阅读说明：本技术 用于耐高应力开裂性和良好的可加工性的聚烯烃树脂共混物 (Polyolefin resin blends for high stress crack resistance and good processability ) 是由 萨兰亚·特莱西兰农 威罗·南塔瑟特蓬 瓦差里·奇瓦斯里伦格隆 于 2019-09-16 设计创作，主要内容包括：包含熔融共混物的聚乙烯组合物,所述熔融共混物包含：a)第一多峰聚乙烯,所述第一多峰聚乙烯具有中等重均分子量或高重均分子量、根据ISO 1183的大于0,950至0,965g/cm～3的密度、以及根据ISO 1133的0.3至2,0g/10min的MFR-2；和b)第二多峰聚乙烯,所述第二多峰聚乙烯具有高重均分子量、根据ISO 1183的0.940至0.950g/cm～3的密度、以及根据ISO 1133的0.03至0.15g/10min的MFR-2；其中聚合物组合物具有根据ISO 16770的至少58小时的全缺口蠕变测试(FNCT)、以及根据ISO 179在23℃的温度下至少4kJ/m～2的简支梁冲击强度。(A polyethylene composition comprising a melt blend, the melt blend comprising: a) a first multimodal polyethylene having a medium or high weight average molecular weight, more than 0,950 to 0,965g/cm according to ISO 1183 3 And an MFR according to ISO 1133 of 0.3 to 2,0g/10min 2 (ii) a And b) a second multimodal polyethylene having a high weight average molecular weight, from 0.940 to 0.950g/cm according to ISO 1183 3 And an MFR according to ISO 1133 of 0.03 to 0.15g/10min 2 (ii) a Wherein the polymer composition has a Full Notch Creep Test (FNCT) according to ISO 16770 for at least 58 hours toAnd at least 4kJ/m at a temperature of 23 ℃ according to ISO 179 2 Impact strength of the simply supported beam.)

1. A polyethylene composition comprising a melt blend, the melt blend comprising:

a) a first multimodal polyethylene, said first multimodal polyethyleneThe peak polyethylene has a medium or high weight average molecular weight, greater than 0.950 to 0.965g/cm according to ISO 1183³And an MFR according to ISO 1133 of 0.3 to 2.0g/10min₂(ii) a And

b) a second multimodal polyethylene having a high weight average molecular weight, from 0.940 to 0.950g/cm according to ISO 1183³And an MFR according to ISO 1133 of 0.03 to 0.15g/10min₂；

Wherein the polymer composition has a Full Notch Creep Test (FNCT) according to ISO 16770 for at least 58 hours and a temperature according to ISO 179 of at least 4kJ/m at 23 DEG C²Impact strength of the simply supported beam.

2. The polyethylene composition according to claim 1, wherein the polymer composition has a FNCT of from 58 to 100 hours, preferably from 60 to 90 hours, more preferably from 60 to 85 hours.

3. The polyethylene composition according to claim 1 or 2, wherein the polyethylene composition has from 4 to 10kJ/m²Preferably 4.5 to 9kJ/m²More preferably 5 to 9kJ/m²Most preferably from 5.5 to 9kJ/m²Impact strength of a simple beam at a temperature of 23 ℃.

4. The polyethylene composition according to any of the preceding claims, wherein the first multimodal polyethylene is a bimodal polyethylene or a trimodal polyethylene and the second multimodal polyethylene is a bimodal polyethylene or a trimodal polyethylene, preferably one of the first multimodal polyethylene and the second multimodal polyethylene is a bimodal polyethylene and the other of the first multimodal polyethylene and the second multimodal polyethylene is a trimodal polyethylene, even more preferably the first multimodal polyethylene is a bimodal polyethylene and the second multimodal polyethylene is a trimodal polyethylene.

5. The polyethylene composition according to claim 4, wherein the bimodal polyethylene comprises 40 to 60% by weight, preferably 45 to 55% by weight, of an ethylene homopolymer and 40 to 60% by weight, preferably 45 to 55% by weight, of an ethylene copolymer, wherein the ethylene copolymer comprises comonomer in an amount of at least 0.30 mol%, preferably 0.30 to 1.0 mol%, relative to the total amount of monomers in the ethylene copolymer, respectively, based on the total weight of the bimodal polyethylene.

6. The polyethylene composition according to claim 5, wherein the comonomer is selected from the group consisting of: 1-butene, 1-hexene, 1-octene, preferably 1-butene and mixtures thereof.

7. The polyethylene composition according to any of claims 4 to 6, wherein the bimodal polyethylene has an MFR according to ISO 1133 of 0.02 to 1.0g/10min, preferably of 0.3 to 1.0g/10min₂And/or 0.945 to 0.960g/cm according to ISO 1138³The density of (c).

8. The polyethylene composition according to any of claims 4 to 7, wherein the bimodal polyethylene has a weight average molecular weight of from 100,000 to 400,000g/mol, preferably from 120,000 to 350,000g/mol, even more preferably from 140,000 to 320,000g/mol, measured by gel permeation chromatography.

9. The polyethylene composition according to any one of claims 4 to 8, wherein the trimodal polyethylene comprises:

(A) 30 to 65% by weight, preferably 43 to 65% by weight, most preferably 44 to 60% by weight, based on the total weight of the trimodal polyethylene, of a low molecular weight polyethylene having an MFR of 500 to 1,000g/10min according to ISO 1133₂And a weight average molecular weight (Mw) of 20,000 to 90,000g/mol as measured by gel permeation chromatography;

(B) 5 to 40% by weight, preferably 10 to 20% by weight, most preferably 10 to 15% by weight, based on the total weight of the trimodal polyethylene; and

(C) 20 to 60% by weight, preferably 25 to 60% by weight, most preferably 35 to 55% by weight, of high molecular weight polyethylene, based on the total weight of the trimodal polyethylene.

10. The polyethylene composition according to any of claims 4 to 9, wherein the trimodal polyethylene has a weight average molecular weight of from 80,000 to 500,000g/mol, preferably from 80,000 to 400,000g/mol, preferably from 150,000 to 350,000g/mol, most preferably from 150,000 to 300,000g/mol, measured by gel permeation chromatography.

11. The polyethylene composition according to any of the preceding claims, wherein the melt blend comprises 70 to 97% by weight, preferably 80 to 95% by weight, of the first multimodal polyethylene; and from 3 to 30% by weight, preferably from 5 to 20% by weight, of said second multimodal polyethylene.

12. The polyethylene composition according to any of the preceding claims, wherein the polyethylene composition has an MFR according to ISO 1133 of 0.05 to 2.0g/10min, preferably of 0.1 to 2.0g/10min, more preferably of 0.3 to 1.5g/10min, even more preferably of 0.3 to 1.0g/10min₂。

13. The polyethylene composition according to any of the preceding claims, wherein the polyethylene composition has a density of from 0.945 to 0.960g/cm according to ISO 1183³Preferably 0.950 to 0.959g/cm³Even more preferably 0.952 to 0.957g/cm³The density of (c).

14. The polyethylene composition according to any of the preceding claims, wherein the polyethylene composition has a weight average molecular weight of 80,000 to 500,000g/mol, preferably 80,000 to 400,000g/mol, most preferably 100,000 to 200,000g/mol, measured by gel permeation chromatography; and/or a polydispersity index of from 10 to 25, preferably from 15 to 22.

15. Article comprising the polyethylene composition according to any of the preceding claims, wherein the article is preferably a blow molded article, a pipe, a film, a cap, a closure, a wire, a cable or a sheet.

Technical Field

The present invention relates to polymer compositions comprising blends of ethylene polymers of different molecular weights and densities. More particularly, the present invention relates to molded articles from injection molding, compression molding and blow molding, in particular caps and closures (closures) comprising the polymer composition.

Background

EP 2746334A 1 discloses polyethylene blends with improved ESCR comprising from 99.0 to 99.5 wt% of a lower molecular weight bimodal HDPE component and from 0.5 to 10 wt% of a higher molecular weight bimodal HDPE, wherein the density of the blend is at least 940kg/m³And FNCT for at least 30 hours measured according to the full notch creep test (ISO 16770) at 50 ℃ and 6 MPa.

US 6,822,051B 2 discloses a polymer blend comprising a bimodal high molecular weight HDPE having NCTL stress crack resistance of about 200 hours or more and a HDPE having NCTL stress crack resistance of 24 hours. The composition of this blend can be used in profile, pipe, chemical waste applications, including sewer or irrigation piping.

US 3,717,054B 2 discloses melt blend HDPE compositions with enhanced physical properties, processability and environmental stress crack resistance for use in the manufacture of corrugated HDPE pipe.

US 7867588B 2 relates to a density of 0.945 to 0.960g/cm³And a melt blend of a linear low density polyethylene resin, a linear medium low density polyethylene resin and a high density polyethylene having a melt flow index of 0.1 to 0.4, which can be used in the manufacture of pipeline storm water and sewer applications.

Disclosure of Invention

It is an object of the present invention to provide a polymer composition overcoming the disadvantages of the prior art, in particular suitable for the preparation of moulded pellets, in particular container closures, from injection moulding, compression moulding, blow moulding and extrusion, which overcomes the disadvantages of the prior art, in particular with respect to stress crack resistance, a good balance between stiffness and processability to achieve high stress crack resistance, for example in caps, and good processability during injection. This object is achieved according to the independent claims. Preferred embodiments follow from the dependent claims.

This object is in particular achieved by a polyethylene composition comprising a melt blend comprising: a) a first multimodal polyethylene having a medium or high weight average molecular weight, according to ISO 1183, of more than 0.950 to 0.965g/cm³And an MFR according to ISO 1133 of 0.3 to 2.0g/10min, preferably of 0.8 to 10.0g/10min₂(ii) a And b) a second multimodal polyethylene having a high weight average molecular weight, according to ISO 1183, of from 0.940 to 0.950g/cm³And an MFR according to ISO 1133 of 0.03 to 0.15g/10min, preferably of 0.003 to 0.05g/10min₂(ii) a Wherein the polymer composition has a Full Notch Creep Test (FNCT) according to ISO 16770 of at least 58 hours and a temperature according to ISO 179 of at least 4kJ/m at 23 ℃²Charpy impact strength (Charpy impact strength).

The inventors have surprisingly found that the inventive polyethylene composition has a better balance of stress crack resistance, stiffness and processability compared to known resins. According to the present invention it has been found that a blend of a first multimodal polyethylene and a second multimodal polyethylene as defined herein shows desirable mechanical properties and processability during injection moulding, extrusion, compression moulding and blow moulding. These effects are even more pronounced with the embodiments of the preparation (or combinations of preferred embodiments) mentioned below.

As used herein, the term "comprising" may be "consisting of. For example, the polyethylene composition comprising the melt blend may be a polyethylene composition consisting of the melt blend.

In one embodiment, the polymer composition has a FNCT of from 58 to 100 hours, preferably from 60 to 90 hours, more preferably from 60 to 85 hours, most preferably from 60 to 77 hours.

In another embodiment, the polyethylene composition has a simple beam impact strength of 4 to 10kJ/m at a temperature of 23 ℃²Preferably 4.5 to 9kJ/m²More preferably 5 to 9kJ/m²Most preferably 5.5 to 9kJ/m²。

Furthermore, the first multimodal polyethylene is a bimodal polyethylene or a trimodal polyethylene and the second multimodal polyethylene is a bimodal polyethylene or a trimodal polyethylene, preferably one of the first multimodal polyethylene and the second multimodal polyethylene is a bimodal polyethylene and the other of the first multimodal polyethylene and the second multimodal polyethylene is a trimodal polyethylene, even more preferably the first multimodal polyethylene is a bimodal polyethylene and the second multimodal polyethylene is a trimodal polyethylene.

Even more preferably, the first multimodal polyethylene is a bimodal polyethylene and the second multimodal polyethylene is a trimodal polyethylene.

In a preferred embodiment, the bimodal polyethylene comprises 40 to 60% by weight, preferably 54 to 55% by weight, of the ethylene homopolymer and 40 to 60% by weight, preferably 45 to 55% by weight, of the ethylene copolymer, respectively, based on the total weight of the bimodal polyethylene, wherein the ethylene copolymer comprises comonomer in an amount of at least 0.30 mol%, preferably 0.30 to 1.0 mol%, even more preferably 0.40 to 10 mol%, relative to the total amount of monomers in the ethylene copolymer.

More preferably, the comonomer is selected from the group consisting of: 1-butene, 1-hexene, 1-octene and mixtures thereof, preferably 1-butene.

In other embodiments, the bimodal polyethylene has an MFR according to ISO 1133 of 0.02 to 1.0g/10min, preferably 0.3 to 1.0g/10min₂And/or 0.945 to 0.960g/cm according to ISO 1138³The density of (c).

In another embodiment, the bimodal polyethylene has a weight average molecular weight of from 100,000 to 400,000g/mol, preferably from 120,000 to 350,000g/mol, even more preferably from 140,000 to 320,000g/mol, as measured by gel permeation chromatography.

Preferably, the trimodal polyethylene comprises:

(A) 30 to 65% by weight, preferably 43 to 65% by weight, most preferably 44 to 60% by weight, based on the total weight of the trimodal polyethylene, of a low molecular weight polyethylene having an MFR according to ISO 1133 of 500 to 1,000g/10min₂And a weight average molecular weight (Mw) of 20,000 to 90,000g/mol as measured by gel permeation chromatography;

(B) 5 to 40% by weight, preferably 10 to 20% by weight, most preferably 10 to 15% by weight, based on the total weight of the trimodal polyethylene, of the first high molecular weight polyethylene or the first ultra high molecular weight polyethylene; and

(C) from 20 to 60% by weight, preferably from 25 to 60% by weight, most preferably from 35 to 55% by weight, of the second high molecular weight polyethylene or the second ultra high molecular weight polyethylene, based on the total weight of the trimodal polyethylene.

The trimodal polymerization in the first, second and third reactors is carried out under different process conditions. As a result, the polyethylene obtained in each reactor has a different molecular weight. These may be variations in the concentration of ethylene and hydrogen in the vapor phase, the temperature, or the amount of comonomer fed to each reactor. Suitable conditions for obtaining the corresponding homopolymer or copolymer having the desired properties, in particular having the desired molecular weight, are well known in the art. On the basis of its general knowledge, the person skilled in the art will be able to select the corresponding conditions on this basis. Preferably, the low molecular weight polyethylene or the medium molecular weight polyethylene is produced in the first reactor, while the high molecular weight polyethylene or the ultra high molecular weight polyethylene is produced in the second and third reactor, respectively.

The term first reactor refers to the stage in which a low molecular weight polyethylene or a medium molecular weight polyethylene is produced. The term second reactor refers to the stage in which the first high or ultra high molecular weight polyethylene is produced. The term third reactor refers to the stage in which the second high molecular weight polyethylene or ultra high molecular weight is produced.

The term low molecular weight polyethylene polymer (LMW) refers to polymerized ethylene monomers having a weight average molecular weight (Mw) of greater than 20,000 to 90,000 g/mol.

The term medium molecular weight polyethylene polymer refers to polymerized ethylene monomers having a weight average molecular weight (Mw) of greater than 90,000 to 200,000g/mol (MMW).

The term high molecular weight polyethylene polymer (HMW1) refers to polymerized ethylene monomers having a weight average molecular weight (Mw) of greater than 200,000 to 1,000,000 g/mol.

The term ultra high molecular weight polyethylene polymer (HMW2) refers to polymerized ethylene monomers having a weight average molecular weight (Mw) of greater than 1,000,000 to 5,000,000 g/mol.

To obtain a homopolymer, LMW or MMW is produced in the first reactor in the absence of comonomer. In addition, MMW, HMW1 or HMW2 ethylene copolymer was produced in the second and third reactors. Alpha-olefin comonomers useful for copolymerization include C4-12, preferably 1-butene and 1-hexene, most preferably 1-butene.

More preferably, the trimodal polyethylene has a weight average molecular weight of 80,000 to 500,000g/mol, preferably 80,000 to 400,000g/mol, preferably 150,000 to 350,000g/mol, most preferably 150,000 to 300,000g/mol, as measured by gel permeation chromatography.

Preparation of multimodal polyethylene

The multimodal polyethylene in the present invention can be prepared using ziegler-natta catalysts or single site or metallocene catalysts using sequential multistage slurry polymerization with at least two or more stages of polymerization.

Preparation of bimodal polyethylene

Bimodal polyethylene can be prepared using a ziegler-natta catalyst using a sequential two-stage slurry polymerization with a hexane diluent. Ethylene is polymerized in the first reactor in the absence of comonomer to obtain a polyethylene homopolymer fraction (fraction ) of a low average molecular weight (LMW) fraction. Density of LMW polyethylene>0.965g/cm³And MFR₂In the range of 10-1000g/10min, more preferably 100-900g/10 min. In the first reactorThe temperature range of (A) is 70 to 90 ℃, preferably 80 to 85 ℃. Hydrogen is fed to the first reactor to control the molecular weight of the polyethylene. The first reactor is operated at a pressure of 250 to 900kPa, preferably 400-850 kPa.

In the second, ethylene may be polymerized with or without an alpha-olefin comonomer to form a High Molecular Weight (HMW) polyethylene of the high molecular weight fraction in the presence of the LMW polyethylene obtained from the first reactor. Alpha-olefin comonomers that may be used for copolymerization include C4-12, preferably 1-butene and 1-hexene, more preferably 1-butene. The polymerization conditions in the second reactor are significantly different from those in the first reactor. The temperature in the second reactor ranges from 65 to 90 c, preferably from 68 to 80 c. The polymerization pressure in the second or third reactor ranges from 100 to 3000kPa, preferably from 150 to 900kPa, more preferably from 150 to 400 kPa.

Preparation of trimodal polyethylene

Trimodal polyethylene can be prepared using a ziegler-natta catalyst using a hexane diluent using a sequential three-stage slurry polymerization. Polymerizing ethylene in the absence of comonomer in a first reactor to obtain a high density LMW polyethylene or MMW polyethylene, the density of which is>0.965g/cm³And MFR₂In the range of 10-1000g/10min, more preferably 100-900g/10min for LMW and 0.1-10g/10min for MMW. The temperature in the first reactor is in the range of 70-90 c, preferably 80-85 c. Hydrogen is fed to the first reactor to control the molecular weight of the polyethylene. The molar ratio of hydrogen to ethylene in the vapor phase may vary depending on the target MFR. However, the preferred molar ratio ranges from 0.01 to 8.0, more preferably from 0.01 to 6.0. The first reactor is operated at a pressure of 250 to 900kPa, preferably 400-850 kPa. Optionally, unreacted hydrogen contained in the polymerized polyethylene obtained from the first reactor is removed in an amount of 98.0 to 99.8% by weight hydrogen, preferably 98.0 to 99.5% by weight hydrogen, and most preferably 98.0 to 99.1% by weight hydrogen, before transfer to the second reactor.

The polymerization conditions in the second or third reactor are significantly different from the polymerization conditions in the first reactor. The temperature in the second and third reactors is in the range of 65-90 c, preferably 68-80 c. The polymerization pressure in the second or third reactor ranges from 100 to 3000kPa, preferably from 150 to 900kPa, more preferably from 150 to 400 kPa.

In the second and third reactors, ethylene may be polymerized with or without an alpha-olefin comonomer to form a HMW1 or HMW2 polyethylene in the presence of the LMW polyethylene or MMW polyethylene obtained from the first reactor. Alpha-olefin comonomers that may be used for copolymerization include C4-12, preferably 1-butene and 1-hexene, more preferably 1-butene.

In case the melt blend comprises more than one bimodal polyethylene or more than one trimodal polyethylene, i.e. in case the first and second multimodal polyethylene are both bimodal polyethylene or the first and second multimodal polyethylene are both trimodal polyethylene, each respective bimodal or trimodal polyethylene may fulfill one or more of the above preferred conditions independently of each other.

In a preferred embodiment, the melt blend comprises from 70 to 97% by weight, preferably from 80 to 95% by weight, of the first multimodal polyethylene and from 3 to 30% by weight, preferably from 5 to 20% by weight, of the second multimodal polyethylene, each based on the total weight of the melt blend.

In a preferred embodiment, the MFR of the polyethylene composition is according to ISO 1133₂From 0.05 to 2.0g/10min, preferably from 0.1 to 2.0g/10min, more preferably from 0.3 to 1.5g/10min, even more preferably from 0.3 to 1.0g/10 min.

In a more preferred embodiment, the polyethylene composition has a density in accordance with ISO 1183 of 0.945 to 0.960g/cm³Preferably 0.950 to 0.959g/cm³And even more preferably from 0.952 to 0.957g/cm³。

In a most preferred embodiment, the polyethylene composition has a weight average molecular weight of from 80,000 to 500,000g/mol, preferably from 80,000 to 400,000g/mol, most preferably from 100,000 to 200,000g/mol, as measured by gel permeation chromatography; and/or a polydispersity index of 10 to 25, preferably 15 to 22.

This object is further achieved by an article comprising the polyethylene composition of the present invention.

In this connection, it is preferable that the article is one selected from the group consisting of blow molding (blow molding), a tube, a film, a cap, a closure, a wire, a cable, and a sheet.

Preferably, the article is obtainable by injection moulding, extrusion, blow moulding or compression moulding.

According to the invention, it may be provided that two or more of the above embodiments are combined to produce the inventive polyethylene composition.

For the purposes of the present invention, a melt blend is a blend of two or more components obtained by melting the respective components and mixing the molten components.

The term "multimodal" as used herein, unless otherwise indicated, refers to multimodality with respect to molecular weight distribution. Generally, a polyethylene composition comprising at least two polyethylene fractions, which polyethylene fractions are produced under different polymerization conditions, resulting in different (weight average) molecular weights and molecular weight distributions of the fractions, is referred to as "multimodal". The prefix "multi" refers to the number of distinguishable polymer fractions present in the polymer. The prefix "multi" is used herein to refer to two or three or more than three distinguishable components in the polymer, preferably two or three. The form of the molecular weight distribution curve of a multimodal polymer, i.e. the appearance of the curve of the polymer weight fraction as a function of its molecular weight, will generally show two or more maxima or will generally be distinctly broadened in comparison with the curves for the individual fractions.

As used herein, the term bimodal refers to a multimodal polymer comprising two components in the polymer that are distinguishable as described above. As used herein, the term trimodal refers to a multimodal polymer comprising three distinguishable components as defined above in the polymer.

Detailed Description

Other features and advantages of the present invention will be apparent from the following detailed description and examples.

Defining and measuring method

_{2 5}MFR and MFR: the melt flow rate of the polymer was measured according to ISO 1133 and is expressed in g/10min, which determines the flowability of the polymer under loads of 2.16 and 5kg under the test conditions at 190 ℃.

Density:the density of the polymer is measured by observing the level of particles (pellet) settled in the liquid column gradient tube, compared to a standard of known density. The method is a method for determining solid plastics after annealing at 100 ℃ according to ISO 1183-2.

Comonomer content:by high resolution¹³C-NMR the comonomer content was determined in mol%. Recording by 500MHz ASCENDTM, Bruker with a low temperature 10mm probe¹³C-NMR spectrum. TCB was used as the main solvent and TCE-d2 as a lock in a 4:1 volume ratio. The NMR experiment was performed at 120 ℃ using a reverse gate 13c (zgig) of a pulse program with a pulse angle of 90 °. The delay time (D1) was set to 10 seconds to achieve full speed spin recovery.

Polydispersity index (PDI) and molecular weight:weight average molecular weight (Mw), number average molecular weight (Mn), and Z-average molecular weight (M) in g/mol were analyzed by Gel Permeation Chromatography (GPC)_Z). The polydispersity index is calculated by Mw/Mn. Gel Permeation Chromatography (GPC): about 8mg of the sample was dissolved in 8ml of 1,2, 4-trichlorobenzene at 160 ℃ for 90 minutes. Then, 200. mu.l of the sample solution was injected into high temperature GPC at a low rate of 0.5ml/min in the area of the column at 145 ℃ and in the area of the detector at 160 ℃ with IR5, an infrared detector (Polymer Char). Data by GPCSoftware, Polymer Char process.

Degree of crystallinity:crystallinity is often used for characterization by Differential Scanning Calorimetry (DSC) following ASTM D3418. Samples were identified by peak temperature and enthalpy and% crystallinity was calculated from the peak area.

Shear thinning index [1/100](SHI[1/100])：The rheological parameters were determined by using the controlled stress rheometer model MCR-301 from Anton-Paar. The geometry being diameterIs a 25mm plate with a measurement gap of 1 mm. The dynamic oscillatory shearing is carried out at 190 ℃ under a nitrogen atmosphere at an angular frequency (. omega.) of 0.01 to 600 rad/s. The samples were preformed into 25mm disks by compression molding at 190 ℃. The shear thinning index is defined by specific shear rates 1 and 100[1/s ]]The ratio of complex viscosities of (A) and (B).

Tensile modulus:the test specimens (type 1B) were compressed and tested according to ISO 527-2. The tensile modulus was achieved in tensile mode using a universal tensile tester at a speed of 1 mm/min.

Impact strength of the simply supported beam:simple beam impact strength testing was performed according to ISO 179 to determine the impact resistance of the material. The impact energy is determined. Notched samples are commonly used to determine the impact energy at a temperature of 23 ℃.

Full Notch Creep Test (FNCT):the full notch creep test according to ISO 16770 is the preferred method for measuring the stress crack resistance of polymers in a 2% Arkopal solution at 50 ℃ and a constant load of 6 MPa.

Examples

The exemplary polyethylene compositions described below were prepared according to the general description above regarding the preparation of "multimodal polyethylene". The compositions of each example were prepared by melt blending techniques through a twin screw extruder at a temperature of 220 ℃ using the different components and formulations shown in tables 1 and 2. The properties of the polymer blend compositions of each example are shown in table 3.

Comparative example 1

Comparative example 1 is a trimodal polyethylene composition produced from a reactor with a ziegler-natta catalyst, the polymer composition of which is shown as component #4 in table 1. The percentage weight fraction ratio of the first ethylene homopolymer, the second ethylene copolymer and the third ethylene copolymer is 50:10: 40. Comparative example 1 butene-1 was used as a comonomer in the composition.

Example 1 (inventive)

Example 1 was prepared by melt blending 80 weight percent of a first bimodal polyethylene (component #1) and 20 weight percent of a second bimodal polyethylene (component #2), respectively. Component #1 is a bimodal polyethylene based on a ziegler-natta catalyst and the weight fraction ratio of the first ethylene homopolymer and the second ethylene copolymer is equal to 50: 50. Component #2 is also a bimodal polyethylene based on a ziegler-natta catalyst and the weight fraction ratio of the first ethylene homopolymer and the second ethylene copolymer is equal to 52: 48. Both component #1 and component #2 used 1-butene as a comonomer in the composition, and the detailed properties of components #1 and #2 are shown in table 1.

Examples 2 to 3 (inventive)

Examples 2-3 were prepared by melt blending from 85, 90 weight percent of the first bimodal polyethylene (component #1) and 15, 10 weight percent of the second trimodal polyethylene (component #3), respectively. Component #3 is a ziegler-natta catalyst based trimodal polyethylene produced by slurry polymerization and the weight fraction ratio of the first ethylene homopolymer, the second ethylene copolymer and the third ethylene copolymer is equal to 43:19:38 and 1-butene is used as comonomer. Table 1 shows detailed attributes of component # 3.

Example 4 (inventive)

Example 4 was prepared by melt blending 80 weight percent of the first trimodal polyethylene (component #4) and 20 weight percent of the second bimodal (component #2), respectively.

The results presented in table 3 show that the inventive samples (examples 1-4) have significantly higher stress cracking resistance, greater than 2 times as shown by the Full Notch Creep Test (FNCT) results, and also have higher impact strength than trimodal polyethylene resin or comparative example 1 as shown in the simple beam impact strength at 23 ℃, without loss of stiffness and processability. The higher stress cracking resistance and impact strength of the polymer blends result from the higher comonomer content and higher high molecular weight fraction, which is shown in a broader PDI compared to comparative example 1.

In addition, these inventive examples show the balanced processability of SHI [1/100] even though they show a lower MFR range than comparative example 1. A higher non-Newtonian index or SHI [1/100] means better processability by extrusion, injection molding and blow molding.

From these polymer properties, the molded article can have benefits.

TABLE 1 Properties of ethylene polymers

TABLE 2 blend compositions of the invention

TABLE 3 physical Properties of the blend compositions

TABLE 4 blend compositions of comparative example 2

Examples	Comparative example 2
		A first multimodal component	Component #1 (bimodal PE)
Weight fraction of first component (%)	50
		A second multimodal component	Component #3 (Sanfeng PE)
Second component weight fraction (%)	50

TABLE 5 physical Properties of comparative example 2

As shown in Table 4, comparative example 2 comprises 50% by weight of the first multimodal polyethylene and 50% by weight of the second multimodal polyethylene, and the impact strength of the simple beam at 23 ℃ is 11.38kg/m²FNCT of 130 hours, and MFR₂Is 0.07g/10min (in claim 12, the MFR of the polyethylene composition₂In the range of 0.05 to 2.0g/10 min) as shown in Table 5. A higher addition fraction of the second multimodal polyethylene (which usually has a higher molecular weight than the first multimodal polyethylene) leads to an increase in ESCR and impact strength and an MFR₂And decreases.

Having high ESCR and impact strength and low MFR₂The blends of (a) show disadvantages in balancing processability. Therefore, the impact strength and MFR of the above-mentioned simple beam₂Is outside the scope of the preferred embodiment according to the present invention and it is not well suited for use in injection cap and closure applications.

The features disclosed in the foregoing description and in the claims may, both separately and in any combination thereof, be material for realizing the invention in diverse forms thereof.