CZ227395A3 - Composition of highly solid propylene-ethylene block copolymer and process for preparing thereof - Google Patents

Abstract

PURPOSE: To obtain a propylene-ethylene block copolymer, capable of satisfying specific conditions and useful for moldings having high impact resistance, etc., from a two-stage process by using a specified catalyst. CONSTITUTION: This composition is obtained by (A) homopolymerizing propylene in the first stage and providing the homopolymer in an amount of 60-95wt.% based on the total weight and then (B) copolymerizing propylene with ethylene in the second stage and affording a propylene-ethylene copolymer having 30-80wt.% ethylene content in an amount of 5-40wt.% based on the total weight. The maximal value [MFR (h)] and the minimal value [MFR (1)] of the polymer in the stage (A) have the relationship of formula I and the isotactic pentad fraction of the propylene polymer in the stage (A) is >=0.96. The Mw /Mn (Q value) of the polymer in the stage (A) is <=6. The homo- and copolymerizations are carried out so that the melt flow rate [MFR (i)] of the polymer in the stage (A) and the melt flow rate [MFR (ii)] of the polymer in the stage (B) may have the relationship of formula II.

Description

The present invention relates to a composition of a high-strength melt block copolymer and a process for its manufacture. More particularly, the present invention relates to the aforementioned polymer composition providing an injection product having high rigidity and high impact strength without the addition of an additive and a process for its manufacture.

BACKGROUND OF THE INVENTION

Crystalline polypropylene (often referred to as polypropylene) as a multipurpose resin is provided with high strength, hardness, and tensile strength. heat resistance, etc. However, it has insufficient high impact strength properties: therefore, there is a problem that it is difficult to use for stamped articles subjected to mechanical impact or used at low temperatures. Furthermore, when compared to other multipurpose resins such as ABS resin or high-performance polystyrene resin, it is excellent not only in high impact strength properties but also in stiffness. In order to extend the use of polypropylene and thus its demand, it is desirable to improve not only the abovementioned impact properties but also its rigidity.

Crystalline polypropylene produced using a stereoregulation catalyst is provided with excellent properties such as stiffness, heat resistance, etc., but on the other hand, there is a problem that its high shear strength, especially high shear toughness properties

they are low at low temperature; this limits its practical scope of use. As a solution to this problem, a method of random or block copolymerization of propylene with another α-olefin such as ethylene is known.

In particular, the resulting random copolymer is insufficient to improve the impact toughness properties especially at low temperatures compared to those of polypropylene and the stiffness, strength, heat resistance, etc. rapidly decrease with increasing ethylene content. Similarly, the block copolymer is improved in terms of low temperature impact resistance properties, but vice versa, its stiffness, hardness, heat resistance, etc. decrease compared to polypropylene. Therefore, many processes have been proposed to overcome the disadvantages of the block copolymer.

For example, Japanese Patent Application No. Sho 50-115296. Sho 52-4-588 and Sho-53-35879, discloses a method for performing block copolymerization of propylene with ethylene by a multistage process. Further, for example, Japanese Patent Publication Nos. Sho 47-8207, Sho 49-13231 and Sho 49-13514 disclose an improvement of the process by adding a third component to the catalyst. Further, Japanese Patent Application Publication No. Sho 55-764, Sho 54-152095, Sho 53-29390 and Sho 55-8011 disclose an improved method using a specific catalyst.

However, these various techniques are directed to the technique of reducing the stiffness range of the resulting block copolymer as low as possible as compared to polypropylene (homopolymer), a value of stiffness similar to or greater than that of the homopolymer was still not achieved. Further, Japanese Patent Application No. Sho 58-201816 discloses a process for producing a high-strength propylene-ethylene block copolymer. having a stiffness similar to or greater than that of polypropylene, but the improvement in high-tenacity properties was insufficient.

Accordingly, the present inventors have conducted intensive research into the manufacturing process of propylene-ethylene block copolymers having high stiffness and high tenacity, without the addition of any additional additive, and as a result have found that the desired copolymer can be obtained under the specific conditions described below and according to the present invention. It is clear from the foregoing that it is an object of the present invention to provide a propylene-ethylene block copolymer composition suitable for molded articles having high stiffness and high impact strength and a process for its manufacture.

The essence of the invention

The present invention has the following features:

(1) In the process for producing propylene-ethylene block copolymers it is characterized by:. A catalyst system having a combined (A) solid catalyst component comprising Ti, Mg, halogen and a polyvalent carboxylic acid ester as insoluble component, (B) an organoalurainium compound and (C) an organosilicon compound of formula R ⁴ x R ⁵ ySi (OR ⁶ ) _z wherein R ⁴ and R ⁶ represent each a hydrocarbon radical, R ⁵ represents a hydrocarbon radical or a hydrocarbon radical containing a heteroatom and X + Y + Z = 4,

1 <.Y <.3, 1 <Z <.3 and the following two polymerization steps are performed in succession:

first a polymerization stage (I) controlled in particular for propylene polymerization, wherein the monomers in the ratio ethylene / (ethylene + propylene) = 0 to 5 wt. fed to two or more polymerization vessels connected in series to form 60 to 95% of the total polymerized amount and a second polymerization stage (II) containing a relatively large amount of ethylene wherein the monomers in an ethylene / (ethylene + propylene) ratio = 10 to 100 wt. are introduced into one or more polymerization vessels, to form 5 to 40% of the total polymerized amount, a process for producing a composition of high-rigidity propylene-ethylene block copolymers characterized in that the composition is produced such that the maximum melt flow rate (hereinafter referred to as The MFR (h)) of the polymer obtained in the vessels of polymerization stage (I) and its minimum value (hereinafter referred to as MFR (1)) may have the relationship

0.1 < log (MFR (h) / MFR (1) < 1 and MFR (i) of polymers obtained in polymerization stage (I) mainly driven by propylene and MFR (ii) of polymers obtained in polymerization stage (II) containing a relatively large amount of ethylene may have the relationship expressed as follows

A method for producing a high-rigid propylene-ethylene block copolymer composition according to (1), wherein the molar ratio of organo 1 icon compound (C) to organoaluminum compound (B) is (B). ) / (C) = 1 to 15.

(3) A propylene-ethylene block copolymer composition produced using a catalyst system having a combined (A) solid catalyst component.

containing Ti, Mg, halogen and a polyvalent carboxylic acid ester as insoluble components, (B) an organoaluminum compound and (C) an organosilicon compound of the formula R ⁴ x R ⁵ y Si (OR ⁶ ) _z wherein R ⁴ and R ⁶ are each a hydrocarbon radical, R ⁵ represents a hydrocarbon radical or a hydrocarbon radical containing a heteroatom and X + Y + Z = 4,

2, 1 (3) and 1 (2), by performing the following two polymerization steps:

first a polymerization stage (I) controlled, in particular, for propylene homopolymerization, in two or more polymerization vessels connected in series to obtain 60 to 95% by weight and a second polymerization stage (II) copolymerization of propylene with ethylene in one or more polymerization vessels to form % of the copolymerized propylene-ethylene portion of 5 to 40% by weight, wherein the ethylene content is 30 to 80% by weight of the composition of the high-strength propylene-ethylene block copolymer. wherein the maximum value of the melt flow rate (hereinafter referred to as MFR (h)) of the polymer obtained in the vessels of polymerization stage (I) and its minimum value (hereinafter referred to as MFR (h)) may have the relationship

O.log (MFR (h) / MFR (1) <1 (1) isotactic pentad ratio (P (propylene polymer obtained in polymerization stage (I) is 0.96 or more; Mw / Mn (Q value) is 6 or and a melt flow rate (hereinafter referred to as MFR (i)) of the polymer obtained in polymerization stage (I), and a melt flow rate (hereinafter referred to as MFR (ii)) of the polymer obtained in polymerization stage (II).

is in a relationship expressed as follows

3 < 1 og (MFR (i) / MFR (i)) &lt; 7 (2).

(4) The high-strength propylene-ethylene block copolymer composition of (3), wherein the MFR of the final polymer obtained is 0.1 to 100.

(5) The high density propylene-ethylene block copolymer composition of (3), wherein the composition is obtained by polymerization in a hydrocarbon solvent.

(6) The high density propylene-ethylene block copolymer composition of (3), wherein the MFR (h) and MFR (1) referred to in (3) have the relationship

0.2 µg (MFR (h) / MFR (1)) δ.5.

(7) The high density propylene-ethylene block copolymer composition according to (3), wherein the MFR (i) and MFR (i i) mentioned in (3) have the relationship

4 <log (MFR (i) / MFR (i)) <6.

Description of the figure in the attached drawings

Giant. 1 is a flow diagram illustrating the production steps of the present invention.

In the present invention, a highly stereoregular catalyst system obtained using as a polymerization catalyst having (A) a solid catalyst component containing Ti, Mg is used. halogen and polyventive carboxylic ester. and (C) an electron yielding compound, but such a catalyst system has no limitation and various known catalyst systems providing highly stereoregular polypropylene can be used.

Such a solid catalyst component (A) can be prepared, for example, according to the procedures described in the following publications:

Japanese laid-open patent applications no .:

Sho 50-108385, Sho 50-126590, Sho 51-20297, Sho 51-28189, Sho

51- 64586, Sho 51-92885, Sho 51-136625, Sho 52-87489, Sho

52- 100596 ,, Sho 52-147688, Sho 52-104593, Sho 53-2580, Sho

53-40093, Sho 53-40094, Sho 55-135102. Sho 55-135103, Sho

55-152710 58-83006. 58-138708 60-23404,

Sho 56-811. Sho 56 — i 1908, Sho 56-18606, Sho Sho 58-138705. Sho 58-138706. Sho 53-138707, ShoSho 58-138709, Sho 58-138710. Sho 58-138715. Sho Sho 61-21109. Sho 61-37802. Sho 61-37803, Sho

62-104810. Sho 62-10481 1

Sho 62-104812. Sho 62-104813. Sho

63-54405 etc.

of the polyvalent carboxylic acid catalyst component (A) are maleic acids substituted with an alcohol having two or more

Specific examples of the acid used in solid esters of phthalic acid, malic acid etc. with carbon atoms.

As the Mg compound used above in (A) of the present invention, various compounds can be used and the Mg compound having or not reducing capacity is used.

Examples of the former are dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, ethylmagnesium chloride, prooylmagnesium chloride, butylmagnesium chloride, and the like.

Examples of the latter are magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, etc., alkoxymagnesium chlorides such as methoxymagnesium chloride, ethoxymagnesium chloride, etc., alkoxymagnesium such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium magnesium, etc. magnesium carboxylate, magnesium carboxylate etc. etc.

Of the above compounds, magnesium halides, alkoxymagnesium chlorides and alkoxymagnesia are particularly preferred.

As the Ti compounds used in the solid catalyst component (A) of the present invention, the optimum compounds are generally represented by the formula Ti (OR) and Xa-a (R: hydrocarbon radical, / halogen; and OAA 4 4). Specific examples are titanium halides such as TiCl 3, TiB 6, etc., alkoxytitanium trihaiogenides such as Ti (OCH 3) Cl 3.

Ti (OCH 2 H 5) C 13 etc, dialkoxytitanium dihalides such as Ti (OCH 3) 2 Cl 2, Ti (OC 2 H 5) 2 Cl 2 etc.

trialkoxy titanium monohalides such as TifOClbCl.

Ti (OC 2 H 5) 3 Cl, etc., tetraalkoxytitanias such as T1 (OCH 3) and. Ti (OCl 2) 5, etc. TlCl 4 is particularly preferred.

In preparing the solid catalyst component (A), if necessary, an electron donor such as an alcohol, ether, phenol, silicone compound, aluminum compound, etc. may be used together with the above Ti compound, Mg compound, and polyvalent carboxylic acid ester .

The organoaluminium compound (B) used in the present invention may be an organoaluminum compound of formula A IR ^{2 and} R ³ nX ³ - (m + n), wherein R ² and R ³ each represent a hydrocarbon radical or a alkoxy group; X is halogen; m and n each preferably represents an Oinil α1 number of 5 m m + n 3 3. Specific examples are trimethylaluminum. triethylaluminum, tri-n-propylaluminium, tri-n-butylaluminium, tri-iso-butylaluminium, diethylaluminum chloride, di-n-propylaluminium monochloride, diethylaluminium iodide, methylaluminium umseskvi chloride. ethylaluminum sesquichloride, ethoxydiethylaluminum etc.

these organoaluminum compounds (B) may be used alone or in a mixture of two types or more.

As an electron donor component (Cj used in the present invention), an organosilicon compound of the formula

R ⁴ x R ⁵ y Si (OR ⁶ ) z wherein R ⁴ and R ⁶ are each a hydrocarbon radical. R ³ represents a hydrocarbon radical or a hydrocarbon radical containing a heteroatom and X-Y + Z = 4.

1 <Y <3, 1 <Z <3.

Specific examples are methyltrimethoxysilane. methyltriethoxysilane, methylpropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropylamide oxysilane. iso-propyltriethoxysilane, n-butyl-trimethoxysilane. isobutyl imethoxysilyl, i-butyltriethoxysilane. t-butyltrimethoxysilane, t-butyltriethoxysilane n-pentyltrimethoxysilane, n-pentyltriethoxysilane, neopentyltrimethoxysilane. neopetyltriethoxysilane, hexadecyl 11 rimethoxysilane, hexadecyl 11 r ethoxysilane.

dime.thyldimethopxysi lan.

d ime thyldi e thoxysilane, d i e thyldime thoxysilane, diethyldiethoxysilane. di-n-propyldimethoxysilane, di-isopropyldimethoxysilane, di-n-butyldimethoxysilane. di-i-butyldimethoxysilane, di-tert-butyldimethoxysilane, di-n-pentyldimethoxysilane, dineopentyldimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, di-phenyldimethoxysilane, di-phenyldimethyloxysoxethoxysilane, di-phenyldimethoxysilane lan, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysila

3-mercaptopropylmethyldimethoxysilane, 3-isocyanatopropyltriethoxysilane,

2- (3-cyclohexenyl) ethyltrimethoxysilane, etc.

These organosilicon compounds may be used alone or in a mixture of two or more types thereof in suitable proportions. Particularly preferred organosilicone compounds are di-isopropyldimethoxysilane, tert-butylene ethoxy silane. tert.buty i trimethoxysílán.

isobutyltrimethoxysilane; and cyclohexyltrimethoxysilane. The preferred amount of organosilicon compound (C) added is in a ratio of (B) / (C) of 1 to 15 based on the amount of the above organoaluminum compound (B). If the amount is less than the above, the stiffness improvement is not sufficient and if too high the catalytic activity decreases; moreover, such amounts are impractical.

The solid catalyst component (A) is then combined with the organoaluminum compound (B) and the organosilicon compound (C) and used as a catalyst for propylene polymerization. Alternatively, α-olefin reacts with it and the resulting pre-activated catalyst is used. The preactivation is carried out using an organoaluminum compound (B) in an amount of 0.3 to 20 moles per mole of titanium in the preactivated catalyst component (A) ^J at 0 C to 50 ° C for one minute to 20 hours and the reaction 0 1 to 10 ml, preferably 0.3 to 3 mol of α-olefin.

The α-olefin reaction during pre-activation can be carried out in an aliphatic or aromatic hydrocarbon solvent or liquefied α-olefin such as liquefied propylene, liquefied 1-butene, etc., without the use of any solvent, and also ethylene, propylene etc. can react in the gas phase. Further, the α-olefin polymer can be obtained in advance or the hydrogen can be produced simultaneously. Still further, in pre-activation, the organosilane compound (C) may be pre-added.

The α-olefins used for pre-activation are linear chain monoolefins such as ethylene, propylene, butene-1.

1-hexene. 1-heptenes, etc., branched monoolefins such as 4-methyl-1-pentene, 2-methyl-1-pentene, 3-methyl-1-butene etc., styrene, etc. These α-olefins can be used in admixture with a- olefins that are polymerized.

Upon completion of pre-activation, the solvent, the organoaluminum compound and unreacted α-olefin can be filtered or removed by decantation, or the resulting material can be dried and used as a powder.

The resulting preactivated catalyst can be used in slurry polymerization where poropylene is polymerized in a hydrocarbon solvent such as n-hexane. n-heptane, n-octane. benzene, toluene, etc., or bulk polymerization carried out in liquefied propylene or gas-phase polymerization.

In the case of suspension polymerization, this is usually carried out at a polymerization temperature of from 20 to 90 ° C, preferably from 50 to 80 ° C and at a polymerization pressure of from 1 to 50 bar. In the case of gas-phase polymerization, this is usually carried out at a polymerization temperature of 20 to 150 ° C and at a polymerization pressure of 0.3 to 5 MPa. Hydrogen is usually used to control the molecular weight and the polymerization is carried out so that the resulting polymer must have an MFR in the range of 0.1 to 1.00.

When the monomer composition is introduced into the polymerization stage (I), this stage is carried out in an ethylene / (ethylene + propylene) ratio of 0 to 5% by weight. If the ethylene content is higher than 5 wt. there is a risk that the physical properties such as stiffness, heat resistance, etc. specific to the polypropylene will be impaired.

Furthermore, 1-butene, 4-methyl-1-pentene, styrene and unconjugated dienes or the like can be added to the propylene in an amount of 0 to 10% as the third monomer component.

The polymerized amount in the polymerization stage (I) is 60 to 95% by weight. based on the total amount of the propylene-ethylene block copolymer composition finally obtained. If the polymerized amount is less than the above range, the product surface stiffness decreases, while greater than this range, the improvement in low temperature impact toughness is insufficient.

The polymerization of the polymerization stage (I) is carried out using two or more polymerization vessels involved in sex and the relationship between the maximum value (MRF (h)) of the melt indexes of the obtained polymer in the corresponding vessel and its minimum value (MRF (1)) is preferably ϋ, ί <log (MFR (h) / MFR (1)) <1.

preferably i

0.2 <log (MFR (h) / MFR (1)) 0,50.5.

If the MFR ratio is lower than the above, the stiffness of the product decreases, while higher than the above, the elongation strength properties and high shear strength of the final propylene-ethylene block copolymer obtained decrease.

Further, the isotactic pentad ratio (P) of the polymer composition obtained in the polymerization stage (I) is 0.96 or higher and the ratio (Q) of the weight average molecular weight (Mw) to the number average molecular weight (Mn). as measured by gel permeation chromatography (GPC) 6 or less. If the isotactic pentad ratio (P) is lower than according to the present invention, the stiffness of the compressed product decreases, while if the Q value is higher than indicated, the high-tenacity toughness of the compressed product is lower.

The polymerization stage (II) is carried out by copolymerizing ethylene with propylene, usually at a polymerization temperature of 20 to 80 ° C, preferably 40 to 70 ° C, and at a pressure of 5 to 5 MPa. The method of feeding ethylene and propylene to the polymerization vessel and the method of polymerization are not limited. Hydrogen is usually used to control the molecular weight and its concentration in the gas phase is 0.1 to 10 mol%. The ratio of ethylene to propylene fed to the polymerization stage (II) is 10 to 100 wt. based on ethylene / (ethylene + propylene). %, preferably 20 to 70 wt. and the polymerized amount is 5 to 40 wt. based on the weight of the final propylene-ethylene block copolymers.

Furthermore, another α-olefin, unconjugated diene, and the like can be added to ethylene and propylene.

The polymerization in the polymerization stage (II) is carried out using a polymerization vessel or two coupled polymerization vessels.

The ethylene content of the polymerized fraction in the polymerization stage is 30 to 80% by weight, preferably 40 to 70% by weight. If the ethylene content is outside this range, the rigidity and high impact strength of the resulting polymer are impaired. The amount of polymerization in the polymerization stage (II) is 5 to 40 wt. based on the total amount of polymer finally obtained.

Along with ethylene and propylene, other α-olefin, unconjugated diene, etc. may be used.

The relationship between the MFR (i) of the polymer obtained in the polymerization stage (I) and the MFR (ii) of the polymer obtained in the polymerization stage (II) is preferably such that it satisfies < 1og (MFR (i) / MFR (i)) < 7.

preferred is log (MFR (h) / MFR (1)) 16.

MFR (i) is the observed value only for the polymer in polymerization stage (I) and MFR (ii) is the value calculated from the observed MFR value (denoted as mFR (i + i)) after completion of the second stage; polymer fraction (WL) in polymerization stage (I) and polymer fraction (W2) in polymerization stage (II) according to the following equations (2) and (3):

L5 log MFF (T) W1 + W2 =

Wl x MFF log (i) + W2 x MFF log (i) (2) (3)

When the log (MFF (i) / MFR (ii) < 3) is a resultant polymer which is poor in terms of low temperature impact strength, tensile elongation, etc. Furthermore, the polymer soluble in the polymerization solvent is formed in large quantities; economics and flow properties of the equipment are impaired.

Furthermore, in the case of log (MFF (i) / MFF (i))> 7, the polymer yield per catalyst unit is low; this case is therefore not suitable for practice.

The MFF of the final polymer obtained is preferably in the range of 0.1 to 100, more preferably in the range of 1 to 30. If the MFR is less than that of the present invention, the solubility decreases. whereas when the MFF is greater than the present invention, the high-tenacity toughness decreases.

In order to improve stiffness, heat resistance (heat-resistant stiffness, thermal deformation temperature, etc.), dimension of stability (percent shrinkage by compression, deformation of the molded product by wrinkling, etc.), coating, abrasion resistance etc. it is possible to mix the inorganic filler with the composition solid propylene-ethylene block copolymers. in the range of an amount that does not damage the object of the present invention and such an amount is, for example, preferably 0.1 to 30 parts by weight, more preferably 0.1 to 25 parts by weight. filler, which may be mixed with 100 wt. parts of a composition of a high-rigid polyene-ethylene block copolymer.

Examples of inorganic fillers are talc, calcium carbonate, potassium titanate whisker, mica, glass fibers, barium sulfate. magnesium sulfate, etc. They may be por in the mixture or individually. Of these inorganic fillers, talc is preferred and its average particle size is 5 µm or greater in terms of high shear toughness and the talc as a component having a particle size in excess of 10 µm is 5 wt%. % or less and is preferably 1 wt. or less in terms of high shear toughness

In order to improve high-tenacity, dimensional stability (linear expansion coefficient, deformation of the molded product by wrinkling, etc.), coating properties, etc., the high-strength propylene-ethylene-block copolymer composition of the present invention may be mixed with a non-crystalline or crystalline ethylene-α-ο1efin copolymer. . polyethylene (high-density polyethylene, low-density polyethylene, linear low-density polyethylene, super-high density polyethylene, etc.) or a styrene group elastomer, in an amount that does not harm the object of the invention and as such may be mixed for example 1 to 20 parts by weight. . % non-crystalline or low crystalline ethylene-α-olefin copolymer, with 100 parts by weight of the composition; a composition of a high-strength propylene-ethylene block copolymer.

The non-crystalline or low-crystalline ethylene-α-ο-olefin copolymer is a non-crystalline ethylene-propylene copolymer. a non-crystalline ethylene-1-butene copolymer. Of these, non-crystalline ethylene-α-olefin copolymers are preferred. An example of non-crystalline ethylene-α-olefin copolymers is a non-crystalline ethylene-propylene copolymer having a propylene content of 20 to 50 wt%, preferably 20 to 35 wt%. Mooney viscosity [ML + 4 (100 ° C)] 5 to 6, preferably 10 to 50 and mFR (230 ° C, 21.18 N) 0.1 to 20 g / 10 min, preferably 0.5 to 10 g / 10 min.

Further, if necessary, it is possible to mix with the high-strength propylene-ethylene block copolymer composition of the present invention one or more types of various additives such as antoxidants, antistatic agents, colorants (pigments), nucleating agents, release agents, substances , flame retardants, ultraviolet absorbers, environmental agents, plasticizers, radical generators, etc., to the extent that the object of the invention is not damaged.

The following are analytical and measurement methods for various physical properties used in the Examples below.

MFR: according to ASTM D-1238 (unit: g / 10 min), 230 ^; C. 2.15 kg load

- ethylene content: by infrared absorption light (unit: * w / w),

- ratio of polymerized amounts (W i Ά 2) in polymerization stage (I) and polymerization stage (II):

It was established as follows:

Prepare copolymers having different reacted ethylene / propylene ratios and then prepare infrared absorption spectrum calibration curves using these copolymers as standard samples, search for the ethylene / propylene reacted amount in the polymerization stage (II) and calculate further from the content of ethylene in the total polymer (w / w).

- bending module: according to JIS K7203 (unit: MPa)

- tensile strength: according to JIS K71L3 (unit: MPa)

- tensile elongation: according to JIS K7113 (unit:%)

- HDT: according to JIS K7207 (unit: ° C)

- Impact strength: according to JIS K7110 (unit: J / t ·

As described above, the present invention is directed to a method of manufacture in which much greater efficiency than the prior art could be achieved and will now be described in more detail in the following examples, which are not intended to limit it in any way.

DETAILED DESCRIPTION OF THE INVENTION

Example 1 (Preparation of solid Ti catalyst component)

A mixture of magnesium ethoxide (150 g), 2-ethyIhexylalkoholu (275 mL) and toluene (300 mL) was stirred at 93 ^C for 3 hours in the 0.3 MPa CO atmosphere and then added toluene (400 mL) and n-decane (400 mL). The resulting solution is then referred to as magnesium carbonate solution.

Toluene (100 ml), chlorobenzene (30 ml), tetraethoxysilane (9 ml), TiCl 3 (8.5 ml) and Isopar G (isoparaffinic hydrocarbon having an average carbon number of 10, mp 156-176 ° C) (100 ml) The mixture was stirred at 30 ° C for 5 minutes and then the above magnesium carbonate solution (50 mL) was added.

The mixture was stirred for 5 minutes, then tetrahydrofuran (22 ml) was added, stirred at 60 ° C for one hour, stirring was stopped, the supernatant was removed, the resulting solids were washed with toluene (50 ml), chlorobenzene (100 ml) was added. ) and TiCl 3 (100 mL) and the mixture was stirred at 135 ° C for 1 h, stirring was stopped, the supernatant was removed, ihlorobenzene (250 mL), TiCl * (100 mL) and di-n-butyl phthalate (2.1 mL) were added. ml), stirred at 135 ° C for 15 hours, the supernatant was discarded, the solids were washed successively with toluene (600 ml), Isopar G (800 ml) and hexane (400 ml) to give the resulting solid catalyst component. The composition of this component was Ti (2.3 wt%), Cl (55 wt%), Mg (17 wt%), and di-n-butyl phthalate (7.5 wt%).

Preparation of pre-activated catalyst

A 50 L stainless steel reactor equipped with oblique blades was flushed with nitrogen gas, then charged with n-hexane (40 L), the above solid product (75 g) and triethyl and 1 µm ini um (13 g) were added at temperature At room temperature, feed with propylene (100 g) over 120 min and unreacted propylene and n-hexane were removed under reduced pressure to give a pre-activated catalyst (150 g).

Polymerization stage (I)

In a 500 L stainless steel polymerization vessel with turbine type stirring blades and flushed with nitrogen gas, n-hexane (250 L) was added, followed by triethylaluminum (89 g) and di-isopropyldimethoxysilane (69 g) as an organosi 1 icon compound, then the above pre-activated catalyst (15 g) is introduced, the internal temperature of the reactor is raised to 70 ° C, propylene and hydrogen are fed while maintaining a total pressure of 0.8 MPa and a hydrogen / propylene concentration of 0.24 in the gas phase polymerization for one hour, the feed of propylene is terminated, the reactor is cooled to an internal temperature of 30 ° C and hydrogen and the unreacted propylene is drained.

A portion of the polymerized suspension is then discarded, MFF measurements are performed, and inductive binding plasma emission stereoscopic analysis (ICP method) determined the Mg content in the polymer to determine polymer yield per unit weight catalyst. The temperature inside the vessel was raised to 70 ° C, then propylene and hydrogen were introduced, and the second polymerization step was carried out for one hour while maintaining a total pressure of 1.0 MPa and a hydrogen / propylene concentration in the gas phase of 0.24. of propylene, the temperature inside the vessel is cooled to 30 ° C, hydrogen and unreacted propylene are removed, then part of the polymer slurry is removed, MFR measurement is performed, and the Mg content of the polymer is determined by ICP, to determine polymer yield in the second stage and determining the fraction of yρο1-directed amounts in the first stage and the second stage using the above-mentioned yield in the first stage. Further, the MFR t and MFF values were obtained in the following equation:

log MFR = a x log MFR: q}! / a] x log MFR3 where a: ζρο1directed ratio in the first stage,

MFR: MFR of the product taken after completion of the second step a

MFR 1 and MFR 2: MFR of the first s second stage to determine MFR2 of the second stage

Then the temperature inside the vessel is raised to 70 ° C, propylene and hydrogen are introduced, polymerization is carried out in the third stage for one hour, maintaining a total pressure of 1.2 MPa and a water / water concentration ratio of i / propylene of 24%, terminating. introducing propylene, reduce the temperature inside the vessel to 30 ° C, vent hydrogen and unreacted propylene, remove a portion of the polymer slurry, determine the MFR and the Mg content of the polymer by the ICP method to determine the polymer fraction in the third step.

Next, the values MFRi, MFR2 and MFRs are inserted into the following equations:

logMFR = a x logMFR1 + b x MFR2 + c x log MFR3 a + b + c = 1 where a: polymerization ratio in the first stage, b: polymerization ratio in the second stage and c: polymerization ratio in the third stage,

MFR: MFR of the product taken after completion of the third stage, to obtain the third stage MFR3.

Foiymerization stage (2)

The temperature inside the flask was increased to 60 ^J C poem is continuously fed ethylene and propylene for 2 hours to obtain a proportion of 35% of ethylene fed hmutn. The total amount of ethylene fed was 4.5 kg. During the polymerization, hydrogen is introduced as such. in that the concentration of hydrogen in the gas phase is 1 X mol. After polymerization for 2 hours, the feed of ethylene and propylene is terminated, the temperature inside the vessel is reduced to 30 ° C, and then unreacted ethylene and propylene are drained.

Methanol (50 L) is introduced into the polymerization vessel, then the temperature inside the vessel is raised to 60 ° C, after which 20% by weight is added after 10 minutes. aqueous NaOH solution (0.5 1) was stirred for 20 minutes, adding purified water (100 1), the temperature inside the reactor was reduced to 30 ³ C, removed aqueous layer, add additional purified water (300 L) Wash with water with stirring for 10 minutes, remove the aqueous layer, remove the hexane suspension.

filtered and dried, and the resulting propylene-ethylene-block copolymer is analyzed, which are shown in Table 1.

Preparation of the product by injection

To the powder of the product obtained above (3.0 kg) was added phenolic heat stabilizer (0.003 kg) and calcium stearate (0.003 kg) and then stirred for 10 min at room temperature using a high speed type mixer (Henschel mixer (trade name)), blend is granulated with an extruder granulator having a screw diameter (40 mm), and the granulated material is injected using an injection molding machine, at a molten resin temperature of 230 ° C and at a mold temperature of 50 ° C to prepare test samples into an JIS mold. in a chamber of 50% humidity and room temperature (23 ° C) for 72 hours. It then constructs the physical property values as shown in Table 1.

Examples 2 and 3 and Comparative Examples 1 and 2

Example 1 was repeated except that the amount of di-iopropyldimethoxysilane added was changed to 27.4 g. 13.7 g.

6.9 g and 172 g. The results are shown in Table 1. If the molar ratio (3 / C) of the organo-umium compound (B) to the organosilicon compound (C) is higher than according to the present invention, the stiffness of the resulting injection product is impaired. if the ratio is lower than this, the polymer yield per catalyst unit decreases and this is inappropriate.

In other words, if the isotactic pentad fraction (P) after the polymer obtained in the polymerization stage (I) is less than according to the present invention, the stiffness of the injection product is poorer.

Table i

Polymerization results and physical properties of the product

Ex.1 Ex.2 Ex .3 cf. l cf. . Ex 2 fixed cat.-component (A) according to -> -> -> -> organoaluminium (B) vyn. TEA -> -> -> -> organosi 1 icon words (C) diPDMS * -> -> -> -> B / C mo1. ratio 2 5 10 20 May 0.8 polymerization stage (I) 1st stage MFR g / 10 min 122 128 118 120 119 2nd stage MFR g / 10 min 100 ALIGN! 105 102 105 103 3rd stage MFR g / 10 min 70 66 78 7 5 69 log (MFR (h) / MFR (i)) 0.24 0.29 0.18 0 .20 0.23 ratio of polymerized quantity l.st:2.st:3.st. 35:33 33:34 34:33 3 3:34 3 4:33 : 32 : 33 : 33 : 33 : 33 MFR (i) g / 10min 96 96 98 98 95 polymerization stage (II) MFR (ii): g / 10 min 0.005 0.006 0.004 0.005 0.005 ratio of polymerized quantity after 1ym (I): after 1ym (II) 88:12 87: 13 88:12 87:13 N 7: 1 3

Table 1 (cont.)

powdered product Ex Example 2 Ex 3 s rov.př. 1 with equ MFR g / 10min 29 27 Mar: 29 27 Mar: 26 1og (MFR) / MFR (i) 4.3 4.2 4.3 4.3 4.3 R-E * wt% 48 5 1 49 50 52 T-E * wt% 6.3 6.4 5.9 6.5 6.8 yield kg 50 60 65 66 30 rozp. polymer% injection molded product 2.2 2.5 2.8 5.1 3.2 MPa bending module 1570 1530 1510 1380 1520 tensile strength MPa 38 37 37 35 38 elongation at tension% 340 380 440 165 182 HDT ⁵ 0 1 18 1 17 117 112 1 17 II 'J / m 98 101 96 95 96

Notes: diPDMS *: di-isopropyldimethoxysi lan (used 1 in Table 2 et seq.)

R-E *: Ethylene content of the polymer ζρο1merized in polymerization stage (II) (also used in Table 2 et seq.)

T-E ': Ethylene content of total polymer (also used in Table 2 et seq.)

II ': Izodt.ráz (also used in Table 2 and beyond)

Example 4

Example 2 is repeated, except that the hydrogen / propylene concentration ratios in the gas phase in 1,2. and 3rd stage of polymerization stage (I) were changed to 0.3, 0.23 and 0.16. The results are shown in Table 2.

Example 5

Example 4 is repeated except that the hydrogen / propylene concentration ratios in the gas phase in stages 1 and 2 of the polymerization stage (I) are changed to 0.22, the polymerization time is changed to 1.5 hours, and the polymerization in 3. degree was deleted. The results are shown in Table 2.

Comparative example

Example 5 is repeated except that the hydrogen / propylene gas phase ratios in the 1st and 2nd stages after the polymerization stage (I) are changed to 0.21 and 0.23, respectively. the polymerization time was changed to 1.5 hours. The results are shown in Table 2. Since the value of 10g (MFS (h) / MFS (1))) is lower than according to the present invention, the stiffness of the injection product is worse than that of the product according to the invention.

Comparative Example 4

Example 4 is repeated except that the hydrogen / propylene concentration ratio in the gas phase in stage 1 of polymerization stage (I) was changed to 0, the IS polymerization time was changed to 3 hours, and stage 2 and 3 polymerization were omitted. The results are shown in Table 2. The stiffness of the injected product is worse

7

Table 2

Results after 1ymeration and physical Product features Ex.4 Ex.5 cf. cf. cf. ex. 3 ρ row 4 př.5 fixed cat.-component (A) according to -> -> -> -> vyn. organoaluminium (B) TEA -> -> -> -> organosi 1 icon words (C) diPDMS * -> -> -> -> B / C mo1. ratio 5 -> -> -> -> polymerization stage (I) 1st stage MFR g / 10 min 200 1 10 105 100 ALIGN! 300 2nd stage MFR g / 10 min 105 80 90 - 100 ALIGN! 3rd stage MFR g / 10 min 40 - - - 20 May log (MFR (h) / MFR (2)) 0. 70 0.14 0.067 - 1. 2 ratio of polymerized quantity 1s t: 2.s t: 3.s t. 33:33 52:48 50: 50 - 45: 35 : 34 : 25 MFR (i) g / 10min 94 94 97 100 ALIGN! 1 10 polymerization stage (II) MFR (i): g / LQ min 0.006 0.004 0.005 0.005 0.00

ratio of polymerized amounts of polymer (I): polymer (II) 88:12

87:13 88:13 87:12 87:12

Table ..... 2

Ex.4 Ex.5 s rov. ex. 3 s r o v. ex. 4 s rov ex. 5 powdered product MFR g / 10min 29 25 28 28 28 log (MFR) / MFR (i) 4.3 4,5 4.3 4.3 4.3 R-E * wt% 48 52 51 5 1 51 T-E * w / w * 6.3 6.8 6.4 6.4 6.4 yield kg 55 62 50 55 55 rozp. polymer% 2.2 2.5 2.6 2.4 2.5 injection molded product MPa bending module 1580 1520 1480 1450 1560 tensile strength MPa 38 37 3 6 35 37 elongation at tension% 180 > 800 > 800 > 800 30 HDT ’C 1 18 117 l 15 1 15 1 17 II J / m 98 102 99 101 86

Comparative example

Example 4 was repeated except that the hydrogen / propylene gas phase concentration ratios in stages 1, 2 and 3 of the polymerization stage (I) were changed to 0.45, 0.23 and 0.10. The results are shown in Table 2. Since the value of 10g (MFR (h) / MFR (1))) is higher than according to the present invention, the impact toughness of the injected product is worse than that of the product according to the invention.

Comparative example 6

Example 2 is repeated except that the hydrogen / propylene gas phase concentration ratios in stages 1, 2 and 3 of the polymerization stage (1) have been changed to 0.35 and the hydrogen concentration in the gas phase polymerization stage (II) was The results are shown in Table 3.

Comparative example 7

Example 2 is repeated except that the hydrogen / propylene gas phase concentration ratios in stages 1, 2 and 3 of the polymerization stage (I) have changed to 0.20 and the hydrogen concentration in the gas phase polymerization stage (II) was The results are shown in Table 3.

Comparative example 6

Example 2 is repeated except that the hydrogen / propylene gas phase concentration ratios in stages 1, 2 and 3 of the polymerization stage (I) are changed to 0.60 and the hydrogen concentration in the gas phase polymerization stage (II) is changed to 0.05 mol% The results are shown in Table 3.

Since the value of 10g (MFF (i) / MFF (i)) in polymerization stage (I) and polymerization stage (II) is higher than according to the present invention, the impact toughness is worse and the polymer yield per catalyst unit also decreases.

Comparative example 7

Example 2 is repeated except that the hydrogen / propylene gas concentration ratios in stages 1, 2 and 3 of the polymerization stage (I) are changed to 0.18 and the hydrogen concentrations in the gas phase of polymerization stage (II) are to 10 mol%. The results are shown in Table 3.

Since the 1og (MFF (i) / MFF (ii)) value in polymerization stage (I) and polymerization stage (II) is lower than according to the present invention, the impact toughness and elongation at break are worse and the polymer soluble in the polymerization also increases. solvent.

Table 3

Results after polymerization and physical properties of the product

Ex. 6 Př.7 cf. s rov fixed cat.-component (A) according to -> Ex 6 -> Ex. 7 -> organoaluminium (B) vyn. TEA -> -> -> organosi 1 icon words (C) diPDMS * -> -> -> B / C mo1. ratio 5 -> -> -> polymerization stage (I) 1st stage MFR g / 10 min 250 100 ALIGN! 400 70 2nd gear MFR g / 10 min 180 70 310 50 3rd stage MFF g / 10 min 120 50 220 i n «* U 1og (MFR (h) / MFR (2)) 0.32 0.30 0, 26 0.24 ratio of polymerized quantity 1s t: 2. with t: 3.s t. 3 4:33 33: 34 34:33 34:33 : 33 : 3 3 : 33 : 33 MFR (i) g / 10min 176 70 302 52 polymerization stage (II) MFR (i): g / 10min 0.00005 0.05 0.00001 0.2 ratio of polymerized quantity Polymer (I): Polymer (II) 88:12 87:13 88: 13 87:

Table 1ka 3 (continued)

powdered product Ex.6 Př.7 s rov. Ex 6 s rov př.7 MFR g / 10min 29 28 32 27 Mar: log (MFR (i) / MFR (ii)) 6.5 3.1 7.5 2.4 R-E * wt 48 51 51 51 T-E * wt 6.3 6.4 6.4 6, yield kg 52 60 35 58 rozp. Polymer X injection molded product 1,8 3.0 2,0 5 ,: MPa bending module 1590 1530 1550 1420 tensile strength MPa 39 38 38 36 elongation at tension X 440 180 220 50 HDT ⁰ C 119 1 18 118 1 15 11 * J / m 106 97 95 SS

í |

í?

and

Example 8

Example 3 is repeated except that the hydrogen / propylene gas concentration ratios in stages 1, 2 and 3 of the polymerization stage (I) have changed to 0.08, the hydrogen gas concentration in the second stage (II) was changed to 0.5 mol% and the total amount of ethylene introduced was changed to 2 kg. The results are shown in Table 4.

Example 9

Example 3 is repeated except that the hydrogen / propylene gas concentration ratios in stages 1, 2 and 3 after the polymerization stage (I) have changed to 0.17, the hydrogen concentration in the gas phase polymerization stage has been changed to 0.5 mol%, the ethylene feed rate was changed to 65 wt%. and the total amount of ethylene introduced was changed to 7 kg. The results are shown in Table 4.

Comparative example 8

Example 9 is repeated except that ethyl benzoate is used as the electron donor in the solid catalyst component (A). The results are shown in Table 4. The stiffness and impact strength were significantly deteriorated compared to the present invention.

Comparative example 9

Example 9 is repeated except that the reduction type catalyst described in Japanese laid-open patent application Sho 58-201816 is used as the solid catalyst component (A). diethylaluminum chloride was used as the organoaluminum compound (B) and methyl p-toluylate was used in place of the organosilicon compound (C).

The results are shown in Table 4. Stiffness and impact strength were poor and the polymer yield per catalyst unit was lower compared to the present invention.

Table 4

Polymerization results and physical properties of the product

Ex.8 Př.9 s rov. s rov. př.8 př.9 fixed cat.-component (A) according to -> on reducing vyn. porters * type* organoaiumini (B) TEA -> -> DEAE organosi 1 icon words (C) diPDMS * -> -> * l B / C mol. ratio 10 -> -> -> polymerization stage (I) 1st stage MFR g / 10 min 30 64 33 31 2nd stage MFR g / 10 min 20 May 44 2 i 22nd log (MFR (h) / MFR (2)) 0.33 0.24 0.29 0.22 ratio of polymerized amount lst: 2.st: 3.st. 38:35 35:32 34:33 34:34 : 32 : 33 : 33 : 32 MFR (i) g / 10min 24 47 23 2 4 polymerization stage (II) MFR (ii): g / 10min 0.001 0,002 0.0006 0.0005

ratio of polymerized amounts of polymer (I) to polymer (II) 94: 6

79:21 78:22 79:21

3ο

Table 4 (cont.)

powdered product Ex.8 Ex.9 - s rov. př.8 s rov. př.9 MFR g / 10min 13 5.7 2.3 2.5 log (MFR (i) / MFR (ii)) 4.4 4.4 4.8 4.7 R-E * wt% 48 65 66 65 T-E * wt% 2.9 13.7 13.9 13.7 yield kg 55 66 60 50 rozp. polymer% injection molded product 1, 5 3.2 6.6 6.4 MPa bending module 1730 1310 980 1260 tensile strength MPa 38 29 22nd 28 elongation at tension % 440 > 800 > 800 5 5 HDT ³ C 1 19 110 96 103 II * J / m 76 190 152 125

on the support *: catalyst obtained using ethyl benzoate as an electron donor reducing type *: catalyst used in the example of Japanese laid-open patent application No. Sho 58-201816 * 1: used methyl p-1o 1ylate

Examples 10 to 14

Example 2 is repeated except that the tert-butyltrimethoxysilane, tert-butyltriethoxysilane, isobutyltrimethoxysilane, cyclohexyltrimethoxysilane, or di-isobutyldimethoxysilane are used as the organosilicon compound. The results are shown in Table 5.

Table 5

Polymerization results and physical properties of the product

Ex.10 Ex.1l Ex.12 Ex 1 3 p ř. 14 fixed cat.-component (A) d 1 e -> -> -> -> organoaluminium (B) vyn. TEA -> -> -> -> organosi 1 icon words (C) t-BTMS 5-BTES * i-BTMS * SHTMSi * diBDMS B / C mo1. ratio 5 -> -> -> *"* of polymerization stage (I) 1st stage MFR g / 10 min 130 128 125 133 129 2nd stage MFR g / 10 min 1 10 108 107 102 108 3rd stage MFR g / 10 min 6 5 61 63 6 6 6 b 1 og (MFR (h) / L ^; R (l)) 0.30 0.32 0.30 0.30 0. 30 ratio of polymerized quantity l.st:2.st:3.st. 34: 33 33:34 35:33 33: 34 34:33 : 33 : 33 : 33 : 33 : 32 MFR (i) g / 10min 98 95 95 96 97 polymerization stage (II) MFR (ii): g / 10min 0.005 0.006 0.006 0.006 0.00

ratio of polymerized amounts after 1 µm (I): after 1 µm (11) 88:12

87:13 88:13 88:12

88:12 i

Table 5 (cont.) Ex. 1 0 powder product

MFR g / 10 min 30 log (MFF (i) / MFR (i) 4.3)

R-weight% 43

T-E wt% 6.1 yield kg 55 sol. polymer% 2.8 injection product MPa bending modulus 1520 tensile strength MPa 37 elongation at tensile% 370

HDT ⁰ C 116

II * J / m 100

ex. 1 L p ř. 1 2 Ex 1 3 ex. 14 27 Mar: 27 Mar: 30 30 4.2 4.2 4.2 4.3 5 1 49 50 52 6.5 6.8 5.9 6.1 52 53 55 62 2.9 2.8 3.1 3.3 1510 1530 1540 1480 37 37 35 36 385 390 350 380 116 117 i 17 1 16 102 99 93 ICL

Note: t-MTMS *: tert-butyltrimethoxysilane t-BTES *: tert-butyltriethoxysilane i-BTMS *: iso-butyltrimethoxysilane SHTMS *: cyclohexyltrimethoxysilane di3DMS *: di-iso-butyldimethoxysilane

Comparative Examples 10-13

Example 2 is repeated except that methyl p-toluylate, triethylamine, acetophenone or diethylene glycol dimethyl ether is used as the electron donor instead of an organosilicon compound.

The results are shown in Table 6. The rigidity was poor and also the amount of polymer soluble in the polymerization solvent produced was greater compared to the present invention.

1

Table 6

Polymerization results and physical properties of the product solid cat. Component (A) organoaluminum column (B) organosi 1 icon column (C) B / C mo1. ratio polymerization stage (I)

Grade 1 MFR g / 10 min

2nd stage MFR g / 10 min

3rd degree MFR g / 10 min log (MFR (h) / MFR (1)) ratio of množstvíρο1ymer quantities ist: 2ndst: 3rdst.

MFR (i) g / 10 min polymerization stage (II) MFR (ii): g / 10 min ratio of množstvíρο1ymered amounts after 1 µm (I): after 1 µm (II)

cf. s rov. s rov. s rov ex. i0 ex. 1 1 ex. 1 2 Ex · according to -> -> -> vyn. TEA -> -> -> AND* B * C* D * 5 -> -> -> 128 129 130 128 110 112 108 105 70 65 63 66 0.26 0.30 0.31 0.29 34:33 33:34 35:33 33:34 : 33 : 33 : 32 : 33 100 ALIGN! 98 97 96 0.006 0,004 0 .006 0.005 87:13 87:13 88: 1 .2 87:

Table 6 (cont.)

cf. ex 1 0 cf. Ex 1 1 cf. Ex 1 2 cf. Ex 1 3 powdered product MFR g / 10min 28 26 30 2 7 log (MFR (i) / MFR (ii)) 4.2 4.4 4.2 4.3 R-E wt% 48 5 1 50 51 T-E wt% 6.2 6.6 6.0 6.6 yield kg 35 45 48 44 rozp. polymer% 5.8 4.9 4,5 6, injection molded product MPa bending module 1230 1380 1330 1240 tensile strength MPa 30 32 3 1 28 elongation at tension% 120 155 145 160 HDT ² C 102 108 106 101 II 'J / m 95 92 98 95 Note: A ': methyl-p- tolvate 3 ': triethylamine C ': acetophenone D *: i thyeng lykoldiraethylether

Example 15 and Comparative Examples 14 and 15

Example 1 was repeated except that the proportion of ethylene fed to the gasification stage (II) was changed to 25% by weight, 15% by weight. and 90 wt. and the total amount of ethylene introduced was changed to 3.5 kg, 2.5 kg and 7.0 kg. The results are shown in Table 7. Compared to Example 15 in Comparative Example 14, the ethylene content of the polymerized portion in the polymerization stage (I) was lower than according to the present invention; therefore, the high injection strength of the resulting injection product is poor and the ethylene content is higher in Comparative Example 15; therefore, tensile elongation and high tenacity are poor.

Table 7

Polymerization results and physical properties of the product

s ro v cf. Ex 1 5 Ex 1 4 Ex fixed cat.-component (A) according to -> -> organoaluminium (B) vyn. TEA -> -> organosi 1 icon words (C) diPDMS * -> -> B / C mo1. ratio 2 2 2 polymerization stage (I) 1st stage MFR g / 10 min 122 122 123 2nd stage MFR g / 10 min 99 100 ALIGN! 99 3rd gear MFR g / 10 min 71 70 71 1og (MFR (h) / MFR (2)) 0.24 0.24 0.24 polymerized ratio quantity 1 s t: 2.s t: 3.s t. 35:33 35:33 35:33 : 32 : 32 : 32 MFR (i) g / 10min 96 96 96 polymerization stage (II) isotactic pentad 0.975 0,975 0.97 fraction (P) Mw / Mn 4.8 4.8 4.8 polymerization stage (II) MFR (ii) g / 10min 0.005 0.005 0.005 ratio of polymerized quantity Polymer (I): Polymer (II) 88:12 88:12 87:12

Table 7 (cont.) ex. 1 5 s rov. Ex 1 4 s rov steed. 15 Dec powdered product MFR g / 10min 29 29 29 1og (MFR) / MFR (i) 4.3 4.3 4.3 R-E * wt% 38 25 85 T-E * wt% 4.6 3 10.2 yield kg 5 1 48 50 rozp. polymer% 3.1 4.2 1,8 injection molded product MPa bending module 1480 1380 1550 tensile strength MPa 36 34 37 elongation at tension% > 800 > 800 30 HDT ³ C 116 112 117 II * J / m 96 85 60

Example 16

To the powder of the product (3.0 kg) of the propylene-ethylene block copolymer composition obtained in Example 2, phenolic heat stabilizer (0.003 kg), calcium stearate (0.003 kg) and talc (0.03 kg) (bulk density: 0.39) were added. and average particle size: 10 µm), then mixed at room temperature for 10 minutes using a high speed mixer (Henschel mixer, trade name). The mixture is granulated with an extruder granulator having a screw diameter of 40 mm, the resulting granulate is injected into an injection molding machine at a molten resin temperature of 230 ° C and at a mold temperature of 50 ° C to prepare JIS mold samples, conditioned in a 50% moisture chamber. % and at room temperature of 23 ° C for 72 hours and the physical property values are measured. The result is a bending modulus of 1750 MPa, a tensile strength of 38 mPa, an elongation at tensile of 380%, an HDT of 127 ° C and an Izodt impact of 119 J / m.

Example 17

Example 16 is repeated except that phenolic heat stabilizer (0.003 kg), calcium stearate (0.003 kg) and talc (0.03 kg) are added to the product powder (0.003 kg) of the propylene-ethylene block copolymer composition obtained in Example 2. ) (bulk density: 0.12 and average particle size: 1.3 µm) and the physical properties of the resulting mixture were measured. The result is a bending modulus of 1870 MPa, a tensile strength of 38 mPa, a tensile elongation of 380%, an HDT 131 ’C and an Izodt impact of 98 J / m.

Example 16 was repeated except that phenolic thermal stabilizer (0.003 kg), calcium stearate (0.003 kg) as a non-crystalline copolymer was added to the product powder (3.0 kg) of the propylene-ethylene block copolymer composition obtained in Example 2. ethylene-α-ο-1-ol, a non-crystalline ethylene-propylene (0.06 kg) copolymer (propylene content: 26 wt% and Mooney viscosity ML1 + 4 (100 ° C): 24, with the following measurements of the physical properties of the resulting mixture. we were icy:

bending modulus 1430 MPa, tensile strength 36 mPa, elongation at tensile 490%, HDT 115 ´C and Izodt impact 121 J / m.

Claims (7)

A process for the production of a propylene-ethylene block copolymer comprising the use of a catalyst system comprising a combined (A) solid catalyst component comprising Ti, Mg, halogen and a polyvalent carboxylic acid ester as insoluble component, (B) an organoaluminum compound and ( C) an organosilicon compound of the formula R ⁴ x R ⁵ y Si (OR ⁶ ) z wherein R ⁴ and R ⁶ represent each a hydrocarbon radical, R ⁵ represents a hydrocarbon radical or a hydrocarbon radical containing a heteroatom and X + Y + Z = 4, 11 Y < 3, 11, and the following two polymerization steps are performed: first a polymerization stage (I) controlled in particular for propylene polymerization, wherein the monomers in the ratio ethylene / (ethylene + propylene) = 0 to 5 wt. fed to two or more polymerization vessels connected in series to form 60 to 95% of the total polymerized amount and a second polymerization stage (II) containing a relatively large amount of ethylene wherein the monomers in an ethylene / (ethylene + propylene) ratio = 10 to 100 wt. are introduced into one or more polymerization vessels, to form 5 to 40% of the total polymerized amount, a process for producing a high-rigid propylene-ethylene block copolymer composition by making the composition such that the maximum melt flow rate (hereinafter referred to as MFR (h)) of polymers obtained in the corresponding containers after the polymerization stage (I) and its minimum value (hereinafter referred to as MFR (1)) may have 0.1 < iog (MFR (h) / MFR (1) < 1 and MFR (i) of polymers obtained in polymerization stage (I), mainly driven by propylene and MFR (ii) of polymers obtained in polymerization stage (II)) containing a relatively large amount of ethylene may have the relationship expressed as follows 3 <log (MFR (i) / MFR (ii)) <7. A process for the preparation of a composition of high-strength propylene-ethylene block copolymers according to claim 1, characterized in that the molar ratio of organosilicon compound (C) to organosilicon icon compound (B) is (B) / (C) = 1 to 15 . A propylene-ethylene block copolymer composition made using a catalyst system comprising a combined (A) solid catalyst component comprising Ti, Mg, halogen and a polyvalent carboxylic acid ester as an insoluble component, (B) an organoalurainium compound and (C) organosilicon icon; a compound of formula R ⁴ x R ⁵ y Si (OR ⁶ ) z wherein R ⁴ and R ⁶ represent each a hydrocarbon radical, R ⁵ represents a hydrocarbon radical or a hydrocarbon radical, or a heteroatom-containing hydrocarbon radical, and carrying out the following two steps: first of a polymerization stage (I) controlled by a propylene homopolymer, .... In two or more polymerization vessels connected in series, to form 60 to 95% of the total polymerized amount and the second polymerization stage (11), copolymerizing propylene with ethylene to produce a polymerized proportion of propylene-ethylene of 5 to 40%. % wt. based on the total weight, wherein the ethylene content is 30 to 80% by weight, wherein the high propylene-ethylene block copolymer composition may have a maximum melt flow rate (hereinafter referred to as MFR (h)) of the polymer obtained in the corresponding vessels of the polymerization stage ( I) and its minimum value (hereinafter referred to as MFR (1)) in relation 0.1 < iog (MFR (h) / MFR (1) < 1 (1) isotactic pentad ratio (P) of the propylene polymer obtained in polymerization stage (I) is 96 or higher, MW / Mn (Q value) is 6 or less and the melt flow rate (hereinafter referred to as MFR (i)) of the polymer obtained in polymerization stage (I) and MFR (ii) of the polymer obtained in polymerization stage (II) have the relationship expressed as follows 3 log (MFR (i) / MFR (ii) £ 7 (2)). The high-strength propylene-ethylene block copolymer composition of claim 3 wherein the MFR of the final polymer obtained is 0.1 to 100. The high-strength propylene-ethylene block copolymer composition of claim 3, obtained by polymerization in a hydrocarbon solvent. The high-strength propylene-ethylene block copolymer composition of claim 3, wherein the MFR (h) and mFR (1) of claim 3 have the relationship 0.2 <log (MFR (h) / MFR (1) <0.05). The high-rigidity propylene-ethylene block copolymer composition of claim 3, wherein the MFR (I) and MFR (ii) mentioned in claim 3 have the relationship