WO2015062787A1

WO2015062787A1 - Multimodal copolymers of propylene and 1-hexene

Info

Publication number: WO2015062787A1
Application number: PCT/EP2014/070322
Authority: WO
Inventors: Monica Galvan; Andreas Neumann; Caroline Cathelin; Francesca Tisi; Giampaolo Pellegatti
Original assignee: Basell Poliolefine Italia S.R.L.
Priority date: 2013-10-30
Filing date: 2014-09-24
Publication date: 2015-05-07
Also published as: BR112016008914A2; EP3063186B1; CN105658687A; EP3063186A1; BR112016008914B1; US20160251463A1; US9567418B2; CN105658687B

Abstract

A propylene-1-hexene copolymer having: i) a content of 1-hexene derived units ranging from 0.6 wt% to 3.0 wt%; ii) melt flow rate (MFR) measured according to the method ISO 1133 (230° C, 5 kg) ranging from 0.5 g/10 min to 5.0 g/10 min iii) the polydispersity (PI) ranges from 4.5 to 10 and the distribution of molecular weight is of multimodal type; iv) the melting point ranges from 160°C to 145°C; v) the DSC curve (temperature/heat of fusion) shows at least two peaks.

Description

TITLE

Multimodal copolymers of propylene and 1-hexene FIELD OF THE INVENTION

[0001] The present invention relates to a multimodal copolymers of propylene and 1-hexene having a content of 1-hexene derived units ranging from 0.6 wt to 3.0 wt especially suitable for the production of industrial sheets.

BACKGROUND OF THE INVENTION

[0002] Copolymers of propylene and hexene-1 having a low 1-hexene content are known in the art. WO 2006/002778 relates to a random polymer of propylene and 1-hexene contains from 0.2 to 5 wt , recurring units derived from hexene-1. The propylene -hexene- 1 polymer exhibits broad molecular weight distribution of monomodal type.

[0003] WO 2009/083500 relates to plastic tanks made from propylene copolymers of

propylene and hexene-1. The 1-hexene derived units ranges from 0.5 wt to 5 wt . This document is mute about the modality of the copolymers, however the copolymer

exemplified has a distribution of the monomodal type.

SUMMARY OF THE INVENTION

[0004] Thus an object of the present invention is a propylene- 1-hexene copolymer having a multimodal distribution of molecular weight having improved mechanical properties in particular improved flexural modulus.

[0005] An object of the present invention is a propylene-hexene-1 copolymers having;

[0006] i) a content of 1-hexene derived units ranging from 0.6 wt to 3.0 wt ; preferably from 0.7 wt to 2,0 wt ; more preferably from 0.8 wt to 1.5 wt ;

[0007] ii) the melt flow rate (MFR) measured according to the method ISO 1133 (230° C, 5 kg) ranging from 0.5 g/10 min to 5.0 g/10 min preferably from 0.6 g/10 min to 4.0 g/10 min; more preferably from 0.7 g/10 min to 2.0 g/10 min;

[0008] iii) the polydispersity (PI) ranges from 4.5 to 10; preferably from 4.5 to 6; [0009] iv) the melting point ranges from 160°C to 145°C ; preferably from 155°C to 147°C; more preferably from 153°C to 150°C;

[0010] v) the DSC curve (temperature/heat of fusion) shows at least two peaks.

[0011] .BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Figure 1 is the DSC thermogram of the propylene- 1-hexene copolymer of example 1;.

[0013] Figure 2 is the DSC thermogram of the propylene- 1-hexene copolymer of comparative example 2.

DETAILED DESCRIPTION OF THE INVENTION

[0014] By "molecular weight distribution of multimodal type" is meant therein that there are at least two peaks in the DSC curve (temperature/heat of fusion). A peak is defined as a point on the DSC curve (temperature/heat of fusion) having the highest value of heat of fusion at a temperature A with respect to the values of heat of fusion in the range + 1 °C with respect to temperature A.

[0015] The propylene-hexene-1 copolymer object of the present invention in endowed with improved value of flexural modulus with respect to a copolymer having a monomodal distribution. In particular the flexural modulus is higher than 1350 MPa and the IZOD is higher than 26 Kj/m 2 ; preferably higher than 28 Kj/m 2.

[0016] Al these properties renders the propylene- 1-hexene object of the present invention specifically fit for the production of industrial sheet. An industrial sheet is defined as a sheet having a thickens higher than 0.1 mm; preferably higher than 0.3 mm.

[0017] Thus a further object of the present invention is an industrial sheet comprising the propylene- 1-hexene of the present invention.

[0018] The propylene-hexene-1 polymers of the present invention can be prepared by

polymerizing propylene and 1-hexene in the presence of highly stereospecific heterogeneous

Ziegler-Natta catalyst.

[0019] The Ziegler-Natta catalysts suitable for producing the propylene polymer of the

invention comprise a solid catalyst component comprising at least one titanium compound having at least one titanium-halogen bond and at least an electron-donor compound (internal donor), both supported on magnesium chloride. The Ziegler-Natta catalysts systems further comprise an organo-aluminum compound as essential co-catalyst and optionally an external electron-donor compound.

[0020] Suitable catalysts systems are described in the European patents EP45977, EP361494, EP728769, EP 1272533 and in the international patent application WO00/63261.

[0021] Preferably, the solid catalyst component comprises Mg, Ti, halogen and an electron donor selected from esters of phthalic acids disclosed in EP45977 and in particular of either diisobutylphathalate or dihexylphthalate or diethylphthalate and mixtures thereof.

[0022] According to a preferred method, the solid catalyst component can be prepared by reacting a titanium compound of formula Ti(OR)_n-_yX_y, where n is the valence of titanium and y is a number between 1 and n, preferably TiCl₄, with a magnesium chloride deriving from an adduct of formula MgCl₂ pROH, where p is a number between 0.1 and 6, preferably from 2 to 3.5, and R is a hydrocarbon radical having 1-18 carbon atoms. The adduct can be suitably prepared in spherical form by mixing alcohol and magnesium chloride in the presence of an inert hydrocarbon immiscible with the adduct, operating under stirring conditions at the melting temperature of the adduct (100-130 °C). Then, the emulsion is quickly quenched, thereby causing the solidification of the adduct in form of spherical particles. Examples of spherical adducts prepared according to this procedure are described in US 4,399,054 and US 4,469,648. The so obtained adduct can be directly reacted with the Ti compound or it can be previously subjected to thermal controlled dealcoholation (80-130 °C) so as to obtain an adduct in which the number of moles of alcohol is generally lower than 3, preferably between 0.1 and 2.5. The reaction with the Ti compound can be carried out by suspending the adduct (dealcoholated or as such) in cold TiCl₄ (generally 0 °C); the mixture is heated up to 80-130 °C and kept at this temperature for 0.5-2 hours. The treatment with TiCl₄ can be carried out one or more times. The internal donor can be added during the treatment with TiCl₄ and the treatment with the electron donor compound can be repeated one or more times. Generally, the internal donor is used in molar ratio with respect to the MgCl₂ of from 0.01 to 1 preferably from 0.05 to 0.5. The preparation of catalyst components in spherical form is described for example in European patent application EP- A-395083 and in the International patent application WO98/44001. The solid catalyst components obtained according to the above method contain the titanium compound, expressed as Ti, generally in an amount from 0.5 to 10% by weight. [0023] Moreover, they show a surface area (by B.E.T. method) generally between 20 and

500 m 2 /g and preferably between 50 and 400 m 2 /g, and a total porosity (by B.E.T. method) higher than 0.2 cm 3 /g preferably between 0.2 and 0.6 cm 3 /g. The porosity (Hg method) due to pores with radius up to 10.000A generally ranges from 0.3 to 1.5 cm /g, preferably from 0.45 to 1 cm³/g.

[0024] The organo-aluminum compound is preferably an alkyl-Al selected from the trialkyl aluminum compounds such as for example triethylaluminum, triisobutylaluminum, tri-n- butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum. It is also possible to use mixtures of trialkylaluminum's with alkylaluminum halides, alkylaluminum hydrides or alkylaluminum sesquichlorides such as AlEt₂Cl and Al₂Et₃Cl₃.

[0025] The Al-alkyl compound is generally used in such a quantity that the Al/Ti ratio be from 1 to 1000.

[0026] Preferred external electron-donor compounds include silicon compounds, ethers, esters such as ethyl 4-ethoxybenzoate, amines, heterocyclic compounds and particularly 2,2,6,6-tetramethyl piperidine, ketones and the 1,3-diethers. Another class of preferred external donor compounds is that of silicon compounds of formula R_a ⁵R_b ⁶Si(OR⁷)_c, where a and b are integer from 0 to 2, c is an integer from 1 to 3 and the sum (a+b+c) is 4; R⁵, R⁶, and R , are alkyl, cycloalkyl or aryl radicals with 1-18 carbon atoms optionally containing heteroatoms. Particularly preferred are methylcyclohexyldimethoxysilane,

diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane, 2- ethylpiperidinyl-2-t-butyldimethoxysilane and 1,1,1 ,trifluoropropyl-2-ethylpiperidinyl- dimethoxysilane and l,l,l,trifluoropropyl-metil-dimethoxysilane. The external electron donor compound is used in such an amount to give a molar ratio between the organo- aluminum compound and said electron donor compound of from 0.1 to 500.

[0027] A further The Ziegler-Natta catalysts that can be used to produce a propylene

polymer of te present invention is a solid catalyst component comprising a magnesium halide, a titanium compound having at least a Ti-halogen bond as above described and at least two electron donor compounds selected from succinates and the other being selected from 1,3 diethers, [0028] The catalysts generally used in the process of the invention are capable of producing polypropylene with a value of xylene insolubility at ambient temperature greater than

90 wt, preferably greater than 95 wt.

[0029] The propylene-hexene-1 polymers of the present invention are produced by a

polymerisation process carried out in a gas-phase polymerization reactor comprising at least two interconnected polymerisation zones.

[0030] The process according to the preferred polymerisation process is illustrated in EP application 782 587.

[0031] In detail, the process is carried out in a first and in a second interconnected

polymerization zones into which propylene and hexene- 1 are fed in the presence of a catalyst system and from which the polymer produced is discharged. In said process the growing polymer particles flow upward through one (first) of the said polymerisation zones (riser) under fast fluidisation conditions, leave said riser and enter another (second) polymerisation zone (downcomer) through which they flow downward in a densified form under the action of gravity, leave said downcomer and are reintroduced into the riser, thus establishing a circulation of polymer between the riser and the downcomer.

[0032] In the downcomer high values of density of the solid are reached, which approach the bulk density of the polymer. A positive gain in pressure can thus be obtained along the direction of flow, so that it becomes possible to reintroduce the polymer into the riser without the help of special mechanical means. In this way, a "loop" circulation is set up, which is defined by the balance of pressures between the two polymerisation zones and by the head loss introduced into the system.

[0033] Generally, the condition of fast fluidization in the riser is established by feeding a gas mixture comprising the relevant monomers to said riser. It is preferable that the feeding of the gas mixture is effected below the point of reintroduction of the polymer into said riser by the use, where appropriate, of gas distributor means. The velocity of transport gas into the riser is higher than the transport velocity under the operating conditions, preferably from 2 to 15 m/s.

[0034] Generally, the polymer and the gaseous mixture leaving the riser are conveyed to a solid/gas separation zone. The solid/gas separation can be effected by using conventional separation means. From the separation zone, the polymer enters the downcomer. The gaseous mixture leaving the separation zone is compressed, cooled and transferred, if appropriate with the addition of make-up monomers and/or molecular weight regulators, to the riser. The transfer can be carried out by means of a recycle line for the gaseous mixture.

[0035] The control of the polymer circulation between the two polymerisation zones can be carried out by metering the amount of polymer leaving the downcomer using means suitable for controlling the flow of solids, such as mechanical valves.

[0036] The operating parameters, such as the temperature, are those that are usual in olefin polymerisation process, for example between 50 to 120 °C.

[0037] The operating pressures can range between 0.5 and 10 MPa, preferably between 1.5 to 6 MPa.

[0038] Optionally, one or more inert gases, such as nitrogen or an aliphatic hydrocarbon, are maintained in the polymerization zones, in such quantities that the sum of the partial pressures of the inert gases is preferably between 5 and 80% of the total pressure of the gases.

[0039] The various catalysts are fed up to the riser at any point of the said riser. However, they can also be fed at any point of the downcomer. The catalyst can be in any physical state, therefore catalysts in either solid or liquid state can be used.

[0040] In order to obtain a distribution of molecular weight of multimodal type the gas composition in the two reactor legs has been differentiated by using the "barrier" feed according to what described in EP 1 012 195 so that in the two zones the concentration of hydrogen is different.

[0041] The propylene-hexene-1 copolymers of the invention may also be blended with any other additives commonly employed in the art, such as antioxidants, light stabilizers, heat stabilizers, phenolic antioxidants, slip agents such as calcium stearate and any other nucleating agents selected among talc, aromatic carboxylic salts, salts of monocarboxylic or polycarboxylic acids, e.g. sodium benzoate, aluminum tert-butylbenzoate or dicetyl peroxydicarbonate. EXAMPLES

[0042] The following examples are given to illustrate the present invention without limiting purpose.

[0043] The data relating to the propylene copolymers of the examples are determined by way of the methods reported below.

[0044] Melting Temperature and Crystallization Temperature: determined by differential scanning calorimetry (DSC). Weighting 6 ±1 mg, is heated to 220 ±1° C at a rate of 20 °C/min and kept at 220 ±1° C for 2 minutes in nitrogen stream and it is thereafter cooled at a rate of 20° C/min to 40 ±2° C, thereby kept at this temperature for 2 min to crystallise the sample. Then, the sample is again fused at a temperature rise rate of 20° C/min up to 220° C ±1. The second melting scan is recorded, a thermogram is obtained, and, from this, temperatures corresponding to peaks are read.

[0045] Melt Flow Rate: Determined according to the method ISO 1133 (230° C, 5 kg).

[0046] Solubility in xylene: Determined as follows.

[0047] 2.5 g of polymer and 250 ml of xylene are introduced in a glass flask equipped with a refrigerator and a magnetical stirrer. The temperature is raised in 30 minutes up to the boiling point of the solvent. The so obtained clear solution is then kept under reflux and stirring for further 30 minutes. The closed flask is then kept for 30 minutes in a bath of ice and water and in thermostatic water bath at 25° C for 30 minutes as well. The so formed solid is filtered on quick filtering paper. 100 ml of the filtered liquid is poured in a previously weighed aluminium container, which is heated on a heating plate under nitrogen flow, to remove the solvent by evaporation. The container is then kept on an oven at 80° C under vacuum until constant weight is obtained. The weight percentage of polymer soluble in xylene at room temperature is then calculated.

[0048] 1-hexene content: Determined by 13 C-NMR spectroscopy:

[0049] NMR analysis. ¹³C NMR spectra are acquired on an AV-600 spectrometer operating at 150.91 MHz in the Fourier transform mode at 120 °C. The peak of the propylene CH was used as internal reference at 28.83. The 13 C NMR spectrum is acquired using the following parameters: Spectral width (SW) 60 ppm

Spectrum centre 30 ppm

(01)

Decoupling WALTZ 65_64pl

sequence

Pulse program ZGPG

Pulse Length (PI) for 90°

Total number of 32K

points (TD)

Relaxation Delay 15 s

Number of transients 1500

[0050] The total amount of 1-hexene as molar percent is calculated from diad using the following relations:

[0051] [P] = PP + 0.5PH

[0052] [H] = HH + 0.5PH

053] Assignments of the 13 C NMR spectrum of propylene/ 1-hexene copolymers have been calculated according to the following table:

plates rheometer model RMS-800 marketed by RHEOMETRICS (USA), operating at an oscillation frequency which increases from 0.1 rad/sec to 100 rad/sec. From the crossover modulus one can derive the P.I. by way of the equation:

[0055] P.I.= 10⁵/Gc

[0056] in which Gc is the crossover modulus which is defined as the value (expressed in Pa) at which G'=G" wherein G' is the storage modulus and G" is the loss modulus.

[0057] Samples for the mechanical measure have been obtained according to ISO 294-2, unless differently indicated.

[0058] IZOD Impact Strength: determined according to ISO 180/1 A.

[0059] Flexural modulus: determined according to ISO 178.

Example 1 and comparative example 2

[0060] Propylene-hexene- 1 polymers are prepared by polymerising propylene and hexene-1 by polymerising propylene and hexene-1 in the presence of a catalyst under continuous conditions in a plant comprising a polymerisation apparatus as described in EP 1 012 195.

[0061] in the presence of a catalyst under continuous conditions in a plant comprising a precontact section, a prepolymerisation section and a polymerisation apparatus that comprises two interconnected cylindrical reactors, riser and downcomer. Fast fluidisation conditions are established in the riser by feeding gas recycled from the gas-solid separator.

[0062] In examples 1 the gas composition in the two reactor legs has been differentiated by using the "barrier" feed according to what described in EP 1 012 195. This stream is propylene fed in the larger upper part of the downcomer. In comparative example 2 the barrier feed has not been used.

[0063] The catalyst employed comprises a catalyst component prepared by analogy with example 5 of EP-A-728769 but using microspheroidal MgCl₂- I.7C₂H₅OH instead of MgCl₂-2.1C₂H₅0H. Such catalyst component is mixed with dicyclopentyl dimethoxy silane (DCPMS) as external donor and with triethylaluminium (TEAL) in the precontact section. The catalyst system is then subjected to pre-polymerisation before introducing it into the polymerisation apparatus. [0064] The polymer particles exiting the reactor are subjected to a steam treatment to remove the reactive monomers and volatile substances and then dried. The polymer particles are extruded with a usual packing of stabilisers.

[0065] The main operative conditions of the polymerisation process are indicated in Table 1.

[0066] In Table 2 are reported the main properties of the polymer.

Table 1

H2 hydrogen; C3 propylene; C6 1-hexene comparative

Table 2

Comparative

[0067] By comparing example 1 of the present invention with comparative example 2 it is clear that the izod is improved together with the flexural modulus.

Claims

CLAIMS What is claimed is:

1. A propylene- 1 -hexene copolymer having : i) a content of 1-hexene derived units ranging from 0.6 wt to 3.0 wt ; ii) melt flow rate (MFR) measured according to the method ISO 1133 (230° C, 5 kg) ranging from 0.5 g/10 min to 5.0 g/10 min iii) the polydispersity (PI) ranges from 4.5 to 10 and the distribution of molecular weight is of multimodal type; iv) the melting point ranges from 160°C to 145°C; v) the DSC curve (temperature/heat of fusion) shows at least two peaks.

2. The propylene-hexene- 1 copolymer according to claim 1 wherein the content of 1-hexene derived units ranges from 0.7 wt to 2.0 wt .

3. The propylene-hexene- 1 copolymer according to claims 1 or 2 wherein the melt flow rate (MFR) measured according to the method ISO 1133 (230° C, 5 kg) ranges from 0.6 g/10 min to 4.0 g/10 min.

4. The propylene-hexene- 1 copolymer according to anyone of claims 1-3 wherein the melting point ranges from 155°C to 147°C.

5. An industrial sheet comprising the propylene- 1-hexene of claims 1-5