Polypropylene composition with improved coatability

文档序号：816754 发布日期：2021-03-26 浏览：4次中文

阅读说明：本技术 可涂覆性改善的聚丙烯系组合物 (Polypropylene composition with improved coatability ) 是由王静波 K·贝恩赖特纳 D·米列娃 G·格雷斯滕贝格尔 M·加莱特纳于 2019-08-23 设计创作，主要内容包括：本发明涉及聚丙烯系组合物、包含所述聚丙烯系组合物的制品以及共聚物(B)用于减少包含所述聚丙烯系组合物的制品的涂料附着失效的用途,所述聚丙烯系组合物包含：(A)40.0至85.0wt％的多相丙烯共聚物,以多相丙烯共聚物的总重量为基准计,所述多相丙烯共聚物的二甲苯冷可溶物(XCS)级分的含量为15wt％至35wt％；(B)5.0至15.0wt％的丙烯与共聚单体单元的无规共聚物,所述共聚单体单元选自乙烯和C-4-C-(12)α-烯烃,所述无规共聚物已在单中心催化剂体系的存在下聚合,所述无规共聚物由差示扫描量热法(DSC)测得的熔融温度Tm低于140℃；(C)5.0至25.0wt％的乙烯共聚物,所述乙烯共聚物具有C-4-C-(12)α-烯烃共聚单体单元,所述乙烯共聚物的密度为850kg/m～3至900kg/m～3；和(D)5.0至25.0wt％的无机填料；其中,组分(A)、(B)、(C)和(D)的量均以聚丙烯系组合物的总重量为基准计；所述聚丙烯系组合物根据ISO 1133在230℃和2.16kg载荷下测得的熔体流动速率(MFR-2)为2.0g/10min至20.0g/10min。(The present invention relates to a polypropylene based composition comprising: (A) from 40.0 to 85.0 wt% of a heterophasic propylene copolymer having a content of Xylene Cold Soluble (XCS) fraction of from 15 wt% to 35 wt%, based on the total weight of the heterophasic propylene copolymer; (B)5.0 to 15.0 wt% of a random copolymer of propylene with comonomer units selected from ethylene and C 4 ‑C 12 An alpha-olefin, the random copolymer having been polymerized in the presence of a single-site catalyst system, the random copolymer having a melting temperature, Tm, as measured by Differential Scanning Calorimetry (DSC), of less than 140 ℃; (C)5.0 to 25.0 wt%The ethylene copolymer having C 4 ‑C 12 Alpha-olefin comonomer units, the density of the ethylene copolymer being 850kg/m 3 To 900kg/m 3 (ii) a And (D)5.0 to 25.0 wt% of an inorganic filler; wherein the amounts of components (A), (B), (C) and (D) are based on the total weight of the polypropylene-based composition; the polypropylene-based composition has a Melt Flow Rate (MFR) measured according to ISO1133 at 230 ℃ and under a load of 2.16kg 2 ) Is 2.0g/10min to 20.0g/10 min.)

1. A polypropylene-based composition, wherein the polypropylene-based composition comprises:

(A) from 40.0 wt% to 85.0 wt% of a heterophasic propylene copolymer having a content of Xylene Cold Soluble (XCS) fraction of from 15 wt% to 35 wt%, based on the total weight of the heterophasic propylene copolymer;

(B)5.0 to 15.0 wt% of a random copolymer of propylene with comonomer units selected from ethylene and C₄-C₁₂An alpha-olefin, the random copolymer having been polymerized in the presence of a single-site catalyst system, and the random copolymer having a melting temperature, Tm, as measured by Differential Scanning Calorimetry (DSC), of less than 140 ℃;

(C)5.0 to 25.0 wt% of an ethylene copolymer having C₄-C₁₂Alpha-olefin comonomer units, the density of the ethylene copolymer being 850kg/m³To 900kg/m³(ii) a And

(D)5.0 to 25.0 wt% of an inorganic filler;

wherein, the contents of the components (A), (B), (C) and (D) are all calculated by the total weight of the polypropylene composition;

the polypropylene-based composition has a Melt Flow Rate (MFR) measured according to ISO1133 at 230 ℃ under a load of 2.16kg₂) Is 2.0g/10min to 20.0g/10 min.

2. The polypropylene-based composition according to claim 1, wherein the comonomer content of the Xylene Cold Soluble (XCS) phase of the heterophasic propylene copolymer (a) is from 25 to 55 wt. -%, based on the total weight of the Xylene Cold Soluble (XCS) phase of the heterophasic propylene copolymer (a).

3. The polypropylene-based composition according to claim 1 or 2, wherein the heterophasic propylene copolymer (a) has a matrix phase being a random copolymer of propylene with comonomer units selected from ethylene and C, and an elastomeric phase dispersed in the matrix phase₄-C₁₂An alpha-olefin, preferably ethylene; based on a heterophasic propylene copolymer (A)The comonomer units are present in an amount of 0.01 to 1.5 wt%, based on the total weight of the phases.

4. The polypropylene-based composition according to any one of the preceding claims, wherein the random copolymer of propylene with comonomer units (B) having a melt flow rate MFR (190 ℃, 2.16kg) from 0.8g/10min to 50.0g/10min, the comonomer units being selected from ethylene and C₄-C₁₂An alpha-olefin.

5. Polypropylene composition according to any of the preceding claims, wherein propylene is reacted with a compound selected from ethylene and C₄-C₁₂The random copolymer of comonomer units of alpha-olefin (B) is a copolymer of propylene with a comonomer selected from ethylene and C₄-C₁₂The amount of Xylene Cold Soluble (XCS) fraction of the random copolymer of comonomer units of alpha-olefin (B) is below 7.5 wt%.

6. The polypropylene-based composition according to any one of the preceding claims, wherein the random copolymer of propylene with 1-hexene comonomer units (B) has a crystallization temperature Tc of at least 85 ℃.

7. Polypropylene composition according to any of the preceding claims, wherein propylene is reacted with a compound selected from ethylene and C₄-C₁₂Random copolymers of comonomer units of alpha-olefins (B) of propylene with a comonomer unit selected from ethylene and C, based on the total weight of the monomer units in the copolymer₄-C₁₂The amount of comonomer units of the random copolymer of comonomer units of alpha-olefin (B) is from 1.0 to 4.5 wt%.

8. The polypropylene-based composition according to any one of the preceding claims, wherein the ethylene copolymer (C) with alpha-olefin comonomer units is an ethylene-based plastomer with comonomer units selected from C₄-C₁₂Alpha-olefins, preferably C₆-C₈Alpha-olefins, most preferably1-octene is preferred.

9. Polypropylene-based composition according to any one of the preceding claims, wherein the inorganic filler (D) is selected from talc, wollastonite, kaolin and mica, preferably talc.

10. The polypropylene-based composition according to any one of the preceding claims, wherein the polypropylene-based composition has a charpy notched impact strength at 23 ℃ of at least 50kJ/m²And/or a Charpy notched impact strength of at least 5.0kJ/m at-20 DEG C²。

11. Polypropylene based composition according to any one of the preceding claims, wherein the flexural modulus of the polypropylene based composition is at least 1300 MPa.

12. Coated article, wherein the article comprises the polypropylene-based composition according to any one of the preceding claims.

13. The article of claim 12 wherein the article has a shrinkage of less than 1.0%.

14. The article of claim 12 or 13, wherein the article has an average peel area of 10.0mm²To 50.0mm²Failure of the paint adhesion.

15. Use of a random copolymer of propylene and comonomer units selected from ethylene and C in a polypropylene based composition for reducing coating adhesion failure of an article comprising said polypropylene based composition₄-C₁₂An alpha-olefin, the polypropylene-based composition comprising:

(B)1.0 to 15.0 wt% of a random copolymer of propylene with comonomer units selected from ethylene and C₄-C₁₂An alpha-olefin, the random copolymer having been polymerized in the presence of a single-site catalyst system, and the random copolymer having a melting temperature, Tm, as measured by Differential Scanning Calorimetry (DSC), of less than 140 ℃;

(C)5.0 to 25.0 wt% of an ethylene copolymer having C₄-C₁₂Alpha-olefin comonomer units, the density of the ethylene copolymer being 850kg/m³To 900kg/m³(ii) a And

(D)5.0 to 25.0 wt% of an inorganic filler;

wherein, the contents of the components (A), (B), (C) and (D) are all calculated by the total weight of the polypropylene composition;

the polypropylene-based composition has a Melt Flow Rate (MFR) measured according to ISO1133 at 230 ℃ under a load of 2.16kg₂) Is 2.0g/10min to 20.0g/10 min.

Technical Field

The present invention relates to a polypropylene based composition comprising a random copolymer of propylene and comonomer units selected from ethylene and C, an article comprising said propylene based composition and the use of said copolymer in said composition for reducing the paint adhesion failure of said article₄-C₁₂An alpha-olefin.

Background

In automotive applications, polyolefins (e.g., polypropylene) are preferred because they can be tailored to the specific purpose desired. For example, heterophasic polypropylenes are widely used in the automotive industry (e.g. bumper applications) due to their good stiffness and reasonable impact strength. However, the surface of the molded articles obtained from the heterophasic polypropylene composition is rather smooth and of low polarity, leading to poor prerequisites for the interaction of said surface with the coating material. For demanding applications, such as automotive parts, it is therefore often necessary to carry out a pretreatment and to apply an adhesion promoter (so-called primer) to ensure proper paint adhesion. For environmental and economic reasons, it is desirable to minimize the use of primers, preferably avoiding the use of primers altogether.

Several different attempts have been made to improve the paint adhesion of primerless (primerless) polypropylene compositions.

WO 2014/191211 discloses a primerless polypropylene composition comprising a defined combination of heterophasic polypropylene copolymer, propylene homopolymer and mineral filler.

WO 2015/082403 discloses a primerless polypropylene composition comprising a defined combination of a propylene copolymer, a heterophasic polypropylene copolymer having a xylene cold soluble fraction with an intrinsic viscosity iV of more than 2.1dl/g and a mineral filler.

WO 2015/082402 discloses a primerless polypropylene composition comprising a defined combination of a propylene copolymer and a mineral filler.

EP 2495264 a1 discloses a primerless polypropylene composition comprising a heterophasic propylene copolymer having a certain amount of regio defects (regio defect) and a mineral filler.

Although these polypropylene compositions exhibit improved paint adhesion, measures to improve the properties often have a negative effect on the mechanical properties, in particular the impact strength necessary for automotive applications.

Accordingly, there remains a need in the art for primerless polypropylene-based compositions having improved properties, including good paint adhesion, good mechanical properties (e.g., good impact strength and flexural modulus), and low shrinkage of articles made from the polypropylene-based compositions.

In the present invention, a polypropylene based composition has been found comprising a defined heterophasic propylene copolymer, propylene and comonomer units selected from ethylene and C₄-C₁₂Alpha-olefins) which have been polymerized in the presence of a single-site catalyst system, ethylene copolymers and inorganic fillers, said polypropylene-based composition showing an improved balance of the following properties: good paint adhesion (low average paint failure rate), good mechanical properties (high charpy notched impact strength and high flexural modulus at 23 ℃ and-20 ℃), and coatings made therefromLow shrinkage of articles made from the polypropylene-based compositions.

Disclosure of Invention

The present invention relates to a polypropylene-based composition comprising:

(A) from 40.0 to 85.0 wt% of a heterophasic propylene copolymer having a content of Xylene Cold Soluble (XCS) fraction of from 15 wt% to 35 wt%, based on the total weight of the heterophasic propylene copolymer;

(B)5.0 to 15.0 wt% of a random copolymer of propylene with comonomer units selected from ethylene and C₄-C₁₂An alpha-olefin, the random copolymer having been polymerized in the presence of a single site catalyst system, the random copolymer having a melting temperature as determined by Differential Scanning Calorimetry (DSC) of less than 140 ℃;

(C)5.0 to 25.0 wt% of an ethylene copolymer having C₄-C₁₂Alpha-olefin comonomer units, the density of the ethylene copolymer being 850kg/m³To 900kg/m³(ii) a And

(D)5.0 to 25.0 wt% of an inorganic filler;

wherein, the contents of the components (A), (B), (C) and (D) are all based on the total weight of the polypropylene composition;

the polypropylene-based composition has a Melt Flow Rate (MFR) measured according to ISO1133 at 230 ℃ under a load of 2.16kg₂) Is 2.0g/10min to 20.0g/10 min.

It has been unexpectedly found that such polypropylene-based compositions exhibit an improved balance of the following properties: good paint adhesion (low average paint failure rate), good mechanical properties (high charpy notched impact strength and high flexural modulus at 23 ℃ and-20 ℃) and low shrinkage of articles made from the polypropylene-based composition.

Further, the present invention relates to an article comprising a polypropylene based composition as described above or below.

The invention further relates to coated articles, for example automotive structural elements, such as bumpers or body panels, comprising said composition.

Still further, the present invention relates to propylene and C₄-C₁₂Use of a random copolymer of α -olefin comonomer units in a polypropylene-based composition for reducing coating adhesion failure of an article comprising said polypropylene-based composition, said polypropylene-based composition comprising:

(B)5.0 to 15.0 wt% of a random copolymer of propylene with comonomer units selected from ethylene and C₄-C₁₂An alpha-olefin, the random copolymer having been polymerized in the presence of a single site catalyst system, the random copolymer having a melting temperature as determined by Differential Scanning Calorimetry (DSC) of less than 140 ℃;

(C)5.0 to 25.0 wt% of an ethylene copolymer having C₄-C₁₂Alpha-olefin comonomer units, the density of the ethylene copolymer being 850kg/m³To 900kg/m³(ii) a And

(D)5.0 to 25.0 wt% of an inorganic filler,

wherein, the contents of the components (A), (B), (C) and (D) are all based on the total weight of the polypropylene composition; the polypropylene-based composition has a Melt Flow Rate (MFR) measured according to ISO1133 at 230 ℃ under a load of 2.16kg₂) Is 2.0g/10min to 20.0g/10 min.

Definition of

Heterophasic propylene copolymers are propylene based copolymers having a crystalline matrix phase, which may be a propylene homopolymer or a random copolymer of propylene with at least one alpha-olefin comonomer, and an elastomeric phase dispersed therein. The elastomeric phase may be a propylene copolymer having a significant amount of comonomer distributed not randomly in the polymer chain but in a comonomer rich block structure and a propylene rich block structure.

Heterophasic propylene copolymers are generally different from monophasic propylene copolymers, because heterophasic propylene copolymers show two different glass transition temperatures Tg due to the matrix phase and the elastomeric phase.

Propylene homopolymers are polymers consisting essentially of propylene monomer units. Due to impurities, in particular in industrial polymerization processes, the propylene homopolymer may comprise less than 0.1 wt% comonomer units, preferably at most 0.05 wt% comonomer units, most preferably at most 0.01 wt% comonomer units.

The propylene random copolymer is a copolymer of propylene monomer units and comonomer units, preferably selected from ethylene and C₄-C₁₂Alpha-olefins in which the comonomer units are randomly distributed over the polymer chain. The propylene random copolymer may comprise comonomer units derived from more than one comonomer unit having different carbon atom weights.

Plastomers are polymers that combine elastomeric and plastic properties (e.g., rubbery properties and processability of the plastic).

Ethylene-based plastomers are plastomers having a majority by mole of ethylene monomer units.

By polypropylene based composition is meant that the majority by weight of the polypropylene based composition is derived from a propylene homopolymer or a propylene copolymer.

Hereinafter, amounts are expressed in weight percent (wt%), unless otherwise indicated.

Detailed Description

In the following, the individual components are defined in more detail.

The polypropylene composition of the present invention comprises:

(A) a heterophasic propylene copolymer;

(B) random copolymers of propylene with comonomer units selected from ethylene and C₄-C₁₂An alpha-olefin;

(D) an inorganic filler.

Heterophasic propylene copolymer (A)

The heterophasic propylene copolymer (a) preferably comprises, more preferably consists of, a matrix phase and an elastomeric phase dispersed therein. Preferably, the matrix phase and the elastomer phase are polymerized using the same polymerization catalyst.

The matrix phase may be a propylene homopolymer or a random copolymer of propylene with comonomer units selected from ethylene and C₄-C₁₂An alpha-olefin.

According to a preferred embodiment, the matrix phase is a random copolymer of propylene with comonomer units selected from ethylene and C₄-C₁₂An alpha-olefin; more preferably, the matrix phase is a random copolymer of propylene and ethylene.

The matrix phase of the heterophasic propylene copolymer (a) has a minor amount of comonomer units, preferably from 0.01 to 1.5 wt%, more preferably from 0.02 to 0.8 wt%, most preferably from 0.05 to 0.4 wt%, based on the total weight of the matrix phase.

The comonomer units of the heterophasic propylene copolymer (A) may be selected from more than one comonomer unit selected from ethylene and C₄-C₁₂An alpha-olefin.

According to another preferred embodiment, the matrix phase is a propylene homopolymer comprising only monomer units derived from propylene.

Thus, the elastomeric phase may include the same comonomer units as the matrix phase, or may include different comonomer units than the matrix phase.

Preferably, the comonomer units of the base resin are selected from one comonomer unit. Thus, the comonomer units of the matrix phase and the elastomer phase are the same.

In a preferred embodiment, the matrix phase and the elastomer phase comprise only propylene monomer units and ethylene comonomer units.

In heterophasic propylene copolymers, the matrix phase and the elastomeric phase are usually not completely separated from each other. In order to characterize the matrix phase and the elastomeric phase of heterophasic propylene copolymers, various methods are known. One method is to extract a fraction comprising a majority of the elastomer phase with xylene, thereby separating a Xylene Cold Soluble (XCS) fraction from a Xylene Cold Insoluble (XCI) fraction. The XCS fraction comprises a major portion of the elastomeric phase and only a minor amount of the matrix phase, whereas the XCI fraction comprises a major portion of the matrix phase and only a minor amount of the elastomeric phase. Xylene extraction is particularly useful for heterophasic propylene copolymers containing a large amount of crystalline matrix phase, e.g. a propylene homopolymer matrix phase or a propylene random copolymer matrix phase containing a small amount of comonomer not exceeding about 3 wt%.

The amount of the XCS fraction of the heterophasic propylene copolymer (a) is from 15 to 35 wt%, preferably from 18 to 32 wt%, most preferably from 20 to 30 wt%, based on the total amount of the heterophasic propylene copolymer (a).

Preferably, the XCS fraction has a comonomer content of 25 to 55 wt%, more preferably 28 to 50 wt%, most preferably 30 to 45 wt%, based on the total amount of monomer units in the XCS phase.

Thus, the remainder of the monomer units that make up the XCS fraction to 100 wt.% is the amount of propylene monomer units.

The comonomer units of the XCS fraction are preferably selected from more than one comonomer unit selected from ethylene and C₄-C₁₂An alpha-olefin; more preferably, the comonomer units are selected from ethylene, 1-butene, 1-hexene and 1-octene.

Preferably, the XCS phase comprises only one comonomer unit as defined above.

In a particularly preferred embodiment, the comonomer units of the XCS fraction are ethylene comonomer units.

Further, the XCS fraction preferably has an intrinsic viscosity, iV, measured with decalin at 135 ℃ of from 2.0dl/g to 6.0dl/g, more preferably from 2.5dl/g to 5.5dl/g, most preferably from 3.5dl/g to 5.0 dl/g.

The XCI fraction is preferably present in the heterophasic propylene copolymer (a) in an amount of from 65 to 85 wt. -%, more preferably from 68 to 82 wt. -%, most preferably from 70 to 80 wt. -%, based on the total amount of the heterophasic propylene copolymer (a).

Preferably, the XCI fraction has a comonomer content of 0.01 wt% to 5.0 wt%, more preferably 0.02 wt% to 3.0 wt%, most preferably 0.05 wt% to 2.0 wt%, based on the total amount of monomer units in the XCI fraction.

Thus, the remainder of the monomer units that make up the XCI fraction to 100% is the amount of propylene monomer units.

The comonomer units of the XCI fraction are preferably selected from more than one comonomer unit selected from ethylene and C₄-C₁₂An alpha-olefin; more preferably, the comonomer units are selected from ethylene, 1-butene, 1-hexene and 1-octene.

Preferably, the XCI fraction comprises only one comonomer unit as defined above.

In a particularly preferred embodiment, the comonomer units of the XCI fraction are ethylene comonomer units.

The melt flow rate MFR (230 ℃, 2.16kg) of the heterophasic propylene copolymer (A) is preferably from 10.0g/10min to 100g/10min, more preferably from 12.0g/10min to 80.0g/10min, most preferably from 14.0g/10min to 70.0g/10 min.

The total amount of comonomer units, preferably ethylene units, in the heterophasic propylene copolymer (a) is preferably from 4.0 to 20.0 wt. -%, more preferably from 5.0 to 15.0 wt. -%, most preferably from 6.0 to 12.0 wt. -%, based on the total weight of the heterophasic propylene copolymer (a). The heterophasic propylene copolymer (a) is preferably the main component in the polypropylene based composition.

The heterophasic propylene copolymer (a) is present in the polypropylene based composition in an amount of from 40.0 wt% to 85.0 wt%, preferably from 45.0 wt% to 80.0 wt%, more preferably from 50.0 wt% to 75.0 wt%, most preferably from 52.0 wt% to 70.0 wt%, based on the total weight of the polypropylene based composition.

Preferably, the matrix phase of the polymeric base resin is polymerized before the elastomeric phase of the heterophasic propylene copolymer (a).

The propylene homopolymer or propylene copolymer of the matrix phase may be polymerized in one polymerization reactor or in more than one (e.g. two) polymerization reactors. The propylene copolymer in the elastomeric phase may be polymerized in one polymerization reactor or in more than one (e.g. two) polymerization reactors.

In a preferred embodiment, the propylene homopolymer or propylene copolymer of the matrix phase is polymerized in two polymerization reactors and the propylene copolymer of the elastomeric phase can be polymerized in one polymerization reactor, which are preferably connected in series.

It is well known to the person skilled in the art that propylene homopolymers or propylene copolymers reflecting the matrix phase are generally different from the XCI phase and propylene copolymers reflecting the elastomeric phase are generally different from the XCS phase.

The propylene copolymer or propylene homopolymer of the matrix phase may be polymerized in a single polymerization reactor. In said embodiment, the matrix phase is a unimodal propylene homopolymer or propylene copolymer.

The propylene copolymer or propylene copolymer of the matrix phase may be polymerized in more than two, e.g. 2,3 or 4, most preferably 2, polymerization reactors connected in series.

This means that in the first polymerization reactor a first part of the propylene copolymer or propylene homopolymer of the matrix phase is polymerized in the presence of a polymerization catalyst resulting in a first part of a first polymerization mixture comprising the first part of the propylene copolymer or propylene homopolymer and the catalyst; transferring the first part of the first polymerization mixture to a second polymerization reactor, polymerizing a second part of the propylene homopolymer or copolymer of the matrix phase in the presence of the polymerization catalyst in the presence of the first part of the propylene homopolymer or propylene copolymer, resulting in a second part of the first polymerization mixture comprising the first and second parts of the propylene homopolymer or propylene copolymer of the matrix phase and the catalyst.

These process steps may be further repeated in one or more other subsequent polymerization reactors.

The polymerization conditions in the first, second and optionally subsequent polymerization reactors in process step a) can be comparable. In said embodiment, the matrix phase is a monomodal propylene copolymer or a propylene homopolymer.

Alternatively, the polymerization conditions (in particular one or more of polymerization temperature, polymerization pressure, comonomer feed or chain transfer agent feed) in the first, second and optionally subsequent polymerization reactors in process step a) may differ from each other. In said embodiment, the matrix phase is a multimodal propylene homopolymer or propylene copolymer. In case of a series of two polymerization reactors of the described embodiment, the matrix phase is a bimodal propylene homopolymer or a propylene copolymer.

In such embodiments, the propylene homopolymer in the one or more polymerization reactors and the propylene random copolymer in the one or more polymerization reactors may be polymerized. In said embodiment, the matrix phase is a multimodal propylene copolymer comprising a propylene homopolymer fraction and a propylene random copolymer fraction. It is particularly preferred to polymerize the propylene homopolymer in one polymerization reactor and the propylene random copolymer in the other polymerization reactor of the two reactor sequence, in order to polymerize the matrix phase with one propylene homopolymer fraction and one propylene random copolymer fraction.

The order of polymerization of the fractions of the matrix phase is not particularly preferred.

Preferably, the elastomeric phase of the heterophasic propylene copolymer (a) is polymerized after and in the presence of the matrix phase of the heterophasic propylene copolymer (a).

The propylene copolymer of the elastomeric phase may be polymerized in a single polymerization reactor. In such embodiments, the elastomeric phase is a unimodal propylene copolymer.

The propylene copolymer of the elastomeric phase may be polymerized in more than two (e.g. 2,3 or 4, most preferably 2) polymerization reactors in series.

This means that in the first polymerization reactor a first part of the propylene copolymer of the elastomeric phase is polymerized in the presence of a polymerization catalyst resulting in a first part of a second polymerization mixture comprising the first part of the propylene copolymer of the elastomeric phase, the propylene homopolymer or the propylene copolymer of the matrix phase and the catalyst; transferring the first part of the second polymerization mixture to a second polymerization reactor, polymerizing a second part of the propylene copolymer of the elastomeric phase in the presence of a polymerization catalyst and said first part of the propylene copolymer, resulting in a second part of the second polymerization mixture comprising the first and second parts of the propylene copolymer of the elastomeric phase, the propylene copolymer or the propylene homopolymer of the matrix phase and the catalyst.

These process steps may be further repeated in one or more other subsequent polymerization reactors.

The polymerization conditions in the first, second and optionally subsequent polymerization reactors may be comparable. In said embodiment, the matrix phase is a monomodal propylene copolymer.

Alternatively, the polymerization conditions (in particular one or more of polymerization temperature, polymerization pressure, comonomer feed or chain transfer agent feed) in the first, second and optionally subsequent polymerization reactors may be different from each other. In said embodiment, the elastomeric phase is a multimodal propylene copolymer. In case of a series of two polymerization reactors of the described embodiment, the elastomeric phase is a bimodal propylene copolymer.

In such embodiments, propylene copolymers having different comonomers may be polymerized in more than two polymerization reactors. In said embodiment, the elastomeric phase is a multimodal propylene copolymer comprising a propylene copolymer fraction with one comonomer and a propylene copolymer fraction with another comonomer.

The polymerization order of the fractions of the elastomer phase is not particularly preferred.

Preferably, the first polymerization reactor is operated in bulk, for example a loop reactor, and subsequently all polymerization reactors, preferably the optional second and subsequent polymerization reactors comprising process step a), are operated in gas phase.

Preferably, the polymerisation step of the process of the present invention is carried out in a series of bulk polymerisation reactors (e.g. loop reactors) followed by one or more (e.g. 1,2, 3 or 4, preferably 1 or 2) gas phase reactors.

The first polymerization step may also be preceded by a prepolymerization step. In said embodiment, preferably, the polymerization step of the process of the invention is carried out in a prepolymerization reactor, a subsequent bulk polymerization reactor, preferably a loop reactor, and subsequently one or more (e.g. 1,2, 3 or 4, preferably 1 or 2) gas phase reactors in series.

The polymerization conditions (e.g., polymerization temperature, polymerization pressure, propylene raw material, comonomer raw material, chain transfer agent raw material or residence time) of the different polymerization steps are not particularly limited. How to adjust these polymerization conditions to adjust the properties of the propylene copolymer of the matrix phase or of the propylene homopolymer and of the propylene copolymer of the elastomeric phase is well known to the person skilled in the art.

Preferably, the residence time in the polymerization reactor is selected such that the weight ratio of propylene homopolymer or propylene copolymer of the matrix phase to propylene copolymer of the elastomeric phase is from 65:35 to 85: 15.

Suitably, the polymerisation step in the process of the present invention is carried out by a "loop-gas phase" process, for example developed by the northern Europe chemical industry (Borealis) and known as BORSTAR^TMThe technology is provided. Examples of such processes are described in EP 0887379, WO 92/12182, WO 2004/000899, WO 2004/111095, WO 99/24478, WO 99/24479 and WO 00/68315. These patent applications also describe suitable polymerization conditions. Another suitable process is known as Spheripol^TMSlurry-gas phase process of the process.

Typically, the polymerization catalyst of the present invention is present in the process. Preferred polymerization catalysts are Ziegler-Natta (Ziegler-Natta) catalysts.

Typically, a ziegler natta polymerization catalyst comprises one or more compounds of a Transition Metal (TM) of groups 4 to 6 (e.g. titanium) as defined by IUPAC (version 2013), a further compound of a group 2 metal (e.g. a magnesium compound) and an Internal Donor (ID).

The components of the catalyst may be supported by a particulate carrier, for example an inorganic oxide such as silica or alumina. Alternatively, magnesium halide may be used as the solid support. It is also possible that the catalyst component is not supported by an external carrier, but the catalyst is prepared by an emulsion-solidification method or a precipitation method, which are well known to those skilled in the art of catalyst preparation.

Preferably, a specific type of Ziegler Natta catalyst is present in the process of the present invention. In this particular type of ziegler-natta catalyst, the internal donor must be a non-phthalic compound. Preferably, no phthalic compound is used throughout the preparation of the specific type of ziegler natta catalyst, and therefore the specific type of ziegler natta catalyst does not comprise any phthalic compound. Thus, this particular type of ziegler-natta catalyst does not contain phthalic compounds. Thus, the polypropylene composition obtained in the third reactor of the process of the present invention is free of phthalic compounds.

Typically, the ziegler natta catalyst of this particular type comprises an Internal Donor (ID) which is selected to be a non-phthalic compound, whereby the ziegler natta catalyst of this particular type is completely free of phthalic compounds. Further, the specific type of ziegler natta catalyst may be a solid catalyst, which is preferably free of any external support material (e.g. silica or MgCl)₂) Thus the solid catalyst is self-supporting.

The solid catalyst was obtained by the following general procedure:

a) the following solutions were provided

a₁) At least one group 2 metal alkoxide (Ax) which is the reaction product of a group 2 metal compound and an alcohol (a) comprising at least one ether moiety in addition to a hydroxyl moiety, optionally in an organic liquid phase reaction medium; or

a₂) At least one group 2 metal alkoxide (Ax') which is the reaction product of a group 2 metal compound and an alcohol mixture comprising an alcohol (a) and a monohydric alcohol of formula ROH (B), optionally in an organic liquid phase reaction medium; or

a₃) A mixture of a group 2 metal alkoxide (Ax) and a group 2 metal alkoxide (Bx) which is the reaction product of a group 2 metal compound and a monohydric alcohol (B), optionally in an organic liquid phase reaction medium; or

a₄) Formula M (OR)₁)_n(OR₂)_mX_2-n-mAlkoxy compound of group 2 metal OR group 2 alkoxide M (OR)₁)_n’X_2-n’And M (OR)₂)_m’X_2-m’Wherein M is a group 2 metal, X is a halogen, R₁And R₂Is different alkyl of 2 to 16 carbon atoms, 0 ≦ n<2，0≤m<2 and n + m + (2-n-m) ═ 2, with the proviso that: n and m are not 0, 0 simultaneously<n' is less than or equal to 2 and 0<m' is less than or equal to 2; and

b) adding the solution of step a) to at least one compound of a group 4 to group 6 transition metal; and

c) obtaining particles of the solid catalyst component;

in at least one step prior to step c), a non-phthalic internal electron donor (ID) is added.

Preferably, the Internal Donor (ID) or a precursor thereof is added to the solution of step a) or the transition metal compound before the addition of the solution of step a).

According to the above procedure, the solid catalyst can be obtained by precipitation or emulsion-solidification, depending on the physical conditions (in particular the temperatures used in step b) and step c)). Emulsions are also known as liquid-liquid two-phase systems. In both processes (precipitation and emulsion-solidification), the catalyst chemistry is the same.

In the precipitation process, the solution of step a) is combined with the at least one transition metal compound of step b), and the entire reaction mixture is maintained at least 50 ℃, more preferably 55 to 110 ℃, more preferably 70 to 100 ℃, to ensure complete precipitation of the catalyst component in the form of solid catalyst component particles (step c).

In the emulsion-solidification process, the solution of step a) is added to at least one transition metal compound in step b), generally at a relatively low temperature (for example-10 to less than 50 ℃, preferably-5 to 30 ℃). During the stirring of the emulsion, the temperature is generally maintained at-10 to less than 40 ℃, preferably-5 to 30 ℃. The droplets of the dispersed phase in the emulsion form the active catalyst component. The solidification of the droplets is suitably carried out by heating the emulsion to a temperature of from 70 to 150 c, preferably from 80 to 110 c (step c). In the present invention, a catalyst prepared by an emulsion-curing method is preferably used.

In step a), preference is given to using a₂) Or a₃) Solution of (2)I.e., a solution of (Ax') or a mixture of (Ax) and (Bx).

Preferably, the group 2 metal is magnesium. In the first step (step a)) of the catalyst preparation process, the magnesium alkoxide compounds (Ax), (Ax') and (Bx) may be prepared in situ by reacting a magnesium compound with an alcohol as described above. Alternatively, the magnesium alkoxide compounds may be prepared separately or they may even be commercially available magnesium alkoxide compounds and used directly in the catalyst preparation process of the present invention.

An illustrative example of the alcohol (A) is ethylene glycol monoalkyl ether. Preferably, the alcohol (A) is C₂To C₄Wherein the ether moiety comprises 2 to 18 carbon atoms, preferably 4 to 12 carbon atoms. Preferred examples are 2- (2-ethylhexyloxy) ethanol, 2-butoxyethanol, 2-hexyloxyethanol and 1, 3-propanediol monobutyl ether, 3-butoxy-2-propanol, of which 2- (2-ethylhexyloxy) ethanol, 1, 3-propanediol monobutyl ether, 3-butoxy-2-propanol are particularly preferred.

An illustrative monohydric alcohol (B) is represented by the formula ROH, wherein R is a straight or branched chain C₂-C₁₆Alkyl radical, preferably C₄-C₁₀Alkyl residue, more preferably C₆-C₈An alkyl residue. The most preferred monohydric alcohol is 2-ethyl-1-hexanol or octanol.

Preferably, a mixture of an alkoxy magnesium compound (Ax) and an alkoxy magnesium compound (Bx) or a mixture of an alcohol (a) and an alcohol (B), Bx: ax or B: the molar ratio of a is 10:1 to 1:10, more preferably 6:1 to 1:6, still more preferably 5:1 to 1:3, most preferably 5:1 to 3: 1.

The magnesium alkoxide compound may be the reaction product of an alcohol and a magnesium compound selected from the group consisting of dialkyl magnesium, alkyl magnesium alkoxides (alkyl magnesium alkoxides), magnesium diols (magnesium alkoxides), alkoxy magnesium halides, and alkyl magnesium halides, as described above. Further, magnesium alkoxides, magnesium diaryloxides, aryloxymagnesium halides, magnesium aryloxides, and magnesium alkylaryloxides may be used. The alkyl group in the magnesium compound may beIs similar or different C₁-C₂₀Alkyl of (3), preferably C₂-C₁₀Alkyl group of (1). Typically, when alkyl-alkoxy magnesium compounds are used, the alkyl-alkoxy magnesium compounds are magnesium ethyl butoxide, magnesium butyl pentoxide, magnesium octyl butoxide and magnesium octyl octoxide. Preferably, a magnesium dialkyl is used. Most preferably, the magnesium dialkyl is butyl octyl magnesium or butyl ethyl magnesium.

The magnesium compound may be reacted with an alcohol (A) and an alcohol (B), and may be reacted with a compound having the formula R' (OH)_mTo obtain the magnesium alkoxide compound. If a polyol is used, preferably, the preferred polyol is such that: wherein R' is a linear, cyclic or branched C₂To C₁₀And m is an integer of 2 to 6.

Thus, the magnesium alkoxide compound of step a) is selected from: magnesium dialkoxides, diaryloxy magnesium (magnesium oxide), alkoxymagnesium halides, aryloxymagnesium halides, alkylmagnesium alkoxides, arylmagnesium alkoxides, and alkylmagnesium aryl oxides or mixtures of magnesium dihalides and magnesium glycols.

The solvent used to prepare the catalyst of the present invention may be selected from aromatic and aliphatic linear, branched and cyclic hydrocarbons having from 5 to 20 carbon atoms, more preferably from 5 to 12 carbon atoms, or mixtures thereof. Suitable solvents include benzene, toluene, cumene, xylene, pentane, hexane, heptane, octane, and nonane. Hexane and pentane are particularly preferred.

The reaction for preparing the magnesium alkoxide compound may be carried out at a temperature of 40 to 70 ℃. The skilled person knows how to select the most suitable temperature depending on the magnesium compound and the alcohol used.

The Transition Metal (TM) compound of groups 4 to 6 as defined by IUPAC (version 2013) is preferably a titanium compound, most preferably a titanium halide, e.g. TiCl₄。

The non-phthalic Internal Donor (ID) used in the preparation of the particular type of Ziegler Natta catalyst used in the present invention is preferably selected from: non-phthalic (di) carboxylic acid (di) esters, 1, 3-diethers, their derivatives and mixtures thereof. Particularly preferred donors are diesters of monounsaturated non-phthalic dicarboxylic acids, in particular esters belonging to the following group: malonic esters, maleic esters, succinic esters, citraconic esters, glutaric esters, cyclohexene-1, 2-dicarboxylic esters and benzoic esters, as well as derivatives thereof and/or mixtures thereof. Preferred examples are, for example, substituted maleates and citraconates, with citraconate being most preferred.

Here and hereinafter, the term derivative includes substituted compounds.

In the emulsion-solidification process, a liquid-liquid biphasic system may be formed by simple stirring and optionally adding (other) solvents and/or additives, such as Turbulence Minimizing Agents (TMAs) and/or emulsifiers and/or emulsion stabilizers, such as surfactants, which are used in a manner known in the art. These solvents and/or additives are used to facilitate the formation of the emulsion and/or to stabilize the emulsion. Preferably, the surfactant is an acrylic polymer or a methacrylic polymer.

Particularly preferred is unbranched C₁₂To C₂₀(meth) acrylates, such as poly (hexadecyl) -methacrylate and poly (octadecyl) -methacrylate and mixtures thereof. If a Turbulence Minimizing Agent (TMA) is used, the Turbulence Minimizing Agent (TMA) is preferably selected from polymers of alpha-olefin monomers of 6 to 20 carbon atoms, such as polyoctene, polynonane, polydecene, polyundecene or polydodecene or mixtures thereof. Most preferred is polydecene.

The solid particulate product obtained from the precipitation process or the emulsion-solidification process may be washed at least once, preferably at least twice, most preferably at least three times. The washing can be carried out using aromatic and/or aliphatic hydrocarbons, preferably toluene, heptane or pentane. TiCl may also be used₄Optionally in combination with aromatic and/or aliphatic hydrocarbons. The washing liquid may also comprise a donor and/or a group 13 compound, such as a trialkylaluminum, a halogenated alkylaluminum compound or an aluminum alkoxide compound. The aluminum compound may also be added during the catalyst synthesis. The catalyst may be further dried, for example, by evaporation or nitrogen purging (flushing), or it may be slurried into an oily liquid without any drying step.

It is desirable to obtain the particular type of Ziegler-Natta catalyst ultimately obtained in the form of particles, typically having an average particle size of from 5 to 200 μm, preferably from 10 to 100 μm. Generally, the particles are dense and have a low porosity, the particles having a surface area of less than 20g/m²More preferably less than 10g/m²。

Typically, the catalyst has Ti present in an amount of 1 to 6 wt% of the catalyst composition, magnesium present in an amount of 10 to 20 wt% of the catalyst composition, and an internal donor present in an amount of 10 to 40 wt% of the catalyst composition. Detailed descriptions of the preparation of the catalysts used in the present invention are disclosed in WO 2012/007430, EP 2610271 and EP 2610272, the contents of which are incorporated herein by reference.

Preferably, an External Donor (ED) is present as a further component in the polymerization process of the present invention. Suitable External Donors (ED) include certain silanes, ethers, esters, amines, ketones, heterocyclic compounds and mixtures thereof. The use of silanes is particularly preferred. Most preferably, silanes having the following general formula (I) are used:

R^a _pR^b _qSi(OR^c)_(4-p-q) (I)

wherein R is^a、R^bAnd R^cRepresents a hydrocarbon group (in particular an alkyl or cycloalkyl group), wherein p and q are numbers from 0 to 3 and their sum p + q is less than or equal to 3. R^a、R^bAnd R^cMay be selected independently of each other and may be the same or different. A specific example of a silane according to formula (I) is (tert-butyl)₂Si(OCH₃)₂(cyclohexyl) (methyl) Si (OCH)₃)₂, (phenyl)₂Si(OCH₃)₂And (cyclopentyl)₂Si(OCH₃)₂. Another most preferred silane is a silane according to formula (II):

Si(OCH₂CH₃)₃(NR³R⁴) (II)

wherein R is³And R⁴May be the same or different and represent a linear, branched or cyclic hydrocarbon group having 1 to 12 carbon atoms. Particularly preferably, R³And R⁴Independently selected from the group consisting of: methyl, ethyl, n-propyl, n-butyl, octyl, decyl, isopropyl, isobutyl, isopentyl, tert-butyl, tert-pentyl, neopentyl, cyclopentyl, cyclohexyl, methylcyclopentyl and cycloheptyl. Most preferably, ethyl is used.

In general, a cocatalyst (Co) may be present in the polymerization process of the present invention in addition to the ziegler-natta catalyst or a specific type of ziegler-natta catalyst and optionally an External Donor (ED). The cocatalyst is preferably a compound of group 13 of the periodic Table of the elements (IUPAC, 2013 version), for example an aluminum compound, for example an organoaluminum compound or an aluminum halide compound. Examples of suitable organoaluminum compounds are aluminum alkyls or aluminum alkyl halides. Thus, in a particular embodiment, the cocatalyst (Co) is a trialkylaluminium, such as Triethylaluminium (TEAL), dialkylaluminium chloride or alkylaluminium dichloride or a mixture thereof. In a particular embodiment, the cocatalyst (Co) is Triethylaluminium (TEAL).

Generally, the molar ratio between the Co-catalyst (Co) and the External Donor (ED) [ Co/ED ] and/or the molar ratio between the Co-catalyst (Co) and the Transition Metal (TM) [ Co/TM ] of each process should be carefully selected. The molar ratio between the cocatalyst (Co) and the External Donor (ED) [ Co/ED ] may suitably be from 2.5 to 50.0mol/mol, preferably from 4.0 to 35.0mol/mol, more preferably from 5.0 to 30.0 mol/mol.

The molar ratio [ Co/TM ] between the Co-catalyst (Co) and the Transition Metal (TM) may suitably be from 20.0 to 500.0mol/mol, preferably from 50.0 to 400.0mol/mol, more preferably from 100.0 to 300.0 mol/mol.

Propylene and comonomer units selected from ethylene and C₄-C₁₂Alpha-olefins) random copolymer (B)

Propylene and comonomer units selected from ethylene and C₄-C₁₂Alpha-olefin), hereinafter referred to as "copolymer (B)", comprising propylene monomer units and comonomer units selected from ethylene and C₄-C₁₂Alpha-olefins), preferably from propylene monomer units and comonomer units (selected from ethylene and C)₄-C₁₂Alpha-olefins).

The copolymer (B) may comprise more than one comonomer unit selected from ethylene and C₄-C₁₂The alpha-olefin is preferably selected from the group consisting of ethylene, 1-butene, 1-hexene and 1-octene, more preferably from the group consisting of ethylene, 1-butene and 1-hexene, most preferably from 1-hexene.

The copolymer (B) may comprise more than one (e.g.2, 3 or 4, preferably 2) different comonomer units selected from ethylene and C₄-C₁₂An alpha-olefin.

However, the copolymer (B) preferably comprises a comonomer unit selected from ethylene and C₄-C₁₂An alpha-olefin.

Most preferably, the copolymer (B) consists of propylene monomer units and 1-hexene comonomer units.

The comonomer units are randomly distributed in the polymer chain such that the copolymer (B) is a random copolymer of propylene and comonomer units selected from ethylene and C₄-C₁₂An alpha-olefin.

Preferably, the comonomer content (preferably 1-hexene content) of the copolymer (B) is from 1.0 to 4.5 wt.%, more preferably from 1.5 to 4.2 wt.%, even more preferably from 2.0 to 4.0 wt.%, even more preferably from 2.2 to 3.7 wt.%, particularly preferably from 2.5 to 3.5 wt.%.

Preferably, the copolymer (B) has a relatively high propylene (C3) content, i.e. from 95.5 to 99.0 wt. -%, more preferably from 95.8 to 98.5 wt. -%, even more preferably from 96.0 to 98.0 wt. -%, even more preferably from 96.3 to 97.8 wt. -%, for example from 96.5 to 97.5 wt. -%.

The melt flow rate MFR of the copolymer (B) determined in accordance with ISO1133₂(230 ℃) is preferably 0.8 to 15.0g/10min, more preferably 1.0 to 40.0g/10min, further more preferably 1.2 to 30.0g/10 min.

Further, the copolymer (B) may be defined according to the Xylene Cold Soluble (XCS) content as measured by ISO 6427. Thus, the propylene polymer is preferably characterized by a Xylene Cold Soluble (XCS) content of less than 7.5 wt%, more preferably not more than 6.0 wt%.

It is therefore to be understood in particular that the xylene cold soluble content of the copolymer (B) is from 0.2 to 6.0% by weight, more preferably from 0.3 to 5.0% by weight.

Still further, the copolymer (B) may be defined by a melting temperature (Tm) measured by DSC according to ISO 11357. Thus, the melting temperature Tm of the propylene polymer is below 140 ℃. The melting temperature Tm is even more preferably from 120 ℃ to 138 ℃, most preferably from 125 ℃ to 137 ℃.

The copolymer (B) should have a crystallization temperature, measured by DSC according to ISO11357, equal to or higher than 85 ℃, preferably ranging from 88 ℃ to 115 ℃, even more preferably ranging from 90 ℃ to 110 ℃.

The copolymer (B) is present in the propylene-based composition in an amount of from 5.0 wt% to 15.0 wt%, preferably from 6.0 wt% to 12.0 wt%, more preferably from 6.5 wt% to 10.0 wt%, based on the total weight of the propylene-based composition.

The copolymer (B) may further be unimodal or multimodal (e.g. bimodal) in view of the molecular weight distribution and/or comonomer content distribution; unimodal and bimodal propylene polymers are equally preferred.

If the copolymer (B) is unimodal, it is preferably produced in one polymerization reactor (R1) in a single polymerization step. Alternatively, unimodal propylene polymers may be produced in a sequential polymerization process using the same polymerization conditions in all reactors.

If the copolymer (B) is multimodal, it is preferably produced in a sequential polymerization process using different polymerization conditions (amount of comonomer, amount of hydrogen, etc.) in the reactor.

The copolymer (B) may be produced in a single polymerization step comprising a single polymerization reactor or a sequential polymerization process comprising at least two polymerization reactors; wherein in the first polymerization reactor a first propylene polymer fraction is produced, which is subsequently transferred to the second polymerization reactor. Then, in a second polymerization reactor, a second propylene polymer fraction is produced in the presence of the first propylene polymer fraction.

If the copolymer (B) is produced in at least two polymerization reactors, it may be

i) Production of propylene in the first reactorHomopolymer, producing a propylene copolymer (wherein the comonomer is selected from ethylene and C) in a second reactor₄-C₁₂α -olefin) to obtain a copolymer (B); or

ii) producing a propylene copolymer (wherein the comonomers are selected from ethylene and C) in a first reactor₄-C₁₂Alpha-olefin) in a second reactor to produce a propylene homopolymer, obtaining a copolymer (B); or

iii) producing a propylene copolymer (wherein the comonomer is selected from ethylene and C) in the first reactor₄-C₁₂Alpha-olefin) in a second reactor to produce a propylene copolymer (wherein the comonomer is selected from ethylene and C₄-C₁₂α -olefin) to obtain copolymer (B).

Suitable polymerization processes for producing the copolymer (B) generally comprise one or two polymerization stages, each of which can be carried out in the form of a solution phase, a slurry, a fluidized bed, a bulk phase or a gas phase.

The term "polymerization reactor" refers to a location where a main polymerization reaction occurs. Thus, in case the process consists of one or two polymerization reactors, this definition does not exclude the option that the whole system comprises a prepolymerization step, for example in a prepolymerization reactor. The term "consisting of …" is of closed construction only with respect to the main polymerization reactor.

The term "sequential polymerization process" means that the copolymer (B) can be produced in at least two reactors connected in series. Such a polymerization system therefore comprises at least a first polymerization reactor and a second polymerization reactor and optionally a third polymerization reactor.

The first (respectively single) polymerization reactor is preferably a slurry reactor and may be any continuous or simple stirred batch reactor or a loop reactor operating in bulk or slurry. Bulk means that the polymerization in the reaction medium comprises at least 60% (w/w) of monomers. The slurry reactor of the present invention is preferably a (bulk) loop reactor.

In case a "sequential polymerization process" is applied, the second and optionally the third polymerization reactor is a Gas Phase Reactor (GPR), i.e. the first and the second gas phase reactor. The Gas Phase Reactor (GPR) according to the invention is preferably a fluidized bed reactor, a fast fluidized bed reactor, a settled bed reactor or a combination thereof.

A preferred multistage process is a "ring-gas phase" process, for example from northern Europe (known as Nordic chemical industry)Technology) in patent documents such as EP 0887379, WO 92/12182, WO 2004/000899, WO 2004/111095, WO 99/24478, WO 99/24479 or WO 00/68315.

Further suitable slurry-gas phase processes are BasellAnd (5) processing.

The copolymer (B) is polymerized in the presence of a single-site catalyst system.

Preferably, the catalyst system comprises a catalyst component according to formula (III):

in the formula (I), the compound is shown in the specification,

m is zirconium or hafnium;

each X is independently a sigma-donor ligand;

l is formula- (ER)¹⁰ ₂)_y-a bridge of;

y is 1 or 2;

e is C or Si;

each R¹⁰Independently is C₁-C₂₀Hydrocarbyl, tri (C)₁-C₂₀Alkyl) silyl, C₆-C₂₀Aryl radical, C₇-C₂₀Arylalkyl radical or C₇-C₂₀Alkylaryl or L is alkylene (e.g., methylene or ethylene);

R¹each independently the same or different from each other, and is CH₂-R¹¹Group, wherein R¹¹Is H or straight or branched C₁-C₆Alkyl radical, C₃-C₈Cycloalkyl radical, C₆-C₁₀An aryl group;

R³、R⁴and R⁵Each independently of the other, identical or different from each other, and is H or C which is linear or branched₁-C₆Hydrocarbyl radical, C₇-C₂₀Arylalkyl radical, C₇-C₂₀Alkylaryl or C₆-C₂₀Aryl, provided that: in total there are more than four R³、R⁴And R⁵The radicals being different from H, more than one R³、R⁴And R⁵Is not a tert-butyl group;

R⁷and R⁸Each independently the same or different from each other, and is H, CH₂-R¹²Group, wherein R¹²Is H or straight or branched C₁-C₆Alkyl, SiR¹³ ₃、GeR¹³ ₃、OR¹³ ₃、SR¹³ ₃、NR¹³ ₃，

Wherein the content of the first and second substances,

R¹³is straight-chain or branched C₁-C₆Alkyl radical, C₇-C₂₀Alkylaryl group, C₇-C₂₀Arylalkyl radical or C₆-C₂₀And (4) an aryl group.

The catalyst system may further comprise

(ii) A cocatalyst system comprising a boron-containing cocatalyst and an aluminoxane cocatalyst;

it should be emphasized that in some cases, the use of such a catalyst is not required.

The catalyst system of the invention can be used in unsupported form or in solid form. The catalyst system of the present invention may be used in the form of a homogeneous catalyst system or a heterogeneous catalyst system.

The catalyst system of the invention in solid form, preferably in the form of solid particles, can be supported on an external support material, for example silica or alumina, or, in a particularly preferred embodiment, no external support is present, but is nevertheless in solid form. For example, the solid catalyst is obtained by the following process:

(a) forming a liquid/liquid emulsion system comprising a solution of catalyst components (i) and (ii) dispersed in a solvent to form dispersed droplets; and

(b) solid particles are formed by solidifying the dispersed droplets.

Specific complexes of the invention include:

rac-trans-dimethylsilanediyl [ 2-methyl-4- (4-tert-butylphenyl) -5,6, 7-trihydro-s-indan (indacen) -1-yl ] [ 2-methyl-4- (4-tert-butylphenyl) -5-methoxy-6-tert-butylindenyl zirconium dichloride or dimethyl;

rac-trans-dimethylsilanediyl [ 2-isobutyl-4- (4-tert-butylphenyl) -5,6, 7-trihydro-s-indan-1-yl ] [ 2-methyl-4- (4-tert-butylphenyl) -5-methoxy-6-tert-butylindenyl zirconium dichloride or dimethyl;

rac-trans-dimethylsilanediyl [ 2-neopentyl-4- (4-tert-butylphenyl) -5,6, 7-trihydro-s-indan-1-yl ] [ 2-methyl-4- (4-tert-butylphenyl) -5-methoxy-6-tert-butylindenyl zirconium dichloride or dimethyl;

rac-trans-dimethylsilanediyl [ 2-benzyl-4- (4-tert-butylphenyl) -5,6, 7-trihydro-s-indan-1-yl ] [ 2-methyl-4- (4-tert-butylphenyl) -5-methoxy-6-tert-butylindenyl zirconium dichloride or dimethyl;

rac-trans-dimethylsilanediyl [ 2-cyclohexylmethyl-4- (4-tert-butylphenyl) -5,6, 7-trihydro-s-indan-1-yl ] [ 2-methyl-4- (4-tert-butylphenyl) -5-methoxy-6-tert-butylindenyl zirconium dichloride or dimethyl;

rac-trans-dimethylsilanediyl [ 2-methyl-4- (3, 5-dimethylphenyl) -5,6, 7-trihydro-s-indan-1-yl ] [ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butylindenyl zirconium dichloride or dimethyl;

rac-trans-dimethylsilanediyl [ 2-isobutyl-4- (3, 5-dimethylphenyl) -5,6, 7-trihydro-s-indan-1-yl ] [ 2-methyl-4- (3,5- (dimethylphenyl) -5-methoxy-6-tert-butylindenyl zirconium dichloride or dimethyl;

rac-trans-dimethylsilanediyl [ 2-neopentyl-4- (3, 5-dimethylphenyl) -5,6, 7-trihydro-s-indan-1-yl ] [ 2-methyl-4- (3,5- (dimethylphenyl) -5-methoxy-6-tert-butylindenyl zirconium dichloride or dimethyl;

rac-trans-dimethylsilanediyl [ 2-benzyl-4- (3, 5-dimethylphenyl) -5,6, 7-trihydro-s-indan-1-yl ] [ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butylindenyl zirconium dichloride or dimethyl zirconium; and

rac-trans-dimethylsilanediyl [ 2-cyclohexylmethyl-4- (3, 5-dimethylphenyl) -5,6, 7-trihydro-s-indan-1-yl ] [ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butylindenyl zirconium dichloride or dimethyl zirconium.

The catalysts described in WO2015/011135 are hereby incorporated by reference. One particularly preferred catalyst is catalyst No. 3 of WO 2015/011135. The preparation of metallocenes is described in WO2013/007650, which is hereby incorporated by reference. The preparation of particularly preferred catalyst complexes is described in WO2013/007650, E2.

For the avoidance of doubt, any narrower definition of a substituent provided above may be combined with any other broader or narrower definition of any other substituent.

Given the narrower definition of a substituent, as disclosed above, this narrower definition is considered to be disclosed in conjunction with all broader and narrower definitions of other substituents in this application.

The ligands required to form the complex, and thus the catalyst/catalyst system of the invention, may be synthesized by any process, and the skilled organic chemist can devise various synthetic schemes to make the necessary ligand materials. For example, WO2007/116034 discloses the necessary chemicals. In general, synthetic schemes can also be found in WO2002/02576, WO2011/135004, WO2012/084961, WO2012/001052, WO2011/076780 and WO 2015/158790. The examples section also provides the skilled person with sufficient direction.

As mentioned above, the cocatalyst is not always required. However, when used, the cocatalyst system includes a boron-containing cocatalyst as well as an aluminoxane cocatalyst.

The aluminoxane cocatalyst can be one of the formulae (X):

wherein n is generally from 6 to 20 and has the following meaning.

Aluminoxanes are formed by partial hydrolysis of an organoaluminum compound, such as of the formula AlR₃、AlR₂Y and Al₂R₃Y₃Wherein R may be, for example, C₁-C₁₀Alkyl, preferably C₁-C₅Alkyl or C₃-C₁₀Cycloalkyl radical, C₇-C₁₂Arylalkyl or alkylaryl and/or phenyl or naphthyl, where Y can be hydrogen, halogen (preferably chlorine or bromine) or C₁-C₁₀Alkoxy (preferably methoxy or ethoxy).

The resulting oxyaluminoxanes are generally not pure compounds but mixtures of oligomers of the formula (X).

The preferred aluminoxane is Methylaluminoxane (MAO). Since the aluminoxane used as a cocatalyst in the present invention is not a pure compound because of its manner of preparation, the molar concentration of the aluminoxane solution is hereinafter expressed on the basis of its aluminum content.

In accordance with the present invention, aluminoxane cocatalysts are used in combination with boron-containing cocatalysts, for example, when cocatalyst systems or cocatalysts which are not normally required are present.

Suitable boron-based cocatalysts include those of the following formula (Z):

BY₃ (Z)

wherein Y is independently the same or different and is a hydrogen atom, an alkyl group of 1 to 20 carbon atoms, an aryl group of 6 to 15 carbon atoms, an alkylaryl group, an arylalkyl group, a haloalkyl group or a haloaryl group, each having 1 to 10 carbon atoms in the alkyl group and 6 to 20 carbon atoms in the aryl group, or fluorine, chlorine, bromine, iodine. Preferred examples of Y are methyl, n-propyl, isopropyl, isobutyl or trifluoromethyl, unsaturated groups (e.g. aryl or haloaryl, such as phenyl, tolyl, benzyl, p-fluorophenyl, 3, 5-difluorophenyl, pentachlorophenyl, pentafluorophenyl, 3,4, 5-trifluorophenyl and 3, 5-di (trifluoromethyl) phenyl). Preferred options are trifluoroborane, triphenylborane, tris (4-fluorophenyl) borane, tris (3, 5-difluorophenyl) borane, tris (4-fluoromethylphenyl) borane, tris (2,4, 6-trifluorophenyl) borane, tris (pentafluorophenyl) borane, tris (tolyl) borane, tris (3, 5-dimethyl-phenyl) borane, tris (3, 5-difluorophenyl) borane and/or tris (3,4, 5-trifluorophenyl) borane.

Particular preference is given to tris (pentafluorophenyl) borane.

Borate salts, i.e. containing borate ions (boron is 3), may be used⁺) The compound of (1). Such ionic cocatalysts preferably comprise non-coordinating anions such as tetrakis (pentafluorophenyl) borate and tetraphenylborate. Suitable counterions are protonated amine or aniline derivatives, for example methylammonium, aniline, dimethylamine, dimethylammonium, diethylammonium, N-methylammonium, diphenylammonium, N-dimethylanilinium, trimethylammonium, triethylammonium, tri-N-butylammonium, methyldiphenylammonium, pyridine, p-bromo-N, N-dimethylanilinium or p-nitro-N, N-dimethylanilinium.

Preferred ionic compounds useful in the present invention include:

triethylammonium tetra (phenyl) borate,

Tributyl tetra (phenyl) ammonium borate,

Trimethyl tetra (tolyl) ammonium borate,

Tributyl tetra (tolyl) ammonium borate,

Tributyl tetrakis (pentafluorophenyl) ammonium borate,

Tripropyl-tetra (dimethylphenyl) ammonium borate,

Tributyl tetrakis (trifluoromethylphenyl) ammonium borate,

Tributyl tetrakis (4-fluorophenyl) ammonium borate,

N, N-dimethylcyclohexylammonium tetrakis (pentafluorophenyl) borate,

N, N-dimethylbenzyl ammonium tetrakis (pentafluorophenyl) borate,

N, N-dimethyl tetra (phenyl) boracic acid aniline,

N, N-diethyl-tetra (phenyl) boronic acid aniline,

N, N-dimethyl-tetrakis (pentafluorophenyl) borate,

N, N-di (propyl) ammonium tetrakis (pentafluorophenyl) borate,

Bis (cyclohexyl) ammonium tetrakis (pentafluorophenyl) borate,

Phosphorus triphenyl tetra (phenyl) borate,

Triethyl tetrakis (phenyl) phosphonium borate,

Diphenyl tetra (phenyl) phosphonium borate,

Phosphorus tris (methylphenyl) tetrakis (phenyl) borate,

Phosphorus tris (dimethylphenyl) tetrakis (phenyl) borate,

Triphenyltetrakis (pentafluorophenyl) borate; or

Ferrocene tetrakis (pentafluorophenyl) borate.

Preference is given to triphenyltetrakis (pentafluorophenyl) borate, N-dimethylcyclohexyltetrakis (pentafluorophenyl) borate or N, N-dimethylbenzyltetrakis (pentafluorophenyl) borate.

Suitable amounts of cocatalyst are well known to those skilled in the art.

The molar ratio of boron to metal ions of the metallocene may be from 0.5:1 to 10:1mol/mol, preferably from 1:1 to 10:1mol/mol, in particular from 1:1 to 5:1 mol/mol.

The molar ratio of A1 to the metallocene ion in the aluminoxane may be from 1:1 to 2000:1mol/mol, preferably from 10:1 to 1000:1, more preferably from 50:1 to 500:1 mol/mol.

The catalysts of the invention may be used in supported or unsupported form. The particulate support material used is preferably an organic or inorganic material, for example silica, alumina or zirconia or mixed oxides, for example silica-alumina, in particular silica, alumina or silica-alumina. Preferably, a silica support is used. The skilled person is aware of the steps required to support the metallocene catalyst. Particularly preferred supports are porous materials such that the complex is loaded into the supported pores, for example using a process similar to that described in WO94/14856(Mobil), WO95/12622(Borealis), WO 2006/097497. The particle size is not critical, but is preferably from 5 to 200. mu.m, more preferably from 20 to 80 μm. The use of these loads is conventional in the art.

In an alternative embodiment, no load is used. Such catalyst systems may be prepared in solution (e.g., an aromatic-based solvent such as toluene), by contacting the metallocene (as a solid or as a solution) with a cocatalyst (e.g., methylaluminoxane previously dissolved in an aromatic-based solvent), or may be prepared by sequentially adding the dissolved catalyst components to the polymerization medium.

In a particularly preferred embodiment, no external support is used, but the catalyst is still present in the form of solid particles. Thus, no external support material is employed, for example an inert organic or inorganic support, such as silica as described above.

In order to provide the catalyst of the invention in solid form without the use of an external carrier, it is preferred to use a liquid/liquid emulsion system. The process comprises dispersing catalyst components (i) and (ii) in a solvent and solidifying the dispersed droplets to form solid particles.

In particular, the method comprises: preparing a solution of more than one catalyst component; dispersing the solution in a solvent to form an emulsion in which one or more catalyst components are present as droplets of a dispersed phase; immobilizing the catalyst components in the dispersed droplets in the absence of an outer particulate porous support to form solid particles comprising the catalyst; optionally recovering the particles.

The process ensures the manufacture of active catalyst particles having improved morphology, e.g. having predetermined spherical, surface properties and particle size, and without the use of any added external porous support material, e.g. inorganic oxides, e.g. silica. The term "preparing a solution of more than one catalyst component" means: the catalyst-forming compounds may be mixed in a solution that is dispersed in an immiscible solvent; alternatively, each portion of the catalyst-forming compound may be prepared as at least two different catalyst solutions, which are then sequentially dispersed in the solvent.

In a preferred method of forming the catalyst, each or each portion of the catalyst-forming compound may be prepared as at least two different catalyst solutions which are then dispersed in turn in immiscible solvents

More preferably, the solution comprising the complex of the transition metal compound and the cocatalyst are mixed with the solvent to form an emulsion; wherein the inert solvent forms a continuous liquid phase and the solution comprising the catalyst component forms a dispersed phase (discontinuous phase) in the form of dispersed droplets. Thereafter, the droplets are solidified to form solid catalyst particles, which are separated from the liquid, optionally washed and/or dried. The solvent forming the continuous phase is at least immiscible with the catalyst solution under the conditions used during the dispersing step.

The term "immiscible with the catalyst solution" means that the solvent (continuous phase) is completely immiscible or partially immiscible, i.e. not completely miscible with the solution of the dispersed phase.

Preferably, the solvent is inert with respect to the compounds of the catalyst system to be produced. A complete disclosure of the necessary processes can be found in WO 03/051934. The inert solvent must at least be chemically inert under the conditions (e.g., temperature) used during the dispersing step. Preferably, the solvent of the continuous phase does not contain any significant amount of catalyst-forming compounds dissolved therein. Thus, the catalyst solid particles are formed in the form of droplets from the compound originating from the dispersed phase (i.e. provided to the emulsion in the form of a solution dispersed to the continuous phase).

The terms "fixed" and "solidified" are used interchangeably herein for the same purpose, i.e., in the absence of an outer porous particle support (e.g., silica), to form a free-flowing solid catalyst particle. Thus, solidification occurs in the droplets. This step may be achieved in a number of ways, as described in WO 03/051934. Preferably, the curing is caused by an external stimulus of the emulsion system, for example a temperature change. Thus, in this step, the catalyst component remains "fixed" in the solid particles formed. In addition more than one catalyst component may also participate in the curing/fixing reaction.

Thus, solid, uniformly structured particles having a predetermined particle size range can be obtained.

In addition, the particle size of the catalyst particles of the present invention can be controlled by the droplet size in the solution, and spherical particles having a uniform particle size distribution can be obtained.

This process is also industrially advantageous because it allows the preparation of solid particles in a one-pot process. Continuous or semi-continuous processes may also be used to produce the catalyst.

In the polymerization process of the present invention, fresh catalyst is preferably introduced only into the first reactor or the prepolymerization reactor or vessel (if present), i.e. no fresh catalyst is introduced into the second reactor or any further first reactor or reactor upstream of the prepolymerization reactor. Fresh catalyst refers to virgin (virgin) catalyst or virgin catalyst that has undergone a prepolymerization reaction.

Having a structure of C₄-C₁₂Ethylene copolymers of alpha-olefin comonomers (C)

Having a structure of C₄-C₁₂The ethylene copolymer (C) of an alpha-olefin comonomer, hereinafter referred to as ethylene copolymer (C), is preferably an ethylene-based plastomer.

The ethylene copolymer (C) is ethylene and C₄-C₁₂Copolymers of alpha-olefins. Suitable C₄-C₁₂The alpha-olefins include 1-butene, 1-hexene and 1-octene, preferably 1-butene or 1-octene, more preferably 1-octene.

Copolymers of ethylene and 1-octene are preferably used.

Suitable ethylene copolymers (C) have a density of 850kg/m³To 900kg/m³Preferably 855kg/m³To 895kg/m³More preferably 860kg/m³To 890kg/m³More preferably 865kg/m³To 885kg/m³。

MFR of the suitable ethylene copolymer (C)₂(ISO 1133; 190 ℃, 2.16kg) is from 0.1 to 20.0g/10min, preferably from 0.2 to 15.0g/10min, more preferably from 0.3 to 10.0/10min, for example from 0.5 to 5.0g/10 min.

Suitable ethylene copolymers (C) have a melting temperature (determined by DSC according to ISO 11357-3) of less than 100 ℃, preferably less than 90 ℃, more preferably less than 80 ℃. Generally, the melting temperature is not lower than 40 ℃.

Further, suitable ethylene copolymers (C) have a glass transition temperature Tg (measured by DMTA according to ISO 6721-7) of less than-25 ℃, preferably less than-30 ℃, more preferably less than-35 ℃.

In the case of ethylene copolymers (C) of ethylene and C₄-C₁₂In the case of copolymers of alpha-olefins, the ethylene content is from 60 to 90% by weight, preferably from 65.0 to 85.0% by weight, more preferably from 67.0 to 82.0% by weight, for example from 70.0 to 80.0% by weight.

Suitable ethylene copolymers (C) generally have a molecular weight distribution Mw/Mn of less than 4.0, for example less than 3.8, but at least 1.7. The molecular weight distribution Mw/Mn is preferably from 3.5 to 1.8.

The ethylene copolymer (C) is present in the propylene-based composition in an amount of from 5.0 wt% to 25.0 wt%, preferably from 7.0 wt% to 22.0 wt%, more preferably from 9.0 wt% to 21.0 wt%, most preferably from 10.0 wt% to 20.0 wt%, based on the total weight of the propylene-based composition.

Suitable ethylene copolymers (C) may be ethylene and propylene or ethylene and C having the above-mentioned properties₄-C₁₂Any copolymer of an alpha-olefin, which is commercially available, i.e., commercially available under the tradename Queo from North European chemical, Engage or Affinity from DOW, or Tafiner from Mitsui.

Alternatively, these ethylene copolymers (C) can be prepared by known processes in a one-stage or two-stage polymerization process (including liquid polymerization, slurry polymerization, gas-phase polymerization or combinations thereof) in the presence of suitable catalysts known to those skilled in the art (e.g. vanadia catalysts or single-site catalysts, such as metallocenes or constrained geometry catalysts).

Preferably, these ethylene copolymers (C) are prepared by a one-stage or two-stage solution polymerization process, in particular by a solution polymerization process at elevated temperatures above 100 ℃.

Such processes are essentially based on the polymerization of monomers and suitable comonomers in liquid hydrocarbon solvents, in which the resulting polymers are soluble. The polymerization reaction is carried out at a temperature higher than the melting point of the polymer, thereby obtaining a polymer solution. The solution is flashed to separate the polymer from the unreacted monomers and solvent. The solvent is then recovered and reused in the process.

Preferably, the solution polymerization process is a high temperature solution polymerization process, using a polymerization temperature above 100 ℃. The polymerization temperature is preferably at least 110 ℃ and more preferably at least 150 ℃. The polymerization temperature may be up to 250 ℃.

The pressure of this solution polymerization process is preferably from 10 to 100 bar, preferably from 15 to 100 bar, more preferably from 20 to 100 bar.

The liquid hydrocarbon solvent used is preferably C_5-12Which may be unsubstituted or substituted by C_1-4Alkyl (e.g., pentane, methylpentane, hexane, heptane, octane, cyclohexane, methylcyclohexane and hydrogenated naphtha) substitution. More preferably, unsubstituted C is used₆-C₁₀A hydrocarbon solvent.

A known solution technique suitable for use in the process of the present invention is COMPACT technology.

Inorganic filler (D)

Further requirements of the composition of the invention are: an inorganic filler (D) is present.

Preferably, the inorganic filler (D) is a mineral filler. Preferably, the inorganic filler (D) is a layered silicate, mica or wollastonite. Even more preferably, the inorganic filler (D) is selected from mica, wollastonite, kaolin, montmorillonite (smectite), montmorillonite (montmorillonite) and talc.

The most preferred inorganic fillers (D) are talc and/or wollastonite.

It is understood that the median particle diameter (D) of the inorganic filler (D)₅₀) 0.5 to 5.0. mu.m, preferably 0.7 to 3.0. mu.m, most preferably 1.0 to 2.5. mu.m.

Further preferably, the BET surface area of the inorganic filler (D) is from 5.0 to 30.0m²A/g, more preferably 7.5 to 25.0m²A/g, most preferably from 10.0 to 20m²/g。

According to the invention, the inorganic filler (D) does not belong to the class of additives.

The inorganic fillers (D) are prior art and are commercially available products.

The inorganic filler (D) is present in the polypropylene-based composition in an amount of 5.0 to 25.0 wt%, preferably 8.0 to 22.0 wt%, more preferably 10 to 20.0 wt%, based on the total weight of the polypropylene-based composition.

Additive agent

The polypropylene-based composition of the present invention may contain additives in addition to the heterophasic propylene copolymer (a), the copolymer (B), the ethylene copolymer (C) and the inorganic filler (D). Typical additives are acid scavengers, antioxidants, colorants, light stabilizers, plasticizers, slip agents, scratch resistance agents, dispersants, processing aids, lubricants, pigments, and the like. As mentioned above, the inorganic filler (D) does not belong to the additives.

Such Additives are commercially available and are described by way of example in the plastics Additives Handbook, 2009, 6 th edition (pages 1141 to 1190) by Hans Zweifel.

Preferred additive levels for the polypropylene-based compositions include no more than 10 wt%, more preferably no more than 5 wt%, and most preferably no more than 3 wt%, based on the weight of the polypropylene-based composition.

Further, according to the present invention, the term "additive" also comprises a carrier material, in particular a polymeric carrier material.

Polymeric carrier material

Preferably, the polypropylene-based composition of the invention contains not more than 5 wt%, preferably not more than 3 wt%, more preferably not more than 1.5 wt% of other polymers than the heterophasic propylene copolymer (a), copolymer (B) and ethylene polymer (C), based on the weight of the polypropylene-based composition.

In a preferred embodiment, the polypropylene based composition does not comprise any other polymers than the heterophasic propylene copolymer (a), the terpolymer (B) (ter polymer) and the ethylene polymer (C).

Any polymer as a carrier material for the additive does not account for the amount of polymeric compound described in the present invention, but is counted as the amount of the respective additive.

The polymeric carrier material of the additive is a carrier polymer to ensure a uniform distribution of the polypropylene composition (C) of the invention. The polymeric carrier material is not limited to a particular polymer. The polymeric carrier material may be an ethylene homopolymer, made from ethylene and an alpha-olefin comonomer (e.g. C)₃-C₈Alpha-olefin comonomer), propylene homopolymers and/or copolymers derived from propylene and alpha-olefin comonomers (e.g. ethylene and/or C)₄-C₈Alpha-olefin comonomer). Preferably, the polymeric support material does not comprise monomer units derived from styrene or derivatives thereof.

Polypropylene composition

The polypropylene composition of the present invention comprises:

(A) from 40.0 to 85.0 wt. -%, preferably from 45.0 wt. -% to 80.0 wt. -%, more preferably from 50.0 wt. -% to 75.0 wt. -% of a heterophasic propylene copolymer having a Xylene Cold Soluble (XCS) fraction content of from 15 wt. -% to 35 wt. -%;

(B)5.0 to 15.0 wt%, preferably 6.0 wt% to 12.0 wt%, more preferably 6.5 wt% to 10.0 wt% of a random copolymer of propylene with comonomer units selected from ethylene and C₄-C₁₂An alpha-olefin, the random copolymer having been polymerized in the presence of a single-site catalyst system, the random copolymer having a melting temperature, Tm, as measured by Differential Scanning Calorimetry (DSC), of less than 140 ℃;

(C)5.0 to 25.0 wt%, preferably 7.0 to 22.0 wt%, more preferably 9.0 wt% to 21.0 wt%, most preferably 10.0 wt% to 20.0 wt% of an ethylene copolymer having C₄-C₁₂Alpha-olefin comonomer units, the density of the ethylene copolymer being 850kg/m³To 900kg/m³(ii) a And

(D)5.0 to 25.0 wt%, preferably 7.5 wt% to 23 wt%, more preferably 10.0 wt% to 21.0 wt%, most preferably 12.0 wt% to 20.0 wt% of an inorganic filler;

wherein the amounts of the components (A), (B), (C) and (D) are based on the total weight of the polypropylene composition.

Components (A), (B), (C), (D) are preferably as defined above or below.

Optionally, the polypropylene based composition may further comprise an additive as defined above or below in an amount of up to 10 wt%.

Further, the polypropylene-based composition may further comprise other polymers different from components (A), (B), (C) in an amount of not more than 5 wt%, preferably not more than 3 wt%, more preferably not more than 1.5 wt%, based on the weight of the polypropylene-based composition.

In a preferred embodiment, the polypropylene based composition does not comprise any other polymers than the heterophasic propylene copolymer (a), the terpolymer (B) and the ethylene polymer (C).

Preferred MFR of the Polypropylene-based composition₂(2.16kg, 230 ℃) of 2.0 to 20.0g/10min, preferably 4.0 to 18.0g/10min, more preferably 6.0 to 16.0g/10min, e.g. 6.5 to 14.0g/10 min.

The polypropylene based composition has a flexural modulus of at least 1300MPa, more preferably at least 1400MPa, most preferably at least 1500 MPa. The upper limit of the flexural modulus is usually not higher than 2500MPa, preferably not higher than 2200 MPa.

Further, the polypropylene-based composition preferably has a Charpy notched impact strength of at least 50kJ/m at 23 ℃²More preferably 55 to 100kJ/m²Most preferably from 60 to 90kJ/m²。

Still further, the polypropylene-based composition preferably has a Charpy notched impact strength of 5.0kJ/m at-20 ℃³More preferably 6.0 to 20kJ/m²Most preferably from 6.5 to 15.0kJ/m²。

Even further, the heat distortion temperature B (HDT-B) of the polypropylene-based composition is preferably from 80 ℃ to 120 ℃, more preferably from 85 ℃ to 115 ℃, and most preferably from 90 ℃ to 110 ℃.

Articles and uses of the invention

The invention further relates to an article comprising a polypropylene-based composition as defined above or below.

In one aspect of the invention, the article comprising the polypropylene-based composition as defined above or below is a coated article.

Preferably, both the article and the coated article are based on a molded article, such as an injection molded article. Particularly preferred are injection molded articles, such as automotive articles, e.g. automotive exterior articles or automotive interior articles.

The term "automotive article" as used in the present invention means that it is a shaped three-dimensional article for use in the interior or exterior of an automobile. Typical automotive articles are bumpers, side trims, step assists, body panels, rocker panels, spoilers, dashboards, interior trim parts and the like. The term "exterior" means that the article is not an interior vehicle portion, but an exterior vehicle portion. Thus, preferred external automotive articles are selected from: bumper, side fascia, footboard supplementary, automobile body panel and spoiler. In contrast, the term "interior" refers to the interior portion of the article rather than the exterior portion of the article. Thus, preferred internal embodiment articles are selected from: threshold board, instrument board and interior trim. The coating may be present on a portion of the visible surface or the entire visible surface of the article.

Preferably, the automotive article (i.e. the exterior automotive article) comprises, even more preferably consists of, 80 wt% or more, more preferably 90 wt% or more, even more preferably 95 wt% or more, even more preferably 99 wt% or more of the polypropylene-based composition.

For mixing the individual components of the polypropylene-based composition of the invention, conventional compounding or blending equipment may be used, such as a Banbury mixer, a two-roll rubber mill, a Buss co-kneader or a twin-screw extruder. The polymeric material recovered from the extruder is typically in the form of pellets. These pellets are then preferably further processed, for example injection molded, to produce articles, i.e. (exterior or interior) automotive articles.

Preferably, the articles of the present invention have a radial shrinkage of less than 1.0%, more preferably less than 0.9%, most preferably less than 0.8%.

Further preferably, the articles of the present invention have an average peel area (i.e., coating adhesion failure) of 10.0mm²To 50.0mm²More preferably 12.0mm²To 35.0mm²More preferably 13.0mm²To 32.0mm²Most preferably 15.0mm²To 30.0mm²。

From the examples section below, it is seen that the presence of the copolymer (B) of propylene with 1-hexene comonomer units in the polypropylene-based composition reduces the coating adhesion failure of the article.

Thus, the present invention further relates to propylene and comonomer units (selected from ethylene and C)₄-C₁₂Alpha-olefin) in a polypropylene based composition for reducing coating adhesion failure of an article comprising said polypropylene based composition, said polypropylene based composition comprising:

(B)5.0 to 15.0 wt% of a random copolymer of propylene with comonomer units selected from ethylene and C₄-C₁₂An alpha-olefin, the random copolymer having been polymerized in the presence of a single-site catalyst system, the random copolymer having a melting temperature, Tm, as measured by Differential Scanning Calorimetry (DSC), of less than 140 ℃;

(C)5.0 to 25.0 wt% of an ethylene copolymer having C₄-C₁₂Alpha-olefin comonomer units, the density of the ethylene copolymer being 850kg/m³To 900kg/m³(ii) a And

(D)5.0 to 25.0 wt% of an inorganic filler,

wherein components (A), (B), (C) and (D) are based on the total weight of the polypropylene-based composition and the composition has:

melt Flow Rate (MFR) measured according to ISO1133 at 230 ℃ and 2.16kg load₂) Is 2.0g/10min to 20.0g/10 min.

Thus, the polypropylene composition and the propylene and comonomer units (selected from ethylene and C)₄-C₁₂Alpha-olefins) The random copolymer of (A) preferably relates to a polypropylene-based composition as defined below or above and propylene and comonomer units (selected from ethylene and C)₄-C₁₂Alpha-olefins) are used.

It is therefore noted that articles prepared from the polypropylene-based compositions defined herein show a good stiffness/impact balance and high paint adhesion. In addition, high paint adhesion can be achieved without the use of primers.

The present invention will be further described in detail by the examples provided below.

Examples

1. The measuring method comprises the following steps:

a) xylene cold soluble fraction at room temperature (XCS, wt%)

The amount of soluble polymer fraction in xylene was measured according to ISO16152: 2005.

b) Melt Flow Rate (MFR)₂)

Melt flow rate is the amount of polymer (in grams) extruded in 10 minutes at a certain temperature under a certain load using a test equipment standardized to ISO 1133.

The melt flow rate MFR of a propylene-based polymer was measured according to ISO1133 at 230 ℃ under a load of 2.16kg₂(MFR230℃/2.16)。

The melt flow rate (MFR190 ℃/2.16) of the ethylene copolymers was measured according to ISO1133 at 190 ℃ under a load of 2.16 kg.

The melt flow rate (MFR230 ℃/2.16) of the polypropylene-based composition was measured according to ISO1133 at 230 ℃ under a load of 2.16 kg.

c) Density of

The density was determined according to ISO 1183D. According to ISO 1872-2: 2007 samples were prepared by compression molding.

d) Comonomer content

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

Comonomer content quantification of poly (propylene-co-ethylene) copolymers

To is directed at¹H and¹³c, using Bruker Advance type III 400 NMRSpectrometer, recording quantification of solution state at 400.15 and 100.62MHz respectively¹³C{¹H } NMR spectrum. Use of¹³C best 10mm extension temperature probe, all spectra were recorded at 125℃ using nitrogen for all atmospheres. About 200mg of the material was mixed with chromium (III) acetylacetonate (Cr (acac)₃) Dissolved together in 3mL of 1, 2-tetrachloroethane-d₂(TCE-d₂) In (5), a 65mM relaxant solution in solvent {8} was obtained. To ensure the solution is homogeneous, after initial sample preparation in the heating block, the NMR tube is further heated in a rotary oven for at least 1 hour. After the magnet was inserted, the tube was rotated at 10 Hz. This setting was chosen primarily for high resolution and quantitative requirements for accurate quantification of ethylene content. Using standard single pulse excitation without NOE, optimal tip angle, 1s cycle delay and two-stage WALTZ16 decoupling scheme {3,4 }. A total of 6144(6k) transient signals were acquired for each spectrum.

Quantification using proprietary computer programs¹³C{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 of the ethylene block (EEE) at 30.00 ppm. This method can be referred to similarly even without this structural unit. A characteristic signal corresponding to ethylene incorporation {7} is observed.

Using the method of Wang et al {6}, by³C{¹H } multiple signals over the entire spectral region of the spectrum were integrated to quantify comonomer fractions. This method was chosen for its stability (robust nature) and ability to account for the presence of regional defects (when needed). The integration zone is adjusted slightly to increase the applicability to the comonomer content encountered over the entire range.

For systems in which only isolated ethylene in the PPEPP sequence was observed, the method of Wang et al was modified to reduce the effect of non-zero integration of sites known to be absent. This method reduces the overestimation of ethylene content in such systems and is achieved by reducing the number of sites used to determine absolute ethylene content to the formula:

E＝0.5(Sββ+Sβγ+Sβδ+0.5(Sαβ+Sαγ))

by using this set of points, the corresponding integral equation becomes:

E＝0.5(I_H+I_G+0.5(I_C+I_D))

the same notation as used in article 6 of Wang et al is used. The equation used for absolute propylene content was not modified.

The mole percentage of incorporated comonomer was calculated from the mole fraction:

E[mol％]＝100*fE

the weight percentage of incorporated comonomer was calculated from the mole fraction:

E[wt％]＝100*(fE*28.06)/((fE*28.06)+((1-fE)*42.08))

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11)Resconi,L.,Cavallo,L.,Fait,A.,Piemontesi,F.,Chem.Rev.2000,100,1253.

comonomer content of poly (propylene-co-hexene)

To is directed at¹H and¹³c, quantification of the melt state was recorded at 500.13MHz and 125.76MHz respectively using a Bruker Advance III 500NMR spectrometer¹³C{¹H } NMR spectrum. Use of¹³C-optimum 7mm Magic Angle Spinning (MAS) probe, all spectra were recorded at 180 ℃ for all atmospheres using nitrogen. About 200mg of material was loaded into a 7mm outer diameter zirconia MAS rotor, rotating at 4 kHz. This setting was chosen primarily for the high sensitivity required for rapid identification and accurate quantification (Klimke, k., Parkinson, m., Piel, c., Kaminsky, w., Spiess, h.w., Wilhelm, m., macromol. chem. phys.2006:207:382., Parkinson, m., Klimke, k., Spiess, h.w., Wilhelm, m., macromol. chem. phys.2007:208:2128., cassignoles, p., Graf, r., Parkinson, m., Wilhelm, m., gaborrieau, m., Polymer 50(2009) 2373). Using 3S of short cycle delayed NOE, standard single pulse excitation (Klimke, k., Parkinson, m., Piel, c., Kaminsky, w., Spiess, h.w., Wilhelm, m., macro mol. chem. phys.2006; 207:382., Pollard, m., Klimke, k., Graf, r., Spiess, h.w., Wilhelm, m., specler, o., Piel, c., Kaminsky, w., Macromolecules 2004: 37) and RS-HEPT decoupling schemes (trilip, x., c., filpon, fillip, c., j.mag.2005: 176,239, Griffin, j.m., Tripon, c., Samoson, saimson, Brown, s.198, brown.84). A total of 16384(16k) transient signals are collected per spectrum.

For quantitative determination¹³C{¹H NMR spectra were processed, integrated and the relevant quantitative properties were determined from the integration. All chemical shifts are referenced internally by 21.85ppm methyl isotactic pentads (mmmm).

A characteristic signal corresponding to the incorporation of 1-hexene was observed, and the comonomer content was quantified in the following manner.

The incorporation of 1-hexene in the PHP isolation sequence was quantified using the ratio of the integral of α B4 sites at 44.2ppm to the number of reporting sites per comonomer:

H＝IαB4/2

the amount of 1-hexene incorporated in the PHHP dual continuous sequence was quantified using the ratio of the integral of α B4 sites at 41.7ppm to the number of reporting sites per comonomer:

HH＝2*ΙααB4

when double continuous incorporation is observed, the amount of 1-hexene incorporation in the PHP separation sequence needs to be compensated for because the signals α B4 and α B4B4 overlap at 44.4 ppm:

H＝(IαB4–2*IααB4)/2

the total 1-hexene content was calculated from the total amount of 1-hexene separated and continuously incorporated:

H_{general assembly}＝H+HH

When no sites indicating continuous incorporation were observed, the total content of 1-hexene comonomer was calculated from this amount only:

H_{general assembly}＝H

Characteristic signals indicating region 2, 1-erythro defects were observed (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., chem.Rev.2000:100,1253).

The presence of 2, 1-erythro regio defects was indicated by the presence of P α β (21e8) and P α γ (21e6) methyl positions at 17.7ppm and 17.2ppm and confirmed by other characteristic signals.

The total amount of secondary (2, 1-erythro) inserted propylene was quantified based on α α 21e9 methylene sites at 42.4 ppm:

P21＝Iαα21e9

the total amount of propylene inserted as one (2, 1-erythro) was quantified from the major S α methylene sites at 46.7ppm and compensating for the relative amounts of 2, 1-erythro, α B4 and α α B4B4 methylene units of unaccounted propylene (note the H and HH counts of the hexene monomers in each sequence rather than the sequence number):

P12＝I_Sαα+2*P21+H+HH/2

the total amount of propylene was quantified as the sum of the primary (1, 2-erythro) and secondary (2, 1-erythro) inserted propylene:

P_{general assembly}＝P12+P21＝I_Sαα+3*Iαα21e9+(IαB4–2*IααB4)/2+IααB4

The method is simplified as follows:

P_{general assembly}＝I_Sαα+3*Iαα21e9+0.5*IαB4

The total mole fraction of 1-hexene in the polymer was then calculated as:

fH＝H_{general assembly}/(H_{General assembly}+P_{General assembly})

The complete integral equation for the mole fraction of 1-hexene in the polymer is:

fH＝(((IαB4–2*IααB4)/2)+(2*IααB4))/((ISαα+3*Iαα21e9+0.5*IαB4)+((IαB4–2*IααB4)/2)+(2*IααB4))

the method is simplified as follows:

fH＝(IαB4/2+IααB4)/(ISαα+3*Iαα21e9+IαB4+IααB4)

the total comonomer incorporation of 1-hexene (in mole percent) was calculated from the mole fraction in a conventional manner:

H[mol％]＝100*fH

the total comonomer incorporation of 1-hexene (in weight percent) was calculated from the mole fraction in the standard manner:

H[wt％]＝100*(fH*84.16)/((fH*84.16)+((1-fH)*42.08))

quantitative comonomer content of poly (ethylene-co-1-octene) copolymer

To is directed at¹H and¹³c, quantification of the melt state was recorded at 500.13MHz and 125.76MHz using a Bruker Advance III 500NMR spectrometer¹³C{¹H } NMR spectrum. By using¹³C-optimum 7mm Magic Angle Spinning (MAS) probe, all spectra were recorded at 150 ℃ for all atmospheres using nitrogen. Approximately 200mg of material was loaded into a 7mm outer diameter zirconia MAS rotor rotating at 4 kHz. This setting was chosen primarily for the high sensitivity required for rapid identification and accurate quantification^{[1],[2],[3],[4]}. Using standard single pulse excitation, with transient NOE at short cyclic delay of 3s^[5],[1]And RS-HEPT decoupling scheme^[6],[7]. A total of 1024(1k) transient signals were collected for each spectrum. This setting was chosen because of its high sensitivity to low comonomer content.

Quantification using a custom spectral analysis automation program¹³C{¹H NMR spectra were processed, integrated and quantitative properties determined. All chemical shifts are referenced internally to the bulk methylene signal (δ +) at 30.00ppm^[8]。

Characteristic signals corresponding to 1-octene incorporation were observed^{[8],[9],[10],[11],[12]}All comonomer contents present in the polymer with respect to all other monomers are calculated.

A characteristic signature resulting from the isolated 1-octene incorporation (i.e., EEOEE comonomer sequence) was observed. The signal integral at 38.32ppm was used to quantify the isolated 1-octene incorporation. The integrals are assigned to the unresolved signals corresponding to the separated (EEOEE) and separated double discontinuous (EEOEE) 1-octene sequences, respectively_*Position B6 and_*β B6B6 site. To compensate for two kinds of_*Influence of β B6B6 site, integration of β β B6B6 site at 24.7ppm was used:

O＝I_*B6+*βB6B6–2*I_ββB6B6

characteristic signals resulting from continuous 1-octene incorporation (i.e., EEOOEE comonomer sequence) were also observed. This continuous 1-octene incorporation was quantified using the ratio of the signal integral assigned to α α B6B6 site at 40.48ppm to the number of reporter sites per comonomer:

OO＝2*I_ααB6B6

a characteristic signature resulting from isolated non-continuous 1-octene incorporation (i.e., eeoeoeee comonomer sequence) was also observed. This isolated discontinuous 1-octene incorporation was quantified using the ratio of the integral of the signal assigned to β β B6B6 site to the number of reporter sites per comonomer at 24.7 ppm:

OEO＝2*I_ββB6B6

characteristic signals resulting from isolated triple-continuous 1-octene incorporation (i.e., EEOOOEE comonomer sequence) were also observed. This isolated triple continuous 1-octene incorporation was quantified using the ratio of the integral of the signal assigned to the α α γ B6B6 site at 41.2ppm to the number of reporter sites per comonomer:

OOO＝3/2*I_ααγB6B6B6

in the absence of observing other signals indicative of other comonomer sequences, the total 1-octene comonomer content was calculated based on the amount of separated (EEOEE), separated doubly continuous (EEOOEE), separated non-continuous (eeoeoeoee) and separated triply continuous (EEOOOEE) 1-octene comonomer sequences only:

O_{general assembly}＝O+OO+OEO+OOO

Characteristic signals resulting from groups at the saturated end are observed. The average integration of the two resolved signals at 22.84ppm and 32.23ppm was used to quantify this saturated end group. The unidentified signals corresponding to the 2B6 and 2S sites of 1-octene and saturated chain ends, respectively, were assigned a 22.84ppm integral. An integration of 32.23ppm was assigned to the undistinguished signals corresponding to the 3B6 and 3S sites of 1-octene and saturated chain ends, respectively. To compensate for the effect of 2B6 and 3B 61-octene sites, the total 1-octene content was used:

S＝(1/2)*(I_2S+2B6+I_3S+3B6–2*O_{general assembly})

The integral of the bulk methylene (bulk) signal at 30.00ppm was used to quantify the ethylene comonomer content. The integral includes the gamma and 4B6 sites and delta from 1-octene⁺A site. The total ethylene comonomer content was calculated based on bulk integration and compensated for the observed 1-octene sequence and end groups:

E_{general assembly}＝(1/2)*[I_Body+2*O+1*OO+3*OEO+0*OOO+3*S]

It should be noted that there is no need to compensate for the bulk integral of the presence of the isolated triple incorporation (EEOOOEE) 1-octene sequence, since the number of insufficient and excess ethylene units is equal.

The total mole fraction of 1-octene in the polymer was then calculated as follows:

fO＝(O_{general assembly}/(E_{General assembly}+O_{General assembly}))

The total mole percentage of 1-octene comonomer incorporation was calculated from the mole fraction in a standard manner:

O[wt％]＝100*(fO*112.21)/((fO*112.21)+((1-fO)*28.05))

[1]Klimke,K.,Parkinson,M.,Piel,C.,Kaminsky,W.,Spiess,H.W.,Wilhelm,M.,Macromol.Chem.Phys.2006:207:382.

[2]Parkinson,M.,Klimke,K.,Spiess,H.W.,Wilhelm,M.,Macromol.Chem.Phys.2007；208:2l28.

[3]Castignolles,P.,Graf,R.,Parkinson,M.,Wilhelm,M.,Gaborieau,M.,Polymer 50(2009)2373

[4]NMR Spectroscopy of Polymers:Innovative Strategies for Complex Macromolecules,Chapter 24,401(2011)

[5]Pollard,M.,Klimke,K.,Graf,R.,Spiess,H.W.,Wilhelm,M.,Sperber,O.,Piel,C.,Kaminsky,W.,Macromolecules 2004；37:8l3.

[6]Filip,X.,Tripon,C.,Filip,C.,J.Mag.Resn.2005,176,239

[7]Griffin,J.M.,Tripon,C.,Samoson,A.,Filip,C.,and Brown,S.P.,Mag.Res.in Chem.200745,Sl,S198

[8]J.Randall,Macromol.Sci.,Rev.Macromol.Chem.Phys.1989,C29,201.

[9]Liu,W.,Rinaldi,P.,McIntosh,F.,Quirk,P.,Macromolecules 2001,34,4757

[10]Qiu,X.,Redwine,D.,Gobbi,G.,Nuamthanom,A.,Rinaldi,P.,Macromolecules 2007,40,6879

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

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

e) DSC analysis, melting temperature (Tm) and crystallization temperature (Tc):

measurements were made on 5 to 7mg samples using a TA instruments Q2000 Differential Scanning Calorimeter (DSC). The DSC was run according to ISO 11357/part 3/method C2 at a temperature of-30 ℃ to +225 ℃ in a heating/cooling/heating cycle and a scan rate of 10 ℃/min.

The crystallization temperature and heat of crystallization (Hc) are measured by the cooling step, while the melting temperature and heat of fusion are measured by the second heating step.

f) Intrinsic viscosity (iV)

Measured according to DIN ISO 1628/1 (10 months 1999) using decalin at 135 ℃.

g) BET surface area

BET surface area to DIN 66131/2 with nitrogen (N)₂) And (4) measuring.

h) Median particle diameter D₅₀(precipitation)

By particle size distribution [ wt.%]Calculating the median diameter D₅₀The particle size distribution was determined by gravity liquid sedimentation (sedimentation diagram) according to ISO 13317-3.

i) Flexural modulus

Dimensions of 80X 10X 4mm, produced by injection moulding according to EN ISO 1873-2, at a test speed of 2mm/min and a force of 100N, according to ISO 178³(length x width x thickness) of the test specimen, wherein the span length between loads is 64 mm.

j) Charpy notched impact strength

80X 10X 4mm prepared according to EN ISO 19069-2 at 23 ℃ and-20 ℃ according to ISO 179/1eA³Charpy notched impact strength was measured on injection molded test specimens.

k) Heat Distortion Temperature (HDT)

Heat distortion temperature B (HDT-B) was determined according to ISO75-2 at 0.45 MPa.

l) adhesion

According to DIN 55662 (method C), the adhesion is characterized by the resistance of the prefabricated scratch template to pressure water jets.

Using Zeller Gmelin1262 clean injection moulded sample plates (150 mm. times.80 mm. times.2 mm). Subsequently, the surface was activated by combustion, wherein the burner spread a mixture of propane (9l/min) and air (180l/min) in a ratio of 1:20 at a speed of 670mm/s on the polymer substrate. Thereafter, the polymeric substrate was coated with two layers, namely a base coat (Iridium Silver Metallic 117367) and a clear coat (Carbon)107062). The combustion step was performed twice. During time T, hot water vapor at temperature T is directed to travel a distance d at an angle α to the test plate surface. The water spray pressure depends on the water flow rate and is determined by the type of nozzle installed at the end of the water pipe.

The following parameters were used:

t (water) ═ 60 ℃; t is 60 s; d is 100mm, alpha is 90 deg., water flow rate is 11.3l/min, and the model of nozzle is MPEG 2506

Adhesion was evaluated by quantifying the area of coating that failed or peeled off for each test line. For each example, 5 plates (150mm x 80mm x 2mm) were tested. The panels were produced by injection moulding with a melting temperature of 240 ℃ and a mould temperature of 50 ℃. The flow front velocities were 100mm/s and 400mm/s, respectively. On each plate, a special pipe line is used in [ mm ]²]The coating performance failure was evaluated in units. For this purpose, images of the test points were taken before and after the steam jet exposure. The area of the peel was then calculated by image processing software. The mean area to failure (i.e., the average of 25 test points in total) of 5 test samples of 5 test lines is reported as the median area to failure.

SD is the standard deviation determined according to the following equation:

wherein the content of the first and second substances,

x is an observed value;

is the average of the observations; and

n is the number of observations.

m) shrinkage ratio

Radial Shrinkage (SH): the Shrinkage (SH) tangent was determined on a center gated (gate) injection molded disk (diameter 180mm, thickness 3mm, flow angle 355 DEG, cut angle 5 deg.). Two samples were molded using two different dwell times (10 s and 20s, respectively). The melt temperature at the gate was 260 ℃ and the average flow front velocity in the die was 100 mm/s. Tool temperature: 40 ℃, back pressure: 600 bar.

After the sample was left at room temperature for 96 hours, the dimensional changes in the radial and tangential directions of the two disks were measured. The average of the values of the two discs is reported as the final result.

2. Examples of the embodiments

a) Catalyst preparation

Ziegler-Natta catalyst for HECO polymerization

To prepare the catalyst, 3.4 liters of 2-ethylhexanol and 810mL of propylene glycol butyl monoether (mole ratio 4/1) were charged to a 20.0L reactor. Thereafter, 7.8 liters of a 20.0% BEM (butyl ethyl magnesium) solution in toluene, supplied by Cromption GmbH, were slowly added to the well-stirred alcohol mixture. During the addition, the temperature was maintained at 10.0 ℃. After the addition, the temperature of the reaction mixture was raised to 60.0 ℃ and stirring was continued at this temperature for 30 minutes. Finally, after cooling to room temperature, the alcoholic Mg is obtained, which is transferred to a storage container.

21.2g of the alcohol Mg prepared above was mixed with 4.0mL of bis (2-ethylhexyl) citrate for 5 minutes. Immediately after mixing, the Mg complex obtained is used in the preparation of the catalyst component.

19.5mL of titanium tetrachloride was added to a 300mL reactor equipped with a mechanical stirrer at 25.0 ℃. The stirring speed was adjusted to 170 rpm. 26.0 g of the Mg complex prepared above was added over 30 minutes, maintaining the temperature at 25.0 ℃. 3.0mL of1-254 and 1.0mL of toluene solution and 2mg of Necadd 447^TM. 24.0mL of heptane was then added to form an emulsion. Mixing was continued at 25.0 ℃ for 30 minutes after which the reactor temperature rose to 90.0 ℃ over 30 minutes. The reaction mixture was stirred at 90.0 ℃ for a further 30 minutes. After that, the stirring was stopped, and the reaction mixture was allowed to stand at 90.0 ℃ for 15 minutes. Wash the solid material 5 times: the washing was carried out at 80.0 ℃ for 30 minutes with stirring at 170 rpm. After the stirring was stopped, the reaction mixture was allowed to stand for 20 to 30 minutes, and then siphoned.

Washing 1: a mixture of 100mL of toluene and 1mL of donor was used for washing.

And (3) washing 2: using 30ml of TiCl₄And 1mL donor mixture.

And (3) washing: the washing was carried out using 100mL of toluene.

And (4) washing: washing was performed using 60mL heptane.

And (5) washing: washing was performed using 60mL heptane while stirring for 10 minutes.

After that, the stirring was stopped, the reaction mixture was allowed to stand for 10 minutes while the temperature was lowered to 70 ℃, followed by siphoning, and then passing through N₂Purge for 20 minutes to obtain an air sensitive powder.

Metallocene catalyst for polymerizing copolymers of propylene and 1-hexene

Synthesis of metallocene:

metallocene (rac-trans-dimethylsilanediyl [ 2-methyl-4-phenyl-5-methoxy-6-tert-butyl-indenyl ] [ 2-methyl-4- (4-tert-butylphenyl) indenyl ] zirconium dichloride was synthesized according to the teachings of WO 2013/007650.

The metallocene-containing catalyst was prepared according to catalyst 3 of WO2015/11135 using the metallocene and a catalyst system of MAO and triphenylmethyl tetrakis (pentafluorophenyl) borate, with the proviso that: the surfactant is 2,3,3, 3-tetrafluoro-2- (1,1,2,2,3,3, 3-heptafluoropropoxy) 1-propanol.

b) Polymerization of heterophasic propylene copolymer HECO

The heterophasic propylene copolymer HECO was produced in a pilot plant with a prepolymerization reactor, one slurry loop reactor and two gas phase reactors. The solid catalyst component as described above, Triethylaluminium (TEAL) as co-catalyst, dicyclopentyldimethoxysilane (D-donor) as external donor were used together in HECO.

The polymerization process conditions, the propylene polymer fractions and the properties of the polypropylene composition are shown in table 1.

Table 1: polymerization process conditions for heterophasic propylene copolymer HECO, propylene polymer fraction and properties of polypropylene composition

Split stream refers to the amount of propylene polymer in each particular reactor

c) Polymerization of random propylene/1-hexene copolymer (C3C6)

Two random propylene/1-hexene copolymers (C3C6-1) and (C3C6-2) with different 1-hexene contents were produced in a multistage process with a prepolymerization reactor followed by a slurry loop reactor and a gas phase reactor. The metallocene-containing catalyst prepared as described above was used as a catalyst.

The conditions of the polymerization process, the propylene polymer fractions and the characteristics of the random propylene/1-hexene copolymers (C3C6-1) and (C3C6-2) are shown in Table 2.

Table 2: conditions of the polymerization Process, characteristics of the propylene Polymer fraction and of the random propylene/1-hexene copolymers (C3C6-1) and (C3C6-2)

d) Other Components

The following components were also used to prepare the polypropylene-based compositions of the examples:

■ random propylene ethylene copolymer (C3C 2): ethylene comonomer Unit content 4.7 wt%, MFR₂About 2g/10min, commercially available from northern Europe chemical as RB801 CF. The copolymer was polymerized in the presence of a Ziegler Natta catalyst, having an XCS content of 8.5 wt.%, a Tm of 138 ℃ and a Tc of 96 ℃.

■ Low Density Polyethylene (LDPE): the density was 918kg/m³，MFR₂7.5g/10min, commercially available from northern Europe chemical company as MA 8200.

■ plastomer: is an ethylene/1-octene copolymer with a density of 882kg/m³，MFR₂(measured at 190 ℃) 1.1g/10min, commercially available as Queo8201 from North Europe chemical Co. The weight average molecular weight of the copolymer was 125kg/mol, the molecular weight distribution Mw/Mn was 2.5, Tm was 70 ℃ and Tc was 56 ℃.

■ Talc: median particle diameter of 1.2 μm and BET surface area of 14.5m²(iv)/g, commercially available as Jetfine 3CA from Imerys.

■ HC 001A: commercially available unimodal propylene homopolymer from northern Europe chemical company HC001A-B1, melt flow Rate MFR₂(230 ℃) was about 2g/10min, and Tm was 160 ℃.

■ carbon Black masterbatch (CB-MB): a "Plasblak PE 4103" carbon black masterbatch is commercially available from Cabot corporation (Germany).

■ Antioxidant (AO): is n-octadecyl 3- (3 ', 5' -di-tert-butyl-4-hydroxyphenyl) propionate (CAS number 2082-79-3), commercially available as Irganox 1076Fd from Pasteur (Germany).

e) Polypropylene composition

The polypropylene-based compositions were prepared by mixing in a co-rotating (co-rotating) twin-screw extruder from Coperion ZSK18 with a typical screw configuration and a melt temperature of 200 to 220 ℃. The melted strand (strand) was solidified in a water bath, followed by strand pelletization.

The composition and properties of the polypropylene-based composition are shown in Table 3.

Table 3: properties of Polypropylene composition

		IE1	IE2	CE1	CE2	CE3
							HECO	[wt％]	55.7	57.7	66.7	56.7	66.7
C3C6-2	[wt％]	8.0	-	-	-	-
							C3C6-1	[wt％]	-	8.0	-	-	-
C3C2	[wt％]	-	-	-	8.0	-
							LDPE	[wt％]	-	-	-	-	5.0
Plastic body	[wt％]	19.0	17.0	16.0	18.0	11.0
							Talc	[wt％]	15.0	15.0	15.0	15.0	15.0
HC001A-B1	[wt％]	1.45	1.45	1.45	1.45	1.45
							CB-MB	[wt％]	0.8	0.8	0.8	0.8	0.8
AO	[wt％]	0.05	0.05	0.05	0.05	0.05
							MFR₂	[g/10min]	7.9	8.0	9.2	8.2	8.8
Flexural modulus	[Mpa]	1707	1690	1898	1693	1864
							Charpy NIS, 23 deg.C	[kJ/m²]	70	67	61	70	51
Charpy NIS-20 deg.C	[kJ/m²]	7	7	7	7	6
							HDT B	[℃]	99	104	104	100	105
Radial shrinkage rate	[％]	0.72	0.76	0.79	0.73	0.83
							Failure of paint adhesion	[mm²]	29	37	39	34	90

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