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 F·贝格尔 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三元共聚物(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)40.0wt％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)5.0wt％至15.0wt％的三元共聚物,所述三元共聚物为丙烯与乙烯共聚单体单元和1-丁烯共聚单体单元的三元共聚物,所述三元共聚物由差示扫描量热法(DSC)测得的熔融温度Tm低于140℃；(C)5.0wt％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；以及(D)5.0wt％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 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 terpolymer of propylene with ethylene comonomer units and 1-butene comonomer units 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 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 terpolymer of propylene with ethylene comonomer units and 1-butene comonomer units 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; the amount of comonomer units is from 0.01 to 1.5 wt%, based on the total weight of the matrix phase of the heterophasic propylene copolymer (a).

4. The polypropylene-based composition according to any one of the preceding claims, wherein the melt flow rate MFR (190 ℃, 2.16kg) of the terpolymer (B) of propylene with ethylene comonomer units and 1-butene comonomer units is from 1.0g/10min to 50.0g/10 min.

5. The polypropylene-based composition according to any one of the preceding claims, wherein the terpolymer (B) of propylene with ethylene comonomer units and 1-butene comonomer units has a content of ethylene comonomer units of from 0.5 to 3.5 wt% and a content of 1-butene comonomer units of from 5.0 to 10.0 wt%, based on the total amount of the terpolymer (B) of propylene with ethylene comonomer units and 1-butene comonomer units.

6. The polypropylene-based composition according to any one of the preceding claims, wherein the amount of Xylene Cold Soluble (XCS) fraction in the terpolymer (B) of propylene with ethylene comonomer units and 1-butene comonomer units is from 3.0 wt% to 20.0 wt%, based on the total weight of the terpolymer (B) of propylene with ethylene comonomer units and 1-butene comonomer units.

7. The polypropylene-based composition according to any one of the preceding claims, wherein the terpolymer (B) of propylene with ethylene comonomer units and 1-butene comonomer units has a crystallization temperature Tc of from 90 ℃ to 120 ℃.

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 preferably 1-octene.

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 terpolymer of propylene with ethylene comonomer units and 1-butene comonomer units in a polypropylene based composition comprising:

(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 terpolymer of propylene with ethylene comonomer units and 1-butene comonomer units 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 terpolymer of propylene with ethylene and 1-butene, an article comprising said propylene based composition and the use of said terpolymer in said composition for reducing paint adhesion failure of said article.

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 a heterophasic polypropylene copolymer, a propylene homopolymer and a 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, it has been found that a polypropylene based composition shows 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; wherein the polypropylene-based composition comprises a heterophasic propylene copolymer, a terpolymer of propylene with ethylene comonomer units and 1-butene comonomer units, an ethylene copolymer and an inorganic filler in defined combinations.

Disclosure of Invention

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

(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 terpolymer of propylene with ethylene comonomer units and 1-butene comonomer units 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 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.

Still further, the present invention relates to the use of a terpolymer of propylene with ethylene comonomer units and 1-butene comonomer units in a polypropylene based composition comprising:

(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 terpolymer of propylene with ethylene comonomer units and 1-butene comonomer units 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 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.

Accordingly, the polypropylene-based composition preferably comprises a polypropylene-based composition as described above or below.

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

Definition of

Terpolymers of propylene are polymers having a majority by weight of propylene monomer units and two different comonomer units. In the present case, the two different comonomer units are an ethylene comonomer unit and a 1-butene comonomer unit. The comonomer units may be in the form of blocks or randomly distributed in the polymer chain.

Propylene random terpolymers are a particular form of propylene random copolymer in which two different comonomer units, such as ethylene comonomer units and 1-butene comonomer units, are randomly distributed along the polypropylene chain.

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) a terpolymer of propylene with ethylene comonomer units and 1-butene comonomer units;

(C) an ethylene copolymer having C₄-C₁₂Alpha-olefin comonomer units; and

(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 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) may 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 the case of two polymerization reactors in series 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) Of group 2 metal alkoxides (Ax) and group 2 metal alkoxides (Bx)A mixture 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) 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 C₂-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) is used, respectively, wherein 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 as described above and a magnesium compound selected from the group consisting of bisAlkyl magnesium, alkyl magnesium alkoxides (alkyl magnesium alkoxides), magnesium dialkoxides (magnesium alkoxides), alkoxy magnesium halides, and alkyl magnesium halides. Further, magnesium alkoxides, magnesium diaryloxides, aryloxymagnesium halides, magnesium aryloxides, and magnesium alkylaryloxides may be used. The alkyl groups in the magnesium compound may be 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 C₂-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.

Transition of groups 4 to 6 as defined by IUPAC (version 2013)The Metal (TM) compound 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 C₁₂-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 combining aromatic hydrocarbonThe aromatic hydrocarbon and/or aliphatic hydrocarbon is washed. 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.

Terpolymer of propylene with ethylene comonomer units and 1-butene comonomer units (B)

The terpolymer (B) of propylene with ethylene comonomer units and 1-butene comonomer units, hereinafter referred to as "terpolymer (B)", comprises, preferably consists of, propylene monomer units, ethylene comonomer units and 1-butene comonomer units.

The terpolymer (B) may comprise further comonomer units selected from C₅-C₁₂Alpha-olefins, preferably selected from 1-hexene and 1-octene.

Preferably, however, the terpolymer (B) consists of propylene monomer units, ethylene comonomer units and 1-butene comonomer units.

Preferably, the comonomer units are randomly distributed in the polymer chain, so that the terpolymer (B) is preferably a terpolymer of propylene with ethylene comonomer units and 1-butene comonomer units.

Preferably, the ethylene content of the terpolymer (B) is from 0.5 to 3.5 wt%, more preferably from 1.0 to 3.0 wt%, even more preferably from 1.2 to 2.8 wt%, even more preferably from 1.3 to 2.7 wt%.

Further preferably, the 1-butene content of the terpolymer (B) is from 5.0 wt% to 10.0 wt%, more preferably from 5.5 wt% to 9.5 wt%, even more preferably from 6.0 wt% to 9.0 wt%, even more preferably from 6.5 wt% to 8.5 wt%.

Preferably, the propylene (C3) content of the terpolymer (B) is rather high, i.e. more than 86.5 wt%, preferably more than 87.0 wt%, more preferably more than 88.0 wt%, e.g. more than 90.0 wt%.

Preferably, the terpolymer (B) has a melt flow rate MFR determined according to ISO1133₂(230 ℃) of 1.0 to 50.0g/10min, preferably 1.2 to 40.0g/10min, more preferably 1.4 to 30.0g/10min, further more preferably 1.5 to 20.0g/10 min.

Further, the terpolymer (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 not more than 20.0 wt. -%, more preferably not more than 15.0 wt. -%.

Thus, it is especially understood that the xylene cold soluble content of the terpolymer (B) is from 3.0 to 20.0 wt. -%, more preferably from 5.0 to 15.0 wt. -%, most preferably from 7.0 to 12.0 wt. -%.

Further, the terpolymer (B) may be defined by the melting temperature (Tm) measured by DSC according to ISO 11357. Thus, the melting temperature Tm of the propylene polymer is below 140 ℃. Even more preferably, the melting temperature Tm is from 120 ℃ to 138 ℃, more preferably from 124 ℃ to 136 ℃.

The terpolymer (B) should have a crystallization temperature, measured by DSC according to ISO11357, equal to or higher than 90 ℃, preferably from 90 ℃ to 120 ℃, even more preferably from 95 ℃ to 115 ℃.

The terpolymer (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 terpolymer (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 terpolymer (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 terpolymer (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 terpolymer (B) is preferably produced in the presence of a Ziegler Natta catalyst system.

The terpolymer (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 propylene polymer (B) is produced in at least two polymerization reactors, it is possible:

i) producing a propylene homopolymer in the first reactor and a propylene terpolymer in the second reactor to obtain terpolymer (B); or

ii) producing a propylene-ethylene copolymer in the first reactor and a propylene-1-butene copolymer in the second reactor to obtain a terpolymer (B); or

iii) producing a propylene-1-butene copolymer in the first reactor and a propylene-ethylene copolymer in the second reactor to obtain a terpolymer (B); or

iv) producing a propylene terpolymer in the first reactor and producing a propylene terpolymer in the second reactor to obtain terpolymer (B).

Suitable polymerization processes for producing the propylene polymer (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 terpolymer (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. By bulk is meant 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.

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

Preferably, the terpolymer (B) is polymerized in the presence of a ziegler natta catalyst system.

If the propylene polymer is produced in a sequential polymerization process, the Ziegler Natta catalyst is added to the first (respectively single) polymerization reactor and is optionally transferred to the subsequent reactor together with the polymer (slurry) obtained in the first polymerization reactor.

If the process also comprises a prepolymerization step, it is preferred to add all the Ziegler Natta catalyst to the prepolymerization reactor. Subsequently, the prepolymerization product comprising the Ziegler-Natta catalyst is transferred to the first (respectively single) polymerization reactor.

Preferably, the ziegler-natta catalyst comprises a high yield ziegler-natta type catalyst with an internal donor component, which can be used at high polymerization temperatures above 80 ℃.

Such high yield ziegler natta catalysts may comprise succinates, diethers, phthalates etc. or mixtures thereof as Internal Donors (ID), e.g. commercially available under the trade name Avant ZN e.g. from LyondellBasell.

Further, useful solid catalysts are disclosed in WO-A-2003/000757, WO-A-2003/000754, WO-A-2004/029112 and WO 2007/137853. These catalysts are solid catalysts of spherical particles with a compact structure and low particle surface area. Further, these catalysts are characterized by a homogeneous distribution of catalytically active sites in the catalyst particles. The catalyst is prepared by an emulsion-cure process, wherein no external carrier is required. The dispersed phase in the form of droplets in the emulsion forms the catalyst portion, which is converted to solid catalyst particles during the solidification step.

Thus, in one embodiment of the invention, the solid catalyst component is prepared by a process comprising:

by reacting a magnesium alkoxide compound with an electron donor or its precursor at C₆-C₁₀To prepare a solution of the magnesium complex;

-reacting said magnesium complex with a tetravalent titanium compound (preferably TiCl)₄) Reacting at a temperature of more than 10 ℃ and less than 50 ℃ to prepare a thick emulsion, wherein the molar ratio of Ti/Mg in a dispersion phase is 0.1 to 10, and the molar ratio of Ti/Mg in a continuous phase is 10 to 100; and

-optionally agitating the emulsion in the presence of an emulsion stabilizer and/or a turbulence minimizing agent to maintain the average size of the droplets in the dispersed phase between 5 and 200 μm.

After solidifying the droplets in the dispersed phase by heating, preferably at 80 to 110 ℃, catalyst particles are obtained. In the process, an alkylaluminum compound of formula AlR3-nXn, wherein R is an alkyl and/or alkoxy group of 1 to 20, preferably 1 to 10 carbon atoms, X is a halogen and n is 0, 1 or 2, is added and brought into contact with the droplets in the dispersed phase of the stirred emulsion. Alternatively, an alkylaluminum compound of the formula AlR3-nXn is contacted with the solidified particles in a washing step before recovering the final solid particles.

Among these, suitable internal donor aromatic (di) carboxylic acid (di) esters. The aromatic carboxylic acid ester or aromatic carboxylic acid diester may be formed in situ by reacting an aromatic carboxylic acid chloride or aromatic carboxylic acid dichloride with a C2-C16 alkanol and/or diol, preferably di-2-ethylhexyl phthalate.

Other suitable catalysts of the invention are solid ziegler natta catalysts comprising a compound of an IUPAC group 4 to 6 transition metal (e.g. titanium), a group 2 metal (e.g. magnesium) compound and an internal donor which is a non-phthalic acid compound, more preferably a non-phthalic acid ester, even more preferably a non-phthalic acid diester as detailed below. Further, the solid catalyst does not contain any external supporting material (e.g. silica or MgCl)₂) But the catalyst is self-supporting.

The ziegler natta catalysts may be further defined by the way in which they are obtained.

Thus, the Ziegler Natta catalyst is preferably obtained by a process comprising the following steps:

a)

a₁) Providing a solution of at least one group 2 metal alkoxide (Ax), said group 2 metal alkoxide (Ax) being 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) Providing a solution of at least one group 2 metal alkoxide (Ax '), said group 2 metal alkoxide (Ax') being 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) Providing a solution of a mixture of a group 2 alkoxide (Ax) and a group 2 metal alkoxide (Bx), said mixture being the reaction product of a group 2 metal compound and a monohydric alcohol (B), optionally in an organic liquid phase reaction medium; or

a₄) Providing a compound of formula M (OR)₁)_n(OR₂)_mX_2-n-mOR a group 2 alkoxide M (OR)₁)_n’X_2-n’And M (OR)₂)_m’X_2-m’Wherein M is 2 ndGroup metal, X is halogen, R₁And R₂Is a different alkyl group 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 both not equal to 0, 0<n’<2 and 0<m’<2; and

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

c) obtaining particles of the solid catalyst component;

in any step prior to step c), a non-phthalic internal donor is added.

Preferably, an internal donor or a precursor thereof is added to the solution of step a).

According to the above steps, the Ziegler-Natta catalyst (ZN-C) can be obtained by precipitation or by emulsion (liquid/liquid two-phase system) -solidification, depending on the physical conditions, in particular the temperatures used in step b) and step C).

In both processes (precipitation and emulsion-solidification), the catalyst chemistry is the same.

In the precipitation process, the solution in step a) is mixed with the at least one transition metal compound in step b), and the entire reaction mixture is maintained at a temperature of at least 50 ℃, more preferably from 55 to 110 ℃, more preferably from 70 to 100 ℃, to ensure complete precipitation of the catalyst component in the form of solid 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 from-10 to less than 40 ℃ and preferably from-5 to 30 ℃. The droplets of the dispersed phase in the emulsion form the active catalyst component. The droplets are suitably solidified 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 a preferred embodiment, in step a), a is used₂) Or a₃) I.e. (Ax') solution or a mixture of (Ax) and (Bx)Compound solution.

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 the magnesium compound with an alcohol as described above, or they may be separately prepared magnesium alkoxide compounds, or they may be even commercially available ready-to-use magnesium alkoxide compounds and used directly in the catalyst preparation process of the present invention.

An illustrative example of alcohol (a) is a monoether of a glycol (ethylene glycol monoalkyl ether). Preferably, the alcohol (A) is C₂-C₄Ethylene glycol monoalkyl ethers wherein the ether moiety comprises from 2 to 18 carbon atoms, preferably from 4 to 13 carbon atoms. Preferred examples are 2- (2-ethylhexyloxy) ethanol, 2-butoxyethanol, 2-hexyloxyethanol and 1, 3-propanediol monobutyl ether, 3-butoxy-2-propanol, with 2- (2-ethylhexyloxy) ethanol, 1, 3-propanediol monobutyl ether, 3-butoxy-2-propanol being particularly preferred.

Illustrative monoalcohols (B) have the formula ROH, wherein R is a straight or branched chain C₆-C₁₀An alkyl residue of (2). Most preferably, the monohydric alcohol is 2-ethyl-1-hexanol or octanol.

Preferably, a mixture of magnesium alkoxide compounds (Ax) and (Bx) or a mixture of alcohols (a) and (B), respectively, is used, wherein Bx: ax or B: the molar ratio of a is from 8:1 to 2:1, more preferably from 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 alkoxide, glycol alcohol, alkoxy magnesium halide, and alkyl magnesium halide) as described above. The alkyl groups may be similar or different C₁-C₂₀Alkyl, preferably C₂-C₁₀An alkyl group. Typically, when an alkyl magnesium alkoxide compound is used, the alkyl magnesium alkoxide compound is magnesium ethylbutoxide, magnesium butylpentanoate, magnesium octylbutoxide, and magnesium octyloctoxide. 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 the alcohol (A) and the alcohol (B)To and having the formula R' (OH)_mThe polyol (C) to obtain the alkoxymagnesium compound. If a polyol is used, the preferred polyols are the following alcohols: wherein R' is a linear, cyclic or branched C₂-C₁₀And m is an integer of 2 to 6.

Thus, the magnesium alkoxide compound of step a) is selected from: magnesium dialkoxides, diaryloxy magnesium, alkoxy magnesium halides, aryloxy magnesium halides, alkyl magnesium alkoxides, aryl magnesium alkoxides, and alkyl magnesium aryl oxides. In addition, mixtures of magnesium dihalides and magnesium diols can also be used.

The solvent used to prepare the catalyst of the invention may be selected from: aromatic and aliphatic straight, 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.

Typically, the magnesium compound is provided as a 10 to 50 wt% solution in the above solvent. Typical commercially available magnesium compounds, especially solutions of dialkylmagnesium, are 20 to 40 wt% solutions in toluene or heptane.

The reaction for preparing the magnesium alkoxide compound may be carried out at a temperature of 40 to 70 ℃. The most suitable temperature is selected according to the magnesium compound and the alcohol used.

The transition metal of groups 4 to 6 is preferably a titanium compound, most preferably a titanium halide, e.g. TiCl₄。

The non-phthalic internal donor useful in the preparation of the catalyst is preferably selected from non-phthalic diesters, 1, 3-diethers and their derivatives and mixtures. Particularly preferred donors are diesters of monounsaturated 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, and any derivatives and/or mixtures thereof. Preferred examples are, for example, substituted maleates and citraconates, most preferably citraconate.

In the emulsion method, the liquid-liquid two-phase system can be realized by simple processStirring and optionally adding (other) solvents and additives to form, for example, Turbulence Minimizing Agents (TMA) and/or emulsifiers and/or emulsion stabilizers, such as surfactants, which are used in a manner known in the art to facilitate the formation of and/or stabilize the emulsion. Preferably, the surfactant is an acrylic polymer or a methacrylic polymer. Particularly preferred is unbranched C₁₂-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 alpha-olefin polymers of alpha-olefin monomers of 6 to 20 carbon atoms, such as polyoctenamer, polynonanene, polydecene, polyundecene, or polydodecene, or mixtures thereof. Most preferred is polydecene.

The solid particulate product obtained by the precipitation or emulsion-solidification process can be washed at least once, preferably at least twice, most preferably at least three times with aromatic and/or aliphatic hydrocarbons, preferably toluene, heptane or pentane. The catalyst may be further dried, for example by evaporation or nitrogen purge, or it may be slurried into an oily liquid without any drying step.

Desirably, the Ziegler-Natta catalyst is 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. Compact particles, low porosity and surface area of less than 20g/m²More preferably less than 10g/m². Typically, the catalyst composition has a Ti content of 1 to 6 wt%, a magnesium content of 10 to 20 wt%, and a donor content of 10 to 40 wt%.

Details of the preparation of the catalysts are disclosed in WO 2012/007430, EP 2415790, EP 2610270, EP 2610271 and EP 2610272.

The ziegler natta catalyst is optionally modified during the prepolymerization step by the so-called BNT technique to introduce a polymeric nucleating agent.

Preferably, such polymeric nucleating agents are vinyl polymers, for example vinyl polymers derived from monomers of the formula:

CH₂＝CH-CHR₁R₂

wherein R is₁And R₂Together with the carbon atoms to which they are attached form an optionally substituted saturated or unsaturated or aromatic or fused ring system, wherein the ring or fused ring portion comprises 4 to 20 carbon atoms, preferably 5 to 12 membered saturated or unsaturated or aromatic or fused ring system, or independently represents straight or branched C₄-C₃₀Alkane, C₄-C₂₀Cycloalkanes or C₄-C₂₀An aromatic ring. Preferably, R₁And R₂Together with the C atom to which they are attached form a five-or six-membered saturated or unsaturated or aromatic ring, or independently represent a lower alkyl group containing 1 to 4 carbon atoms. In particular, the preferred vinyl compounds for preparing the polymeric nucleating agents used in the present invention are vinylcycloalkanes, in particular Vinylcyclohexane (VCH), vinylcyclopentane and vinyl-2-methylcyclohexane, 3-methyl-1-butene, 3-ethyl-1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene or mixtures thereof. VCH is a particularly preferred monomer.

In the modification step of the polymerization catalyst, the weight ratio of the vinyl compound to the polymerization catalyst is preferably 0.3 or more and 40 (e.g., 0.4 to 20) or more preferably 0.5 to 15 (e.g., 0.5 to 2.0).

The polymerization of the vinyl compound (e.g., VCH) can be carried out in any inert fluid that does not dissolve the polymer formed (e.g., poly VCH). It is important to ensure that the viscosity of the final catalyst/polymeric vinyl compound/inert fluid mixture is sufficiently high to prevent settling of the catalyst particles during storage and transport.

The adjustment of the viscosity of the mixture can be carried out before or after the polymerization of the vinyl compound. For example, the polymerization can be carried out in a low-viscosity oil, and after the polymerization of the vinyl compound, the viscosity can be adjusted by adding a high-viscosity substance. Such highly viscous substances may be "waxes", such as oils or mixtures of oils with solids or highly viscous substances (oil-grease). The viscosity of such viscous substances is usually 1,000cP to 15,000cP at room temperature. The advantage of using wax is improved catalyst storage and feeding. The catalyst activity is maintained since no washing, drying, sieving and transferring are required.

The weight ratio of oil to solid or highly viscous polymer is preferably less than 5: 1.

in addition to viscous substances, liquid hydrocarbons, such as isobutane, propane, pentane and hexane, can also be used as medium in the modification step.

The polypropylene produced with the polymerized vinyl compound-modified catalyst is substantially free of free (unreacted) vinyl compounds. This means that the vinyl compound should be completely reacted in the catalyst modification step. For this purpose, the weight ratio of the (added) vinyl compound to the catalyst should be from 0.05 to 10.0, preferably less than 3.0, more preferably from about 0.1 to 2.0, in particular from about 0.1 to 1.5. It should be noted that no benefit is obtained by using an excess of vinyl compound.

Furthermore, the reaction time of the catalyst modification by polymerization of the vinyl compound should be sufficient to allow complete reaction of the vinyl monomer, i.e. to continue the polymerization until the amount of unreacted vinyl compound in the reaction mixture (comprising polymerization medium and reactants) is less than 0.5% by weight, in particular less than 2000ppm by weight (shown by analysis). Thus, when the prepolymerized catalyst contains up to about 0.1 wt% vinyl compound, the final vinyl compound content in the polypropylene will be below the limit measured using the GCMS method (< 0.01ppm by weight). Generally, when operating on an industrial scale, a polymerization time of at least 30 minutes is required, preferably a polymerization time of at least 1 hour, in particular at least 5 hours. Even polymerization times of 6 to 50 hours can be used. The modification can be carried out at a temperature of from 10 ℃ to 60 ℃, preferably from 15 ℃ to 55 ℃.

General conditions for catalyst modification are also disclosed in WO 00/6831, the contents of which are incorporated herein by reference with respect to polymerization catalyst modification.

The preferred embodiments described earlier in this application with respect to the vinyl compound also apply to the polymerization catalyst of the present invention and to the preferred polypropylene composition according to the present invention.

Suitable media for the modification step include, in addition to oils, inert aliphatic organic solvents of low viscosity, such as pentane and heptane. In addition, small amounts of hydrogen may be used in the modification process.

Preferably, the Ziegler-Natta catalyst is used in combination with an aluminum alkyl co-catalyst and optionally an external donor.

Preferably, an external donor is present as a further component in the present polymerization process. Suitable external donors include: certain silanes, ethers, esters, amines, ketones, heterocyclic compounds, and blends thereof. The use of silanes is particularly preferred. Most preferably, silanes of the general formula:

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

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 equal to or less than 3. R^a、R^bAnd R^cMay be selected independently of each other and may be the same or different. A specific example of such a silane is (tert-butyl)₂Si(OCH₃)₂(cyclohexyl) (methyl) Si (OCH)₃)₂, (phenyl)₂Si(OCH₃)₂And (cyclopentyl)₂Si(OCH₃)₂Or a silane having the general formula:

Si(OCH₂CH₃)₃(NR³R⁴)

wherein R is³And R⁴May be the same or different and represents a hydrocarbon group having 1 to 12 carbon atoms.

R³And R⁴Independently selected from: a straight chain aliphatic hydrocarbon group having 1 to 12 carbon atoms, a branched chain aliphatic hydrocarbon group having 1 to 12 carbon atoms and a cyclic aliphatic hydrocarbon group having 1 to 12 carbon atoms. Particularly preferably, R³And R⁴Independently selected from: methyl, ethyl, n-propyl, n-butyl, octyl, decyl, isopropyl, isobutyl, isopentyl, tert-butyl, tert-pentyl, neopentyl, cyclopentyl, cyclohexyl, methylcyclopentyl and cycloheptyl.

More preferably, R³And R⁴Same, even more preferably, R³And R⁴Are all ethyl groups.

Particularly preferred external donors are dicyclopentyldimethoxysilane donors (D-donors) or cyclohexylmethyldimethoxysilane donors (C-donors).

In addition to the ziegler natta catalyst and optional external donor, a co-catalyst may be used. Preferably, the cocatalyst is a compound of group 13 of the periodic table (IUPAC), such as an organoaluminium, for example an aluminium compound (e.g. an aluminium alkyl, aluminium halide or aluminium alkyl halide compound). Thus, in one embodiment, the cocatalyst is a trialkylaluminum, such as Triethylaluminum (TEAL), dialkylaluminum chloride or alkylaluminum dichloride or mixtures thereof. In one embodiment, the cocatalyst is Triethylaluminum (TEAL).

Preferably, the ratio of promoter (Co) to External Donor (ED) [ Co/ED ] and/or the ratio of promoter (Co) to Transition Metal (TM) [ Co/TM ] should be carefully selected.

Therefore, the temperature of the molten metal is controlled,

(a) the molar ratio of cocatalyst (Co) to External Donor (ED) [ Co/ED ] must be from 5.0 to 45.0, preferably from 5.0 to 35.0, more preferably from 5.0 to 25.0; and optionally

(b) The molar ratio [ Co/TC ] of the cocatalyst (Co) to the Titanium Compound (TC) must be higher than 80.0 to 500.0, preferably 100.0 to 350.0, even more preferably 120.0 to 300.0.

Preferably, therefore, the propylene copolymers used according to the invention are prepared in the presence of:

(a) a ziegler natta catalyst comprising an internal donor;

(b) an optional promoter (Co); and

(c) an optional External Donor (ED).

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 60.0 to 90.0 wt%, preferably from 65.0 to 85.0 wt%, more preferably from 67.0 to 82.0 wt%, for example from 70.0 to 80.0 wt%.

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., available under the trade name Queo is commercially available from northern Europe chemical company, from DOW under the trade name Engage or Affinity, or from Mitsui under the trade name Tafiner.

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 terpolymer (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 no more than 5 wt%, preferably no more than 3 wt%, more preferably no more than 1.5 wt% of other polymers than the heterophasic propylene copolymer (a), terpolymer (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) 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 wt% 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 to 12.0 wt%, more preferably 6.5 to 10.0 wt% of a terpolymer of propylene with ethylene comonomer units and 1-butene comonomer units having a melting temperature Tm of less than 140 ℃ as measured by Differential Scanning Calorimetry (DSC);

(C)5.0 to 25.0 wt%, preferably 7.0 to 22.0 wt%, more preferably 9.0 to 21.0 wt%, most preferably 10.0 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 to 23 wt%, more preferably 10.0 to 21.0 wt%, most preferably 12.0 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. 7.0 to 14.0g/10 min.

The flexural modulus of the polypropylene-based composition is preferably 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 ℃²More 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 coated article.

Preferably, the automotive article (i.e. the exterior automotive article) comprises, even more preferably consists of, 80.0 wt% or more, more preferably 90.0 wt% or more, even more preferably 95.0 wt% or more, even more preferably 99.0 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 50mm²More preferably 12.0mm²To 35.0mm²More preferably 13.0mm²To 32.0mm²Most preferably 15.0mm²To 30.0mm²。

As will be seen from the examples section below, the presence of the terpolymer (B) of propylene with ethylene comonomer units and 1-butene comonomer units in a polypropylene-based composition reduces the coating adhesion failure of the article.

Accordingly, the present invention further relates to the use of a terpolymer of propylene with ethylene comonomer units and 1-butene comonomer units in a polypropylene based composition comprising:

(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 terpolymer of propylene with ethylene comonomer units and 1-butene comonomer units having a melting temperature Tm, as measured by Differential Scanning Calorimetry (DSC), below 140 ℃;

(C)5.0 to 25.0 wt.%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.

Accordingly, the polypropylene-based composition and the terpolymer of propylene with ethylene comonomer units and 1-butene comonomer units preferably comprise the polypropylene-based composition and the terpolymer (B) of propylene with ethylene comonomer units and 1-butene comonomer units as defined below or above.

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, quantitative determination of the state of the solution was recorded at 400.15 and 100.62MHz, respectively, using a Bruker Advance III 400 NMR spectrometer¹³C{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 whole spectral region of spectrumThe multiple signals of the domains are integrated to quantify the comonomer fraction. 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))

reference documents:

1)Busico,V.,Cipullo,R.,Prog.Polym.Sci.26(2001)443.

2)Busico,V.,Cipullo,R.,Monaco,G.,Vacatello,M.,Segre,A.L.,Macromolecules 30(1997)6251.

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

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

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

6)Wang,W-J.,Zhu,S.,Macromolecules 33(2000),1157.

7)Cheng,H.N.,Macromolecules 17(1984),1950.

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

9)Kakugo,M.,Naito,Y.,Mizunuma,K.,Miyatake,T.Macromolecules 15(1982)1150.

10)Randall,J.Macromol.Sci.,Rev.Macromol.Chem.Phys.1989,C29,201.

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

comonomer content of poly (propylene-co-ethylene-co-butylene)

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. Approximately 200mg of material was loaded into a 7mm outer diameter zirconia MAS rotor, rotating at 4.5 kHz. This setting was chosen primarily for the high sensitivity 1,2,6 required for fast identification and accurate quantification. NOEs with short cycle delays, standard single-pulse excitation 3,1 and RS-HEPT decoupling schemes 4,5 are used. A total of 1024(1k) transient signals were collected for each 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).

No signature 11 corresponding to a regional defect was observed. The amount of propylene was quantified based on the predominant S.alpha.methylene sites at 44.1 ppm.

P is total ═ I_Sαα

A characteristic signal corresponding to the incorporated 1-butene was observed, the comonomer content being quantified in the following manner. The amount of 1-butene incorporated in the PPBPP sequence was quantified using the integral of α B2 sites at 44.1ppm over the number of reporter sites per comonomer:

B＝I_αB2/2

the amount of 1-butene continuously incorporated in the PPBBPP sequence was quantified using the integral of α α B2 sites at 40.5ppm over the number of reporter sites per comonomer:

BB＝2*I_ααB2

the total 1-butene content was calculated based on the sum of the separated 1-butene and the continuously incorporated 1-butene:

total of B is B + BB

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

fB ═ B total/(E total + P total + B total)

A characteristic signal corresponding to the ethylene incorporation was observed, and the comonomer content was quantified in the following manner. The amount of isolated ethylene incorporated in the PPEPP sequence was quantified using the ratio of the integral of S α γ sites at 37.9ppm to the number of reporter sites per comonomer:

E＝ISαγ/2

no sites indicating continuous incorporation were observed, and the total ethylene comonomer content was calculated only from this quantity:

e Total ═ E

The total mole fraction of ethylene in the polymer was then calculated:

fE ═ E (E total/(E total + P total + B total)

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

B[mol％]＝100*fB

E[mol％]＝100*fE

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

B[wt％]＝100*(fB*56.11)/((fE*28.05)+(fB*56.11)+((1-(fE+fB))*42.08))

E[wt％]＝100*(fE*28.05)/((fE*28.05)+(fB*56.11)+((1-(fE+fB))*42.08))

reference documents:

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；208:2128.

3)Pollard,M.,Klimke,K.,Graf,R.,Spiess,H.W.,Wilhelm,M.,Sperber,O.,Piel,C.,Kaminsky,W.,Macromolecules 2004；37:813.

4)Filip,X.,Tripon,C.,Filip,C.,J.Mag.Resn.2005,176,239.

5)Griffin,J.M.,Tripon,C.,Samoson,A.,Filip,C.,and Brown,S.P.,Mag.Res.in Chem.2007 45,S1,S198.

6)Castignolles,P.,Graf,R.,Parkinson,M.,Wilhelm,M.,Gaborieau,M.,Polymer50(2009)2373.

7)Busico,V.,Cipullo,R.,Prog.Polym.Sci.26(2001)443.

8)Busico,V.,Cipullo,R.,Monaco,G.,Vacatello,M.,Segre,A.L.,Macromoleucles 30(1997)6251.

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

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

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

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.

Automated program with customized spectral analysisFor quantitative determination¹³C{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 1-octene incorporation isolated. The integrals were assigned to the unresolved signals corresponding to the B6 and B6B6 sites of the isolated (EEOEE) and isolated double-discontinuous (EEOEE) 1-octene sequences, respectively. To compensate for the effect of the two abb 6B6 sites, the integral of the 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 reporting sites per comonomer:

OO＝2*I_ααB6B6

characteristic signals resulting from isolated non-continuous 1-octene incorporation (i.e., eeoeoeoe comonomer sequence) were 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 integral of the two resolved signals at 22.84ppm and 32.23ppm was used to quantify this saturated radical. 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) were measured from the cooling step, while the melting temperature and heat of fusion (Hf) were measured from 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. At the time ofWithin T, hot water vapor at temperature T is guided a distance d to move 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

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 as above was mixed with 4.0mL of bis (2-ethylhexyl) citraconate 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 ℃ 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 30mLTiCl₄And 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.

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 means the amount of propylene polymer in each specific reactor

c) Polymerization of random propylene/ethylene/1-butene terpolymer (C3C2C4)

Random propylene/ethylene/1-butene terpolymers (C3C2C4) are produced in a loop process (known as the classical Spheripol process with a prepolymerization reactor and a slurry loop reactor). Avant ZN180M, a catalyst commercially available from Lyondell Basell, was used as catalyst and cyclohexylmethyldimethoxysilane (C-donor) as donor.

The polymerization process conditions, the properties of the propylene polymer fraction and the properties of the polypropylene composition are shown in table 2.

Table 2: polymerization Process conditions, Properties of the propylene Polymer fraction and Properties of the random propylene/ethylene/1-butene terpolymer (C3C2C4)

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 XCS content of the copolymer was 8.5 wt%, Tm was 138 ℃ and Tc was 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 72 ℃ 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 001: a 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-based composition