Impact-modified propylene polymers with reduced stress-whitening

0001The present invention relates to propylene polymers.

0002The present invention further relates to a process for the preparation of these polymers and their use as films, fibers and moldings.

0003The production of propylene homopolymers by Ziegler-Natta polymerization has long been known. The catalyst components used contain, inter alia, compounds of polyvalent titanium, aluminum halides and / or alkyls, and also electron donor compounds, silanes, esters, ketones or lactones being mostly used (<patcit id="pcit0001" dnum="DE4216548A"><text>DE-A 42 16 548</text></patcit>, <patcit id="pcit0002" dnum="DE4419438A"><text>DE-A 44 19 438</text></patcit>, <patcit id="pcit0003" dnum="EP171200A"><text>EP-A 171 200</text></patcit>, <patcit id="pcit0004" dnum="EP530599A"><text>EP-A 530 599</text></patcit>, <patcit id="pcit0005" dnum="US4857613A"><text>US-A 4 857 613</text></patcit>).

0004According to this process, propylene homopolymers with very different properties can be obtained, for example with a significantly different stiffness, impact strength or flowability. Some fields of application, in which propylene polymers are preferably used, require in particular those propylene polymers which, in addition to having high impact strength for optical reasons, also have a significantly reduced tendency to form white cracks and high rigidity.

0005In addition to the production of propylene polymers by Ziegler-Natta catalysts, there has also been the possibility for some years to produce polymers of propylene and ethylene using metallocene catalysts with cyclic ligands (<patcit id="pcit0006" dnum="EP519237A"><text>EP-A 519 237</text></patcit>, <patcit id="pcit0007" dnum="EP692499A"><text>EP-A 692 499</text></patcit>).

0006In the <patcit id="pcit0008" dnum="DE4407327A"><text>DE-A 4407327</text></patcit> propylene polymers are described which consist of a propylene homopolymer and a nucleating agent and which are characterized, inter alia, by high rigidity and flowability. For certain areas of application of propylene polymers, however, one is interested in a further increased stiffness and in an improved whitening behavior.

0007From the <patcit id="pcit0009" dnum="EP593221A"><text>EP-A 593 221</text></patcit> are mixtures of propylene polymers and ethylene copolymers with polymerized C₄-C₁₈-Alk-1-enes known whose density is less than or equal to 0.913 g / cm³ is. The mixtures listed therein have good values ​​in terms of their impact strength and stiffness, but it is not mentioned how the whitening behavior of such products can be improved.

0008Furthermore, in the <patcit id="pcit0010" dnum="WO9406859A"><text>WO-A 94/06859</text></patcit> Mixtures of thermoplastic polymers and linear ethylene copolymers with copolymerized C₃-C₂₀-Alk-1-enes which, inter alia, have high transparency and good impact strength at low temperatures. Of the<patcit id="pcit0011" dnum="WO9406859A"><text>WO-A 94/06859</text></patcit> However, it cannot be seen how one can improve the whitening behavior of such mixtures and at the same time increase their rigidity.

0009Subject of <patcit id="pcit0012" dnum="WO9606132A"><text>WO-A 96/06132</text></patcit> are mixtures of propylene homopolymers and copolymers of ethylene with C.₃-C₈-Alk-1-enes, which may also contain 0.1 to 5% by weight, based on the mixture, of inorganic fillers. Mixtures of this type are distinguished, inter alia, by good impact strength and surface hardness. Similar mixtures of polypropylene, copolymers of ethylene with but-1-ene and at least 5% by weight, based on the mixture, of talc are the teaching of<patcit id="pcit0013" dnum="EP605180A"><text>EP-A 605 180</text></patcit> refer to. Both from the<patcit id="pcit0014" dnum="WO9606132A"><text>WO-A 96/06132</text></patcit>, as well as from the <patcit id="pcit0015" dnum="EP605180A"><text>EP-A 605 180</text></patcit> However, it cannot be determined how the whitening behavior of such mixtures can be improved.

0010The present invention was therefore based on the object to remedy the disadvantages described and to develop a propylene polymer which is distinguished by a favorable profile of properties with regard to good impact strength, flowability and processability and, moreover, has a high rigidity and has as little tendency to white breakage as possible .

0011Accordingly, propylene polymers have been developed containing<ol id="ol0001" ol-style=""><li>a) 50 to 95 parts by weight of a propylene homopolymer with a melt flow index of 0.1 to 100 g / 10 min., at a temperature of 230 ° C and under a weight of 2.16 kg, according to ISO standard 1133 and one Isotacticity index, in xylene according to ISO standard 6427b, from 98.0 to 99.5%,</li><li>b) 5 to 50 parts by weight of an ethylene copolymer with 4 to 40% by weight of copolymerized C₄-C₂₀-Alk-1-en, a density of 0.865 to 0.920 g / cm³ and a melt flow index of 0.1 to 100 g / 10 min, at 230 ° C and under a weight of 2.16 kg, according to ISO standard 1133 and</li><li>c) 0 to 1.5 parts by weight of a nucleating agent, the sum of the parts by weight of the propylene homopolymer a) and the ethylene copolymer b) always giving 100 parts by weight.</li></ol>

0012Preferred propylene polymers are in particular:<ol id="ol0002" ol-style=""><li>a) 60 to 90, in particular 75 to 90 parts by weight of the propylene homopolymer a),</li><li>b) 10 to 40, in particular 10 to 25 parts by weight of the ethylene copolymer b) and</li><li>c) have 0 to 1.5, in particular 0.05 to 1.5 parts by weight of the nucleating agent c).</li></ol>

0013The sum of the parts by weight of the propylene homopolymer and the ethylene copolymer b) always gives 100 parts by weight.

0014Such a propylene homopolymer a) is preferably used which has a melt flow index of 0.2 to 50 g / 10 min, at a temperature of 230 ° C. and under a weight of 2.16 kg, according to ISO standard 1133. The melt flow index corresponds to the amount of polymer in grams which is pressed out of the test device standardized according to ISO standard 1133 at a temperature of 230 ° C. and under a weight of 2.16 kg.

0015The propylene polymer according to the invention contains in particular such a propylene homopolymer a), the isotacticity index of which is 98.0% to 99.5%. The isotacticity index is understood to mean the proportion of polymer which is insoluble in xylene according to ISO standard 6427 b). The isotacticity index is a measure of the stereospecificity of the propylene homopolymer.

0016The process leading to these propylene homopolymers a) can be carried out either batchwise or preferably continuously in the customary reactors used for the polymerization of propylene. Suitable reactors include continuously operated stirred tanks. The reactors contain a fixed bed of finely divided polymer, which is usually kept in motion by stirring.

0017The process can be carried out using the Ziegler-Natta catalysts customary in polymerization technology. In addition to a titanium-containing solid component, these also contain a cocatalyst. An aluminum compound can be used as a cocatalyst. In addition to this aluminum compound, an electron donor compound is preferably also used as a further component of the cocatalyst.

0018Halides or alcoholates of tri- or tetravalent titanium are generally used as titanium compounds to produce the titanium-containing solid component, with the chlorides of titanium, in particular titanium tetrachloride, being preferred. The titanium-containing solid component advantageously contains a finely divided carrier, for which silicon and aluminum oxides, and aluminum silicates of the gross formula SiO₂·eel₂O₃, where a stands for a value from 0.001 to 2, in particular from 0.01 to 0.5, have proven successful.

0019The carriers preferably used have a particle diameter of 0.1 to 1000 μm, in particular 10 to 300 μm, and a pore volume of 0.1 to 10 cm³/ g, especially from 1.0 to 5.0 cm³/ g and a specific surface area of ​​10 to 1000 m²/ g, especially from 100 to 500 m²/ g on.

0020A finely divided inorganic oxide which has a pH of 1 to 6, an average particle diameter of 5 to 200 µm, in particular of 20 to 70 µm and an average particle diameter of the primary particle of 1 can in particular also be used as the finely divided carrier for the titanium-containing solid component up to 20 µm, in particular from 1 to 5 µm. The so-called primary particles are porous, granular oxide particles which are obtained from a corresponding hydrogel by grinding, if necessary after sieving. The hydrogel is generated in the acidic range, ie in a range with a pH value between 1 and 6, or else aftertreated and cleaned with correspondingly acidic washing solutions.

0021Furthermore, the finely divided inorganic oxide is also characterized, inter alia, by the fact that it has cavities or channels with an average diameter of 0.1 to 20 µm, in particular 1 to 15 µm, the macroscopic volume fraction of the total particle in the range of 5 to 30% , in particular in the range of 10 to 30%. The finely divided inorganic oxide furthermore has, in particular, a pore volume of 0.1 to 10 cm³/ g, preferably from 1.0 to 4.0 cm³/ g and a specific surface area of ​​10 to 1000 m²/ g, preferably from 100 to 500 m²/ g on. The pH value, ie the negative logarithm of the proton concentration of the inorganic oxide, is in the range from 1 to 6, in particular in the range from 2 to 5.

0022Preferred inorganic oxides are, in particular, oxides of silicon, aluminum, titanium or one of the metals of main group I or II of the periodic table. In addition to aluminum oxide or magnesium oxide or a layered silicate, silica gel (SiO₂) used, which can be obtained in particular by spray drying. So-called cogels, ie mixtures of two different inorganic oxides, can also be used. Such finely divided inorganic oxides are also commercially available.

0023Furthermore, compounds of magnesium are used in the production of the titanium-containing solid component. Magnesium halides, magnesium alkyls and magnesium aryls, as well as magnesium alkoxy and magnesium aryloxy compounds are particularly suitable as such, preferably magnesium dichloride, magnesium dibromide and magnesium di- (C₁-C₁₀-alkyl) compounds are used. In addition, the titanium-containing solid component can also contain halogen, preferably chlorine or bromine.

0024In addition, the titanium-containing solid component also contains electron donor compounds, for example mono- or polyfunctional carboxylic acids, carboxylic anhydrides and carboxylic esters, ketones, ethers, alcohols, lactones, and organophosphorus and organosilicon compounds. Preferred electron donor compounds within the titanium-containing solid component are phthalic acid derivatives of the general formula I<chemistry id="chem0001" num="0001"><img file="EP0826728B2_D0001.tif" /></chemistry>used, where X and Y are each chlorine or a C₁- to C₁₀-Alkoxy radical or together represent oxygen. Particularly preferred electron donor compounds are phthalic acid esters, where X and YC₁-C₈Alkoxy radicals, for example methoxy, ethoxy, propyloxy or butyloxy radicals.

0025Further preferred electron donor compounds within the titanium-containing solid component include diesters of 3- or 4-membered, optionally substituted cycloalkyl-1,2-dicarboxylic acids, and monoesters of optionally substituted benzophenone-2-carboxylic acids. The hydroxyl compounds used in these esters are the alcohols customary in esterification reactions, including C₁- to C₁₅Alkanols, C₅- to C₇-Cycloalkanols, which in turn are C₁- to C₁₀-Alkyl groups can also carry phenols, naphthols and the C₁-C₁₀Alkyl derivatives of these compounds.

0026The titanium-containing solid component can be produced by methods known per se. Examples of this are in the<patcit id="pcit0016" dnum="EP171200A"><text>EP-A 171 200</text></patcit>, of the <patcit id="pcit0017" dnum="GB2111066A"><text>GB-A 2 111 066</text></patcit>, of the <patcit id="pcit0018" dnum="US4857613A"><text>US-A 4 857 613</text></patcit> and the <patcit id="pcit0019" dnum="US5288824A"><text>US-A 5 288 824</text></patcit> described.

0027The following three-stage process is preferably used in the production of the titanium-containing solid component.

0028In the first stage, a finely divided carrier, preferably silicon dioxide or SiO, is first added₂·eel₂O₃ - where a is a number in the range from 0.001 to 2, in particular in the range from 0.01 to 0.5 - with a solution of the magnesium-containing compound in a liquid alkane, after which this mixture is kept for 0.5 to 5 hours Temperature between 10 and 120 ° C stirred. Preferably 0.1 to 1 mol of the magnesium compound is used per mole of the carrier. Then, with constant stirring, a halogen or a hydrogen halide, in particular chlorine or hydrogen chloride, is added in at least a two-fold, preferably in at least a five-fold, molar excess, based on the magnesium-containing compound. After about 30 to 120 minutes, the solid is separated from the liquid phase.

0029In the second stage, the product obtained in this way is introduced into a liquid alkane and then a C is added₁- to C₈Alkanol, in particular ethanol, a halide or an alcoholate of trivalent or tetravalent titanium, in particular titanium tetrachloride, and an electron donor compound, in particular a phthalic acid derivative of the general formula I. 1 to 5 mol, in particular 2 to 4 mol, alkanol, 2 to 20 mol, in particular 4 to 10 mol, of the tri- or tetravalent titanium and 0.01 to 1 mol are used per mol of magnesium in the solid obtained from the first stage , in particular 0.1 to 1.0 mol, of the electron donor compound. This mixture is stirred for at least one hour at a temperature between 10 and 150 ° C., the solid substance thus obtained is then filtered off and washed with a liquid alkane, preferably with hexane or heptane.

0030In the third stage, the solid obtained from the second stage is extracted for a few hours at temperatures between 100 and 150 ° C with excess titanium tetrachloride or an excess solution of titanium tetrachloride in an inert solvent, preferably an alkylbenzene, the solvent being at least 5% by weight .-% contains titanium tetrachloride. The product is then washed with a liquid alkane until the titanium tetrachloride content of the washing liquid is less than 2% by weight.

0031The titanium-containing solid component obtainable in this way is used with a cocatalyst as the Ziegler-Natta catalyst system. Aluminum compounds are suitable as cocatalysts.

0032In addition to trialkyl aluminum, suitable aluminum compounds are also those compounds in which an alkyl group is replaced by an alkoxy group or by a halogen atom, for example by chlorine or bromine.

0033Trialkylaluminum compounds are preferably used, the alkyl groups of which each have 1 to 8 carbon atoms, for example trimethyl, triethyl or methyldiethylaluminum.

0034In addition to the aluminum compound, preference is given to using electron donor compounds, such as, for example, monofunctional or polyfunctional carboxylic acids, carboxylic acid anhydrides and carboxylic acid esters, ketones, ethers, alcohols, lactones, and organophosphorus and organosilicon compounds, as a further cocatalyst. Particularly suitable electron donor compounds are organosilicon compounds of the general formula II         R '_nSi (OR ")_4-n     II where R 'is the same or different and a C₁- to C₂₀-Alkyl group, a 5- to 7-membered cycloalkyl group, which in turn is a C₁- to C₁₀-Alkylgruppe can carry, or a C₆- to C₂₀Arylalkyl group, R "is the same or different and a C₁- to C₂₀Denotes alkyl group and n represents the numbers 1, 2 or 3. Compounds in which R 'is a C are particularly preferred₁- to C₈-Alkyl group or a 5- to 7-membered cycloalkyl group, R "is a C₁- to C₄-Alkylgruppe and n are the numbers 1 or 2.

0035Among these compounds are dimethoxydiisopropylsilane, dimethoxyisobutylisopropylsilane, dimethoxydiisobutylsilane, dimethoxydicyclopentylsilane, dimethoxysek-butylisopropylsilane, diethoxydicyclopentylsilane, diethoxysek.butylisopropylsilanobutylisopropylsilanobutylisopropylsilanodisiloxysilane.

0036Catalyst systems are preferably used in which the atomic ratio between aluminum from the aluminum compound and titanium from the titanium-containing solid component is 10: 1 to 800: 1, in particular 20: 1 to 200: 1, and the molar ratio between the aluminum compound and the electron donor compound used as cocatalyst 1: 1 to 100: 1, in particular 2: 1 to 20: 1. The catalyst components can be introduced into the polymerization system individually or as a mixture of the components in any order.

0037The polymerization for the preparation of the propylene homopolymers a) is usually carried out at a pressure of 20 to 40 bar, a temperature of 60 to 90 ° C. and an average residence time of the reaction mixture of 0.5 to 5 hours. Pressures of 25 to 35 bar, temperatures of 65 to 85 ° C. and average residence times of 1.0 to 4 hours are preferred. The polymerization conditions are usually chosen such that 0.05 to 2 kg, preferably 0.1 to 1.5 kg, of the propylene homopolymer a) are formed per mmol of the aluminum component.

0038As is customary, the molecular weight of the polymers obtainable here can be controlled by adding regulators, in particular hydrogen. C₂- to C₆Alk-1-enes, for example ethylene or but-1-enes, can be used. In this case, the propylene homopolymer a) can contain up to 0.1% by weight of other C₂- to C₆-Alk-1-ene included.

0039The ethylene copolymer b) used is, in particular, a copolymer which has 4 to 40% by weight, preferably 7 to 30% by weight, of copolymerized C₄-C₂₀-Alk-1-ene. Preferred comonomers in the ethylene copolymer b) C₄-C₁₂-Alk-1-enes, preferably but-1-ene, pent-1-ene, 4-methyl-pent-1-ene, hex-1-ene, hept-1-ene or oct-1-ene and mixtures from these C₄-C₁₂-Comonomers can be used. Particularly suitable comonomers are but-1-ene, hex-1-ene or oxt.1-ene.

0040The ethylene copolymers b) present in the ethylene copolymers b) according to the invention have a density of 0.865 to 0.920 g / cm³, in particular from 0.868 to 0.910 g / cm³ on. Their melt flow index, at 230 ° C and under a weight of 2.16 kg, according to ISO standard 1133, is 0.1 to 100 g / 10 min., In particular 1 to 30 g / 10 min.

0041The ethylene copolymers b) contained in the propylene polymers according to the invention are usually prepared by appropriate polymerization with metal-containing catalysts, for example with catalysts based on a metallocene complex or with the aid of titanium and aluminum-containing Ziegler catalysts, or with Phillips catalysts based of chromium-containing compounds. The polymerization reaction can be carried out using the reactors customary in industry, both in the gas phase, in solution, in liquid monomers or in a slurry. The polymerization can be carried out continuously, semi-continuously or batchwise.

0042The ethylene copolymers b) are preferably obtained by polymerizing ethylene and the corresponding C.₄-C₂₀-Alk-1-enes with the help of catalyst systems that<ol id="ol0003" ol-style=""><li>A) optionally an inorganic carrier,</li><li>B) at least one metallocene complex,</li><li>C) at least one compound forming metallocenium ions and</li><li>D) optionally at least one organic metal compound of an alkali or alkaline earth metal or a metal of III. Main group of the periodic table included.</li></ol>

0043The polymerization with the aid of such metallocene-containing catalyst systems, which leads to the ethylene copolymers b), is carried out in particular at temperatures in the range from -50 to 300 ° C., preferably in the range from 0 to 150 ° C., and at pressures in the range from 0 to 150 ° C. 5 to 3000 bar, preferably in the range of 1 to 80 bar. In this process, the residence times of the respective reaction mixtures should be set to 0.5 to 5 hours, in particular 0.7 to 3.5 hours. Antistatic agents and molecular weight regulators, for example hydrogen, can also be used in the polymerization.

0044The polymerization can be carried out in solution, in suspension, in liquid monomers or in the gas phase. The polymerization is preferably carried out in suspension or in the gas phase.

0045The polymerization process for the preparation of the copolymers b) can be carried out either continuously or batchwise. Suitable reactors include continuously operated stirred tanks, it also being possible, if appropriate, to use a number of several stirred tanks connected in series (reactor cascade).

0046Such metallocene-containing catalyst systems optionally contain an inorganic support as component A). In particular, an inorganic oxide is used as the inorganic carrier, which has a pH from 1 to 6 and cavities and channels, determined according to SR Morrison, "The Chemical Physics of Surfaces", Plenum Press, New York [1977], page 130ff has a macroscopic volume fraction of the total particle in the range of 5 to 30%. In particular, preference is given to using inorganic oxides whose pH, ie the negative decimal logarithm of the proton concentration, is in the range from 2 to 5.5 and in particular in the range from 2 to 5. In addition, inorganic oxides which have cavities and channels and whose macroscopic volume fraction of the total particle is 8 to 30%, preferably 10 to 30% and particularly preferably 15 to 25% are furthermore used as inorganic carriers.

0047Other inorganic carriers which are preferably used are also those inorganic oxides which have an average particle diameter of 5 to 200 μm, in particular 20 to 90 μm, and an average particle diameter of the primary particles of 1 to 20 μm, in particular 1 to 5 μm. The so-called primary particles are porous, granular particles. The primary particles have pores with a diameter of in particular 1 to 1000 · 10^-10 m (Å). Furthermore, such inorganic oxides are also characterized in that they have cavities and channels with an average diameter of 0.1 to 20 μm, in particular 1 to 15 μm. The inorganic oxides also have, in particular, a pore volume of 0.1 to 10 cm³/ g, preferably from 1.0 to 5.0 cm³/ g, and a specific surface area of ​​10 to 1000 m²/ g, preferably from 100 to 500 m²/ g, on.

0048Because of the voids and channels present in the finely divided inorganic oxides, there is a significantly improved distribution of the active catalyst components in the support material. The acidic centers on the surface of the inorganic oxide additionally cause a homogeneous loading of the catalyst components. In addition, a material with cavities and channels in this way has a positive effect on the diffusion-controlled supply of monomers and cocatalysts and thus also on the polymerization kinetics.

0049Such a finely divided inorganic oxide can be obtained, among other things, by spray drying ground, appropriately sieved hydrogels, which are mixed with water or an aliphatic alcohol for this purpose. During spray drying, the required pH from 1 to 6 can also be adjusted by using appropriate acidic primary particle suspensions. Such a fine-particle inorganic oxide is also commercially available.

0050Preferred inorganic carriers are, in particular, oxides of silicon, aluminum, titanium or one of the metals of main group I or II of the periodic table. In addition to aluminum oxide or magnesium oxide or a layered silicate, silica gel (SiO₂) used, which can be obtained in particular by spray drying.

0051So-called cogels, ie mixtures of at least two different inorganic oxides, can also be used as component A).

0052Preferably, per gram of carrier, ie component A₎, 0.1 to 10000 µmol, in particular 5 to 200 µmol, of the metallocene complex, ie component B).

0053The preferably used metallocene-containing catalyst system contains at least one or more metallocene complexes as component B). Particularly suitable metallocene complexes are those of the general formula IV<chemistry id="chem0002" num="0002"><img file="EP0826728B2_D0002.tif" /></chemistry>in which the substituents have the following meaning:<dl id="dl0001"><dt>M</dt><dd>Titanium, zirconium, hafnium, vanadium, niobium or tantalum, as well as elements of III. Subgroup of the periodic table and the lanthanoids,</dd><dt>X</dt><dd>Fluorine, chlorine, bromine, iodine, hydrogen, C₁- to C₁₀-Alkyl, C₆- to C₁₅Aryl, alkylaryl with 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical, -OR¹⁰ or -NR¹⁰R¹¹,</dd><dt>n</dt><dd>an integer between 1 and 3, where n corresponds to the valency of M minus the number 2,</dd></dl>in which<dl id="dl0002"><dt>R¹⁰ and R¹¹</dt><dd>C.₁- to C₁₀-Alkyl, C₆- to C₁₅Aryl, alkylaryl, arylalkyl, fluoroalkyl or fluoroaryl each having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical,</dd><dt>R⁵ to R⁹</dt><dd>Hydrogen, C₁- to C₁₀-Alkyl, 5- to 7-membered cycloalkyl, which in turn is a C₁- to C₁₀-Alkyl can carry as a substituent, C₆- to C₁₅Aryl or arylalkyl, where optionally also two adjacent radicals together can represent saturated or unsaturated cyclic groups having 4 to 15 carbon atoms, or Si (R¹²)₃ With</dd><dt>R¹²</dt><dd>C.₁- to C₁₀-Alkyl, C₃- to C₁₀Cycloalkyl or C₆- to C₁₅-Aryl,</dd><dt>Z.</dt><dd>for X or<chemistry id="chem0003" num="0003"><img file="EP0826728B2_D0003.tif" /></chemistry>stands,</dd></dl>being the leftovers<dl id="dl0003"><dt>R¹³ to R¹⁷</dt><dd>Hydrogen, C₁- to C₁₀-Alkyl, 5- to 7-membered cycloalkyl, which in turn is a C₁- to C₁₀-Alkyl can carry as a substituent, C₆- to C₁₅-Aryl or arylalkyl and where optionally two adjacent radicals together can represent saturated or unsaturated cyclic groups having 4 to 15 carbon atoms, or Si (R¹⁸)₃ With</dd><dt>R¹⁸</dt><dd>C.₁- to C₁₀-Alkyl, C₆- to C₁₅-Aryl or C₃- to C₁₀Cycloalkyl,</dd></dl>or the radicals R⁸ and Z together form a grouping -R¹⁹-A- form in the R¹⁹<chemistry id="chem0004" num="0004"><img file="EP0826728B2_D0004.tif" /></chemistry><chemistry id="chem0005" num="0005"><img file="EP0826728B2_D0005.tif" /></chemistry>= BR²⁰, = AlR²⁰, -Ge-, -Sn-, -O-, -S-, = SO, = SO₂, = NO²⁰, = CO, = PR²⁰ or = P (O) R²⁰ is in which<dl id="dl0004" compact="compact"><dt>R²⁰, R²¹ and R²²</dt><dd>are identical or different and represent a hydrogen atom, a halogen atom, a C₁-C₁₀Alkyl group, a C₁-C₁₀-Fluoroalkyl group, a C₆-C₁₀-Fluoroarylgruppe, a C₆-C₁₀Aryl group, a C₁-C₁₀Alkoxy group, a C₂-C₁₀Alkenyl group, a C₇-C₄₀Arylalkyl group, a C₈-C₄₀Arylalkenyl group or a C₇-C₄₀-Alkylarylgruppe mean or where two adjacent radicals each form a ring with the atoms connecting them, and</dd><dt>M²</dt><dd>Is silicon, germanium or tin,</dd><dt>A</dt><dd>―O―, ―S―,〉 NO²³ or〉 PR²³ mean with</dd><dt>R²³</dt><dd>C.₁- to C₁₀-Alkyl, C₆- to C₁₅-Aryl, C₃- to C₁₀-Cycloalkyl, alkylaryl or Si (R²⁴)₃,</dd><dt>R²⁴</dt><dd>Hydrogen, C₁- to C₁₀-Alkyl, C₆- to C₁₅-Aryl, which in turn with C₁- to C₄Alkyl groups can be substituted or C₃- to C₁₀Cycloalkyl</dd></dl>or the radicals R⁸ and R¹⁶ together a grouping -R¹⁹- form.

0054Of the metallocene complexes of the general formula IV are<chemistry id="chem0006" num="0006"><img file="EP0826728B2_D0006.tif" /></chemistry><chemistry id="chem0007" num="0007"><img file="EP0826728B2_D0007.tif" /></chemistry><chemistry id="chem0008" num="0008"><img file="EP0826728B2_D0008.tif" /></chemistry>and<chemistry id="chem0009" num="0009"><img file="EP0826728B2_D0009.tif" /></chemistry>prefers.

0055The radicals X can be the same or different, they are preferably the same.

0056Of the compounds of the formula IVa, those are particularly preferred in which<dl id="dl0005"><dt>M</dt><dd>Titanium, zirconium or hafnium,</dd><dt>X</dt><dd>Chlorine, C₁-to C₄-Alkyl or phenyl,</dd><dt>n</dt><dd>the number 2 and</dd><dt>R⁵ to R⁹</dt><dd>Hydrogen or C₁- to C₄-Alkyl mean.</dd></dl>

0057Preferred compounds of the formula IVb are those in which<dl id="dl0006"><dt>M</dt><dd>represents titanium, zirconium or hafnium,</dd><dt>X</dt><dd>Chlorine, C₁-to C₄-Alkyl or phenyl,</dd><dt>n</dt><dd>the number 2,</dd><dt>R⁵ to R⁹</dt><dd>Hydrogen, C₁- to C₄-Alkyl or Si (R¹²)₃,</dd><dt>R¹³ to R¹⁷</dt><dd>Hydrogen, C₁- to C₄-Alkyl or Si (R¹⁸)₃ mean.</dd></dl>

0058The compounds of the formula IVb in which the cyclopentadienyl radicals are identical are particularly suitable.

0059Examples of particularly suitable compounds include: bis (cyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, bis (n-butylethyldiryl) zirconium dichloridyldiryldiumchloride as well as the corresponding dimethyl zirconium compounds.

0060Of the compounds of the formula IVc, those in which<dl id="dl0007" compact="compact"><dt>R⁵ and R¹³</dt><dd>are the same and for hydrogen or C₁- to C₁₀Alkyl groups are available,</dd><dt>R⁹ and R¹⁷</dt><dd>are the same and represent hydrogen, a methyl, ethyl, isopropyl or tert-butyl group,</dd><dt>R⁶, R⁷, R¹⁴ and R¹⁵</dt><dd>the meaning R⁷ and R¹⁵ C.₁- to C₄-Alkyl R⁶ and R¹⁴ Have hydrogen or two adjacent radicals R⁶ and R⁷ as well as R¹⁴ and R¹⁵ together represent cyclic groups having 4 to 12 carbon atoms,</dd><dt>R¹⁹</dt><dd>For<chemistry id="chem0010" num="0010"><img file="EP0826728B2_D0010.tif" /></chemistry>stands,</dd><dt>M</dt><dd>for titanium, zirconium or hafnium and</dd><dt>X</dt><dd>for chlorine, C₁- to C₄-Alkyl or phenyl are available.</dd></dl>

0061Examples of particularly suitable complex compounds include<ul id="ul0001" list-style="none" compact="compact"><li>Dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride,</li><li>Dimethylsilanediylbis (indenyl) zirconium dichloride,</li><li>Dimethylsilanediylbis (tetrahydroindenyl) zirconium dichloride,</li><li>Ethylene bis (cyclopentadienyl) zirconium dichloride,</li><li>Ethylene bis (indenyl) zirconium dichloride,</li><li>Ethylene bis (tetrahydroindenyl) zirconium dichloride,</li><li>Tetramethylethylene-9-fluorenylcyclopentadienylzirconium dichloride,</li><li>Dimethylsilanediylbis (-3-tert.butyl-5-methylcyclopentadienyl) zirconium dichloride,</li><li>Dimethylsilanediylbis (-3-tert.butyl-5-ethylcyclopentadienyl) zirconium dichloride,</li><li>Dimethylsilanediylbis (-2-methylindenyl) zirconium dichloride,</li><li>Dimethylsilanediylbis (-2-isopropylindenyl) zirconium dichloride,</li><li>Dimethylsilanediylbis (-2-tert.butylindenyl) zirconium dichloride,</li><li>Diethylsilanediylbis (-2-methylindenyl) zirconium dibromide,</li><li>Dimethylsilanediylbis (-3-methyl-5-methylcyclopentadienyl) zirconium dichloride,</li><li>Dimethylsilanediylbis (-3-ethyl-5-isopropylcyclopentadienyl) zirconium dichloride,</li><li>Dimethylsilanediylbis (-2-ethylindenyl) zirconium dichloride,</li><li>Dimethylsilanediylbis (-2-methylbenzindenyl) zirconium dichloride</li><li>Dimethylsilanediylbis (2-ethylbenzindenyl) zirconium dichloride,</li><li>Methylphenylsilanediylbis (2-ethylbenzindenyl) zirconium dichloride,</li><li>Methylphenylsilanediylbis (2-methylbenzindenyl) zirconium dichloride,</li><li>Diphenylsilanediylbis (2-methylbenzindenyl) zirconium dichloride,</li><li>Diphenylsilanediylbis (2-ethylbenzindenyl) zirconium dichloride, and</li><li>Diphenylsilanediylbis (-2-methylindenyl) hafnium dichloride</li></ul>as well as the corresponding dimethyl zirconium compounds.

0062Other examples of suitable complex compounds include<ul id="ul0002" list-style="none" compact="compact"><li>Dimethylsilanediylbis (-2-methyl-4-phenylindenyl) zirconium dichloride,</li><li>Dimethylsilanediylbis (-2-methyl-4-naphthylindenyl) zirconium dichloride,</li><li>Dimethylsilanediylbis (-2-methyl-4-isopropylindenyl) zirconium dichloride and</li><li>Dimethylsilanediylbis (-2-methyl-4,6-diisopropylindenyl) zirconium dichloride and the corresponding dimethylzirconium compounds.</li></ul>

0063In the case of the compounds of the general formula IVd, those in which<dl id="dl0008"><dt>M</dt><dd>for titanium or zirconium,</dd><dt>X</dt><dd>for chlorine, C₁-to C₄-Alkyl or phenyl are available.</dd><dt>R¹⁹</dt><dd>For<chemistry id="chem0011" num="0011"><img file="EP0826728B2_D0011.tif" /></chemistry>stands,</dd><dt>A</dt><dd>for ―O―, ―S―,〉 NR²³</dd></dl>and<dl id="dl0009" compact="compact"><dt>R⁵ to R⁷ and R⁹</dt><dd>for hydrogen, C₁- to C₁₀-Alkyl, C₃- to C₁₀Cycloalkyl, C₆- to C₁₅Aryl or Si (R¹²)₃ stand, or where two adjacent radicals stand for cyclic groups having 4 to 12 carbon atoms.</dd></dl>

0064Such complex compounds can be synthesized by methods known per se, the reaction of the appropriately substituted cyclic hydrocarbon anions with halides of titanium, zirconium, hafnium, vanadium, niobium or tantalum being preferred.

0065Examples of corresponding manufacturing processes are in <nplcit id="ncit0001" npl-type="s"><text>Journal of Organometallic Chemistry, 369 (1989), 359-370</text></nplcit> described.

0066Mixtures of different metallocene complexes can also be used.

0067As component C), the metallocene-containing catalyst system which is preferably used for the production of the ethylene copolymers b) contains a compound which forms metallocenium ions.

0068Suitable compounds forming metallocenium ions are strong, neutral Lewis acids, ionic compounds with Lewis acid cations and ionic compounds with Bronsted acids as the cation.

0069Compounds of the general formula V are strong, neutral Lewis acids         M³X¹X²X³     V preferred in the<dl id="dl0010"><dt>M³</dt><dd>an element of III. Main group of the periodic table means, in particular B, Al or Ga, preferably B,</dd><dt>X¹, X² and X³</dt><dd>for hydrogen, C1 to C10 alkyl, C6 to C15 aryl, alkylaryl, arylalkyl, haloalkyl or haloaryl, each with 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical or fluorine, chlorine, bromine or Iodine, especially for haloaryls, preferably for pentafluorophenyl.</dd></dl>

0070Compounds of the general formula V in which X¹, X² and X³ are the same, preferably tris (pentafluorophenyl) borane.

0071Compounds of the general formula VI are ionic compounds with Lewis acid cations         [(Y^{a +}) Q₁Q₂... Q_e.g.]^{d +}     VI suitable in which<dl id="dl0011"><dt>Y</dt><dd>an element of I. to VI. Main group or the I. to VIII. Subgroup of the periodic table means</dd><dt>Q₁ to Q_e.g.</dt><dd>for simply negatively charged residues like C₁- to C₂₈-Alkyl, C₆- to C₁₅Aryl, alkylaryl, arylalkyl, haloalkyl, haloaryl each having 6 to 20 C atoms in the aryl and 1 to 28 C atoms in the alkyl radical, C₃- to C₁₀-Cycloalkyl, which is optionally with C₁- to C₁₀-Alkyl groups can be substituted, halogen, C₁- to C₂₈-Alkoxy, C₆- to C₁₅Aryloxy, silyl or mercaptyl groups</dd><dt>a</dt><dd>for integers from 1 to 6 and</dd><dt>e.g.</dt><dd>represents integers from 0 to 5,</dd><dt>d</dt><dd>corresponds to the difference az, but d is greater than or equal to 1.</dd></dl>

0072Carbonium cations, oxonium cations and sulfonium cations as well as cationic transition metal complexes are particularly suitable. The triphenylmethyl cation, the silver cation and the 1,1'-dimethylferrocenyl cation should be mentioned in particular. They preferably have non-coordinating counterions, in particular boron compounds, such as those in the<patcit id="pcit0020" dnum="WO9109882A"><text>WO 91/09882</text></patcit> be mentioned, preferably tetrakis (pentafluorophenyl) borate.

0073Ionic compounds with Bronsted acids as cations and preferably also non-coordinating counterions are in the <patcit id="pcit0021" dnum="WO9109882A"><text>WO 91/09882</text></patcit> called, preferred cation is the N, N-dimethylanilinium.

0074The amount of compounds forming metallocenium ions is preferably 0.1 to 10 equivalents, based on the metallocene complex IV.

0075Open-chain or cyclic alumoxane compounds of the general formula II or III are particularly suitable as compound C) forming metallocenium ions<chemistry id="chem0012" num="0012"><img file="EP0826728B2_D0012.tif" /></chemistry><chemistry id="chem0013" num="0013"><img file="EP0826728B2_D0013.tif" /></chemistry>in which<dl id="dl0012" compact="compact"><dt>R⁴</dt><dd>a C₁- to C₄Alkyl group, preferably a methyl or ethyl group and m is an integer from 5 to 30, preferably 10 to 25.</dd></dl>

0076These oligomeric alumoxane compounds are usually prepared by reacting a solution of trialkylaluminum with water and is described in, inter alia <patcit id="pcit0022" dnum="EP284708A"><text>EP-A 284 708</text></patcit> and the <patcit id="pcit0023" dnum="US4794096A"><text>US A 4,794,096</text></patcit> described.

0077As a rule, the oligomeric alumoxane compounds obtained are mixtures of different lengths, both linear and cyclic chain molecules, so that m is to be regarded as the mean. The alumoxane compounds can also be present in a mixture with other metal alkyls, preferably with aluminum alkyls.

0078Both the metallocene complexes (component B) and the metallocenium ion-forming compounds (component C) are preferably used in solution, with aromatic hydrocarbons having 6 to 20 carbon atoms, in particular xylenes and toluene, being particularly preferred.

0079Furthermore, as component C) aryloxyalumoxanes, as in the <patcit id="pcit0024" dnum="US5391793A"><text>US-A 5,391,793</text></patcit> described, aminoaluminoxanes, as in the <patcit id="pcit0025" dnum="US5371260A"><text>US-A 5,371,260</text></patcit> described, aminoaluminoxane hydrochloride, as in the <patcit id="pcit0026" dnum="EP633264A"><text>EP-A 633 264</text></patcit> described, siloxyaluminoxanes, as in the <patcit id="pcit0027" dnum="EP621279A"><text>EP-A 621 279</text></patcit> described, or mixtures thereof are used.

0080It has proven advantageous to use the metallocene complexes and the oligomeric alumoxane compound in amounts such that the atomic ratio between aluminum from the oligomeric alumoxane compound and the transition metal from the metallocene complexes is in the range from 10: 1 to 10⁶: 1, especially in the range of 10: 1 to 10⁴: 1, lies.

0081The metallocene-containing catalyst system preferably used for the production of the ethylene copolymers b) can be used as component D₎ optionally a metal compound of the general formula I         M¹ (R¹)_r (R²)_s (R³)_t     I. in the<dl id="dl0013"><dt>M¹</dt><dd>an alkali, an alkaline earth metal or a metal of III. Main group of the periodic table, ie boron, aluminum, gallium, indium or thallium,</dd><dt>R¹</dt><dd>Hydrogen, C₁- to C₁₀-Alkyl, C₆- to C₁₅Aryl, alkylaryl or arylalkyl each having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical,</dd><dt>R² and R³</dt><dd>Hydrogen, halogen, C₁- to C₁₀-Alkyl, C₆- to C₁₅Aryl, alkylaryl, arylalkyl or alkoxy, each having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical,</dd><dt>r</dt><dd>an integer from 1 to 3</dd></dl>and<dl id="dl0014" compact="compact"><dt>s and t</dt><dd>are integers from 0 to 2, the sum r + s + t of the valency of M¹ corresponds to</dd></dl>contain.

0082Of the metal compounds of the general formula I, those are preferred in which<dl id="dl0015"><dt>M¹</dt><dd>Lithium, magnesium or aluminum means and</dd><dt>R¹ to R³</dt><dd>for C₁- to C₁₀-Alkyl stand.</dd></dl>

0083Particularly preferred metal compounds of the formula I are n-butyl lithium, n-butyl-n-octyl magnesium, n-butyl-n-heptyl magnesium, tri-n-hexyl aluminum, tri-iso-butyl aluminum, triethyl aluminum and trimethyl aluminum.

0084If component D) is used, it is preferably in an amount of 800: 1 to 1: 1, in particular 500: 1 to 50: 1 (molar ratio of M¹ from I to transition metal M from IV) contained in the catalyst system.

0085Components B) and C) and optionally A) and D) are used together as a metallocene-containing catalyst system for the preparation of the ethylene copolymers b) to be used according to the invention.

0086In addition to the propylene homopolymer a) and the ethylene copolymer b), the propylene polymers according to the invention optionally also contain a nucleating agent c) which, by definition, accelerates nucleation during crystallization from the melt. The nucleating agents commonly used in plastics technology are used as nucleating agents, for example mineral additives such as talc, silica or kaolin, or organic compounds such as mono- and polycarboxylic acids and their salts, or polymers such as ethylene-acrylic ester copolymers.

0087As the nucleating agent c) present in the propylene polymers according to the invention, dibenzylidene sorbitol and its C₁-C₈alkyl-substituted derivatives, for example methyldibenzylidensorbitol or dimethyldibenzylidensorbitol, and salts of diesters of phosphoric acid, for example sodium 2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate.

0088As a particularly preferred nucleating agent c), finely divided talc is used in the propylene polymer according to the invention. The finely divided talc should preferably have an average particle size of less than 5 μm, in particular less than 3 μm.

0089The nucleating agents c) described above are customary commercially available additives. In addition to the nucleating agents c), conventional stabilizers such as calcium stearate and phenolic antioxidants, heat stabilizers, UV stabilizers and processing aids can also be added to the propylene polymer according to the invention.

0090If nucleating agent c) is present in the propylene polymers according to the invention, the propylene homopolymer a), the ethylene copolymer b) and the nucleating agent c) are usually used in such proportions that per 100 parts by weight of the propylene copolymer a) and the ethylene copolymer b ) 0.05 to 1.5 parts by weight, in particular 0.05 to 1.0 part by weight and particularly preferably 0.1 to 0.5 part by weight of the nucleating agent b).

0091The propylene polymers according to the invention are prepared by admixing the optionally used nucleating agent c) and the ethylene copolymer b) to the propylene homopolymer a) in the apparatuses usually used in plastics processing for mixing substances, for example in drum mixers, in mills, in extruders, in particular in screws - or disc extruders, in rolling mills or kneaders. The propylene homopolymer a), the ethylene copolymer b) and optionally the nucleating agent c) are usually mixed with one another in the mixing apparatus at a temperature of 200 to 250 ° C., in particular 210 to 240 ° C. The mixing process is usually carried out at pressures from 1 to 100 bar and average residence times from 0.5 to 60 minutes. The exact values ​​for the pressure and the mean residence time depend on the mixing equipment used.

0092Furthermore, the nucleating agent c) can also be sprayed onto the propylene homopolymer a) and onto the ethylene copolymer b).

0093The propylene polymers according to the invention are distinguished, inter alia, by very high rigidity and flowability, while still having good impact strength. In addition, they are easy to process and show only a very low tendency to break white. Because of the low tendency to white whitening, the propylene polymers according to the invention are particularly suitable for consumer articles in which the appearance plays a role. They can also be used generally as films, fibers and moldings.

Examples

Examples 1 to 9 and Comparative Examples A to F

0094The following polymers were used:<ul id="ul0003" list-style="none"><li>a₁₎ Propylene homopolymer with a melt flow index (MFR) of 12.8 g / 10 min., At 230 ° C and under a weight of 2.16 kg, according to ISO standard 1133 and an isotacticity index, in xylene according to ISO standard 6427b) of 98 , 6%.</li><li>a₂₎ Propylene homopolymer with a melt flow index (MFR) of 10.7 g / 10 min., At 230 ° C and under a weight of 2.16 kg, according to ISO standard 1133 and an isotacticity index, in xylene according to ISO standard 6427b) of 96 , 7%.</li><li>b₁₎ Ethylene copolymer with 10% copolymerized but-1-ene, a density of 0.903 g / cm³ and a melt flow index (MFR) of 3.9 g / 10 min., at 230 ° C. and under a weight of 2.16 kg, according to ISO standard 1133, produced with the aid of a metallocene-containing catalyst based on a complex of the general formula IV b.</li><li>b₂₎ Ethylene copolymer with 17% copolymerized but-1-ene, a density of 0.891 g / cm³ and a melt flow index (MFR) of 3.7 g (10 min., at 230 ° C. and under a weight of 2.16 kg, according to ISO standard 1133), and with the aid of a metallocene-containing catalyst based on a complex of the general Formula IV b.</li><li>b₃₎ Ethylene copolymer with 19% copolymerized but-1-ene, a density of 0.878 g / cm³ and a melt flow index (MFR) of 6.7 g / 10 min., at 230 ° C. and under a weight of 2.16 kg, according to ISO standard 1133, produced with the aid of a metallocene-containing catalyst based on a complex of the general formula IV b.</li><li>b₄₎ Ethylene copolymer with 24% polymerized oct-1-ene, a density of 0.870 g / cm³ and a melt flow index (MFR) of 2.3 g / 10 min., at 230 ° C. and under a weight of 2.16 kg, according to ISO standard 1133, produced with the aid of a metallocene-containing catalyst based on a complex of the general formula IV b.</li><li>b₅₎ Ethylene copolymer with 25% polymerized oct-1-ene, a density of 0.868 g / cm³ and a melt flow index (MFR) of 1.0 g / 10 min., at 230 ° C. and under a weight of 2.16 kg, according to ISO standard 1133, produced with the aid of a metallocene-containing catalyst based on a complex of the general formula IV b.</li><li>b₆₎ Ethylene copolymer with 24% polymerized oct-1-ene, a density of 0.870 g / cm³ and a melt flow index (MFR) of 9.0 g / 10 min., at 230 ° C. and under a weight of 2.16 kg, according to ISO standard 1133, produced using a metallocene-containing catalyst based on a complex of the general formula IV b.</li><li>b₇₎ Ethylene-propylene copolymer with 30% copolymerized propylene, a density of 0.890 g / cm³ and a melt flow index (MFR) of 0.3 g / 10 min., at 230 ° C. and under a weight of 2.16 kg, according to ISO standard 1133, produced with the aid of a Ziegler-Natta catalyst.</li></ul>

0095The polymers were mixed on a twin-screw extruder ZSK 30 from Werner &amp; Pfleiderer with a length / diameter ratio of 33. The polymers used in Examples 1-9 and Comparative Examples AD were granulated together with 0.35% by weight. Parts of a finely divided talc are fed to the extruder and mixed at about 230 ° C.

0096In comparative examples E and F, so-called block copolymers of propylene were used, which were produced in a two-stage process. It was analogous to that in the<patcit id="pcit0028" dnum="EP515855A"><text>EP-A 515 855</text></patcit> described process produces a propylene homopolymer in a first stage, to which a mixture of propylene and ethylene was polymerized in a second stage.

0097The following, each with 0.35 part by weight of a finely divided talc, based on 100 parts by weight of the propylene polymer V₁ or V₂, equipped products used:<ul id="ul0004" list-style="none"><li>V₁) Propylene-ethylene copolymer consisting of 90 parts by weight of a propylene homopolymer and 10 parts by weight of an ethylene-propylene copolymer with 55% by weight of copolymerized ethylene.</li><li>V₂) Propylene-ethylene copolymer consisting of 86 parts by weight of a propylene homopolymer and 14 parts by weight of an ethylene-propylene copolymer with 50% by weight of copolymerized ethylene.</li></ul>

0098The composition of the polymers used in Examples 1-9 and Comparative Examples AF and the results obtained are summarized in Tables 1 and 2.

0099The results listed in Tables 1 and 2 were determined as follows:

Determination of the melt flow index (MFR):

0100according to ISO standard 1133, at 230 ° C and under a weight of 2.16 kg.

Determination of the modulus of elasticity (tensile modulus of elasticity):

0101according to ISO standard 527-2, at 23 ° C measuring temperature

Determination of stiffness, shear modulus (G modulus):

0102according to ISO standard 6721-2 at 23 ° C measuring temperature

Determination of impact strength:

0103According to ISO standard 179 / 1eU, at 23 ° C, 0 ° C and -20 ° C measuring temperature.

Determination of the white break:

0104The whitening behavior was assessed in two ways. In the dome method, the white fracture was determined with the aid of a darting bolt apparatus in accordance with DIN 53 443 part 1, using a darting bolt with a mass of 250 g, an impact body of 5 mm diameter and a dome radius of 25 mm. The fall height was 50 cm.

0105An injection molded round disk with a diameter of 60 mm and a thickness of 2 mm was used as the test specimen. The test specimen was injection molded at a melt temperature of 250 ° C and a mold surface temperature of 30 ° C.

0106The test was carried out at temperatures of 23 ° C and 60 ° C, whereby each test specimen was only subjected to an impact test. The test specimen was first placed on a support ring without it being clamped, and then the drop bolt was released. 5 specimens were tested for averaging.

0107The diameter of the visible white break marking is given in mm and was determined by measuring it on the side of the circular disc facing away from the joint in the direction of flow and perpendicular to it and determining the mean value from both values.

0108When determined by the volume method, the increase in volume was measured at 23 ° C during the deformation due to tensile loads. The method was described in detail by F. Ramsteiner (<nplcit id="ncit0002" npl-type="s"><text>Acta Polymerica 42, 1991, pp.584-589</text></nplcit>) described. The values ​​(determined as d (V / V₀) / dε) can be between 0 and 1, whereby low values ​​mean a small increase in volume and thus a low tendency to crack.<tables id="tabl0001" num="0001"><table frame="all"><title>Table 1</title><tgroup cols="11"><colspec colnum="1" colname="col1" colwidth="40mm" /><colspec colnum="2" colname="col2" colwidth="18mm" /><colspec colnum="3" colname="col3" colwidth="12mm" /><colspec colnum="4" colname="col4" colwidth="12mm" /><colspec colnum="5" colname="col5" colwidth="12mm" /><colspec colnum="6" colname="col6" colwidth="12mm" /><colspec colnum="7" colname="col7" colwidth="12mm" /><colspec colnum="8" colname="col8" colwidth="12mm" /><colspec colnum="9" colname="col9" colwidth="12mm" /><colspec colnum="10" colname="col10" colwidth="12mm" /><colspec colnum="11" colname="col11" colwidth="12mm" /><thead><row><entry valign="top">example</entry><entry align="center" valign="top" /><entry align="center" valign="top">1</entry><entry align="center" valign="top">2</entry><entry align="center" valign="top">3</entry><entry align="center" valign="top">4</entry><entry align="center" valign="top">5</entry><entry align="center" valign="top">6</entry><entry align="center" valign="top">7</entry><entry align="center" valign="top">8</entry><entry align="center" valign="top">9</entry></row></thead><tbody><row rowsep="0"><entry>Polymer a)</entry><entry align="center">Weight</entry><entry align="center">a1)</entry><entry align="center">a1)</entry><entry align="center">a1)</entry><entry align="center">a1)</entry><entry align="center">a1)</entry><entry align="center">a1)</entry><entry align="center">a1)</entry><entry align="center">a1)</entry><entry align="center">a1)</entry></row><row><entry>Proportion of polymer a)</entry><entry align="center">Parts</entry><entry align="center">90</entry><entry align="center">85</entry><entry align="center">80</entry><entry align="center">75</entry><entry align="center">90</entry><entry align="center">90</entry><entry align="center">90</entry><entry align="center">90</entry><entry align="center">90</entry></row><row rowsep="0"><entry>Polymer b)</entry><entry align="center">Weight</entry><entry align="center">b1)</entry><entry align="center">b1)</entry><entry align="center">b1)</entry><entry align="center">b1)</entry><entry align="center">b2)</entry><entry align="center">b3)</entry><entry align="center">b4)</entry><entry align="center">b5)</entry><entry align="center">b6)</entry></row><row><entry>Proportion of polymer b)</entry><entry align="center">Parts</entry><entry align="center">10</entry><entry align="center">15</entry><entry align="center">20</entry><entry align="center">25</entry><entry align="center">10</entry><entry align="center">10</entry><entry align="center">10</entry><entry align="center">10</entry><entry align="center">10</entry></row><row><entry>MFR 230/2, 16^a)</entry><entry align="center">g / 10min</entry><entry align="center">12,2</entry><entry align="center">10,5</entry><entry align="center">10,8</entry><entry align="center">9,7</entry><entry align="center">11,9</entry><entry align="center">13,0</entry><entry align="center">12,0</entry><entry align="center">11,1</entry><entry align="center">13,7</entry></row><row><entry>G module^b)</entry><entry align="center">MPa</entry><entry align="center">850</entry><entry align="center">740</entry><entry align="center">670</entry><entry align="center">570</entry><entry align="center">780</entry><entry align="center">760</entry><entry align="center">820</entry><entry align="center">790</entry><entry align="center">790</entry></row><row><entry>Tensile modulus^c)</entry><entry align="center">MPa</entry><entry align="center">1580</entry><entry align="center">1510</entry><entry align="center">1430</entry><entry align="center">1280</entry><entry align="center">1530</entry><entry align="center">1540</entry><entry align="center">1510</entry><entry align="center">1510</entry><entry align="center">1510</entry></row><row rowsep="0"><entry>Impact strength ^d)</entry><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /></row><row rowsep="0"><entry align="right">23 ° C</entry><entry align="center">kJ / m²</entry><entry align="center">152</entry><entry align="center">NB *</entry><entry align="center">NB *</entry><entry align="center">NB *</entry><entry align="center">210</entry><entry align="center">NB *</entry><entry align="center">NB *</entry><entry align="center">156</entry><entry align="center">NB *</entry></row><row rowsep="0"><entry align="right">0 ° C</entry><entry align="center">kJ / m²</entry><entry align="center">76</entry><entry align="center">114</entry><entry align="center">128</entry><entry align="center">158</entry><entry align="center">73</entry><entry align="center">92</entry><entry align="center">86</entry><entry align="center">81</entry><entry align="center">98</entry></row><row><entry align="right">-20 ° C</entry><entry align="center">KJ / m²</entry><entry align="center">29</entry><entry align="center">47</entry><entry align="center">59</entry><entry align="center">82</entry><entry align="center">26</entry><entry align="center">28</entry><entry align="center">36</entry><entry align="center">55</entry><entry align="center">38</entry></row><row rowsep="0"><entry>Whitening</entry><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /></row><row rowsep="0"><entry>Volume method</entry><entry align="center" /><entry align="center">0,23</entry><entry align="center">0,18</entry><entry align="center">0,16</entry><entry align="center">0,19</entry><entry align="center">0,21</entry><entry align="center">0,23</entry><entry align="center">0,19</entry><entry align="center">0,30</entry><entry align="center">0,21</entry></row><row rowsep="0"><entry>Calotte method 23 ° C</entry><entry align="center" /><entry align="center">7,2</entry><entry align="center">7,2</entry><entry align="center">7,1</entry><entry align="center">6,4</entry><entry align="center">6,5</entry><entry align="center">5,3</entry><entry align="center">8,0</entry><entry align="center">10,6</entry><entry align="center">5,0</entry></row><row><entry>Calotte method 60 ° C</entry><entry align="center" /><entry align="center">7,8</entry><entry align="center">7,7</entry><entry align="center">7,6</entry><entry align="center">7,3</entry><entry align="center">9,5</entry><entry align="center">10,0</entry><entry align="center">11,6</entry><entry align="center">12,8</entry><entry align="center">9,5</entry></row></tbody></tgroup><tgroup cols="11" rowsep="0"><colspec colnum="1" colname="col1" colwidth="40mm" /><colspec colnum="2" colname="col2" colwidth="18mm" /><colspec colnum="3" colname="col3" colwidth="12mm" /><colspec colnum="4" colname="col4" colwidth="12mm" /><colspec colnum="5" colname="col5" colwidth="12mm" /><colspec colnum="6" colname="col6" colwidth="12mm" /><colspec colnum="7" colname="col7" colwidth="12mm" /><colspec colnum="8" colname="col8" colwidth="12mm" /><colspec colnum="9" colname="col9" colwidth="12mm" /><colspec colnum="10" colname="col10" colwidth="12mm" /><colspec colnum="11" colname="col11" colwidth="12mm" /><tbody><row><entry namest="col1" nameend="col11" align="justify">a) according to ISO standard 1133, at 23 ° C and 2.16 kg b) according to ISO standard 6721-2, at 23 ° C c) according to ISO standard 527-2, at 23 ° C d) according to ISO standard 179 / 1eU *) without break</entry></row></tbody></tgroup></table></tables><tables id="tabl0002" num="0002"><table frame="all"><title>Table 2</title><tgroup cols="8"><colspec colnum="1" colname="col1" colwidth="36mm" /><colspec colnum="2" colname="col2" colwidth="18mm" /><colspec colnum="3" colname="col3" colwidth="12mm" /><colspec colnum="4" colname="col4" colwidth="12mm" /><colspec colnum="5" colname="col5" colwidth="12mm" /><colspec colnum="6" colname="col6" colwidth="12mm" /><colspec colnum="7" colname="col7" colwidth="12mm" /><colspec colnum="8" colname="col8" colwidth="12mm" /><thead valign="top"><row><entry>Comparative examples</entry><entry /><entry align="center">A</entry><entry align="center">B</entry><entry align="center">C.</entry><entry align="center">D</entry><entry align="center">E</entry><entry align="center">F</entry></row></thead><tbody><row rowsep="0"><entry>Polymer a)</entry><entry /><entry align="center">a2)</entry><entry align="center">a2)</entry><entry align="center">a2)</entry><entry align="center">a1)</entry><entry align="center">V₁)</entry><entry align="center">V₂)</entry></row><row><entry>Proportion of polymer a)</entry><entry align="center">% By weight</entry><entry align="center">90</entry><entry align="center">85</entry><entry align="center">80</entry><entry align="center">90</entry><entry align="center">90</entry><entry align="center">86</entry></row><row rowsep="0"><entry>Polymer b)</entry><entry /><entry align="center">b1)</entry><entry align="center">b1)</entry><entry align="center">b1)</entry><entry align="center">b7)</entry><entry align="center">V₁)</entry><entry align="center">V₂)</entry></row><row><entry>Proportion of polymer b)</entry><entry align="center">% By weight</entry><entry align="center">10</entry><entry align="center">15</entry><entry align="center">20</entry><entry align="center">10</entry><entry align="center">10</entry><entry align="center">14</entry></row><row><entry>MFR 230 / 2.16^a)</entry><entry align="center">g / 10min</entry><entry align="center">9,7</entry><entry align="center">9,0</entry><entry align="center">8,7</entry><entry align="center">10,9</entry><entry align="center">6,5</entry><entry align="center">15,9</entry></row><row><entry>G module^b)</entry><entry align="center">MPa</entry><entry align="center">750</entry><entry align="center">680</entry><entry align="center">620</entry><entry align="center">760</entry><entry align="center">620</entry><entry align="center">820</entry></row><row><entry>Tensile modulus^c)</entry><entry align="center">MPa</entry><entry align="center">1430</entry><entry align="center">1320</entry><entry align="center">1320</entry><entry align="center">1500</entry><entry align="center">1290</entry><entry align="center">1570</entry></row></tbody></tgroup><tgroup cols="8"><colspec colnum="1" colname="col1" colwidth="36mm" /><colspec colnum="2" colname="col2" colwidth="18mm" /><colspec colnum="3" colname="col3" colwidth="12mm" /><colspec colnum="4" colname="col4" colwidth="12mm" /><colspec colnum="5" colname="col5" colwidth="12mm" /><colspec colnum="6" colname="col6" colwidth="12mm" /><colspec colnum="7" colname="col7" colwidth="12mm" /><colspec colnum="8" colname="col8" colwidth="12mm" /><thead valign="top"><row><entry>Impact strength^d)</entry><entry /><entry /><entry /><entry /><entry /><entry /><entry /></row></thead><tbody><row rowsep="0"><entry>23 ° C</entry><entry align="center">kJ / m²</entry><entry align="center">152</entry><entry align="center">NB *</entry><entry align="center">NB *</entry><entry align="center">NB *</entry><entry align="center">NB *</entry><entry align="center">155</entry></row><row rowsep="0"><entry>0 ° C</entry><entry align="center">kJ / m²</entry><entry align="center">68</entry><entry align="center">108</entry><entry align="center">126</entry><entry align="center">104</entry><entry align="center">157</entry><entry align="center">94</entry></row><row><entry>-20 ° C</entry><entry align="center">KJ / m²</entry><entry align="center">21</entry><entry align="center">38</entry><entry align="center">56</entry><entry align="center">62</entry><entry align="center">115</entry><entry align="center">61</entry></row></tbody></tgroup><tgroup cols="8"><colspec colnum="1" colname="col1" colwidth="36mm" /><colspec colnum="2" colname="col2" colwidth="18mm" /><colspec colnum="3" colname="col3" colwidth="12mm" /><colspec colnum="4" colname="col4" colwidth="12mm" /><colspec colnum="5" colname="col5" colwidth="12mm" /><colspec colnum="6" colname="col6" colwidth="12mm" /><colspec colnum="7" colname="col7" colwidth="12mm" /><colspec colnum="8" colname="col8" colwidth="12mm" /><thead valign="top"><row><entry>Whitening</entry><entry /><entry /><entry /><entry /><entry /><entry /><entry /></row></thead><tbody><row rowsep="0"><entry>Volume method</entry><entry /><entry align="center">0,23</entry><entry align="center">0,20</entry><entry align="center">0,17</entry><entry align="center">0,40</entry><entry align="center">0,37</entry><entry align="center">0,46</entry></row><row rowsep="0"><entry morerows="1">Calotte method 23 ° C</entry><entry morerows="1" /><entry align="center">7,3</entry><entry align="center">7,2</entry><entry align="center">7,0</entry><entry align="center">12,6</entry><entry align="center">16,3</entry><entry align="center">16,2</entry></row><row rowsep="0"><entry align="center">7,8</entry><entry align="center">7,6</entry><entry align="center">7,6</entry><entry align="center">15,0</entry><entry align="center">15,4</entry><entry align="center">15,1</entry></row><row><entry>Calotte method 60 ° C</entry><entry /><entry /><entry /><entry /><entry /><entry /><entry /></row></tbody></tgroup><tgroup cols="8" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="36mm" /><colspec colnum="2" colname="col2" colwidth="18mm" /><colspec colnum="3" colname="col3" colwidth="12mm" /><colspec colnum="4" colname="col4" colwidth="12mm" /><colspec colnum="5" colname="col5" colwidth="12mm" /><colspec colnum="6" colname="col6" colwidth="12mm" /><colspec colnum="7" colname="col7" colwidth="12mm" /><colspec colnum="8" colname="col8" colwidth="12mm" /><tbody><row><entry namest="col1" nameend="col8" align="justify">^a) according to ISO standard 1133, at 23 ° C and 2.16 kg</entry></row><row><entry namest="col1" nameend="col8" align="justify">^b) according to ISO standard 6721-2, at 23 ° C</entry></row><row><entry namest="col1" nameend="col8" align="justify">^c) according to ISO standard 527-2, at 23 ° C</entry></row><row><entry namest="col1" nameend="col8" align="justify">^d) according to ISO standard 179 / 1eU</entry></row><row><entry namest="col1" nameend="col8" align="justify">*) without break</entry></row></tbody></tgroup></table></tables>

0109A comparison between Tables 1 and 2 shows, inter alia, that the propylene polymers according to the invention (Table 1, Examples 1 to 9) differ, inter alia, from a reduced tendency to white breakage and from an increased rigidity (G modulus, tensile modulus of elasticity) award.