WO2003099883A1

WO2003099883A1 - Butene-1 (co)polymers and process for their preparation

Info

Publication number: WO2003099883A1
Application number: PCT/EP2003/003593
Authority: WO
Inventors: Gianni Vitale; Giampiero Morini; Giuliano Cecchin
Original assignee: Basell Poliolefine Italia S.P.A.
Priority date: 2002-05-29
Filing date: 2003-04-07
Publication date: 2003-12-04
Also published as: CN1537122A; JP2005527676A; EP1507806B1; ATE342288T1; BR0304880A; JP5670495B2; US20040254313A1; DE60309020D1; RU2315063C2; ES2272981T3; DE60309020T2; PL372289A1; AR039858A1; TR200302316T1; EP1507806A1; KR100892901B1; JP2013136770A; CA2452034A1; AU2003229617A1; CN1294161C

Abstract

The present invention relates to butene-1 homopolymers, or copolymers containing up to 20 % by weight of alpha olefins having from 2 to 10 carbon atoms other than butene-1, characterized by the following properties: (i) a Molecular Weight Distribution (MWD) in terms of Mw/Mn, measured by GPC analysis according to the method specified, of lower than 6; and (ii) a melt strength (measured according to the method specified below) higher than 2.8.

Description

BUTENE-1 (CO) POLYMERS AND PROCESS FOR THEIR PREPARATION

The present invention relates to butene-1 (co)polymers and to a process for their preparation. The invention further relates to the articles obtained from the butene-1 (co)polymers of the invention, hi particular the present invention relates to butene-1 (co)polymers characterized by a specific set of chemical and physical properties.

Butene-1 (co)polymers are well known in the art. In view of their good properties in terms of pressure resistance, creep resistance, and impact strength they are mainly used in the manufacture of pipes to be used in the metal pipe replacement. Despite their good properties, the performances of butene-1 articles, and in particular pipes, sometimes resulted to be not completely satisfactory in terms of general mechanical performances and in particular with respect to pressure resistance after long times (1000 Hrs Burst Stress). Therefore, it would be desirable to improve said butene-1 (co)polymers, so as to have articles (in particular pipes) having a set of mechanical properties capable to provide both long time pressure resistance and easy workability.

The butene-1 (co)polymers can be prepared by polymerizing butene-1 in the presence of TiC based catalysts components together with diethylaluminum chloride (DEAC) as cocatalyst. In some cases diet yl aluminum iodide (DEAT) is also used in mixtures with DEAC. The polymers obtained, however, generally do not show satisfactory mechanical properties. Furthermore, in view of the low yields obtainable with the TiCl based catalysts, the polybutenes prepared with these catalysts have a high content of catalyst residues (generally more than 300 ppm of Ti) which lowers the properties of the polymers making it necessary a deashing step.

Butene-1 (co)polymers can also be obtained by polymerizing the monomers in the presence of a stereospecific catalyst comprising (A) a solid component comprising a Ti compound and an electron-donor compound supported on MgCl₂; (B) an alkylaluminum compound and, optionally, (C) an external electron-donor compound.

A process of this type is disclosed in EP -A- 172961. This process allows the preparation of butene-1 polymers having an intrinsic viscosity [η] of from 1.5 to 4, as measured in decalin at 135°C, an isotacticity value of at least 95% and a Molecular Weight Distribution (MWD), expressed in terms of Mw/Mn, of not more than 6. The melt strength of the polymer was not reported. The applicant has replicated the preparation of the polybutenes (example 1) described in the said application and has determined the melt strength that is resulted to be 2.5g. The mechanical properties shown by the polymers disclosed in said application are not completely satisfactory especially in terms of long times pressure resistance.

In WO 99/45043 a butene-1 having high cristallinity and a broad molecular weight distribution is described. The polymer is obtained by sequential polymerization in two reactors under different conditions in the presence of a stereospecific MgCl₂ supported catalyst thereby obtaining MWD of 8 or higher. In the Example 1 of this patent application, where the MWD is very broad (10.3), the 1000 Hrs Burst Stress is good (8.2 MPa) but the Flexural Modulus is so high (570 Mpa) that the workability of the articles (especially pipes) is limited. On the other hand, when the MWD is lower (Example 2 Mw/Mn 8) the Flexural Modulus reaches much lower values which also impact the long times pressure resistance (1000 Hrs Burst Stress drops to 7.3).

The applicant has now discovered butene-1 (co)polymers that although are characterized by a medium/narrow MWD are surprisingly capable to couple suitable mechanical properties and long times pressure resistance.

It is therefore an object of the present invention to provide butene-1 homopolymers, or copolymers containing up to 20% by weight of α-olefms having from 2 to 10 carbon atoms other than butene-1, characterized by the following properties:

(i) a Molecular Weight Distribution (MWD) in terms of Mw/Mn, measured by GPC analysis according to the method specified below, of lower than 6; and (ii) a melt strength (measured according to the method specified below) higher than

2.8g.

The butene-1 (co)polymers of the invention preferably have a MWD in the range 4-5.8 more preferably in the range 4.5-5.5. It is especially preferred that in correspondence of such values of MWD the isotactic index, expressed in terms of isotactic pentads (mmmm%) measured by NMR, is higher than 97 and more preferably higher than 98.5 and most preferably higher than 99. The melt strength is preferably higher than 3 g and more preferably higher than 3.5. As explained above, also copolymers of butene-1 containing up to 20% by weight of α-olefins, provided that they fulfill the above conditions, are within the scope of the present invention. Among the α-olefins different from butene particularly preferred are those selected from the group consisting of ethylene, propylene and hexene-1. The copolymers of the present invention preferably contain from 2 to 15% by weight of such olefins and more preferably from 5 to 10% by weight.

While there is no particular limitation as to the molecular weight of the polymers, it is preferred that the (co)polymers have a Mw such that the Melt Index "E" is comprised in the range of from 100 to 0.01, more preferably from 10 to 0.1. hi particular, when the polymers are used in the extrusion devices for the manufacture of pipes, polymers having a Melt Index in the range of from 1 to 0.1 and particularly from 0.2 to 0.6 are preferred. The polymers of the present invention can be prepared by polymerization of the monomers in the presence of a stereospecific catalyst comprising (A) a solid component comprising a Ti compound and an internal electron-donor compound supported on MgC ; (B) an alkylaluminum compound and, optionally, (C) an external electron-donor compound. Magnesium dichloride in active form is preferably used as a support. It is widely known from the patent literature that magnesium dichloride in active form is particularly suited as a support for Ziegler-Natta catalysts. In particular, USP 4,298,718 and USP 4,495,338 were the first to describe the use of these compounds in Ziegler-Natta catalysis. It is known from these patents that the magnesium dihalides in active form used as support or co-support in components of catalysts for the polymerization of olefins are characterized by X-ray spectra in which the most intense diffraction line that appears in the spectrum of the non-active halide is diminished in intensity and is replaced by a halo whose maximum intensity is displaced towards lower angles relative to that of the more intense line.

The preferred titanium compounds used in the catalyst component of the present invention are TiCU and TiCl₃; furthermore, also Ti-haloalcoholates of formula Ti(OR)_n-yX_y, where n is the valence of titanium and y is a number between 1 and n, can be used.

The internal electron-donor compound is preferably selected from esters and ethers, and more preferably from alkyl, cycloalkyl or aryl esters of monocarboxylic acids, for example benzoic acids, or polycarboxylic acids, for example phthalic or succinic acids, the said alkyl, cycloalkyl or aryl groups having from 1 to 18 carbon atoms. Examples of the said electron-donor compounds are methyl benzoate, ethyl benzoate, diisobutyl phthalate and 2,3-alkyl disubstituted succinates.

The preparation of the solid catalyst component can be carried out according to several methods.

Accordmg to one of these methods, the magnesium dichloride in an anhydrous state and the internal electron donor compound are milled together under conditions in which activation of the magnesium dichloride occurs. The so obtained product can be treated one or more times with an excess of TiCl at a temperature between 80 and 135°C. This treatment is followed by washings with hydrocarbon solvents until chloride ions disappeared. According to a further method, the product obtained by co-milling the magnesium chloride in an anhydrous state, the titanium compound and the internal electron donor compound is treated with halogenated hydrocarbons such as 1,2-dichloroethane, chlorobenzene, dichloromethane etc. The treatment is carried out for a time between 1 and 4 hours and at temperature of from 40°C to the boiling point of the halogenated hydrocarbon. The product obtained is then generally washed with inert hydrocarbon solvents such as hexane.

According to another method, magnesium dichloride is preactivated accordmg to well known methods and then treated with an excess of TiCl₄ at a temperature of about 80 to 135°C which contains, in solution, an internal electron donor compound. The treatment with TiCl is repeated and the solid is washed with hexane in order to eliminate any non-reacted TiCl . A further method comprises the reaction between magnesium alcoholates or chloroalcoholates (in particular chloroalcoholates prepared according to U.S. 4,220,554) and an excess of TiCl₄ comprising the internal electron donor compound in solution at a temperature of about 80 to 120°C.

According to a preferred method, the solid catalyst component can be prepared by reacting a titanium compound of formula Ti(OR)_n-yXy, 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 USP 4,399,054 and USP 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) i cold TiC (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 electron donor compound can be added during the treatment with TiCl₄. The treatment with the electron donor compound can be repeated one or more times. The preparation of catalyst components in spherical form is described for example in European Patent Applications EP-A-395083, EP-A-553805, EP-A-553806, EPA-601525 and WO98/44001.

The solid catalyst components obtained according to the above method show a surface area (by B.E.T. method) generally between 20 and 500 m /g and preferably between 50 and 400 m /g, and a total porosity (by B.E.T. method) higher than 0,2 cm /g preferably between 0,2 and 0,6 cm /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 cm /g.

A further method to prepare the solid catalyst component of the invention comprises halogenating magnesium dihydrocarbyloxide compounds, such as magnesium dialkoxide or diaryloxide, with solution of TiCl₄ in aromatic hydrocarbon (such as toluene, xylene etc.) at temperatures between 80 and 130°C. The treatment with TiCl in aromatic hydrocarbon solution can be repeated one or more times, and the internal electron donor compound is added during one or more of these treatments.

Generally, the internal electron donor compound is used in molar ratio with respect to the MgCl₂ of from 0.01 to 1 preferably from 0.05 to 0.5.

The alkyl-Al compound (B) is preferably chosen among 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.

The external donor (C) can be of the same type or it can be different from the internal donor described above. Suitable external electron donor compounds include sihcon compounds of formula Ra Rb Si(OR )_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; R , R , and R , are alkyl, cycloalkyl or aryl radicals with 1-18 carbon atoms optionally containing heteroatoms. Particularly preferred are the silicon compounds in which a is 1, b is 1, c is 2, at least one of R and R⁶ is selected from branched alkyl, cycloalkyl or aryl groups with 3-10 carbon atoms optionally containing heteroatoms and R is a Ci-Cio alkyl group, in particular methyl. Examples of such preferred silicon compounds are methylcyclohexyldimethoxysilane, diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, 2-ethylpiperidinyl-2-t- butyldimethoxysilane and 1,1,1 ,trifluoropropyl-2-ethylpiperidinyl-dimethoxysilane.

Moreover, are also preferred the silicon compounds in which a is 0, c is 3, R is a branched η alkyl or cycloalkyl group, optionally containing heteroatoms, and R is methyl. Examples of such preferred silicon compounds are cyclohexyltrimethoxysilane, t-butyltrimethoxysilane and thexyltrimethoxysilane. The use of ti exyltrimethoxysilane is particularly preferred. The electron donor compound (c) is used in such an amount to give a molar ratio between the organoaluminum compound and said electron donor compound (c) of from 0.1 to 500, preferably from 1 to 300 and more preferably from 3 to 100.

The polymerization process can be carried out according to known techniques, for example slurry polymerization using as diluent an inert hydrocarbon solvent, or solution polymerization using for example the liquid butene-1 as a reaction medium. Moreover, it may also be possible to carry out the polymerization process in the gas-phase, operating in one or more fluidized or mechanically agitated bed reactors. The polymerization carried out in the liquid butene-1 as a reaction medium is highly preferred.

The polymerization is generally carried out at temperature of from 20 to 120°C, preferably of from 40 to 90°C. In the bulk polymerization the operating pressure is generally between 1 and 6 MPa preferably between 1.5 and 4 MPa. The polymerization can be carried out in one or more reactors that can work under same or different reaction conditions such as concentration of molecular weight regulator, monomer concentration, temperature, pressure etc. Working in more than one reactor under different conditions can lead to the preparation of polybutenes with different average Molecular Weight in the two reactors and therefore with a broader MWD optionally of bimodal type. Moreover, working in more than one reactor under different conditions has the advantage that the various polymerization step can be properly modulated so as to properly tailoring the properties of the final polymer. In addition in order to make the catalyst particularly suitable for the polymerization step, it is possible to prepolymerize said catalyst in a prepolymerization step. Said prepolymerization can be carried out in liquid, (slurry or solution) or in the gas-phase, at temperatures generally lower than 100°C, preferably between 20 and 70°C. The prepolymerization step is carried out with small quantities of monomers for the time which is necessary to obtain the polymer in amounts of between 0.5 and 2000g per g of solid catalyst component, preferably between 5 and 500 and, more preferably, between 10 and lOOg per g of solid catalyst component. The monomer used in the prepolymerization can be butene-1 and/or another α-olefin having from 2 to 10 carbon atoms. Preferably, the prepolymerization is carried out with propylene. hi this case it is particularly preferable to carry out the prepolymerization with monomer amounts and polymerization times necessary to obtain a polypropylene content of from 0.5 to 20%, preferably from 1 to 15% based on the weight of the final butene-1 product. Although reactor blend are preferable in terms of homogeneity of the polymer, good results can be obtained by blending the butene-1 of the invention with an amount of propylene homopolymer or copolymer ranging from 0.5 to 20% by weight of the resulting composition.

The polybutenes of the invention can be used as such in all the applications for which polybutenes are generally employed. However, as it is known to the experts in this field, and as it can be easily determined by routine tests, it is possible to add further polymer components, additives (such as stabilizers, antioxidants, anticorrosives, nucleating agents, processing aids, etc.) and both organic and inorganic fillers which can give specific properties to the products of the invention.

The following examples are given in order to better illustrate the invention without limiting it.

CHARACTERIZATION

Determination of Isotactic Index (mmmm%). by ¹³C NMR

The measurement is carried out by preparing a 10%wt solution of the polymer in C C1₄D₂ and recording the spectra at a temperature of 120°C with a Bruker DPX 400MHz instrument operating at 100.7 MHz under proton Waltz 16 decoupling in FT mode, with lOKhz spectral width, 90° pulse angle and 16 sec. puls repetition and 3600 scans. The assignment of the pentad signals in the region of branch methylene carbons was made according to Carbon- 13

NMR Spectral Assignment of Five Polyolefins Determined from the Chemical Shift

Calculation and the Polymerization Mechanism, T. Asakura and others, Macromolecules

1991, 242334-2340.

The experimental pentad distribution was fitted using the method described in Two-site

13 model analysis of C NMR of polypropylene polymerized by Ziegler -Natta catalyst with external alkoxysilane donors, R. Chύjό, Y. Kogure, T. Vάάnάnen, Polymer, 1994, 35, 339-

342. The Isotactic Index is the value of mmmm pentad of the polymer generated from the

"asymmetric bernoullian site" defined according to Chϋjδ.

Determination of Melt Index

ASTM D 1238 condition "E"

Determination of Melt Strength

The apparatus used in the Rlieotens melt tension instrument model 2001, manufactured by

Gottfert (Germany): the method consists of measuring in g the tensile strength of a strand of molten polymer operating at a specific stretch velocity. In particular, the polymer to be tested is extruded at 190°C through a die with a capillary hole 22 mm long and 1 mm in diameter; the exiting strand is then stretched, by using a system of traction pulleys, at a constant acceleration of 0.012 cm/sec , measuring the tension until the breaking point. The apparatus registers the tension values of the strand (resistance in g) as a function of the stretching. The maximum tension value corresponds to the melt strength.

MWD Determination by Gel Permeation Chromatography (GPC)

This is determined using a Waters 150-C ALC/GPC system equipped with a TSK column set (type GMHXL-HT) working at 135°C with 1,2-dichlorobenzene as solvent (ODCB)

(stabilized with 0.1 vol. of 2,6-di-t-butyl p-cresole (BHT)) at flow rate of lml/min. The sample is dissolved in ODCB by stirring continuously at a temperature of 140°C for 1 hour.

The solution is filtered through a 0.45μm Teflon membrane. The filtrate (concentration

0.08-1.2g/l injection volume 300μl) is subjected to GPC. Monodisperse fractions of polystyrene (provided by Polymer Laboratories) were used as standard. The universal calibration for PB copolymers was performed by using a linear combination of the Mark-

Houwink constants for PS (K=7.11xl0^"5dl/g; α=0.743) and PB (K=1.18xl0^"4dl/g; α=0.725)

Burst Stress Resistance

Determination is carried out according to ISO 1167: 1996 with water at 95 °C on pipes having an outer diameter of 22 mm.

Strength at Yield: ASTM D 638

Strength at Break: ASTM D 638

Elongation at Break: ASTM D 638

Flexural Modulus: ASTM D 790

EXAMPLES

Example 1

Preparation of Solid Catalyst Component

Into a 500 ml four-necked round flask, purged with nitrogen, 225 ml of TiCl₄ were introduced at 0°C. While stirring, 6.8 g of microspheroidal MgCl «2.7C H₅OH (prepared as described in

Ex. 2 of USP 4,399,054 but operating at 3,000 rpm instead of 10,000) were added. The flask was heated to 40°C and 4.4 mmoles of diisobutylphthalate were thereupon added. The temperature was raised to 100°C and maintained for two hours, then stirring was discontinued, the solid product was allowed to settle and the supernatant liquid was siphoned off.

200 ml of fresh TiCl were added, the mixture was reacted at 120°C for one hour then the supernatant liquid was siphoned off and the solid obtained was washed six times with anhydrous hexane (6 x 100 ml) at 60°C and then dried under vacuum. The catalyst component contained 2.8 wt% of Ti and 12.3 wt% of phthalate. Bulk polymerization of butene-1

In a 4 liter autoclave, purged with nitrogen flow at 70 °C for one our, 75 ml of anhydrous hexane containing 7mmols of AliBu₃, 0.12 mmols of thexyltrimethoxysilane and 7 mg of solid catalyst component prepared as reported above were introduced in nitrogen flow at 30 °C. The autoclave was closed. 0.15 Nl of hydrogen were added and then, under stirring, 1,3 Kg of liquid butne-1 were fed. The temperature was raised to 70°C in five minutes and the polymerization was carried out at this temperature for 1.5 hours. Then, 8N1 of hydrogen were fed and the temperature increased to 75°C. The polymerization was continued under these conditions for additional 30 minutes. After that time the reaction was stopped, the unreacted butene-1 was vented and the polymer was recovered and dried at 70 °C under vacuum for six hours. The polymerization activity was 50Kg polymer/g catalyst. The final butene-1 product had the following characteristics: Isotactic Index (%mmmm) 99 MWD: 5.1 Melt Strength: 3.85 MIE (g/lOmin): 0,42

The results of the mechanical test to which the polybutene obtained was subjected are listed in table 1. Example 2

In a 4 liter autoclave, purged with nitrogen flow at 70 °C for one our, 75 ml of anhydrous hexane containing 7mmols of AliBu., 0.175 mmols of thexyltrimethoxysilane and 7 mg of solid catalyst component prepared as reported above were introduced in nitrogen flow at 30 °C. The autoclave was closed. 0.15 Nl of hydrogen were added and then, under stirring, 1,3 Kg of liquid butne-1 were fed. The temperature was raised to 75°C in five minutes and the polymerization was carried out at this temperature for 1.5 hours. Then, 8N1 of hydrogen were fed and, under the same temperature, the polymerization was continued for additional 30 minutes. After that time the reaction was stopped, the unreacted butene-1 was vented and the polymer was recovered and dried at 70 °C under vacuum for six hours. The polymerization activity was 40Kg polymer/g catalyst. The final butene-1 product had the following characteristics: Isotactic Index (%mmmm) 99%

MWD: 4.8

Melt Strength: 3.61

MIEO.36

Comparison Example 1

The characteristics of the polybuetene-1 obtained accordmg to the procedure reported in

Example 1 of EP172961 having a Melt Strength of 2.5 and a Mw/Mn of 4.7 are reported in

Table 1.

TABLE 1

Claims

1. Butene-1 homopolymers, or copolymers containing up to 20% by weight of alpha olefins having from 2 to 10 carbon atoms other than butene-1, characterized by the following properties:

(i) a Molecular Weight Distribution (MWD) in terms of Mw/Mn, measured by GPC analysis according to the method specified above, of lower than 6; and

(ii) a melt strength (measured according to the method specified above) higher than 2.8.

2. The butene-1 homo or copolymers according to claim 1 having an isotactic index expressed in terms of isotactic pentads (n__mmm%) higher than 97.

3. The butene-1 homo or copolymers according to claim 2 having an isotactic index higher than 98.5

4. The butene-1 homo or copolymers according to claim 1 having a MWD in the range 4-5.8.

5. The butene-1 homo or copolymers according to claim 4 having a MWD in the range 4.5-5.5.

6. The butene-1 homo or copolymers according to claim 1 having a melt strength higher than 3.

7. The butene-1 homo or copolymers according to claim 6 having a melt strength higher than 3.5.

8. The butene-1 copolymers according to claim 1 in which the alpha olefins are selected from the group consisting of ethylene, propylene and hexene-1.

9. The butene-1 copolymers according to claim 8 in which the content of said olefins is from 2 to 15% by weight.

10. The butene-1 copolymers according to claim 9 in which the content of said olefins is from 5 to 10% by weight.

11. The butene-1 homo or copolymers according to claim 1 having a MIE comprised in the range of from more preferably from 10 to.0.1.

12. The butene-1 homo or copolymers according to claim 11 having a MIE comprised in the range of from 1 to 0.1 and particularly from 0.2 to 0.6.

13. The butene-1 homo or copolymers according to any of the preceding claims containing of from 0.5 to 20% by weight of polypropylene.

14. The butene-1 homo or copolymers accordmg to claim 12 containing from 1 to 10% by weight of polypropylene.

15. Manufactured articles obtained from the butene-1 homo or copolymers accordmg to anyone of the preceding claims.

16. Pipes obtained by the butene-1 homo or copolymers according to claim 1.

17. Process for the preparation of the butene-1 homo or copolymers accordmg to anyone of claims 1-14 carried out in the presence of a stereospeciflc catalyst comprising (A) a solid component comprising a Ti compound and an internal electron-donor compound selected from phthalates, supported on MgCl₂; (B) an alkylaluminum compound and, (C) an external electron-donor compound.

18. Process according to claim 17 in which the external electron donor compound is thexyltrimethoxysilane.

19. Process accordmg to claim 17 carried out in liquid monomer.