Process for preparing polybutene compositions with elevated crystallization temperatures

Abstract

A method for preparing a polybutene-1 composition with an elevated crystallization temperature, comprising blending as components A) 99.5-99.9% by weight, relative to the total weight of A)+B), of a butene-1 homopolymer, said butene-1 polymer being brought into or maintained in the molten state during the blending step, with B) 0.1-0.5% by weight, relative to the total weight of A)+B), of one or more alkanoyl hydrazines of specific formulas, the polybutene-1 composition thus obtained having a crystallization temperature T satisfying the following relationship: c C has. [0010] JPEG2024542582000029.jpg4092 Here, T c A is the crystallization temperature of butene-1 polymer A).

Description

[Technical Field]

[0001] The present disclosure relates to a method for preparing polybutene-1 compositions with elevated crystallization temperatures and to methods for preparing the resulting compositions. [Background technology]

[0002] It is generally known that the crystallization temperature of polyolefins can be increased by adding nucleating agents. These nucleating agents are usually foreign substances that promote the crystallization of the polymer from the melt (heterogeneous nucleation). As a result of the nucleation effect, in addition to increasing the crystallization temperature, other valuable properties, especially optical and mechanical properties, are improved.

[0003] Therefore, there is a continuing effort in the art to find nucleating agents that can significantly increase the crystallization temperature of polyolefins.

[0004] The most valuable nucleating agents for polybutene-1 are capable of further increasing the crystallization temperature of already highly crystalline polybutene-1 materials, so that relatively high crystallization temperatures can be obtained even in the absence of crystallization, resulting in improved mechanical properties that are highly desirable for use in the water pipe sector.

[0005] Furthermore, in the pipe forming step, which is generally performed by extrusion molding, a sufficiently short crystallization time is required to increase the speed of extrusion molding.

[0006] More generally, in many polymer molding processes, short crystallization times are advantageous to achieve high throughput rates.

[0007] Applicant has discovered that the above effect can be successfully achieved by nucleating polybutene-1 with a specific class of alkanoylhydrazines. Summary of the Invention

[0008] Therefore, the present disclosure provides a process for the preparation of a polybutene-1 composition with an increased crystallization temperature, Tc, comprising: A) 99.5 to 99.9% by weight, preferably 99.6 to 99.85% by weight, based on the total weight of A)+B), of a butene-1 polymer chosen from butene-1 homopolymers, butene-1 copolymers and mixtures thereof, said butene-1 polymer being brought into or maintained in a molten state during the blending step; B) blending 0.1-0.5% by weight, preferably 0.15-0.4% by weight, based on the total weight of A)+B), of one or more alkanoyl hydrazines of formula (I), The polybutene-1 composition thus obtained has a crystallization temperature T c C and

number

[0009] The use of said hydrazine derivative compounds as stabilizers in polyolefins, including butene-1 polymers, is known, for example, from US Pat. No. 3,773,722 and US Pat. No. 4,812,500.

[0010] However, it has not been previously known that such compounds have a nucleating effect in crystalline butene-1 polymers with sufficiently high crystallization temperatures.

[0011] The process of the present invention therefore also involves the additional use of alkanoylhydrazine B) in the above proportions in order to increase the crystallization temperature of component A).

[0012] The present disclosure also provides A) 99.5 to 99.9% by weight, preferably 99.6 to 99.85% by weight, based on the total weight of A)+B), of a butene-1 polymer chosen from butene-1 homopolymers, butene-1 copolymers and mixtures thereof, said butene-1 polymer having a crystallization temperature TcA of 60° C. or higher, preferably 65° C. or higher; B) 0.1 to 0.5% by weight, preferably 0.15 to 0.4% by weight, of one or more alkanoylhydrazines of formula (I) above, relative to the total weight of A)+B), Said composition provides a polybutene-1 composition having said crystallization temperature TcC satisfying the following relationship:

number

[0013] The polybutene-1 composition of the present invention preferably has a crystallization temperature TcC that satisfies the following relationship:

number

number

[0014] A further advantage of component B) is the short crystallization time of the polybutene-1 compositions of the present invention.

[0015] Preferably, it has a crystallization half-life at 95°C of 50 to 150 seconds, especially 65 to 130 seconds.

[0016] This determination is made by DSC, which first melts the sample, then rapidly cools it to the desired temperature (in this case 95°C), and measures the heat flow due to the release of heat from crystallization. The integral of the heat transfer is recorded as a function of time until crystallization is complete, i.e., when heat transfer stops.

[0017] The crystallization half time is the time it takes for the heat transfer integral to reach half of its final value. Furthermore, the polybutene-1 compositions of the present invention preferably have at least one of the following additional characteristics: -T c C The temperature should be 85°C or higher, especially 85°C to 98°C. - Tensile modulus measured at 23 °C by DMTA analysis according to ISO 6721-4:2019 on a compression-molded plaque of 1 mm thickness of 500 to 800 MPa, more preferably 550 to 750 MPa - Charpy impact resistance values ​​of 3 to 20 kJ / m at 23°C measured according to ISO 179-1:2010 1eA 2 , especially 5 to 15 kJ / m 2 Being - Charpy impact resistance values ​​at 0°C measured according to ISO 179-1:2010 1eA are between 1 and 10 kJ / m 2, especially 1 to 5 kJ / m 2 Being

[0018] - Charpy impact resistance values ​​at -23°C measured according to ISO 179-1:2010 1eA are between 1 and 8 kJ / m 2 , especially 1-3 kJ / m 2 Being

[0019] When the butene-1 polymer component A) consists of or comprises one or more butene-1 copolymers, such copolymers may also comprise one or more comonomers preferably selected from ethylene, propylene and CH=CHR alpha-olefins, where R is a C-C alkyl radical, in particular pentene-1,4-methyl-pentene-1, hexene-1 and octene-1.

[0020] Ethylene, propylene, and hexene-1 are preferred.

[0021] From the above definition, it is clear that "copolymer" includes polymers containing more than one comonomer.

[0022] The butene-1 polymers component A) are known in the art and commercially available as shown in the examples.

[0023] The butene-1 polymer component A) is preferably a linear polymer with high isotacticity.

[0024] In particular, butene-1 polymer component A) operates at 150.91 MHz 13 It has an isotacticity of 90 to 99%, more preferably 93 to 99%, and most preferably 95 to 99%, as measured by C-NMR as mmmm pentads / total pentads or as the amount by weight of xylene insolubles at 0°C.

[0025] The butene-1 polymer component A) preferably has an MI value of 0.05 to 50 g / 10 min, more preferably 0.1 to 10 g / 10 min, where MI is the melt flow index at 190°C under a load of 2.16 kg, measured according to ISO 1133-1:2011.

[0026] Butene-1 polymer component A) MI 10 The value is preferably 1 to 100 g / 10 min, more preferably 2 to 50 g / 10 min, where MI 10 is the melt flow index MI at 190°C under a load of 10 kg, measured according to ISO 1133-1:2011.

[0027] Butene-1 polymer component A) MI 10 The / MI2 ratio is preferably 20-40, and more preferably 25-35.

[0028] In one embodiment, the butene-1 polymer component A) may be selected from homopolymers.

[0029] In a further embodiment, the butene-1 polymer A) may be chosen from copolymers having a comonomer content, in particular a copolymerized ethylene content, of 0.5 to 10 mol %, preferably 0.7 to 9 mol %.

[0030] In a further embodiment, the butene-1 polymer component A) may be a butene-1 copolymer composition comprising: A1) butene-1 homopolymers or copolymers of butene-1 with at least one comonomer selected from ethylene, propylene, the CH2=CHR olefins defined above and mixtures thereof, with a copolymerized comonomer content of up to 2 mol %. A2) Copolymers of butene-1 with at least one comonomer selected from ethylene, propylene, the CH═CHR olefins defined above and mixtures thereof, having a copolymerized comonomer content of 3 to 25 mol %.

[0031] Said composition has a total copolymerizable comonomer content of 0.5 to 18 mol %, preferably 0.7 to 15 mol %, relative to the sum of A1)+A2).

[0032] The relative amounts of A1) and A2) range from 10% to 40% by weight, in particular 15% to 35% by weight, of A1) and 90% to 60% by weight, in particular 85% to 65% by weight, of A2), based on the total of A1)+A2).

[0033] In one embodiment, the butene-1 polymer component A) may have at least one of the following additional features: -The upper limit of the crystallization temperature is 80°C. - Flexural modulus values ​​measured according to standard ISO 178:2010 after 10 days of molding are between 100 and 800 MPa, more preferably between 250 and 600 MPa, most preferably between 300 and 600 MPa the molecular weight distribution Mw / Mn is greater than or equal to 4, preferably greater than or equal to 5, the upper limit being in all cases preferably 10, Mw being the weight-average molar mass measured by gel permeation chromatography, and Mn being the number-average molar mass measured by gel permeation chromatography; The melting point TmII, measured by DSC (differential scanning calorimetry) in the second heating run at a scanning rate of -10°C / min, is not more than 125°C, preferably not more than 120°C, the lower limit being preferably 75°C in all cases. - the content of fractions soluble in xylene at 0°C, based on the total weight of A), is not more than 15% by weight, more preferably not more than 10% by weight, the lower limit being preferably 0.5% by weight in all cases; -X-ray crystallinity is 25-65%

[0034] Optionally, the butene-1 polymer component A) may have at least one of the following further additional characteristics: Intrinsic viscosity (IV) measured in tetrahydronaphthalene (THN) at -135°C, not more than 5 dl / g, preferably not more than 3 dl / g, the lower limit in all cases preferably being 0.4 dl / g. Mw is greater than or equal to 100,000 g / mol, in particular between 100,000 and 650,000 g / mol -The melting point TmI measured by DSC at a scanning rate of 10°C / min is 95°C to 135°C. -Density: 885-925kg / m 3 , preferably 900 to 920 kg / m 3 , especially 912-920 kg / m 3 Being

[0035] The homopolymers and copolymers can be obtained by low-pressure Ziegler-Natta polymerization of butene-1 (with any comonomer) using a catalyst based on titanium halide compounds (especially TiCl4) supported on TiCl3 or magnesium chloride and a cocatalyst (especially an alkyl compound of aluminum). Electron donor compounds can be added to the catalyst components to adjust polymer properties such as molecular weight and isotropy. Examples of electron donor compounds are esters of carboxylic acids and alkylalkoxysilanes.

[0036] In particular, butene-1 polymer component A) can be prepared by polymerizing monomers in the presence of a stereospecific catalyst comprising a solid component comprising (i) a Ti compound supported on MgCl2 and an internal electron donor compound, (ii) an alkylaluminum compound, and, optionally, (iii) an external electron donor compound.

[0037] The preferred support is magnesium dichloride in activated form. It is widely known from the patent literature that activated magnesium dichloride is particularly suitable as a support for Ziegler-Natta catalysts. In particular, U.S. Patent Nos. 4,298,718 and 4,495,338 were the first to describe the use of these compounds in Ziegler-Natta catalysis. From these patents, it is known that activated magnesium dihalides used as supports or co-supports in catalyst components for olefin polymerization can be characterized by their X-ray spectra. In this X-ray spectrum, the intensity of the inactive halides is reduced and replaced by a halo, the maximum intensity of which shifts to lower angles compared to the intensity of the more intense lines.

[0038] The titanium compounds used in catalyst component (i) are preferably TiCl4 and TiCl3, and also have the formula Ti(OR) n-y X y Titanohaloalkoxides represented by the formula (wherein n is the valence of titanium, X is a halogen, preferably chlorine, and y is a number ranging from 1 to n) can also be used.

[0039] The internal electron donor compound is preferably selected from esters, more preferably alkyl, cycloalkyl, or aryl esters of monocarboxylic acids (e.g., benzoic acid) or polycarboxylic acids (e.g., phthalic acid, succinic acid, glutaric acid), where the alkyl, cycloalkyl, or aryl has 1 to 18 carbon atoms. Examples of the electron donor compound include diisobutyl phthalate, diethyl phthalate, dihexyl phthalate, and diethyl or diisobutyl 3,3-dimethylglutarate. Typically, the molar ratio of the internal electron donor compound to MgCl2 is 0.01 to 1, preferably 0.05 to 0.5.

[0040] The alkyl-Al compound (ii) is preferably selected from among the trialkylaluminum compounds, such as triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, etc. It is also possible to use mixtures of the trialkylaluminum compounds with alkylaluminum halides, alkylaluminum hydrides or alkylaluminum sesquichlorides, such as AlEt2Cl and Al2Et3Cl3.

[0041] The external electron donor compound (iii) is R a 1 R b 2 Si(OR 3 ) c (wherein a and b are integers of 0 to 2, c is an integer of 1 to 3, (a+b+c) is 4, and R 1 , R 2 and R 3 is alkyl, cycloalkyl, or aryl having 1 to 18 carbon atoms, which may contain a heteroatom.) A particularly preferred group of silicon compounds is one in which a is 0, c is 3, b is 1, and R 2 is a branched alkyl or cycloalkyl which may contain a heteroatom, and R 3 is methyl. Examples of such preferred silicon compounds are cyclohexyltrimethoxysilane, t-butyltrimethoxysilane, diisopropyltrimethoxysilane and thexyltrimethoxysilane. Particularly preferably, hexyltrimethoxysilane is used.

[0042] The external electron donor compound (iii) is used in such an amount that the molar ratio of the organoaluminum compound to the external electron donor compound (iii) is 0.1 to 500, preferably 1 to 300, and more preferably 3.

[0043] To make the catalyst particularly suitable for the polymerization step, the catalyst can be prepolymerized in a prepolymerization step. The prepolymerization may be carried out in a liquid (slurry or solution) or gas phase, usually at a temperature below 100°C, preferably 20 to 70°C. The prepolymerization step is carried out with a small amount of monomer, in an amount of 0.5 to 2000 g, preferably 5 to 500 g, more preferably 10 to 100 g per 1 g of the solid catalyst component, for a period of time required to obtain a polymer.

[0044] Alternatively, the butene-1 polymer component A) can be obtained by polymerizing the monomers in the presence of a metallocene catalyst system obtained by contacting: stereorigid metallocene compounds, a compound capable of forming an aluminoxane or alkylmetallocene cation, and optionally -organoaluminum compounds.

[0045] The polymerization process can be carried out with said catalyst by operating in the liquid phase, optionally in the presence of an inert hydrocarbon solvent, or in the gas phase using a fluidized bed or mechanically agitated gas phase reactor.

[0046] The hydrocarbon solvent may be aromatic (eg, toluene) or aliphatic (eg, propane, hexane, heptane, isobutane, cyclohexane, and 2,2,4-trimethylpentane, isododecane, and the like).

[0047] Preferably, the polymerization process is carried out by using liquid butene-1 as the polymerization medium.

[0048] The polymerization temperature may be between 20°C and 150°C, particularly between 50°C and 90°C, for example between 65°C and 82°C.

[0049] To control the molecular weight, molecular weight regulators, especially hydrogen, are provided to the polymerization environment.

[0050] Mw / Mn values ​​of 4 or greater and MI as previously defined10 The value of the / MI2 ratio is generally considered to result in a broad molecular weight distribution (MWD).

[0051] Broad molecular weight butene-1 polymers can be obtained in several ways. One method is to use a catalyst that can produce broad MWD polymers when (co)polymerizing butene-1. Another possibility is to mechanically blend butene-1 polymers with sufficiently different molecular weights using conventional mixing equipment.

[0052] It is also possible to carry out a multi-stage polymerization process in which butene-1 polymers of different molecular weights are prepared sequentially in two or more reactors under different reaction conditions, such as the concentration of molecular weight regulator fed to each reactor.

[0053] It is also possible to feed different amounts of monomer to each reactor.

[0054] In particular, when the butene-1 polymer component A) of the present invention comprises the two aforementioned components A1) and A2), the polymerization process can be carried out in two or more reactors connected in series, in which components B1) and B2) are prepared in separate subsequent stages, each stage except the first, operating in the presence of the formed polymer and the catalyst used in the previous stage.

[0055] The catalyst may be added to only the first reactor, or may be added to multiple reactors.

[0056] High MI values ​​can be achieved directly during polymerization, or by subsequent chemical treatment (chemical visbreaking).

[0057] Chemical visbreaking of polymers is carried out in the presence of a free radical initiator such as a peroxide.

[0058] The decomposition temperature of the peroxide most suitably used in the polymer visbreaking step is preferably 150° C. to 250° C. Commercially available examples of the peroxide include ditert-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne, and 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane.

[0059] The amount of peroxide required for the visbreaking process is preferably in the range of 0.001 to 0.5% by weight of the polymer, more preferably 0.001 to 0.2%.

[0060] Particularly preferred examples of alkyl R1 and R2 in the alkanoylhydrazine A) of formula (I) are methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, and t-butyl.

[0061] The alkanoyl hydrazine A) preferably has the following formula (II): [ka] (In formula (I), R1 and R2 have the same meanings as described in formula (I) above.)

[0062] A particularly preferred alkanoyl hydrazine A) is the compound N,N'-bis-β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionyl-hydrazine, also known as 2',3-bis[[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyl]]propionohydrazide, having the formula (III):

[0063] [ka]

[0064] The alkanoylhydrazines A) can be prepared by reaction of hydrazine with an ester of an alkylhydroxyphenylalkanoic acid, followed by further acylation, as exemplified in US Pat. No. 3,773,722.

[0065] Alkanoylhydrazines of formula (III) are sold under the trade name Irganox 1024 by BASF. The polybutene-1 composition of the present invention may also contain talc as optional component C). The preferred amount of component C) is 0.15 to 2.5 wt %, more preferably 0.2 to 2 wt %, most preferably 0.2 to 1.5 wt %, based on the total weight of A)+B)+C). Particularly preferred is talc in the form of particles having a volume-based (volume) particle size distribution Dv(0.95) of 45 μm or less, preferably 35 μm or less, more preferably 25 μm or less, and in particular 20 μm or less, the volume-based (volume) particle size distribution Dv being determined by laser light diffraction, the lower limit in all cases preferably being 5 μm. In addition to said Dv(0.95) value, component C) preferably has at least one of the following volume-based particle size distribution characteristics: -Dv(0.99) is 100 μm or less, or 50 μm or less, or 30 μm or less, with the lower limit preferably being 10 μm in all cases. -Dv(0.90) is 20μm or less, or 15μm or less, with the lower limit being 3μm in all cases -Dv(0.50) is 10μm or less, or 8μm or less, with the lower limit being 2μm -Dv(0.10) is 5 μm or less, or 4 μm or less, and the lower limit is preferably 1 μm. The volumetric particle size refers to the diameter of an equivalent sphere having the same volume as the particle in question. Therefore, the volume-based particle size distribution value means that particles with a specified volume fraction (for example, 95% by volume for Dv(0.95)) have an equivalent diameter smaller than a predetermined value. Such determination is made by laser diffraction. The analytical device used is preferably a Malvern Mastersizer instrument. Talc is known to be magnesium silicate hydrate. Its formula is usually reported to be Mg3Si4O10(OH)2. In essence, it is a mineral that consists primarily or substantially of said hydrated magnesium silicate, optionally in association with other mineral materials such as chlorite (hydrated magnesium aluminum silicate) and dolomite. To achieve the above values ​​of particle size distribution, the talc can be milled using known techniques such as air classifying mills, compressed air, steam and impact milling. The polybutene-1 compositions of the present invention can be obtained by blending components A), B), and optionally C) using blending techniques and equipment well known in the art.

[0066] Thus, extruders commonly known in the art can be used, including single-screw extruders, conventional and CoKneader (such as Buss), twin-screw co-rotating extruders or mixers (continuous and batch). Such blending equipment can be equipped with separate feed systems for components A), B), and optionally C), respectively. Component B) and optional component C) can be added to the polymer mass inside the blending equipment, particularly the extruder, either at the same feed port or downstream from the point at which A) is fed to the blending equipment, allowing A) to reach the form of a molten, homogeneous mass.

[0067] Components B) and C) may be supplied in the form of a masterbatch in a polymeric carrier, more preferably a polyolefin carrier, especially a polybutene carrier of the same type as the butene-1 polymer component A).

[0068] The processing temperature during the blending step must be sufficient to bring (and maintain) component A) in a molten state, or, if component A) is already molten when B) and, optionally, C) are added, to maintain component A) in a molten state. Such temperatures preferably range from 100°C to 220°C, more preferably from 150°C to 220°C, and most preferably from 180°C to 220°C.

[0069] In preparing the polymer composition, in addition to the main components A) and B) and any other polymer components, additives commonly used in the art such as stabilizers (heat, light, UV), plasticizers, antacids, antistatic and water repellents, pigments, etc. may be added.

[0070] As mentioned above, the preferred use of the polybutene-1 compositions of the present invention is in the manufacture of pipes, especially pipes for conveying water and thermal fluids, and pipe fittings. In general, they can be advantageously used in any application requiring improved mechanical and processing properties. [Example]

[0071] Examples and advantages of the various embodiments, compositions, and methods provided herein are disclosed in the following examples, which are merely illustrative and are not intended to limit the scope of the appended claims in any way.

[0072] The following analytical methods are used to characterize the polymer compositions.

[0073] Crystallization and Melting Temperatures

[0074] Crystallization temperature (T c ) and melting temperature values ​​were determined using the following procedure.

[0075] Differential scanning calorimetry (DSC) data were obtained using a Perkin Elmer DSC-7 instrument. A weighed sample (5–10 mg) was placed in an aluminum disk and heated to 200 °C at a scan rate equivalent to 10 °C / min. The sample was held at 200 °C for 5 min to completely melt all crystallites and eliminate the thermal history of the sample. It was then cooled to -20 °C at a scan rate of 10 °C / min, and the peak temperature was determined as the crystallization temperature (T c ) and the area was taken as the crystallization enthalpy. After standing at -20 °C for 5 min, the sample was heated a second time to 200 °C at a scan rate corresponding to 10 °C / min. In this second heating run, the peak temperature was taken as the melting temperature of polybutene-1 crystalline form II (TmII), and the area was taken as the melting enthalpy (ΔHfII).

[0076] To determine the melting temperature (TmI) of polybutene-1 crystalline form I, a sample was melted, held at 200 °C for 5 min, and then cooled to 20 °C at a cooling rate of 10 °C / min. The sample was then stored at room temperature for 10 days. After 10 days, the sample was subjected to DSC, cooled to -20 °C, and then heated to 200 °C at a scanning rate corresponding to 10 °C / min. In this heating run, the first peak temperature from the low temperature side of the thermogram was taken as the melting temperature (TmI).

[0077] Crystallization half time at 95℃

[0078] Differential scanning calorimetry (DSC) data were obtained using a Perkin Elmer DSC-7 instrument. Weighed samples (5–10 mg) were enclosed in aluminum discs and heated from room temperature to 180 °C at a scan rate equivalent to 10 °C / min.

[0079] The sample was kept at 180°C for 5 minutes to completely melt all the crystallites and to eliminate the thermal history of the sample.

[0080] The sample was then cooled to 95°C at a scan rate equivalent to 60°C / min, and the heat flow due to the crystallization exotherm at 95°C was measured. The integral of the heat transfer was recorded as a function of time until crystallization was complete, i.e., until heat transfer stopped.

[0081] The crystallization half time is the time it takes for the heat transfer integral to reach half of its final value.

[0082] Particle size distribution

[0083] Particle size distribution (PSD) was measured by laser diffraction according to ISO 13320:2009.

[0084] The equipment used is a Mastersizer (Proprietary Application) 2000 with a sample dispersion unit manufactured by Malvern, UK.

[0085] The detection system has the following features: -Red light: forward scatter, side scatter, back scatter; - Blue light: wide-angle back and forth scattering; -Light source: red light He-Ne laser; blue light solid light source; -Optical alignment system: automatic high-speed alignment system with dark-field optical reticle; -Laser system: Class 1 laser product.

[0086] PSD determination is based on the principle of optical diffraction, where monochromatic laser light is scattered through a dispersed particulate sample. The signal is received by a computer connected to the instrument, which processes the received signal and converts it into a dimensional physical quantity.

[0087] The results are presented by a PSD report consisting of 106 class diameters (virtual sieves) and associated cumulative percentages for volume and additional derived parameters.

[0088] In addition to background electrical noise, measurement data can also be contaminated by scattered data from dust on the optics or contaminants suspended in the dispersant, so it is important to ensure that the sample dispersion unit is clean and that all traces of impurities and residual materials have been removed.

[0089] Therefore, background measurements with pure dispersant (solvent) and electrical background measurements were performed. The resulting total background values ​​were subtracted from the sample measurements to obtain the true sample data.

[0090] For background measurements, anhydrous n-heptane solvent containing 2 g / 1 SPAN 80 Pure as an antistatic agent was introduced into the sample dispersion unit. Before each measurement, residual air in the solvent was removed by ultrasonic treatment (60 s).

[0091] The solvent was then pumped into the measurement cell while the stirrer and circulation pump were operated in the power range of 2205 rpm.

[0092] measurement

[0093] The sample, suspended in anhydrous n-heptane by stirring, was added directly to the sample unit.

[0094] Circulation of the sample suspension was required for 2 min to facilitate the breakup of aggregates (if present).

[0095] The obscuration bar can be seen on the monitor to reach the optimum volume concentration of the sample. The sample concentration must correspond to an obscuration value in the range of 10% to 30%. This range ensures representative and stable results.

[0096] The refractive index (RI) was set as follows: Particle RI:1.596; Dispersant RI: 1.390.

[0097] The measurement time is 4 seconds.

[0098] The signal received from the laser device was processed and then the PSD was calculated using software provided with the Mastersizer device.

[0099] Melt Flow Index MI

[0100] Determined at 190°C and a specified load according to ISO 1133-12012-03.

[0101] intrinsic viscosity

[0102] Determined in tetrahydronaphthalene at 135° C. according to standard ASTM D 2857-16.

[0103] Tensile modulus (MET-DMTA)

[0104] It was determined on 1 mm thick compression molded plaques by dynamic mechanical thermal analysis (DMTA) at 23 °C according to ISO 6721-4:2019.

[0105] Flexural modulus

[0106] Measurements were taken 10 days after molding according to standard ISO 178:2019.

[0107] Izod impact resistance at 23°C and 0°C

[0108] Measured 10 days after molding according to ISO 179-1:2010 1eA.

[0109] Comonomer Content

[0110] The comonomer content of the butene-1 polymers was determined by FT-IR.

[0111] The spectra of pressed polymer films are expressed as absorbance versus wavenumber (cm -1 The ethylene content was calculated from the following measurements: a) 4482–3950 cm, used for spectroscopic normalization of film thickness -1 The area of ​​the combined absorption band (A t ). b) The subtraction coefficient (FCR) of the digital subtraction between the spectrum of the polymer sample and the absorption bands due to the methylene group sequences BEE and BEB (B: butene unit, E: ethylene unit). C2 )(CH2 Shake Vibration). c) Area of ​​the remaining band after subtracting the C2PB spectrum (A C2,block ) It is derived from the methylene group sequence EEE (CH shake vibration).

[0112] Device

[0113] A Fourier transform infrared spectrophotometer (FTIR) capable of providing the above-mentioned spectral measurements was used.

[0114] A hydraulic press (Carver or equivalent) with platens heatable to 200°C was used.

[0115] method

[0116] (BEB+BEE) sequence calibration

[0117] %(BEB+BEE)wt vs. FCR C2 / A t The calibration line was obtained by plotting the slope r and intercept I r was calculated by linear regression.

[0118] EEE sequence calibration

[0119] %(EEE)wt vs. A C2,block / A t The calibration line was obtained by plotting the slope G H and intercept I H was calculated by linear regression.

[0120] Sample preparation

[0121] A thick sheet was obtained by pressing approximately 1.5 g of sample between two sheets of aluminum foil using a hydraulic press. If uniformity is an issue, it is recommended to perform at least two pressing operations. A small portion was cut from this sheet to form a membrane. The recommended membrane thickness is 0.1 to 0.3 mm.

[0122] The press temperature is 140°C (10°C).

[0123] Because changes in the crystalline phase occur over time, we suggest collecting IR spectra of sample films immediately after casting.

[0124] procedure

[0125] The equipment data acquisition parameters are as follows: Purge time: minimum 30 seconds Collection time: Minimum 3 minutes Apodization: Happ-Genzel Resolution: 2cm -1 IR spectra of the samples were collected against an air background.

[0126] calculation The weight concentration of the BEE+BEB sequence of ethylene units was calculated.

number

number

number

[0127] Determination of isotactic pentad content 13 C NMR spectra were acquired at 120 °C on polymer solutions (8–12 wt %) in deuterated 1,1,2,2-tetrachloroethane. 13 C NMR spectra were obtained on a Bruker AV-600 spectrometer equipped with a cryogenic probe, operating in Fourier transform mode at 120 °C and 150.91 MHz. 1 H- 13 A 90° pulse was used with a 15-second delay between the pulse and the CPD (WALTZ 16) to remove C bonds. Approximately 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 assignment was carried out as described in the literature (Macromolecules 1991, 24, 2334-2340, by Asakura T.). The percentage value (mmmm%) of pentad tacticity of butene-1 polymer is the percentage of stereoregular pentads (isotactic pentads) calculated from the relevant pentad signals (peak areas) in the NMR region of the branched methylene carbons, as follows:

number

[0128] Fractions soluble and insoluble in xylene at 0°C (XS-0°C)

[0129] A 2.5 g polymer sample was stirred at 135 °C and dissolved in 250 ml of xylene. After 30 minutes, the solution was cooled to 100 °C while stirring, then placed in an ice-water bath and cooled to 0 °C. The solution was then left to stand in the ice-water bath for 1 hour. The precipitate was filtered using filter paper. During filtration, the flask was left in the ice-water bath to maintain the internal temperature as close to 0 °C as possible. After filtration, the filtrate temperature was maintained at 25 °C, and the volumetric flask was immersed in a running water bath for approximately 30 minutes. Two 50 ml aliquots were then separated. The solution aliquots were evaporated in a stream of nitrogen gas, and the residue was dried in a vacuum at 80 °C until a constant weight was reached. The weight difference between the two residues should be less than 3%. Otherwise, the test should be repeated. The weight percentage of the polymer solubles (xylene solubles at 0 °C = XS0 °C) was calculated 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 as follows:

number

[0130] X-ray crystallinity determination

[0131] X-ray crystallinity was measured using an X-ray powder diffractometer using Cu-Kα1 radiation with a fixed slit, collecting spectra between diffraction angles 2θ = 5° and 2θ = 35° in steps of 0.1° every 6 seconds.

[0132] The measurements were carried out on disk-shaped compression-molded test pieces with a thickness of approximately 1.5 to 2.5 mm and a diameter of approximately 2.5 to 4.0 cm. These test pieces were obtained by compression molding at a temperature of 200°C ± 5°C for 10 minutes without applying a particularly large pressure, and then subjected to a pressure of approximately 10 kg / cm. 2 The pressure was applied for several seconds, and the last operation was repeated three times.

[0133] The diffraction pattern was used to define an appropriate linear baseline across the spectrum, and all components required for crystallinity were derived by calculating the total area (Ta) (expressed in counts / sec·2θ) between the spectral profile and the baseline. Next, along the entire spectrum, we defined an appropriate amorphous profile that separates the amorphous and crystalline regions according to a two-phase model. Therefore, the amorphous area (Aa), expressed in counts / sec·2θ, may be calculated as the area between the amorphous profile and the baseline, and the crystalline area (Ca), expressed in counts / sec·2θ, as Ca = Ta - Aa.

[0134] The crystallinity of the sample was then calculated based on the following formula:

number

[0135] Determination of Mw / Mn by GPC

[0136] Determination of the average Mn and Mw, and the derived Mw / Mn, was carried out using a Waters GPCV 2000 instrument equipped with a column set consisting of four PLgel Olexis mixed gels (Polymer Laboratories) and an IR4 infrared detector (PolymerChar). The column dimensions were 300 × 7.5 mm, with a particle size of 13 μm. The mobile phase was 1,2,4-trichlorobenzene (TCB), and its flow rate was maintained at 1.0 ml / min. All measurements were performed at 150 °C. The solution concentration in TCB was 0.1 g / dL, and 0.1 g / l of 2,6-dibutyl-p-cresol was added to prevent decomposition. For GPC calculations, a universal calibration curve was obtained using 10 polystyrene (PS) standard samples (peak molecular weights ranging from 580 to 8,500,000) supplied by Polymer Laboratories. A third-order polynomial fit was used to interpolate the experimental data and obtain the relevant calibration curve. Data acquisition and processing were performed using Empower (Waters). The Mark-Houwink relationship was used to determine the molecular weight distribution and the associated average molecular weight. The K values ​​of PS and polybutene (PB) were calculated using K PS =1.21×10 -4 dL / g and K PB=1.78×10 -4 dL / g, and the Mark-Hwink index α = 0.706 for PS and the Mark-Hwink index α = 0.725 for PB are used in combination.

[0137] For butene-1 / ethylene copolymers, the composition was assumed to be constant over all molecular weights for data evaluation, and the K value of the Mark-Houwink relationship was calculated using the linear combination:

number

[0138] density

[0139] It was determined at 23°C according to standard ISO 1183-1:2019.

[0140] Examples 1 and 2 and Comparative Examples 1 and 2

[0141] The following materials were used to prepare the polybutene-1 composition:

[0142] Butene-1 Polymer A)

[0143] Prepared by liquid monomer polymerization using Ziegler-Natta catalyst, flexural modulus 450 MPa, MI 10 12g / 10min, MI 20.4g / 10min, content of fraction soluble in xylene at 0℃ 2% by weight, density 914kg / cm 3 is a butene-1 homopolymer.

[0144] It is available on the market under the trademark Toppyl PB 0110M and is sold by LyondellBasell.

[0145] Alkanoyl hydrazine component B)

[0146] Alkanoylhydrazines having the above formula (III) are sold by BASF under the trademark Irganox 1024.

[0147] Talc C)

[0148] Talc, free of additives, having a particle size distribution by volume as set forth in Table 1, is sold by Imifabi under the trademark HM05.

[0149] Irgafos 168 (registered trademark)

[0150] Tris(2,4-di-tert-butylphenyl)phosphite, sold by Ciba Geigy, heat stabilizer. [Table 1]

[0151] Preparation of Polybutene-1 Compositions

[0152] The ingredients were melt blended in a Leistritz Micro27 extruder equipped with co-rotating twin screws, a split screw diameter of 27 mm, an L / D ratio of 40:1, and a maximum screw speed of 500 rpm.

[0153] Main extrusion parameters: Temperature: 200℃ Screw speed: 200 rpm Output: 15kg / h

[0154] The component amounts and properties of the final compositions thus obtained are listed in Table 3. Table 2 Note: nm = Not measured.

Claims

1. A process for preparing a polybutene-1 composition, comprising the following components: A) 99.5 to 99.9% by weight, based on the total weight of A)+B), of a butene-1 polymer chosen from butene-1 homopolymers, butene-1 copolymers and mixtures thereof, said butene-1 polymer being brought to or maintained in a molten state during the blending step; B) 0.1 to 0.5% by weight, based on the total weight of A)+B), of one or more alkanoyl hydrazines of formula (I), The polybutene-1 composition thus obtained has a crystallization temperature T ｃ Ｃ and [Equation 1] Here, T ｃ Ａ and T ｃ Ｃ is expressed in ° C., and T ｃ Ａ is the crystallization temperature of the butene-1 polymer A), said crystallization temperature being determined by differential scanning calorimetry (DSC) at a heating and cooling rate of 10° C. / min. 【number】 (In the formula, R １ is alkyl having 1 to 6 carbon atoms, and R ２ is hydrogen or alkyl having 1 to 6 carbon atoms, and n is an integer of 0 to 5.

2. 10. The method of claim 1, wherein talc C) is added in the blending step.

3. 3. The method of claim 2, wherein the talc C) is in the form of particles having a volume-based particle size distribution Dv(0.95) of 45 μm or less, as determined by laser light diffraction.

4. The method of claim 1 or 2, wherein the blending step is carried out at a temperature of from 100°C to 220°C.

5. 3. The method of claim 1 or 2, wherein the alkanoyl hydrazine B) has the formula (II): 【Chemistry 2】 (In the formula, R １ is alkyl having 1 to 6 carbon atoms, and R ２ is hydrogen or alkyl having 1 to 6 carbon atoms.

6. 6. The method of claim 5, wherein B) has the formula (III): 【Transformation 3】

7. 1. A polybutene-1 composition comprising: A) 99.5 to 99.9% by weight, based on the total weight of A) + B), of a butene-1 polymer chosen from butene-1 homopolymers, butene-1 copolymers and mixtures thereof, said butene-1 polymer having a crystallization temperature T ≥ 60°C. ｃ Ａ the butene-1 polymer having B) 0.1 to 0.5% by weight, based on the total weight of A)+B), of one or more alkanoylhydrazines of formula (I), The polybutene-1 composition has a crystallization temperature T ｃ Ｃ and [Equation 2] A polybutene-1 composition, wherein said crystallization temperature is determined by differential scanning calorimetry (DSC) at a heating and cooling rate of 10° C. / min. 【number】 (In the formula, R １ is alkyl having 1 to 6 carbon atoms, and R ２ is hydrogen or alkyl having 1 to 6 carbon atoms, and n is an integer of 0 to 5.

8. 8. The polybutene-1 composition of claim 7, further comprising talc C).

9. 9. Polybutene-1 composition according to claim 8, wherein said talc C) is in the form of particles having a particle size distribution by volume Dv(0.95) of less than or equal to 45 μm, as determined by laser light diffraction.

10. Polybutene-1 composition according to claim 8 or 9, wherein said talc C) is present in an amount of 0.15 to 2.5% by weight, based on the total weight of A)+B)+C).

11. 9. Polybutene-1 composition according to claim 7 or 8, wherein said alkanoyl hydrazine B) has formula (II): 【Transformation 5】 (In the formula, R １ is alkyl having 1 to 6 carbon atoms, and R ２ is hydrogen or alkyl having 1 to 6 carbon atoms.

12. 12. The polybutene-1 composition of claim 11, wherein said B) has formula (III): 【Transformation 6】

13. T ｃ Ｃ 9. Polybutene-1 composition according to claim 7 or 8, wherein the value is between 85°C and 98°C.

14. 9. An article containing the polybutene-1 composition according to claim 7 or 8.

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