FIELD OF THE INVENTION

[0001] The present disclosure concerns a process for producing polybutene- 1 compositions with increased crystallization temperature and the compositions thus obtained.

BACKGROUND OF THE INVENTION

[0002] It is known in the art that the crystallization temperature of polyolefins 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). 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.

[0003] Thus there is a continuous effort in the art to find nucleating agents able to increase significantly the crystallization temperature of polyolefins.

[0004] The most valuable 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.

[0005] Moreover, in order to achieve a high speed in extrusion in the pipe molding process, which is generally carried out by extrusion, a sufficiently short crystallization time is required.

[0006] More generally, a short crystallization time is beneficial in many polymer molding processes in order to achieve a high processing speed.

[0007] The applicant has now found that the said effects can be satisfactorily achieved by nucleating polybutene-1 with a specific class of alkanoyl hydrazines.

SUMMARY OF THE INVENTION

[0008] Thus the present disclosure provides a process for producing a polybutene-1 composition having increased crystallization temperature Tc, comprising the step of blending the following components:

A) from 99.5 to 99.9% by weight, preferably from 99.6 to 99.85% by weight, with respect to the total weight of A) + B), of a butene- 1 polymer selected from butene- 1 homopolymers, butene-1 copolymers and their mixtures, said butene-1 polymer being brought to the molten state or maintained in the molten state during the blending step;

B) from 0.1 to 0.5% by weight, preferably from 0.15 to 0.4% by weight, with respect to the total weight of A) + B), of one or more alkanoyl hydrazines of formula (I): wherein Ri is an alkyl group containing from 1 to 6 carbon atoms, R2 is hydrogen or an alkyl group containing from 1 to 6 carbon atoms and n is an integer number from 0 to 5; the so obtained polybutene-1 composition having a crystallization temperature T _c ^c satisfying the following relation:

T _c ^c > T _C ^A + 5 where T _C ^A and T _c ^c are expressed in °C, T _C ^A is the crystallization temperature of the butene-1 polymer A) and is preferably equal to or higher than 60 °C, more preferably equal to or higher than 65 °C, said crystallization temperatures being determined by differential scanning calorimetry (DSC), with a heating and cooling rate of 10 °C/minute.

[0009] The use of said hydrazine derivative compounds as stabilizers in polyolefins, including butene-1 polymers, is known, for instance from US3773722 and US4812500.

[0010] However it has never been appreciated that such compounds can have a nucleating effect in crystalline butene-1 polymers having a sufficiently high crystallization temperature.

[0011] Thus the present process also amounts to a new use of the alkanoyl hydrazines B), in the said proportions, to increase the crystallization temperature of component A).

[0012] The present disclosure also provides a polybutene-1 composition comprising:

A) from 99.5 to 99.9% by weight, preferably from 99.6 to 99.85% by weight, with respect to the total weight of A) + B), of a butene-1 polymer selected from butene-1 homopolymers, butene-1 copolymers and their mixtures, said butene-1 polymer having crystallization temperature T _C ^A equal to or higher than 60 °C, preferably equal to or higher than 65 °C;

B) from 0.1 to 0.5% by weight, preferably from 0.15 to 0.4% by weight, with respect to the total weight of A) + B), of one or more alkanoyl hydrazines of the above said formula (I); said composition having a crystallization temperature T _c ^c satisfying the following relation:

TC ^C > T _C ^A + 5.

DETAILED DESCRIPTION OF THE INVENTION

[0013] Preferably the present polybutene-1 compositions have a crystallization temperature T _c ^c satisfying the following relation:

TC ^C > T _C ^A + 10.

[0014] More preferably the present polybutene-1 compositions have a crystallization temperature T _c ^c satisfying the following relation:

TC ^C > T _C ^A + 15.

[0015] The said crystallization temperatures are determined after one melting cycle, with a scanning speed of 10°C/minute.

[0016] Consequently, due to the fact that the crystallization temperatures are measured in a cooling run carried out after first melting the polymer sample (using DSC as previously said), such crystallization temperatures are attributable to the crystalline form II of the butene- 1 polymer.

[0017] Should more than one crystallization peak be detected, the temperature of the most intense peak is to be taken as the Tc value for both the butene- 1 polymer component A) and the present polybutene-1 composition.

[0018] A further effect of component B) is that the present polybutene-1 composition has a short crystallization time.

[0019] Preferably it has a crystallization half-time at 95°C of from 50 to 150 seconds, in particular from 65 to 130 seconds.

[0020] This determination is made by DSC, by first melting the sample, then rapidly cooling it to the desired temperature (in the present case to 95°C) and measuring the heat flow caused by the crystallization exotherm. The integral of heat transfer is recorded as a function of time until the crystallization is complete, i.e., heat transfer ceases.

[0021] The crystallization half-time is the time at which the heat transfer integral reaches half of its final value.

[0022] Moreover, the present polybutene-1 composition has preferably at least one of the following additional features: - a T _c ^c value equal to or higher than 85 °C, in particular from 85 °C to 98 °C;

- a tensile elastic modulus from 500 to 800 MPa, more preferably from 550 to 750 MPa, measured at 23°C via DMTA analysis according to ISO 6721-4:2019 on 1mm thick compression molded plaque;

- a value of Charpy impact resistance at 23°C from 3 to 20 kJ/m ² , in particular from 5 to 15 kJ/m ² , measured according to ISO 179-1 :2010 leA;

- a value of Charpy impact resistance at 0°C from 1 to 10 kJ/m ² , in particular from 1 to 5 kJ/m ² , measured according to ISO 179-1 :2010 leA;

- a value of Charpy impact resistance at -23°C from 1 to 8 kJ/m ² , in particular from 1 to 3 kJ/m ² , measured according to ISO 179-1 :2010 leA.

[0023] When the butene- 1 polymer component A) is made of or comprises one or more butene- 1 copolymers, such copolymers can contain one or more comonomer(s) preferably selected from ethylene, propylene and CH2=CHR alpha-olefins, where R is a Cs-Cs alkyl radical, in particular pentene-1, 4-methyl-pentene-l, hexene-1 and octene-1.

[0024] Ethylene, propylene and hexene-1 are preferred.

[0025] From the above definitions it is evident that the term “copolymers” includes polymers containing more than one kind of comonomers.

[0026] The butene-1 polymer component A) is known in the art and commercially available, as shown in the examples.

[0027] The said butene-1 polymer component A) is preferably a linear polymer which is highly isotactic.

[0028] In particular the butene-1 polymer component A) has an isotacticity from 90 to 99%, more preferably from 93 to 99%, most preferably from 95 to 99%, measured as mmmm pentads/total pentads with ¹³ C-NMR operating at 150.91 MHz, or as quantity by weight of matter insoluble in xylene at 0 °C.

[0029] The butene-1 polymer component A) has preferably a Mb value of from 0.05 to 50 g/10 min., more preferably from 0.1 to 10 g/10 min., wherein Mb is the Melt Flow Index MI at 190°C with a load of 2.16 kg, measured according to ISO 1133-1 :2011.

[0030] The Mho value of the butene-1 polymer component A) is preferably of 1 to 100 g/10 min., more preferably of 2 to 50 g/10 min., wherein Mho is the Melt Flow Index MI at 190°C with a load of 10 kg, measured according to ISO 1133-1 :2011.

[0031] Preferably, the butene-1 polymer component A) has a ratio Mho/Mh of from 20 to 40, more preferably from 25 to 35. [0032] In one embodiment, the butene- 1 polymer component A) may be selected from homopolymers.

[0033] In one further embodiment, the butene- 1 polymer A) may be selected from copolymers having a comonomer content, in particular a copolymerized ethylene content, of from 0.5% to 10% by mole, preferably of from 0.7% to 9% by mole.

[0034] In one further embodiment, the butene- 1 polymer component A) may be a butene- 1 polymer composition comprising:

Al) a butene-1 homopolymer or a copolymer of butene- 1 with at least one comonomer selected from ethylene, propylene, the previously defined CH2=CHR olefins and mixtures thereof, having a copolymerized comonomer content of up to 2% by mole;

A2) a copolymer of butene-1 with at least one comonomer selected from ethylene, propylene, the previously defined CH2=CHR olefins and mixtures thereof, having a copolymerized comonomer content of from 3 to 25% by mole;

[0035] said composition having a total copolymerized comonomer content of 0.5 - 18% by mole, preferably of from 0.7 to 15% by mole, referred to the sum of Al) + A2).

[0036] The relative amounts of Al) and A2) may range from 10% to 40% by weight, in particular from 15% to 35% by weight of Al) and from 90% to 60% by weight, in particular from 85% to 65% by weight of A2), said amounts being referred to the sum of Al) + A2).

[0037] In one embodiment, the butene-1 polymer component A) may have at least one of the following additional features:

- an upper limit of the crystallization temperature of 80 °C;

- a flexural modulus value from 100 to 800 MPa, more preferably from 250 to 600 MPa, most preferably from 300 to 600 MPa, measured according to norm ISO 178:2010, 10 days after molding;

- a molecular weight distribution Mw/Mn equal to higher than 4, preferably equal to or higher than 5, the upper limit being preferably of 10 in all cases, wherein Mw is the weight average molar mass and Mn is the number average molar mass, measured by Gel Permeation Chromatography;

- melting point Tmll, measured by DSC (Differential Scanning Calorimetry) in the second heating run with a scanning speed of 10 °C/min., equal to or lower than 125°C, preferably equal to or lower than 120°C, the lower limit being preferably in all cases of 75°C;

- a content of fraction soluble in xylene at 0°C of 15% by weight or lower, more preferably of 10% by weight or lower, referred to the total weight of A), the preferred lower limit being of 0.5% by weight in all cases;

- X-ray crystallinity of from 25 to 65%. [0038] Optionally, the butene- 1 polymer component A) may have at least one of the following further additional features:

- intrinsic viscosity (I V.) measured in tetrahydronaphtalene (THN) at 135°C, equal to or lower than 5 dl/g, preferably equal to or lower than 3 dl/g, the lower limit being preferably of 0.4 dl/g in all cases;

- Mw equal to or greater than 100000 g/mol, in particular from 100000 to 650000 g/mol;

- melting point Tml, measured by DSC with a scanning speed of 10 °C/min., from 95°C to 135°C;

- a density of 885-925 kg/m ³ , preferably of 900-920 kg/m ³ , in particular of 912-920 kg/m ³ .

[0039] The butene- 1 polymer component A) 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 TiCh, or halogenated compounds of titanium (in particular TiCh) supported on magnesium chloride, and a co-catalyst (in particular alkyl compounds of aluminium). Electrondonor 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.

[0040] In particular, the butene-1 polymer component A) can be prepared by polymerization of the monomers in the presence of a stereospecific catalyst comprising (i) a solid component comprising a Ti compound and an internal electron-donor compound supported on MgCh; (ii) an alkylaluminum compound and, optionally, (iii) an external electron-donor compound.

[0041] 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.

[0042] The preferred titanium compounds used in the catalyst component (i) are TiCh and TiCh; furthermore, also Ti-haloalcoholates of formula Ti(OR)n-y X _y , where n is the valence of titanium, X is halogen, preferably chlorine, and y is a number between 1 and n, can be used.

[0043] The internal electron-donor compound is preferably selected from esters and more preferably from alkyl, cycloalkyl or aryl esters of monocarboxylic acids, for example benzoic acids, or polycarboxylic acids, for example phthalic, succinic or glutaric acids, the said alkyl, cycloalkyl or aryl groups having from 1 to 18 carbon atoms. Examples of the said electron-donor compounds are diisobutyl phthalate, diethylphtahalate, dihexylphthalate, diethyl or diisobutyl 3,3

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

[0044] The alkyl-Al compound (ii) 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 compounds with alkylaluminum halides, alkylaluminum hydrides or alkylaluminum sesqui chlorides such as AlEt2Cl and AhEtsCh.

[0045] The external electron-donor compounds (iii) are preferably selected among silicon compounds of formula R _a ¹ Rb ² Si(OR ³ ) _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 ¹ , R ² , and R ³ , are alkyl, cycloalkyl or aryl radicals with 1-18 carbon atoms optionally containing heteroatoms. A particularly preferred group of silicon compounds is that in which a is 0, c is 3, b is 1 and R ² is a branched alkyl or cycloalkyl group, optionally containing heteroatoms, and R ³ is methyl. Examples of such preferred silicon compounds are cyclohexyltrimethoxysilane, t-butyltrimethoxysilane diisopropyldrimethoxysilane and thexyltrimethoxysilane. The use of thexyltrimethoxysilane is particularly preferred.

[0046] The external electron-donor compound (iii) is used in such an amount to give a molar ratio between the organoaluminum compound and said external electron-donor compound (iii) of from 0.1 to 500, preferably from 1 to 300 and more preferably from 3 to 100.

[0047] In order to make the catalyst particularly suitable for the polymerization step, it is possible to pre-polymerize said catalyst in a pre-polymerization 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 2000 g per g of solid catalyst component, preferably between 5 and 500 and, more preferably, between 10 and 100g per g of solid catalyst component.

[0048] In alternative, the butene- 1 polymer component A) can be obtained by polymerizing the monomer(s) in the presence of a metallocene catalyst system obtainable by contacting:

- a stereorigid metallocene compound;

- an alumoxane or a compound capable of forming an alkyl metallocene cation; and, optionally,

- an organo aluminum compound. [0049] The polymerization process can be carried out with the said catalysts by operating in liquid phase, optionally in the presence of an inert hydrocarbon solvent, or in gas phase, using fluidized bed or mechanically agitated gas phase reactors.

[0050] The hydrocarbon solvent can be either aromatic (such as toluene) or aliphatic (such as propane, hexane, heptane, isobutane, cyclohexane and 2,2,4-trimethylpentane, isododecane).

[0051] Preferably, the polymerization process is carried out by using liquid butene- 1 as polymerization medium.

[0052] The polymerization temperature can be from 20°C to 150°C, in particular from 50°C to 90°C, for example from 65°C to 82°C.

[0053] To control the molecular weights, a molecular weight regulator, in particular hydrogen, is fed to the polymerization environment.

[0054] Mw/Mn values equal to or higher than 4, as well as the previously defined values of the MI10/MI2 ratio, are generally considered to amount to a broad molecular weight distribution (MWD).

[0055] 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 a conventional mixing apparatus.

[0056] It is also possible to operate according to a multistep polymerization process, wherein the said butene-1 polymers with different molecular weights are prepared in sequence in two or more reactors with different reaction conditions, such as the concentration of molecular weight regulator fed in each reactor.

[0057] It is also possible to feed different monomer amounts in each reactor.

[0058] In particular, when the present butene-1 polymer component A) comprises the previously said two components Al) and A2), the polymerization process can be carried out in two or more reactors connected in series, wherein components Bl) and B2) are prepared in separate subsequent stages, operating in each stage, except for the first stage, in the presence of the polymer formed and the catalyst used in the preceding stage.

[0059] The catalyst can be added in the first reactor only, or in more than one reactor.

[0060] High MI values can be obtained directly in polymerization. High MI values can also be obtained by subsequent chemical treatment (chemical visbreaking).

[0061] The chemical visbreaking of the polymer is carried out in the presence of free radical initiators, such as the peroxides. [0062] The peroxides which are most conveniently used in the polymer visbreaking process have a decomposition temperature preferably ranging from 150°C to 250°C. Examples of said peroxides are di-tert-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di(tert- butylperoxy)hexyne and 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, all of which are commercially available.

[0063] The quantity of peroxide necessary for the visbreaking process preferably ranges from 0.001 to 0.5% by weight of the polymer, more preferably from 0.001 to 0.2%.

[0064] Illustrative examples of alkyl groups Ri and R2 in the alkanoyl hydrazines A) of formula (I) are methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl and hexyl, t-butyl being particularly preferred.

[0065] Preferably, the alkanoyl hydrazines A) have the following formula (II): wherein Ri and R2 have the same meaning as previously reported in formula (I).

[0066] A particularly preferred alkanoyl hydrazine A) is the compound N, N’- bis - [3-(3 , 5-di- tert-butyl-4-hydroxyphenyl)-propionyl-hydrazine, also called 2’,3-Bis[[3-[3,5-di-tert-butyl-4- hydroxyphenyl]propionyl]]propionohydrazide, having formula (III): [0067] The said alkanoyl hydrazines A) can be prepared by the reaction between hydrazine and an ester of an alkylhydroxyphenylalkanoic acid, followed by further acylation, as illustrated in US3773722.

[0068] The alkanoyl hydrazine of formula (III) is commercially available with the trade name Irganox 1024, sold by BASF.

[0069] The present polybutene- 1 composition can also contain talc as optional component C). [0070] Preferred amounts of component C) are from 0.15% to 2.5% by weight, more preferred are from 0.2% to 2% by weight, most preferred from 0.2% to 1.5% by weight, referred to the total weight of A) + B) + C).

[0071] Particularly preferred is talc in form of particles having a volume based (volumetric) particle diameter distribution Dv (0.95) of 45 pm or lower, preferably of 35 pm or lower, more preferably of 25 pm or lower, in particular of 20 pm or lower, determined by means of laser light diffraction, the lower limit being preferably in all cases of 5 pm;

[0072] In addition to the said Dv (0.95) values, component C) has preferably at least one of the following volume based particle diameter distribution features:

- Dv (0.99) of 100 pm or lower, or of 50 pm of lower, or of 30 pm or lower, the lower limit being preferably in all cases of 10 pm;

- Dv (0.90) of 20 pm or lower, or of 15 pm of lower, the lower limit being preferably in all cases of 3 pm;

- Dv (0.50) of 10 pm or lower, or of 8 pm or lower, the lower limit being preferably of 2 pm.

- Dv (0.10) of 5 pm or lower, or of 4 pm or lower, the lower limit being preferably of 1 pm.

[0073] For volume based particle diameter, the diameter of an equivalent sphere having the same volume as the subject particle is meant.

[0074] Thus the said values of volume based particle diameter distribution mean that the specified volume fraction of particles, for instance 95% by volume for Dv (0.95), have an equivalent diameter of less than the given value.

[0075] Such determination is carried out by laser diffraction.

The analytical equipment used is preferably a Malvern Mastersizer instrument.

[0076] As well known, talc is a hydrated magnesium silicate.

[0077] It is generally reported to have formula Mg ₃ Si40io(OH) ₂ .

[0078] In nature it is a mineral mainly or substantially composed of the said hydrated magnesium silicate, optionally associated with other mineral materials, such as chlorite (hydrated magnesium aluminum silicate) and dolomite.

[0079] To achieve the said values of particle diameter distribution, talc can be milled with known techniques, for instance with air classified mills, compressed air, steam and impact grinding.

[0080] The present polybutene- 1 composition can be obtained by blending the components A), B) and optionally C) with blending techniques and apparatuses well known in the art.

[0081] Thus, one can use extruders commonly known in the art, including single-screw extruders, traditional and CoKneader (like the Buss), twin corotating screw extruders or mixers (continuous and batch). Such blending apparatuses can be equipped with separate feeding systems for component A), B) and optionally C) respectively. The component B) and the optional component C) 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.

[0082] Components B) and C) can be fed in form of masterbatch in a polymer carrier, more preferably in a polyolefin carrier, in particular a polybutene carrier of the same kind as the butene- 1 polymer component A).

[0083] 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) and optionally C) are added. Such temperatures preferably range from 100 °C to 220 °C, more preferably from 150 to 220 °C, most preferably 180 to 220 °C.

[0084] During the preparation of the polybutene- 1 composition, besides the main components A) and B), optionally C) and other optional components, it is possible to introduce additives commonly employed in the art, such as stabilizing agents (against heat, light, U. V.), plasticizers, antiacids, antistatic and water repellant agents, pigments.

[0085] As previously mentioned, a preferred use for the present polybutene-1 composition is for making pipes, in particular for carrying water and hot fluids, and pipe joints. In general it can be advantageously used for any application where the improved mechanical and processing properties are desirable.

EXAMPLES

[0086] The practice and advantages of the various embodiments, compositions and methods as provided herein are disclosed below in the following examples. These Examples are illustrative only, and are not intended to limit the scope of the appended claims in any manner whatsoever.

[0087] The following analytical methods are used to characterize the polymer compositions and filaments. [0088] Crystallization and melting temperature

[0089] The crystallization temperature (T _c ) and the melting temperature values were determined using the following procedure.

[0090] Differential scanning calorimetric (DSC) data were obtained using a Perkin Elmer DSC-7 instrument. A weighted sample (5-10 mg) was sealed into aluminum pans and heated at 200°C with a scanning speed corresponding to 10°C/minute. The sample was kept at 200°C for 5 minutes to allow a complete melting of all the crystallites thus cancelling the thermal history of the sample. Successively, by cooling to -20°C with a scanning speed corresponding to 10°C/minute, the peak temperature was taken as crystallization temperature (T _c ) and the area as the crystallization enthalpy. After standing 5 minutes at -20°C, the sample was heated for the second time to 200°C with a scanning speed corresponding to 10°C/min. In this second heating run, the peak temperature was taken as the melting temperature of the polybutene- 1 crystalline form II (Tmll) and the area as the melting enthalpy (AHfll).

[0091] In order to determine the melting temperature of the polybutene- 1 crystalline form I (Tml), the sample was melted, kept at 200°C for 5 minutes and then cooled down to 20°C with a cooling rate of 10°C/min. The sample was then stored for 10 days at room temperature. After 10 days the sample was subjected to DSC, it was cooled to -20°C, and then it was heated at 200°C with a scanning speed corresponding to 10°C/min. In this heating run, the first peak temperature coming from the lower temperature side in the thermogram was taken as the melting temperature (Tml).

[0092] Crystallization half-time at 95°C

[0093] Differential scanning calorimetric (DSC) data were obtained using a Perkin Elmer DSC-7 instrument. A weighted sample (5-10 mg) was sealed into aluminum pans and heated from room temperature to 180°C with a scanning speed corresponding to 10°C/minute.

[0094] The sample was kept at 180°C for 5 minutes to allow a complete melting of all the crystallites thus cancelling the thermal history of the sample.

[0095] Successively, it was cooled to 95°C with a scanning speed corresponding to 60°C/minute and the heat flow caused by the crystallization exotherm at 95°C was measured. The integral of heat transfer was recorded as a function of time until the crystallization was complete, i.e., heat transfer ceased.

[0096] The crystallization half-time is the time at which the heat transfer integral reaches half of its final value.

[0097] Particle size distribution [0098] Particle size distribution (PSD) was measured by laser diffraction according to ISO 13320:2009.

[0099] The equipment used was a Mastersizer ® 2000 with sample dispersion unit, from Malvern UK.

[0100] The detection system had the following features:

- Red light: forward scattering, side scattering, back scattering;

- Blue light: wide angle forward and back scattering;

- Light sources: Red light He-Ne Laser; Blue light solid state light source;

- Optical alignment system: Automatic rapid align system with dark field optical reticule;

- Laser system: Class 1 laser product.

[0101] PSD determination is based on the optical diffraction principle of the laser monochromatic light scattered through a dispersed particulate sample. The signal is received by a computer interfaced to the instrument, for processing the received signals and turning them into a dimensional physical quantities.

[0102] The results are expressed by a PSD report consisting of 106 classes of diameter (virtual sieves) with related cumulative percentages in terms of volume and additional derived parameters. [0103] The measurement data are contaminated by background electrical noise and also by scattering data from dust on the optics and contaminants floating in the dispersant. For this reason it is necessary to make sure that the sample dispersion unit is clean and all traces of impurities and residual material have been removed.

[0104] Thus, a background measurement with pure dispersant (solvent) as well as a measurement of the electrical background was made. The total background value obtained was subtracted from the sample measurement to obtain the real sample data.

[0105] For the background measurement, 250 cc. of anhydrous n-heptane solvent containing 2 g/1 SPAN 80 Pure as antistatic agent were introduced into the sample dispersion unit. Air residual in solvent was removed by ultrasonic treatment (60 seconds) prior to every measurement.

[0106] The solvent was then sent to the measurement cell, while stirrer and recycle pump were operating at an output range of 2205 rpm.

[0107] Measurement

[0108] The sample, kept in suspension in anhydrous n-heptane by stirring, was added directly into the sample unit.

[0109] A 2 minutes sample suspension recycling is needed to promote disaggregation of aggregates (if present). [0110] On the monitor it was possible to see the obscuration bar, allowing to reach the optimal volume concentration of sample. The concentration of sample must correspond to obscuration values ranging from 10 % to 30%. This range guarantees a representative and stable result.

[oni] The refractive index (RI) was set to:

Particle RI: 1.596;

Dispersant RI: 1.390.

[0112] The measurement time was of 4 seconds.

[0113] The signals received from the laser equipment were processed. The PSD was then calculated by the software provided with the Mastersizer apparatus.

[0114] Melt Flow Index MI

[0115] Determined according to ISO 1133-1 :2011 at 190°C with the specified load.

[0116] Intrinsic viscosity

[0117] Determined according to norm ASTM D 2857-16 in tetrahydronaphthalene at 135 °C.

[0118] Tensile elastic modulus (MET-DMTA)

[0119] Determined at 23°C via Dynamic Mechanical Thermal Analysis (DMTA) according to ISO 6721-4:2019 on 1mm thick compression molded plaque, measured 10 days after molding.

[0120] Flexural modulus

[0121] Measured according to norm ISO 178:2019, measured 10 days after molding.

[0122] Charpy impact resistance at 23°C, 0°C and -23°C

[0123] Measured according to ISO 179-1 :2010 leA, 10 days after molding.

[0124] Comonomer contents

[0125] The comonomer content of the butene- 1 polymers was determined via FT-IR.

[0126] The spectrum of a pressed film of the polymer was recorded in absorbance vs. wavenumbers (cm ^-1 ). The following measurements were used to calculate the ethylene content: a) area (At) of the combination absorption bands between 4482 and 3950 cm' ¹ which is used for spectrometric normalization of film thickness. b) factor of subtraction (FCRc2) of the digital subtraction between the spectrum of the polymer sample and the absorption band due to the sequences BEE and BEB (B: 1, butene units, E: ethylene units) of the methylenic groups (CEE rocking vibration). c) Area (Ac2, block) of the residual band after subtraction of the C2PB spectrum. It comes from the sequences EEE of the methylenic groups (CEE rocking vibration).

[0127] APPARATUS [0128] A Fourier Transform Infrared spectrometer (FTIR) was used, which is capable of providing the spectroscopic measurements above reported.

[0129] A hydraulic press with platens heatable to 200 °C (Carver or equivalent) was used.

[0130] METHOD

[0131] Calibration of (BEB + BEE) sequences

[0132] A calibration straight line was obtained by plotting %(BEB + BEE)wt vs. FCRc2/At. The slope Gr and the intercept Irwere calculated from a linear regression.

[0133] Calibration of EEE sequences

[0134] A calibration straight line was obtained by plotting %(EEE)wt vs. Ac2, block/ At. The slope GH and the intercept IH were calculated from a linear regression.

[0135] Sample preparation

[0136] Using a hydraulic press, a thick sheet was obtained by pressing about g 1.5 of sample between two aluminum foils. If homogeneity is in question, a minimum of two pressing operations are recommended. A small portion was cut from this sheet to mold a film. Recommended film thickness ranges between 0.1-0.3 mm.

[0137] The pressing temperature was 140 ± 10 °C.

[0138] A crystalline phase modification takes place with time, therefore it is recommended to collect the IR spectrum of the sample film as soon as it is molded.

[0139] Procedure

[0140] The instrument data acquisition parameters were as follows:

Purge time: 30 seconds minimum.

Collect time: 3 minutes minimum.

Apodization: Happ-Genzel.

Resolution: 2 cm' ¹ .

Collect the IR spectrum of the sample vs. an air background.

[0141] CALCULATION

Calculate the concentration by weight of the BEE + BEB sequences of ethylene units:

Calculate the residual area (AC2, block) after the subtraction described above, using a baseline between the shoulders of the residual band.

Calculate the concentration by weight of the EEE sequences of ethylene units:

Calculate the total amount of ethylene percent by weight:

%C2 n7 = [%(BEE + BEB)\vt + %(££ /]

[0142] Determination of isotactic pentads content

The ¹³ C NMR spectra were acquired on a polymer solution (8-12 wt%) in dideuterated 1, 1,2,2- tetrachloro-ethane at 120 °C. The ¹³ C NMR spectra were acquired on a Bruker AV-600 spectrometer operating at 150.91 MHz in the Fourier transform mode at 120 °C equipped with cryo-probe, using a 90° pulse, 15 seconds of delay between pulses and CPD (WALTZ 16) to remove ³ H- ¹³ C coupling. About 512 transients were stored in 32K data points using a spectral window of 60 ppm (0-60 ppm). The mmmm pentad peak (27.73 ppm) was used as the reference. The assignments were made as described in the literature (Macromolecules 1991, 24, 2334-2340, by Asakura T ).

The percentage value of pentad tacticity (mmmm%) for butene-1 polymers is the percentage of stereoregular pentads (isotactic pentad) as calculated from the relevant pentad signals (peak areas) in the NMR region of branched methylene carbons as: mmmm%= 100 A1/(A1+A2) where Al is the area between 28.0 and 27.59 ppm;

A2 is the area between 27.59 and 26.52 ppm.

[0143] Fractions soluble and insoluble in xylene at 0°C (XS-0°C)

[0144] 2.5 g of the polymer sample were dissolved in 250 ml of xylene at 135°C under agitation. After 30 minutes the solution was allowed to cool to 100°C, still under agitation, and then placed in a water and ice bath to cool down to 0°C. Then, the solution was allowed to settle for 1 hour in the water and ice bath. The precipitate was filtered with filter paper. During the filtering, the flask was left in the water and ice bath so as to keep the flask inner temperature as near to 0°C as possible. Once the filtering is finished, the filtrate temperature was balanced at 25°C, dipping the volumetric flask in a water-flowing bath for about 30 minutes and then, divided in two 50 ml aliquots. The solution aliquots were evaporated in nitrogen flow, and the residue dried under vacuum at 80° C until constant weight was reached. The weight difference in between the two residues must be lower than 3%; otherwise the test has to be repeated. Thus, one calculates the percent by weight of polymer soluble (Xylene Solubles at 0°C = XS 0°C) from the average weight of the residues. The insoluble fraction in o-xylene at 0°C (xylene Insolubles at 0°C = XI%0°C) is:

XI%0°C=100-XS%0°C. [0145] Determination of X-ray crystallinity

[0146] The X-ray crystallinity was measured with an X-ray Diffraction Powder Diffractometer using the Cu-Kal radiation with fixed slits and collecting spectra between diffraction angle 20 = 5° and 20 = 35° with step of 0.1° every 6 seconds.

[0147] Measurements were performed on compression molded specimens in the form of disks of about 1.5-2.5 mm of thickness and 2.5-4.0 cm of diameter. These specimens are obtained in a compression molding press at a temperature of 200°C ± 5°C without any appreciable applied pressure for 10 minutes, then applying a pressure of about 10 kg/cm ² for about few second and repeating this last operation 3 times.

[0148] The diffraction pattern was used to derive all the components necessary for the degree of crystallinity by defining a suitable linear baseline for the whole spectrum and calculating the total area (Ta), expressed in counts/sec20, between the spectrum profile and the baseline. Then a suitable amorphous profile was defined, along the whole spectrum, that separate, according to the two phase model, the amorphous regions from the crystalline ones. Thus it is possible to calculate the amorphous area (Aa), expressed in counts/sec20, as the area between the amorphous profile and the baseline; and the crystalline area (Ca), expressed in counts/sec20, as Ca = Ta- Aa.

[0149] The degree of crystallinity of the sample was then calculated according to the formula: %Cr = 100 x Ca / Ta

[0150] Mw/Mn determination by GPC

[0151] The determination of the means Mn and Mw, and Mw/Mn derived therefrom was carried out using a Waters GPCV 2000 apparatus, which was equipped with a column set of four PLgel Olexis mixed-gel (Polymer Laboratories) and an IR4 infrared detector (PolymerChar). The dimensions of the columns were 300 x 7.5 mm and their particle size 13 /m. The mobile phase used was 1-2-4-tri chlorobenzene (TCB) and its flow rate was kept at 1.0 ml/min. All the measurements were carried out at 150°C. Solution concentrations were 0.1 g/dl in TCB and 0.1 g/1 of 2,6-diterbuthyl-/?-chresole were added to prevent degradation. For GPC calculation, a universal calibration curve was obtained using 10 polystyrene (PS) standard samples supplied by Polymer Laboratories (peak molecular weights ranging from 580 to 8500000). A third order polynomial fit was used for interpolating the experimental data and obtaining the relevant calibration curve. Data acquisition and processing was done using Empower (Waters). The Mark- Houwink relationship was used to determine the molecular weight distribution and the relevant average molecular weights: the K values were KPS = 1.21 x 10' ⁴ dL/g and KPB = 1.78 X 10' ⁴ dL/g for PS and PB respectively, while the Mark-Houwink exponents a = 0.706 for PS and a = 0.725 for PB were used. [0152] For butene- 1 /ethylene copolymers, as far as the data evaluation is concerned, it is assumed that the composition is constant in the whole range of molecular weight and the K value of the Mark-Houwink relationship is calculated using a linear combination as reported below: where KEB is the constant of the copolymer, KPE (4.06 x 10 ^-4 , dL/g) and KPB (1.78 x 10 ^-4 dl/g) are the constants of polyethylene and polybutene and XE and XB are the ethylene and the butene- 1 weight% content. The Mark-Houwink exponents a = 0.725 is used for all the butene- 1 /ethylene copolymers independently of their composition.

[0153] Density

[0154] Determined according to norm ISO 1183-1 :2019 at 23°C, 10 days after molding.

[0155] Examples 1 and 2 and Comparison Examples 1 and 2

[0156] The following materials are used to prepare the polybutene- 1 composition.

[0157] Butene- 1 polymer A)

[0158] Butene- 1 homopolymer prepared with a Ziegler-Natta catalyst in liquid monomer polymerization, having a flexural modulus of 450 MPa, MIio of 12 g/10 min., Mh of 0.4 g/10 min., a content of fraction soluble in xylene at 0°C of 2% by weight and a density of 914 kg/cm ³ .

[0159] It is available on the market with trademark Toppyl PB 0110M, sold by LyondellBasell.

[0160] Alkanoyl hydrazine component B)

[0161] Alkanoyl hydrazine having formula (III) as reported above, sold by BASF with trademark Irganox 1024.

[0162] Talc C)

[0163] Talc having the volume based particle diameter distribution reported in Table 1, free from additives, sold by Imi Fabi with trademark HM05.

[0164] Irgafos 168®

[0165] Tris (2,4-di-tert-butylphenyl) phosphite, marketed by Ciba Geigy. It is a thermal stabilizer. Table I

[0166] Preparation of the polybutene- 1 composition

[0167] The said components were melt-blended in a Leistritz Micro 27 extruder with corotating twin screw, 27mm screw diameter segmented, 40: 1 L/D ratio, 500 rpm max screw speed.

[0168] The main extrusion parameters were:

- Temperature: 200°C;

- Screw speed: 200 rpm;

- Output: 15 kg/h.

[0169] The amounts of the components and the properties of the so obtained final compositions are reported in Table 2.

Table 2

Note: n. m. = not measured.