Butene-1 polymer composition with high melt flow rate

Abstract

A butene-1 polymer composition having a MFR value, measured according to ISO 1133 at 190°C with a load of 2.16 kg, of 100 to 300 g / 10 min, comprising: A) a butene-1 homopolymer or a butene-1 copolymer with one or more comonomers selected from the group consisting of ethylene and higher alpha-olefins, having a comonomer content of at most 5 mol%; B) a butene-1 copolymer with one or more comonomers selected from the group consisting of ethylene and higher alpha-olefins, said copolymer having a comonomer content of 6 mol% to 20 mol%; said composition having a total comonomer content of 4 mol% to 15 mol% relative to the sum of A) and B), and a content of the fraction soluble in xylene at 0°C of 75 wt% or less based on the total weight of A) and B).

Description

Technical Field

[0001] This disclosure relates to a butene-1 polymer composition having a melt flow rate of not less than 100 g / min, measured at 190 °C with a load of 2.16 kg according to standard ISO 1133, and thus exhibiting high fluidity in the molten state.

[0002] The butene-1 polymer composition provides high tensile properties, low hardness, low flexural modulus and low glass transition temperature, while still maintaining measurable crystallinity.

[0003] The butene-1 polymer composition of the present invention has many applications. In particular, the butene-1 polymer composition of the present invention can be used in the production of films and fibers, as a component of hot melt adhesives, as a polymer additive to enhance the rheological, mechanical and optical properties of polymer compositions, or as a fluidizing agent for lubricants. Background Technology

[0004] Polymers of butene-1 with high melt flow rates are disclosed in the art, particularly in US4677025, US4960820, WO2006045687, WO2015074830, and EP0314495. These polymers have been used in numerous applications due to their valuable properties, such as chemical inertness, mechanical properties, and non-toxicity.

[0005] In particular, due to their high fluidity in the molten state and their physical properties, butene-1 polymers with high melt flow rates can be used to produce films and fibers, optionally blended with other polyolefins, and used in a variety of hot melt formulations.

[0006] As described in US4677025, the molecular weight and molecular weight distribution of butene-1 polymers affect the final polymer properties.

[0007] It has now been found that a favorable performance profile can be obtained by combining at least two butene-1 polymers with different and specific comonomer contents, and by appropriately selecting the melt flow rate and optional molecular weight and molecular weight distribution, which can be achieved by using a metallocene catalyst. Summary of the Invention

[0008] Therefore, this disclosure provides a butene-1 polymer composition having a melt flow rate of 100 to 300 g / 10 min, preferably 110 to 300 g / 10 min, more preferably 150 to 250 g / 10 min, measured according to ISO 1133 at 190 °C with a load of 2.16 kg (hereinafter referred to as "MFR"), and comprising:

[0009] A) Butene-1 homopolymer or copolymer of butene-1 with one or more comonomers selected from ethylene and higher α-olefins, having a comonomer content of up to 5 mol%, preferably up to 4 mol% (C A );

[0010] B) A copolymer of butene-1 with one or more comonomers selected from ethylene and higher α-olefins, having a comonomer content of 6 mol% to 20 mol%, preferably 8 mol% to 18 mol% (C B );

[0011] The composition has a total monomer content of 4 mol% to 15 mol%, preferably 5 mol% to 15 mol%, relative to the sum of A) and B), and a content of 75 wt% or less, preferably 70 wt% or less, of xylene soluble at 0°C, based on the total weight of A) and B).

[0012] The butene-1 polymer composition provided in this article can be obtained directly in polymerization without the need for free radical generating agents such as peroxides to increase the MFR value, thus avoiding chemical pollution and unpleasant odors caused by the introduction of free radical generating agents.

[0013] Such butene-1 polymer compositions have low hardness, low flexural modulus, high elongation at break and low glass transition temperature, which are useful properties in films and fibers. The butene-1 polymer compositions of the present invention can be used in blends with other polyolefins (especially propylene polymers) commonly used in the production of said articles, and can also be used in hot melt compositions. Detailed Implementation

[0014] For the butene-1 polymer composition provided herein, the specific amount of the xylene-soluble fraction at 0°C (expressed as the weight content of the fraction measured by extraction, based on the total weight of A and B) is 35% to 75% by weight, or 35% to 70% by weight, particularly 40% to 70% by weight, or 40% to 65% by weight.

[0015] When A) is a copolymer, the specific lower limit of the comonomer content is 1 mol%.

[0016] Preferably, when both A) and B) are copolymers, the difference between the percentage values ​​of comonomer content in B) and A) satisfies the following relationship:

[0017] C B )-C A ≥5; or

[0018] C B )-C A )≥6.

[0019] The relative amounts of components A) and B) can be readily determined based on the expected total content of the total copolymer monomers, the content of the individual component comonomers, and the content of their xylene-soluble fractions at 0°C.

[0020] The preferred amounts are 30% to 70% by weight, preferably 35% to 65% by weight of A) and 30% to 70% by weight, preferably 35% to 75% by weight of B), all relative to the total weight of A) and B).

[0021] In components A) and B), specific examples of higher α-olefins that can exist as comonomers other than or as a substitute for ethylene are α-olefins of the formula CH2=CHR, where R is methyl or an alkyl group containing 3-8 or 3-6 carbon atoms, such as propylene, hexene-1, octene-1.

[0022] However, ethylene is the preferred comonomer, especially for component B).

[0023] The butene-1 polymer composition of the present invention has measurable crystallinity, as demonstrated by the presence of melting temperature peaks of crystalline butene-1 polymer in differential scanning calorimetry (DSC) patterns.

[0024] Specifically, the butene-1 polymer of the present invention exhibits one or more melting peaks in a second DSC heating scan. These temperature peaks typically appear at temperatures equal to or below 90°C, or equal to or below 85°C, particularly between 40°C and 90°C, or between 45°C and 85°C, at temperatures attributed to the melting point (TmII) of crystal form II of the butene-1 polymer, and the area under the peak (or multiple peaks) is taken as the total enthalpy of fusion (DH TmII). However, if more than one peak is present, the highest (strongest) peak is taken as TmII.

[0025] The specific total DH TmII value of the butene-1 polymer of the present invention is 15 J / g or less, particularly 4 to 15 J / g, measured at a scan rate corresponding to 10 °C / min.

[0026] Furthermore, the butene-1 polymer of the present invention exhibits one or more melting peaks, typically occurring in DSC heating scans performed after aging at temperatures equal to or below 100°C, or equal to or below 98°C, particularly between 30°C and 100°C, or between 30°C and 98°C. These one or more temperature peaks are attributed to the melting point (TmI) of crystal form I of the butene-1 polymer, and the area under the peak (or peaks) is taken as the total enthalpy of fusion (DH TmI). However, if more than one peak exists, the highest (strongest) peak is taken as TmI.

[0027] The specific total DH TmI value of the butene-1 polymer of the present invention is 50 J / g or less, particularly 25 to 50 J / g, or 30 to 50 J / g, measured at a scan rate corresponding to 10 °C / min.

[0028] The butene-1 polymer of this invention may also have a detectable amount of crystal form III. Crystal form III can be detected by X-ray diffraction, a method described in the Journal of Polymer Science Part B: Polymer Letters Volume 1, Issue 11, pages 587-591, November 1963, or Macromolecules, Vol. 35, No. 7, 2002.

[0029] The specific X-ray crystallinity value of the butene-1 polymer of the present invention is 10%-50%, particularly 15%-45%.

[0030] Specific MFR values ​​for components A) and B) can be widely selected, provided that the MFR values ​​for the entire composition are obtained.

[0031] In this regard, it is well known that the logarithm of the MFR value of polyolefin blends (and therefore blends of butene-1 polymers) is usually given by the sum of the products of the weight fraction of the individual component and the logarithm of the MFR value.

[0032] Therefore, the MFR value of the composition made from the blend of components A) and B) is determined by the following relationship:

[0033] log MFR(A+B)=wA log MFR(A)+wB log MFR(B)

[0034] Where MFR(A+B) is the MFR value of the blend of A) and B), MFR(A) and MFR(B) are the MFR values ​​of components A) and B) respectively, and wA and wB are their respective weight fractions. For example, when the blend is made of 50 wt% component A) and 50 wt% component B), wA and wB are both 0.5.

[0035] However, in order to obtain good flowability in the molten state, it is preferable to keep the MFR values ​​of individual components A) and B) sufficiently high, especially in the range of 50-400 g / 10 min or 80-350 g / 10 min.

[0036] Furthermore, the butene-1 polymer composition of the present invention preferably has at least one of the following further features:

[0037] - The intrinsic viscosity (IV) measured in tetrahydronaphthalene (THN) at 135°C is equal to or less than 0.70 dl / g, or equal to or less than 0.65 dl / g, particularly 0.50 dl / g to 0.70 dl / g or 0.50 dl / g to 0.65 dl / g;

[0038] -Mw / Mn value, where Mw is the weight-average molar mass and Mn is the number-average molar mass, both measured by GPC (gel permeation chromatography), equal to or less than 3.5, or equal to or less than 2.5, with a lower limit of 1.5 in all cases;

[0039] -Mz value, 90,000 g / mol or higher, or 100,000 g / mol or higher, especially 90,000 to 200,000 g / mol or 100,000 to 190,000 g / mol;

[0040] -Mw, equal to or greater than 50,000 g / mol, or equal to or greater than 70,000 g / mol, especially 50,000 to 180,000 g / mol, or 70,000 to 150,000 g / mol;

[0041] - For operation at 150.91MHz 13 C-NMR measurements of isosteretic five-unit groups (mmmm) above 90%; particularly above 93% or above 95%;

[0042] - Used as a 4,1 insertion that is undetectable by 13C-NMR at 150.91MHz;

[0043] - Yellowness index, below 0; especially 0 to -10 or -1 to -9 or -1 to -5;

[0044] - Shore D value, equal to or less than 50, or equal to or less than 45, especially 15 to 50 or 15 to 45;

[0045] - Fracture tensile stress, measured according to ISO 527, is 10 MPa to 45 MPa, particularly 10 MPa to 35 MPa;

[0046] - Elongation at break, measured according to ISO 527, is 400% to 900%; particularly 450% to 700%.

[0047] - Glass transition temperature, which is -19°C or lower, especially -20°C or lower, with the lower limit being -23°C.

[0048] - Density, 0.880 g / cm³ 3 Or even higher, especially 0.885 g / cm³ 3 Or greater; where the upper limit is 0.910 g / cm³. 3 , or 0.899 g / cm 3 ;

[0049] Butene-1 polymer components A) and B) can be obtained by polymerizing monomers in the presence of a metallocene catalyst system, which can be obtained by contacting the following substances:

[0050] -Stereorigid metallocene compounds;

[0051] -Aluminoxanes or compounds capable of forming alkyl metallocene cations; and optionally,

[0052] - Organoaluminum compounds.

[0053] Preferably, the stereolithic metallocene compound belongs to the following formula (I):

[0054]

[0055] in:

[0056] M is an atom selected from transition metals belonging to Group 4; preferably, M is zirconium.

[0057] X, which may be the same as or different from each other, is a hydrogen atom, a halogen atom, or an R, OR, OR′O, OSO2CF3, OCOR, SR, NR2, or PR2 group, wherein R is a straight-chain or branched, saturated or unsaturated C1-C group. 20 Alkyl, C3-C 20 cycloalkyl, C6-C 20 Aryl, C7-C 20 alkylaryl or C7-C 20 Arylalkyl group, optionally containing heteroatoms belonging to groups 13-17 of the periodic table; and R′ is C1-C 20 Alkylene, C6-C 20 Alpha-aryl, C7-C 20 Alkyl arylide or C7-C 20 Arylalkylene; preferably, X is a hydrogen atom, a halogen atom, an OR′O or an R group; more preferably, X is chlorine or methyl;

[0058] R 1 R 2 R 5 R 6 R 7 R 8 and R 9They may be the same or different from each other, they may be hydrogen atoms, straight-chain or branched, saturated or unsaturated C1-C atoms. 20 Alkyl, C3-C 20 cycloalkyl, C6-C 20 Aryl, C7-C 20 alkylaryl or C7-C 20 Arylalkyl group, optionally containing heteroatoms belonging to groups 13-17 of the periodic table; or R 5 and R 6 , and / or R 8 and R 9 Saturated or unsaturated 5- or 6-membered rings can be optionally formed, and the rings may have C1-C2 elements. 20 Alkyl groups are used as substituents; the condition is R. 6 Or R 7 At least one of them is a straight-chain or branched, saturated or unsaturated C1-C 20 Alkyl groups, optionally containing heteroatoms belonging to groups 13-17 of the periodic table; preferably C1-C2. 10 alkyl;

[0059] R 3 and R 4 They may be the same or different from each other, straight or branched, saturated or unsaturated C1-C 20 Alkyl group, optionally containing heteroatoms belonging to groups 13-17 of the periodic table; preferably R 3 and R 4 C1-C represents the similarity or difference between the two. 10 Alkyl; more preferably R 3 It is methyl or ethyl; R 4 It can be methyl, ethyl, or isopropyl.

[0060] Preferably, the compound of formula (I) has formula (Ia):

[0061]

[0062] in:

[0063] M, X, R 1 R 2 R 5 R 6 R 8 and R 9 As mentioned above;

[0064] R 3 It is either straight-chain or branched, saturated or unsaturated C1-C. 20 Alkyl group, optionally containing heteroatoms belonging to groups 13-17 of the periodic table; preferably R 3 For C1-C 10 Alkyl; more preferably R3 It is methyl or ethyl.

[0065] Specific examples of metallocene compounds are dimethylsilyl{(2,4,7-trimethyl-1-indenyl)-7-(2,5-dimethyl-cyclopentane[1,2-b:4,3-b′]-dithiophene)}zirconium dichloride; dimethylsilidinediyl{(1-(2,4,7-trimethylindenyl)-7-(2,5-dimethyl-cyclopentane[1,2-b:4,3-b′]-dithiophene)}zirconium dichloride and dimethylsilidinediyl{(1-(2,4,7-trimethylindenyl)-7-(2,5-dimethyl-cyclopentane[1,2-b:4,3-b′]-dithiophene)}dimethylzirconium.

[0066] Examples of aluminum oxanes are methylaluminoxane (MAO), tetra-(isobutyl)aluminoxane (TIBAO), tetra-(2,4,4-trimethylpentyl)aluminoxane (TIOAO), tetra-(2,3-dimethylbutyl)aluminoxane (TDMBAO) and tetra-(2,3,3-trimethylbutyl)aluminoxane (TTMBAO).

[0067] Examples of compounds capable of forming alkyl metallocene cations are compounds of the formula D+E-, where D... + It is a Briensteinic acid, capable of donating a proton and reacting irreversibly with the metallocene substituent X of formula (I), and E- is a compatible anion capable of stabilizing the active catalyst derived from the reaction of the two compounds, and is sufficiently unstable to be removed by the olefin monomer. Preferably, the anion E- contains one or more boron atoms.

[0068] Examples of organoaluminum compounds are trimethylaluminum (TMA), triisobutylaluminum (TIBA), tri(2,4,4-trimethylpentyl)aluminum (TIOA), tri(2,3-dimethylbutyl)aluminum (TDMBA) and tri(2,3,3-trimethylbutyl)aluminum (TTMBA).

[0069] Examples of the catalyst system and polymerization processes using such catalyst systems can be found in WO2004099269 and WO2009000637.

[0070] By operating under known polymerization conditions in the presence of the above-mentioned catalyst, the two components A) and B) of the butene-1 polymer composition of the present invention can be prepared separately and then blended together in a melt state using known polymer processing equipment such as single-screw and twin-screw extruders.

[0071] However, as mentioned above, the butene-1 polymer composition of the present invention can be prepared directly during polymerization.

[0072] Therefore, the polymerization process for preparing the composition includes at least two consecutive stages carried out in two or more reactors connected in series, wherein components A) and B) are prepared in separate subsequent stages, and are operated in each stage except the first stage in the presence of the polymer formed and a catalyst for the preceding stage.

[0073] The polymerization process can be carried out in the liquid phase, optionally in the presence of an inert hydrocarbon solvent, or in the gas phase, using a fluidized bed or mechanically stirred gas-phase reactor.

[0074] The catalyst may be added to the first reactor only, or to more than one reactor.

[0075] The hydrocarbon solvent can be aromatic (such as toluene) or aliphatic (such as propane, hexane, heptane, isobutane, cyclohexane, 2,2,4-trimethylpentane and isododecane).

[0076] Preferably, the polymerization process is carried out using liquid butene-1 as the polymerization medium. The polymerization temperature can be 20°C-150°C, particularly 50°C-90°C, for example 65°C-82°C.

[0077] The concentration of hydrogen in the liquid phase during the polymerization reaction (mol H2 / butene-1 monomer) is typically 1000 ppm to 1900 ppm, especially 1100 ppm to 1800 ppm.

[0078] When preparing copolymers, the amount of comonomer, particularly ethylene, in the liquid phase can be from 0.1% to 8% by weight, particularly from 0.2% to 6% by weight, relative to the total weight of the comonomer and butene-1 monomer present in the polymerization reactor.

[0079] Specifically, for the preparation of component A), the amount of comonomer can be from 0.1% to 0.9% by weight or from 0.2% to 0.8% by weight, while for the preparation of component B), it can be from 1% to 8% by weight or from 1.5% to 6% by weight.

[0080] In hot melt adhesive applications, the butene-1 polymer composition of the present invention may optionally be blended with other materials commonly used in the relevant fields.

[0081] In particular, in addition to the butene-1 polymer composition of the present invention comprising components A) and B), the hot melt adhesive polyolefin composition may comprise one or more of the following optional components:

[0082] I) At least one other polymer, particularly selected from amorphous poly-α-olefins, thermoplastic polyurethanes, ethylene / (meth)acrylate copolymers, ethylene / vinyl acetate copolymers, and mixtures thereof;

[0083] II) At least one resin material that is different from (I) and is selected from aliphatic hydrocarbon resins, terpene / phenolic resins, polyterpenes, rosin, rosin esters and their derivatives and mixtures thereof.

[0084] III) at least one wax or oil, particularly selected from mineral, paraffin, or naphthenic waxes or oils; and

[0085] IV) Nucleating agents.

[0086] Examples of nucleating agents are isotactic polypropylene, polyethylene, and amides such as stearamide or talc.

[0087] When present and independent of each other, the preferred weight of the optional components relative to the total weight of the hot melt adhesive polyolefin composition is:

[0088] -0.1% by weight to 25% by weight, especially 1% by weight to 25% by weight of I);

[0089] -10% to 75% by weight, especially 10% to 40% by weight (II);

[0090] -0.1% to 50% by weight, especially 1% to 30% by weight of III);

[0091] -0.01% by weight to 1% by weight, especially 0.1% by weight to 1% by weight of IV).

[0092] The components can be added and blended in a molten state with the butene-1 polymer composition of the present invention using known polymer processing equipment such as single and twin screw extruders.

[0093] The hot melt adhesive composition can be used in several fields, such as the paper and packaging industry, furniture manufacturing, for example for edge sealing tape, especially square edges, and flexible molding applications, for paneling in high humidity environments, and for the production of nonwoven products such as disposable diapers.

[0094] Example

[0095] The various embodiments, compositions, and methods provided herein are disclosed in the following examples. These examples are merely illustrative and are not intended to limit the scope of the invention.

[0096] The following analytical methods are used to characterize polymer compositions.

[0097] Thermal properties (melting temperature and enthalpy)

[0098] As described below, the determination was made by differential scanning calorimetry (DSC) on a Perkin Elmer DSC-7 instrument.

[0099] To determine TmII (the melting temperature measured during the second heating run), a weighed sample (5-10 mg) obtained from polymerization was sealed in an aluminum pan and heated at 200 °C with a scan rate corresponding to 10 °C / min. The sample was held at 200 °C for 5 minutes to allow all crystallites to completely melt, thus eliminating the thermal history of the sample. Then, after cooling to -20 °C with a scan rate corresponding to 10 °C / min, the peak temperature was taken as the crystallization temperature (Tc). After standing at -20 °C for 5 minutes, the sample was heated a second time at 200 °C with a scan rate corresponding to 10 °C / min. The peak temperature measured during this second heating run was (TmII). If more than one peak existed, the highest (strongest) peak was taken as TmII. The area under the peak (or multiple peaks) was taken as the total enthalpy of fusion (DH TmII).

[0100] - The melting enthalpy and melting temperature were also measured after aging (without eliminating thermal history) using differential scanning calorimetry (DSC) on a Perkin Elmer DSC-7 instrument. A weighed sample (5-10 mg) obtained from polymerization was sealed in an aluminum pan and heated at 200 °C with a scan rate corresponding to 10 °C / min. The sample was held at 200 °C for 5 minutes to allow all microcrystals to completely melt. 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 at 200 °C with a scan rate corresponding to 10 °C / min. During this heating run, the peak temperature was taken as the melting temperature (TmI). If more than one peak was present, the highest (strongest) peak was taken as TmI. The area under the peak (or multiple peaks) was taken as the total melting enthalpy (DH TmI) after 10 days.

[0101] MFR

[0102] Determined according to standard ISO 1133 at 190°C (standard die head) with a load of 2.16 kg.

[0103] Intrinsic viscosity

[0104] Determined in tetrahydronaphthalene at 135°C according to standard ASTM D2857.

[0105] density

[0106] According to ISO 1183-1 (ISO 1183-1 Method A "Determination of density of non-foamed plastics - Part 1: Impregnation method, liquid hydrometer method and titration method"); Method A: Impregnation method, for solid plastics (excluding powders) in non-porous form. Test specimens were taken from compressed boards conditioned for 10 days prior to density measurement.

[0107] Comonomer content

[0108] The comonomer content was determined by FT-IR.

[0109] The spectrum of polymer pressed films is expressed as absorbance relative to wavenumber (cm²). -1 Record the following measurements used to calculate the ethylene content:

[0110] a) 4482-3950cm -1 Area of ​​the combined absorption band (A) t ), used for spectral normalization of film thickness.

[0111] b) Due to the sequence of the methylene group (CH2 rocking vibration) BEE and BEB (B: 1, butene unit, E: ethylene unit), the numerical subtraction factor (FCR) between the spectra and absorption bands of the polymer sample is significant. C2 ).

[0112] c) The area of ​​the remaining bandwidth after subtracting the C2PB spectrum (A) C2，块 It originates from the EEE sequence (CH2 rocking vibration) of the methylene group.

[0113] Device

[0114] The spectral measurements reported above can be provided using a Fourier transform infrared spectrometer (FTIR).

[0115] Use a hydraulic press with a pressure plate that can be heated to 200°C (for engravers or equivalents).

[0116] method

[0117] Calibration of (BEB+BEE) sequence

[0118] By plotting (BEB+BEE)wt% relative to FCR C2 / A t The calibration line is obtained. Slope G r and intercept I r Calculated by linear regression.

[0119] EEE sequence calibration

[0120] By plotting (EEE)wt% relative to A C2，块 / A t The calibration line is obtained. Slope G H and intercept I H Calculated by linear regression.

[0121] Sample preparation

[0122] Using a hydraulic press, a thick sheet is obtained by pressing approximately 1.5g of sample between two aluminum foils. If uniformity is a concern, at least two pressing operations are recommended. A small portion is then cut from this sheet to mold a film. The recommended film thickness range is 0.1–0.3 mm.

[0123] The pressing temperature is 140±10℃.

[0124] Since crystalline phase modification occurs over time, it is recommended to collect the IR spectrum of the sample film as soon as it is molded.

[0125] process

[0126] The instrument data acquisition parameters are:

[0127] Purge time: 30 seconds minimum.

[0128] Collection time: Minimum 3 minutes.

[0129] Happ-Genzel method.

[0130] Resolution: 2cm -1 .

[0131] Collect the IR spectrum of the sample relative to the air background.

[0132] calculate

[0133] Calculate the weight concentration of the BEE+BEB sequence in the ethylene unit:

[0134]

[0135] Using the baseline between the shoulders of the remaining strip, calculate the remaining area (AC2, block) after the above subtraction.

[0136] Calculate the weight concentration of the EEE sequence of the ethylene unit:

[0137]

[0138] Calculate the total weight percentage of ethylene:

[0139] %C2wt=[%(BEE+BEB)wt+%(EEE)wt]

[0140] NMR analysis of chain structure

[0141] 13 C10 NMR spectra were obtained on a Bruker Av-600 spectrometer equipped with a cryoprobe, operated at 150.91 MHz in Fourier transform mode at 120 °C.

[0142] T βδCarbon peaks (according to CJ Carman, RA Harrington, and CE Wilkes, macromolecules, 10, 3 The nomenclature of 536 (1977) was used as an internal standard at 37.24 ppm. The sample was dissolved at 120 °C in 1,1,2,2-tetrachloroethane-d2 at a concentration of 8 wt / v%. A 90° pulse was applied, with a 15-second delay between the pulse and the CPD to remove [the sample]. 1 H- 13 C-coupling was used to obtain each spectrum. Approximately 512 transients were stored in 32K data points using a spectral window of 9000 Hz.

[0143] According to Kakugo [M. Kakugo, Y. Naito, K. Mizunuma and T. Miyatake, Macromolecules, 16, 4 [1160 (1982)] and Randall [J.R.Randall, Macromol. Chem. Phys., C30, 211 (1989)] used the following for spectral assignment, triplet distribution and compositional assessment:

[0144] BBB = 100(T) ββ ) / S=I5

[0145] BBE = 100T βδ / S=I4

[0146] EBE = 100P δδ / S=I14

[0147] BEB = 100S ββ / S=I13

[0148] BEE = 100S αδ / S=I7

[0149] EEE = 100(0.25S) γδ +0.5S δδ ) / S=0.25I9+0.5I10

[0150]

[0151] For the first approximation, mmmm is calculated using 2B2 carbon as follows:

[0152] area Chemical shift distribute B1 28.2-27.45 mmmm B2 27.45-26.30

[0153] mmmm=B1*100 / (B1+B2-2*A4-A7-A 14 )

[0154] GPC method to determine Mw / Mn and Mz

[0155] 1,2,4-Trichlorobenzene (TCB) was measured by gel permeation chromatography (GPC). Molecular weight parameters (Mn, Mw, Mz) and molecular weight distribution (Mw / Mn) were measured for all samples using a PolymerChar GPC-IR system equipped with four PLgel Olexis mixed-bed (Polymer Lab) columns and an IR5 infrared detector (PolymerChar). The columns were 300 × 7.5 mm in size and had a particle size of 13 μm. The mobile phase flow rate was maintained at 1.0 mL / min. All measurements were performed at 150 °C. The solution concentration was 2.0 mg / mL (150 °C) with 0.3 g / L of 2,6-dibutyryl-p-chloroether (2,6-diterbuthyl-p-chresole) added to prevent degradation. For GPC calculations, universal calibration curves were obtained using 12 polystyrene (PS) standards (peak molecular weights ranging from 266 to 1,220,000) provided by PolymerChar. The experimental data were interpolated using cubic polynomial fitting to obtain the corresponding calibration curves. Data acquisition and processing were performed using Empower3 (Waters). The molecular weight distribution and associated average molecular weight were determined using the Mark-Houwink relation: the K values ​​for PS and polybutene (PB) were K0 and K1, respectively. PS =1.21×10 -4 dl / g and K PB =1.78×10 -4 The Mark-Houwink exponents for dl / g, PS, and PB were α = 0.706 and α = 0.725, respectively.

[0156] For butene / ethylene copolymers, for data evaluation purposes, it is assumed that the composition is constant across the entire molecular weight range for each sample, and the K value of the Mark-Houwink relationship is calculated using the linear combination reported below:

[0157] K EB =x E K PE +x B K PB

[0158] Where K EB K is a constant of the copolymer. PE (4.06×10 -4 , dl / g) and K PB (1.78×10 -4 dl / g) is a constant for polyethylene (PE) and PB, x E and x B x represents the relative weights of ethylene and butene, where xE +x B =1. The Mark-Howwink index α = 0.725 was used independently for the composition of all butene / ethylene copolymers. Final processing data for all samples were fixed to include the fraction with a molecular weight equivalent up to 1000. The fraction with a molecular weight equivalent below 1000 was studied by GC.

[0159] In 0 ℃ (XS-0 ℃ The fractions that are soluble in and insoluble in xylene.

[0160] Mix 2.5g of polymer composition with 250cm 3 o-Xylene was introduced into a glass flask equipped with a refrigerator and a magnetic stirrer. The temperature was raised to the boiling point of the solvent within 30 minutes. The resulting clear solution was then refluxed and stirred for another 30 minutes. The sealed flask was then cooled to 100°C in air for 10–15 minutes with stirring, and then kept in a constant temperature water bath at 0°C for 30–60 minutes. The solid thus formed was filtered through rapid filter paper at 0°C. A 100 cm⁻¹ filter was then used. 3 The filtered liquid was poured into a pre-weighed aluminum container, which was heated on a hot plate under a nitrogen stream to remove the solvent by evaporation. Therefore, the weight percentage of polymer-soluble matter (xylene-soluble matter at 0°C = XS0°C) was calculated from the average weight of the residue. The insoluble portion in o-xylene at 0°C (xylene-insoluble matter at 0°C = XS0°C) was:

[0161] XI%0℃=100-XS%0℃.

[0162] X-ray crystallinity determination

[0163] X-ray crystallinity was measured using an X-ray powder diffractometer (XDPD) that uses Cu-Kα1 radiation with a fixed slit and is capable of collecting spectra between diffraction angles 2Θ = 5° and 2Θ = 35° in steps of 0.1° every 6 seconds.

[0164] The samples were prepared by compression molding into discs approximately 1.5-2.5 mm thick and 2.5-4.0 cm in diameter. The discs were aged at room temperature (23°C) for 96 hours.

[0165] Following this preparation, the sample is inserted into the XDPD sample holder. The XRPD instrument is set to collect XRPD spectra of the sample from diffraction angles 2Θ = 5° to 2Θ = 35° using a counting time of 6 seconds in steps of 0.1°, and finally collects the final spectrum.

[0166] Ta is defined as the total area between the spectral profile and the baseline, expressed in counts / second·2Θ, and Aa is defined as the total amorphous area, expressed in counts / second·2Θ. Ca is the total crystalline area, expressed in counts / second·2Θ.

[0167] Analyze the spectrum or diffraction pattern using the following steps:

[0168] 1) Define a suitable linear baseline for the entire spectrum and calculate the total area (Ta) between the spectral profile and the baseline;

[0169] 2) Define a suitable amorphous profile along the entire spectrum based on the two-phase model, which separates the amorphous region from the crystalline region;

[0170] 3) Calculate the amorphous area (Aa) as the area between the amorphous profile and the baseline;

[0171] 4) The crystallization area (Ca), which is the area between the spectral profile and the amorphous profile, is calculated as Ca = Ta - Aa.

[0172] 5) Calculate the crystallinity (%Cr) of the sample using the following formula:

[0173] %Cr = 100x Ca / Ta

[0174] Flexural modulus

[0175] Measurements were taken 10 days after molding, according to standard ISO 178.

[0176] Xiao's D

[0177] Measurements were taken 10 days after molding, according to standard ISO 868.

[0178] Tensile stress and elongation at break

[0179] According to standard ISO527, measurements were taken on the compression molding plate 10 days after molding.

[0180] Glass transition temperature via DMTA (Dynamic Mechanical Thermal Analysis) A 76mm × 13mm × 1mm molded specimen was fixed onto a DMTA machine for tensile stress. The frequency of the tension and its dependence on the specimen were fixed at 1Hz. DMTA converted the elastic response of the specimen from -100℃ to 130℃. This allowed for the plotting of the elastic response versus temperature. The elastic modulus of a viscoelastic material is defined as E = E' + iE”. DMTA can separate the two components E' and E” through their resonance and plot the curve of E' versus temperature, and E' / E” = tan(δ) versus temperature.

[0181] Assume that the glass transition temperature Tg is the temperature at the maximum value of the curve E' / E”=tan(δ) with respect to temperature.

[0182] Yellowness Index

[0183] Determined according to ASTM D1925.

[0184] Example 1 and Comparative Example 1

[0185] Preparation of metallocene catalyst (A-1)

[0186] Dimethylsilyl{(2,4,7-trimethyl-1-indenyl)-7-(2,5-dimethyl-cyclopentane[1,2-b:4,3-b′]-dithiophene)}zirconium dichloride (A-1) was prepared according to Example 32 of WO0147939.

[0187] Preparation of catalytic solution

[0188] Under a nitrogen atmosphere, 8.1 L of a 4.5% wt / v solution of TIBA in isododecane (1.84 mol TIBA) and 760 mL of a 30% wt / wt solution of MAO in toluene (3.65 mol MAO) were loaded into a 20 L jacketed glass reactor equipped with an anchor stirrer and allowed to react at room temperature with stirring for about 1 hour.

[0189] Subsequently, metallocene A-1 (1.6 g, 2.75 mmol) was added and dissolved with stirring for about 30 minutes.

[0190] The final solution is discharged from the reactor into a cylinder through a filter to remove any solid residues (if any).

[0191] The solution composition is as follows:

[0192]

[0193] polymerization

[0194] The polymerization was carried out continuously in a test apparatus comprising two stirred reactors connected in series, wherein liquid butene-1 constituted the liquid medium.

[0195] The catalytic solution is fed into two reactors.

[0196] The aggregation conditions are reported in Table 1.

[0197] Table 1

[0198] Example 1 Operating conditions (first reactor) Temperature (°C) 75 <![CDATA[H2 (ppm mol) in liquid phase]]> 1540 <![CDATA[C2H4 (wt%) in the liquid phase]]> 0.36 Mileage (kg / gMe) 2777 Splitting (wt%) 42 <![CDATA[C2H4 content (wt%) of (A)]]> 0.9 <![CDATA[C2H4 content (mol%) of (A)]]> 1.8 Operating conditions (second reactor) Temperature (°C) 75 <![CDATA[H2 (ppm mol) in the liquid phase]]> 1560 <![CDATA[C2H4 (wt%) in the liquid phase]]> 4.1 Splitting (wt%) 58 <![CDATA[C2H4 content (wt%) of (B)]]> 6.4 <![CDATA[C2H4 content (mol%) of (B)]]> 12 Total Mileage 2747 <![CDATA[Total C2H4 content (mol%)]]> 7.7

[0199] Note: C2H4 = ethylene; kg / g Me = number of kilograms of polymer per gram of metallocene catalyst (A-1); splitting = amount of polymer produced in the relevant reactor.

[0200] The performance of the final product is specified in Table 2.

[0201] Table 2 also reports the properties of a comparative butene-1 polymer (Comparative Example 1), a commercial copolymer containing 6.8 mol% ethylene, prepared with a Ziegler-Natta catalyst and subsequently peroxide-treated to increase the MFR value.

[0202] Table 2

[0203] Example 1 Comparative Example 1 MFR 190° 2.16kg g / 10min 210 200 Intrinsic viscosity dl / g 0.61 0.69 <![CDATA[C2H4 IR]]> mol% 7.7 6.8 TmII ℃ 83.4 81.4 DH TmII J / g 11.7 16.5 TmI ℃ 93 92.5 DH TmI J / g 40.2 40.4 X-ray crystallinity ％ 34 38 Xylene solubles at 0°C ％ 55.7 63.4 Mw g / mol 87903 88370 Mn g / mol 40726 28182 Mw / Mn 2.2 3.1 Mz g / mol 149487 148561 density <![CDATA[g / cm 3 ]]> 0.898 0.899 Flexural modulus MPa 130 140 Fracture strength MPa 17.9 21.1 Elongation at break ％ 580 470 Shore hardness D D 37.8 40.3 Glass transition temperature ℃ -21.6 -18

Claims

1. A butene-1 polymer composition having an MFR value of 100 to 300 g / 10 min, measured according to ISO 1133 at 190°C with a load of 2.16 kg, and comprising: A) A copolymer of butene-1 and a comonomer selected from ethylene, having a comonomer content of 1 mol% to 5 mol% C A ; B) A copolymer of butene-1 and ethylene comonomers, having a comonomer content of 6 mol% to 20 mol% C B ; The composition has a total copolymer content of 4 mol% to 15 mol% relative to the sum of A) and B), and a xylene-soluble fraction of 75 wt% or less based on the total weight of A) and B), and the difference between the percentage values ​​of the copolymerized comonomer content of B) and A) satisfies the following relationship: C B -C A ≥6, and with a Mw / Mn range of 1.5 to 2.

2.

2. The butene-1 polymer composition according to claim 1, wherein, relative to the total weight of A) and B), 30% to 70% by weight of A) and 30% to 70% by weight of B).

3. The butene-1 polymer composition according to claim 1, wherein the DH TmII value is 4-15 J / g, measured at a scan rate corresponding to 10 °C / min, wherein, to determine TmII, a weighed sample obtained from polymerization is sealed in an aluminum pan and heated at 200 °C at a scan rate corresponding to 10 °C / min; the sample is held at 200 °C for 5 minutes to allow all microcrystals to completely melt, thereby eliminating the thermal history of the sample; then, after cooling to -20 °C at a scan rate corresponding to 10 °C / min, the peak temperature is taken as the crystallization temperature; after standing at -20 °C for 5 minutes, the sample is heated a second time at 200 °C at a scan rate corresponding to 10 °C / min; during this second heating run, the measured peak temperature is taken as TmII; if more than one peak exists, the highest peak is taken as TmII; the area under the peak is taken as the total enthalpy of fusion DH TmII.

4. The butene-1 polymer composition according to claim 1, having an Mz value of 90,000 g / mol or higher as measured by GPC.

5. The butene-1 polymer composition according to claim 1, having a Mw value equal to or greater than 50,000 g / mol.

6. A process for preparing the butene-1 polymer composition of claim 1, said process comprising at least two consecutive stages carried out in two or more reactors connected in series, wherein components A) and B) are prepared in separate subsequent stages, and are operated in each stage except the first stage in the presence of the polymer formed and a catalyst for the preceding stage.

7. The process according to claim 6, wherein it is carried out in the presence of a metallocene catalyst, which can be obtained by contacting the following substances: -Stereorigid metallocene compounds; -Aluminoxanes or compounds capable of forming alkyl metallocene cations; and optionally, - Organoaluminum compounds.

8. An article comprising or containing the butene-1 polymer composition according to claim 1 or 2.

9. The article according to claim 8, wherein it is in the form of a film or fiber.

10. A hot melt adhesive composition comprising or containing the butene-1 polymer composition according to claim 1 or 2.

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