Compositions of random copolymers of propene containing an alpha−olefin as comonomer

Description of the invention

The present invention relates to a semi-crystalline polyolefin composition and a method for its preparation and use.

Products whose production requires the use of high temperatures can be made from the polyolefin compositions of the invention. For example, certain types of laminate products, i.e. sheets and films, require such processing conditions. For example, the indicated polymer compositions are suitable for the production of metallized articles, in particular metallized films. The films can be both monolayer and multilayer. Therefore, such compositions can be useful in the production of metallized single-layer and multi-layer films.

The articles prepared from the compositions according to the invention are particularly suitable for use in the food industry due to the low content of xylene soluble components at room temperature. Thus, such products can be used in the field of food packaging.

Polyolefin compositions containing a mixture of two or three propylene copolymers with an α-olefin, mainly 1-butene, are known. The compositions known in the art are suitable for the production of low temperature heat sealable films.

For example, U.S. Patent 4,211,852 discloses a thermoplastic olefin resin composition consisting of a poly (propylene-co-butene-1) polymer with at least 15 mole% repeating units derived from 1-butene and a copolymer of propylene with ethylene or 1-butene. containing up to 10 mole% of repeating units derived from the comonomer. However, in the examples, the compositions made from the two copolymers do not contain the two poly (propylene-co-butene-1) polymers, and the poly (propylene-co-butene-1) polymer has a content of about 35% by weight.

European Patent Application EP-560326 also describes a thermoplastic olefin resin composition comprising a random poly (propylene-co-butene-1) polymer with 1-10% by weight of repeating units derived from 1-butene and a random poly (propylene-co-butene) polymer. -1) containing from 15 to 40% by weight of repeating units derived from 1-butene.

European patent application EP-719829 describes polyolefin compositions containing a mixture of three copolymers of propylene with an α-olefin, mainly 1-butene. At least one copolymer contains a high amount of comonomer (25% by weight or more). The films made from the compositions described herein have low heat seal temperatures as shown in the embodiments where the value is 92 ° C or less.

Although the compositions known from the prior art cited above have high melting points, they are not suitable for metallization. The main disadvantage of these compositions is that the amount of the polymer fraction with low crystallinity is too high, as a result of which the films produced from these prior art compositions are heat-sealable at low temperatures.

The applicants have now developed new compositions having high melting points and VICAT values. These properties allow the polymer to be subjected to high temperatures such as required for the metallization process.

A particular advantage of the copolymer compositions of the invention is that they have low solubility in xylene at room temperature and can have good transparency. These properties are especially desirable in the food industry.

Moreover, the compositions according to the invention have rather high stiffness. Due to this property, films of a uniform thickness can be produced.

Thus, the present invention provides a semi-crystalline polyolefin composition containing, by weight percent:

a) 25-40%, preferably 28-38% of a random copolymer of propylene with 1-butene as comonomer, containing from 2 to 10% of repeating units derived from the comonomer,

b) 25-40%, preferably 26-36% of a random copolymer of propylene with 1-butene as comonomer containing from 10 to 20% of repeating units derived from a comonomer,

c) 25-40%, preferably 28-38% of a random copolymer of propylene with 1-butene as comonomer, containing 6 to 12% of repeating units derived from a comonomer, the total content of repeating units from this comonomer, based on the composition is equal to or greater than 6%, and the relative percentages of the content of these repeating units in each of the copolymers a), b) and c) differ from the other two the difference with the percentage of repeat units in each of the other two copolymers being at least 1 unit, preferably 1.5 units.

It follows from the above definitions that the term "copolymer" as used herein means polymers containing more than one type of comonomer.

Examples of such C.₄-C₁₀ The α-olefins are 1-butene, 1-pentene, 1-hexene, 1-octene, and 4-methyl-1-pentene. 1-butene is particularly preferred.

Preferred semi-crystalline polyolefin compositions are those in which the comonomers of the copolymers (a), (b) and (c) are the same.

Such compositions typically have a Seal Initiation Temperature (SIT) of 110 ° C to 120 ° C. The VICATA softening point values ​​are generally from 115 to 140 ° C, preferably 125-135 ° C.

Moreover, such compositions generally have a Heat Deflection Temperature (HDT) in the range of 65 to 75 ° C.

Moreover, flexural modulus values ​​are generally in the range from 900 to 1300 MPa, preferably 950-1250 MPa. The haze value is generally 40%_about or less and is marked on a 1 mm thick plate. The value of the melt flow rate (condition L) is generally from 0.1 to 100 g / 10 minutes. The above properties are determined by the methods described in the examples.

The invention also relates to a process for the preparation of a semi-crystalline polyolefin composition, wherein propylene and 1-butene monomers are polymerized in the presence of stereospecific Ziegler-Natta catalysts supported on active magnesium dihalides in active form, in at least three separate and consecutive stages in which it produces copolymers (a), (b) and (c) follow, and in each subsequent step after the first, polymerization takes place in the presence of the polymer formed and the catalyst used in the immediately preceding step.

Preferably, all polymerization steps are carried out in the gas phase.

Another object of the present invention is the use of a composition as defined above for the production of laminated articles, including in particular monolayer films and multilayer films, wherein at least one outer layer comprises a composition according to the invention.

In a preferred embodiment, the further layer comprises an olefinic polymer.

In particular, the laminated articles are metallized articles that preferably contain a metal selected from aluminum and zinc.

The compositions according to the invention can also be prepared by known methods.

One method is to mechanically mix the copolymers (a), (b) and (c) in the molten state. The mixing process is carried out at or above the melting point of the copolymers.

However, a sequential polymerization method as indicated above, in which the monomers are polymerized in the presence of a catalyst, such as a stereospecific Ziegler-Natta catalyst, is preferred.

As mentioned above, the sequential polymerization is preferably carried out in at least three separate and sequential steps in which the copolymers (a), (b) and (c) are produced according to the invention. In each subsequent step after the first step, polymerization takes place in the presence of the polymer obtained and the catalyst used in the previous step. Preferably, the first random copolymer containing the least amount of co-monomer is produced first, followed by the other two copolymers.

The polymerization process can be carried out in the liquid phase, in the presence or absence of an inert solvent, or in the gas phase or in a mixed phase (liquid / gas). Preferably, the polymerization is carried out in the gas phase.

The control of the molecular weight is carried out using known regulators, preferably hydrogen.

Polymerization can be carried out using a prepolymerization step in which the catalyst is brought into contact with a small amount of olefins.

As previously described, Ziegler-Natta catalysts contain a solid catalyst component and a cocatalyst. The solid catalyst component comprises a titanium compound containing at least one titanium-halogen bond and an electron donor compound (internal donor) supported on a magnesium dihalide. The magnesium dihalide support is preferably in the form of spheroidal particles with a narrow particle size distribution.

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The internal donor is generally selected from ethers, ketones, lactones, compounds containing N, P and / or S atoms, and esters of mono- and dicarboxylic acids. Particularly suitable electron donors are phthalic acid esters such as diisobutyl, dioctyl, diphenyl and benzylbutyl phthalate.

Other preferred electron donors are 1,3-diethers of formula (R.^AND) (R^II) C (CH2OR^III) (CH2OR^IV) in which R.^AND and r^II they are the same or different and represent a C1-C18 alkyl, C3-C18 cycloalkyl or C7-C18 aryl radical; R^III and r^IV they are the same or different and represent C1-C4 alkyl radicals or are 1,3-diethers in which the carbon atom in position 2 belongs to a cyclic or polycyclic structure made of 5, 6 or 7 carbon atoms, containing two or three unsaturations.

Ethers of this type are described in European patent applications EP-361493 and EP-728769.

Representative examples of such diethers are 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2-isopropyl-2- - isoamyl-1,3-dimethoxypropane, 9,9-is (methoxymethyl) fluorene.

The preparation of the catalyst solids described above is carried out by various methods.

For example, an MgCl2.nROH adduct (particularly as spheroidal particles) where n is generally from 1 to 3 and ROH is ethanol, butanol or isobutanol is reacted with an excess of electron donating compound containing TiCl4. The reaction temperature is generally from 80 to 120 ° C. The solid component is then isolated and re-reacted with TiCl4, in the presence or absence of an electron donor compound, then isolated and washed with aliquots of hydrocarbon until all chloride ions have disappeared.

In the solid catalyst component, the titanium compound, expressed as Ti, is generally present in an amount of from 0.5 to 10% by weight. The amount of electron donating compound which is deposited on the solid catalyst component is generally 5 to 20% by mole with respect to the magnesium dihalide.

The titanium compounds that can be used in the preparation of the solid catalyst component are titanium halides and titanium alkoxide halides. A preferred compound is titanium tetrachloride.

The above-described reactions lead to the formation of a magnesium halide in active form. Other reactions are known from the literature which yield a magnesium halide in active form starting from magnesium compounds other than halides, such as magnesium carboxylates.

The active form of the magnesium halide in the solid catalyst component can be recognized by the fact that the X-ray spectrum of the catalyst component no longer shows the maximum reflection intensity, which appears in the spectrum of the unactivated magnesium halide (having a specific surface area of ​​less than 3 m²/ g), and in its place appears a halogen with a maximum intensity shifted with respect to the position of maximum reflection intensity for inactive magnesium dihalide, or by the fact that the maximum reflection intensity shows a width at half the peak height at least 30% greater than for the maximum intensity which appears in the spectrum of the inactive magnesium halide. The most active forms are those for which the above-mentioned halogen appears in the X-spectrum of the solid catalyst component.

Of the magnesium halides, magnesium chloride is preferable. For the most active forms of magnesium chloride, the X spectrum of the solid catalyst component shows a halogen instead of reflection which appears in the spectrum of the inactive chloride at 2.56 A.

The co-catalyst is generally an Al-alkyl compound, alone or in combination with an electron donor compound (external donor).

Generally the Al-Alkyl Compound is a trialkylaluminum type compound such as triethyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum and linear or cyclic alkyl aluminum compounds containing two or more O or N linked Al atoms or SO2, SO3 and SO4 groups.

Examples of such compounds are:

(C2H5) 2Al-O-Al (C2H5) 2;

(C2H5) 2Al-N (C6H5) -Al (C2H5) 2;

(C2H5) 2Al-SO2-Al (C2H5) 2;

CH3 [(CH3) Al-O] n-Al (CH3) 2;

- [(CH3) Al-O-] n;

where n is a number from 1 to 20.

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Compounds AlR2H and compounds AlR2OR ', in which R is an alkyl radical of 1 to 6 carbon atoms, and R' is an aryl radical substituted at one or more positions, can also be used.

The alkylaluminum compounds are generally present in amounts such that the Al / Ti ratio ranges from 1 to 1000.

The external electron donor compound may be selected from aromatic acid esters (such as alkyl benzoates), heterocyclic compounds (such as 2,2,6,6-tetramethylpiperidine and 2,6-diisopropylpiperidine), and certain silicone compounds containing at least one Si bond -OR (where R is a hydrocarbon radical). Examples of silicone compounds are (t-C4H9) 2Si (OCH3) 2, (C5H9) 2Si (OCH3) 2, (C6H11) 2Si (OCH3) 2, (C6H11) (CH3) Si (OCH3) 2, and (C6H5) 2Si ( OCH3) 2.

Preferably 1,3-diethers of formula (I) can also be used as external electron donor compounds. In case the internal electron donating compound is one of the 1,3-diethers of the formula (I), the external electron donating compound may not be added.

The compositions of the invention may also contain additives commonly used in the art such as antioxidants, light stabilizers, heat stabilizers, pigments and the like.

As previously indicated, the compositions of the invention are particularly suitable for the manufacture of laminated articles, including films and sheets.

Due to the characteristics of the polymer compositions, it is possible to produce metallized laminates, in particular films. The films are generally characterized by a thickness of less than 100 µm, while the sheets are of a thickness equal to or greater than 100 µm.

The films of the invention may be cast or preferably bi-oriented.

Films and sheets can be single-layer or multi-layer.

The multi-layer film or multi-layer sheet has at least one as cast or bi-oriented layer containing the composition of the invention. The layer containing the composition of the invention may be an outer layer or an inner layer.

The remainder of the layer (s) may contain olefinic polymers or other polymers. The preferred olefin polymers are propylene polymers. Such further layer may include, for example, a polymer having low temperature heat seal properties. A practical example of a multilayer film with such properties is a three-layer film with an ABC structure, in which one of the outer layers comprises a composition according to the invention. The middle layer may be a crystalline propylene homopolymer. The outer layer may be a random propylene copolymer with a small amount (less than 10% by weight) of ethylene and / or butene-1 derived repeating units.

The films of the invention can be produced by known methods such as extrusion, calendering and foaming.

As mentioned above, the films of the invention can be used to make metallized laminates. Both single-layer and multi-layer laminated products (sheets or, preferably, films) can be subjected to the metallization process. When a multilayer laminate article is metallized, the outer layer is made of the composition of the invention.

When the laminated article is metallized, the metallizing process is carried out, for example, by sublimating the metal on the film surface by known methods. The metal used generally belongs to groups IB to IIIB of the periodic table, such as aluminum or zinc.

The article may be in the form of a multilayer laminate obtained by extrusion lamination of a polymer on a layer containing the polymer composition of the invention. This layer can be metallized as well as non-metallized. The polymer used in the extrusion lamination process preferably has a melting point equal to or less than 150 ° C, for example polyethylene or polyethylene terephthalate.

The metallized films according to the invention have good barrier properties. This advantageous effect is due to the presence of the composition according to the invention, which allows good adhesion of the metal to the polymer layer.

The following examples illustrate, but are not limited to, the preparation process and the characteristics of the compositions of the invention.

The data presented in the tables were obtained using the following analytical methods:

- molar ratios of introduced gases: determined by gas chromatography;

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- 1-butene content: determined by IR spectroscopy;

- xylene soluble fraction: 2.5 g of polymer was dissolved in 250 ml of xylene at 135 ° C with stirring. After 20 minutes, the solution was allowed to cool to 25 ° C with continued stirring and then allowed to solidify for 30 minutes. The precipitate was filtered off through filter paper, the solution was evaporated under nitrogen flow and the residue was dried in vacuo at 80 ° C until a constant weight was obtained. In this way, the weight percent of xylene insoluble polymer at ambient temperature (i.e. 25 ° C) was calculated.

- Melt Flow Rate (MFRL): Determined by ASTM D 1238 Method, Condition L;

- VICAT: determined using the ISO 306 method;

- HDT: determined using the ISO 75 method;

- bending modulus: determined by the ASTM D 790 method;

- RCI IZOD (impact strength): determined using the ISO 180 / 1A method;

Rockwell R hardness: determined by internal method MA 17013, available upon request. A Durometer Galileo A-200 was used. A 5 mm thick sample with a side of 12.7 mm was cut from the injection molded plate.

The test was carried out at 23 ° C; at 50% relative humidity. A pressure of 588.4 N was applied to the sample for 15 seconds. The weight was shaped like a spherical stamp. The punch diameter was 12.7 mm. After removing the stamp, a waiting period of 1 second was before reading the hardness value on the durometer scale. At least 5 tests were performed at different locations on the sample.

Rockwell alpha hardness (R._and) is calculated according to the following formula:

Ra = 150 - (d_h - d_m) where dh is the value read on the durometer scale and dm is the elastic constant of the durometer.

- fisheye: determined according to the internal method MTM 17108E, available on request. A 50 µm thick sample was cut from the film produced on a Bandera 45 extruder equipped with a film discharge unit and cooling rolls (Dolci). The foil sample was placed in a special projector with a slit (Neo Solex 1000 projector with a 1000 W lamp and a Neo Solex F 300 lens equipped with a foil winding apparatus). The foil sample was then examined on the wall chart by counting the number of gels and recording their dimensions.

- WVTR (water vapor transmission rate): determined according to the internal method MA 18073, available on request. The test was carried out on a sample of the foil.

The film sample was placed in a small stainless steel vessel (diameter 59 mm, height 37 mm) containing 5 ml of distilled water. After this vessel was weighed, the vessel was turned upside down so that the water was in contact with the foil and placed at room temperature of 23 (+/- 1) ° C and 50 (+/- 5)% relative humidity for at least 120 hours. The vessel was weighed every 24 hours.

The transmittance index for the film was calculated using the following formula:

(Gs) / (at) where G is expressed in grams and means the average reduction in the weight of water every 24 hours, s is the thickness of the foil, the value of a is 1 m², and t is 24 hours.

- OTR (Oxygen Transmission Rate): determined according to internal method MA 17275, available upon request. The test was carried out on the same film as used for the WVTR test. A sample having a diameter of about 75 mm was cut from the foil. The sample was previously kept in an oven at 23 ° C under vacuum (about 1 Pa, i.e. 0.01 mbar) for 24 hours.

The sample was placed in the center of a sealed steel vessel in such a way that the vessel was divided into two chambers. The vessel was lowered to 0.1 Pa (0.001 mbar) of air pressure using a Datametrics type 1500 vacuum gauge. Oxygen was then introduced into one chamber until a pressure of 0.05 MPa (0.5 bar) was reached; the oxygen pressure was measured with an Edward EPV 251 manometer. The pressure in the second chamber was then measured at regular intervals until a regular increase in pressure was observed.

After determining the linear regression line from the experimental pressure values, the gas permeability coefficient (CP) through the foil was calculated using the following formula:

CP = V. [dP (t) / dt]. [273 / (273 + T)]. 76^-1 . (L / A). P1^-1 where V is the volume of the vessel (ml); P = pressure of the filtered gas; [dP (t) / d (t)] = angular coefficient of the interpolation line; T is the temperature in ° C at which the test was performed; L = sample thickness; A = area of ​​the sample exposed to the gas flow; P1 = gas inlet pressure; t = time.

- haze: determined by ASTM D 1003 method;

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- Gloss: Determined by ASTM D 2457 method

- melting point: determined by DSC (Differential Scanning Calorimetry)

- Sealing Initiation Temperature (SIT): was determined by preparing a 50 μm thick film by extrusion against samples of the compositions of the examples at a temperature of about 200 ° C. Each of the thus obtained film was applied to a polypropylene plate with a xylene solubility of 4% by weight, a melt flow rate of 2 g / 10 minutes. The applied foil and plate were bonded in a flat press at a temperature of 200 ° C with a pressure of 9000 kg. The pressure was held for 5 minutes. The obtained welded test sample was then stretched six times the length and width of a TM LONG stretcher, thereby obtaining a film about 20 µm thick. Samples of 5x10 cm were obtained from the film. Sealing values ​​were obtained by applying a pressure of 200 g to the heat-sealed samples. For each measurement, two of the above samples were covered with heat-sealable layers prepared from the compositions according to the examples, by bringing them together. Then, the samples prepared in this way were welded along a 5 cm side using a laboratory Xentinel model 12-12 AS sealer. The welding time was 5 seconds, the pressure was about 0.12 MPa (1.2 atm), and the width of the weld was 2.5 cm. The welding temperature was increased by 2 ° C after welding each sample for measurement. The welded samples were then cut into 2.5x10 cm strips, the non-welded ends of which were attached to a dynamometer, and the minimum welding temperature at which the joint did not break under a load of 200 g was determined. This temperature is the welding initiation temperature (SIT).

Examples 1-2 and Comparative Example 1c

The compositions were prepared by sequential polymerization, i.e. the polymerization was carried out continuously in a series of reactors equipped with devices for transferring the product from one reactor to the next one next to it.

The catalyst used for the polymerization was a highly stereospecific Ziegler-Natta catalyst containing a magnesium chloride-supported solid component containing about 2.5% by weight of titanium and diisobutylphthalate as the internal electron donor component. The solid component of the catalyst was prepared analogously to the method described in the examples of European patent application EP-674991.

During the polymerization, the gas phase was continuously analyzed by gas chromatography to determine the content of propylene, 1-butene, hydrogen and propane. The above-mentioned gases were introduced in such a way that their gas-phase concentrations remained constant during the polymerization.

Prior to introducing the catalyst system into the polymerization reactors, the solid catalyst component was contacted at 20 ° C for 9 minutes with triethylaluminum (TEA) and dicyclopenethyldimethoxysilane (DCPMS) in liquid propane. The weight ratio TEAL / solid catalyst component was 10 and the ratio TEA / DCPMS was 4.

The catalyst system was then transferred to a reactor containing excess liquid propylene and propane for prepolymerization at 25 ° C for 30 minutes before being introduced into the first polymerization reactor.

In the first gas phase polymerization reactor, poly (propylene-co-butene-1) (copolymer (a)) was produced by the continuous and constant flow feeding of the prepolymerized catalyst system, hydrogen (used as molecular weight regulator) and monomers of propylene and 1- butene and propane gas.

The copolymer produced in the first reactor was discharged and, after purification of unreacted monomers, was continuously fed to the second gas phase polymerization reactor along with quantitatively constant flows of hydrogen, propylene and 1-butene and propane gas.

The polymer produced in the second reactor (copolymer (b)) was discharged and, after purification from unreacted monomers, fed, in continuous flow, to the third gas phase polymerization reactor together with hydrogen, propylene and 1-butene and propane gas (quantitatively solid flow) to form the copolymer (c).

The polymer particles present in the third reactor were steam treated to remove reactive monomers and volatile substances and then dried.

The polymerization temperature was 70 ° C in all steps.

The polymerization conditions, weight ratios of the reactants, the composition of the copolymer produced in each step and the composition of the final polymer and its properties are given in Table 1.

The composition of Example 1 and Comparative Example 1c was used to produce a bi-oriented 25 µm thick three-layer film. The foil layers were as follows:

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- 1 μm thick outer layer (layer A) made of a random propylene copolymer containing 3.3 wt% and 6 wt% repeating units derived from ethylene and 1-butene respectively;

- 23 μm thick middle layer (layer B) made of crystalline propylene homopolymer;

outer layer 1 μm thick (layer C) prepared from the composition according to Example 1 or from Comparative Example 1c.

This three-layer film was prepared by coextrusion using an extrusion system

Briickner. Then, the foil was subjected to a metallization process using known methods, and the C layer was metallized with aluminum.

The thus obtained film was subjected to the WVTR (water vapor transmission rate) test and the OTR (oxygen transmission rate) test.

Table 2 shows the mechanical and physical properties of films or tiles prepared from the compositions of the invention.

Table 1

<td>Example and comparative example</td><td>1c</td><td> 1</td><td> 2</td>

<td colspan="4">Stage (i)</td>

<td>Pressure (MPa)</td><td> 2,1</td><td> 1,7</td><td> 1,9</td>

<td>H2 / C3 (mol)</td><td> 0,046</td><td> 0,017</td><td> 0,015</td>

<td>C4 (C4 + C3) (mol)</td><td> -</td><td> -</td><td> 0,06</td>

<td>Content¹) copolymer (a) (wt%)</td><td> 66</td><td> 35</td><td> 35</td>

<td>butene-1 content in copolymer (a) (wt%)</td><td> 8,3</td><td> 5,9</td><td> 3,1</td>

<td>MFRL (g / 10min)</td><td> 6,3</td><td> 5,8</td><td> 6,0</td>

<td colspan="4">Stage (ii)</td>

<td>Pressure (MPa)</td><td> 2,1</td><td> 1,9</td><td> 1,9</td>

<td>H2 / C3 (mol)</td><td> 0,077</td><td> 0,060</td><td> 0,053</td>

<td>C4 / (C4 + C3) (mol)</td><td> 0,15</td><td> -</td><td> 0,23</td>

<td>Content¹) copolymer (b) (wt%)</td><td> 34</td><td> 30</td><td> 30</td>

<td>butene-1 content in copolymer (b) (wt%)</td><td> 10,4</td><td> 12,2</td><td> 15,4</td>

<td>MFRL (g / 10min)</td><td> 5,8</td><td> 7,1</td><td> 5,2</td>

<td colspan="4">Stage (iii)</td>

<td>Pressure (MPa)</td><td> -</td><td> 1,9</td><td> 1,9</td>

<td>H2 / C3 (mol)</td><td> -</td><td> 0,064</td><td> 0,057</td>

<td>C4 (C4 + C3) (mol)</td><td> -</td><td> 0,15</td><td> 0,16</td>

<td>Content¹) copolymer (c) (wt%)</td><td> 0</td><td> 35</td><td> 35</td>

<td>butene-1 content in copolymer (c) (wt%)</td><td> 0</td><td> 9,1</td><td> 9,1</td>

<td colspan="4">Final composition</td>

<td>MFRL (g / 10min)</td><td> 5,8</td><td> 5,5</td><td> 4,5</td>

<td>butene-1 content (wt%)</td><td> 9,0</td><td> 8,9</td><td> 8,9</td>

<td>xylene soluble fraction (wt%)</td><td> 2,5</td><td> 2,5</td><td> 6,2</td>

<td>melting point (° C)</td><td> 145</td><td> 145</td><td> 151</td>

<td>temperature at which 30% of the composition melted (° C)</td><td> 117,5</td><td> 118,5</td><td> 120,0</td>

¹⁾ denotes the polymer content with respect to the final composition

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Table 2

<td>Example and comparative example</td><td>1c</td><td> 1</td><td> 2</td>

<td>VICAT (° C)</td><td> 128</td><td> 129</td><td> 132</td>

<td>SIT (° C)</td><td> 118</td><td> 118</td><td> 116</td>

<td>HDT 455 kPa (° C)</td><td> 73</td><td> 71</td><td> 72</td>

<td>modulus of elasticity during bending (MPa)</td><td> 1080</td><td> 1110</td><td> 1140</td>

<td>PCI IZOD impact strength (kJ / m²)</td><td> 5,3</td><td> 6,4</td><td> 6,9</td>

<td>Rockwell hardness R (° R)</td><td> 100,8</td><td> 102</td><td> 101</td>

<td>fishery&gt; 1.5 mm (n ° / m²)</td><td> 0</td><td> 0</td><td> 0</td>

<td>fish meshes 0.7 - 1.5 mm (n ° / m²)</td><td> 2</td><td> 1</td><td> 0</td>

<td>fish mesh 0.5 - 0.7 mm (n ° / m²)</td><td> 7</td><td> 4</td><td> 2</td>

<td>fisheye&gt; 0.1 mm (n ° / m²)</td><td> 500</td><td> 270</td><td> 250</td>

<td>turbidity of 50 μιτι of the film thickness (%)</td><td> 1,7</td><td> 1,6</td><td> 1,5</td>

<td>haze of 1 mm of the plate thickness (%)</td><td> 34,7</td><td> 35,0</td><td> 36,7</td>

<td>gloss 60 ° 1 mm plate thickness (% o)</td><td> 83,0</td><td> 84,8</td><td> 84,5</td>

<td>gloss 45 ° 1 mm tile thickness (%)</td><td> 58,0</td><td> 59,6</td><td> 59,6</td>

<td>WVTP (water vapor) (g / (m². 24 hours))</td><td> 0,25</td><td> -</td><td> 0,17</td>

<td>OTR (oxygen¹)) (ml / (m². 24 hours))</td><td> 45</td><td> -</td><td> 30</td>

1) means that the test was carried out at ambient temperature for 20 minutes, the surface of the test sample - 5 cm².