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WO2008064957A1 - Procédé permettant de préparer des compositions de polybutène présentant une température de cristallisation plus élevée - Google Patents

Procédé permettant de préparer des compositions de polybutène présentant une température de cristallisation plus élevée Download PDF

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Publication number
WO2008064957A1
WO2008064957A1 PCT/EP2007/061142 EP2007061142W WO2008064957A1 WO 2008064957 A1 WO2008064957 A1 WO 2008064957A1 EP 2007061142 W EP2007061142 W EP 2007061142W WO 2008064957 A1 WO2008064957 A1 WO 2008064957A1
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Prior art keywords
butene
crystallization temperature
polymer
salts
metal salts
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PCT/EP2007/061142
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English (en)
Inventor
Fiorella Pradella
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Basell Poliolefine Italia SRL
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Basell Poliolefine Italia SRL
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Publication of WO2008064957A1 publication Critical patent/WO2008064957A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids

Definitions

  • the present invention relates to a process for producing polybutene-1 compositions with increased crystallization temperature and to the compositions thus obtained.
  • the crystallization temperature of polyolefms in general can be increased by adding nucleating agents.
  • These nucleating agents are normally foreign materials that promote the crystallization of the polymer from the melt (heterogeneous nucleation).
  • heterogeneous nucleation As a consequence of the nucleation effect, in addition to the increase of crystallization temperature, other valuable properties, in particular optical and mechanical, are enhanced.
  • the increase of crystallization temperature makes it possible to reduce the process time in manufacturing finished articles from the molten polymer.
  • nucleating agent ethyl benzoate which is highly effective for polypropylene, is substantially ineffective in polybutene-1, even as regards the increase of crystallization temperature.
  • nucleating agents for polybutene-1 should be able to further increase the crystallization temperature of polybutene-1 materials already having a high degree of crystallinity, thus a relatively high crystallization temperature even in the absence of nucleation, as the consequent enhancement of mechanical properties is highly desirable for use in the field of water pipes.
  • one object of the present invention is a process for producing a polybutene-1 composition having increased crystallization temperature T c c , comprising the step of blending the following components:
  • DSC differential scanning calorimetry
  • the content (in the processed material) of any additional polyolefin component different from the said butene-1 polymers, if present, is of 10% by weight or less, in particular from 0.1 to 10% by weight with respect to the total weight of A) and the said additional polyolefin component. More preferably the process of the present invention is carried out in the absence of other polyolefin components (different from the said butene-1 polymers).
  • Another object of the present invention is a polybutene-1 composition
  • a polybutene-1 composition comprising:
  • DSC differential scanning calorimetry
  • the content of any additional polyolefin component (hereinafter called component A 1 )) different from the said butene-1 polymers, if present, is of 10% by weight or less, in particular from 0.1 to 10% by weight with respect to the total weight of A) and the said additional polyolefin component. More preferably, in the compositions of the present invention no additional polyolefin component (different from the said butene-1 polymers) is present.
  • T C A in the compositions of the invention is from 50 0 C or 55 0 C to 75 0 C; more preferably it is from 50 0 C or 55 0 C to 70 0 C.
  • compositions according to the present invention are those having a crystallization temperature T c c satisfying the following relation: T c c > T C A + 20.
  • compositions according to the present invention are those having a crystallization temperature T c c satisfying the following relation: T c c > T C A + 22.
  • T c c values of up to 40-45 0 C higher than the corresponding (starting) T C A value.
  • crystallization temperatures are measured by first melting and then cooling the polymer sample (using DSC as previously said), such crystallization temperatures are attributable to the crystalline form II.
  • the crystallization temperatures are determined after one melting cycle, followed by cooling.
  • compositions of the present invention Another important property for the compositions of the present invention is the rate of transformation from the said crystalline form II to the more stable crystalline form I.
  • Such transformation rate can be expressed as the time required to reach 80% of transformation from the form II to the form I.
  • Such transformation time (hereinafter called tVs) can be measured with DSC by comparing the melting peak areas of the said two crystalline forms in a sufficient number of samples after increasing time from a melting and cooling cycle, and drawing a curve correlating the relative volume of form I with time. The tVs value is reached when such a relative value becomes 80%.
  • Preferred tVs values for the compositions of the present invention are from 48 to 100 hours, particularly for those compositions where A) comprises one or more butene-1 homoploymers.
  • compositions of the present invention are:
  • Flexural Modulus from 400 to 550 MPa, more preferably from 450 to 550 MPa, measured after 10 days from melting and cooling to solid state; Strength at Break: from 32 to 40 N/mm 2 , more preferably from 34 to 40 N/mm 2 , measured after 10 days from melting and cooling to solid state; Elongation at Break: from 280 to 380%, more preferably from 280 to 350%, measured after
  • the butene-1 polymers preferably employed in the process and compositions of the present invention are linear homopolymers that are semicrystalline and highly isotactic (having in particular an isotacticity from 90 to 99%, preferably from 95 to 99%, measured both as mmmm pentads/total pentads using NMR and as quantity by weight of matter soluble in xylene at 0 0 C), typically obtained by polymerization of butene-1 with a stereospecific catalyst.
  • the isotacticity index can be expressed as the weight fraction that is insoluble in xylene, still at 0 0 C, and is preferably from 40% to 98%.
  • the butene-1 polymers used in the process and compositions of the present invention have a melting point from 80 to 125 0 C, more preferably from 100 to 125 0 C, measured with the previously said DSC method, during the first heating run.
  • Suitable copolymers of butene-1 are preferably those containing up to 5% by moles of olefinic comonomers, in particular from 0.1% to 5% by moles, more preferably from 0.1% to 3% by moles.
  • the said homo- and copolymers can be obtained by low- pressure Ziegler-Natta polymerization of butene-1, for example by polymerizing butene-1 (and any comonomers) with catalysts based on TiCl 3 , or halogenated compounds of titanium (in particular TiCU) supported on magnesium chloride, and suitable co-catalysts (in particular alkyl compounds of aluminium).
  • Electron-donor compounds can be added to the said catalyst components to tailor the polymer properties, like molecular weights and isotacticity. Examples of the said electron-donor compounds are the esters of carboxylic acids and alkyl alkoxysilanes.
  • 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 is also possible to carry out the polymerization process in the gas-phase, operating in one or more fluidized or mechanically agitated bed reactors. Solution and gas-phase processes are highly preferred.
  • butene polymers can also be prepared by polymerization in the presence of catalysts obtained by contacting a metallocene compound with an alumoxane.
  • the (co) polymers have a Melt Index' ⁇ " (measured according to ASTM D 1238 condition "E", at 190 °C/2.16 kg) of from 100 to 0.01, more preferably from 10 to 0.1 g/10 min..
  • Melt Index' ⁇ measured according to ASTM D 1238 condition "E"
  • High values of MFR can be obtained directly in polymerization or by successive chemical treatment (chemical visbreaking) of the polymer.
  • the chemical visbreaking of the polymer is carried out in the presence of free radical initiators, such as the peroxides.
  • free radical initiators such as the peroxides.
  • radical initiators that can be used for this purpose are the 2,5-dimethyl-2,5-di (tert-butylperoxide)-hexane and dicumyl-peroxide.
  • Preferred intrinsic viscosity values for the butene-1 polymers are from 1.5 to 4 dl/g, as measured in decalin at 135 0 C.
  • MWD molecular weight distribution
  • M w /M n values of greater than 6 are generally considered to amount to a broad MWD.
  • Butene-1 polymers with a broad MWD can be obtained in several ways.
  • One of the methods consists in using, when (co) polymerizing butene-1, a catalyst intrinsically capable of producing broad MWD polymers.
  • Another possible method is that of mechanically blending butene-1 polymers having different enough molecular weights using the conventional mixing apparatus.
  • butene-1 polymers employed in the process and compositions of the present invention are:
  • Flexural Modulus from 300 to 450 MPa, more preferably from 350 to 450 MPa, measured after 10 days from melting and cooling to solid state; Strength at Break: from 32 to 40 N/mm 2 , more preferably from 34 to 40 N/mm 2 , measured after 10 days from melting and cooling to solid state; Elongation at Break: from 350 to 500%, more preferably from 350 to 450%, measured after
  • any additional polyolefm be present in amounts of 10% by weight or less.
  • they can be present in amounts from 0.1% to 10% by weight, more preferably from 0.1% to 5% by weight, with respect to the total weight of A) and the said additional polyolef ⁇ n(s).
  • the preferred values of Melt Index"L" (measured according to ASTM D 1238 condition "L", at 230 0 C, 2.16 kg load) for the said propylene homopolymers and copolymers are from 0.1 to lOO g/lO min..
  • ethylene polymers are the high density polyethylene (HDPE, typically having a density from 0.940 to 0.965 g/cm ), and linear low density polyethylene (LLDPE, typically having a density from 0.900 to 0.939 g/cm 3 ), usually obtained by low pressure polymerization, and low density polyethylene (LDPE, typically having a density from 0.917 to 0.935 g/cm 3 ), usually obtained by high pressure polymerization.
  • HDPE high density polyethylene
  • LLDPE linear low density polyethylene
  • LDPE low density polyethylene
  • the said low pressure polymerization is carried out in the presence of Ziegler-Natta catalysts, while the high pressure polymerization is carried out in the presence of radical initiators, such as peroxides.
  • the previously said component B) employed in the process and compositions of the present invention is selected from metal salts of carboxylic acids containing two or more carboxylic groups bonded to a cyclic or polycyclic aliphatic or aromatic structure.
  • Preferred metals in the said salts are those having valence from 1 to 3, in particular the metals of groups I and II of the Periodic System, Al, Fe and Cr. Particularly preferred are Li,
  • salts preferred are the metal salts of carboxylic acids containing two carboxylic groups.
  • metal salts of polycyclic saturated or unsaturated carboxylic acids containing two carboxylic groups are particularly preferred.
  • the salts of bicyclic acids having up to 8 carbon atoms in the bicyclic structure, wherein one or more hydrogen atoms can be optionally substituted (with alkyl and/or aryl groups, optionally containing heteroatoms), are preferred.
  • Examples of such salts and of their preparation are disclosed in the previously mentioned WO98/29494 and WO03/040230.
  • Particularly preferred among the said class are the salts of bicyclo [2.2.1] heptane-2,3- dicarboxylic acid, the disodium salt of which is commercially available as HPN-68 (sold by Milliken).
  • Suitable salts within the definition of the present invention are the metal salts of acids wherein the carboxylic groups are bonded to aromatic cyclic structures, like the salts of phthalic acids (also substituted, as, for example, tetramethyl terephthalic acid), or to aliphatic cyclic structures, like the salts of cyclohexanedircarboxylic acids. All the said cyclic structures can contain heteroatoms, like O, N, S.
  • metal salts of acids containing more than two carboxylic groups like benzene- 1, 2, 3 -tricarboxylic acid, benzene- 1,2,4-tricarboxylic acid, benzene-1,3,5- tricarboxylic acid, benzene- 1,2, 3, 4-tetracarboxylic acid, benzene- 1, 2,4, 5-tetracarboxylic acid.
  • All the said salts are known in the art and can be obtained by reacting the said acids with basic meal compounds, as LiOH, NaOH, or by reacting metal salts of the said acids, for instance sodium salts, with inorganic salts of other metals, like aluminum sulfate, optionally in the presence of a strong base, like NaOH.
  • the process of the present invention can be carried out by blending the components A) and
  • extruders commonly known in the art, including single-screw extruders, traditional and CoKneader (like the Buss), twin corotating screw extruders, mixers
  • Such blending apparatuses can be equipped with separate feeding systems for component A) and for the component B) respectively.
  • the component B) can be added to the polymer mass inside the blending apparatus, in particular the extruder, either in the same feed port or downstream from the point at which A) is fed into the blending apparatus, so that the distance between will allow A) to have reached the form of a melted, homogeneous mass.
  • premix components A) and B) before the blending step.
  • any method and apparatus used in the art can be adopted, in particular medium and high speed mixers like Nauta mixer, Mixaco and
  • the processing temperatures during the blending step must be sufficient to bring (and keep) component A) in the molten state, or to keep component A) in the molten state if A) has been already molten when B) is added.
  • Such temperatures preferably range from 100 0 C to
  • 220 0 C more preferably from 100 to 200 0 C, most preferably 120 to 200 0 C.
  • polybutene-1 compositions of the present invention are for making pipes, in particular for water and hot fluids. In general they can be advantageously used for any application where the improved mechanical properties produced by nucleation are desirable.
  • the crystallization temperature (T c c and T C A ) and the melting temperature values are determined using the following procedure according to ISO 11357 Part 3. Differential scanning calorimetric (DSC) data is obtained using a DSC QlOOO TA Instruments. Samples weighing approximately 6-8 mg are sealed in aluminum sample pans. The samples are subjected to a heating run from 5 0 C to 180 0 C with a heating rate of 10 °C/minute, and kept at 180 0 C under isothermal conditions for 5 minutes. The melting temperature is determined during such heating run.
  • DSC Differential scanning calorimetric
  • the samples are cooled from 180 0 C to 5 0 C for butene-1 homopolymers, or to -20 0 C for butene-1 copolymers, with a cooling rate of 10 °C/minute.
  • the crystallization temperature is determined during the said cooling run. t'n ⁇ determination
  • the t'o 8 values are determined by first calculating the apparent melting enthalpies, based on the area of the melting peaks, of the I and II forms. Then, by dividing the apparent enthalpy of the respective melting peaks by the corresponding fusion heats of the pure crystalline phase, namely 32.5 cal/g for form I and 16 cal/g for form II, the weight, in grams, of each crystalline form present in the sample is calculated. From the weight values, the corresponding volumes (VolForm I and VolForm II) are calculated, by dividing by the corresponding densities, namely 0.95 g/cm 3 for form I and 0.90 g/cm 3 for form II. Then the volume percentage of form I (Vol%Form I) is calculated according to the following formula:
  • Vol%Form I VolForm I x 100/(VolForm I + VolForm II).
  • the measurement is carried out by preparing a 10%wt solution of the polymer in C 2 Cl 4 D 2 and recording the spectra at a temperature of 120 0 C with a DRX 500MHz instrument operating at 125,7 MHz under proton Waltz 16 decoupling in FT mode, with lOKhz spectral width, 90° pulse angle and 16sec. puls repetition and 3600 scans.
  • the Isotactic index is then calculated 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.
  • Butene-1 homopolymer (PB), with Melt Index E of 0.3 g/10 min., melting point TmI, measured in the first heating run of, 124.5 0 C, isotacticity index of 98% and M w /M n of 5.5, in form of pellets.
  • Irganox 1010 pentaerytrityl tetrakis 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propanoate, marketed by Ciba Geigy;
  • Irgafos 168 tris (2,4-di-tert-butylphenyl) phosphite, marketed by Ciba Geigy;
  • the process according to the present invention is carried out by a dry blend preparation in Turbomix and extrusion using a Leistritz 27 mm co-rotating twin screw extruder equipped with two K-Tron Loss in Weight feeders and a strand die plate having two holes of 3 mm diameter.
  • Running conditions Capacity: lO kg/h; Screw speed: 220 rpm; Torque: 30%;
  • Die plate 2 x 3 mm; Die pressure: 10 bar.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Cette invention concerne un procédé permettant de produire une composition de polybutène-1 présentant une température de cristallisation TcA plus élevée, lequel procédé comprend l'étape qui consiste à mélanger les composants suivants: A) une composition polymère de butène-1 ou polymère présentant une température de cristallisation TcA égale ou supérieure à 50 °C; B) de 5 à 3000 ppm en poids, par rapport au poids total de A) et B), d'un ou de plusieurs sels métalliques d'acides carboxyliques contenant au moins deux groupes carboxyliques liés à une structure aromatique ou aliphatique polyclique ou cyclique. La composition polymère de butène-1 ou polymère A) étant amenée à l'état fondu ou maintenue à l'état fondu pendant l'étape de mélange.
PCT/EP2007/061142 2006-12-01 2007-10-18 Procédé permettant de préparer des compositions de polybutène présentant une température de cristallisation plus élevée Ceased WO2008064957A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP06125201 2006-12-01
EP06125201.1 2006-12-01
US87301306P 2006-12-05 2006-12-05
US60/873,013 2006-12-05

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8557913B2 (en) 2008-12-19 2013-10-15 Basell Poliolefine Italia S.R.L. Filled polyolefin compositions
WO2018095720A1 (fr) 2016-11-23 2018-05-31 Basell Poliolefine Italia S.R.L. Composition de polyoléfine chargée

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005047383A1 (fr) * 2003-11-07 2005-05-26 Milliken & Company Concentres de sels de dicarboxylate bicycliques satures utilises en tant qu'additifs de nucleation polymeres et procedes de nucleation de produits thermoplastiques
WO2005066247A1 (fr) * 2003-12-24 2005-07-21 Petroquimica Cuyo S.A.I.C. Compositions de resine utiles comme couches de scellement
US20060135679A1 (en) * 2004-12-22 2006-06-22 Advantage Polymers, Llc. Thermoplastic compositions and method of use thereof for molded articles

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005047383A1 (fr) * 2003-11-07 2005-05-26 Milliken & Company Concentres de sels de dicarboxylate bicycliques satures utilises en tant qu'additifs de nucleation polymeres et procedes de nucleation de produits thermoplastiques
WO2005066247A1 (fr) * 2003-12-24 2005-07-21 Petroquimica Cuyo S.A.I.C. Compositions de resine utiles comme couches de scellement
US20060135679A1 (en) * 2004-12-22 2006-06-22 Advantage Polymers, Llc. Thermoplastic compositions and method of use thereof for molded articles

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8557913B2 (en) 2008-12-19 2013-10-15 Basell Poliolefine Italia S.R.L. Filled polyolefin compositions
WO2018095720A1 (fr) 2016-11-23 2018-05-31 Basell Poliolefine Italia S.R.L. Composition de polyoléfine chargée

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