CZ306881B6 - A polyolefin powder, the method of its manufacture and use - Google Patents

Abstract

The polyolefin powder contains particles with fasciculated morphology. The method of preparation of the polyolefin powder is carried out by co-ordinating polymerization of 1-olefins on a heat-treated Ziegler-Natt precatalyst activated by an organoaluminum cocatalyst.

Description

The present invention relates to a polyolefin powder, to a process for its production and use, and to a process for treating a Ziegler-Natta precatalyst for the production of a polyolefin powder.

BACKGROUND OF THE INVENTION

Known thermoplastic polymers such as polyethylene, polypropylene, and various copolymers and terpolymers of ethylene and propylene with higher α-olefins are usually produced on ZieglerNatt catalytic systems, in which the so-called precatalyst is usually composed of MgCl ₂ , TiCl ₄ and an internal donor. To activate this precatalyst for the polymerizable form thus the catalyst used is usually an organoaluminum cocatalyst, the general structure A1R ₃ wherein R is n-alkyl or iso-alkyl. Alternatively, the catalyst may be modified by various types of external donors to increase its stereospecificity and stereoregularity of the resulting thermoplastic polyolefin.

The character of the resulting polymer particles of these polyolefins depends on the composition of the precatalyst and its morphology, as well as on the nature and content of individual reactants (cocatalyst, external donor, hydrogen, monomers) in the reaction mixture and last but not least on polymerization conditions (temperature, pressure, phase). environment). The resulting polymer particles are spherical to oval in shape with varying dimensions (0.2 to 2.0 mm), the surface of these particles usually being more or less smooth, and the bulk density relative to their morphology and particle size distribution is relatively high (350 to 500 g / l). ). Due to their shape and high bulk density, such polymer particles are easy to transport and store. In another aspect, the morphology of these polymer particles is disadvantageous, for example, for utilizing this polymer in terms of sorption properties.

SUMMARY OF THE INVENTION

SUMMARY OF THE INVENTION It is an object of the present invention to provide a polyolefin powder with altered morphology, to find a preferred process for its production, and a preferred Ziegler-Natta precatalyst for carrying out this process. According to the invention, this is largely achieved by a polyolefin powder which contains particles with a tuft morphology of at least 40% by weight.

These particles consist of polyolefin fibers having different diameters and lengths. The fibers typically have a diameter of 5 to 100 µm, preferably 10 to 50 µm, and a length of 10 to 2000 µm, preferably 50 to 1000 µm. These particles are not compact, since the length of the fibers is always several times higher than their diameter. As a result, these subject particles differ from conventional compact polyolefin particles which exhibit uniformity in all 3 dimensions. The fibers of the polyolefin powder particles of the invention are intertwined differently to form a three-dimensional structure with different sized interspaces depending on their number, diameter and length. These fiber interfaces contain air (or can be filled with another substance). The interspaces between the fibers play an important role in the absorption and insulating properties of the polymer formed by these particles. The particulate polyolefin having a fibrous structure in the form of a powder has a macroscopic size of from 0.1 to 4 mm, preferably from 0.2 to 2 mm, depending on the particle size of the polymerization catalyst used, its thermal activation conditions and polymerization conditions.

The term tuft morphology polyolefin of the present invention refers to a polyolefin particle having a three-dimensional structure formed by interwoven fibers of polyolefin with interwoven interspaces.

- 1 GB 306881 B6

With regard to practical application, it also appears to be advantageous if the polyolefin powder is a polyolefin having a bulk density in the range of 20 to 300 g / l, in the range of 20 to 200 g / l in terms of sorption and thermal insulation properties. The bulk density (SH) of the polymer powder was determined according to ISO 60 (E).

A preferred method of preparing the polyolefin powder is in particular by coordinating the polymerization of 1-olefins on a thermally treated Ziegler-Natta precatalyst activated with an organoaluminium cocatalyst.

The term Ziegler-Natta precatalyst of the invention is a compound comprising a transition metal compound of IV. - VIII. groups. These are generally the halides or oxyhalides of Ti, V or Cr, in particular Ti. Preferred Ziegler-Natta precatalysts are, in particular, TiCl ₃ , TiCl ₄ , mixtures of VOCl ₃ with TiCl ₄ , and mixtures of VCl ₄ with TiCl ₄ . Suitable carriers for Ziegler Natt precatalysts are silica or magnesium compounds such as magnesium halides, especially MgCl ₂ ; and magnesium alkoxides, dialkyl magnesium compounds, and organic magnesium halides. They are compounds known and commonly used in olefin polymerization. In the case of Ziegler Natt precatalysts bound to the support surface and intended for polymerizing propylene and copolymerizing propylene with other 1-olefins, a compound called an internal donor designed to enhance the stereospecificity of these precatalysts is attached to the support surface by electrondonomy. Depending on the type of internal donor used, Ziegler-Natta precatalysts can be divided into, for example, phthalate, diether or succinate.

The heat treatment of the Ziegler-Natta precatalyst is carried out under reduced pressure below 1 kPa or under an inert gas flow selected from the group consisting of nitrogen, helium or argon, preferably nitrogen, at temperatures ranging from 50 ° C to 150 ° C for 1 minute to 10 hours. Subsequent activation of the heat-treated Ziegler-Natta precatalyst is accomplished by reaction with an organoaluminum compound of the formula AIR "Zun, where R is a C 1 -C ₂₀ alkyl group, Z is a halogen selected from the group consisting of F, Cl, Br or I and n is 0 , 1, 2 or 3, e.g. by reaction with any of the organoaluminum compounds including trimethyl aluminum (TMA), triethyl aluminum (TEA), triisobutyl aluminum (TIBA), tri-n-hexyl aluminum (THA), tri-iso-hexyl aluminum (TÍHA), tri -noctyl-aluminum (TOA) and tri-n-decyl-aluminum (TDA).

The coordination polymerization of 1-olefins can be carried out in a gaseous or liquid 1-olefin environment or a non-polar hydrocarbon solvent saturated with 1-olefin, resulting in ethylene or propylene homopolymers, ethylene or propylene copolymers with higher 1-olefins, and ethylene terpolymers; propylene with higher 1-olefins, which always contain particles with tuft morphology.

The term non-polar hydrocarbon solvent of the invention includes solvents selected from the group consisting of liquefied propane, liquefied butane, isomers of pentane, hexane, heptane and other C8-C8 linear saturated hydrocarbons, cyclopentane, cyclohexane, benzene, toluene, xylene and mineral oils.

A suitable precatalyst for the heat treatment and subsequent coordination polymerization of 1-olefins to advantageously prepare a polyolefin powder with fluff morphology is the Ziegler-Natta precatalyst, which contains one or more internal donors selected from the group of compounds of formulas I, II and III:

-2GB 306881 B6

(ΙΠ) which contain 2 oxygen functional groups in the ether group -OR bonded to the carbon atoms C ¹ and C ^{3 of the} carbon atom group CC ² -C ³ according to the general formula I, generally called diethers or contain 2 oxygen functional groups in the ester group -O -CO-R bound to the carbon atoms C ¹ and C ³ atomic grouping C'-C ² -C ³ according to formula II, generally called diesters or 2 oxygen containing functional group in position 2 and 6 in 2,6-bound dioxoheptandioátu the carbon atoms C ¹ and C ³ atomic group C * -C ² -C ³ according to formula III wherein R ether group, -OR, or R in the ester group -OCOR is selected from alkyl, cycloalkyl, or aryl and R the dioate groups are selected from the group consisting of alkyl, optionally the alkyls of the two dioate groups may be joined together to form an aliphatic ring; and where either

a) the C ¹ , C ² and C ³ carbon atoms form an aliphatic chain which is optionally disubstituted at the C ² carbon atom, wherein the substituents are selected from the group consisting of alkyl, cycloalkyl or aryl, wherein C ^{1 and} C ³ are optionally substituted by alkyl; or

(b) the carbon atoms C ¹ , C ² and C ³ form an aliphatic chain, where C ₂ is part of a cyclic or polycyclic structure consisting of a cycle or cycles of 5, 6 or 7 carbon atoms and containing 2 or 3 unsaturated bonds and carbons C ^{1 and} C ³ are attached to this C ² atom, wherein C ¹ and C ³ are optionally substituted with alkyls and the resulting cyclic or polycyclic structure is optionally substituted with substituents selected from the group consisting of halogens, preferably Cl or F, alkyls, cycloalkyls, aryl, alkaryls or aralkyls; or

c) the carbon atoms C ^1, C ² and C ³ are part of a polycyclic structure made up of at least two cycles of a 5, 6 or 7 carbon atoms and in each cycle, two or three unsaturated bonds, wherein C ¹ and C ³ are optionally substituted alkyl and the resulting polycyclic structure is optionally substituted with substituents selected from the group consisting of halogens, preferably Cl or F, alkyls, cylcoalkyls, aryls, alkaryls or aralkyls; or

d) the C ¹ , C ² and C ³ carbon atoms are part of a cyclic structure formed from a cycle of 5, 6 or 7 carbon atoms, the resulting cyclic structure being optionally substituted with substituents selected from the group consisting of halogens, preferably Cl or F, alkyls, cycloalkyls, aryls, alkaryls or aralkyls.

For example, the following internal donor structures are selected from the group:

(a) 1,3-diether compounds including:

2-methyl-2-isopropyl-1,3-dimethoxypropane;

2-isopropyl-2-isobutyl-1,3-dimethoxypropane;

2-isopropyl-2-isopentyl-1,3-dimethoxypropane;

2-heptyl-2-pentyl-1,3-dimethoxypropane;

2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane;

2-isopropyl-2-cyclohexyl-1,3-dimethoxypropane; 2-isopropyl-2-cyclohexylmethyl-1,3-dimethoxypropane;

2,2-dipropyl-1,3-dimethoxypropane;

2,2-diisopropyl-1,3-dimethoxypropane;

2,2-diisobutyl-1,3-dimethoxypropane;

2,2-diisobutyl-1,3-diethoxypropane;

2,2-diisobutyl-1,3-dibutoxypropane;

2,2-dicyclohexyl-1,3-dimethoxypropane;

2,2-diphenyl-1,3-dimethoxypropane;

2,2-dibenzyl-1,3-dimethoxypropane;

2,2-dicyclopentyl-1,3-dimethoxypropane;

2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane;

1,1-bis (methoxymethyl) -cyclopentadiene;

1,1-bis (methoxymethyl) -2,3,4,5-tetramethylcyclopentadiene;

1,1-bis (methoxymethyl) -2,3,4,5-tetrafenylcyclopentadiene;

1,1-bis (methoxymethyl) -3,4-dicyclopentylcyclopentadiene;

1,1-bis (methoxymethyl) indene;

1,1-bis (methoxymethyl) -2,3-dimethylindene;

1,1-bis (methoxymethyl) -4,7-dimethylindene;

1,1-bis (methoxymethyl) -4,7-dimethylindene;

1,1-bis (methoxymethyl) -7-methylindene;

1,1-bis (methoxymethyl) -7-isopropylindene;

1,1-bis (methoxymethyl) -7-cyclopentylindene;

1,1-bis (methoxymethyl) -7-cyclohexylindene;

9.9- bis (methoxymethyl) fluorene;

9.9-bis (methoxymethyl) -2,3,6,7-tetramethylfluorene;

9.9-bis (methoxymethyl) -2,7-diisopropylfluorene;

9.9-bis (methoxymethyl) -2,7-dicyclopentylfluorene;

b) compounds of 1,8-naphthyl diesters and 1,8-naphthyl diaryloates, including: naphthalene-1,8-diyl-dicyclohexanecarboxylate; naphthalene-1,8-diyl-dicyclohexanecarboxylate;

naphthalene-1,8-diyl-dicyclo-1-hexene-carboxylate; naphthalene-1,8-diyl-dicyclo-2-hexene-carboxylate; naphthalene-1,8-diyl bis (3,3-dimethylbutanoate);

8- (Cyclohexanecarbonyloxy) naphthalen-1-yl-benzoate; 8- (Cyclo-1-hexene-carbonyloxy) -naphthalen-1-yl-benzoate; 8- (cyclohexanecarbonyloxy) naphthalen-1-yl-2-methylbenzoate; 8- (2-methylcyclohexanecarbonyloxy) naphthalen-1-yl-benzoate;

8- (1-cyclohexenecarbonyloxy) naphthalen-1-yl-benzoate; decahydronaphthalene-1,8-diyl dibenzoate;

1,8-naphthyl dibenzoate;

-4GB 306881 B6

1,8-naphthyl-di-2-methylbenzoate;

1,8-naphthyl di-3-methylbenzoate;

1,8-naphthyl-di-4-methylbenzoate;

1,8-naphthyl di-4-fluorobenzoate;

(c) 2,6-dioxoheptanedioate compounds, including:

dimethyl 2,6-dioxaheptanedioate;

diethyl 2,6-dioxaheptanedioate;

diethyl 2,6-dioxa-3,5-dimethylheptanedioate; diethyl 2,6-dioxa-3,5-diisopropylheptanedioate;

diisopropyl-2,6-dioxa-3,5-diisopropylheptanedioate; diisobutyl-2,6-dioxa-3,5-diisopropylheptanedioate;

diethyl 2,6-dioxa-3-isopropyl-5-isobutylheptanedioate.

The tuft morphology polyolefin powder can be advantageously used as a sorbent of substances selected from the group of hydrophobic hydrocarbon compounds including petroleum, vegetable and mineral oils, gasoline, diesel, kerosene and non-polar hydrocarbon solvents formed from C5-C20 carbons.

The tufted morphology polyolefin powder can be advantageously used for the thermal insulation material.

The tuft morphology polyolefin powder can be advantageously used as a material for producing a concentrate of inorganic pigments, organic pigments and polyolefin additives including antistatic agents, nucleating agents and glidants.

Clarification of drawings

The invention will be explained in more detail using the following figures:

Giant. 1A shows the character of tufted polypropylene particles prepared on a KAT A precatalyst heat treated at 105 ° C for 4 hours at a pressure reduced below 10 Pa and activated by the THA cocatalyst. The bulk density of the resulting polypropylene with these tuft particles was 97 g / l.

Giant. 1B shows the character of tufted polypropylene particles prepared on a KAT B precatalyst heat treated at 105 ° C for 4 hours at a pressure reduced below 10 Pa and activated by the TIBA cocatalyst. The bulk density of the resulting polypropylene with these tuft particles was 100 g / l.

Giant. 2 depicts the effect of the bulk density of polypropylene due to the tuft morphology of its polypropylene particles on its ability to absorb mineral oil or petroleum.

Giant. 3 shows the effect of the bulk density of polypropylene given by the tuft morphology of its polypropylene particles on its thermal conductivity.

DETAILED DESCRIPTION OF THE INVENTION

The tufted particle polyolefins of the present invention can be prepared on Ziegler-Naphthalene catalysts which contain as internal donor a compound selected from the group of gamma-diether compounds, gamma-diester compounds or compounds formed by

-5GB 306881 B6

2,6-dioxoheptanedioate. In order to be able to produce polyolefins with tuft particles, such a catalyst must first be heat treated, either under reduced pressure conditions or under an inert atmosphere. Suitable conditions for the heat treatment of Ziegler-Natta precatalysts are 50 to 150 ° C for 1 min to 10 h under reduced pressure conditions (below 1 kPa), but 90 to 120 ° C for 1 to 4 hours under reduced pressure conditions (below 10 Pa). The catalyst thus treated has a significantly lower polymerization activity and is suitable for preparing polyolefins with tuft morphology, for example in the synthesis of a polypropylene homopolymer, in the synthesis of propylene-ethylene copolymers and propylene-ethylene terpolymers with higher α-olefins. The particles with the fibrous structure of the polyolefins thus prepared have a size of from 0.1 to 4 mm. The size and nature of the fiber structure of these particles depends on the particle size of the polymerization catalyst used, the type of internal donor present, the thermal modification conditions of the Ziegler-Natta precatalyst, and the polymerization conditions related in particular to the type of cocatalyst used to activate the Ziegler-Natta precatalyst. design.

The resulting polyolefin has a significantly reduced bulk density in the range of 20 to 300 g / l due to tuft morphology caused by the above-mentioned factors affecting the size and nature of the fiber structure of the particles. Other polymer properties such as melt flow index and polyolefin isotacticity vary only slightly. Synthesis parameters such as hydrogen concentration and the presence of an external donor and its concentration have a minor effect on the bulk density of the resulting polyolefins.

The resulting tufted particle polyolefin has the polymeric properties (flow index, isotacticity) of conventional polyolefins as the material. Thus, it can be further processed in the melt to form a granulate according to conventional extrusion technology. The mechanical properties of the resulting granulate correspond to those of the original powdered polymer prepared on the catalyst without heat treatment and do not differ from the conventional values.

Due to its tuft morphology, it is advantageous to use polyolefins prepared in this way in various industrial applications:

1) It is a material suitable for the sorption of hydrophobic liquids such as oil and petroleum products such as mineral oils. The sorption properties of these newly prepared materials significantly increase with a decrease in their bulk density and reach up to nine times the value of the net weight of these polyolefins. This property of absorbing the hydrophobic liquid is reversible, i.e. the sorbed substance can then be separated by centrifugation and the polyolefin prepared according to the invention reused for the same purpose.

2) It is a material suitable for thermal insulation due to its significantly reduced thermal conductivity. The thermal conductivity of these polyolefins decreases significantly with a decrease in their bulk density and reaches the values usual for advanced thermal insulation materials such as extruded polystyrene.

3) It is a material suitable as carrier of various additives and pigments for polyolefins. By using the polyolefins prepared according to the invention, the final concentration of the additive, e.g., glycerol esters of higher fatty acid esters, can be increased up to double that of a conventional polymer powder or granulate. By using the polyolefins prepared according to the invention, the dispersion of the organic pigment in the polyolefins can be improved in the preparation of the organic pigment concentrate in the polyolefins, which results in a lower pressure increase measured before the filter screen during the filter test of these materials.

The invention further describes a process for treating a Ziegler-Natta precatalyst, the subsequent synthesis of polyolefins with tuft particles on a treated, activated catalyst, and the possibilities of using the polyolefins with tuft morphology particles:

-6GB 306881 B6

a) Selection of the preferred Ziegler-Natta precatalyst for subsequent heat treatment

It has been found that polyolefin with fluff morphology can be prepared using a Ziegler-Natta precatalyst. The Ziegler-Natta precatalyst preferably contains a halogenate compound and a selected internal electron donor compound, both of which are supported on a halogen-magnesium support.

According to yet another embodiment of the invention, the internal donor compound comprises 2 oxygen functional groups in the ether group -OR ^ ² of the general formula Ia attached to the carbon atoms C ¹ and C ^{3 of the} carbon atom CC ² -C ³ or contains 2 oxygen functional groups in the ester group - O-CO-R ^ ² of formula IIa attached to the carbon atoms C ^{1 and} C ^{3 of the} carbon atom CC ² -C ³ or 2 oxygen functionalities in positions 2 and 6 in the 2,6-dioxoheptanedioate attached to the carbon atoms C ¹ and ³ atomic grouping C C * -C ² -C ³ in the compound of formula IIIa, wherein either

(has),

(a) the carbon atoms C ¹ , C ² and C ³ form an aliphatic chain wherein R ³ and R ⁴ are the same or different and are selected from the group consisting of hydrogen or linear or branched C 1 -C 20 alkyls, and R ⁵ and R ⁶ are the same or different and are selected from the group consisting of hydrogen or linear or branched C ₁ -C ₂₀ alkyls, and R ¹ and R ² are the same or different and are selected from the group consisting of linear or branched C 1 -C ₂₀ alkyls, C ₄ -C ₂₀ cycloalkyls, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ alkaryl, C ₇ -C ₂₀ aralkyl, according to formulas Ia, IIIa and IIIa above; or

(b) the carbon atoms C ¹ , C ² and C ³ form an aliphatic chain, wherein C ² is part of a cyclic structure consisting of a 5-7 membered ring and containing 2 or 3 unsaturated bonds in each cycle and R ⁵ and R ⁶ are the same or different; are selected from the group consisting of hydrogen or linear or branched C 1 -C 20 alkyls, and R ⁷ is selected from the group consisting of hydrogen; halogens, preferably Cl or F; linear or branched C ₁ -C ₂₀ alkyls, C ₄ -C ₂₀ cycloalkyls, C ₆ -C ₂₀ aryls, C ₇ -C ₂₀ alkaryls, C ₇ -C ₂₀ aralkyls, and R ¹ and R ² are different or the same and are selected C 1 -C ₂₀ alkyl, C ₄ -C ₂₀ cycloalkyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ alkaryl, C ₇ -C ₂₀ aralkyl, according to formula IV below

or

(c) the carbon atoms C ¹ , C ² and C form an aliphatic chain, where C ² is part of a polycyclic structure consisting of a 5 to 7 membered ring and containing 2 or 3 unsaturated bonds in each cycle and C ¹ and C ³ where R ⁵ and R ^{6 are} different or the same and are selected from hydrogen or linear or branched C 1 -C 20 alkyl, wherein R ⁸ is selected from hydrogen; halogens, preferably Cl or F; linear or branched Ci-C2o alkyl, C ₄ -C ₂₀ cycloalkyl, C 6 -C ₂ o aryl, C ₇ -C ₂ o alkaryl, C ₇ -C ₂ o aralkyl and R ¹ and R ² are different or identical and selected from the group consisting of linear or branched C 1 -C ₂ alkyls, C ₄ -C ₂₀ cycloalkyls, C ₆ -C ₂ aryls, C ₇ -C ₂₀ alkaryls, C ₇ -C ₂ aralkyls, according to formula V below

d) the C ¹ , C ² and C ³ carbon atoms are part of a polycyclic structure consisting of 5 to 7 membered rings and containing 2 or 3 unsaturated bonds in each cycle, wherein R ⁹ is selected from hydrogen; halogens, preferably Cl or F; linear or branched C 1 -C 20 alkyl, C 4 -C 20 cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 alkaryl or C 7 -C 20 aralkyl, and R ¹ and R ² are different or the same and are selected from the group consisting of linear or branched C 1 -C 20 alkyl , C ₄ -C ₂ cycloalkyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ alkaryl, C ₇ -C ₂ aralkyl, according to general formula VI below

The selected internal donor compounds preferably include:

(1) The 1,3-diether compounds of formula (Ia) and including, for example:

2-methyl-2-isopropyl-1,3-dimethoxypropane;

2-methyl-2-isopropyl-1,3-dimethoxypropane;

2-isopropyl-2-isopentyl-1,3-dimethoxypropane;

2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane;

2-isopropyl-2-cyclohexyl-1,3-dimethoxypropane;

2,2-diisobutyl-1,3-dimethoxypropane;

-8GB 306881 B6

2,2-diisobutyl-1,3-diethoxypropane;

2,2-diisobutyl-1,3-dibutoxypropane;

2,2-dicyclohexyl-1,3-dimethoxypropane;

2,2-diphenyl-1,3-dimethoxypropane;

2,2-dibenzyl-1,3-dimethoxypropane;

2,2-dicyclopentyl-1,3-dimethoxypropane a

2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane.

2) Compounds of 1,3-diesters of the general formula IIa and comprising e.g.

diethyl 2,2-dibenzyl malonate;

diethyl 2-isobutyl-2-cyclohexylmalonate;

dimethyl 2-n-butyl-2-isobutylmalonate;

diethyl 2-methyl-2-isopropylmalonate;

diethyl 2-methyl-2-isobutylmalonate; and diethyl 2-isopropyl-2-isobutylmalonate.

3) The 2,6-dioxoheptanedioate compounds of formula IIIa including, for example: dimethyl 2,6-dioxaheptanedioate;

diethyl 2,6-dioxaheptanedioate; diethyl 2,6-dioxa-3,5-dimethylheptanedioate;

diethyl 2,6-dioxa-3,5-diisopropylheptanedioate; and diisopropyl 2,6-dioxa-3,5-diisopropylheptanedioate.

(4) The 1,3-diether compounds of formula (IV), including, for example:

1,1-bis (methoxymethyl) cyclopentadiene;

1,1-bis (methoxymethyl) -2,3,4,5-tetramethylcyclopentadiene;

1,1-bis (methoxymethyl) -3,4-dicyclopentylcyclopentadiene a

1,1-bis (methoxymethyl) -2,3,4,5-tetrafenylcyclopentadiene.

(5) The 1,3-diether compounds of formula (V), including, for example:

9.9- bis (methoxymethyl) fluorene;

9.9-bis (methoxymethyl) -2,3,6,7-tetramethylfluorene;

9.9-bis (methoxymethyl) -2,7-diisopropylfluorene;

9.9- bis (methoxymethyl) -2,7-diisopropylfluorene a

9.9- bis (methoxymethyl) -2,7-dicyclopentylfluorene.

6) The 1,8-naphthyl diester compounds of the general Formula VI including, for example: naphthalene-1,8-diyl-dicyclohexanecarboxylate;

naphthalene-1,8-diyl bis (3,3-dimethylbutanoate);

8- (Cyclohexanecarbonyloxy) naphthalen-1-yl-benzoate;

8- (cyclohexanecarbonyloxy) naphthalen-1-yl-2-methylbenzoate;

1,8-naphthyl dibenzoate;

1,8-naphthyl-di-2-methylbenzoate;

-9EN 306881 B6

1,8-naphthyl di-3-methylbenzoate a

1,8-naphthyl-di-4-methylbenzoate.

Further, a tuft morphology polyolefin can also be prepared using a Ziegler-Natta precatalyst which contains 1 or more selected internal electron donor compounds described above, along with another internal donor compound from a variety of ethers and esters. These internal donor compounds together with the halo-titanium compound are supported on a halo-magnesium carrier.

The preparation of such Ziegler-Natta precatalysts containing a selected internal donor compound is well known in the literature. They are prepared by reacting an anhydrous magnesium magnesium support with an alcohol, depositing the halogen-titanium component thereon and then reacting the titanium-saturated support with a selected internal donor, optionally with another type of internal donor. For example, the resulting Ziegler-Natta precatalyst may contain 2 to 7 wt. % Ti, 10 to 25 wt. % Mg and 5 to 30 wt. internal donor.

b) Heat treatment of the preferred diether Ziegler-Natta precatalysts

The present invention involves the use of a heat treatment of a preferred type of Ziegler-Natta precatalysts for the subsequent synthesis of a polyolefin with an altered type of polyolefin particle morphology. The effect of this change, ie the resulting tuft morphology of polymer particles, leads to significant changes in the properties of the resulting polyolefins. One property that quantitatively and reproducibly describes these changes in the polymer particle morphology and has therefore been used to describe these changes is the bulk density of the resulting polyolefin. Depending on the nature of the composition of the Ziegler-Natta precatalysts, its temperature and time treatment, the nature of the composition of the reaction mixture and the polymerization conditions, this bulk density of the resulting polyolefin is significantly reduced to 20-300 g / l.

It has been found in the present invention that tufted morphology polyolefin can be prepared using the preferred diether Ziegler-Natta precatalysts described above, which need to be heat treated in a specific manner.

This specific heat treatment method of the preferred diether Ziegler-Natta precatalyst is carried out either under reduced pressure conditions (below 1 kPa) or under an inert gas (e.g. nitrogen) flow at a temperature above 30 ° C, typically under reduced pressure conditions (below 10 Pa). ) in the temperature range between 50 ° C and 150 ° C, preferably under reduced pressure conditions (below 10 Pa) in the temperature range between 90 ° C and 120 ° C. It has been found that under the preferred conditions of specific heat treatment, i.e. reduced pressure (below 10 Pa) and elevated temperature (90 ° C to 120 ° C), a period of more than 1 minute is sufficient for the specific heat treatment of Ziegler-Natta precatalysts described. preferably 5 minutes to 10 hours, more preferably 30 minutes to 4 hours. The specific heat treatment of Ziegler-Natta precatalysts can of course last for more than 10 hours, but the resulting tuft morphology of polyolefins prepared on such heat treated selected Ziegler-Natta precatalysts does not change further with increasing time period (longer than 10 hours). The polyolefins do not decrease further.

This heat treatment of the Ziegler-Natta precatalysts results in the preferred diether Ziegler-Natta diether precatalysts activated with tri-n-hexyl aluminum (THA) cocatalyst, for example as follows:

1) For KAT A, the bulk density of polypropylene drops from 395 g / l for a catalyst without heat treatment to a bulk density of 97 g / l for four hours at 105 ° C under reduced pressure (below 10 Pa), ie 24.6 % of the original value as described in Example 2,

- 10GB 306881 B6

2) For KAT B, the bulk density of polypropylene drops from 345 g / l for a catalyst without heat treatment to a bulk density of 87 g / l for four hours at 105 ° C under reduced pressure (below 10 Pa), ie 25.2 % of the original value as described in Example 3.

The polyolefinic particles with tuft morphology of the invention are shown for the heat treated diether Ziegler-Natta recatalysts KAT A and KAT B in FIG. 1A and 1B.

c) Synthesis of polyolefin with tuft morphology on a heat treated and activated Ziegler-Natta precatalyst

It has been found that a polyolefin powder containing tuft morphology particles according to the invention can be prepared using the preferred Ziegler-Natta diether precatalyst, which has to be heat treated in a specific manner according to the invention. The method of activating the Ziegler-Natta precatalyst thus prepared (polymerizable form) further influences the nature of the resulting tuft morphology of the polyolefin particles.

Activation of a preferred Ziegler-Natta diether precatalyst comprises reaction with an organoaluminum compound (cocatalyst) of the formula AlR _n Z _{3 -n} , wherein R is C 1 -C 20 alkyl, Z is halogen and _n is 0, 1, 2 or 3. Suitable examples of such cocatalysts are trimethyl aluminum (TMA), triethyl aluminum (TEA), triisobutyl aluminum (TIBA), tri-n-hexyl aluminum (BODY), tri-iso-hexyl aluminum (THA), tri-n-octyl aluminum (TOA) and tri-n-decyl aluminum (TDA) .

It has been found that the character of the cocatalysts used to activate the preferred, heat-treated Ziegler-Natta diether precatalyst further significantly influences the tuft morphology of the resulting polyolefin. Depending on the structure of the cocatalysts, the bulk density of the resulting polyolefin with tuft morphology achieves different values. The lowest bulk density values of the resulting polyolefins were obtained when the preferred, heat-treated Ziegler-Natta precatalyst was activated by higher cocatalysts such as 25-isobutyl aluminum (TIBA), tri-n-hexyl aluminum (THA), tri-iso-hexyl aluminum (TÍHA) and tri-n-decyl aluminum (TDA).

For example, for polypropylene prepared on a KAT B precatalyst, heat-treated for 4 hours at 105 ° C under reduced pressure (below 10 Pa), the bulk density is:

268 g / l for TMA cocatalyst activated,

179 g / l for TEA cocatalyst activated,

100 g / l for TIBA cocatalyst, g / 1 for THA cocatalyst, and

112 g / L for TDA cocatalyst activated catalyst as described in Example 4.

Depending on the polymerization technology used and the type of Ziegler-Natta diether precatalyst, a suitable amount of organoaluminum compound fed to the polymerization reactor in a molar ratio to the transition metal of the Ziegler-Natta diether precatalyst is in the range of 10 to 1000 mol / mol, more preferably 30 to 300 mol / mol. mol. The amount of cocatalysts used is also partially reflected in the quality of the resulting polyolefin with tuft morphology.

For example, for polypropylene prepared on a KAT B precatalyst, heat-treated for 4 hours at 105 ° C under reduced pressure (below 10 Pa) and activated by cocatalyst 10 TIBA, the bulk density is:

116 g / l for a precatalyst activated at a TIB A / Ti ratio of 15 mol / mol,

- 11 GB 306881 B6

102 g / l for a precatalyst activated at a TIB A / Ti ratio of 50 mol / mol,

100 g / L of precursor catalyst activated at TIBA / Ti ratio = 150 mol / mol, g / L of precursor catalyst activated at TIBA / Ti ratio = 500 mol / mol ag / L of precursor catalyst activated at TIBA / Ti ratio = 1000 mol / mol as described in Example 4.

A preferred, heat-treated Ziegler-Natta diether precatalyst upon activation is capable of producing a polyolefin with tuft morphology in the polymerization of one type of olefin (homopolymerization) or multiple types of olefins (copolymerization or terpolymerization).

The other reactant present in these polymerizations may optionally be an external donor as a modifier of stereregularity of the synthesized polyolefin. Suitable structures for such external donors are silanes, ethers and esters, for example the widely used dimethoxysilane structures such as diisopropyl dimethoxysilane, diisobutyl dimethoxysilane, methylcyclohexyl dimethoxysilane and dicyclopentyl dimethoxysilane. Depending on the technology used and the type of Ziegler-Natta precatalyst, a suitable amount of external electron donor is fed to the polymerization reactor, in a molar ratio to the transition metal of the Ziegler-Natta precatalyst, in the range of 0.5 to 100 mol / mol or molar ratio of organoaluminum cocatalyst to the external donor is in the range of 0.5 to 100 mol / mol, more preferably the molar ratio of organoaluminum cocatalyst to external donor is 0.5 to 50 mol / mol.

The other reactant present in these polymerizations is typically hydrogen acting as a regulator of the molecular weight and melt index of the resulting polyolefin.

The polymerization with a suitable heat-treated Ziegler-Natta precatalyst can be carried out in a solvent medium of a non-polar hydrocarbon solvent (eg, isohexane, heptane), a gasified monomer (ethylene, propylene, higher α-olefins) or monomers, a liquid monomer (propylene) , higher α-olefins), or individual polymerization phases carried out in several types of polymerization medium can be combined (eg polymerization in liquid monomer followed by polymerization in gasified monomer environment) under all standard polymerization conditions. Depending on the polymerization technology and the desired properties of the synthesized polyolefin with tuft morphology, the olefin polymerization with the selected heat-treated Ziegler-Natta catalyst can be carried out at temperatures ranging from 50 to 120 ° C and pressures of 0.5 to 10 MPa. 105 ° C and pressures of 1 to 4 MPa.

Thus, various types of polyolefin powders with tuft morphology can be prepared. By polyolefin powder according to the invention is meant the coordination polymerization products on Ziegler-Natta catalysts consisting of homopolymers, copolymers of two or more 1-olefins and mixtures thereof prepared in two or more step polymerizations. Preferred are homopolymers of propylene and ethylene, random copolymers of propylene and ethylene, ethylene and 1-butene, propylene and 1-butene, ethylene and 1-hexene, propylene and 1-hexene; random terpolymers of ethylene, propylene and 1-butene and ethylene, propylene and 1-hexene; block copolymers consisting of polypropylene homomatrice and random propylene / ethylene random copolymer, block copolymers consisting of polypropylene homomatrice and randomized ethylene copolymer with 1-butene, block copolymers consisting of polypropylene homomatic and random ethylene with 1-hexene random copolymer and copolymer of homomeric propylene polymer ethylene and 1-butene, block copolymers consisting of polypropylene homomatration and random propylene terpolymer with ethylene and 1-hexene.

The best polyolefin powders of the invention are isotactic polypropylene (i-PP), random copolymers of propylene with ethylene, and block copolymers consisting of polypropylene homomatics and random copolymers of propylene and ethylene.

- 12GB 306881 B6

This process for the preparation of the polyolefins of the invention on a specifically heat treated Ziegler-Natt diether precatalyst activated by a THA cocatalyst is manifested, for example, as follows:

(1) For polyolefin prepared on KAT A polymerised by THA, the bulk density falls from 276 g / l for the catalyst without heat treatment to a bulk density of 99 g / l for the catalyst heat treated for 4 hours at 105 ° C under reduced pressure (below 10 Pa) in the case of the synthesis of a polyethylene homopolymer in a solvent medium of hexane, i.e. to 35.9% of the original value as described in Example 6.

2) For a polyolefin prepared on a CAT catalyst polymerized with THA cocatalyst, the bulk density decreases from 395 g / l for a catalyst without heat treatment to a bulk density of 97 g / l for a catalyst heat treated for 4 hours at 105 ° C under reduced pressure 10 Pa) in the case of the synthesis of a polypropylene homopolymer in a gasified propylene medium, i.e. to 24.6% of the initial value as described in Example 1.

3) For a polyolefin prepared on a CAT catalyst polymerized with THA cocatalyst, the bulk density decreases from 415 g / l for a catalyst without heat treatment to a bulk density of 61 g / l for a catalyst heat treated for 4 hours at 105 ° C under reduced pressure 10 Pa) in the case of the synthesis of a polypropylene homopolymer in a liquid propylene medium, i.e. to 14.7% of the initial value as described in Example 1.

4) For a polyolefin prepared on a KAT A polymerized activated THA cocatalyst, the bulk density decreases from 364 g / l for a catalyst without heat treatment to a bulk density of 84 g / l for a catalyst heat treated for 4 hours at 105 ° C under reduced pressure 10 Pa) for the synthesis of ethylene-propylene copolymers, a 2 step polymerization consisting of homopolymerization of propylene and random copolymerization of propylene with ethylene, to 23.1% of the original value as described in Example 7.

5) For a polyolefin prepared on a CAT catalyst polymerized with THA cocatalyst, the bulk density decreases from 411 g / l for a catalyst without heat treatment to a bulk density of 128 g / l for a catalyst heat treated for 4 hours at 105 ° C under reduced pressure 10 Pa) in the case of the synthesis of an ethylene, propylene and 1-butene terpolymer, a two-step polymerization consisting of homopolymerization of propylene and a random copolymerization of ethylene with 1-butene, to 31.1% of the original value as described in Example 8.

The present invention further describes the possibilities of utilizing tufted particulate polyolefins thus prepared in the following applications:

d) Polyolefin with tuft morphology as a material suitable for sorption of hydrophobic liquids

The tufted morphology polyolefin prepared according to the method described above is a material of petroleum origin and thus of a hydrophobic nature. Due to its morphology, which can generally be described as tuft, it is characterized by a large number of interdigital spaces. Since these interfacial spaces within the polyolefin tuft particle are readily accessible, this material is suitable for the sorption of hydrophobic liquids, such as oil and products, such as mineral oils. The sorption properties of these materials increase significantly as their bulk density decreases, reaching up to six times the net weight of these polyolefins, as documented in Example 9. This value is comparable to the absorbency values of polypropylene nonwovens and greatly exceeds the absorbency values of conventional inorganic sorption materials. they amount to 1 to 2 g of mineral oil / g of sorbents (eg in the case of expanded and hydrophobised perlite, which is an amorphous aluminum silicate of volcanic origin).

- 13 GB 306881 B6

It can be seen from Example 9 that the decreasing bulk density and thus the increasing tuft character of the resulting polyolefins is directly proportional to their sorption properties regardless of the type of precatalyst and the type of cocatalyst used to activate it, as shown in Figure 2.

The sorption properties of these materials may, depending on the further decrease in their bulk density, reach even higher values of the absorbed amount of hydrophobic liquids than shown in Example 9. These may be up to nine times their own weight of these polyolefins. Decreasing the bulk density of these materials and the associated increase in their tuft character is dependent upon a suitable combination of this property-determining assumptions, including the choice of precatalyst (influence of internal donor type), nature of heat treatment of the precatalyst (effect of treatment temperature, duration of treatment, reduced conditions). characterization of this precatalyst (cocatalyst type effect), polymerization mode character (polymerization in liquid monomer medium, gasified monomer medium, nonpolar hydrocarbon solvent), polymerization component character (cocatalyst concentration, external donor, hydrogen) and polymerization mode conditions (polymerization temperature, polymerization pressure, polymerization duration). By a suitable combination of these bulk density polyolefins with tuft morphology determining assumptions, a final bulk density of about 20 g / l can be achieved, which corresponds to sorption capabilities close to nine times the intrinsic weight of these polyolefins.

The hydrophobic liquid sorption property of these materials is reversible, i.e. the sorbed material can then be separated by centrifugation, and the tuft morphology polyolefin prepared according to the invention can be reused for the same purpose. For example:

1) Five-fold repeated sorption and subsequent desorption of mineral oil resulted in a polypropylene homopolymer with a bulk density of 87 g / l, prepared on a catalytic system KAT B / THA (KAT B was treated for 4 hours at 105 ° C at a pressure below 10 Pa) in the individual sorption and desorption cycles the removal of 96.7%, 96.8%, 96.8%, 96.9% and 96.7% of the absorbed amount of mineral oil as documented in Example 10.

2) With five-fold repeated sorption and subsequent desorption of crude oil, a polypropylene homopolymer with a bulk density of 87 g / l, prepared on a catalyst system KAT B / THA (KAT B was treated for 4 hours at 105 ° C at a pressure below 10 Pa) individual sorption and desorption cycles of removal of 96.4%, 96.3%, 96.2%, 96.2% and 96.2% of the adsorbed amount of crude oil as documented in Example 10.

e) Polyolefin with tuft morphology as a material suitable for thermal insulation

Synthetic polymers such as polypropylene are themselves poor heat conductors and hence good thermal insulators. In the case of the tuft morphology polyolefins of the present invention prepared according to the method described above, a high content of air enclosed in the interspaces between the fibers of the individual particles is added. Since air is one of the worst heat conductors (one of the best thermal insulators), even the material containing these tuft particles has a significantly reduced thermal conductivity and is therefore suitable for thermal insulation. Depending on the decrease in bulk density of these materials, the proportion of air content in their particles also increases, causing a decrease in thermal conductivity and an increase in thermal insulation properties.

For example, in the case of polypropylene with a fluff morphology and a bulk density of 115 g / l, prepared on a KAT B precatalyst, treated for 4 hours at 105 ° C under reduced pressure and activated with THA cocatalyst, a thermal conductivity decrease of 43% is achieved. morphology with a bulk density of 447 g / l, prepared on the same precatalyst without heat treatment.

It is apparent from Example 11 that the decreasing bulk density and thus the increasing tuft character of the resulting polyolefins is directly proportional to their thermal conductivity and hence the thermal-insulation

- 14GB 306881 B6 regardless of the type of precatalyst and the type of cocatalyst used to activate it, as shown in Figure 3. The thermal conductivity for polymer materials with the lowest bulk density is about 0.040 W / (m * K). These values are fully comparable to the thermal conductivity of EPS (expanded polystyrene), which ranges from 0.043 to 0.035 W / (m * K) depending on the density of EPS (the higher the EPS density, the lower its thermal conductivity).

The heat-insulating properties of these materials may, depending on the further decrease in their bulk density, reach even lower thermal conductivity values than those given in Example 11. These may be close to a thermal conductivity value of about 0.030 W / (m * K). The reduction in bulk density of these materials and the associated increase in their thermal insulation capacity is dependent on a suitable combination of determinants of this property, including the choice of precatalyst (internal donor type), the nature of the precatalyst's thermal treatment (treatment temperature, treatment duration, conditions of depressurization), characterization of this precatalyst (cocatalyst type effect), characterization of polymerization mode (polymerization in liquid monomer block or gasified monomer), characterization of polymerization components (concentration of cocatalyst, external donor, hydrogen) and characterization of polymerization conditions (polymerization temperature, polymerization pressure, polymerization duration). By suitable combination of these bulk density polyolefins with tuft morphology determining assumptions, a final bulk density of about 20 g / l can be achieved, which corresponds to a 60% decrease in thermal conductivity compared to polypropylene with classical particle morphology of 447 g / l bulk density.

f) Polyolefin with tuft morphology as a carrier of additives and pigments

The tuft morphology polyolefin particle, in contrast to the standard polyolefin particle, contains a large number of interdigital space spaces. This free, particulate volume can be used to cause particles of the additive (antistatic, nucleating agent, glidant, etc.) or pigment (inorganic or organic) to penetrate into the polyolefin particle even while stirring at room temperature (23 ± 2 ° C). . The mixture thus formed makes it possible to produce an additive or pigment concentrate with a higher concentration of active ingredient (antistatic, nucleating agent, glidant, etc.) or pigment (inorganic or organic) than is possible using a polyolefin with standard polyolefin particles. E.g. using tufted morphology polypropylene prepared according to the present invention, the resulting additive concentration in the polyolefin, e.g., glycerol esters of higher fatty acid esters, can be increased up to twice that of a conventional polymer powder or granulate as described in Example 12 or improved dispersing the organic pigment in the polyolefin in the preparation of the organic pigment concentrate in the polyolefin, which results in a reduction of the pressure increase in front of the filter screen in the filtration test by about half compared to the use of a conventional polymer powder as described in Example 13.

DETAILED DESCRIPTION OF THE INVENTION

Heat treatment of Ziegler-Natta precatalyst

The heat treatment of selected Ziegler-Natta precatalysts was performed as follows:

For the treatment of Ziegler-Natta diether precatalysts KAT A, KAT B and KAT C with a 1,3-diether internal donor, namely 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, an apparatus consisting of a glass flask was used. Teflon cap, glycerine baths connected to a thermostat and oil rotary vacuum pumps. During the heat treatment of the Ziegler-Natta precatalyst, the precatalyst in powder form was dosed in an amount of about 1 g under a nitrogen blanket in a dry box into a 50 ml glass flask and sealed with a Teflon cap. Subsequently, the glass flask with the precatalyst was powdered

The mold is transferred to the apparatus itself and connected to a nitrogen source. Under a protective nitrogen flow, the Teflon seal was removed and replaced with a gland packing. The nitrogen flow was stopped and the flask pressure was reduced to below 10 Pa using a rotary oil pump. After reaching the desired vacuum, the precatalyzer flask was immersed in a glycerin bath tempered to a predetermined temperature. In this assembly, the precatalyst was heat treated at a given bath temperature, for a specified period of time and under reduced pressure. At the end of the precatalyst heat treatment period, evacuation was terminated, nitrogen was charged to the flask at atmospheric pressure, and the flask was cooled to room temperature under constant nitrogen flow. After reaching room temperature, the flask was sealed with a Teflon cap. The heat-treated Ziegler-Natta precatalyst was ready for use in polymerization to produce polyolefin with tuft morphology.

In this way, the treatment temperature of the Ziegler-Natta precatalyst with 1.3-diether internal donor KAT A was tested at 60 ° C, 90 ° C, 105 ° C, 120 ° C and 150 ° C, the Ziegler-Natta precatalyst with 1.3-diether internal donor KAT B at 90 ° C, 105 ° C and 120 ° C and a Ziegler-Natta precatalyst with a 1,3-diether internal donor KAT C at 105 ° C.

Preparation of polyolefin powder containing particles with tuft morphology and its use

The preparation of polyolefin with tuft morphology and its use is described in the following examples. Exemplary embodiments were realized using 3 diether ZieglerNatt precatalysts KAT A, KAT B and KAT C with a 1,3-diether internal donor, namely 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, but a process for preparing polyolefin with tuft morphology is not limited to this type of Ziegler-Natta precatalyst but also includes combinations of this precatalyst with other types of internal donors as described above. The individual precatalysts contained the following amounts of Ti: KAT A 2.8 wt%, KAT B - 3.7 wt%. and KAT C - 2.4 wt. and also differed in the amount of internal donor deposited on the MgCl ₂ support.

The resulting polyolefin comprises tuft morphology particles consisting of polyolefin fibers having a diameter of 10 to 50 µm and a length of 50 to 1000 µm. The fibers of the polyolefin powder particles are intertwined differently and form a three-dimensional structure with differently sized interspaces depending on their number, diameter and length. These fiber interfaces contain air (or can be filled with another substance). The interspaces between the fibers play an important role in the absorption and insulating properties of the polymer formed by these particles. The polyolefin particles having a fiber structure in the form of a powder preferably have a macroscopic size of from 0.2 to 2 mm. These particles form a polyolefin powder whose bulk density is in the range of 20 to 300 g / l, in terms of sorption and heat-insulating properties, a range of 20 to 200 g / l seems more advantageous.

Propylene polymerizations were carried out in a 1.8 liter batch stainless steel batch reactor equipped with a spiral-shaped stirrer. The reactor was connected to a thermostatic circuit allowing external regulation of its internal temperature. The amount of propylene metered before and during polymerization was measured based on the weight loss of the propylene storage vessel, for other monomers and hydrogen, by integrating their flow through the mass feeders. The reactor pressure was measured with a digital pressure gauge and the temperature at the bottom (Tr) and top (Tr2) of the E-type thermocouples.

During the purification procedure, the reactor was purged with a nitrogen stream for about 30 min at 95 ° C. A leak pressure test (30 min at 95 ° C and 3.0 MPa propylene) was then carried out. After the pressure test, the reactor was cooled to 40 ° C, the agitation was turned off, and the cocatalyst and possibly an external donor were metered in. During dosing of these polymerization components, the reactor interior was protected from contamination by a protective nitrogen flow. After all the components were metered in, the reactor was sealed and filled with an appropriate amount of monomer and hydrogen. The partial pressure of residual nitrogen in the reactor was about 0.1 MPa (a).

The polymerization was started by injecting the precatalyst into the reactor by passing it through liquid propylene at

- 16GB 306881 B6 at 40 ° C. Subsequent rise to polymerization temperature and pressure took less than 5 min. The mixing rate before and during polymerization was 500 rpm for gasification in gasified propylene or gasified monomer mixture and 250 rpm for polymerization in liquid propylene medium. The composition of the vapor phase in the reactor was analyzed every 10 min throughout the entire polymerization using a gas chromatograph. The polymerizations were carried out at 75 ° C and pressure

2.2 MPa for homopolymerization in gasified propylene and at a temperature of 70 ° C and a pressure of 3.1 MPa for homopolymerization in liquid propylene medium. The polymerization time was mostly set to a time period of 60 min after the polymerization conditions were reached.

The whole process of raiding and polymerization was controlled and monitored by a computer. After reaching the desired polymerization temperature and pressure, the polymerization conditions were subsequently maintained at the desired level until the polymerization was completed. In the case of homopolymerization in gasified propylene, a constant pressure was maintained by continuous monomer feed, in the case of copolymerization by continuous feed of a mixture of monomers of a given ratio. Depending on the consumption of propylene, in the case of polymerization in gasified propylene, hydrogen was continuously metered during the polymerization, maintaining its constant concentration in the vapor phase throughout the polymerization.

At the end of the polymerization, the reactor was carefully depressurized and the residual monomer and cocatalyst removed by pressurizing several times with nitrogen to 0.5 MPa. Subsequently, the polymer powder was removed from the reactor, weighed and dried for 2 hours at 70 ° C in a vacuum oven.

The following standard analytical methods were used to determine the effect of treatment and activation of the selected Ziegler-Natta precatalyst and the effect of subsequent polymerization conditions on the properties of synthesized polyolefins:

Polypropylene flow index (IT) was measured according to ISO 1133 (E) at 230 ° C and a piston force of 21.6 N. Polyethylene melt flow index was measured according to the same standard at 190 ° C and a load of 49 N. Polypropylene content The cold xylene soluble (XS) was determined according to ISO 6427 (E). The bulk density of the polymer powder (SH) was determined according to ISO 60 (E).

Example 1

Synthesis of polypropylene homopolymer with tuft morphology

The polypropylene homopolymer in Example 1 was synthesized on a 1,3-diether precatalyst of KAT A, both uncooked (KAT A) and heat treated (KAT A, KAT B) at 105 ° C for 4 hours, at a pressure below 10 ° C. 10 Pa. In both cases, the precatalyst was polymerized by the THA cocatalyst.

Polymerizations in gasified propylene were carried out under the following conditions: polymerization temperature 75 ° C, polymerization pressure 2.2 MPa (g), polymerization duration 60 min after polymerization conditions were reached, Al / Ti = 150, without addition of external donor, H2 - initial charge - 10 mmol, H2 / C3 = 5.0 mmol / mol.

The polymerization in the liquid propylene block was carried out under the following conditions: polymerization temperature 70 ° C, polymerization pressure 3.1 MPa (g), polymerization duration 60 min after polymerization conditions were reached, Al / Ti = 500, without addition of external donor, H2 - initial charge - 15 mmol, H2 / C3 = 5.5 - 5.7 mmol / mol (gas phase).

The resulting catalyst activity and polymer properties are shown in Table 1 on a case-by-case basis:

- 17GB 306881 B6

Table 1

Repair of precatalyst Cat. system Catalog activity kg / (g * hr) Flow Index 21.6 N g / 10 min X.S. hm. % Bulk density g / i Liquid propylene block polymerization without modification KAT A / THA 36.0 6.0 3.2 415 105’C-4h KAT A / THA 2.4 9.5 4.6 61 105 ° C-4h KAT B / THA 1.8 13.8 8.3 48 Polymerization in gasified propylene without modification KAT A / THA 28.0 9.0 2.8 395 105 ° C-4h KAT A / THA 3.8 8.8 3.2 97 105 ° C-4h KAT B / THA 4.3 14.6 7.5 87

As described in Table 1, heat treatment of the KAT A precatalyst at a pressure below 10 Pa (4 hours at 105 ° C) resulted in a significant reduction in the bulk density of the polypropylene prepared thereon, as in the polymerization in a liquid polymer block, polypropylene weight decreased from 415 g / l to 61 g / l, as was the case with gasification propylene polymerization, when the bulk density of polypropylene dropped from 395 g / l to 97 g / l. This is related to the change in the character of polypropylene particles from normal morphology (spherical to oval) to tuft (fibrous) morphology. Heat treatment of the precatalyst at a pressure below 10 Pa (4 hours at 105 ° C) also resulted in a significant reduction in catalyst activity, as in polymerization in a liquid polymer block, when catalyst activity decreased from 36.0 kg / (g * hr) to value of 2.4 kg / (g * hr) as well as in gasification propylene polymerization, where the catalyst activity decreased from 28.0 kg / (g * hr) to 3.8 kg / (g * hr).

Example 2

Influence of temperature during heat treatment of precatalyst under reduced pressure conditions on morphology of polypropylene

The polypropylene homopolymer in Example 2 was synthesized on KAT A 1,3-diether precatalyst, both uncooked and heat treated for 4 hours, at a pressure below 10 Pa, at 60 ° C, 90 ° C, 105 ° C, 120 ° C, 150 ° C. This precatalyst was in all cases polymerized by the THA cocatalyst.

The polymerizations were carried out in gasified propylene under the following conditions: polymerization temperature 75 ° C, polymerization pressure 2.2 MPa (g), polymerization duration 60 min after polymerization conditions were reached, Al / Ti = 150, without addition of external donor, H2 - initial charge - 10 mmol, H2 / C3 = 4.9 -

5.3 mmol / mol.

The resulting catalyst activity and polymer properties are shown in Table 2 on a case-by-case basis:

-18GB 306881 B6

Table 2

Precatalyst modification Kat system Catalog activity kg / (g * hr) Flow Index 21.6 N g / 10 min X.S. hm. % Bulk density g / i Polymerization in gasified propylene without modification KAT A / THA 28.0 9.0 2.8 395 60 ° C - 240 min KAT A / THA 8.6 7.4 3.6 251 90 ° C * 240min KAT A / THA 6.5 7.4 3.3 177 105 ° C - 240 min KAT A / THA 3.8 8.8 3.2 97 120 [deg.] C.-240 min KAT A / THA 2.1 10.0 3.8 131 150 ° C-240min KAT A / THA 0.4 n.d. 3.4 187

Table 2 describes the effect of the temperature treatment of the KAT A precatalyst under reduced pressure conditions on the bulk density of the polypropylene prepared on the THA activated cocatalyst. It can be seen from Table 2 that with the temperature increase from 60 ° C to 105 ° C when the precatalyst is heat treated for 4 hours at a pressure below 10 Pa, the bulk density of the polypropylene decreases from 251 g / l to 97 g / 1. Conversely, by increasing the temperature from 105 ° C to 150 ° C, the bulk density of the polypropylene increases from 97 g / l to 187 g / l. The rate of decrease of bulk density of polypropylene from 97 g / l to 187 g / l. The bulk density decrease reflects the increase in the fibrous character of the tuft morphology of the polypropylene particles. Heat treatment of the precatalyst under reduced pressure conditions also leads to a significant decrease in catalyst activity as the treatment temperature rises. As the precatalyst treatment temperature rises at 60 ° C to 150 ° C, catalyst activity decreases from 8.6 kg / (g * hr) to 0.4 kg / g * hr).

Example 3

Influence of duration of heat treatment of precatalyst under reduced pressure conditions on morphology of polypropylene

The polypropylene homopolymer in Example 3 was synthesized on KAT B 1,3-diether precatalyst, both uncooked and heat treated at 105 ° C, at a pressure below 10 Pa, for 5 minutes, 15 minutes, 30 minutes, 60 minutes , 150 minutes and 240 minutes. This precatalyst was in all cases polymerized by the THA cocatalyst.

The polymerizations were carried out in gasified propylene under the following conditions: polymerization temperature 75 ° C, polymerization pressure 2.2 MPa (g), polymerization duration 60 min after polymerization conditions were reached, Al / Ti = 150, without addition of external donor, H2 - initial charge - 10 mmol, H2 / C3 = 4.8 5.2 mmol / moL

The resulting catalyst activity and polymer properties are shown in Table 3 on a case-by-case basis:

-19GB 306881 B6

Table 3

Precatalyst modification Kat system Catalog activity kg / (g * hr) Flow Index 21.6 N g / 10 min X.S. hm. % Bulk density g / i Polymerization in gasified propylene without modification KAT B / THA 28.6 13.6 5.6 345 1O5'C-5m! N KAT B / THA 20.8 13.9 6.3 171 1O5'C-15mln KAT B / THA 13.0 12.9 6.3 172 105'C-30mln KAT B / THA 10.8 12.9 6.6 104 105’0-60 min KAT B / THA 10.5 15.3 6.9 93 105’0-150 min CAT 8 / THA 5.8 15.1 7.5 84 105 ° C - 240 min KAT B / THA 4.3 14.6 7.5 87

Table 3 describes the effect of the thermal treatment time of the KAT B precatalyst at 105 ° C at a pressure below 10 Pa on the bulk density of polypropylene prepared on THA-activated precatalysts. It can be seen from Table 3 that with the increase in the cooking time (at 105 ° C, at a pressure below 10 Pa) of the KAT B precatalyst from 5 minutes to 240 minutes, the bulk density of polypropylene decreases significantly from 171 g / l to 87 g / l. The bulk density decrease reflects the increase in the fibrous character of the tuft morphology of the polypropylene particles. The effect of the thermal treatment time of the KAT B precatalyst at 105 ° C at a pressure below 10 Pa also results in a significant decrease in catalyst activity. As the precatalyst treatment time increased from 5 minutes to 240 minutes, catalyst activity decreased from 20.8 kg / (g * hr) to

4.3 kg / (g * hr).

Example 4

Influence of cocatalyst type and its concentration upon activation of precatalyst on polypropylene morphology

The polypropylene homopolymer of Example 4 was synthesized on a 1,3-diether precatalyst KAT B heat treated at 105 ° C for 4 hours at a pressure reduced below 10 Pa. This precatalyst was polymerized by the following cocatalysts: trimethyl aluminum (TMA), triethyl aluminum (TEA), triisobutyl aluminum (TIBA), trihexyl aluminum (THA) and tridecyl aluminum (TDA).

The polymerizations were carried out in gasified propylene under the following conditions: polymerization temperature of 75 ° C, polymerization pressure of 2.2 MPa (g), polymerization duration of 60 min after reaching polymerization conditions, Al / Ti = 50 (activation of TMA and TEA), Al / Ti = 15, 50, 150, 500, 1000 (TIBA activation), Al / Ti = 150 (THA activation, TDA), without addition of external donor, H2 - initial dose - 10 mmol, H2 / C3 = 4.4-5.2 mmol / mol.

The resulting catalyst activity and polymer properties are shown in Tables 4a and 4b on a case-by-case basis:

-20GB 306881 B6

Table 4a

Precatalyst modification Kat system Activity katai. kg / (g * hr) Flow Index 21.6 N g / 10 min X.S. hm. % Bulk density g / i Polymerization in gasified propylene environment 105´C - 240 min KAT B / TMA 11,4 24.7 6.8 268 105’0-240 min CAT B / TEA 11.6 14.8 5.7 179 105'C-240min CAT B / TIBA 8.6 10.9 6.3 100 ALIGN! 105Ό - 240 min KAT B / THA 4.3 14.6 7.5 87 105'0 - 240 min CAT B / TDA 2.2 13.8 8.0 112

Table 4b

Precatalyst modification Kat system AI / TI ratio Activity katai. kg / (g * hr) Flow Index 21.6 N g / 10 min X.S. hm. % Bulk density g / i Polymerization in gasified propylene 105Ό - 240 min CAT B / TIBA 15 5.2 18.0 7.8 116 105'C-240 min CAT B / TIBA 50 7.2 12.6 7.2 102 105’0-240 min CAT B / TIBA 150 8.6 10.9 6.3 10Q 105'C-240min CAT B / TIBA 500 8.2 10.2 5.6 80 105Ό-240 min CAT B / TIBA 1000 8.1 10.9 5.4 77

Table 4a describes the effect of the activation pattern (TMA, TEA, TIBA, THA and TDA cocatalysts) of the KAT B precatalyst, treated at 105 ° C for 4 hours at a pressure below 10 Pa, on the bulk density of polypropylene prepared on such activated catalysts. It is apparent from Table 4a that the precatalyst activation pattern significantly influences the resulting bulk density of the polypropylene and hence the fibrous nature of the tuft morphology of the polypropylene particles. It is further evident from Table 4a that as the alkyl length of the cocatalyst increases, the bulk density of the resulting polypropylene gradually decreases and reaches a minimum of 87 g / l when activated by the cocatalyst THA. Similarly, the activity of the catalyst decreases, reaching the lowest value of 2.2 kg / (g * hr) in the case of TDA cocatalyst activation.

Example 5

Influence of external donor concentration on polypropylene morphology

The polypropylene homopolymer of Example 5 was synthesized on a 1,3-diether precatalyst KAT A heat treated at 105 ° C for 4 hours at a pressure reduced below 10 Pa. This precatalyst was in all cases polymerized by the THA cocatalyst.

The polymerizations were carried out in gasified propylene under the following conditions: polymerization temperature of 75 ° C, polymerization pressure of 2.2 MPa (g), polymerization duration of 60 min after reaching the polymerization conditions, Al / Ti = 150, Si / Ti = 0 and 5, H2 - initial dose - 10 mmol, H2 / C3 = 5.2 - 5.3 mmol / mol.

The resulting catalyst activity and polymer properties are shown in Table 5 on a case-by-case basis:

-21 GB 306881 B6

Table 5

Precatalyst modification Kat system Si / TI ratio Catalog activity kg / (g‘hod) Flow Index 21.6 N g / 10 min X.S. hm. % Bulk density g / i Polymerization in gasified propylene 105'0-240 min KAT A / THA 0 4.0 9.8 3.5 115 105'0-240 min KAT A / THA 5 1.1 6.0 2.2 136

Table 5 describes the effect of external donor concentration on polypropylene bulk density. This was polymerization on a heat treated precatalyst KAT A (heat treatment at 105 ° C for 4 hours at a pressure below 10 Pa), which was activated by a THA cocatalyst. It is apparent from Table 5 that the presence of the external donor and its concentration has only a minor effect on the bulk density.

Example 6

Synthesis of polyethylene homopolymer with tuft morphology

The polyethylene homopolymer of Example 6 was synthesized on KAT A 1,3-diether precatalyst, both uncooked and heat treated at 105 ° C, for 4 hours, at a pressure below 10 Pa. In both cases, the precatalyst was polymerized by the THA cocatalyst.

The polymerization in gasified ethylene was carried out in isohexane (500 ml) under the following conditions: polymerization temperature 65 ° C, polymerization pressure 1.2 MPa (g), polymerization duration 60 min after polymerization conditions were reached, Al / Ti = 200, without addition of external donor, H2 (initial dose) - 200 mmol.

The resulting catalyst activity and polymer properties are shown in Table 6 on a case-by-case basis:

Table 6

Precatalyst modification Cat. system Catalog activity kg / (g * hr) Flow index 49 N g / 10 min Bulk density g / i Polymerization in gasified ethylene without KAT A / THA 2.5 treatment 0.178 276 105 ° C - 240 min KAT A / THA 0.7 0,034 99

As described in Table 6, heat treatment of the precatalyst at a pressure reduced below 10 Pa (4 hours at 105 ° C) resulted in a significant reduction in the bulk density of the polyethylene prepared there (polymerization in isohexane environment) when the bulk density of polyethylene decreased from 276 g. / 1 to 99 g / l. This is related to the change in the morphology of polyethylene particles routine to the tuft morphology as described above. Heat treatment of the precatalyst at a pressure below 10 Pa (4 hours at 105 ° C) also reduced the catalyst activity from 2.5 kg / (g * hr) to 0.7 kg / (g * hr).

-22GB 306881 B6

Example 7

Synthesis of copolymers of ethylene and propylene with tuft morphology

The synthesis of ethylene-propylene copolymers in Example 7 was carried out on a 1,3-diether precatalyst KAT A heat treated at 105 ° C for 4 hours at a pressure reduced below 10 Pa. This precatalyst was polymerized by THA cocatalyst.

The polymerization proceeded in 2 steps:

In step 1, homopolymerization in gasified propylene was carried out for 30 minutes under the following conditions: polymerization temperature 75 ° C, polymerization pressure 2.2 MPa (g), Al / Ti = 150, without addition of external donor, H2 (initial charge) - 10 mmol H2 / C3 = 5.0 mmol / mol.

In Step 2, a random gas-phase copolymerization of ethylene with propylene was carried out for 30 minutes at a polymerization temperature of 75 ° C. This copolymerization was carried out at two different C2 / C3 ratios:

a) polymerization pressure 2.25 MPa (g), C2 / C3 dosage: 2.4 g C2 / 100 g C3,

b) polymerization pressure 2.30 MPa (g), C2 / C3 feed: 4.8 g C2 / 100 g C3.

The resulting catalyst activity and polymer properties are shown in Table 7 on a case-by-case basis:

Table 7

Adjustment Cat Dosing H2 / C3 C2 / C3 Contents Activity I.T. X.S. Bulk precatalyst ethylene system 2nd step ethylene step cat. 21.6 N weight gC2 / 100gC3 mmol / mol mmol / mol wt% kg / (g * hr) g / 10mln wt% g / l

2-step polymerization: in step 1 of propylene, in step 2 of ethylene and propylene

without modification KAT A / THA 2.4 5.1 12.7 1.5 18.1 7.5 5.0 364 105 ° C-4h KAT A / THA 2.4 4.9 20.0 2.9 6.7 7.4 8.9 84 2-step polymerization: in step 1 of propylene, in step 2 of ethylene and propylene without modification KAT A / THA 4.8 4.8 23.8 3.3 28.7 6.4 10.6 399 105-C-4 hours, KAT A / THA 4.8 4.9 33.8 5.8 7.9 4.6 21.3 136

As described in Table 7, heat treatment of the KAT A precatalyst at a pressure reduced below 10 Pa (4 hours at 105 ° C) resulted in a significant reduction in bulk density of ethylene and propylene copolymers prepared thereon. The bulk density of the copolymers dropped from 364 g / l to 84 g / l when ethylene was metered in at 2.4 g per 100 g propylene in the second polymerization step. With ethylene feed of 4.8 g per 100 g propylene in the second polymerization step, the bulk density of the copolymers decreased from 399 g / l to 136 g / l. This is related to changing the morphology of copolymer particles to tuft as described above. Heat treatment of the precatalyst at a pressure below 10 Pa (4 hours at 105 ° C) also resulted in both catalyst activity decreasing to about one third and an increase in the resulting ethylene content of the copolymers and an X.S. content. in copolymers to about twice the value.

-23 GB 306881 B6

Example 8

Synthesis of ethylene-propylene-butene terpolymer with tuft morphology

The synthesis of the ethylene, propylene, butene terpolymer in Example 8 was carried out on a 1,3-diether precatalyst KAT A heat-treated at 105 ° C for 4 hours at a pressure reduced below 10 Pa. This precatalyst was polymerized by THA cocatalyst.

The polymerization proceeded in 2 steps:

In step 1, homopolymerization in gasified propylene was carried out for 30 minutes under the following conditions: polymerization temperature 75 ° C, polymerization pressure 2.2 MPa (g), Al / Ti = 150, without addition of external donor, H2 (initial charge) - 30 mmol H2 / C3 = 16 mmol / mol.

In Step 2, the random copolymerization of ethylene and 1-butene was carried out for 30 minutes at a polymerization temperature of 75 ° C and a polymerization pressure of 0.6 MPa (g).

The resulting catalyst activity and polymer properties are shown in Table 8 on a case-by-case basis:

Table 8

Adjustment Cat Content Content Content Activity Flow index X.S. Sypná precatalyst system ethylene propylene butone cat. 21.6 N mass hm. % hm. % hm. % Wh ° d) g / 10 min hm. % 21 2-step polymerization: in step 1 of propylene, in step 2 of ethylene and 1-butene without modification KAT A / THA 28.7 70.0 1.3 20.6 7.0 1,8 411 106 * 0-240 min KAT A / THA 50.8 47.8 1.5 4.1 6.3 1.4 128

As described in Table 8, heat treatment of the KAT A precatalyst at a pressure reduced below 10 Pa (4 hours at 105 ° C) resulted in a significant reduction in bulk density of the ethylene-propylene-butene terpolymer prepared thereon. The bulk density of the terpolymer decreased from 411 g / l to 128 g / l. This is related to the change in the morphology of the terpolymer particles to tuft as described above. Heat treatment of the precatalyst at a pressure below 10 Pa (4 hours at 105 ° C) also reduced the catalyst activity from 20.6 kg / (g * hr) to 4.1 kg / (g * hr).

Example 9

Influence of the tuft morphology of polypropylene on the absorption of mineral oil and oil

To study the absorption of mineral oil, polypropylene prepared on 1,3-diether precatalysts KAT A and KAT B was used, both uncooked and heat treated at 105 ° C, for 4 hours, at a pressure below 10 Pa. These precatalysts were polymerized by TEA, TIBA and THA cocatalysts for mineral oil sorption as shown in Table 9a and TIBA and THA cocatalysts for oil sorption as shown in Table 9b. The sorption properties of these polyolefins were as follows: white medical oil (paraffinum liquidum) with a density of 870 g / dm ³ (at 15 ° C) and medium-heavy oil with a density of 863 g / dm ³ (at 15 ° C).

The procedure for determining the absorption of mineral oil was as follows:

-24GB 306881 B6

1) Polyolefin of a given bulk density was accurately weighed at 4.0 ± 0.1 g and left for 10 minutes in a mixture with 100 ml of white medicinal oil or 100 ml of moderate oil with occasional mixing (3 times for 10 minutes).

2) Subsequently, it was filtered on a 0.2 mm sieve for 30 minutes. This time was sufficient to filter out any non-polymer-absorbed mineral oil or petroleum. The resulting polymer with mineral oil or petroleum adsorbed was weighed and the amount of mineral oil or petroleum adsorbed was calculated from its resulting weight.

The resulting amount of mineral oil or oil absorbed is shown in Tables 9a and 9b on a case-by-case basis:

Table 9a

Precatalyst modification Kat system Ratio ΑΙ / ΤΪ Bulk density g / i Water absorption min. oil g min. oil / g PP Polymerization in gasified propylene without modification KAT A / TEA 50 447 0.8 without modification KAT B / THA 150 395 0.8 105 ° C-4h KAT A / TEA 50 242 1.9 105 ° C-4h KAT A / TIBA 150 149 3.2 105 ° C-4h KAT A / THA 150 115 4.6 105 ° C-4h KAT B / THA 150 87 5.7

Table 9b

Precatalyst modification Kat system AI / TI ratio Bulk density g / i Oil absorption g oil / g PP Polymerization in gasified propylene 105 ° C-4h KAT A / TIBA 150 149 3.8 105 ° C-4h KAT A / THA 150 115 5.3 105 ° C-4h KAT B / THA 150 87 6.2

As described in Tables 9a and 9b and Figure 2, the absorbability of mineral oil and petroleum with tufted morphology by polypropylene increases proportionally with decreasing bulk density. The nature of tuft morphology, given the bulk density value, is therefore decisive for the sorption properties of these materials. When comparing the absorption of mineral oil in polypropylene with classical morphology prepared on KAT A, polymerized activated cocatalyst TEA, with a bulk density of 447 g / l, with polypropylene with tuft morphology prepared on KAT B, polymerized activated cocatalyst with THA, 30 with a bulk density of 87 g / l, it can be stated that the prepared polypropylene with tuft morphology has an absorption of mineral oil about 7 times higher (increase of absorption from 0.8 g min. oil / g PP to 5.7 g min. oil / g PP) .

-25 GB 306881 B6

Example 10

Influence of tuft morphology of polypropylene on the possibility of repeated desorption of sorbed mineral oil and crude oil

Polypropylene prepared on 1,3diether precatalysts KAT A and KAT B heat treated at 105 ° C for 4 hours at a pressure lower than 10 Pa was used to study the repeated desorption of mineral oil. These precatalysts were polymerically activated by TIBA and THA cocatalysts as shown in Tables 10a and 10b. To study the desorptive properties of these polyolefins, white medical oil (paraffinum liquidum) at a density of 870 g / dm (at 15 ° C) and medium heavy oil at a density of 863 g / dm (at 15 ° C) were reused as sorbed medium.

The procedure for determining repeated desorption of mineral oil was as follows:

1) Polyolefin of a given bulk density was accurately weighed in an amount of 0.50 ± 0.02 g and placed in a thick-walled centrifuge cuvette with an internal diameter of 1.5 cm and a length of 7.5 cm, underneath a 1.0 cm long capillary with an internal diameter 1 mm. The polymer was embedded with a sorbent medium (mineral oil or petroleum) so that the sorbent medium level was about 1 cm above the polyolefin. The cuvette with the mixture of tuft polymer and sorbed medium was left upright for 15 minutes so that the remainder of the unabsorbed medium could spontaneously flow through the capillary at the bottom of the cuvette.

2) Subsequently, the sample was centrifuged at 4000 rpm for 60 minutes in a cuvette. and then weighed.

Subtracting from grams of the sample after centrifugation (PO _C ) the grams of the sample before sorption (POo) in grams, we obtain the weight of the non-desorbed medium (Y _ND es) in grams according to formula (i)

Yndes ⁼ POc-POo (i).

This amount of non-desorbed medium (Y _NDES ) in grams relative to the total, pre-known amount of polyolefin-absorbed medium (Ys) in grams results in each of the sorption / desorption cycles the percentage of desorbed medium (DES) field of formula (ii):

P £ S (%) = -1-1 L -100 (Η)

X J

This sorption / desorption cycle was repeated a total of five times.

The resulting percentage of desorbed mineral oil or petroleum for each desorption step is shown in Tables 10a and 10b, respectively.

Table 10a

Adjustment Cat Sypná Repeated desorption min. polymer oils precatalyst system mass 1. desorption 2. desorption 3. desorption 4. desorption 5. desorption desorb. oil desorb. oil desorb. oil desorb. oil desorb. oil g / i % wt. % wt. % wt. % wt. % wt. Polymerization in gasified propylene 105 ° C-4h KAT A / TIBA 149 95.2 96.2 95.2 95.2 95.1 105 ° C-4h KAT A / THA 115 96.0 96.0 96.1 96.2 96.1 105’C-4h KAT B / THA 87 96.7 96.8 96.8 96.9 96.7

-26GB 306881 B6

Table 10b

Precatalyst modification Kat system Bulk weight Sd Repeated desorption of petroleum from polymer 1. desorption 2. desorption 3. desorption desorb. Crude oil% wt. 4. desorption desorb. Crude oil% wt. 5. desorption desorb. Crude oil% wt. desorb. Crude oil% wt. desorb. Crude oil% wt. Polymerization in gasified propylene 105´C-4hr KAT A / TIBA 149 95.0 94.6 94.4 94.5 94.4 105 ° C-4h KAT A / THA 115 95.3 95.1 95.0 95.0 95.0 105 * 0-4 hr KATB / THA 87 96.4 96.3 96.2 96.2 96.2

As described in Tables 10a and 10b, after repeated sorption and desorption of both mineral oil and oil, depending on the bulk density of the polypropylene with tuft morphology, a similar amount of sorbed medium is released after each cycle (approx. 96% for absorbed mineral oil and approx. 95% in the case of absorbed oil). Thus, the desorption pattern, expressed by the desorbed amount of mineral oil and oil, suggests that the desorption efficiency does not substantially change in the individual cycles. For example, in the case of polypropylene with tuft morphology and a bulk density of 87 g / l, prepared on a heat treated (105 ° C, 4 hours, reduced pressure) precatalyst KAT B, polymerized by THA cocatalyst, practically unchanged mineral oil desorption (96.7% - 96.9%) and petroleum desorption (96.2% 96.4%) in individual desorption steps

Example 11

Influence of tuft morphology of polypropylene on thermal conductivity of polypropylene

Polypropylene prepared on 1,3-diether precatalysts KAT A and KAT B heat treated at 105 ° C for 4 hours at a pressure lower than 10 Pa was used to study the thermal conductivity of polyolefin with tuft morphology. These precatalysts were polymerically activated by the cocatalysts TEA, TIBA and THA as shown in Table 11.

To study the thermal insulation properties of polymers with tuft morphology, a thermal conductivity analyzer TCi (C-Therm TCi apparatus) calibrated to foam materials was used, which allows thermal analysis in the thermal conductivity range from 0.01 to 100 W / (m * K).

This device measured the thermal conductivity of a total of 4 polyolefin materials, which differed in bulk density and corresponding morphology. A total of 10 measurements were performed for each analysis, from which the resulting thermal conductivity of the material was determined as an average value.

The resulting thermal conductivity values are given in Table 11 for each case.

-27GB 306881 B6

Table 11

Precatalyst modification Kat system AI / TI ratio Bulk density g / i Pulse. polymer conductivity W / m‘K Environmental polymerization! gasified propylene without modification KATA / TEA 50 447 0,070 without modification KAT B / THA 150 395 0,064 105’C-4h KATA / TEA 50 242 0.050 105’0-4 hours KAT A / TIBA 150 149 0.040

As described in Table 11 and Figure 3, the thermal conductivity of polypropylene with tuft morphology decreases proportionally (i.e., the insulating ability of the material increases) as its bulk density decreases. The character of tuft morphology, given the bulk density, is therefore decisive for the thermal conductivity of these materials. with particle tuft morphology (heat treated KAT A polymerised by TIBA cocatalyst) with a bulk density of 149 g / l, polypropylene with tuft morphology has a thermal conductivity of about 40% lower (thermal conductivity decreased from 0.070 W / ( m * K) to 0.040 W / (m * K)).

Example 12

Polyolefin with tuft morphology as additive carrier

Polypropylene prepared on a 1,3-diether precatalyst KAT C heat treated at 105 ° C for 4 hours at a pressure lower than 10 Pa activated by THA cocatalyst was used to study the ability of the polyolefin with fluff morphology to act as a carrier additive. This tufted morphology polypropylene is designated in Table 12a as polypropylene B and its ability to function as an additive carrier is compared to polypropylene A with conventional particle morphology prepared on a 1,3-diether precatalyst without heat treatment activated by TEA cocatalyst. Table 12a compares the properties of both types of polypropylene. Polypropylene B with tuft morphology has a significantly reduced bulk density compared to polypropylene A with conventional morphology, as evidenced in particular by its altered morphology and the degree of character of this change as described above.

To study the ability of polyolefin with tuft morphology to function as a carrier additive, a procedure was used in which the antistatic Dimodan PV (glycerol monostearate containing other glycerol and free glycerol derivatives at a maximum of 3% by weight, manufactured by Danisco) was admixed sequentially at 20% by weight. . (based on a blend of polypropylene, additive and stabilizer) to polypropylene A with conventional morphology and in an amount of 20 wt.%, 30 wt.%. and 40 wt. (based on a blend of polypropylene, additive and stabilizer) to polypropylene B with tuft morphology (see Table 12b). The individual polypropylene / additive blends were stabilized with Irganox B225 (Irganox 1010 blend - i.e., [methylene-3, (3 ', 5'-di- / tert -butyl) -4'-hydroxyphenyl propionate)] methane and Irgafos 168 - i.e. tris (2,4-di-tert-butylphenyl) phosphite in a ratio of 1: 1 by weight, manufactured by BASF) in an amount of 0.25 wt. (based on blend of polypropylene, additive and stabilizer.

The mixing conditions in the Thyssen Henschel mixer were as follows: raw material inlet temperature - 23.5 ° C, mixer volume - 5 liters, stirrer speed - 200 rpm, mixing time - 5 minutes. During mixing, the mixture warmed to 31.2 ° C but remained free-flowing.

-28 GB 306881 B6

The prepared powder blends were processed on a Wemer & Pfleiderer ZSK 25 co-rotating screw auger (D = 25 mm, L / D = 53). Individual mixtures were dosed into the first feed of raw materials. Granules were prepared from strings on the head with two 4 mm holes. The strings were cooled in water and blown with compressed air before cutting. The following temperatures (from hopper to head) were set on the extruder: 100, 150, 160, 170, 180, 180, 180, 180, 180, 180, 180, 180 ° C and 200 rpm. The melt was degassed under reduced pressure conditions at a distance of 40D from the feed inlet.

Table 12a

Polypropylene Morphology Flow Index 21.6 N g / 10 min X.S. hm. % Bulk weight AND common 19.0 1.6 441 (B) chomáčková 20.5 4.7 189

Table 12b

Polypropylene Dimodan Irganox B225 Result Incorporated type wt% wt% extrusion additives AND 20 May 0.25 with problems partly (B) 20 May 0.25 seamlessly completely (B) 30 0.25 seamlessly completely (B) 40 0.25 seamlessly completely

As described in Table 12b, 20% wt. Dimodan PV additive to polypropylene with conventional type A morphology followed the extrusion of this stabilized mixture with problems, namely, already at this amount of additive, the string breakage occurred and the additive itself was not sufficiently incorporated into the melt by visual assessment. Conversely, after mixing 20 wt.%, 30 wt. i 40 wt. Dimodan PV additive to polypropylene with tuft type B morphology was followed by extrusion of these stabilized mixtures without problems, in particular none of the strings broke and the additive itself was, according to visual evaluation, completely incorporated into the melt. These results indicate that when polyolefins with tuft morphology are used, the final additive concentration in the granulate can be significantly increased by admixing the additives.

This example has shown that by using a tuft polymer, the amount of antistatic agent (based on glycerol esters of higher fatty acids) incorporated into the polymeric material can be increased up to twice that of a conventional polymeric powder or granulate and can achieve 40 wt. % additive incorporated in the resulting polypropylene granulate.

Example 13

Polyolefin with tuft morphology as a carrier of organic color pigments

To study the ability of polyolefins with tuft morphology to function as a carrier for organic pigments, polypropylene prepared on 1,3-diether KAT C precatalysts heat treated at 105 ° C for 4 hours at a pressure below 10 Pa activated with THA cocatalyst was used. This polypropylene with tuft morphology is indicated in Table 13a

306881 B6 as polypropylene B and its ability to function as a carrier for organic pigments is compared to polypropylene A with conventional particle morphology prepared on a 1,3-diether precatalyst without heat treatment activated by TEA cocatalyst. Table 13a compares the properties of both types of polypropylene. Polypropylene B with tuft morphology has a significantly reduced bulk density compared to polypropylene A with conventional morphology, as evidenced in particular by its altered morphology and the degree of character of this change as described above.

To study the ability of polyolefins with tuft morphology to function as a carrier of organic pigments, a process was used in which the organic pigment was admixed gradually in an amount of 30% by weight. (based on a blend of polypropylene, pigment, stabilizer and dispersant) to polypropylene A having a conventional morphology and in an amount of 30 wt. (based on a blend of polypropylene, organic pigment, stabilizer and dispersant) to polypropylene B with tuft morphology as documented in Table 13b. The organic pigment was A3BN Versal Red (manufactured by SYNTHESIA a.s., Pardubice-Semtín, Czech Republic) having the Color Index Pigment Red 177/65300 and CAS Number 4051-63-2 belonging to the group of anthraquinone organic pigments. Individual blends of polypropylene, organic pigment and dispersant were stabilized with Irganox B225 stabilizer (Irganox 1010-ie, [methylene-3, (3 ', 5'-di-tert-butyl) -4'-hydroxyphenyl propionate)] methane and Irgafos stabilizer 168 - i.e. tris (2,4-di-tert-butylphenyl) phosphite in a ratio of 1: 1 by weight (manufacturer BASF) in an amount of 0.5 wt. (based on a mixture of polypropylene, organic pigment, stabilizer and dispersant) and a liquid copolymer of ethylene oxide with propylene oxide (trade name SLOVACID S-44P, manufactured by Sasol) was used as a dispersant in an amount of 0.5% by weight. (based on a blend of polypropylene, organic pigment, stabilizer and dispersant) as also documented in Table 13b.

The mixing conditions in the Thyssen Henschel mixer were as follows: feed temperature -23.8 ° C, mixer volume - 5 liters, mixer speed - 200 rpm, mixing time - 5 minutes. During mixing, the mixture was heated to 32.7 ° C but remained free-flowing.

The prepared powder blends were processed on a Wemer & Pfleiderer ZSK 25 co-rotating screw auger (D = 25 mm, L / D = 53). Individual mixtures were dosed into the first feed of raw materials. Granules were prepared from strings on the head with two 4 mm holes. The strings were cooled in water and blown with compressed air before cutting. The following temperatures (from hopper to head) were set on the extruder: 130, 180, 200, 200, 200, 200, 200, 200, 200, 200, 200, 200 ° C and 500 rpm.

Table 13a

Polypropylene Morphology Flow Index 21.6 N g / 10 min X.S. hm. % Bulk density g / i AND common 19.0 1.6 441 (B) chomáčková 20.5 4.7 189

Table 13b

Polypropylene type Versal red A3BN wt% Irganox B225 wt% Slovacid S-44P wt% The pressure upstream of the filter screen with holes of 125 pm MPa AND 30 0.5 5.0 18 (B) 30 0.5 5.0 10

-30GB 306881 B6

The organic pigment concentrates were prepared in the form of a granulate and then subjected to the ASTM standard D 6265-98: Separation of Contaminants in Polymers Using an Extruder Filter Test.

The standard morphology polypropylene powder based concentrate A showed a pressure increase of 18 MPa on a 125 micron sieve after passing 600 g of the concentrate through the filter.

Concentrate based on polypropylene powder B with tuft morphology showed a pressure increase of 10 MPa after passing 600 g of the concentrate through a filter on a 125 micron sieve.

The advantage of the polypropylene powder with tuft morphology prepared according to the present invention is also evident in the preparation of the organic pigment concentrate, because under otherwise identical technological conditions, the polypropylene with tuft morphology more effectively disperses the organic pigment in the polypropylene melt. .

Claims (9)

CLAIMS 1. Polyolefin powder, characterized in that it consists of polyolefin particles having a tufted morphology of a fibrous nature. Polyolefins according to claim 1, characterized in that the corresponding polyolefin is selected from the group of polyolefins including propylene homopolymer, ethylene homopolymer, random copolymer of propylene and ethylene, ethylene and 1-butene, propylene and 1-butene, ethylene and 1-hexene, propylene and 1-hexene; a random terpolymer of ethylene, propylene and 1-butene and ethylene, propylene and 1-hexene; 2-step polymerization consisting of homopolymerization of propylene followed by random copolymerization of propylene with ethylene, 2-step polymerization consisting of homopolymerization of propylene followed by random copolymerization of ethylene with 1-butene, 2-step polymerization consisting of homopolymerization of propylene followed by random copolymerization of ethylene with 1-ethylene step polymerization consisting of homopolymerization of propylene followed by random terpolymerization of propylene with ethylene and 1-butene, a polymer of 2 step polymerization consisting of homopolymerization of propylene followed by random terpolymerization of propylene with ethylene and 1-hexene. Polyolefin powder according to claim 1 or claim 2, characterized in that its bulk density is in the range of 20 to 300 g / l. A process for preparing a polyolefin powder according to any one of claims 1 to 3, wherein the Ziegler-Natta precatalyst comprises one or more internal donors selected from the group consisting of: 2-methyl-2-isopropyl-1,3-dimethoxypropane; 2-isopropyl-2-isobutyl-1,3-dimethoxypropane; 2-isopropyl-2-isopentyl-1,3-dimethoxypropane; 2-heptyl-2-pentyl-1, 3-dimethoxypropane; 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane; 2-isopropyl-2-cyclohexyl-1,3-dimethoxypropane; 2-isopropyl-2-cyclohexylmethyl-1,3-dimethoxypropane; 2,2-dipropyl-1,3-dimethoxypropane; -31 GB 306881 B6 2,2-diisopropyl-1,3-dimethoxypropane; 2,2-diisobutyl-1,3-dimethoxypropane; 2,2-diisobutyl-1,3-diethoxypropane; 2,2-diisobutyl-1,3-dibutoxypropane; 2,2-dicyclohexyl-1,3-dimethoxypropane; 2,2-diphenyl-1,3-dimethoxypropane; 2,2-dibenzyl-1,3-dimethoxypropane; 2,2-dicyclopentyl-1,3-dimethoxypropane; 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane; 1,1-bis (methoxymethyl) cyclopentadiene; 1,1-bis (methoxymethyl) -2,3,4,5-tetramethylcyclopentadiene; 1,1-bis (methoxymethyl) -2,3,4,5-tetrafenylcyclopentadiene; 1,1-bis (methoxymethyl) -3,4-dicyclopentylcyclopentadiene; 1,1-bis (methoxymethyl) indene; 1,1-bis (methoxymethyl) -2,3-dimethylindene; 1,1-bis (methoxymethyl) -4,7-dimethylindene; 1,1-bis (methoxymethyl) -4,7-dimethylindene; 1,1-bis (methoxymethyl) -7-methylindene; 1,1-bis (methoxymethyl) -7-isopropylindene; 1,1-bis (methoxymethyl) -7-cyclopentylindene; 1,1-bis (methoxymethyl) -7-cyclohexylindene; 9.9- bis (methoxymethyl) fluorene; 9.9-bis (methoxymethyl) -2,3,6,7-tetramethylfluorene; 9.9-bis (methoxymethyl) -2,7-diisopropylfluorene; 9.9-bis (methoxymethyl) -2,7-dicyclopentylfluorene; naphthalene-1,8-di-1-di-cyclopentanecarboxylate; naphthalene-1,8-diyl-dicyclohexanecarboxylate; naphthalene-1,8-diyl-dicyclo-1-hexene-carboxylate; naphthalene-1,8-diyl-dicyclo-2-hexene-carboxylate; naphthalene-1,8-diyl bis (3,3-dimethylbutanoate); 8- (Cyclohexanecarbonyloxy) naphthalen-1-yl-benzoate; 8- (Cyclo-1-hexene-carbonyloxy) -naphthalen-1-yl-benzoate; 8- (cyclohexanecarbonyloxy) naphthalen-1-yl-2-methylbenzoate; 8- (2-methylcyclohexanecarbonyloxy) naphthalen-1-yl-benzoate; 8- (1-cyclohexenecarbonyloxy) naphthalen-1-yl-benzoate; decahydronaphthalene-1,8-diyldibenzoate; 1,8-naphthyl dibenzoate; 1,8-naphthyl-di-2-methylbenzoate; 1,8-naphthyl di-3-methylbenzoate; 1,8-naphthyl-di-1-methyl Ibenzoate; 1,8-naphthyl-di-4-fluorobenzoate. dimethyl 2,6-dioxaheptanedioate; -32EN 306881 B6 Diethyl 2,6-dioxaheptanedioate; diethyl 2,6-dioxa-3,5-dimethylheptanedioate; diethyl 2,6-dioxa-3,5-diisopropylheptanedioate; diisopropyl-2,6-dioxa-3,5-diisopropylheptanedioate; diisobutyl-2,6-dioxa-3,5-diisopropylheptanedioate; diethyl 2,6-dioxa-3-isopropyl-5-isobutylheptanedioate; heat treated under reduced pressure below 10 Pa and at an elevated temperature in the range of 90 ° C to 120 ° C for 5 minutes to 10 hours, then activated by reaction with an organoaluminum compound of the formula AlR _n Z _{3 n} where R is C 1 - A C ₂₀ alkyl group, Z is halogen and n is 0, 1, 2 or 3, and then the coordinated polymerization of 1-olefins is carried out on the Ziegler-Natta precatalyst thus activated. The method of claim 4, wherein the organoaluminum compound comprises trimethyl aluminum TMA, triethyl aluminum TEA, triisobutyl aluminum TIBA, tri-n-hexyl aluminum THA, tri-iso-hexyl aluminum THA, tri-n-octyl-aluminum TOA, and tri- n-decyl-aluminum TDA. The process of claim 4 or claim 5 wherein the polymerization is carried out in a gaseous or liquid 1-olefin environment or in a non-polar hydrocarbon solvent saturated with 1-olefin selected from the group consisting of liquefied propane, liquefied butane, isomers of pentane, hexane, heptane, and C ₈ -C ₁₈ linear saturated hydrocarbons, cyclopentane, cyclohexane, benzene, toluene, xylene, and mineral oil. Use of a polyolefin powder according to any one of claims 1 to 3 as a sorbent of substances selected from the group of hydrophobic hydrocarbon compounds including petroleum, vegetable and mineral oils, gasoline, diesel, kerosene and non-polar hydrocarbon solvents consisting of C ₅ -C ₂₀ carbons. Use of a polyolefin powder according to any one of claims 1 to 3 as a thermal insulation material. Use of a polyolefin powder according to any one of claims 1 to 3 as a material for the production of a concentrate of inorganic pigments, organic pigments and additives for polyolefins including antistatic agents, nucleating agents and glidants.