃, 2.16kg) is in the range of 1.0 to 20.0g/10min, preferably in the range of 1.5 to 15.0g/10min, more preferably in the range of 2.0 to 12.0g/10min, still more preferably in the range of 3.0 to 10.0g/10 min.

According to a further embodiment of the invention, the copolymer of 1-butene and ethylene has a content of 1-butene of at least 70.0% by weight, preferably in the range of from 70.0 to 92.0% by weight, more preferably in the range of from 75.0 to 90.0% by weight, still more preferably in the range of from 80.0 to 88.0% by weight, based on the total weight of the copolymer of 1-butene and ethylene.

According to one embodiment of the invention, the copolymer of 1-butene and ethylene has a melting temperature Tm determined according to ISO 11357 lower than 130 ℃, preferably in the range from 90 to lower than 130 ℃, more preferably in the range from 100 to 125 ℃, still more preferably in the range from 105 to 115 ℃.

According to a first embodiment of the invention, the limonene (or limonene) content of the blend (A), determined by using solid phase microextraction (HS-SPME-GC-MS), is from 1ppm to 100ppm, preferably from 1ppm to 50ppm, more preferably from 2ppm to 50ppm, most preferably from 3ppm to 35 ppm. In a second embodiment, the limonene content of the blend (A), as determined by using solid phase microextraction (HS-SPME-GC-MS), is from 0.10ppm to less than 1ppm, preferably from 0.10ppm to less than 0.85ppm, most preferably from 0.10ppm to less than 0.60 ppm.

According to another embodiment of the present invention, the relative amount of units derived from ethylene in blend (a) is more than 20 wt. -%, preferably more than 27 wt. -%, more preferably more than 30 wt. -%, still more preferably more than 35 wt. -%, most preferably more than 40 wt. -%, based on the total weight of blend (a).

It is particularly preferred that the blend (A) contains, based on the total weight of the blend (A)

i) Up to 6.0% by weight, preferably from 0.1 to 6.0% by weight, of polystyrene, and/or

ii) up to 3% by weight, preferably from 0.1 to 3% by weight, of talc, and/or

iii) up to 5.0% by weight, preferably from 0.2 to 5.0% by weight, of a polyamide, and/or

iv) chalk in an amount of up to 3% by weight, preferably 0.1 to 3% by weight.

According to one embodiment of the invention, the polyethylene-polypropylene composition has a melt flow rate MFR determined according to ISO 1133 in the range of 0.1 to 50.0g/10min, preferably in the range of 1.0 to 20.0g/10min, more preferably in the range of 2.0 to 15.0g/10min, still more preferably in the range of 4.0 to 10.0g/10min₂(2.16kg，230℃)。

According to one embodiment of the invention, the polyethylene-polypropylene composition has at least 6.0kJ/m²Preferably from 6.0 to 15.0kJ/m²In the range ofMore preferably from 7.0 to 10.0kJ/m²Still more preferably in the range of 7.0 to 9.0kJ/m²A Charpy notched impact strength (impact strength) of the simple beam determined according to ISO 179/1eA at 23 ℃.

According to a further embodiment of the present invention, the polyethylene-polypropylene composition has a tensile modulus determined according to ISO 527-2 of at least 600MPa, preferably in the range of 600 to 830MPa, more preferably in the range of 620 to 820MPa, still more preferably in the range of 640 to 770 MPa.

The invention further relates to an article comprising the above polyethylene-polypropylene composition.

The present invention also relates to a process for preparing the above polyethylene-polypropylene composition comprising the steps of:

a) blend (A) is provided in an amount of 75.0 to 94.0 wt. -%, based on the total weight of the polyethylene-polypropylene composition,

b) the compatibilizer (B) is provided in an amount of 6.0 to 25.0 weight percent based on the total weight of the polyethylene-polypropylene composition,

c) melting and mixing the blend of blend (A) and compatibilizer (B), optionally in the presence of 0 to 1.0 weight percent of a stabilizer or stabilizer mixture, and

d) optionally granulating.

It is particularly preferred that the process comprises a granulation step d).

The invention further relates to the use of a compatibilizer (B), which is a copolymer of 1-butene and ethylene and has a copolymer of 1-butene and ethylene, for improving the impact-stiffness balance of the blend (A)

i) 930kg/m or less³Preferably 860 to 925kg/m³More preferably in the range of 880 to 920kg/m³Still more preferably from 890 to 915kg/m³A density determined according to ISO 1183, and/or

ii) a melt flow rate MFR determined according to ISO 1133 in the range from 1.0 to 20.0g/10min, preferably in the range from 1.5 to 15.0g/10min, more preferably in the range from 2.0 to 12.0g/10min, still more preferably in the range from 3.0 to 10.0g/10min₂(230℃，2.16kg)，

The blend (A) comprises

a) Polypropylene, and

b) the Polyethylene (PE) is added to the polyethylene,

wherein the weight ratio of polypropylene to polyethylene is 3: 7 to 7: 3, and

wherein blend (a) is recycled material recovered from waste plastic material derived from post-consumer waste and/or industrial waste.

Detailed Description

The present invention will be described in more detail below.

Polyethylene-polypropylene composition

As outlined above, the present invention relates to a polyethylene-polypropylene composition comprising a blend (a) of polypropylene and polyethylene and a compatibilizer (B) which is a copolymer of 1-butene and ethylene.

In particular, the polyethylene-polypropylene composition of the invention is obtainable by blending,

based on the total weight of the polyethylene-polypropylene composition,

a)75.0 to 94.0 wt.%, preferably 76.0 to 92.0 wt.%, more preferably 78.0 to 90.0 wt.%, still more preferably 80.0 to 85.0 wt.%, for example 80.0 to 82.0 wt.% of blend (a), and

b)6.0 to 25.0 wt. -%, preferably 8.0 to 24.0 wt. -%, more preferably 10.0 to 22.0 wt. -%, still more preferably 15.0 to 20.0 wt. -%, e.g. 18.0 to 20.0 wt. -% of a compatibilizer (B).

The polyethylene-polypropylene composition according to the present invention may further comprise an Additive (AD).

It is therefore preferred that the polyethylene-polypropylene composition of the invention is obtainable by blending,

based on the total weight of the polyethylene-polypropylene composition,

a)75.0 to 94.0 wt. -%, preferably 76.0 to 92.0 wt. -%, more preferably 78.0 to 90.0 wt. -%, still more preferably 80.0 to 85.0 wt. -%, for example 80.0 to 82.0 wt. -% of blend (A),

b)6.0 to 25.0 wt. -%, preferably 8.0 to 24.0 wt. -%, more preferably 10.0 to 22.0 wt. -%, still more preferably 15.0 to 20.0 wt. -%, e.g. 18.0 to 20.0 wt. -% of a compatibilizer (B), and

c) optionally 0.001 to 3.0 wt%, more preferably 0.01 to 2.0 wt%, e.g. 0.1 to 1.0 wt% of an Additive (AD).

Additives (AD) will be described in more detail below.

Furthermore, it is preferred that the weight ratio between blend (a) and compatibilizer (B) is between 15: 1 to 3: 1, more preferably in the range of 11: 1 to 3: 1, still more preferably in the range of 9: 1 to 8: 2, for example 8: 2.

the polyethylene-polypropylene composition according to the invention preferably has a melt flow rate MFR determined according to ISO 1133 in the range of from 0.1 to 50.0g/10min, more preferably in the range of from 1.0 to 20.0g/10min, still more preferably in the range of from 2.0 to 15.0g/10min, e.g.in the range of from 4.0 to 10.0g/10min₂(230℃，2.16kg)。

As outlined above, it is understood that the polyethylene-polypropylene composition according to the present invention is characterized by good impact strength without compromising stiffness properties.

It is therefore preferred that the polyethylene-polypropylene composition of the invention has a value of at least 6.0kJ/m²More preferably from 6.0 to 15.0kJ/m²Still more preferably in the range of 7.0 to 10.0kJ/m²In the range of, for example, 7.0 to 9.0kJ/m²Simple beam notched impact strength measured at 23 ℃ according to ISO 179/1 eA.

Furthermore, it is preferred that the polyethylene-polypropylene composition of the invention has a tensile modulus determined according to ISO 527-2 of at least 600MPa, more preferably in the range of 600 to 830MPa, still more preferably in the range of 620 to 820MPa, for example in the range of 640 to 770 MPa.

The blend of polypropylene and polyethylene (a) and the compatibilizer (B) which is a copolymer of 1-butene and ethylene will be described in more detail below.

Blend (A)

The polyethylene-polypropylene composition according to the invention comprises 75.0 to 94.0 wt.% of blend (a). The essence of the present invention is that the blend (a) is obtained from a recycled waste stream. The blend (a) may be recycled post-consumer waste or industrial waste (such as for example waste from the automotive industry), or alternatively a combination of both.

It is particularly preferred that the blend (a) consists of recycled post-consumer waste and/or industrial waste.

For the purposes of this specification and the appended claims, the term "recycled waste" is used to denote material recovered from post-consumer waste and industrial waste, rather than virgin polymer. Post-consumer waste means that the article has at least completed its first use cycle (or life cycle), i.e. has been used for its first purpose; whereas industrial waste refers to manufacturing waste that does not typically reach the consumer.

On the other hand, the term "virgin" refers to materials and/or articles that were newly produced prior to their first use, which have not been recycled.

Many different types of polyethylene or polypropylene may be present in "recycled waste".

In particular, the polypropylene fraction may comprise: isotactic propylene homopolymer, propylene with ethylene and/or C₄-C₈Random copolymers of alpha-olefins, heterophasic copolymers comprising a propylene homopolymer and/or at least one copolymer of C2 or C4-C8 alpha-olefins, and elastomeric fractions comprising copolymers of ethylene with propylene and/or C4-C8 alpha-olefins, optionally containing small amounts of dienes.

Likewise, the polyethylene fraction may comprise ethylene homopolymers or random copolymers of ethylene with propylene and/or C4-C8 alpha-olefins. The polyethylene fraction in the recycled material may comprise recycled high density polyethylene (rhpe), recycled medium density polyethylene (rMDPE), recycled low density polyethylene (rhldpe), recycled linear low density polyethylene (rLLDPE) and mixtures thereof. In a certain embodiment, the recycled material is high density polyethylene having an average density greater than 0.7g/cm³Preferably greater than 0.75g/cm³Most preferably greater than 0.8g/cm³。

The term "recycled material" as used herein means material that is reprocessed from "recycled waste".

A polymer blend is a mixture of two or more polymer components. Typically, the blend may be prepared by mixing two or more polymer components. A suitable mixing procedure known in the art is a post-polymerization blending procedure. Post-polymerization blending can be dry blending of the polymer components (e.g., polymer powder and/or composite polymer pellets), or melt blending by melt mixing the polymer components.

The polypropylene/polyethylene weight ratio in blend (a) was in the range of 7: 3 to 3: 7, in the above range.

Preferably, blend (a) is obtained from recycled waste by plastic recycling processes known in the art. Such recyclates are commercially available from, for example, Corepla (Italian treasures, responsible for the collection, recovery and Recycling of packaging plastic waste), Resource Plastics Corp (Brampton, ON), Kruschitz GmbH, Plastics and Recycling (AT), Vogt Plastics GmbH (DE), Mtm Plastics GmbH (DE), and the like. Non-exhaustive examples of polyethylene rich recycled materials include DIPOLEN S (Mtm Plastics GmbH), food grade rhhdpe (bifapaplc) and a range of polyethylene rich materials such as HD-LM02041 by PLASgran ltd.

In a certain preferred embodiment, the recycled polyethylene rich material is DIPOLEN (mtm Plastics gmbh), such as DIPOLEN S or DIPOLEN H, DIPOLEN PP or DIPOLEN SP, preferably DIPOLEN S.

The relative amount of units derived from ethylene in the combined polypropylene and polyethylene fraction of blend (a) may be more than 20 wt%, preferably more than 27 wt%, more preferably more than 30 wt%, still more preferably more than 35 wt%, most preferably more than 40 wt%, relative to the total weight of blend (a).

Furthermore, the relative amount of propylene-derived units in the combined polypropylene and polyethylene fraction of blend (a) may be greater than 30 wt% but less than 70 wt%, relative to the total weight of blend (a).

According to a first embodiment of the present invention, it is preferred that blend (A) has a limonene content as determined using solid phase microextraction (HS-SPME-GC-MS) of from 1ppm to 100ppm, preferably from 1ppm to 50ppm, more preferably from 2ppm to 50ppm, most preferably from 3ppm to 35 ppm. Limonene is commonly found in recycled polyolefin materials and originates from packaging applications in the field of cosmetics, detergents, shampoos and similar products. Thus, when blend (A) contains materials derived from such domestic waste streams, blend (A) contains limonene. In a second embodiment of the present invention, the blend (A) has a limonene content of from 0.10ppm to less than 1ppm, preferably from 0.10 to less than 0.85ppm, most preferably from 0.10 to less than 0.60ppm, as determined by using solid phase microextraction (HS-SPME-GC-MS) the blend (A) according to the second embodiment can be prepared by subjecting the blend (A) according to the first embodiment to washing and/or aeration. Washing may be achieved by an industrial scrubber (e.g. supplied by Herbold mecksheim GmbH). Depending on the source of the waste stream, multiple wash cycles may be required. Various aeration methods as described in US 5,767,230 are also known in the art. US 5,767,230 is incorporated herein by reference. The process described in US 5,767,230 is preferably combined with a washing stage as described above.

The fatty acid content is another indication of the source of recycling of blend (a).

Due to the recycling source, the blend (A) may also contain

i) An organic filler, and/or

ii) an inorganic filler, and/or

iii) additives

The content thereof is at most 4% by weight relative to the weight of blend (A).

The blend (A) preferably contains

(i) Up to 6.0 wt% polystyrene; and/or

(ii) Up to 3 wt% talc; and/or

(iii) Up to 5.0 wt.% of a polyamide; and/or

(v) Chalk in an amount of up to 3% by weight.

The blend (A) typically contains

(i)0.1 to 6.0 wt% polystyrene; and/or

(ii)0.1 to 3 weight percent talc; and/or

(iii)0.2 to 5.0 wt.% of a polyamide; and/or

(v)0.1 to 3% by weight of chalk.

The blend (a) may further contain polyethylene terephthalate (PET) and polyvinyl chloride (PVC). Preferably, the blend (A) further contains, based on the total weight of the blend (A)

(vi) Up to 5.0 wt.%, more preferably 0.2 to 5.0 wt.% of polyethylene terephthalate (PET), and/or

(vii) Up to 5.0 wt%, more preferably 0.2 to 5.0 wt% of polyvinyl chloride (PVC).

Compatibilizer (B)

The polyethylene-polypropylene composition of the present invention further comprises a compatibilizer (B).

A "compatibilizer" is a substance in polymer chemistry that is added to an immiscible polymer blend to increase its stability.

The compatibilizer (B) according to the invention is a copolymer of 1-butene and ethylene.

Preferably, the copolymer of 1-butene and ethylene has a 1-butene content of at least 70.0 wt. -%, more preferably in the range of 70.0 to 92.0 wt. -%, still more preferably in the range of 75.0 to 90.0 wt. -%, for example in the range of 80.0 to 88.0 wt. -%, based on the total weight of the copolymer of 1-butene and ethylene.

Further preferred are melt flow rates MFR, determined according to ISO 1133, of copolymers of 1-butene and ethylene₂(230 ℃, 2.16kg) is in the range of 1.0 to 20.0g/10min, more preferably in the range of 1.5 to 15.0g/10min, still more preferably in the range of 2.0 to 12.0g/10min, for example in the range of 3.0 to 10.0g/10 min.

Preferably the copolymer of 1-butene and ethylene has a melting temperature Tm, determined according to ISO 11357, below 130 ℃, more preferably in the range of from 90 to below 130 ℃, still more preferably in the range of from 100 to 125 ℃, for example in the range of from 105 to 115 ℃.

The density of the compatibilizer (B) is equal to or lower than 930kg/m determined according to ISO 1183³More preferably 860 to 925kg/m³Still more preferably in the range of 880 to 920kg/m³In the range of, for example, 890 to 915kg/m³Within the range of (1).

Preferably the compatibilizer (B) is a copolymer of butene-1 and ethylene known in the art, for example a copolymer of butene-1 and ethylene of the TAFMER series commercially available from Mitsui.

Additive (AD)

As indicated above, the polyethylene-polypropylene composition according to the invention may contain additives.

In particular, the polyethylene-polypropylene composition of the invention may contain up to 1.0% by weight of a stabilizer or stabilizer mixture. The content of the stabilizer is preferably 0.1 to 1.0% by weight, based on the total weight of the polyethylene-polypropylene composition.

Stabilizers are well known in the art and may be, for example, antioxidants, antacids, anti-blocking agents, anti-uv agents, nucleating agents or antistatic agents.

Examples of antioxidants commonly used in the art are sterically hindered phenols (e.g. CAS No. 6683-19-8, also available from BASF as Irganox1010FF^TMOr Irganox 225 by BASF^TMSold), phosphorus based antioxidants (e.g., CAS number 31570-04-4, also by Clariant as Hostanox PAR 24(FF)^TMSold or otherwise available from BASF as Irgafos 168(FF)^TMSold), sulfur based antioxidants (e.g., CAS number 693-36-7, Irganox PS-802FL available from BASF^TMSold), nitrogen-based antioxidants (such as 4,4 '-bis (1, 1' -dimethyl-benzyl) -diphenylamine), or antioxidant blends.

Antacids are also well known in the art. Examples are calcium stearate, sodium stearate, zinc stearate, oxides of magnesium and zinc, synthetic hydrotalcite (e.g. SHT, CAS No. 11097-59-9), lactate (or lactate) and lactate (lactylate), and calcium stearate (CAS No. 1592-23-0) and zinc stearate (CAS No. 557-05-1).

A common anti-caking agent is a natural silica, such as diatomaceous earth (e.g., CAS No. 60676-86-0 (SuperfFloss)^TM) CAS number 60676-86-0(SuperFloss E)^TM) Or CAS number 60676-86-0(Celite 499)^TM) Synthetic silica (e.g., CAS No. 7631-86-9, CAS No. 112926-00-8, CAS No. 7631-86-9, or CAS No. 7631-86-9), silicates (e.g., aluminum silicate (kaolin) CAS No. 1318-74-7, sodium aluminum silicate CAS No. 1344-00-9, calcined kaolin CAS No. 92704-41-1, aluminum silicate CAS No. 1327-36-2, or calcium silicate CAS No. 1344-95-2), synthetic zeolites (e.g., hydrated calcium aluminum silicate CAS No. 1344-01-0, or calcium aluminum silicate hydrate CAS No. 1344-01-0).

Examples of the ultraviolet screening agent include bis- (2,2,6, 6-tetramethyl-4-piperidyl) -sebacate (CAS No. 52829-07-9, Tinuvin 770); 2-hydroxy-4-n-octyloxy-benzophenone (CAS No. 1843-05-6, Chimassorb 81).

Nucleating agents are, for example, sodium benzoate (CAS No. 532-32-1); 1,3:2, 4-bis (3, 4-dimethylbenzylidene) sorbitol (CAS 135861-56-2, Millad 3988).

Suitable antistatics are, for example, glycerol esters (CAS No. 97593-29-8) or ethoxylated amines (CAS No. 71786-60-2 or 61791-31-9) or ethoxylated amides (CAS No. 204-393-1).

These stabilizers are generally added in amounts of 100 to 2000ppm for each individual component of the polymer.

The polyethylene-polypropylene composition preferably contains between 1.0 and 2.0 wt% of PO ash.

Method

The process according to the present invention for providing a polyethylene-polypropylene composition comprises the steps of:

a) blend (A) is provided in an amount of 75.0 to 94.0 wt. -%, based on the total weight of the polyethylene-polypropylene composition,

b) the compatibilizer (B) is provided in an amount of 6.0 to 25.0 weight percent based on the total weight of the polyethylene-polypropylene composition,

c) melting and mixing the blend of blend (A) and compatibilizer (B), optionally in the presence of 0 to 1.0 weight percent of a stabilizer or stabilizer mixture, and

d) optionally granulating.

It is particularly preferred that the process comprises a granulation step d).

Thus, it is preferred that the process for providing a polyethylene-polypropylene composition comprises the following steps

a) Blend (A) is provided in an amount of 75.0 to 94.0 wt. -%, based on the total weight of the polyethylene-polypropylene composition,

b) the compatibilizer (B) is provided in an amount of 6.0 to 25.0 weight percent based on the total weight of the polyethylene-polypropylene composition,

c) melting and mixing the blend of blend (A) and compatibilizer (B), optionally in the presence of 0 to 1.0 weight percent of a stabilizer or stabilizer mixture, and

d) and (6) granulating.

All preferred aspects, definitions and embodiments as described above shall also apply to the method.

Use of

The invention further relates to the use of a compatibilizer (B), which is a copolymer of 1-butene and ethylene and has a copolymer of 1-butene and ethylene, for improving the impact-stiffness balance of the blend (A)

i) 930kg/m or less³According to ISO 1183, and/or

ii) a melt flow rate MFR determined according to ISO 1133 in the range of 1.0 to 20.0g/10min₂(230℃，2.16kg)

The blend (A) comprises

a) Polypropylene, and

b) the Polyethylene (PE) is added to the polyethylene,

wherein the weight ratio of polypropylene to polyethylene is 3: 7 to 7: 3, and

wherein blend (a) is recycled material recovered from waste plastic material derived from post-consumer waste and/or industrial waste.

All preferred aspects, definitions and embodiments as described above shall also apply for this use.

Experimental part

The following examples are included to demonstrate certain aspects and embodiments of the invention as set forth in the claims. However, those skilled in the art will appreciate that the following description is illustrative only and should not be construed as limiting the invention in any way.

Test method

Tensile Modulus (TM) was measured according to ISO 527-2 (crosshead speed 1mm/min for modulus determination, then switched to 50mm/min until fracture at 23 ℃) using injection moulded specimens (dog bone shape, 4mm thickness) as described in EN ISO 5247-2. The measurement was carried out after a conditioning time of 96 hours for the sample.

Impact strength was determined according to ISO 179-1eA at +23 ℃ as simple beam Notched Impact Strength (NIS) on 80X 10X 4mm injection-molded specimens prepared according to EN ISO 1873-2. The test was carried out after 96 hours according to this standard sample.

Comonomer content of poly (co-butene-co-ethylene)

Quantitative Nuclear Magnetic Resonance (NMR) spectroscopy was used to quantify the comonomer content of the polymer.

Use pair¹H and¹³c Bruker Advance III 400NMR spectrometers operating at 400.15 and 100.62MHz respectively record quantitative measurements in solution¹³C{¹H } NMR spectrum. All pneumatic units were purged with nitrogen at 125 deg.C¹³C-optimized 10mm extended temperature probe records all spectra. About 200mg of material was mixed with chromium (III) acetylacetonate (Cr (acac)₃) Dissolved together in 3ml of 1, 2-tetrachloroethane-d₂(TCE-d₂) In (5), a 60mM solution of relaxant in solvent { singh09}, was obtained. About 3mg of BHT (2, 6-di-tert-butyl-4-methylphenol, CAS 128-37-0) was added as a stabilizer. To ensure homogeneity of the solution, after preparation of the initial sample in the heating block, the NMR tube was further heated in a rotary oven for at least 1 hour. After insertion into the magnet, the tube was rotated at 10 Hz. This setting is chosen primarily for high resolution and is quantitatively needed due to the quantification of accurate ethylene content. Using NOE-free standard single pulse impulseExcitation, optimized tip angle (tip angle), 1s cycle delay and a dual stage WALTZ16 decoupling scheme { zhou07, busico07 }. A total of 6144(6k) transient signals were acquired per spectrum.

For quantitative determination¹³C{¹H NMR spectra were processed, integrated and relevant quantitative properties were determined from the integrations. Using the chemical shifts of the solvent, all chemical shifts are indirectly referenced to the central methylene group of the ethylene block (EEE) at 30.00 ppm. This approach allows comparable referencing even if the structural unit is not present.

A characteristic signal corresponding to isolated incorporation of ethylene was observed, and the integration of the signal at 24.4ppm assigned to the S β β site was used to quantify the ethylene content, taking into account the number of reporter nuclei per comonomer.

f moles of E ═ IS β

The butene content was quantified using the integration of the S.alpha.signal between 41.3ppm and 39.0ppm { brandolini01} taking into account the number of reported nuclei per comonomer.

One butenyl group is missing for each isolated vinyl group. Compensation is made by adding one S β β to the mole fraction of butenes (fmol B).

f moles of B ═ IS α + IS β

The mole percent of ethylene (mole% E) and the mole percent of butene (mole% B) were calculated from mole fractions, respectively:

mole% E ═ fmol E100/(fmol E + fmol B)

Mole% B ═ fmol B100/(fmol E + fmol B)

The weight percentage of ethylene (E [ wt.%) and the weight percentage of butene (B [ wt.%) are calculated from mole%:

e [ wt% ]100mol% E28.05/[ (mol% E28.05) + (mol% B56.11) ]

B [ wt% ]100mol% B56.11/[ (mol% E28.05) + (mol% B56.11) ]

Reference to the literature

brandolini01

A.J.Brandolini,D.D.Hills,“NMR spectra of polymers and polymer additives”,Marcel Deker Inc.,2000

zhou07

Zhou,Z.,Kuemmerle,R.,Qiu,X.,Redwine,D.,Cong,R.,Taha,A.,Baugh,D.Winniford,B.,J.Mag.Reson.187(2007)225

busico07

Busico,V.,Carbonniere,P.,Cipullo,R.,Pellecchia,R.,Severn,J.,Talarico,G.,Macromol.Rapid Commun.2007,28,1128

singh09

Singh,G.,Kothari,A.,Gupta,V.,Polymer Testing 28 5(2009),475

Ratio of units derived from C2 and C3: the ethylene content of the blend (A) was determined by quantitative Fourier transform Infrared Spectroscopy (FTIR) and compared with the quantitative¹³The results obtained by C NMR spectroscopy were phase-calibrated.

The film was pressed at 190 ℃ to a thickness between 300 and 500 μm and the spectrum was recorded in transmission mode. The associated instrument settings include 5000 to 400 wave numbers (cm)^-1) Spectral window of 2.0cm^-1And 8 scans.

Use pair¹H and¹³c Bruker Advance III 400NMR spectrometers operating at 400.15 and 100.62MHz respectively record quantitative measurements in solution¹³C{¹H } NMR spectrum. All spectral uses¹³C optimized 10mm extended temperature probe was recorded at 125 ℃, using nitrogen for all pneumatic devices. About 200mg of material was mixed with chromium (III) acetylacetonate (Cr (acac)₃) Dissolved together in 3ml of 1, 2-tetrachloroethane-d 2(TCE-d2) to give a 65mM solution of relaxant in solvent (Singh, G., Kothari, A., Gupta, V., Polymer Testing 285 (2009), 475). To ensure homogeneity of the solution, after preparation of the initial sample in the heating block, the NMR tube was further heated in a rotary oven for at least 1 hour. After insertion into the magnet, the tube was rotated at 10 Hz. This setting is chosen primarily for high resolution and is quantitatively needed due to the quantification of accurate ethylene content. Using NOE-freeStandard single pulse excitation, using optimized tip angles (tip angle), 1s cycle delay and a dual-stage WALTZ16 decoupling scheme (Zhou, z., Kuemmerle, r., Qiu, x., Redwine, d., Cong, r., Taha, a., Baugh, d.winnifond, b., j.mag.reson.187(2007) 225; Busico, v., Carbonniere, p., Cipullo, r., pellec, r., Severn, j., talaro, g., macromol.rapid Commun.2007,28,1128). A total of 6144(6k) transient signals were acquired per spectrum. For quantitative determination¹³C{¹H NMR spectra were processed, integrated and the relevant quantitative properties were determined from the integration. Using the chemical shifts of the solvent, all chemical shifts are indirectly referenced to the central methylene group of the ethylene block (EEE) at 30.00 ppm. This approach allows comparable referencing even if the structural unit is not present. A characteristic signal corresponding to the incorporation of ethylene was observed (Cheng, h.n., Macromolecules 17(1984),1950), and the ethylene fraction was calculated as the fraction of ethylene in the blend relative to all monomers in the polymer: by applying the method of Wang et al (Wang, W-j., Zhu, s., Macromolecules 33(2000),1157) to (E/(P + E))¹³C{¹H spectrum the ethylene fraction is quantified by integrating multiple signals over the entire spectral region. This method was chosen for its robustness and ability to account for the presence of regional defects when needed. The integration region is adjusted slightly to improve applicability over the entire range of comonomer contents encountered. Mole percent ethylene was calculated from mole fraction: e [ mol%]100 × fE. The weight percentage of comonomer incorporation was calculated from the mole fraction: e [ wt.%]＝100*(fE*28.06)/((fE*28.06)+((1-fE)*42.08))

iPP, PE, PS, PA and PE content:

calibration standards were prepared by blending iPP and HDPE to establish a calibration curve. The film thickness of the calibration standard was 300. mu.m. To quantify the iPP, PS and PA6 content in the samples, quantitative infrared spectra were recorded in the solid state using a Bruker Vertex 70 FTIR spectrometer. The spectra were recorded on 25X 25mm square films 50 to 100 μm thick, prepared by compression moulding at 190 ℃ and 4 to 6 mPa. Using standard transmission FTIR spectroscopy, the spectral range used was 4000 to 400cm^-1Aperture of 6mm, spectral resolutionIs 2cm^-116 background scans, 16 spectral scans, a zero fill factor of 32 for the interferogram, Norton Beer strong apodization.

Measuring iPP at 1167cm^-1The absorption of the band and the iPP content was quantified according to a calibration curve (absorption/thickness (cm) versus iPP content (% by weight)).

Measurement 1601cm^-1(PS) and 3300cm^-1(PA6) and quantification of PS and PA6 contents according to calibration curves (absorption/thickness (cm) versus PS and PA contents (% by weight)). The PE content was obtained by subtracting iPP, PS and PA6 from 100. The analysis was performed as a double assay.

Talc and chalk content: measured by thermogravimetric analysis (TGA); experiments were performed using a Perkin Elmer TGA 8000. Approximately 10 to 20mg of material was placed in a platinum pan. The temperature was equilibrated at 50 ℃ for 10 minutes and then raised to 950 ℃ under nitrogen at a ramp rate of 20 ℃/min. Will lose Weight (WCO) between about 550 ℃ and 700 DEG C₂) Ascribed to CaCO₃CO liberated₂The chalk content was therefore evaluated as:

chalk content 100/44 × WCO₂

The temperature was then reduced to 300 ℃ at a cooling rate of 20 ℃/min. The gas was then switched to oxygen and the temperature was again raised to 900 ℃. The weight loss in this step is attributed to carbon black (Wcb). With known carbon black and chalk content, the ash content excluding chalk and carbon black is calculated as:

ash content (ash) -56/44 x WCO₂–Wcb

Wherein the ash is the weight% measured at 900 ℃ in the first step carried out under nitrogen. The ash content was estimated to be the same as the talc content of the recyclates studied.

MFR: as indicated, the melt flow rate was 2.16kg load (MFR) at 230 ℃ or 190 ℃₂) Measured as follows. The melt flow rate is the amount of polymer extruded in grams at a temperature of 230 ℃ (or 190 ℃) under a load of 2.16kg over a period of 10 minutes according to the test equipment of ISO 1133 standard.

Melting temperature was determined by DSC according to ISO 11357.

The glass transition temperature Tg is determined by dynamic mechanical analysis according to ISO 6721-7. Compression moulding of a sample (40X 10X 1 mm) at a heating rate of 2 ℃/min and a frequency of 1Hz between-100 ℃ and +150 DEG C³) The measurement was performed in the torsional mode.

The density is determined according to ISO 1183.

Limonene content in DIPELEN

Measuring

The quantification of limonene was performed by standard addition using solid phase microextraction (HS-SPME-GC-MS).

50mg of the ground sample was weighed into a 20mL headspace vial, and after the addition of different concentrations of limonene and a glass-coated magnetic stir bar, the vial was capped with a silicone/PTFE lined magnetic cap. A known concentration of diluted limonene standard was added to the sample using a microcapillary tube (10 pL). The addition of 0, 2, 20 and 100ng amounts corresponded to 0mg/kg, 0.1mg/kg, 1mg/kg and 5mg/kg of limonene, furthermore standard amounts of 6.6mg/kg, 11mg/kg and 16.5mg/kg of limonene were used in combination with some of the samples tested in this application. Ions 93 collected in SIM mode are used for quantification. The volatile components were enriched by headspace solid phase microextraction using a 2cm stationary flex 50/30pm DVB/Carboxen/PDMS fiber, enriched for 20 minutes at 60 ℃. The desorption was carried out directly at the heated inlet of the GCMS system at 270 ℃.

GCMS parameters:

column: 30m HP 5MS 0.25X 0.25

Sample injector: no split, with 0.75mm SPME liner, 270 deg.C

Temperature program: -10 ℃ (1min)

Carrier gas: helium 5.0, 31cm/s linear velocity, constant flow

MS: a single quadrupole rod, a direct interface, the interface temperature of 280 DEG C

Collecting: SIM scanning mode

Scanning parameters are as follows: 20 to 300amu

SIM parameters: m/Z93, 100ms residence time

Table 1: limonene content in DIPOLENE (blend (A))

Sample (I)	Limonene [ mg/kg]HS-SPME-GC-MS[1]
		Dipolen S	31.5±2.6

^[1]And (4) headspace solid phase microextraction. The material is available from mtm plastics GmbH, according to 2018 specification.

Total free fatty acid content

Quantification of fatty acids was performed by standard addition using headspace solid phase microextraction (HS-SPME-GC-MS).

50mg of the ground sample was weighed into a 20mL headspace vial, and after the addition of different concentrations of limonene and a glass-coated magnetic stir bar, the vial was capped with a silicone/PTFE lined magnetic cap. Diluted free fatty acid mixture (acetic, propionic, butyric, valeric, caproic and caprylic) standards of known concentration were added to the samples at three different levels using 10 μ L microcapillaries. The addition of 0, 50, 100 and 500ng corresponded to 0mg/kg, 1mg/kg, 2mg/kg and 10mg/kg of each individual acid. All acids except propionic acid (here ion 74) were quantified using ion 60 collected in SIM mode.

GCMS parameters:

column: 20m ZB Wax plus 0.25 × 0.25

Sample injector: split ratio (split)5:1, split gasket with glass liner, 250 deg.C

Temperature program: 40 deg.C (1min) @6 deg.C/min to 120 deg.C and @15 deg.C to 245 deg.C (5min)

Carrier gas: helium 5.0, 40cm/s linear velocity, constant flow

MS: a single quadrupole rod is directly connected with the interface, and the temperature of the interface is 220 DEG C

Collecting: SIM scanning mode

Scanning parameters are as follows: 46 to 250amu 6.6 scans/sec

SIM parameters: m/z 60.74, 6.6 scans/sec

Table 2: total fatty acid content in Dipolen (blend (A))

Sample (I)	Total fatty acid concentration [ mg/kg][1]
		Dipolen S	70.6

^[1]The concentrations of acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, pelargonic acid and capric acid in each sample were added together to give the total fatty acid concentration value.

Experiment of

Many blends were produced using DIPOLEN S as blend (a), a polyethylene-polypropylene blend from Mtm Plastics GmbH, a material meeting 2018 month 8 specification.

5 to 10% by weight of a compatibilizer (B) derived from the reactor is added to each blend. The following commercially available copolymers were used as compatibilizers (B):

table 3: properties of the compatibilizer (B)

Compatibilizer		B1	B2
						Tafmer BL3110	Tafmer BL3450
MFR	[g/10min]	3.0	9.0
				Tm	[℃]	110	110
Density of	[kg/m3]	910	900
				C2	[ weight% ]]	12.0	17.0
C4	[ weight% ]]	88.0	83.0

The compositions were prepared by melt blending on a co-rotating twin screw extruder with 0.3 wt% of Irganox B225F (AO) as a stabilizer. The polymer melt mixture is discharged and pelletized. To test mechanical properties, test specimens were produced and tested according to ISO179 using a 1eA notched specimen to measure simple beam Notched Impact Strength (NIS) and according to ISO 527-1/2 using a 1A specimen to measure tensile properties at room temperature. The results are summarized in table 4.

Table 4: compositions and Properties of examples and comparative examples of the present invention

		CE1	CE2	IE1	IE2	CE3	IE3	IE4
									A	[ weight% ]]	99.7	94.7	89.3	79.3	94.7	89.3	79.3
B1	[ weight% ]]	-	5	10	20
									B2	[ weight% ]]	-				5	10	20
AO	[ weight% ]]	0.3	0.3	0.3	0.3	0.3	0.3	0.3
									NIS	[kJ/m2]	5.7	6.2	6.6	8.4	5.8	6.7	7.6
TM	[MPa]	850	796	762	698	793	739	690

As can be seen from table 4, the compositions according to the examples of the present invention have higher impact strength than the reference without compatibilizer while the tensile modulus is maintained at a high level.