KR101473075B1 - Propylene/1-hexene copolymer composition with low sealing temperature - Google Patents

Abstract

The present invention relates to a propylene copolymer composition (P) comprising:
(a) a propylene copolymer (A) having a comonomer content of at least 1.0 wt.%, wherein said comonomer is a C ₅ to C ₁₂ alpha-olefin, and
(b) 4.0 to 20.0 propylene copolymer having a comonomer content in weight% (B) (wherein the comonomer is C ₅ to C ₁₂ α- olefin Lim),
Also,
(i) the comonomer content in the propylene copolymer (A) is lower than the comonomer content in the propylene copolymer (B)
(ii) the propylene copolymer composition (P) has a comonomer content of 2.0 to 10.0 wt.% or more, said comonomer being a C ₅ to C ₁₂ alpha-olefin,
(iii) the weight ratio of propylene copolymer (A) to propylene copolymer (B) is in the range of 30/70 to 80/20.

Description

PROPYLENE / 1-HEXENE COPOLYMER COMPOSITION WITH LOW SEALING TEMPERATURE < RTI ID = 0.0 >

The present invention relates to novel propylene copolymer compositions, their preparation and their use.

Polypropylene is suitable for many applications. For example, polypropylene is applicable in areas where sealing properties play an important role, such as the food packaging industry. Regardless of the polymer type, the polymer should meet all desired desired properties to the greatest extent and additionally be easily processable (i. E., Must withstand stress). However, target and processing characteristics often work in a conflicting manner.

In many cases, the seal formed between the surfaces to be sealed is still in a warm state while under load. This means that the high temperature cohesive properties of polypropylene are crucial to ensure that a strong seal is formed even before cooling. However, not only the high-temperature adhesive strength should be somewhat high but also the heat seal initiation temperature should be somewhat low. By operating at low temperatures, there is an advantage that the article to be sealed is not exposed to high temperatures. Of course, there is also an economic advantage because lower temperatures are cheaper to generate and maintain.

In addition to the sealing properties in the food industry, small amounts of extracts are also needed.

In addition, the impact resistance performance of polymers must meet the needs of the food packaging industry.

Accordingly, an object of the present invention is to provide a polypropylene composition having a high high-temperature cohesive strength, a low heat seal initiation temperature (SIT) and a good impact resistance performance.

The discovery of the present invention is to provide a propylene copolymer composition having a somewhat higher comonomer content, wherein said comonomer is a long chain alpha-olefin, said propylene copolymer composition comprising two different parts, It differs in content.

Accordingly, the present invention relates to a propylene copolymer composition (P) comprising:

(a) a propylene copolymer (A) having a comonomer content of at least 1.0 wt.%, wherein said comonomer is a C ₅ to C ₁₂ alpha-olefin, and

(b) 4.0 to 20.0 propylene copolymer having a comonomer content in weight% (B) (wherein the comonomer is C ₅ to C ₁₂ α- olefin Lim),

Also,

(i) the comonomer content in the propylene copolymer (A) is lower than the comonomer content in the propylene copolymer (B)

(ii) the propylene copolymer composition (P) has a comonomer content of at least 2.0 wt.%, the comonomer is a C ₅ to C ₁₂ alpha-olefin,

(iii) the weight ratio of the propylene copolymer (A) to the propylene copolymer (B) is in the range of 20/80 to 80/20, preferably 25/75 to 75/25, more preferably 30/70 70/30.

Preferably, the propylene copolymer composition (P) contains the propylene copolymer (A) and the propylene copolymer (B) as the only polymer component.

Surprisingly, it has been found that such propylene copolymer composition (P) has a low heat seal initiation temperature (SIT) and excellent impact resistance properties (see the following examples).

The present invention will be described in more detail below.

The propylene copolymer composition (P) according to the invention is characterized by a somewhat higher comonomer content. A somewhat higher comonomer content is achieved due to the fact that the propylene copolymer composition (P) of the present invention comprises two parts of a propylene copolymer as defined herein. A "comonomer" according to the present invention is a polymerizable monomer unit different from propylene. Accordingly, the propylene copolymer composition (P) according to the present invention preferably contains not less than 2.0 wt%, more preferably not less than 2.4 wt%, more preferably not less than 3.0 wt%, still more preferably not less than 3.5 wt%, such as not less than 3.8 wt% Or more comonomer content. Accordingly, the propylene copolymer composition (P) according to the present invention is used in an amount of 2.0 to 10.0 wt%, more preferably 2.4 to 8.0 wt%, even more preferably 3.0 to 8.0 wt%, still more preferably 3.5 To 8.0% by weight, for example, 3.5 to 6.5% by weight, based on the total weight of the composition.

The comonomers of the propylene copolymer composition (P) are C ₅ to C ₁₂ ? -Olefins, for example 1-hexene and / or 1-octene. The propylene copolymer composition (P) of the present invention may contain one or more types of comonomers. Thus, the propylene copolymer composition (P) of the present invention may contain one, two or three different comonomers, which may be selected from C ₅ ? -Olefins, C ₆ ? -Olefins, C ₇ ? -Olefins , C ₈ ? -Olefins, C ₉ ? -Olefins, C ₁₀ ? -Olefins, C ₁₁ ? -Olefins and C ₁₂ ? -Olefins. However, it is preferred that the propylene copolymer composition (P) contains only one type of comonomer. Preferably, the propylene copolymer composition (P) contains only 1-hexene and / or 1-octene in addition to propylene. In a particularly preferred embodiment, the comonomer of the propylene copolymer composition (P) is only 1-hexene.

The propylene copolymer (A) and the propylene copolymer (B) as well as the propylene copolymer composition (P) according to the present invention are preferably random propylene copolymers. The term "random copolymer" should preferably be understood in accordance with IUPAC (Pure Appl. Chem., Vol. 68, 8, pp. 1591-1595, 1996). Preferably the molar concentration of the comonomer diad, such as 1-hexene diad, is according to the following relationship:

[HH] < [H] ²

In the formula,

[HH] is the mole fraction of adjacent comonomer units, such as adjacent 1-hexene units,

[H] is the mole fraction of the total comonomer units in the polymer, e.g., total 1-hexene units.

Preferably, the propylene copolymer (A) and the propylene copolymer (B) as well as the propylene copolymer composition (P) as defined in detail below are isotactic. Thus, the propylene copolymer composition (P), the propylene copolymer (A) and the propylene copolymer (B) have a somewhat higher stereoregular triad concentration, i.e. greater than 90%, more preferably greater than 92% , Preferably greater than 93%, even more preferably greater than 95%, such as greater than 97%.

The molecular weight distribution (MWD) is the relationship between the number of molecules in the polymer and the individual chain length. The molecular weight distribution (MWD) is expressed as the ratio of weight average molecular weight (M _w) to number average molecular weight (M _n). A number average molecular weight (M _n) average molecular weight of a polymer expressed as the first moment of a plot of the number of molecules in each molecular weight range for the molecular weight. In practice, this is the total molecular weight of all molecules divided by the number of molecules. Next, the weight average molecular weight (M _w ) is the first moment of the plot of the polymer weight within each molecular weight range relative to the molecular weight.

The number average molecular weight (M _n) and weight average molecular weight (M _w) as well as molecular weight distribution (MWD) using Waters Alliance GPCV 2000 instrument with online viscometer are determined by size exclusion chromatography (SEC). The oven temperature is 140 占 폚. Trichlorobenzene is used as a solvent (ISO 16014).

Therefore, it is preferable that the propylene copolymer composition (P) of the present invention has a weight average molecular weight (M _w ) of 100 to 700 kg / mol, more preferably 150 to 400 kg / mol.

The number average molecular weight (M _n ) of the polypropylene is preferably 25 to 200 kg / mol, more preferably 30 to 150 kg / mol.

It is also understood that the molecular weight distribution (MWD) measured according to ISO 16014 is 4.0 or less, more preferably 3.5 or less, such as 3.0 or less. Therefore, the molecular weight distribution (MWD) of the propylene copolymer composition (P) is preferably in the range of 2.0 to 4.0, more preferably 2.0 to 3.5, such as 2.0 to 3.0.

It is also preferred that the propylene copolymer composition (P) of the present invention has a given melt flow rate (MFR) within a certain range. The melt flow rate (ISO 1133) measured at 230 ° C under a load of 2.16 kg is expressed as MFR ₂ (230 ° C). Accordingly, in the present invention, the propylene copolymer composition (P) has a melt flow rate in the range of 2.0 to 50.0 g / 10 min, more preferably 3.0 to 25.0 g / 10 min, still more preferably 4.0 to 20.0 g / 10 min to have a melt flow rate MFR ₂ (230 ℃) are preferred.

As mentioned above, the propylene copolymer composition (P) of the present invention will be particularly suitable for the packaging industry. Therefore, good sealing characteristics such as good mechanical properties (for example, good impact behavior) are required along with a somewhat low heat seal initiation temperature (SIT).

Thus, the propylene copolymer composition (P) has a hot seal initiation temperature (SIT) of less than or equal to 120 占 폚, more preferably less than or equal to 110 占 폚, more preferably in the range of from 90 to 120 占 폚, .

Not only the heat seal initiation temperature (SIT) is somewhat low, but the melting temperature (T _m ) will be somewhat high. Thus, the difference between the melting temperature (T _m ) and the hot seal initiation temperature (SIT) will be somewhat larger. Therefore, it is preferable that the propylene copolymer composition (P) satisfies the following equation (I), more preferably the following equation (Ia):

Tm - SIT ≥ 22 ° C (I)

Tm - SIT ≥ 24 ° C (Ia)

In the formula,

Tm is the melting temperature given in degrees Celsius [deg.] C of the propylene copolymer composition (P)

SIT is the heat seal initiation temperature (SIT) given in degrees centigrade [deg.] C of the propylene copolymer composition (P).

Measured according to ISO 11357-3 of the propylene copolymer composition (P) a melting temperature (T _m) is preferably not less than 125.0 ℃, more preferably not less than 128 ℃. Accordingly, it is understand that in particular the melting temperature (T _m) is 125 to 145 ℃ range, more preferably in the range 128 to 140 ℃ of the propylene copolymer composition (P) measured according to ISO 11357-3.

It is further understood that the propylene copolymer composition (P) of the present invention has a crystallization temperature (T _c ) of 88 ° C or more, more preferably 90 ° C or more, measured according to ISO 11357-3. The polypropylene therefore preferably has a crystallization temperature (T _c ) in the range of 88 to 110 ° C, more preferably in the range of 90 to 105 ° C, measured according to ISO 11357-3.

In addition, the propylene copolymer can be defined by the xylene-cooled solubles (XCS) content measured according to ISO 6427. Thus, the propylene copolymer composition (P) preferably has a xylene solubility (XCS) content of less than 20.0 wt%, more preferably less than 15.0 wt%, even more preferably less than 10.0 wt% Is less than 5.0% by weight, such as less than 4.0% by weight. Therefore, the propylene copolymer composition (P) of the present invention has a xylene-cooling solubility (XCS) in the range of 0.3 to 20.0 wt%, more preferably in the range of 0.5 to 10.0 wt%, even more preferably in the range of 0.5 to 5.0 wt% It is particularly understood that it has a content.

Similar to xylene cooled solubles (XCS), hexane hot solids (HHS) exhibit low stereoregularity and crystallinity and represent some of the polymers that are soluble in hexane at 50 &lt; 0 &gt; C.

Accordingly, it is preferred that the propylene copolymer composition (P) of the present invention has a hexane hot water solubility (HHS) of 2.5% by weight or less, more preferably 2.0% by weight or less, such as 1.5% by weight or less as measured in accordance with FDA 177.1520 .

The propylene copolymer composition (P) of the present invention is further defined by the presence of the polymer portion thereof. Accordingly, the propylene copolymer composition (P) of the present invention comprises at least two portions, that is, the propylene copolymer (A) and the propylene copolymer (B), and preferably the propylene copolymer composition (P).

The propylene copolymer (A) is preferably a comonomer lean fraction while the propylene copolymer (B) is a comonomer-rich portion. Therefore, the comonomer content in the propylene copolymer (A) is lower than the comonomer content in the propylene copolymer (B). Therefore, the propylene copolymer composition (P) meets the correlation com (P) / com (A) in the range of more than 1.0 to 10.0, more preferably 1.2 to 6.0, still more preferably 1.5 to 5.0 It is understood that, at this time:

Com (A) is the comonomer content of the propylene copolymer (A) given in percent by weight (% by weight)

com (P) is the comonomer content of the propylene copolymer composition (P) given in weight percent (% by weight).

Thus, the propylene copolymer (A) has a comonomer content of 1.0 wt.% Or more, more preferably a comonomer content of more than 1.0 to 4.0 wt.%, Even more preferably 1.2 to 3.5 wt.% It is understood.

Propylene comonomer of the copolymer (A) is a C ₅ to C ₁₂ α- olefin, more preferably the comonomer of the propylene copolymer (A) is C ₅ α- olefin, C ₆ α- olefin, C ₇ α- Olefin, a C ₈ ? -Olefin, a C ₉ ? -Olefin, a C ₁₀ ? -Olefin, a C ₁₁ ? -Olefin and a C ₁₂ ? -Olefin, and still more preferably selected from the group of a propylene copolymer (A) The monomers are 1-hexene and / or 1-octene. The propylene copolymer (A) may contain more than one type of comonomer. Thus, the propylene copolymer (A) of the present invention may contain one, two or three different comonomers. However, it is preferred that the propylene copolymer (A) contains only one type of comonomer. Preferably, the propylene copolymer (A) contains only 1-hexene and / or 1-octene in addition to propylene. In a particularly preferred embodiment, the comonomer of propylene copolymer (A) is only 1-hexene.

Thus, propylene copolymer (A) is a propylene copolymer of propylene and 1-hexene alone in one preferred embodiment wherein the 1-hexene content is in the range of more than 1.0 to 4.0 wt%, more preferably 1.2 to 3.5 wt% to be.

As mentioned above, the propylene copolymer (B) has a higher comonomer content than the propylene copolymer (A). Therefore, the propylene copolymer (B) has a comonomer content of 2.5 to 20.0% by weight, preferably more than 3.0 to 18.0% by weight, more preferably 4.0 to 15.0% by weight.

The comonomer of the propylene copolymer (B) is a C ₅ to C ₁₂ α- olefin and, more preferably, the comonomer of the propylene copolymer (B) is C ₅ α- olefin, C ₆ α- olefin, C ₇ α- (B) is selected from the group of olefin, C ₈ ? -Olefin, C ₉ ? -Olefin, C ₁₀ ? -Olefin, C ₁₁ ? -Olefin and C ₁₂ ? -Olefin, The monomers are 1-hexene and / or 1-octene. The propylene copolymer (B) may contain more than one type of comonomer. Thus, the propylene copolymer (B) of the present invention may contain one, two or three different comonomers. However, it is preferred that the propylene copolymer (B) contains only one type of comonomer. Preferably, the propylene copolymer (B) contains only 1-hexene and / or 1-octene in addition to propylene. In a particularly preferred embodiment, the comonomer of the propylene copolymer (B) is only 1-hexene.

Thus, the propylene copolymer (B) is a propylene copolymer of propylene and 1-hexene alone in a preferred embodiment wherein the 1-hexene content is 2.5 to 20.0 wt%, preferably more than 3.0 to 18.0 wt% 4.0 to 15.0 wt%.

It is particularly preferable that the comonomers of the propylene copolymer (A) and the propylene copolymer (B) are the same. Thus, in one preferred embodiment, the propylene copolymer composition (P) of the present invention comprises propylene copolymer (A) and propylene copolymer (B), preferably propylene copolymer (A) and propylene copolymer ), And in both polymers the comonomer is only 1-hexene.

An important aspect of the present invention is that the propylene copolymer (A) and the propylene copolymer composition (P) differ in comonomer content. In addition, the propylene copolymer (A) and the propylene copolymer composition (P) may also differ in melt flow rate. Therefore, the ratio of MFR (A) / MFR (P) is preferably in the range of 0.25 to 10.0, more preferably in the range of 0.5 to 5.0, still more preferably in the range of 0.7 to 2.5,

The MFR (A) is the melt flow rate MFR ₂ (230 캜) [g / 10 min] of the propylene copolymer (A) measured according to ISO 1133,

The MFR (P) is the melt flow rate MFR ₂ (230 캜) [g / 10 min] of the propylene copolymer composition (P) measured according to ISO 1133.

Further, it is preferable that the propylene copolymer (A) is in a range of 0.5 g / 10 min or more, more preferably 2.0 g / 10 min or more, still more preferably 0.5 to 70 g / 10 min, It is understood that it has a melt flow rate MFR ₂ (230 ° C) in the range of 2.0 to 50.0 g / 10 min, for example 5.5 to 20.0 g / 10 min.

(A) is in the range of less than 450 kg / mol, more preferably less than 400 kg / mol, even more preferably in the range of less than 150 to less than 450 kg / mol, for example because the high melt flow rate has a low molecular weight Has a weight average molecular weight (M _w ) in the range of 180 to 400 kg / mol.

The propylene copolymer (A) preferably has a propylene content in the range of less than 2.0 wt%, more preferably less than 1.5 wt%, even more preferably in the range of 0.3 to 2.0 wt%, and still more preferably in the range of 0.5 to 1.5 wt% (XCS) content. It is particularly preferred that the propylene copolymer (A) has a lower xylene solubility (XCS) content than the propylene copolymer (B).

The propylene copolymer composition (P) may contain additives known in the art, such as antioxidants, nucleating agents, slip agents and antistatic agents. The sum of the polymer portion, preferably the propylene copolymer (A) and the propylene copolymer (B) portion, is at least 90 wt%, more preferably at least 95 wt%, even more preferably at least 98 wt% %.

The propylene copolymer composition (P) is particularly obtainable and preferably obtained by a method as defined in detail below.

The present invention also relates to the use of the present propylene copolymer composition (P) as a film, such as a cast film, an extrusion blown film or a biaxially stretched polypropylene (BOPP) film. The propylene copolymer composition (P) of the present invention can also be used as a coating of an extrusion coated substrate.

The present invention therefore also relates to a sealing layer of a film layer, preferably a cast film, an extrusion blown film or a biaxially stretched polypropylene (BOPP) film, wherein said film layer (sealing layer) comprises at least 70 wt% (P) of at least 80% by weight, for example at least 90% by weight, of the propylene copolymer composition according to the invention. In a particularly preferred embodiment, the film layer (sealing layer) consists of the propylene copolymer composition (P) as defined herein.

The present invention also relates to an extrusion coated substrate comprising a coating, wherein said coating comprises at least 70 wt%, more preferably at least 90 wt%, such as at least 95 wt% of the propylene copolymer composition (P) . In a particularly preferred embodiment, the coating of the extrusion coated substrate consists of the propylene copolymer composition (P) as defined herein. The substrate may be, for example, paper, paperboard, fabric and metal foil.

The present invention further relates to the production of the propylene copolymer composition (P) of the present invention. The process for preparing a propylene copolymer composition (P) as defined above is thus a sequential polymerization process comprising two or more reactors connected in series, the process comprising the steps of:

(A) polymerizing propylene and at least one C ₅ to C ₁₂ alpha-olefin, preferably 1-hexene, in a first reactor (R-1) which is a slurry reactor (SR), preferably a loop reactor To obtain a propylene copolymer (A) as defined in the present invention, preferably as defined in any one of claims 1, 8 to 10,

(B) moving the propylene copolymer (A) and the unreacted comonomer of the first reactor in a second reactor (R-2) which is a gas phase reactor (GPR-1)

(C) feeding propylene and at least one C ₅ to C ₁₂ alpha-olefin to the second reactor (R-2)

(D) polymerizing propylene and at least one C ₅ to C ₁₂ ? -Olefin in the presence of said first propylene copolymer (A) in a second reactor (R-2) (B) as defined in any one of claims 1, 8 or 9, wherein the propylene copolymer (A) and the propylene copolymer (B) Forming a propylene copolymer composition (P) as defined above, preferably as defined in any one of claims 1 to 7,

Also,

Polymerization takes place in the first reactor (R-1) and the second reactor (R-2) in the presence of a solid catalyst system (SCS), the solid catalyst system (SCS) comprising:

(i) a transition metal compound of formula (I)

R _n (Cp ') ₂ MX ₂ (I)

[Wherein,

"M" is zirconium (Zr) or hafnium (Hf)

Each "X" is independently a monovalent anionic sigma-ligand,

Each "Cp" " is a cyclopentadienyl-type organic ligand independently selected from the group consisting of substituted cyclopentadienyl, substituted indenyl, substituted tetrahydroindenyl, and substituted or unsubstituted fluorenyl , The organic ligand is coordinated to the transition metal (M)

"R" is a divalent bridging group connecting the organic ligand (Cp '),

"n" is 1 or 2, preferably 1, and

(Co) comprising a cocatalyst (Co), preferably a compound of Al, optionally comprising an element (E) of Group 13 of the Periodic Table (IUPAC).

With respect to the definitions of the propylene copolymer composition (P), the propylene copolymer (A) and the propylene copolymer (B), this means the definition given above.

Due to the use of the catalyst system (SCS) in the sequential polymerization process, it is possible to prepare the propylene copolymer composition (P) as defined above. In particular, the preparation of the propylene copolymer in the first reactor (R-1), that is, the propylene copolymer (A) and the transfer of the propylene copolymer, particularly the unreacted comonomer into the second reactor (R-2) , A propylene copolymer composition (P) having a high comonomer content can be produced by a sequential polymerization method. Generally, the preparation of propylene copolymers with high comonomer content by sequential polymerization methods results in contamination or, in severe cases, occlusion of the transfer line, as the unreacted comonomer condenses on the transfer line. However, using the new method, the conversion of the comonomer is increased, and with it the better incorporation into the polymer chain, the comonomer content is increased, and the stickiness problem is reduced.

The term " sequential polymerization process "indicates that the propylene copolymer composition (P) is prepared in two or more reactors connected in series. More precisely, the term "sequential polymerization process" indicates that in this application the polymer of the first reactor (R-1) is transported directly to the second reactor (R-2) along with the unreacted comonomer. Thus, a critical aspect of the process is the preparation of the propylene copolymer composition (P) in two different reactors, wherein the reactants of the first reactor (R-1) are transported directly to the second reactor (R-2). Thus, the process comprises at least a first reactor (R-1) and a second reactor (R-2). In one particular embodiment, the process comprises two polymerization reactors (R-1) and (R-2). The term "polymerization reactor" will indicate that the main polymerization occurs. Thus, when the process consists of two polymerisation reactors, this definition does not preclude the option that the entire process comprises, for example, a prepolymerisation step in a prepolymerization reactor. The term "consisting of" is only a closing formulation in terms of the main polymerization reactor.

The first reactor (R-1) is preferably a slurry reactor (SR) and may be any continuous or simple stirred batch tank reactor or loop reactor (operating in bulk or slurry). Bulk means polymerization in a reaction medium comprising 60% (w / w) or more, preferably 100% monomer. According to the present invention, the slurry reactor (SR) is preferably a (bulk) loop reactor (LR).

The second reactor (R-2) and any subsequent reactor are preferably gas phase reactors (GPR). Such a gas phase reactor (GPR) may be any mechanical mixing or fluidized bed reactor. Preferably, the gas phase reactor (GPR) comprises a mechanically stirred fluidized bed reactor having a gas velocity of at least 0.2 m / s. It is therefore to be understood that the gas phase reactor is preferably a fluid bed type reactor having a mechanical stirrer.

The conditions (temperature, pressure, reaction time, monomer feed) in each reactor depend on the desired product and are known to those skilled in the art. The first reactor R-1 is preferably a slurry reactor SR, for example a loop reactor LR, while the second reactor R-2 is preferably a gas phase reactor GPR -1). If present, the subsequent reactor is also preferably a gas phase reactor (GPR).

technology 로 알려져 있음) 에 의해 개발된 것과 같은, 예를 들어 EP 0 887 379 또는 WO 92/12182 와 같은 특허 문헌에서 기재된 "루프-기체상"-방법이다.A preferred multi-step method is Borealis A / S, Denmark (BORSTAR

loop-gaseous "method described in patent documents such as EP 0 887 379 or WO 92/12182, for example,

The multimodal polymers may be prepared according to various methods as described, for example, in WO 92/12182, EP 0 887 379 and WO 98/58976. The contents of these documents are incorporated herein by reference.

Preferably, in the present process for producing a propylene copolymer composition (P) as defined above, the first reactor (R-1) of step (A), i.e. the slurry reactor (SR) Can be as follows: &lt; RTI ID = 0.0 &gt;

- the temperature is in the range of 40 ° C to 110 ° C, preferably 60 ° C to 100 ° C, 70 ° C to 90 ° C,

The pressure is in the range of 20 bar to 80 bar, preferably 40 bar to 70 bar,

- Hydrogen can be added for controlling the molar mass in a manner known per se.

Thereafter, the reaction mixture from step (A) is transferred to the second reactor (R-2), i.e. the gas phase reactor (GPR-1), i.e. to step (D) Lt; / RTI &gt;

- the temperature is in the range of 50 ° C to 130 ° C, preferably 60 ° C to 100 ° C,

- the pressure is in the range from 5 bar to 50 bar, preferably from 15 bar to 40 bar,

- Hydrogen can be added for controlling the molar mass in a manner known per se.

The residence time can be variable in both reactor zones.

In one embodiment of the process for preparing the propylene copolymer composition (P), the residence time in the bulk reactor, for example a loop reactor, is in the range of 0.2 to 4 hours, for example 0.3 to 1.5 hours, The time will generally be from 0.2 to 6.0 hours, such as from 0.5 to 4.0 hours.

If necessary, the polymerization can be carried out in a first reactor (R-1), i.e. in a slurry reactor (SR), for example in a loop reactor (LR), in a manner known under supercritical conditions and / or in a gas phase reactor (GPR- .

If present, the conditions in the other gas phase reactor (GPR) are similar to the second reactor (R-2).

The process may also comprise a prepolymerization prior to the polymerization in the first reactor (R-1). The prepolymerization can be carried out in the first reactor (R-1), but it is preferred that the prepolymerization takes place in a separate reactor, the so-called prepolymerization reactor.

In one particular embodiment, the solid catalyst system (SCS) has a porosity of less than 1.40 ml / g measured in accordance with ASTM 4641 and / or a surface area of less than 25 m2 / g measured in accordance with ASTM D 3663.

Preferably, the solid catalyst system (SCS) has a surface area of less than 15 m 2 / g, more preferably less than 10 m 2 / g, and most preferably less than 5 m 2 / g, which is the lower limit of measurement. The surface area according to the invention is measured according to ASTM D 3663 (N ₂ ).

Alternatively, or additionally, it is understood that the solid catalyst system (SCS) has a porosity of less than 1.30 ml / g, more preferably less than 1.00 ml / g. The porosity is measured according to ASTM 4641 (N ₂ ). In another preferred embodiment, the porosity is undetectable when measured by a method applied in accordance with ASTM 4641 (N ₂ ).

In addition, the solid catalyst system (SCS) usually has an average particle size in the range of 500 占 퐉 or less, that is, preferably in the range of 2 to 500 占 퐉, and more preferably in the range of 5 to 200 占 퐉. It is particularly preferred that the average particle size is less than 80 [mu] m, more preferably less than 70 [mu] m. The preferred range for the average particle size is 5 to 70 mu m, or even 10 to 60 mu m.

As mentioned above, the transition metal (M) is zirconium (Zr) or hafnium (Hf), preferably zirconium (Zr).

The term " sigma-ligand "is understood in its entirety in a manner known per se (i.e., a group bound to a metal via sigma bonding). Thus the anionic ligands "X" are independently, halogen, or, R ', OR', SiR '3, OSiR' 3, OSO 2 CF 3, OCOR ', SR', NR '2 or PR' ₂ in the group consisting of may be selected, the R 'are independently hydrogen, linear or branched, cyclic or acyclic, C ₁ to C ₂₀ alkyl, C ₂ to C ₂₀ alkenyl, C ₂ to C ₂₀ alkynyl, C ₃ to to C ₁₂ cycloalkyl, C ₆ to C ₂₀ aryl, C ₇ to C ₂₀ arylalkyl, C ₇ to C ₂₀ alkylaryl, C ₈ to C a alkenyl ₂₀ aryl, wherein said R 'groups optionally group 14 to group 16 Lt; RTI ID = 0.0 &gt; heteroatom &lt; / RTI &gt; In a preferred embodiment, the anionic ligand "X" is the same and is halogen, such as Cl, or methyl or benzyl.

Preferred monovalent anionic ligands are halogens, especially chlorine (Cl).

Substituted cyclopentadienyl type ligand (s) is a halogen, hydrocarbyl, e.g., C ₁ to C ₂₀ alkyl, C ₂ to C ₂₀ alkenyl, C ₂ to C ₂₀ alkynyl, C ₃ to C ₂₀ Cycloalkyl, such as one or more substituents selected from the group consisting of C ₁ to C ₂₀ alkyl substituted C ₅ to C ₂₀ cycloalkyl, C ₆ to C ₂₀ aryl, C ₅ to C ₂₀ cycloalkyl substituted C ₁ to C ₂₀ alkyl , Wherein said cycloalkyl moiety is optionally substituted with one or more substituents selected from the group consisting of C ₁ to C ₂₀ alkyl, C ₇ to C ₂₀ arylalkyl, C ₃ to C ₁₂ cycloalkyl (having 1, 2, 3 or 4 heteroatoms s) containing from), C ₆ to C ₂₀ heteroaryl, C ₁ to C _{20 haloalkyl, -SiR "3, -SR",} -PR "2 or -NR" is substituted by _2, each R " are independently hydrogen or hydrocarbyl (e.g. C ₁ to C ₂₀ alkyl, C ₁ to C ₂₀ alkenyl, C ₂ to C ₂₀ alkynyl, C ₃ to C ₁₂ cycloalkyl Or keel or C ₆ to C ₂₀ aryl), for example, -NR _"2, the case of two substituents R" can form a 5-membered or 6-membered ring containing a ring, together with the nitrogen atom to which they are attached .

The further "R" of formula (I) is preferably a bridging of from 1 to 4 atoms and the atoms may independently be carbon, silicon, And each of the bridge atoms may independently comprise a substituent such as a C ₁ to C ₂₀ hydrocarbyl, tri (C ₁ to C ₂₀ alkyl) silyl, tri (C ₁ to C ₂₀ alkyl) siloxy, more preferably, "R" is one atom bridge, e.g., -SiR "_'2 -, and wherein each R"' independently are C ₁ to C ₂₀ alkyl, C ₂ to C ₂₀ alkenyl, C ₂ to C ₂₀ alkynyl, C ₃ to C ₁₂ cycloalkyl, C ₆ to C ₂₀ aryl, alkylaryl or arylalkyl, or tri (C ₁ to C ₂₀ alkyl) silyl-residue (e.g. trimethylsilyl -), or two R "May be part of a ring system comprising Si bridge atoms.

In a preferred embodiment, the transition metal compound has the formula (II)

[Wherein,

M is zirconium (Zr) or hafnium (Hf), preferably zirconium (Zr)

X is a ligand having a sigma-bond to the metal "M ", preferably they are as defined above for formula (I)

Is preferably a chlorine (Cl) or methyl (CH _3), and chlorine are particularly preferred,

R ¹ are the same or different and are preferably the same and are selected from linear saturated C ₁ to C ₂₀ alkyl, linear unsaturated C ₁ to C ₂₀ alkyl, branched saturated C _{1 to} C ₂₀ alkyl, branched unsaturated C ₁ to C ₂₀ alkyl, C ₃ to C ₂₀ cycloalkyl, C ₆ to C ₂₀ aryl, C ₇ to C ₂₀ alkylaryl and C ₇ to C ₂₀ arylalkyl (optionally at least one heteroatom of Group 14 to Group 16 of the periodic table (IUPAC) Atom), and the compound is selected from the group consisting of

Are preferably the same or different and are preferably the same and are C ₁ to C ₁₀ linear or branched hydrocarbyl, more preferably identical or different, preferably identical, C ₁ to C ₆ Linear or branched alkyl,

R ² to R ⁶ are the same or different from each other and represent hydrogen, linear saturated C ₁ -C ₂₀ alkyl, linear unsaturated C ₁ -C ₂₀ alkyl, branched saturated C ₁ -C ₂₀ alkyl, branched unsaturated C ₁ -C ₂₀ Alkyl, C ₃ -C ₂₀ cycloalkyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ alkylaryl and C ₇ -C ₂₀ arylalkyl, optionally substituted with one or more heteroatoms of Group 14 to Group 16 of the Periodic Table (IUPAC) ), &Lt; / RTI &gt;

Are preferably identical or different and are C ₁ to C ₁₀ linear or branched hydrocarbyl, more preferably they are the same or different and are C ₁ to C ₆ Linear or branched alkyl,

R ⁷ and R ⁸ are the same or different and are selected from hydrogen, linear saturated C ₁ to C ₂₀ alkyl, linearly unsaturated C ₁ to C ₂₀ alkyl, branched saturated C ₁ to C ₂₀ alkyl, branched unsaturated C ₁ to C ₂₀ Alkyl, C ₃ to C ₂₀ cycloalkyl, C ₆ to C ₂₀ aryl, C ₇ to C ₂₀ alkylaryl, C ₇ to C ₂₀ arylalkyl (optionally with one or more heteroatoms of Group 14 to Group 16 of the Periodic Table (IUPAC) , SiR ¹⁰ ₃ , GeR ¹⁰ ₃ , OR ¹⁰ , SR ¹⁰ and NR ¹⁰ ₂ , wherein

R ¹⁰ is a linear saturated C ₁ -C ₂₀ alkyl, a linear unsaturated C ₁ to C ₂₀ alkyl, a branched saturated C ₁ to C ₂₀ alkyl, a branched unsaturated C ₁ to C ₂₀ alkyl, a C ₃ to C ₂₀ cycloalkyl, a C Selected from the group consisting of C ₆ to C ₂₀ aryl, C ₇ to C ₂₀ alkylaryl and C ₇ to C ₂₀ arylalkyl (optionally containing one or more heteroatoms of Group 14 to Group 16 of the Periodic Table of the Elements (IUPAC)) and / Or,

R ⁷ and R ⁸ together with the indenyl carbon to which they are attached are part of a C ₄ to C ₂₀ carbon ring system, preferably a C ₅ ring, and optionally one carbon atom is replaced by a nitrogen, sulfur or oxygen atom Lt; / RTI &gt;

R ⁹ are the same or different and are selected from the group consisting of hydrogen, linear saturated C ₁ to C ₂₀ alkyl, linearly unsaturated C ₁ to C ₂₀ alkyl, branched saturated C ₁ to C ₂₀ alkyl, branched unsaturated C ₁ to C ₂₀ alkyl, C Selected from the group consisting of C ₃ to C ₂₀ cycloalkyl, C ₆ to C ₂₀ aryl, C ₇ to C ₂₀ alkylaryl, C ₇ to C ₂₀ arylalkyl, OR ¹⁰ and SR ¹⁰ ,

Preferably R ⁹ are the same or different and are selected from H or CH ₃ with each other, wherein

R ¹⁰ is defined as before,

L is a divalent bridge connecting two indenyl ligands, preferably a C ₂ R ¹¹ ₄ unit or SiR ¹¹ ₂ or GeR ¹¹ ₂ ,

R ¹¹ is selected from the group consisting of H, linear saturated C ₁ to C ₂₀ alkyl, linearly unsaturated C ₁ to C ₂₀ alkyl, branched saturated C ₁ to C ₂₀ alkyl, branched unsaturated C ₁ to C ₂₀ alkyl, C ₃ to C ₂₀ cycloalkyl , C ₆ to C ₂₀ aryl, C ₇ to C ₂₀ alkylaryl or C ₇ to C ₂₀ arylalkyl (optionally containing one or more heteroatoms of Group 14 to Group 16 of the Periodic Table of the Elements (IUPAC)). And,

Preferably Si (CH ₃ ) ₂ , SiCH ₃ C ₆ H ₁₁ or SiPh ₂ , and C ₆ H ₁₁ is cyclohexyl.

Preferably, the transition metal compound of formula (II) is C ₂ -symmetric or pseudo-C ₂ -symmetric. With regard to the definition of symmetry, [Resconi et al. Chemical Reviews, 2000, Vol. 100, No. 4 1263] and references cited herein.

Preferably, residue R ¹ is the same as or different from each other, more preferably the same, and linear saturated C ₁ to C ₁₀ alkyl, linear unsaturated C ₁ to C ₁₀ alkyl, branched saturated C ₁ to C ₁₀ alkyl, branched Unsaturated C ₁ to C ₁₀ alkyl and C ₇ to C ₁₂ arylalkyl. And more preferably, residues R ¹ are each other the same or different, more preferably identical, and linear saturated C ₁ to C ₆ alkyl, linear unsaturated C ₁ to C ₆ alkyl, branched saturated C ₁ to C ₆ alkyl, min is selected from branched unsaturated C ₁ to C ₆ alkyl and C ₇ to C ₁₀ arylalkyl group consisting of a. More preferably, R ¹ moiety is the same or different from each other, and are more preferably the same, selected from linear or branched C ₁ to C ₄ hydrocarbyl, for example, the group consisting of methyl or ethyl.

Preferably, residues R ² to R ⁶ are the same or different and are linear saturated C ₁ to C ₄ alkyl or branched saturated C ₁ to C ₄ alkyl. Even more preferably, the residues R ² to R ⁶ are the same or different and are more preferably identical and are selected from the group consisting of methyl, ethyl, iso-propyl and tert-butyl.

Preferably, R ⁷ and R ⁸ are the same or different from each other and are part of a 5-methylene ring containing two indenyl ring carbons selected from hydrogen and methyl, or to which they are attached. In another preferred embodiment, R ⁷ is selected from OCH ₃ and OC ₂ H ₅ , and R ⁸ is tert-butyl.

In a preferred embodiment, the transition metal compound is rac-methyl (cyclohexyl) silanediylbis (2-methyl-4- (4-tert-butylphenyl) indenyl) zirconium dichloride.

In a second preferred embodiment the transition metal compound is selected from the group consisting of rac-dimethylsilanediylbis (2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl) zirconium dichloride to be.

In a third preferred embodiment, the transition metal compound is rac-dimethylsilanediylbis (2-methyl-4-phenyl-5-methoxy-6-tert-butylindenyl) zirconium dichloride.

As a further requirement, the solid catalyst system (SCS) according to the invention comprises a cocatalyst (Co) comprising a group 13 element (E) of the periodic table (IUPAC), for example a cocatalyst (Co) comprising a compound of Al, .

An example of such a cocatalyst (Co) is an organoaluminum compound such as an aluminoxane compound.

Such a compound of Al, preferably aluminoxane, can be used as the only compound in the cocatalyst (Co) or in combination with other cocatalyst compound (s). Thus, besides the compound of Al, i.e. aluminoxane, or in addition thereto, other cation complexing promoter compounds such as boron compounds can be used. The cocatalyst may be commercially available or may be prepared according to the prior art documents. However, preferably, only the compound of Al is used as the co-catalyst (Co) in the production of the solid catalyst system.

Particularly preferred cocatalysts (Co) are aluminoxanes, in particular C ₁ to C ₁₀ alkylaluminoxanes, most particularly preferably methylaluminoxanes (MAO).

Preferably, the organic zirconium compound of formula (I) and the cocatalyst (Co) of the solid catalyst system (SCS) comprise at least 70 wt%, more preferably at least 80 wt%, even more preferably at least 90 wt% Or more, still more preferably 95 wt% or more. Thus, it is believed that the solid catalyst system does not include the fact that it is self-supporting, i.e. it does not include any catalytically inert support materials such as silica, alumina or MgCl ₂ or porous polymeric materials (otherwise commonly used in heterogeneous catalyst systems) I.e. the catalyst is not supported on an external support or carrier material. Because the solid catalyst system (SCS) is self-supporting, it has a somewhat lower surface area.

In one embodiment, the solid metallocene catalyst system (SCS) is obtained by emulsion coagulation technique, the basic principle of which is described in WO 03/051934. Which is incorporated herein by reference in its entirety.

Thus, the solid catalyst system (SCS) is preferably in the form of a solid catalyst particle obtainable by a process comprising the following steps:

a) preparing a solution of one or more catalyst components;

b) dispersing the solution in a second solvent to form an emulsion in which at least one catalyst component is present in a droplet of dispersed phase, and

c) coagulating said dispersed phase to convert said droplets to solid particles, optionally recovering said particles to obtain said catalyst.

Preferably, the solution is formed using a first solvent, more preferably a first organic solvent. More preferably, the organic solvent is selected from the group consisting of linear alkanes, cyclic alkanes, aromatic hydrocarbons and halogen-containing hydrocarbons.

Moreover, the second solvent which forms the continuous phase is a solvent which is inert to the catalyst component. The second solvent may be immiscible with the solution of the catalyst component at least under conditions (e.g., temperature) during the dispersion step. The term " incompatible with the catalyst solution "means that the second solvent (continuous phase) is completely incompatible or partially incompatible, i.e. not completely miscible, with the dispersed phase solution.

Preferably, the immiscible solvent comprises a fluorinated organic solvent and / or a functionalized derivative thereof, more preferably the immiscible solvent comprises a semi-high- or perfluorinated hydrocarbon and / or a functionalized derivative thereof . Particularly preferably, said immiscible solvent is selected from the group consisting of perfluorohydrocarbons or functionalized derivatives thereof, preferably C ₃ -C ₃₀ perfluoroalkanes, -alkenes or -cycloalkanes, more preferably C ₄ -C ₁₀ purple Perfluoroheptane, perfluoro (methylcyclohexane) or perfluoro (1, 3-dimethylcyclohexane, perfluoroheptane, perfluorohexane or perfluoro Hexane) or mixtures thereof.

Further, it is preferable that the fluid containing the continuous phase and the dispersed phase is an extreme system or a multi-phase system as known in the art. Emulsifiers can be used to form and stabilize emulsions. After formation of the emulsion, the catalyst is formed in situ from the catalyst component in the solution.

In principle, the emulsifier may be any suitable agent which contributes to the formation and / or stabilization of the emulsion and has no adverse effect on the catalytic activity of the catalyst. The emulsifier may be, for example, a hydrocarbon optionally blocked with a heteroatom (s), preferably a halogenated hydrocarbon optionally having a functional group, preferably a semi-high- or perfluorinated hydrocarbon such as is known in the art Lt; / RTI &gt; Alternatively, the emulsifying agent can be prepared, for example, by reacting the surfactant precursor with the compound of the catalyst solution, during emulsion preparation. The surfactant precursor may be a halogenated hydrocarbon having one or more functional groups, for example, a high-fluorinated Cl-n (preferably C4-30 alkyl, such as C4-30 alkyl), which reacts with a cocatalyst component such as aluminoxane to form a " Or C5-15) alcohols (e.g., high-fluorinated heptanol, octanol or nonanol), oxides (e.g., propenoxide) or acrylate esters.

In principle, any solidification method can be used to form solid particles from the dispersion droplets. According to one preferred embodiment, the solidification is effected by the temperature change treatment. Accordingly, the emulsion is subjected to a gradual temperature change of 10 DEG C / min or less, preferably 0.5 to 6 DEG C / min, more preferably 1 to 5 DEG C / min. Even more preferably, the emulsion is subjected to a temperature change of greater than 40 DEG C, preferably greater than 50 DEG C in less than 10 seconds, preferably less than 6 seconds.

For further details, implementations and examples of continuous and dispersed phase systems, emulsion forming, emulsifying and coagulation methods, see, for example, the above-cited international patent application WO 03/051934.

All or part of the manufacturing steps may be performed in a continuous manner. See WO 2006/069733 which describes the principle of such continuous or semi-continuous production of solid catalyst types prepared via the latex / coagulation process.

The catalyst components described above are prepared according to the process described in WO 01/48034.

The present invention also relates to the preparation of extrusion coated substrates by conventional extrusion coating of a propylene copolymer composition (P) as defined herein.

Films according to the invention can be obtained in a customary manner, for example by cast film technology or extrusion blown film technology. When the film is stretched (i.e., biaxially stretched polypropylene film), it is preferably prepared as follows: First, a cast film is produced by extrusion of the propylene copolymer composition (P) in the form of pellets. The cast film produced may have a thickness of 50 to 100 [mu] m, as is usually used for further film stretching. A stack of cast films can then be produced from the plurality of cast film sheets, for example, to achieve a specific stack thickness of 700 to 1000 [mu] m. The stretching temperature is usually set to be slightly less than the melting point, for example, less than 2 to 4 캜 of the melting point, and the film is stretched in the longitudinal direction and the transverse direction at a specific stretching ratio.

Extrusion coating methods can be carried out using conventional extrusion coating techniques. Therefore, the propylene copolymer composition (P) obtained from the polymerization method defined above is fed to the extruder in the form of a pellet (optionally containing an addition agent). The polymer melt from the extruder is preferably passed through a flat die to the substrate to be coated. Due to the distance between the die lip and the nip, the molten plastic is oxidized in the air for a short period of time, typically improving the adhesion between the coating and the substrate. The coated substrate is cooled on a chill roll and then wound by passing through an edge trimmer. The width of the line may be, for example, 500 to 1500 mm, for example 800 to 1100 mm, and the line speed may be variable to 1000 m / min or less, for example 300 to 800 m / min. The temperature of the polymer melt is usually from 275 to 330 캜. The propylene copolymer composition (P) of the present invention can be extruded into the substrate as one layer in coextrusion or as a single layer coating. In these cases, the propylene copolymer composition (P) can be used as such or the propylene copolymer composition (P) can be blended with other polymers. The blending can take place after the reactor treatment or just before extrusion in the coating process. However, it is preferred that only the propylene copolymer composition (P) as defined in the present invention is extrusion coated. In a multilayer extrusion coating, the other layer may comprise any polymeric resin having the desired properties and processability. Examples of such polymers include: barrier layers PA (polyamide) and EVA; Polar copolymers of ethylene, such as copolymers of ethylene and vinyl alcohol or copolymers of ethylene and acrylate monomers; Adhesive layers, for example, ionomers, copolymers of ethylene and ethyl acrylate, and the like; HDPE for stiffness; An LDPE resin produced by a high-pressure process; LLDPE resins prepared by polymerizing ethylene and alpha-olefin comonomers in the presence of a Ziegler, chromium or metallocene catalyst; And MDPE resin.

The present invention therefore relates to an extrusion coated substrate which preferably comprises a substrate and at least one layer of a propylene copolymer composition (P) extrusion coated onto said substrate as defined according to the invention.

The invention also relates to the use of the article of the invention as a packaging material, in particular as a packaging material for food and / or pharmaceutical products.

Hereinafter, the present invention will be described by way of examples.

Example

A. Measurement

Unless otherwise defined, the following definitions of terms and measurements apply to the following examples as well as the above detailed description of the invention.

NMR  Quantification of microstructure by spectroscopy

Regioregularity, regio-regularity and comonomer content of the polymer were quantified using quantitative nuclear-magnetic resonance (NMR) spectroscopy.

A quantitative ¹³ C { ¹ H} NMR spectrum was recorded in the molten state using a Bruker Advance III 500 NMR spectrometer operating at 500.13 and 125.76 MHz for ¹ H and ¹³ C, respectively. All spectra were recorded using a ¹³ C-optimized 7 mm magic-angle spinning (MAS) probe head at 180 ° C with nitrogen gas for all pneumatic devices. Approximately 200 mg of material was packed in a 7 mm outer diameter zirconia MAS rotor and spun at 4 kHz. NOE at short recirculation delay (Pollard, M., Klimke, K., Graf, R., Spiess, HW, Wilhelm, M., Sperber, O., Piel, C., Kaminsky, W., Macromolecules 2004, , As described in Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, HW, Wilhelm, M., Macromol. Chem. Phys. 2006,207,382) and RS-HEPT decoupling J, Tripon, C., Samoson, A., Filip, C., &lt; RTI ID = 0.0 &gt; C., Filip, C., J. Mag. Resn. 2005,176,239, and Brown, SP, Mag. Res. in Chem., 2007, 45, S1, S198) was used. A total of 1024 (1k) transients per spectra were obtained.

The quantitative ¹³ C { ¹ H} NMR spectrum was processed, integrated and the relevant quantitative characteristics were determined from the integration values. All chemical shifts were internal referenced to the methyl stereoregular pentad (mmmm) at 21.85 ppm.

^The tacticity distribution was quantified by integration of the methyl portion of the ¹³ C { ¹ H} spectrum to modify any signal not related to the major (1,2) inserted propene stereo array (Busico, V., Cipullo, R., Prog. Polym. Sci. 2001,26,443 and Busico, V., Cipullo, R., Monaco, G., Vacatello, M., Segre, AL, Macromolecules 1997,30,6251 Bar).

Characteristic signals corresponding to regio defects were observed (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000,100,1253). The effects of site defects on the quantification of the stereoregularity distribution were corrected by subtracting the representative site defect integrals from the specific integration values of the stereo array.

Stereographic diagrams were measured at the triad level and reported as% of the stereoregular triad mm for all triad arrays:

% mm = (mm / (mm + mr + rr)) * 100

A characteristic signal corresponding to the incorporation of 1-hexene was observed and the 1-hexene content was calculated as mol%, H (mol%) of 1-hexene in the polymer as follows:

[H] = H _tot / (P _tot + H _tot )

In the formula,

_{H tot = I (αB 4)} / 2 + I (ααB 4) x 2 , and

Wherein, I (αB ₄₎ is ₄ parts of αB at 44.1 ppm and the integrated value PPHPP check my mixing the isolated 1-hexene and arrangement, I (ααB ₄₎ is the integral of the area at 41.6 ppm ααΒ ₄ And confirming the continuously incorporated 1-hexene in the PPHHPP sequence]

P _tot = the integral of all CH 3 regions at the methyl site, corrected for overestimation due to underestimation of other propene units not described at this site and other sites found at this site,

H (mol%) = 100 x [H]

It is converted to weight% using the following correlation;

H (wt%) = (100 x H mol% x 84.16) / (H mol% x 84.16 + (100 - H mol%) x 42.08).

The statistical distribution is given by the relationship between the hexene content present in the comonomer sequences incorporated into the isolated (PPHPP) and continuous (PPHHPP)

[HH] < [H] ²

Propylene calculated comonomer content of the copolymer (B):

[Wherein,

w (A) is the weight fraction of the propylene copolymer (A)

w (B) is the weight fraction of the propylene copolymer (B)

C (A) is the comonomer content (% by weight) as measured by ¹³ C NMR spectroscopy of the product of the propylene copolymer (A), i.e. the first reactor (R1)

C (CPP) is measured by ¹³ C NMR spectroscopy of the product obtained in the second reactor (R2), that is, a mixture of propylene copolymer (A) and propylene copolymer (B) [of propylene copolymer composition By weight, comonomer content [wt%],

C (B) is the calculated comonomer content (% by weight) of the propylene copolymer (B).

Mw , Mn , MWD

Mw / Mn / MWD is determined by gel permeation chromatography (GPC) according to the following method:

The weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (MWD = Mw / Mn) are measured by a method based on ISO 16014-1: 2003 and ISO 16014-4: 2003. A Waters Alliance GPCV 2000 instrument equipped with a refractive index detector and on-line viscometer was charged with 3 x TSK gel column (GMHXL-HT) (TosoHaas) and 1,2,4-trichlorobenzene (TCB, 200 mg / Di-tert-butyl-4-methyl-phenol) at a constant flow rate of 145 占 폚 and 1 ml / min. 216.5 [mu] l of sample solution was injected per assay. The column set was calibrated using relative calibrations to 19 narrow MWD polystyrene (PS) standards ranging from 0.5 kg / mol to 11,500 kg / mol and a well-resolved wide-range polypropylene standard set. 5 to 10 mg of polymer were dissolved in 10 ml of stabilized TCB (same as the mobile phase) and held for 3 hours with continuous shaking before sampling in GPC instrument (at 160 占 폚) to prepare all samples.

The melt flow rate ( MFR )

The melt flow rate was measured at a load of 2.16 kg (MFR ₂ ) at 230 ° C. The melt flow rate is the amount of polymer (g) extruded within 10 minutes at a temperature of 230 DEG C under a load of 2.16 kg, the test apparatus standardized for ISO 1133.

Melt Flow Rate MFR ₂ (230 캜) of Propylene Copolymer (B)

[Wherein,

w (A) is the weight fraction of polypropylene (A)

w (B) is the weight fraction of the propylene copolymer (B)

The MFR (A) is the melt flow rate MFR ₂ (230 캜) [g / 10 min] of the polypropylene (A) measured according to ISO 1133,

The MFR (P) is the melt flow rate MFR ₂ (230 캜) [g / 10 min] of the propylene copolymer composition (P) measured according to ISO 1133,

MFR (B) is the calculated melt flow rate MFR ₂ (230 캜) [g / 10 min] of propylene copolymer (B).

Xylene cooling Solubility  Fraction XCS  weight%)

The fraction of xylene-cooled solids (XCS) is measured at 23 ° C in accordance with ISO 6427.

Hexane Solubility

FDA Section 177.1520

1 g of a polymer film having a thickness of 100 占 퐉 was added to 400 ml of hexane at 50 占 폚 for 2 hours while stirring with a reflux condenser.

After 2 hours the mixture was immediately filtered on filter paper N ° 41.

The precipitate was collected in an aluminum-based receiving and evaporated on a steam bath and the residue hexane under N ₂ flow.

The amount of hexane solubles was determined by the formula {((sample weight + crucible weight) - (crucible weight)) / (sample weight) 占 100}.

The melting temperature T _m , the crystallization temperature T _c is measured with a Mettler TA820 differential scanning calorimeter (DSC) for 5-10 mg samples. Both crystallization and melting curves were obtained at 10 [deg.] C / min cooling and heating scans (30 [deg.] C to 225 [deg.] C). Melting and crystallization temperatures were selected as endothermic and exothermic peaks.

In addition, the melting and crystallization enthalpy ( Hm and Hc ) was measured by the DSC method according to ISO 11357-3.

Porosity : BET, use of N ₂ gas, ASTM 4641, apparatus Micromeritics Tristar 3000;

Sample preparation: at a temperature of 50 ° C, under vacuum for 6 hours.

Surface area : BET, use of N ₂ gas, ASTM D 3663, apparatus Micromeritics Tristar 3000;

Sample preparation: at a temperature of 50 ° C, under vacuum for 6 hours.

Tensile modulus :

The longitudinal and transverse tensile moduli were measured according to ISO 527-3 for films having a thickness of 100 mu m at a crosshead speed of 1 mm / min. The longitudinal and transverse elongation ratios were then measured according to ISO 527-3 for the same specimen using a crosshead speed of 50 mm / min. The post-strain test rate of 0.25% was varied. Sample Type 2 according to ISO 527-3, a stripe type having a width of 15 mm and a length of 200 mm, was used.

Sealing initiation temperature ( SIT ); Sealing Final Temperature ( SET ), Sealing Range :

In this way, the sealing temperature range (sealing range) of a polypropylene film, in particular a blown film or a cast film, is measured. The sealing temperature range is the temperature range in which the film can be sealed according to the given conditions given below. The lower limit (heat seal initiation temperature (SIT)) is a sealing temperature at which a sealing strength of > 3 N is attained. The upper limit (sealing final temperature (SET)) is reached when the film is attached to the sealing device.

The sealing range was measured at J & B Universal Sealing Machine Type 3000 using a 100 탆 thick film with the following additional parameters:

Specimen width: 25.4 mm

Sealing pressure: 0.1 N / mm &lt; 2 &gt;

Sealing time: 0.1 second

Cooling time: 99 seconds

Peel Speed: 10 mm / sec

Starting temperature: 80 ° C

Final temperature: 150 ℃

Growth rate: 10 ℃

The specimens were sealed from A to A at each sealbar temperature and the sealing strength (force) was measured at each step.

The temperature at which the sealing strength reached 3 N was measured.

High temperature cohesion :

The following additional parameters were used to measure high temperature cohesion in a J & B high temperature cohesion tester using a film having a thickness of 100 [mu] m:

Specimen width: 25.4 mm

Sealing pressure: 0.3 N / mm &lt; 2 &gt;

Sealing time: 0.5 sec

Cooling time: 99 seconds

Peeling speed: 200 mm / sec

Starting temperature: 90 ° C

Final temperature: 140 ° C

Growth rate: 10 ℃

The maximum value of the maximum high temperature cohesion, that is, the force / temperature plot, was measured and reported.

B. Example

Polymers of the following Table 1 were polymerized in a gas phase reactor after the polymerization was initiated in a bulk phase loop reactor in a two-step polymerization process and the ethylene and hexene content as well as the molecular weight were modified by suitable hydrogen and comonomer feeds, Borstar PP pilot plant. The catalyst used in the polymerization process was a metallocene catalyst as described in Example 1 of EP 1 741 725 A1.

[Table 1: Preparation of Examples]

The loop defines a polypropylene (A)

GPR defines a propylene copolymer (B)

The final defines a propylene copolymer composition (P)

C6 is a 1-hexene content,

C2 is the ethylene content.

[Table 2: Example characteristics]

TM (MD) is the tensile modulus in the machine direction,

TM (TD) is the tensile modulus in the transverse direction,

SIT is the heat seal initiation temperature,

SET is the heat sealing final temperature,

SET - SIT is the difference between SET and SIT,

ST is the sealing temperature,

HTF is a high temperature cohesive force,

TPE is the total transmission energy.

Claims (16)

A propylene copolymer composition (P) comprising:
(a) a propylene copolymer (A) having a comonomer content of at least 1.0 wt.%, wherein said comonomer is a C ₅ to C ₁₂ alpha-olefin, and
(b) 4.0 to 20.0 propylene copolymer having a comonomer content in weight% (B) (wherein the comonomer is C ₅ to C ₁₂ α- olefin Lim),
Also,
(i) the comonomer content in the propylene copolymer (A) is lower than the comonomer content in the propylene copolymer (B)
(ii) the propylene copolymer composition (P) has a comonomer content of 3.5 to 6.5 wt.%, the comonomer is a C ₅ to C ₁₂ alpha-olefin,
(iii) the weight ratio of the propylene copolymer (A) to the propylene copolymer (B) is in the range of 20/80 to 80/20,
(iv) The propylene copolymer composition (P) has a crystallization temperature (T _c ) in the range of 88 to 110 ° C measured according to ISO 11357-3. The propylene copolymer composition (P) according to claim 1, wherein com (P) / com (A) is in the range of 1.0 to 10.0:
Com (A) is the comonomer content of the propylene copolymer (A) given in weight percent (% by weight)
Com (P) is the comonomer content of the propylene copolymer composition (P) given in weight percent (% by weight). The propylene copolymer composition (P) according to claim 1 or 2, which satisfies the following equation (I):
Tm - SIT ≥ 22 ° C (I)
[Wherein,
Tm is the melting temperature of the propylene copolymer (P) given in degrees Celsius,
SIT is the heat seal initiation temperature (SIT) of the propylene copolymer (P) given in degrees Celsius. The propylene copolymer composition (P) according to claim 1 or 2, having a hot seal initiation temperature (SIT) of 120 ° C or less. The propylene copolymer composition (P) according to any one of claims 1 to 3, having at least one selected from the group consisting of (a), (b) and (c)
(a) a melt flow rate MFR ₂ (230 ° C) in the range of 2.0 to 50.0 g / 10 min measured according to ISO 1133,
(b) a melting temperature Tm of 125 캜 or higher, and
(c) a xylene solubles content (XCS) of less than 20.0% by weight measured at 23 DEG C in accordance with ISO 6427. A process as claimed in any one of the preceding claims wherein the comonomer is selected from the group consisting of C ₅ alpha-olefins, C ₆ alpha-olefins, C ₇ alpha-olefins, C ₈ alpha-olefins, C ₉ alpha-olefins, C ₁₀ alpha-olefins, C ₁₁ propylene copolymer composition (P) selected from the group consisting of? -Olefins and C ₁₂ ? -Olefins. The propylene copolymer composition (P) according to any one of claims 1 to 3, having a molecular weight distribution (MWD) of 4.0 or less as measured by gel permeation chromatography (GPC). 3. The propylene copolymer composition (P) according to claim 1 or 2, wherein the ratio of MFR (A) / MFR (P) is in the range of 0.25 to 10.0:
The MFR (A) is the melt flow rate MFR ₂ (230 캜) [g / 10 min] of the propylene copolymer (A) measured according to ISO 1133,
The MFR (P) is the melt flow rate MFR ₂ (230 캜) [g / 10 min] of the propylene copolymer composition (P) measured according to ISO 1133. The propylene copolymer composition (P) according to claim 1 or 2, wherein the propylene copolymer (A) has at least one selected from the group consisting of the following (a), (b)
(a) a comonomer content in the range of from 1.0 to 4.0% by weight,
(b) a melt flow rate MFR ₂ (230 캜) of 0.5 g / 10 min or more, measured in accordance with ISO 1133, and
(c) a xylene solubles content (XCS) of less than 2.0 wt%. The propylene resin composition according to claim 1 or 2, wherein the propylene copolymer (A), the propylene copolymer (B), or the propylene copolymer (A) and the propylene copolymer (B) Copolymer composition (P). A film comprising the propylene copolymer composition (P) according to claim 1 or 2. An extrusion coated substrate comprising a coating comprising the propylene copolymer composition (P) according to claim 1 or 2. A process for the preparation of the propylene copolymer composition (P) according to claims 1 or 2, comprising a step of polymerizing two or more reactors connected in series, the process comprising the steps of:
(A) polymerizing propylene and at least one C ₅ to C ₁₂ ? -Olefin in a first reactor (R-1) which is a slurry reactor (SR) to produce a propylene copolymer A ), &Lt; / RTI &gt;
(B) moving the propylene copolymer (A) and the unreacted comonomer of the first reactor in a second reactor (R-2) which is a gas phase reactor (GPR-1)
(C) feeding propylene and at least one C ₄ to C ₁₀ alpha-olefin to the second reactor (R-2)
(D) polymerizing propylene and at least one C ₅ to C ₁₂ ? -Olefin in the presence of said first propylene copolymer (A) in a second reactor (R-2) to obtain a propylene copolymer (B), and the propylene copolymer (A) and the propylene copolymer (B) are reacted to form a propylene copolymer composition (P) as defined in claim 1 or 2,
Also,
Polymerization takes place in the first reactor (R-1) and the second reactor (R-2) in the presence of a solid catalyst system (SCS), said solid catalyst system (SCS) comprising:
(i) a transition metal compound of formula (I)
R _n (Cp ') ₂ MX ₂ (I)
[Wherein,
"M" is zirconium (Zr) or hafnium (Hf)
Each "X" is independently a monovalent anionic sigma-ligand,
Each "Cp"" is a cyclopentadienyl-type organic ligand independently selected from the group consisting of substituted cyclopentadienyl, substituted indenyl, substituted tetrahydroindenyl, and substituted or unsubstituted fluorenyl , The organic ligand is coordinated to the transition metal (M)
"R" is a divalent bridging group linking the organic ligand (Cp '), where "R" is carbon (C), silicon (Si), germanium ) Bridging atoms selected from the group consisting of C ₁ to C ₂₀ hydrocarbyl, tri (C ₁ to C ₂₀ alkyl) silyl, and tri (C ₁ to C ₂₀ alkyl) And a siloxy group,
"n" is 1 or 2, and
(ii) a cocatalyst (Co) comprising a Group 13 element (E) of the Periodic Table (IUPAC). The method of claim 13, wherein the transition metal compound of formula (I) is a transition metal compound of formula (II)
[Formula (II)] &lt;

[Wherein,
M is zirconium (Zr) or hafnium (Hf)
X is a ligand having a sigma-bond to the metal "M"
R ¹ is the same as or different from each other, a linear saturated C ₁ to C ₂₀ alkyl, linear unsaturated C ₁ to C ₂₀ alkyl, branched saturated C ₁ -C ₂₀ alkyl, branched unsaturated C ₁ to C ₂₀ alkyl, C ₃ to C ₂₀ to cycloalkyl, C ₆ to C ₂₀ aryl, C ₇ to C ₂₀ alkylaryl and C ₇ to C ₂₀ aryl (which may contain one or more heteroatoms of a Group 14 to Group 16 of the periodic table (IUPAC)) &Lt; / RTI &gt;
R ² to R ⁶ are the same or different from each other and represent hydrogen, linear saturated C ₁ -C ₂₀ alkyl, linear unsaturated C ₁ -C ₂₀ alkyl, branched saturated C ₁ -C ₂₀ alkyl, branched unsaturated C ₁ -C ₂₀ Alkyl, C ₃ -C ₂₀ cycloalkyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ alkylaryl and C ₇ -C ₂₀ arylalkyl (containing at least one heteroatom of Group 14 to Group 16 of the Periodic Table (IUPAC) ), And is selected from the group consisting of
R ⁷ and R ⁸ are the same or different and are selected from hydrogen, linear saturated C ₁ to C ₂₀ alkyl, linearly unsaturated C ₁ to C ₂₀ alkyl, branched saturated C ₁ to C ₂₀ alkyl, branched unsaturated C ₁ to C ₂₀ Alkyl, C ₃ to C ₂₀ cycloalkyl, C ₆ to C ₂₀ aryl, C ₇ to C ₂₀ alkylaryl, C ₇ to C ₂₀ arylalkyl (containing at least one heteroatom of Group 14 to Group 16 of the Periodic Table (IUPAC) , SiR ¹⁰ ₃ , GeR ¹⁰ ₃ , OR ¹⁰ , SR ¹⁰ and NR ¹⁰ ₂ ,
At this time, R ¹⁰ is a linear saturated C ₁ -C ₂₀ alkyl, linear unsaturated C ₁ to C ₂₀ alkyl, branched saturated C ₁ to C ₂₀ alkyl, branched unsaturated C ₁ to C ₂₀ alkyl, C ₃ to C ₂₀ cycloalkyl, , C ₆ to C ₂₀ aryl, C ₇ to C ₂₀ alkylaryl, and C ₇ to C ₂₀ arylalkyl (which may contain one or more heteroatoms of Group 14 to Group 16 of the Periodic Table of the Elements (IUPAC)). And,
R ⁷ and R ⁸ together with the indenyl carbon to which they are attached are part of a C ₄ to C ₂₀ carbon ring system and one carbon atom may be substituted by a nitrogen,
R ⁹ are the same or different and are selected from the group consisting of hydrogen, linear saturated C ₁ to C ₂₀ alkyl, linearly unsaturated C ₁ to C ₂₀ alkyl, branched saturated C ₁ to C ₂₀ alkyl, branched unsaturated C ₁ to C ₂₀ alkyl, C Selected from the group consisting of C ₃ to C ₂₀ cycloalkyl, C ₆ to C ₂₀ aryl, C ₇ to C ₂₀ alkylaryl, C ₇ to C ₂₀ arylalkyl, OR ¹⁰ and SR ¹⁰ ,
Wherein R &lt; ¹⁰ &gt; is defined as before,
L is a divalent bridge connecting two indenyl ligands, a C ₂ R ¹¹ ₄ unit or SiR ¹¹ ₂ or GeR ¹¹ ₂ ,
Wherein R ¹¹ is selected from H, linear saturated C ₁ to C ₂₀ alkyl, linearly unsaturated C ₁ to C ₂₀ alkyl, branched saturated C ₁ to C ₂₀ alkyl, branched unsaturated C ₁ to C ₂₀ alkyl, C ₃ to C ₂₀ (Which may contain one or more heteroatoms of group 14 to group 16 of the Periodic Table of the Elements (IUPAC)), cycloalkyl, C ₆ to C ₂₀ aryl, C ₇ to C ₂₀ alkylaryl and C ₇ to C ₂₀ arylalkyl Selected in. A propylene copolymer composition (P) obtained by the process according to claim 13. delete