Polyolefin Powder, Method of Production and Use thereof Field of the Invention

The invention concerns a polyolefin powder, method of production and use thereof, as well as a method of modifying the Ziegler-Natta precatalyst intended for the production of polyolefin powder.

Description of the Related Art

The well-known thermoplastic polymers, such as polyethylene, polypropylene and various copolymers and terpolymers of ethylene and propylene with higher 1 -olefins are usually produced with Ziegler-Natta catalytic systems, in which the so-called precatalyst is usually made up of MgC , TiCI ₄ and an internal electron donor. To activate this precatalyst to a form capable of polymerisation, namely the catalyst, an organoa!uminium cocatalyst with a general structure AIR ₃ is commonly used, where R is an n-a!kyl or iso-aiky! group, if need be this catalyst can be modified by various types of external electron donor in order to increase its stereospecificity as well as the stereoregularity of the resulting thermoplastic polyolefin.

The nature of the resulting polymer particles of these polyolefins depends on the composition of the precatalyst and its morphology, as well as the nature and presence of individual reaction components (cocatalyst, external electron donor, hydrogen, monomer) in the reaction mixture, and not least also on the polymerisation conditions (temperature, pressure, phase). The resulting polymer particles are round to oval in shape, varying in size (0.2 - 2.0 mm), with more or less smooth surface, and the bulk powder density, due to their morphology and the distribution of particle size, tends to be relatively high (350 - 500 g/l). Such polymer particles, thanks to their shape and high bulk powder density, are easy to store and transport. However from another perspective the morphology of these polymer particles is not ideal, for example when it comes to their sorptive capacity. Summary of the Invention

The aim for the invention is to prepare the polyolefin powder with altered morphology, and to find the preferred method of its production, as well as the preferred Ziegler-Natta precatalyst to perform this method. It is particularly done with the polyolefin powder containing particles with fluffy morphology respectively at least in 40 % by weight.

These particles are formed by fibres of polyolefin with various diameter and length. The fibres commonly grow to the diameter from 5 to 100 μιτι, preferably from 10 to 50 μιτ! and to the length from 10 to 2000 μιη, preferably from 50 to 1000 μηι. These particles are non-compact, since the length of fibres is always several times greater than their diameter. This makes the particles in question differ from the conventional compact polyolefin particles, which have uniform size in all 3 dimensions. According to this invention, the fibres of polyolefin powder particles are variously intertwined and create a three-dimensional structure with differently sized interspaces, depending on their number, dimension and length. These spaces within the fibres contain air (optionally they can be filled up with another substance). The spaces within the fibres have an important role in absorption and heat-insulation properties of polymer formed by these particles. Polyolefin particles with a fibrous structure in the form of powder reach macroscopic size from 0.1 to 4 mm, preferably from 0.2 to 2 mm - this size depends on the particle size of the used polymerization catalyst, on conditions of its thermal activation and polymerization conditions.

The terms „poiyolefin particle with fluffy morphology" or "polyolefin with fluffy morphology" according to the invention mean the polyolefin particle having a three dimensional structure formed of different polyolefin fibres, variously intertwined, with interstices of different size within the fibres. In terms of practical use, the polyolefin powder is considered suitable if it is made up of polyolefin with a bulk powder density in the range 20 - 300 g/l; from the viewpoint of absorption and thermal-insulation properties it is more preferable range from 20 to 200 g/l. Bulk density (B.D.) of the polymer powder was assessed according to the ISO 60(E) standard. The preferred method of preparation of poiyolefin powder lies above all in the coordination polymerisation of 1 -olefins being carried out on the thermally treated Ziegler-Natta precatalyst activated by an organoaluminium cocatalyst.

The term„Ziegler-Natta precatalyst" according to the invention is a substance consisting of a compound containing a transition metal of the IV to VIII group of the periodic table. The common Ziegler-Natta precatalysts are halides or oxyhalides of Ti, V or Cr, especially Ti, Preferred Ziegler-Natta precatalysts are particularly TiCI ₃ , TiCi ₄ , mixtures of VOCI ₃ with TiCU and mixtures of VCI ₄ with TiCI ₄ . Suitable carrier materials for Ziegler-Natta precatalysts are silica or magnesium compounds such as halides of magnesium, in particular MgCI ₂ ; also magnesium afkoxides, dialkyl magnesium compounds and organic magnesium halides. They are known compounds and are commonly used in olefin polymerization. In the case of Ziegler-Natta precatalysts anchored to the carrier surface and intended for propylene polymerization and copolymerization of propylene with other 1 -olefins, an electron donor compound called "internal donor" is also bonded to the surface of the carrier. The internal donor is designed to increase the stereospecificity of the precatalyst. Depending on the type of internal donor we can classify Ziegler-Natta precatalysts as phthalate-type, diether-type or succinate-type.

The thermal treatment of Zieg!er-Natta precatalyst is carried out at reduced pressure below 1 kPa or under a flow of inert gas selected from the group containing nitrogen, helium or argon, preferably nitrogen, at temperatures ranging from 50°C to 50°C for 1 minute to 10 hours. Subsequent activation of this thermally treated Ziegler- Natta precatalyst is accomplished by reacting with an organoaluminium compound of the general formula AIRnZ _3-n , wherein R is C ₁ -C ₂ 0 alkyl group, Z is a halogen selected from the group containing F, CI, Br or I and n is 0, 1 , 2 or 3, e.g. by reaction with organoaluminium compounds comprising trimethy!aluminium (TMA), triethylaiuminium (TEA), triisobutylaluminiurrt (TIBA), tri-n-hexylaiuminium (THA), tri-iso-hexylaluminium (TIHA), tri-n-octyl-a!uminium (TOA) and tri-n-decy!-aluminium (TDA).

Coordination polymerisation of 1 -olefins can be carried out in gaseous or liquid 1- olefin or in a non-polar hydrocarbon solvent saturated with 1 -olefin, and the result of this polymerisation can be homopolymers of ethylene or propylene, or copolymers of ethylene or propylene with higher 1 -olefins or even terpolymers of ethylene and propylene with higher 1-olefins, always containing particles with the fluffy morphology. The term„nonpolar hydrocarbon solvent" according to the invention comprises the solvents selected from the group containing liquefied propane, liquefied butane, isomers of pentane, hexane, heptane and other Cs - Ci ₈ linear saturated hydrocarbons, cyclopentane, cyclohexane, benzene, toluene, xylene and mineral oils.

The suitable precataiyst for thermal treatment and subsequent coordination polymerisation of 1-olefins with the aim of favouring the preparation of the polyolefin powder with fluffy morphology is a Ziegler-Natta precataiyst which contains one or more internal electron donors selected from the group of compounds of general formulas I, II and III:

(I) (II) (III)

which contains two oxygen functional groups in the ether -O-R arrangement bonded to the carbon atoms C and C ³ of the atomic group C ¹ -C ² -C ³ having a general formula I, generally called diethers, or contains two oxygen functional groups in the ester -O-CO-R arrangement bonded to the carbon atoms C ¹ and C ³ of the atomic group C ¹ -C -C ³ having a general formula II, generally called diesters, or contains two oxygen functional groups in positions 2 and 6 in the 2,6-dioxoheptandioate bonded to the carbon atoms C and C ³ of the atomic group C -C ² -C ³ having a general formula III, wherein R in the ether groups -OR or R in the ester groups -OCOR is selected from the group containing alkyl, cycloalkyi, or aryl and R in dioate groups is selected from the group containing alkyl, or optionally alkyl of the two dioate groups can be joined together to form an aliphatic cycle; and wherein either

a) the carbon atoms C ¹ , C ² a C ³ form an aliphatic chain, which is optionally disubstituted on the carbon atom C ² , wherein the substituents are selected from the group containing alkyl, cycloalkyi, or aryl and where carbon atoms C ¹ and C ³ are alternatively substituted by alkyl; or

b) the carbon atoms C ¹ , C ² a C ³ form an aliphatic chain, wherein the carbon atom C ² is part of cyclic or po!ycyc!ic structures consisted of the cycle or the cycles with 5, 6 or 7 carbon atoms and containing in each cycle 2 or 3 unsaturated bonds and the carbon atoms C and C ³ are bonded to the carbon atom C ² and where the carbon atoms C and C ³ are optionally substituted by alkyls and the resulting cyclic or polycyclic structure is optionally substituted by the substituents selected from the group containing halogen, preferably CI or F, alkyl, cycloalkyl, aryl, alkaryl or aralkyi; or

c) the carbon atoms C ¹ , C ² a C ³ are the part of the polycyclic structure consisted of at least two cycles with 5, 6 or 7 carbon atoms and containing in each cycle 2 or 3 unsaturated bonds and the resulting polycyclic structure is optionally substituted by the substituents selected from the group containing halogen, preferably CI or F, alkyl, cycloalkyl, aryl, alkaryl or aralkyi; or

d) the carbon atoms C ¹ , C ² a C ³ are the part of cyclic structure consisted of a cycle with 5, 6 or 7 carbon atoms and the resulting cyclic structure is optionally substituted by the substituents selected from the group containing halogen, preferably CI or F, alkyl, cycloalkyl, aryl, alkaryl or aralkyi.

For example it concerns the following structures of internal electron donors selected from the groups:

a) 1 ,3-diether compounds comprising:

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

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

2-isopropyl-2-isopenty!-1 ,3-dimethoxypropane;

2-heptyl-2-penty!- ,3-dimethoxypropane;

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

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

2-isopropyl-2-cyclohexylmethyi-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-diisobuty ,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;

I -bisfmethoxymethyl^^^^-tetramethylcyclopentadiene; I -bisimethoxymethyO^^^^-tetraphenylcyclopentadiene;

1 , 1 -bis(met oxymethyl)-3,4-dicyclopentylcyc[opentadiene;

1 ,1-bis(methoxymethyl)-indene;

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

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

1 -b!s{methoxymethyl)-47Hjimethylindene;

1 , 1 -bis(methoxymethyl)-7-methyli ndene;

1 , 1 -bis(methoxymethy!)-7-isopropyiindene;

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

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

9,9-bis(methoxymethyl)f!uorene;

9,9-bis(methoxymethyl)-2,3,6,7-tetramethylfluorene;

9,9-bis(methoxymethyI)-2 -diisopropylfluorene;

9,9-bis(methoxymethyl)-2,7-dicyclopentylfluorene;

compounds of 1.8-naphthvi diesters and 1 ,8-naphthyl diaryloates comprising: naphthalene-1 ,8-diyl-dicyciohexane-carboxyiate;

naphthalene-1,8-diyl-dicyc!ohexane-carboxytate;

naphthalene-1 ,8-diyl-dicyclo-1 -hexene-carboxyiate;

naphthalene-1 ,8-diyl-dicyclo-2-hexene-carboxyiate;

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

8-(cyclohexanecarbonyloxy)naphthalene-1-yl-benzoate;

8-(cyclo-1 -hexene-carbonyloxy)naphthalene-1 -yl-benzoate;

8-( cyciohexanecarbonyloxy)naphtha!ene-1 -yl-2-methylbenzoate;

8-(2-methyicyciohexanecarbonyloxy)naphthalene-1-yl-benzoa te;

8-(1 -cyclohexenecarbonyIoxy)naphthalene-1 -yl-benzoate;

decahydronaphthalene-1 ,8-diyl~dibenzoate;

1 ,8-naphthyl-dibenzoate;

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

1 ,8-naphthyl li-3-methylbenzoate;

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

1 ,8-naphthyl-di-4-fluorobenzoate; .

compounds of 2,6-dioxoheptandioate comprising:

dimethyl-2,6-dioxaheptandioate;

diethyl-2,6-dioxaheptandioate; diethyl-2,6-dioxa-3,5-dimethylheptandioate;

diethyl-2,6-dioxa-3,5-diisopropylheptandioate;

diethy[-2,6-dioxa-3,5-diisopropyiheptandioate;

diisopropy!-2,6-dioxa-3,5-diisopropy!heptandioate;

diisobutyl-2,6-dioxa-3,5-diisopropylheptandioate;

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

It is possible to use the polyolefin powder with fluffy morphology as a sorbent for hydrophobic hydrocarbon compounds comprising crude oil, vegetable and mineral oil, petrol, diesei, paraffin and non-polar hydrocarbon solvents consisted of C5-C20 carbon atoms.

Furthermore it is possible to use polyolefin powder with fluffy morphology as a material for thermal insulation.

Moreover it is possible to use polyolefin powder with fluffy morphology as a materia! for the production of concentrates of inorganic and organic pigment and additives for polyolefins including antistatic agents, nucleation reagents and lubricants.

Brief Summary of Figures

The invention will be clarified in detail using these figures:

Fig. 1A depicts polypropylene particles with fluffy character prepared on the precatalyst KAT A thermally treated at 105°C for 4 hours under the pressure reduced below 10 Pa and activated by the cocatalyst THA. The bulk powder density of the resulting polypropylene with these fluffy particles was 97 g/i.

Fig. 1 B depicts polypropylene particles with fluffy character prepared on the precatalyst KAT B thermally treated at 105°C for 4 hours under the pressure reduced below 10 Pa and activated by the cocatalyst TIBA. The bulk powder density of the resulting polypropylene with these fluffy particles was 100 g/l.

Fig. 2 depicts the influence of the bulk powder density of polypropylene, arising from the fluffy morphology of its polypropylene particles, on its ability to act as the sorbent for mineral oil or crude oil.

Fig. 3 depicts the influence of the bulk powder density of polypropylene arising from the fluffy morphology of its polypropylene particles on its thermal conductivity. Detailed Description of the Invention According to this invention, polyolefins with fluffy particles can be prepared on a

Ziegler-Natta catalyst, which as an internal electron donor contains a compound chosen from the groups of gamma-diethers, gamma-diesters or compounds formed of 2,6- dioxoheptandioate. For such a catalyst to be capable of producing polyolefins with fluffy particles, it first has to be thermally treated, either under reduced pressure or in an inert atmosphere. Suitable conditions for thermal treatment of Ziegler-Natta precatalysts are 50 to 150°C for 1 min to 10h under the conditions of reduced pressure (below 1 kPa), or more preferably 90 to 120°C for 1 to 4 hours under the conditions of reduced pressure (below 10 Pa). Thus treated catalysts have significantly lower polymerisation activity and are suitable for the preparation of polyolefins with fluffy morphology, for example in the synthesis of the homopolymer polypropylene, in the synthesis of copolymers of propylene with ethylene and terpolymers of propylene with ethylene and higher a- olefins. The polyolefin particles having a fibrous structure prepared this way attain the size from 0.1 to 4 mm - this size is dependent upon the particle size of the used polymerization catalyst, on the type of internal donor applied, on the conditions of the Ziegler-Natta precatalyst thermal treatment and on the polymerization conditions, mainly related to the type and quantity of co-catalyst used to activate Ziegler-Natta precatalyst.

The resulting polyolefin, due to the influence of its fluffy morphology, has a significantly reduced bulk powder density in the range from 20 to 300 g/l. Other polymer characteristics such as melt flow index and isotacticity of the polyolefin are only insignificantly changed. Another significant factor, that influences the bulk powder density of the resulting polyolefin during polymerisation, is the character of the cocatalyst and its concentration. Synthesis parameters such as hydrogen concentration and the presence of an external electron donor and its concentration have a minor influence on the bulk powder density of the resulting polyolefin.

The resulting polyolefin with fluffy particles has, as a material, the polymer properties (flow index, isotacticity) related to standard polyolefins. It can be further worked as a melt into granulate form following standard extrusion procedures. The mechanical properties of the resulting granulate correspond to the properties of the original polymer powder, prepared on a catalyst without thermal treatment and does not otherwise vary from the standard values.

The polyo!efin with fluffy morphology according to the invention can be preferably used in various industrial applications:

1) It is suitable for the sorption of hydrophobic liquids, such as for example crude oil and its products such as mineral oil. The sorptive capacity of this new material significantly increases with the decrease in its bulk powder density and it reaches nine times the typical value for these poiyolefins. This property as a sorbent for hydrophobic liquids is reversible, the absorbed substance can subsequently be separated by centrifugation and a polyolefin prepared according to the invention can be reused for the same purpose.

2) It is the material suitable for thermal insulation due to its significantly reduced thermal conductivity. The thermal conductivity of these poiyolefins decreases significantly with decreasing bulk powder density and reaches values normal for advanced thermal insulation materials such as extruded polystyrene.

3) It is the material suitable as a carrier for various additives and pigments for poiyolefins. Using poiyolefins prepared according to this invention it is possible to increase the resulting concentration of additive, e.g. antistatic agents based on esters of glycerol with the higher fatty acids, up to double that achieved using standard polymer powders or granulates. Using poiyolefins prepared according to the invention it is possible to improve the dispersal of organic pigments in poiyolefins when preparing organic pigment concentrates in poiyolefins, which is manifested in less of an increase in pressure measured before the filter in a filter pressure test of this material.

The invention further describes a method of treating a Ziegler-Natta precatalyst and subsequent synthesis of the polyolefin with fluffy particles on thus treated, activated catalyst. Each step is described below:

a) Preferred Ziegler-Natta precatalyst for subsequent thermal treatment.

It was found that poiyolefins with fluffy morphology can be prepared using a preferred Ziegler-Natta precatalyst. The preferred Ziegler-Natta precatalyst contains preferably halogen-titanium compound and a selected internal electron donor compound, wherein both the compounds are deposited on a halogen-magnesium carrier.

According to yet another embodiment of the invention the internal electron donor compound contains two oxygen functional groups in an ether -0-R ¹ R ² arrangement having a general formula la bonded to carbon atoms C ¹ and C ³ of an atomic group C - C ² -C ³ or contains two oxygen functional groups in an ester -0-CO-R ¹ R ² arrangement having a general formula Ma bonded to carbon atoms C and C ³ of an atomic group C ¹ - C ² -C ³ or has two oxygen functional groups in positions 2 and 6 in 2,6-dioxoheptandioate bonded to carbon atoms C ¹ and C ³ of an atomic group C ¹ -C ² -C ³ in the compound having a general formula Ilia; wherein either

(la), (lla), (Ilia), a) the carbon atoms C ¹ , C ² a C ³ form an aliphatic chain, wherein R ³ a R ⁴ are either same or different and are selected from the group containing hydrogen, linear or branched C-i- C ₂₀ alkyl, and R ⁵ a R ⁶ are either same or different and are selected from the group containing hydrogen, linear or branched C1-C20 alkyi, and R ¹ a R ² are either same or different and are selected from the group containing linear or branched C1-C ₂ 0 alkyl, C ₄ -C ₂ o cycloalkyl, C6-C20 aryl, C7-C20 alkaryl, C ₇ ~C ₂ o aralkyl, having a general formulas la, lla a Ilia; or

b) the carbon atoms C ¹ , C ² a C ³ form an aliphatic chain, wherein the carbon atom C ² is part of cyclic structure consisted of 5, 6 or 7 carbon atoms and containing in this cycle 2 or 3 unsaturated bonds and R ⁵ a R ⁶ are either the same or different and are selected from the group containing hydrogen, linear or branched C-1-C ₂ 0 alkyl, and R ⁷ is selected from the group containing hydrogen; halogen, preferably CI or F; linear or branched C C ₂ o alkyl, C ₄ -C ₂ o cycloalkyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ alkaryl, C ₇ -C ₂ o aralkyl, and R ¹ a R ² are either same or different and are selected from the group containing linear or branched C1-C20 alkyl, C ₄ -C ₂₀ cycloalkyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂ o alkaryl, C ₇ -C ₂ o aralkyi, having a general formula IV below

(IV),

or

c) the carbon atoms C ¹ , C ² a C ³ form an aliphatic chain, wherein the carbon atom C ² is part of polycyclic structure consisted of the cycles with 5, 6 or 7 carbon atoms and containing in each cycle 2 or 3 unsaturated bonds and R ⁵ a R ⁶ are either same or different and are selected from the group containing hydrogen, linear or branched Ci- C ₂₀ alkyl, and R ⁸ is selected from the group containing hydrogen; halogen, preferably CI or F; linear or branched Ci-C ₂₀ alkyl, C ₄ -C ₂ o cycloalkyl, C ₆ -C ₂ o aryl, C ₇ -C ₂₀ alkaryl, C ₇ - C ₂₀ aralkyi, and R ¹ a R ² are either same or different and are selected from the group containing linear or branched Ci-C ₂₀ alkyl, C ₄ -C ₂₀ cycloalkyl, C ₆ -C ₂ o aryl, C ₇ -C ₂₀ alkaryl, C ₇ -C ₂ o aralkyi, having a general formula V below

(V),

or

d) the carbon atoms C, C ² a C ³ are part of polycyclic structure consisted of the cycles with 5, 6 or 7 carbon atoms and containing in each cycle 2 or 3 unsaturated bonds and R ⁹ is selected from the group containing hydrogen; halogen, preferably CI or F; linear or branched C ₁ -C20 alkyl, C ₄ ~C ₂ Q cycloalkyl, C6-C ₂₀ aryl, C ₇ -C ₂₀ alkaryl, C ₇ -C ₂₀ aralkyi, and R a R ² are either same or different and are selected from the group containing linear or branched CrC ₂₀ alkyl, C ₄ -C ₂ o cycioalkyl, C ₆ -C ₂ o aryl, C ₇ -C ₂₀ alkaryl, C ₇ -C ₂ o aralkyl, according to a genera! formula VI below

(VI).

Preferably selected internal electron donor compounds are as follows:

1 ) Structures of 1 ,3-diethers having a general formula la and comprising for pie:

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

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

2-isopropyl-2-isopenty!-1 ,3-dimethoxypropane;

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

2-isopropyi-2-cyclohexyl-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 _I 2-dibenzyl-1 ,3-dimethoxypropane;

2,2-dicyclopentyl-1 ,3-dimethoxypropane and

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

2) Structures of 1 ,3-diesters having a general formula lla and comprising for example:

diethyl 2,2-dibenzylmalonate;

diethyl 2-isobutyl-2-cyklohexylmalonate;

dimethyl 2-n-butyl-2-isobutylmalonate;

diethyl 2-methyl-2-isopropylmalonate; diethyl 2-methyl-2-isobuty!ma!onate and

diethyl 2-isopropyl-2-isobutylmaIonate.

3) Structures of 2,6-dioxoheptandioates having a general formula Ilia and comprising for example:

dimethyl-2,6-dioxaheptandioate;

diethyl-2,6-dioxaheptandioate;

diethyl-2,6-dioxa-3,5-dimethylheptandioate;

diethyl-2,6-dioxa-3,5-diisopropyiheptandioate and

diisopropyl-2,6-dioxa-3,5-diisopropyiheptandioate.

4) Structures of 1 ,3-diethers having a general formula IV and comprising for example:

1 ,1-bis(methoxymethyl)-cyclopentadiene;

,1 -bisfmethoxymethylJ^.S^^-tetramethylcyclopentadiene;

1 ,1-bis(methoxymethyl)-3,4-dicyciopentylcyclopentadiene and

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

5) Structures of 1 ,3-diethers having a general formula V and comprising for example:

9,9-bis(methoxymethyl)fluorene;

9,9-bis(methoxymethyi)-2,3,6,7-tetramethylfluorene;

9,9-bis(methoxymethyi)-2,7-diisopropylfluorene;

9,9-bis(methoxymethyl)-2,7-diisopropylfluorene and

9,9-bis{methoxymethyl)-2,7-dicyklopentylfluorene.

6) Structures of 1 ,8-naphthyl diesters having a general formula VI and comprising for example:

naphthalene-1 ,8-diyl dicyclohexane-carboxylate;

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

8-(cyclohexanecarbonyloxy)naphthalene-1 -yl benzoate;

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

1 ,8-naphthyl-dibenzoate;

1 ,8-naphthyl-di-2-methylbenzoate; 1 ,8-naphthyi-di-3-methylbenzoate and

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

Polyolefins with fluffy morphology can also be prepared using a Ziegler-Natta precatalyst which contains one or more of the selected interna! electron donor compounds described above, and together with them the other internal electron donor compounds from among the ethers and esters. These internal electron donor compounds are supported together with halogen-titanium compounds on a halogen- magnesium carrier.

The preparation of such Ziegler-Natta precatalysts containing selected internal electron donor compounds is well-known from the literature. They are prepared by reaction of an anhydrous halogen-magnesium carrier with alcohol, the supporting of halogen-titanium components on this carrier and subsequently reacting the titanium saturated carrier with selected internal electron donors, even possibly further with other types of internal electron donor. The resulting Ziegler-Natta precatalyst can for example contain 2 - 7 wt% Ti, 10 - 25 wt% Mg and 5 - 30 wt% of the internal electron donor.

b) Thermal treatment of the preferred Ziegler-Natta precatalyst.

In the case of this invention it concerns the thermal treatment of the preferred diether type of Ziegler-Natta precatalyst for the subsequent synthesis of polyolefins with altered particle morphology. The effects of these changes, resulting in the fluffy morphology polymer particles, lead to significant changes in the properties of the resulting polyolefins. The bulk powder density of the resulting poiyolefin is one of the properties which quantitatively and reproducib!y describes these changes in polymer particle morphology. Depending on the composition of the Ziegler-Natta precatalyst, the temperature and duration of its treatment, the composition of the reaction mixture and polymerisation conditions, the bulk powder density of the resulting poiyolefin can be significantly reduced to values of 20 - 300 g/l.

It was described according to the invention that polyolefins with fluffy morphology can be prepared using the preferred diether Ziegler-Natta precatalyst described above, which must be thermally treated according to a specific method. This specific method of thermal treatment of the preferred diether Ziegler-Natta precata!yst is carried out either under reduced pressure (below 1 kPa) or under inert gas flow (e.g. nitrogen) at a temperature higher than 30°C, typically under reduced pressure (below 10 Pa) in a temperature range between 50°C and 150°C, and more preferably under reduced pressure (below 10 Pa) in a temperature range between 90°C and 120°C. It was found that under the given preferred conditions for the specific thermal treatment, that is reduced pressure (below 0 Pa) and raised temperature (90 - 120 ° C), a period for the thermal treatment of the Ziegler-Natta precatalyst longer than 1 minute, preferably 5 minutes to 10 hours, and more preferably 30 minutes to 4 hours, is sufficient. The specific thermal treatment of the Ziegler-Natta precatalyst can of course last more than 10 hours, but the resulting fluffy morphology of polyoleftns prepared on such a thermally treated selected Ziegler-Natta precatalyst will not further change with longer periods (longer than 10 hours), that is the bulk powder density of thus prepared polyolefins will not decrease any further.

This thermal treatment of the Ziegler-Natta precatalyst in a preffered diether

Ziegler-Natta catalyst activated by the cocatalyst tri-n-hexyl-aluminium (THA) for example shows results thus:

1 ) In KAT A: the bulk powder density of polypropylene decreases from 395 g/l for catalyst without thermal treatment to the bulk powder density of 97 g/l with 4 hours of thermal treatment at 105°C under reduced pressure (below 10 Pa), that is to 24.6% of the original value as described in Example 2,

2) In KAT B: the bulk powder density of polypropylene decreases from 345 g/l for catalyst without thermal treatment to the bulk powder density of 87 g/l with 4 hours of thermal treatment at 105°C under reduced pressure (below 10 Pa), that is to 25.2% of the original value as described in Example 3.

Polyolefin particles with fluffy morphology according to the invention are depicted for the thermally treated diether Ziegler-Natta precatalysts KAT A and KAT B in Figs. 1 A and 1 B. c) Synthesis of polyolefins with fluffy morphology on such a thermally treated and activated Ziegler-Natta precatalyst.

It was found that polyoiefin powder, comprising particles having fluffy morphology, according to the invention, can be prepared using the preferred diether Ziegler-Natta precatalyst, which must be thermally treated by the specific method according to the invention. The method of activation of thus prepared Ziegler-Natta precatalyst (to its form capable of polymerisation) further affects the nature of the resulting fluffy morphology of the polyoiefin particles.

Activation of the preferred Ziegler-Natta diether precatalyst includes reaction with an organoaluminium compound (cocatalyst) with the general formula AIR _n Z ₃ . _n , where R is C1-C20 alkyl group, Z is halogen and n is 0, 1 , 2 or 3. Suitable examples of such cocatalysts are trimethylaluminium (TMA), triethy!aluminium (TEA), triisobutylaluminium (TIBA), tri-n-hexyialuminium (THA), tri-iso-hexylaluminium (TIHA), tri-n-octyl-aluminium (TOA) and tri-n-decyl-aluminium (TDA).

It was found that the character of the cocatalyst used to activate the preferred, thermally treated diether Ziegler-Natta precatalyst significantiy influences the character of the fluffy morphology of the resulting polyoiefin. Depending on the cocatalyst structure, the bulk powder density values of the resulting polyoiefin with fluffy morphology vary. The lowest values of the bulk powder density for the resulting polyolefins were reached in the case of the activation of suitable, thermally treated Ziegler-Natta precatalysts by higher cocatalysts such as tri-iso-butylaluminium (TIBA), tri-n-hexylaluminium (THA), tri-iso-hexylaluminium (TIHA) and tri-n-decyl-aluminium (TDA),

For example the reached bulk powder density values of polypropylene prepared on precatalyst KAT B, thermally treated for 4 hours at 105°C under reduced pressure (below 10 Pa) were as follows:

268 g/l in the case of precatalyst activated by cocatalyst TMA,

179 g/l in the case of precatalyst activated by cocatalyst TEA,

100 g/l in the case of precatalyst activated by cocatalyst TIBA,

87 g/l in the case of precatalyst activated by cocatalyst THA and

1 12 g/l in the case of precatalyst activated by cocatalyst TDA,

as described in Example 4. Depending on the polymerisation technology used and the type of diether Ziegler-Natta precatalyst, the suitable amount of organoaluminium compounds added to the polymerisation reactor in a molar ratio to transition metal of diether Ziegier-Natta precatalyst is in the range 10 - 1000 mol/mol, and preferably 30 - 300 mol/mol. The amount of cocatalyst used also had a partial impact on the quality of the resulting polyolefin with fluffy morphology.

For example the reached bulk powder density values of polypropylene prepared on the precatalyst KAT B, thermally treated for 4 hours at 105°C under reduced pressure (below 0 Pa) and activated by the cocatalyst TIBA were as follows:

116 g/l in precatalyst activated at a ratio TIBA Ti = 15 mol/mol,

102 g/l in precatalyst activated at a ratio TIBA/Ti = 50 mo!/mol,

00 g/l in precatalyst activated at a ratio TIBA/Ti = 150 mol/mol,

80 g/l in precatalyst activated at a ratio T!BA Ti = 500 mol/mol and

77 g/l in precatalyst activated at a ratio TIBA/Ti = 1000 moi/mol,

as described in Example 4.

After activation, the preferred, thermally treated diether Ziegler-Natta precatalyst, is able to produce polyolefin with fluffy morphology in the polymerisation of one type of olefin (homopolymerisation) or more types of olefin (copolymerisation or terpolymerisation).

Another optional reaction component present in this polymerisation can be an external electron donor as a modifier of the stereoregularity of the synthesised polyolefin. Suitable structures for such external electron donors are silanes, ethers and esters; for example dimethoxysi!anes are commonly used, such as diisopropyl- dimethoxysiiane, diisobutyl-dimethoxysilane, methyl-cyciohexyl-dimethoxysilane and dicyclopentyl-dimethoxysilane. Depending on the technology used and the type of Ziegler-Natta precatalyst, the molar ratio of external electron donor to the transition metal of Ziegler-Natta precatalyst being fed into the polymerisation reactor, is in the range of 0.5 -100 mol/mol, and the molar ratio of organoaluminium co-catalyst to external electron donor is in the range of 0.5 - 100 mol/mol, more preferably the molar ratio of organoaluminium co-catalyst to an external electron donor is 0.5 - 50 mol/mol.

Another reaction component usually present in this polymerisation is hydrogen, which acts as a regulator of the molecular mass and melt flow index of the resulting polyolefin. Polymerisation with the preferred , thermally treated Ziegler-Natta precatalyst can be carried out in a nonpolar hydrocarbon solvent (e.g. isohexane, heptane), in gaseous monomer (ethylene, propylene, higher 1 -olefins) or monomers, in liquid monomer (propylene, higher -olefins), possibly individual polymerisation phases can be carried out combined in several types of polymerisation environment (e.g. polymerisation in liquid monomer followed by polymerisation in gaseous monomer) under all standard polymerisation conditions. Depending on the polymerisation technology and desired properties of the synthesised polyolefin with fluffy morphology the polymerisation of olefins with selected, thermally treated Ziegler-Natta catalysts can be carried out at temperatures in the range 50 to 120°C and pressures from 0.5 to 10 MPa, while temperatures of 70 to 105°C and pressures of 1to 4 MPa are typical.

In this way various types of polyolefin powder with fluffy morphology can be prepared. The polyolefin powders according to the invention are the products of coordination polymerisation on a Ziegler-Natta catalyst comprising homopo!ymers, copolymers of two and more 1-olefins and mixtures of them prepared in two or more step polymerisation. 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; impact copolymers composed of polypropylene homomatrix and random copolymers of propylene and ethylene, impact copolymers comprising polypropylene homomatrix and random copolymers of ethylene and 1-butene, impact copolymers comprising polypropylene homomatrix and random copolymer of ethylene and 1-hexene, impact copolymers comprising polypropylene homomatrix and random terpolymer of propylene, ethylene and 1-butene, impact copolymers composed of polypropylene homomatrix and random terpolymer of propylene, ethylene and 1-hexene.

The most preferred polyolefin powders according to the invention are isotactic polypropylene (i-PP), random copolymers of propylene with ethylene and impact copolymers consisting of polypropylene homomatrix and random copolymer of propylene and ethylene.

This method of preparation of polyolefin according to the invention on a specific thermally treated diether Ziegler-Natta precatalyst activated by the cocatalyst THA gives results for example as follows: 1 ) In the polyolefin prepared on the precatalyst KAT A activated for polymerisation by the cocatalyst THA the bulk powder density decreased from 276 g/l for the catalyst without thermal treatment to 99 g/l for the catalyst thermally treated for 4 hours at 105°C under reduced pressure (below 10 Pa) in the case of the synthesis of the homopolymer polyethylene in the solvent hexane, i.e. to 35.9% of the original value as described in Example 6.

2) In the polyolefin prepared on the precatalyst KAT A activated for polymerisation by the cocatalyst THA the bulk powder density decreased from 395 g/l for the catalyst without thermal treatment to 97 g/l for the catalyst thermally treated for 4 hours at 105°C under reduced pressure (below 10 Pa) in the case of the synthesis of the homopolymer polypropylene in gaseous propylene, i.e. to 24.6% of the original value as described in Example 1.

3) In the polyolefin prepared on the precatalyst KAT A activated for polymerisation by the cocatalyst THA the bulk powder density decreased from 415 g/l for the catalyst without thermal treatment to 61 g/l for the catalyst thermally treated for 4 hours at 105°C under reduced pressure (below 10 Pa) in the case of synthesis of the homopolymer polypropylene in liquid propylene, i.e. to 14.7% of the original value as described in Example 1.

4) in the polyolefin prepared on the precatalyst KAT A activated for polymerisation by the cocatalyst THA the bulk powder density decreased from 364 g/l for the catalyst without thermal treatment to 84 g/l for the catalyst thermally treated for 4 hours at 105°C under reduced pressure (below 10 Pa) in the case of the synthesis of the copolymer of ethylene and propylene in the 2 step polymerisation made up of the homopolymerisation of propylene and the random copolymerisation of propylene with ethylene, i.e. to 23.1% of the original value as described in Example 7.

5) In the polyolefin prepared on the precatalyst KAT A activated for polymerisation by the cocatalyst THA the bulk powder density decreased from 411 g/l for the catalyst without thermal treatment to 128 g/l for catalyst thermally treated for 4 hours at 105°C under reduced pressure (below 10 Pa) in the case of the synthesis of the terpolymer of ethylene, propylene and 1-butene in the 2 step polymerisation made up of the homopolymerisation of propylene and the random copolymerisation of ethylene with 1-butene, i.e. to 31.1% of the original value as described in Example 8, This invention further describes possible uses of thus prepared polyolefins with fluffy particles in each application:

d) Poiyolefin with fluffy morphology as a material suitable for the sorption of hydrophobic liquids.

The poiyolefin with fluffy morphology, prepared according to the method given above, is a material based on crude oil having hydrophobic nature. Due to its morphology, which can generally be described as fluffy, it is characterised by a large amount of varied voluminous inner spaces. Given that these inner spaces of the fluffy poiyolefin particles are easily accessible; this material is suitable for the sorption of hydrophobic liquids, such as crude oil and its products, e.g. mineral oil. The sorptive capacity of these materials significantly increases with decreasing bulk powder density and reaches up to six times the actual mass of these polyolefins, as documented in Example 9. This value is comparable with absorption values of non- woven polypropylene textiles and greatly exceeds absorption values for standard inorganic sorptive materials, which reach 1 - 2 g oil / g sorbent {e.g. in the case of expanded and hydrophobised perlite, which is the amorphous aluminium silicate of volcanic origin).

It is clear from Example 9 that decreasing bulk powder density and thus increasing fluffy character of the resulting polyolefins is directly related to their sorptive capacity regardless of the type of precatalyst and the cocatalyst used for its activation, as shown in Figure 2.

The sorptive capacity of these materials can, depending on the further decrease in their bulk powder density, reach even higher values for the amount of hydrophobic liquids absorbed than those given in Example 9. These can reach almost nine times the actual mass of these polyolefins. The reduction of the bulk powder density of these materials and with it the accompanying increase in their fluffy character is dependent on the suitable combination of preconditions determining this property, which include the choice of precatalyst (influence of the type of internal electron donor), the thermal treatment of this precatalyst (influence of temperature of treatment, duration of treatment, reduced pressure conditions), character of activation of this precatalyst (influence of the type of cocatalyst), polymerisation mode (polymerisation in liquid monomer, in gaseous monomer, or in a non-polar hydrocarbon solvent), polymerisation components (concentration of cocatalyst, external electron donor, hydrogen) and polymerisation conditions (polymerisation temperature, polymerisation pressure, duration of polymerisation). A suitable combination of these preconditions determining the bulk powder density of poiyolefin powder with fluffy morphology can achieve the resulting bulk powder density of about 20 g/l, which corresponds to a sorptive capacity nearing nine times the actual mass of these polyolefins.

The property of absorbance of hydrophobic liquids in these materials is reversible; that is the absorbed substance can subsequently be separated by centrifuging and a poiyolefin powder with fluffy morphology prepared according to this invention can be reused for the same purpose. For example:

1 ) During 5 times repeated sorption and desorption of mineral oil in the homopolymer polypropylene with the bulk powder density of 87 g/l, prepared on the catalytic system KAT B / THA (KAT B was treated for 4 hours at 105°C under reduced pressure below 10 Pa) in individual cycles of sorption and desorption 96.7%, 96.8%, 96.8%, 96.9% and 96.7% of the absorbed amount of mineral oil was removed, as documented in Example 10.

2) During 5 times repeated sorption and desorption of crude oil in the homopolymer polypropylene with the bulk powder density of 87 g/l, prepared on the catalytic system KAT B / THA (KAT B was treated 4 hours at 105°C under reduced pressure below 10 Pa) in individual cycles of sorption and desorption 96.4%, 96.3%, 96.2%, 96.2% and 96.2% of the absorbed amount of crude oil was removed, as documented in Example 10.

e) Polyolefins with fluffy morphology as the material suitable for thermal insulation.

Synthetic polymers, such as polypropylene, are in themselves poor thermal conductors and thus good thermal insulators. In the case of polyolefins with fluffy morphology according to the invention, prepared according to the method described above, high content of air is enclosed in the interstices within the fibres of individual particles. Since air is one of the worst thermal conductors (one of the best thermal insulators), even material made up of these fluffy particles has significantly reduced thermal conductivity and so is suitable for thermal insulation. With decreasing of the bulk powder density of these materials there is an increase in the proportion of air in their particles, which leads to the decrease in heat conductivity and an increase in thermal insulating capacity.

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

From Example 11 it is clear that decreasing bulk powder density and thus increasing fluffy character of the resulting polyolefins, is directly related to their heat conductivity and thus their thermal insulating capacity, regardless of the type of precatalyst and the cocatalyst used for its activation, as depicted in Figure 3. Thermal conductivity in the case of polymer materials with the lowest bulk powder density reaches values of about 0.040 W/(m*K). These values are completely comparable with the thermal conductivity of EPS (expanded polystyrene), which reaches values in the range 0.043 - 0.035 W/(m ^* K) depending on the density of the EPS (the higher the density of the EPS, the lower the thermal conductivity).

The thermal insulating ability of these materials, depending on the further decreases in their bulk powder density, can reach even lower values of heat conductivity than those given in Example 11. These can approach the heat conductivity of about 0.030 W/(m*K). The reduction in the bulk powder density of these materials and the accompanying increase in their thermal insulating capacity is dependent on the suitable combination of preconditions determining this property, which include the choice of precatalyst (influence of the type of internal electron donor), the thermal treatment of this precatalyst (influence of temperature of treatment, duration of treatment, reduced pressure conditions), character of activation of this precatalyst (influence of the type of cocatalyst), polymerisation mode (polymerisation in liquid monomer, in gaseous monomer, or in a non-polar hydrocarbon solvent), polymerisation components (concentration of cocatalyst, external electron donor, hydrogen) and polymerisation conditions (polymerisation temperature, polymerisation pressure, duration of polymerisation). A suitable combination of these preconditions determining the bulk powder density of polyolefins with fluffy morphology can achieve the resulting bulk powder density of about 20 g/l, which corresponds to a decrease in heat conductivity by 60% in comparison with polypropylene with classical particle morphology and the bulk powder density of 447 g/l.

f) Polyolefins with fluffy morphology as carriers of additives and pigments.

Particles of polyolefins with fluffy morphology contain, in contrast to the standard poiyolefin particles, large amounts of varied voluminous intrafibrous space. This free particle volume can be used so that during mixing at laboratory temperature (23 ± 2°C) there is penetration of additive (antistatic agents, nucleation reagents, lubricants, etc.) or pigment (organic or inorganic) into polyolefin particles. A mixture created in this way makes it possible to manufacture additive or pigment concentrates with the higher concentration of active ingredients (antistatic agents, nucleation reagents, lubricants, etc.) or pigments (organic or inorganic) than is possible when using polyolefins with standard polyolefin particles. For example with the use of polypropylene with fluffy morphology prepared according to this invention it is possible to increase the resulting additive concentration in the polyolefin, such as antistatic agents based on esters of glycerol with higher fatty acids, to as much as double compared to standard polymer powders or granulates, as described in Example 12 or to improve the dispersal of organic pigments in polyolefins when preparing organic pigment concentrates in polyolefin, which is shown in less of an increase in pressure before the filter during a filter pressure test, approximately half of that for standard polymer powders, as described in Example 13.

Preferred embodiments of the invention

Examples

Thermal treatment of the Ziegler-Natta precatalyst Procedure for thermal treatment of selected Ziegler-Natta precatalyst was carried out as follows:

For thermal treatment of the Ziegler-Natta precatalysts KAT A, KAT B and KAT C with 1,3-diether internal electron donor, namely 2-isopropyl-2-isobutyl-1,3- dimethoxypropane, the apparatus was used consisting of glass flasks with Teflon valve closures, the glycerine bath linked to the thermostat and the vacuum pump. During thermal treatment of the Ziegler-Natta precatalyst the precatalyst was added in powder form in amounts of about 1 g under the protective atmosphere of nitrogen in the drybox to a 50 ml glass flask and sealed with the Teflon valve closure. Subsequently the glass flask with the precatalyst in powder form was transferred to the special apparatus and connected to the nitrogen source. Under the protective flow of nitrogen the Teflon valve closure was removed and replaced by the stopper with the seal. The nitrogen flow was stopped and pressure in the flask reduced with the aid of the vacuum pump to below 10 Pa. After reaching the required underpressure the flask with precatalyst was immersed in the glycerine bath heated to the preset temperature. In this set-up, the precatalyst was thermally treated at the temperature of the bath, for the set period and under reduced pressure. After the set period for thermal treatment of the precatalyst evacuation was ended, nitrogen was run into the flask to atmospheric pressure and under the constant flow of nitrogen the flask was cooled to laboratory temperature. After reaching laboratory temperature the flask was sealed with the Teflon valve closure. This thermally treated Ziegler-Natta precatalyst was prepared for use in polymerisation to prepare the polyolefin with fluffy morphology.

Using this method of thermal treatment: Ziegler-Natta precatalyst KAT A with the 1,3-diether internal electron donor was treated at 60°C, 90°C, 105°C, 120°C and 150°C, Ziegler-Natta precatalyst KAT B with the 1 ,3-diether internal electron donor at 90°C, 105°C and 120°C and Ziegler-Natta precatalyst KAT C with the 1 ,3-diether internal electron donor at 105°C. Preparation of polyolefin powder comprising particles with fluffy morphology and its utilization

The procedure for the preparation of polyolefins with fluffy morphology and their use is described in following examples. The model preparation was carried out using 3 Ziegler-Natta precatalysts KAT A, KAT B and KAT C with 1 ,3-diether internal electron donor, namely 2-isopropyl-2-isobutyl-1,3-dimethoxypropan, nonetheless the discovery of the procedure for the preparation of polyo!eftns with fluffy morphology is not limited only to this type of Ziegler-Natta precatalyst, but includes also combinations of this precatalyst with other types of internal electron donor, as described above. 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 different quantities of intemal donor supported on MgCl ₂ carrier.

The resulting polyolefin comprises particles with fluffy morphology, consisting of fibers of polyolefin having a diameter from 10 to 50 μι ^η and the length from 50 to 1000 μπν Fibers of specific polyolefin powder particles are variously intertwined and create three-dimensional structure with interstices of different size, depending on the number, diameter and length of fibers. These interstices within the fibres contain air (optionally it can be filled with another substance). The interstices within the fibres have an important role in absorption and insulation ability of the polymer formed by these particles. Particles of polyolefin with a fibrous structure in the form of powder preferably reach macroscopic size of 0.2 to 2 mm. These particles form a polyolefin powder whose bulk density ranges from 50 to 300 g/l, from the viewpoint of absorption and thermal- insulating properties it seems preferable range from 50 to 200 g/l.

The polymerisation of propylene was carried out in the discontinuous stainless steel reactor of volume 1.8 L equipped with spiral stirrer. The reactor was connected to the thermostatic circuit enabling external regulation of its intemal temperature. The amount of propylene added before and during polymerisation was measured on the basis of the decline in the mass of the supply pressure vessel with propylene, in the case of other monomers and hydrogen on the basis of integration of their mass flow. Pressure in the reactor was measured with the digital manometer and temperature in the lower (Tr) and upper parts (Tr2) of the reactor with type E thermocouples.

During the cleaning procedure the reactor was flushed with a stream of nitrogen for about 30 min at 95°C. Subsequently a pressure test for tightness was carried out (30 min at 95°C and 3.0 MPa). After pressure testing the reactor was cooled to 40°C, stirring was halted and cocatalyst and where required the external electron donor were added. During addition of this polymerisation ingredient the internal space of the reactor was protected from contamination by the stream of nitrogen. After addition of ail ingredients the reactor was sealed and filled up with the correct amount of monomer and hydrogen. The partial pressure of the remaining nitrogen in the reactor was about 0.1 MPa (a).

Polymerisation commenced with feeding of the precatalyst into the reactor pushed by liquid propylene at temperature of 40°C. The subsequent approach to polymerisation temperature and pressure took less than 5 min. The speed of stirring before and during polymerisation was 500 rpm in the case of polymerisation in gaseous propylene or in the gaseous mixture of monomers and 250 rpm in the case of polymerisation in liquid propylene. The composition of the vapour phase in the reactor was analysed every 10 min throughout the polymerisation using the gas chromatograph. Polymerisation was carried out at temperature of 75°C and pressure of 2.2 MPa in the case of homopolymerisation in gaseous propylene and at temperature of 70°C and pressure of 3.1 MPa in the case of homopolymerisation in liquid propylene. The polymerisation period was mostly set as 60 min after achieving polymerisation conditions.

The whole process of initiation and actual polymerisation was controlled and monitored by computer. After reaching the required polymerisation temperature and pressure the polymerisation conditions were subsequently maintained at the required level until completion of polymerisation. In the case of homopolymerisation in gaseous propylene constant pressure was maintained by continually adding monomer, and in the case of copolymerisation by continual dosing with the mix of monomers of the given ratio. Depending on the consumption of propylene, in the case of polymerisation in gaseous propylene, hydrogen was continually added during polymerisation to maintain its constant concentration in the vapour phase throughout polymerisation.

On completion of polymerisation the reactor was carefully depressurised and the remnants of monomer and cocatalyst removed by flushing several times with nitrogen at 0.5 MPa. Subsequently the polymer powder was removed from the reactor, weighed and dried for 2 hours at 70°C in a vacuum drier. To establish the influence of the treatment and activation of the selected Ziegler- Natta precatalyst and influence of the subsequent polymerisation conditions on the properties of synthesised poiyolefins the standard analytical methods were used:

The melt flow range of polypropylene was measured according to standard ISO 1133(E) at 230°C and under a load of 216 N. The melt flow range of polyethylene was measured according to the same standard at a temperature of 190°C and under a load of 49 N. The content of polypropylene soluble in cold xylene (XS) was determined according to standard ISO 6427(E). The bulk powder density of polymer powders was determined according to the standard ISO 60(E).

Example 1

Synthesis of homopolymer polypropylene with fluffy morphology.

The synthesis of the homopolymer polypropylene in Example 1 was carried out on the ,3-diether precatalyst KAT A, both without thermal treatment and thermally treated at a temperature of 05°C, for 4 hours, at pressure reduced below 10 Pa. In both cases this precatalyst was activated for polymerisation by the cocatalyst THA.

Polymerisation in gaseous propylene was carried out under these conditions: polymerisation temperature 75°C, polymerisation pressure 2.2 MPa (g), duration of polymerisation 60 min after achieving polymerisation conditions, Al Ti = 150 mol/mo!, without addition of the external electron donor, H2 - initial dose - 10 mmol, H2/C3 = 5.0 mmol/mol.

Polymerisation in liquid propylene was carried out under these conditions: polymerisation temperature 70°C, polymerisation pressure 3.1 MPa (g), duration of polymerisation 60 min after achieving polymerisation conditions, Al/Ti = 500 mol/mol, without addition of the external electron donor, H2 - initial dose - 15 mmol, H2/C3 = 5.5 - 5.7 mmol/mol (in the gas phase).

The resulting activity of the catalyst and characteristics of the polymers are given for individual cases in Table 1 : Table 1

T he rmal treatme nt Caia lyst Catalyst Melt flow rate X.S. Bulk powder of the precatalyst system activity (21.6 N) density

kg/(g* ) g/10 min wt.% g/l

Polymerisation in liquid propylene

without treatme nt KAT A / THA 36.0 6.0 3.2 415

105°C - 240 min KAT A / THA 2.4 9.5 4.6 61

105°C - 240 min KAT B / THA 1.8 13.8 8.3 48

Polymerisation in gaseous propylene

without treatment KAT A / THA 28.0 9.0 2.8 395

105°C - 240 min KAT A / THA 3.8 8.8 3.2 97

105°C - 240 min KAT B / THA 4.3 14.6 7.5 87

As described in Tabie 1, thermal treatment of precatalyst KAT A at pressure reduced below 10 Pa (4 hours at 105°C) led, after activation by THA, to the significant reduction in the bulk powder density of polypropylene prepared on it, both during polymerisation in liquid polymer, where the bulk powder density of polypropylene decreased from 415 g/t to 61 g/l, and during polymerisation in gaseous propylene, where the bulk powder density of polypropylene decreased from 395 g/l to 97 g/l. This fact is due to the change in the character of polypropylene particles from standard (round to oval shape) to fluffy morphology (fibrous character). Thermal treatment of the precatalyst at pressure reduced below 10 Pa (4 hours at 105°C) led also to a significant reduction in the activity of the catalyst, both during polymerisation in liquid polymer, where the activity of the catalyst fell from 36.0 kg/(g ^* h) to 2.4 kg/(g*h), and during polymerisation in gaseous propylene, where the activity of the catalyst fell from 28.0 kg/(g ^* h) to 3.8 kg/(g*h).

Example 2

Effect of temperature during thermal treatment of the precatalyst under conditions of reduced pressure on the morphology of the polypropylene

The synthesis of the homopolymer polypropylene in Example 2 was carried out on the 1 ,3-diether precatalyst KAT A, both without thermal treatment and thermally treated for 4 hours, at pressure reduced below 10 Pa, at temperatures of 60°C, 90°C, 105°C, 120°C and 15CTC. In all cases this precatalyst was activated for polymerisation by the cocatalyst THA.

Polymerisation was carried out in gaseous propylene under these conditions: polymerisation temperature 75°C, polymerisation pressure 2.2 MPa (g), duration of polymerisation 60 min after achieving polymerisation conditions, Al/Ti = 150 mol/mol, without addition of an external electron donor, H2 - initial dose - 10 mmol, H2/C3 = 4.9 - 5.3 mmol/mol.

The resulting activity of the catalyst and characteristics of the polymers are given for individual cases in Table 2:

Table 2

Thermal treatment Catalyst Catalyst Melt flow rate X.S. Bulk powder of the precatalyst system activity (21.6 N) density

kg/(g*h) g/10 min wt.% ≠

Polymerisation in gaseous propylene

without treatment 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 - 240 min 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"C - 240 min KATA / THA 2.1 10.0 3.8 131

150°C - 240 min KAT A / THA 0.4 n.d. 3.4 187

In Table 2 the influence of temperature during thermal treatment of the precatalyst KAT A under reduced pressure on the bulk powder density of polypropylene, prepared on this treated precatalyst, activated by the cocatalyst THA, is described. From Table 2 it is clear that the increase in temperature from 60°C to 105°C of thermal treatment of the precatalyst for 4 hours at pressure reduced below 10 Pa, leads to the significant decrease in the bulk powder density of polypropylene from 251 g/l to 97 g/I. The further increase in temperature from 105°C to 150°C leads rather to the increase in the bulk powder density of polypropylene from 97 g/l to 187 g/l. The rate of decrease in the bulk powder density reflects the increase in the fibrous character (fluffy morphology) of the polypropylene particles. Thermal treatment of the precatalyst under reduced pressure also leads with increasing temperature of the treatment to the significant decrease in the activity of the catalyst. An increase in the temperature of treatment of the precatalyst from 60°C to 150°C leads to a decrease in activity of the catalyst from 8.6 kg/(g*h) to 0.4 kg/(g*h). Example 3

Influence of the duration of thermal treatment of the precatalyst under reduced pressure on the morphology of polypropylene.

The synthesis of the homopoiymer polypropylene in Example 3 was carried out on the 1 ,3-diether precatalyst KAT B, both without thermal treatment and thermally treated at temperature of 105°C, at pressure reduced below 10 Pa, for 5 minutes, 15 minutes, 30 minutes, 60 minutes, 150 minutes and 240 minutes. In all cases this precatalyst was activated for polymerisation by the cocatalyst THA.

Polymerisation was carried out in gaseous propylene under these conditions: polymerisation temperature 75°C, polymerisation pressure 2.2 MPa (g), duration of polymerisation 60 min after achieving polymerisation conditions, Al/Ti = 150 mol/mol, without addition of an external electron donor, H2 - initial dose - 10 mmol, H2/C3 = 4.8 - 5.2 mmol/mol.

The resulting activity of the catalyst and characteristics of the polymers are given for individual cases in Table 3:

Table 3

Thermal treatment Catalyst Catalyst Melt flow rate X.S. Bulk powder of the precatalyst system activity (21.6 N) density

kg/(g ^* h) g/10 min wt.% ≠

Polymerisation in gaseous propylene

without treatment KAT B / THA 28.6 13.6 5.6 345

105°C - 5 min KAT B / THA 20.8 13.9 6.3 171

105°C - 15 min KAT B / THA 13.0 12.9 6.3 172

105°C - 30 min KAT B / THA 10.8 12.9 6.6 104

105*C - 60 min KAT B / THA 10.5 15.3 6.9 93

105°C - 150 min KAT B / THA 5.8 15.1 7.5 84

105°C - 240 min KAT B / THA 4.3 14.6 7.5 87

In Table 3 the influence of the duration of thermal treatment of the precatalyst KAT B at 105°C at pressure reduced below 10 Pa on the bulk powder density of polypropylene prepared on a thus prepared precatalyst, activated by the cocatalyst THA, is described. From Table 3 it is clear that the increase in duration of thermal treatment (at temperature of 105°C, at pressure reduced below 10 Pa) of the precatalyst KAT B from 5 to 240 minutes leads to a significant decrease in the bulk powder density of polypropylene from a value of 171 g/l to 87 g/l. The rate of the decrease in bulk powder density reflects the increase in fibrous character (fluffy morphology) of the polypropylene particles. The influence of duration of thermal treatment of the precatalyst KAT B at 105°C under reduced pressure also shows the significant decrease in the activity of the catalyst. An increase in duration of treatment of the precatalyst from 5 to 240 minutes leads to the decrease in activity of the catalyst from 20.8 kg/(g*h) to 4.3 kg/(g*h).

Example 4

Influence of type of cocatalyst, and its concentration during activation of the precatalyst, on the morphology of polypropylene.

The synthesis of the homopo!ymer polypropylene in Example 4 was carried out on the 1,3-diether precatalyst KAT B that had been thermally treated at temperature of 105°C, for 4 hours, at pressure reduced below 10 Pa. This precatalyst was in individual cases activated for polymerisation by these cocatalysts: trimethylaluminium (T A), triethylaluminium (TEA), triisobutylaluminium (TIBA), trihexylaluminium (THA) and tridecylaluminium (TDA).

Polymerisation was carried out in gaseous propylene under these conditions: polymerisation temperature 75°C, polymerisation pressure 2.2 MPa (g), duration of polymerisation 60 min after achieving polymerisation conditions, Al Ti = 50 (activation by TMA and TEA), Al/Ti = 15, 50, 150, 500, 1000 (activation by TIBA), Al Ti = 150 (activation by THA, TDA), without addition of the external electron donor, H2 - initial dose - 10 mmol, H2/C3 = 4.4 - 5.2 mmol/mol.

The resulting activity of the catalyst and characteristics of the polymers are given for individual cases in Tables 4a and 4b: Table 4a

Thermal treatment Catalyst Catalyst Melt flow rate X.S. Bulk powder of the precatalyst system activity (21.6 N) density

kg/(g ^* ) g/10 min wt.% g/i

Polymerisation in gaseous propylene

105°C - 240 min KAT B / TNIA 11.4 24.7 6.8 268

105°C - 240 min KAT B / TEA 11.6 14.8 5.7 179

105°C - 240 min KAT B / TIBA 8.6 10.9 6.3 100

105°C - 240 min KAT B / THA 4.3 14.6 7.5 87

105°C - 240 min KAT B / TDA 2.2 13.8 8.0 112

Table 4b

Thermal treatment Catalyst Al/Ti Catalyst Melt flow rate x.s. Bulk powder of the precatalyst system ratio activity (21.6 N) density

mol/mol kg/(g*h) g/10 min wt.% g/i

Polymerisation in gaseous propylene

105 ^c C - 240 min KAT B / TIBA 15 5.2 18.0 7.8 116

105°C - 240 min KAT B / ΠΒΑ 50 7.2 12.6 7.2 102

105°C - 240 min KAT B / TIBA 150 8.6 10.9 6.3 100

105°C - 240 min KAT B / TIBA 500 8.2 10.2 5.6 80

105°C - 240 min KAT B / TIBA 1000 8.1 10.9 5.4 77

In Table 4a the influence of the character of activation (cocatalysts T A, TEA, TIBA, THA and TDA) of precatalyst KAT B, treated for 4 hours at 105°C at pressure reduced below 10 Pa, on the bulk powder density of polypropylene prepared on this activated catalyst, is described. It is clear from Table that the nature of the activation of the precatalyst significantly influences the resulting bulk powder density of polypropylene and thus also the fibrous character of the fluffy morphology of polypropylene particles. It is also apparent from Table 4a that with increasing alkyl length in the cocatalyst the bulk powder density of the resulting polypropylene gradually decreases and the minimum of 87 g/l is reached with activation by the cocatalyst THA. Correspondingly the activity of the catalyst decreases, reaching a lowest value of 2.2 kg/(g ^* h) in the case of activation by the cocatalyst TDA. Example 5

Influence of the concentration of external electron donor on the morphology of polypropylene.

The synthesis of the homopo!ymer polypropylene in Example 5 was carried out on the 1 ,3-diether precataiyst KAT A thermally treated at 105°C, for 4 hours, at pressure reduced below 10 Pa. In all cases this precataiyst was activated for polymerisation by the cocatalyst THA.

Polymerisation was carried out in gaseous propylene under these conditions: polymerisation temperature 75°C, polymerisation pressure 2.2 MPa (g), duration of polymerisation 60 min after achieving polymerisation conditions, Al/Ti = 150, Si/Ti = 0 and 5, H2 - initial dose - 10 mmoi, H2/C3 = 5.2 - 5.3 mmol/mol.

The resulting activity of the catalyst and characteristics of the polymers are given for individual cases in Table 5:

Table 5

Thermal treatment Catalyst Si/Ti Catalyst Melt flow rate x.s. Bulk powder of the precataiyst system ratio activity (21.6 N) density

mol/mol kg/(g* ) g/10 min wt.% ≠

Polymerisation in gaseous propylene

105°C - 240 min KAT A / THA 0 4.0 9.8 3.5 115

105°C - 240 min KAT A / THA 5 1.1 6.0 2.2 136 The influence of the concentration of external electron donor on the bulk powder density of polypropylene is described in Table 5. This concerned polymerisations on the thermally treated precataiyst KAT A (thermal treatment at 105°C for 4 hours under reduced pressure), which was activated by the cocatalyst THA. From Table 5 it is clear, that the presence of the external electron donor and its concentration has only minor influence on the bulk powder density. Example 6

Synthesis of the homopolymer polyethylene with fluffy morphology. The synthesis of the homopolymer polyethylene in Example 6 was carried out on the 1 ,3-diether precatalyst KAT A, both non thermally treated and then thermally treated at temperature of 105°C, for 4 hours, at pressure reduced below 10 Pa. In all cases this precatalyst was activated for polymerisation by the cocatalyst THA.

Polymerisation of gaseous ethylene was carried out in isohexane (500 ml) under these conditions: polymerisation temperature 65°C, polymerisation pressure 1.2 MPa (g), duration of polymerisation 60 min after achieving polymerisation conditions, Al/Ti = 200, without addition of the external electron donor, H2 (initial dose) - 200 mmol.

The resulting activity of the catalyst and characteristics of the polymers are given for individual cases in Table 6:

Table 6

Thermal treatment Catalyst Catalyst Melt flow rate Bulk powder

of the precatalyst system activity (21.6 N) density

kg/(g ^* h) g/10 min ≠

Polymerisation in gaseous ethylene

without treatment KAT A / THA 2.5 0.178 276

105°C - 240 min KAT A / THA 0.7 0.034 99

As described in Table 6, thermal treatment of the precatalyst at pressure reduced below 10 Pa (4 hours at 105°C) led to a significant reduction in the bulk powder density of polyethylene prepared on it (polymerisation in isohexane), with the bulk powder density of polyethylene decreasing from 276 g/l to 99 g/l. This result is linked to the change in polyethylene particle morphology from standard to fluffy, as described above. Thermal treatment of the precatalyst at pressure reduced below 10 Pa (4 hours at 105°C) also led to the reduction in the activity of the catalyst from 2.5 kg/{g ^* h) to 0.7 kg/(g*h). Example 7

Synthesis of the copolymer of ethylene and propylene with fluffy morphology.

The synthesis of the copolymer of ethylene and propylene in Example 7 was carried out on the 1 ,3-diether precatalyst KAT A thermally treated at temperature of 105°C, for 4 hours, at pressure reduced below 10 Pa. This precatalyst was activated for polymerisation by the cocatalyst THA.

Polymerisation was carried out in 2 steps:

In the first step homopolymerisation in gaseous propylene was carried out for 30 minutes under these conditions: polymerisation temperature 75°C, polymerisation pressure 2.2 MPa (g), Al/Ti = 150, without addition of an external electron donor, H2 (initial dose) - 10 mmo , H2/C3 - 5.0 mmol/mol.

In the second step random copolymerisation of ethylene with propylene was carried out for 30 minutes in the gas phase at polymerisation temperature of 75°C. This copolymerisation was carried out at two different ratios C2/C3:

a) polymerisation pressure 2.25 MPa (g), dose C2/C3: 2.4 g C2 / 100 g C3, b) polymerisation pressure 2.30 MPa (g), dose C2/C3: 4.8 g C2 / 100 g C3. The resulting activity of the catalyst and characteristics of the polymers are given for individual cases in Table 7:

Table 7

Thermal treatment Catalyst Ethylene H2/C3 C2/C3 Ethylene Catalyst Melt flow rata X.S. Bulk powder of the precatalyst system flow 2nd step 2nd step content activity (21.6 N) density

g C2/l00g C3 mmol/mol mmol/mol wt.¾ kg/(g*h) g/ 0 min wt.% g/i

2-steps olymerization: 1st step - propylene homopolym., 2nd step - ethylene and propylene copolym.

without treatment KAT A / THA 2.4 5.1 12.7 1.5 18.1 7.5 5.0 364

10S°C - 240 min KAT A / THA 2.4 4.9 20.0 2.9 6.7 7.4 8.9 84

2-steps polymerization: 1st step - propylene homopolym., 2nd step - ethylene and propylene copolym.

without treatment KAT A / THA 4.8 4.8 23.8 3.3 28.7 6.4 10.6 399

105"C - 240 min KAT A I THA 4.8 4.9 33.6 5.6 7.9 4.6 21.3 136

As described in Table 7, thermal treatment of the precatalyst KAT A at pressure reduced below 10 Pa (4 hours at 105°C) led to the significant reduction in the bulk powder density of the copolymer of ethylene and propylene prepared on it. On adding ethylene in the amount 2.4 g per 00 g propylene in the second step of polymerisation the bulk powder density of the copolymer decreased from a value of 364 g/l to 84 g/l. On adding ethylene in the amount 4.8 g per 100 g propylene in the second step of polymerisation the bulk powder density of the copolymer decreased from a value of 399 g/l to 136 g/l. This result is linked to the change in the copolymer particle morphology to fluffy, as described above. Thermal treatment of the precatalyst at pressure reduced below 10 Pa (4 hours at 105°C) led in both cases to reduced activity of the catalyst to about a third and to an increase in the resulting content of ethylene in the copolymer and content of xylene soluble fraction (X.S.) in the copolymer to about double.

Example 8

Synthesis of the ethylene-propylene-butene terpolymer with fluffy morphology.

Synthesis of the terpolymer of ethylene, propylene and butene in Example 8 took place on the 1 ,3-diether precatalyst KAT A thermally treated at temperature of 105°C, for 4 hours, at pressure reduced below 10 Pa. This precatalyst was activated for polymerisation by the cocatalyst THA.

Polymerisation took place in 2 steps:

In the first step homopolymerisation in gaseous propylene took 30 minutes under these conditions: polymerisation temperature 75°C, polymerisation pressure 2.2 Pa (g), Al/Ti = 150, without addition of the external electron donor, H2 (initial dose) - 30 mmo!, H2/C3 = 16 mmol/mol.

In the second step random copolymerisation of ethylene and -butene lasted 30 minutes at polymerisation temperature of 75°C and polymerisation pressure 0.6 MPa

(g)- The resulting activity of the catalyst and characteristics of the polymers are given for individual cases in Table 8:

Table 8

[Thermal treatment Catalyst Ethylene Propylene Butene Catalyst Melt flow rate X.S. Bulk powder of the precatalyst system content content content activity (21.6 N) density

wt.% wt.% wt.% kg/tg'h) g/10 min wt.%

2 -steps polymerization: 1st step - propylene homopolym., 2nd step - ethylene and 1-butene copolym.

without treatment KAT A / THA 28.7 70.0 1,3 20.6 7.0 1.8 411

105°C - 240 min KAT A / THA 50.8 47.8 1.5 4.1 6.3 1.4 128 As described in Table 8, thermal treatment of precatalyst KAT A under reduced pressure (4 hours at 105°C) led to the significant reduction in the bulk powder density of the terpolymer ethylene-propylene-butene prepared on it. The bulk powder density of the terpolymer decreased from a value of 41 1 g/l to 128 g/l. This result is connected to the change in the terpolymer particle morphology to fluffy, as described above. Thermal treatment of the precatalyst at pressure reduced below 0 Pa (4 hours at 105°C) led likewise to a reduction in the activity of the catalyst from a value of 20.6 kg/(g ^* h) to 4.1 kg/(g ^* h).

Example 9

Influence of the fluffy morphology of polypropylene on the absorption of oil and crude oil.

In studying the absorbance of oil, polypropylene prepared on the 1 ,3-diether precatalysts KAT A and KAT B, both without thermal treatment and thermally treated at temperature of 105°C, for 4 hours, at pressure reduced below 10 Pa, was used. These precatalysts were activated for polymerisation by the cocatalysts TEA, TIBA and THA in the case of the sorption of mineral oil, as shown in Table 9a and the cocatalysts TIBA and THA in the case of the sorption of crude oil, as shown in Table 9b. In studying the sorptive capacity of these polyotefins the absorbed media were: white medicinal oil (paraffinum liquidum) with density of 870 g/dm ³ (at 5°C) - mineral oil and medium heavy crude oil with density of 863 g/dm ³ (at 15°C).

The procedure for establishing the absorbance of oil was as follows:

1 ) Polyolefin with the given bulk powder density was accurately weighed in amount of 4.0+ 0.1 g and was left for 10 minutes mixed with 100 ml medicinal white oil or 100 ml medium heavy crude oil and occasionally stirred (3x in 10 minutes).

2) Subsequently it was filtered for 30 minutes on the filter with pore size 0.2 mm. This period was sufficient to filter off any mineral oil or crude oil not absorbed by the polymer. The resulting polymer with absorbed mineral oil or crude oil was weighed and the amount of absorbed mineral oil or crude oil was calculated from the resulting mass.

The resulting amounts of absorbed mineral oil or crude oil for individual cases is shown in Tables 9a and 9b: Table 9a

Thermal treatment Catalyst Al/Ti Bulk powder Absorbance

of the precataiyst system ratio density of mineral oil

mol/mol g/l g oil / g PP

Polymerisation in gaseous propylene

without treatment KAT A / TEA 50 447 0.8

without treatment KAT B / THA 150 395 0.8

105°C - 240 min KAT A / TEA 50 242 1.9

105°C - 240 min KAT A / TIB A 150 149 3.2

105°C - 240 min KAT A / THA 150 115 4.6

105°C - 240 min KAT B / THA 150 87 5.7

Table 9b

Thermal treatment Catalyst Al/Ti Bulk powder Absorbance

of the precataiyst system ratio density of crude oil

mol/mol g/l g crude oil / g PP

Polymerisation in gaseous propylene

105°C - 240 min KAT A / TIBA 150 149 3.8

105°C - 240 min KAT A / THA 150 115 5.3

105°C - 240 min KAT B / THA 150 87 6.2

As described in Tables 9a and 9b and in Fig. 2, the absorbance of mineral oil and crude oil by polypropylene with fluffy morphology increases in direct relation to the decrease in its bulk powder density. The character of the fluffy morphology, given by the bulk powder density, is thus decisive for the sorptive capacity of this material. Comparing the absorbance of oil in polypropylene with classical morphology, prepared on precataiyst KAT A, activated for polymerisation by the cocatalyst TEA, with the bulk powder density of 447 g/l, with that in polypropylene with fluffy morphology, prepared on the precataiyst KAT B, activated for polymerisation by the cocatalyst THA, with the bulk powder density of 87 g/l, it can be said that polypropylene with fluffy morphology prepared in this way has an absorbance of mineral oil about 7x higher (increased absorbance from 0.8 g oil/g PP to 5.7 g oil/g PP). Example 10

Influence of the polypropylene fluffy morphology on the possibility of repeated desorption of absorbed mineral oil and crude oil

Polypropylene prepared on the 1 ,3-diether precatalysts KAT A and KAT B thermally treated at a temperature of 105°C, for 4 hours, at pressure reduced below 10 Pa, was used to study the repeated desorption of oil . These precatalysts were activated for polymerisation by the cocatalyst TIBA and THA, as shown in Tables 10a and 10b. In studying the desorptive capacity of these polyo!efins once again the absorbed media were: white medicinal oil (paraffinum liquidum) with density of 870 g/dm ³ {at 15°C) - mineral oil and medium heavy crude oil with density of 863 g/dm ³ (at 15°C).

The procedure for establishing the repeated desorption of oil was as follows: 1 ) Polyolefin of the given bulk powder density was accurately weighed in an amount of 0.50 ± 0.02 g and it was placed to thick-walled centrifuge cuvettes of internal diameter 1.5 cm and length 7.5 cm, at the bottom ending in a 1.0 cm long capillary of internal diameter 1 mm. The absorbed media (mineral oil or crude oil) were poured over the polymer, so that the surface of the absorbed medium was about 1 cm above the polyolefin. The cuvette with the mix of the fluffy polymer and absorbed medium was left for 15 minutes in an upright position so that the rest of the unabsorbed medium could freely drain out of the capillary in the bottom of the cuvette.

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

Subtracting the mass of the sample before sorption in grammes (PO ₀ ) from the mass of the sample after centrifuging in grammes (PO _c ), we obtain the mass of undesorbed media in grammes (YNDES) according to the formula (i): YND _E S = PO _C - PO (j)

This amount of undesorbed medium (YNDES) in grammes related to the total, previously calculated amount of medium absorbed (Y _S ) by the polyolefin in grammes gives as the result in each sorption/desorption cycle the percentage of desorbed medium (DES) according to the formula (ii):

This sorption/desorption cycle was repeated 5 times in total.

The resulting percentage of desorbed mineral oil or crude oil for individual desorption steps for individual cases is shown in Tables 10a and 10b.

Table 10a

As described in Tables 10a and 10b, during repeated sorption and desorption of mineral oil and crude oil, depending on the bulk powder density of polypropylene with fluffy morphology, after each cycle a similar amount of absorbed medium (about 96% in the case of absorbed mineral oil and about 95% in the case of absorbed crude oil) is released. The character of desorption expressed in the desorbed amount of mineral oil and crude oil thus indicates that the efficiency of desorption in individual cycles basically does not change. For example in the case of polypropylene with fluffy morphology with the bulk powder density of 87 g/l, prepared on the thermally treated (105°C, 4 hours, at pressure reduced below 0 Pa) precatalyst KAT B, activated by the cocatalyst THA, during 5 times repeated sorption and subsequent desorption, individual desorption steps showed practically unchanged desorption of mineral oil (96.7% - 96.9%) and crude oil (96.2% - 96.4%)

Example 11

The influence of the fluffy morphology of polypropylene on the thermal conductivity of polypropylene In studying the thermal conductivity of polyolefins with fluffy morphology polypropylene samples prepared on the 1 ,3-diether precatalyst KAT A and KAT B thermally treated at temperature of 105°C, for 4 hours, at pressure reduced below 10 Pa, were used. These precatalysts were activated for polymerisation by the cocatalysts TEA, TIBA and THA, as shown in Table 1 1.

For the study of the thermal insulating capacity of polymers with fluffy morphology a TCi (instrument C-Therm TCi) heat conductivity analyser was used. It is calibrated for foam materials and enables thermal analysis of heat conductivity in the range from 0.01 to 100 W/(m ^* K).

The thermal conductivity of 4 polyolefln materials having the bulk powder density varied was measured. There were10 measurements made in each analysis, from which the average was taken to establish the resulting thermal conductivity value of the material.

The resulting values of heat conductivity for individual cases are given in Table

11 .

Table 11

Thermal treatment Catalyst Al/Ti Bulk powder Thei ma I conductivity of the precatalyst system ratio density of polymer

mol/mol g/i W/m ^* K

Polymerisation in gaseous propylene

without treatment KAT A / TEA 50 447 0.070

without treatment KAT B / THA 150 395 0.064

105°C - 240 min KAT A / TEA 50 242 0.050

105°C - 240 min KAT A / TIBA 150 149 0.040 As described in Table 11 and in Fig. 3, the thermal conductivity of polypropylene with fluffy morphology decreases in direct proportion (the insulating capacity of the material increases) to the decrease in its bulk powder density. The character of the fluffy morphology, given by the bulk powder density, determines the thermal conductivity of this material. Comparing thermal conductivity in polypropylene with classical particle morphology (non-thermally treated precatalyst KAT A activated by the cocatalyst TEA) with the bulk powder density of 447 g/l with polypropylene with fluffy particle morphology (thermally treated precatalyst KAT A activated by the cocatalyst TIBA) with the bulk powder density of 149 g/l, it can be stated that polypropylene with fluffy morphology has a thermal conductivity about 40% lower (the reduction in heat conductivity from 0.070 W/(m*K) to 0.040 W/(m ^* K)).

Example 12

Polyolefin with fluffy morphology as carriers of additives

In studying the capacity of polyoiefins with fluffy morphology function as carriers of additives, polypropylene prepared on the 1 ,3-diether precatalyst KAT C thermally treated at temperature of 105°C, for 4 hours, at pressure reduced below 10 Pa, activated by cocatalyst THA, was used. This polypropylene with fluffy morphology is labelled in Table 12a as polypropylene B and its ability to function as an additive carrier is compared with polypropylene A with standard particle morphology, prepared on a 1,3- diether precatalyst without thermal treatment, activated by the cocatalyst TEA. The properties of both types of polypropylene are compared in Table 12a. Polypropylene B with fluffy morphology has, compared to polypropylene A with standard morphology, significantly reduced bulk powder density, which documents in particular its changed morphology and measures the character of these changes, as described above.

In studying the ability of polyoiefins with fluffy morphology to function as additive carriers a procedure was used in which the antistatic agent Dimodan PV (giyceroimonostearate containing other glycerol derivatives and max. 3 wt% free glycerol, producer Danisco) was mixed gradually in an amount of 20 wt% (related to a mixture of polypropylene, additive and stabiliser) into polypropylene A with standard morphology, and in an amount of 20 wt%, 30 wt% and 40 wt% (related to the mixture of polypropylene, additive and stabiliser) into polypropylene B with fluffy morphology (see Table 12b). Individual mixtures of polypropylene and additive were stabilised by Irganox B225 (mixture Irganox 1010 - tj, [methylene-3,(3\5'-di-ferc.buty!)-4'- hydroxyphenyl-propionate)]methane and Irgafos 168 - tj. tris(2,4-di- ferc.butyiphenyl)phosphite in the ratio 1 :1 by weight, producer BASF) in an amount of 0.25 wt% (related to a mixture of polypropylene, additive and stabiliser).

The conditions of mixing in the Thyssen Henschel mixer were: initial temperature of ingredients 23.5°C, mixer volume 5 litres, mixer speed 200 rpm, mixing time 5 minutes. During mixing the mixture warmed to 31 ,2°C, but remained the powder.

The prepared powder mixtures were processed on Werner&Pfleiderer ZSK 25

(D=25 mm, L D=53) twin-screw extruder with co-rotating screws. Individual mixtures were added to the first ingredient feed. Granules were prepared from wire at the die with two outlets of diameter 4 mm. Wires were cooled in water and dried with compressed air before cutting. These temperatures were set (from hopper to die): 100, 150, 160, 170, 180, 180, 180, 180, 180, 80, 180, 180°C and a speed of 200 rpm on the extruder. The melt was degassed under reduced pressure at the distance of 40D from the ingredient feed.

Table 12a

Table 12b

As described in Table 12b, after mixing 20 wt% of additive Dimodan PV into polypropylene with standard morphology type A the subsequent extrusion of these stabilised mixtures took place with difficulty, specifically already with this amount of additive there was tearing of wires and the additive itself was not, according to visual evaluation, sufficiently processed into the me!t. Conversely, after mixing of 20 wt%, 30 wt% and even 40 wt% of additive Dimodan PV into polypropylene with fluffy morphology type B the subsequent extrusion of this stabilised mixture took place without difficulty, and specifically there was no tearing of wires and the additive was, according to visual evaluation, completely processed into the melt. From these results it follows that using po!yolefin with fluffy morphology it is possible to increase significantly the resulting concentration of additive in granulate.

The given example showed that using the fluffy polymer increased the amount of antistatic agent (based on esters of glycerol with higher fatty acids) incorporated into the polymer material to up to double the amount when using standard polymer powders or granulates and that without production problems even values of 40 wt% additive incorporated into the resulting polypropylene granulate cou!d be achieved.

Example 13

Polyolefins with fluffy morphology as carriers of organic coloured pigments

Polypropylene prepared on the 1 ,3-diether precatalyst KAT C thermally treated at 05°C, for 4 hours, at pressure reduced below 10 Pa, activated by the cocataiyst THA, was used to study the ability of polyolefins with fluffy morphology to function as carriers of organic pigments. This polypropylene with fluffy morphology is labelled in Table 3a as polypropylene B and its ability to function as the carrier of organic pigments is compared with polypropylene A with standard particle morphology, prepared on the 1 ,3- diether precatalyst without thermal treatment, activated by the cocataiyst TEA. The properties of both types of polypropylene are compared in Table 13a. Polypropylene B with fluffy morphology has, compared to polypropylene A with standard morphology, significantly reduced the bulk powder density, which documents in particular its changed morphology and the character of these changes, as described above.

To study the ability of polyolefins with fluffy morphology to function as carriers of organic pigments the procedure was used in which the organic pigment was gradually mixed in the amount of 30 wt% (related to a mixture of polypropylene, pigment, stabiliser and dispersant) into polypropylene A with standard morphology and in the amount of 30 wt% (related to a mixture of polypropylene, organic pigment, stabiliser and dispersant) into polypropylene B with fluffy morphology, as documented in Table 13b. The organic pigment was versal red A3BN (producer SYNTHESIA a.s., Pardubice-Semtin, Czech Republic) with the Colour Index Pigment Red 77/65300 and CAS Number 4051-63-2, belonging to the group of anthraquinone organic pigments. Individual mixtures of polypropylene, organic pigment and dispersant were stabilised by the stabiliser Irganox B225 (mixture Irganox 1010 - [methylene-3,(3',5'-di-ferc.butyl)- 4'-hydroxyphenyl-propionate)]methane and Irgafos 168 - tris(2,4-di- rerc.butylphenyl)phosphite in the ratio 1 :1 by weight, producer BASF) in the amount of 0.5 wt% (related to a mixture of polypropylene, organic pigment, stabiliser and dispersant) and as dispersant the liquid copolymer of ethylene oxide with propylene oxide (commercial name SLOVACID S-44P, producer Saso!) was used in the amount of 0.5 wt% (related to a mixture of polypropylene, organic pigment, stabiliser and dispersant), as is also documented in Table 13b.

The conditions for mixing in Thyssen Henschel mixer were: initial temperature of ingredients 23.8°C, mixer volume 5 litres, mixer speed 200 rpm, mixing period 5 minutes. During mixing the mixture warmed to 32.7°C, but remained a powder.

Prepared powder mixtures were processed on Werner&Pf!eiderer ZSK 25 (D=25 mm, LJD=53) twin-screw extruder with co-rotating screws. Individual mixtures were added to the first ingredient feed. Granules were prepared from wire at the die with two outlets of diameter 4 mm. Wires were cooled in water and dried with compressed air before cutting. On the extruder these temperatures were set (from hopper to die): 30, 180, 200, 200, 200, 200, 200, 200, 200, 200, 200, 200°C and a speed of 500 rpm.

Table 13a

Table 13b

Versal Irganox B225 Slovacid Pressure

Polypropylene red A3BN S-44P before the filter

with 125 micrometre pores wt.% wt.% wt.% MPa

A 30 0.5 5.0 18

B 30 0.5 5.0 10

Organic pigment concentrates were produced in granulate form and then subjected to the test according to ASTM Standard D 6265 - 98: "Separation of Contaminants in Polymers Using an Extruder Filter Test" .

The concentrate based on polypropylene powder A with standard morphology showed, on a filter with 125 micrometre pores, an increase in pressure of 18 MPa after passage of 600 g of concentrate through the filter.

The concentrate based on polypropylene powder B with fluffy morphology showed, on a filter with 125 micrometre pores, an increase in pressure of 10 MPa after passage of 600 g of concentrate through the filter.

The advantage of polypropylene powder with fluffy morphology prepared in accordance to the invention is also evident in the preparation of organic pigment concentrate, because under otherwise identical conditions in polypropylene with fluffy morphology there is more efficient dispersal of organic pigment in the polypropylene melt, which subsequently shows less of the increase in pressure before the filter.