Adhesive polyethylene composition

Abstract

The present invention relates to an adhesive polyethylene composition comprising (A) 60 to 90 wt.-% of a non-elastomeric polyethylene; (B) 9.0 to 38 wt.-% of an ethylene-based elastomer which is a copolymer of ethylene and alpha-olefin comonomer units having 4 to 12 carbon atoms; wherein an acidic grafting agent (C) has been grafted onto component (A) or components (A) and (B) in an amount of 0.01 to 3.0 wt.-%, all amounts being based on the total weight of the adhesive polyethylene composition; a multilayer structure comprising the adhesive polyethylene composition; and the use of the adhesive polyethylene composition for producing a multilayer structure.

Description

Technical Field

[0001] The present invention relates to an adhesive polyethylene composition, a multilayer coating comprising a layer containing the adhesive polyethylene composition, and the use of the adhesive polyethylene composition in the production of multilayer structures having improved peel strength, such as an adhesive layer of a three-layer metal tube coating. Background Technology

[0002] Multilayer structures, including two, three, four, or more layers, are known for a variety of applications. In these multilayer structures, the different layers are typically composed of different materials, and therefore have different physical and chemical properties. This leads to problems such as adjacent layers not adhering to each other or having insufficient adhesion. Therefore, it is well known to construct multilayer structures with intermediate adhesive layers to improve the adhesion between adjacent layers composed of different materials and thus avoid delamination.

[0003] A prominent example of a multilayer structure is the coating used for metal pipes. Typically, a three-layer coating is applied to the outer surface of the metal pipe to protect it from mechanical damage and corrosion. This three-layer coating usually consists of an epoxy resin layer, an intermediate adhesive layer, and an outer polyolefin protective layer. The epoxy resin layer is designed to adhere firmly to the outer surface of the pipe's metal wall, and the outer polyolefin protective layer is typically made of high-density polyethylene, cross-linked polyethylene, or polypropylene. Compared to previously known single-layer coatings, the three-layer structure exhibits improved performance. On the one hand, the epoxy resin layer shows improved bonding with the metal wall, preventing cathodic disbondment and providing less oxygen permeation; on the other hand, the outer polyolefin protective layer provides good mechanical protection and less water permeation. However, to prevent delamination between the polyolefin protective layer and the epoxy resin layer, which would lead to damage to the multilayer coating, an adhesive layer is required between the two layers.

[0004] Adhesive compositions and methods for producing such adhesive compositions are known from EP 1 316 598 A1. Such adhesive compositions comprise blends of non-elastomeric polyethylene and elastomers polymerized in the presence of a single active site catalyst, wherein the non-elastomeric polyethylene or blend has been grafted with an acidic grafting agent. Coatings comprising an adhesive layer containing said adhesive composition exhibit good adhesive properties in the form of good peel strength.

[0005] For three-layer pipe coatings, ISO 21809-1:2011 specifies the minimum peel strength requirements: Class A coatings must have a peel strength of at least 100 N / cm at 23°C, Class B coatings at least 150 N / cm at 23°C, and Class C coatings at least 250 N / cm at 23°C; Class A coatings must have a peel strength of at least 20 N / cm at 60°C, Class B coatings at least 30 N / cm at 80°C, and Class C coatings at least 40 N / cm at 90°C.

[0006] The metal pipe coating market, particularly the steel pipe coating market, is evolving towards faster production line speeds and thicker steel pipes, resulting in shorter water cooling times and often limiting the cooling capacity available for the coating. Currently used adhesive compositions, such as those disclosed, for example, in EP 1 316 598 A1, are sensitive to these conditions and frequently fail to meet peel strength requirements.

[0007] Therefore, there is a need for adhesive compositions suitable for multilayer structures such as three-layer metal tube coatings, which can improve the peel strength of coatings that have undergone short water cooling times.

[0008] Surprisingly, adhesive compositions containing blends of non-elastomeric polyethylene and vinyl elastomers grafted with an acidic grafting agent exhibited improved adhesive properties, such as improved peel strength when used in coatings that have undergone shorter water cooling times. Summary of the Invention

[0009] This invention relates to an adhesive polyethylene composition comprising...

[0010] (A) 60 to 90% by weight of non-elastomeric polyethylene;

[0011] (B) 9.0 to 38% by weight of a vinyl elastomer, wherein the vinyl elastomer is a copolymer of ethylene and an α-olefin comonomer unit having 4 to 12 carbon atoms;

[0012] The acidic grafting agent (C) has been grafted onto component (A) or components (A) and (B) in an amount of 0.01 to 3.0% by weight, all amounts being based on the total weight of the adhesive polyethylene composition.

[0013] Furthermore, the present invention relates to a multilayer structure comprising a layer containing an adhesive polyethylene composition as described above or below.

[0014] Furthermore, the present invention relates to the use of the adhesive polyethylene composition as described above or below for the production of multilayer structures.

[0015] definition

[0016] Polyethylene is a polymer in which the total molar amount of monomer units is at least 50 mol% of the total amount of ethylene monomer units.

[0017] "Ethylene homopolymer" refers to a polymer that is essentially composed of ethylene monomer units. Due to the requirements of large-scale polymerization, ethylene homopolymers may include a small amount of comonomer units, typically less than 0.1 mol%, preferably less than 0.05 mol%, and most preferably less than 0.01 mol%.

[0018] If the polymer is derived from ethylene monomer units and at least one α-olefin comonomer, then the polymer is referred to as an "ethylene copolymer". The α-olefin comonomer is preferably selected from α-olefin comonomers having 4 to 12 carbon atoms, more preferably 4 to 10 carbon atoms, and most preferably 4 to 8 carbon atoms. Suitable types of α-olefin comonomers are 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, or mixtures thereof. Preferred are 1-hexene and 1-octene. A copolymer of ethylene and 1-octene comonomer units is a polymer comprising a large molar amount of ethylene monomer units and a small molar amount of 1-octene comonomer units, preferably a polymer composed of a large molar amount of ethylene monomer units and a small molar amount of 1-octene comonomer units.

[0019] If the polymer is derived from ethylene monomer units and two different α-olefin comonomer units, then the polymer is referred to as an "ethylene terpolymer". A terpolymer of ethylene with 1-butene comonomer units and 1-hexene comonomer units is a polymer comprising, preferably, a large molar amount of ethylene monomer units and small molar amounts of 1-butene and 1-hexene comonomer units, respectively.

[0020] Polymers that include more than one fraction that differs from each other in at least one property (such as weight-average molecular weight or comonomer content) are called "multimodal". If a multimodal polymer includes two different fractions, it is called "bimodal", and correspondingly, if it includes three different fractions, it is called "trimodal". The form of the molecular weight distribution curve of such a multimodal polymer, that is, the appearance of the curve of polymer weight fraction as a function of its molecular weight, will, depending on the morphology, show two or more maximum values, or at least be significantly broader than the curve of a single fraction.

[0021] Compared to multi-peak polymers, unimodal polymers exhibit only a single maximum value in their molecular weight distribution curves. Unimodal polymers consist of only one polymer fraction and cannot be distinguished by weight-average molecular weight or comonomer content.

[0022] Elastomers are polymers that exhibit viscoelasticity (i.e., both viscosity and elasticity) and very weak intermolecular forces, and typically possess low Young's modulus and high breaking strain compared to other materials. Elastomers are amorphous polymers that remain above their glass transition temperature.

[0023] The vinyl elastomer according to the invention is characterized by a highly amorphous structure, which is particularly understood as low crystallinity, low crystallization temperature, low melting temperature, and low density. Preferably, the vinyl elastomer according to the invention has a density not exceeding 900 kg / m³. 3 Preferably, it does not exceed 885 kg / m3 More preferably, not exceeding 880 kg / m 3 The optimal value is no more than 875 kg / m³. 3 The density.

[0024] The difference between non-elastomeric polyethylene and vinyl elastomers lies in its more crystalline structure, which is specifically understood as higher crystallinity, higher crystallization temperature, higher melting temperature, and higher density. Preferably, the non-elastomeric polyethylene according to the invention has a density of at least 900 kg / m³. 3 Preferably at least 920 kg / m 3 The optimal value is at least 925 kg / m³. 3 The density.

[0025] Acidic grafting agents are components containing acidic functional groups grafted onto the polymer backbone. Suitable grafting methods include chemical treatment, photoradiation, or high-energy radiation, by which free radicals are formed on the polymer backbone. The acidic grafting agent then reacts with the free radicals and forms bonds with the polymer backbone. Most preferably, chemical treatment is initiated by an organic peroxide.

[0026] An extruder is a conveying device that, based on the Archimedes' screw principle, forces a solid uniformly through the forming orifice into a viscous substance under high pressure and temperature. An extruder essentially consists of a screw shaft (also called the screw) located within what is called the barrel. The nominal diameter of the barrel's orifice is equal to the outer diameter of the screw. At the downstream end of the barrel is the forming orifice opening, commonly called the die. Further downstream of the barrel is the drive, usually an electric motor with a gear mechanism (extruder gears), which ensures the rotation of the screw. The screw itself is typically divided into three sections to perform different tasks. Downstream in the barrel is the so-called feed section. In the feed section, the material to be extruded is fed into the extruder through a hopper ("feed"). Next is the compression section, where the material is conveyed, melted, and compacted. Further downstream within the compression section, the material is further compressed by the decreasing screw channel depth, thus increasing the pressure required for discharge into the die. Finally, the discharge section ensures a uniform flow of material towards the die. In this invention, the term "barrel section" includes the following portions of the barrel surrounding the screw's compression and discharge sections upstream of the feed section and downstream of the die section. The barrel section is heated. Heating of the barrel section can be independently controlled within a so-called "control zone." In this invention, the so-called "first control zone" refers to a first control zone within the barrel section downstream of the feed section, in which the material, typically component (A) and / or (B) and optionally component (C), begins to melt. Therefore, the temperature of the first control zone is set to a temperature above 85°C to 180°C.

[0027] Unless otherwise specified, quantities below are given as weight percentages (wt%). Attached Figure Description

[0028] Figure 1 A comparison of the GPC curves in the normalized LS 15 concentration versus log M plots for Examples CE1, IE1, and IE2 is shown.

[0029] Figure 2 A comparison of the GPC curves in the normalized LS 15 concentration versus log M plots for Examples CE2, IE3, IE4, and IE5 is shown.

[0030] Figure 3 A comparison of the GPC curves in the normalized LS 15 concentration versus log M plots for Examples CE3, IE4, and IE6 is shown. Detailed Implementation

[0031] Non-elastomeric polyethylene (A)

[0032] The non-elastomeric polyethylene (A) is preferably a homopolymer of ethylene or a copolymer of ethylene with one or more α-olefin comonomers. The non-elastomeric polyethylene (A) may also be a mixture of ethylene homopolymers and ethylene copolymers. If the ethylene copolymer forms part of the non-elastomeric polyethylene (A), the comonomer preferably comprises an α-olefin having 3 to 12 carbon atoms, more preferably 4 to 10 carbon atoms, and most preferably 4 to 8 carbon atoms.

[0033] Examples of α-olefin comonomers include, for example, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, styrene, and mixtures thereof. Particularly preferred comonomers are 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene. Most preferred α-olefin comonomers are 1-butene, 1-hexene, and 1-octene.

[0034] In one embodiment, the non-elastomeric polyethylene (A) is a copolymer of ethylene as described above and one of an α-olefin comonomer having 3 to 12 carbon atoms.

[0035] In the described embodiment, it is preferred that the non-elastomeric polyethylene (A) is a copolymer of ethylene and 1-hexene or a copolymer of ethylene and 1-octene, with the copolymer of ethylene and 1-octene being the most preferred.

[0036] Typically, the amount of comonomer in the copolymer is at most 30.0% by weight of the total copolymer weight, more preferably at most 10.0% by weight of the total copolymer weight, and most preferably at most 6.0% by weight of the total copolymer weight.

[0037] The lower limit of the amount of comonomer in the copolymer is generally 0.5% by weight of the total copolymer weight, more preferably 1.0% by weight of the total copolymer weight.

[0038] In another embodiment, the non-elastomeric polyethylene (A) is a terpolymer of ethylene and two different α-olefin comonomer units selected from α-olefins having 4 to 12 carbon atoms.

[0039] The “difference” in the context refers to the different number of carbon atoms in the α-olefin comonomer unit, which in turn results in different lengths of short-chain side chains in the polymer chain of the terpolymer.

[0040] The two different α-olefin comonomer units are preferably selected from 1-butene, 1-hexene, 1-octene, and 1-decene, and most preferably selected from 1-butene and 1-hexene.

[0041] Therefore, non-elastomeric polyethylene is particularly preferred as a terpolymer of ethylene with 1-butene comonomer units and 1-hexene comonomer units.

[0042] The terpolymer of ethylene with two different α-olefin comonomer units selected from α-olefins having 4 to 12 carbon atoms, preferably 1-butene and 1-hexene, may contain additional comonomer units selected from α-olefins other than the two different α-olefin comonomer units, such as propylene, 1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, styrene, and mixtures thereof.

[0043] However, preferably, the terpolymer of ethylene and two different α-olefin comonomer units selected from α-olefins having 4 to 12 carbon atoms is composed of ethylene and the two different α-olefin comonomer units, preferably composed of ethylene, 1-butene and 1-hexene.

[0044] Typically, the total amount of comonomer units in the terpolymer is at most 30.0% by weight of the total weight of the copolymer, more preferably at most 10.0% by weight of the total weight of the terpolymer, and most preferably at most 6.0% by weight of the total weight of the terpolymer.

[0045] The lower limit of the total amount of comonomer units in the copolymer is typically 0.5% by weight of the total weight of the terpolymer, more preferably 1.0% by weight of the total weight of the terpolymer.

[0046] The amount of the first α-olefin comonomer unit, preferably the 1-butene comonomer unit, in the terpolymer is preferably at most 10.0% by weight of the total weight of the terpolymer, more preferably at most 4.0% by weight of the total weight of the terpolymer, and most preferably at most 1.5% by weight of the total weight of the terpolymer.

[0047] The lower limit of the total amount of the first α-olefin comonomer unit, preferably the 1-butene comonomer unit, is generally 0.1% by weight of the total weight of the terpolymer, more preferably 0.3% by weight of the total weight of the terpolymer.

[0048] The amount of the second α-olefin comonomer unit, preferably the 1-hexene comonomer unit, in the terpolymer is preferably at most 20.0% by weight of the total weight of the terpolymer, more preferably at most 6.0% by weight of the total weight of the terpolymer, and most preferably at most 4.5% by weight of the total weight of the terpolymer.

[0049] The lower limit of the total amount of the second α-olefin comonomer unit, preferably the 1-hexene comonomer unit, is generally 0.4% by weight of the total weight of the terpolymer, more preferably 0.7% by weight of the total weight of the terpolymer.

[0050] The non-elastomeric polyethylene (A) is preferably present in the adhesive polyethylene composition in an amount of 60 to 90% by weight, preferably 65 to 85% by weight, and particularly 70 to 80% by weight.

[0051] More preferably, prior to grafting, the non-elastomeric polyethylene (A) has a melt flow rate MFR2 of 1.0 to 10.0 g / 10 min, more preferably 3.0 to 8.0 g / 10 min.

[0052] MFR2 was measured according to ISO 1133 at a temperature of 190°C under a load of 2.16 kg.

[0053] The density of non-elastomeric polyethylene (A) is preferably 900 to 960 kg / m³. 3 More preferably 920 to 950 kg / m 3 And the most preferred value is 925 to 945 kg / m³. 3 .

[0054] Furthermore, when measured by GPC-VISC-LS analysis, non-elastomeric polyethylene (A) preferably has a polydispersity (PDI-LS) of 1.5 to 6.0, more preferably 1.7 to 5.5, and most preferably 1.9 to 5.0 as the weight-average molecular weight to number-average molecular weight ratio Mw / Mn.

[0055] When polymerized in the presence of a single active site catalyst, the non-elastomeric polyethylene (A) preferably has a narrow polydispersity (PDI-LS) Mw / Mn, suitably 1.5 to 4.0, more preferably 1.7 to 3.5 Mw / Mn.

[0056] When polymerized in the presence of a Ziegler-Natta catalyst, the non-elastomeric polyethylene (A) preferably has a wide polydispersity (PDI), Mw / Mn, suitably 2.5 to 6.0, more preferably 2.7 to 5.5, and most preferably 3.0 to 5.0, Mw / Mn.

[0057] Furthermore, when measured by GPC-VISC-LS analysis, the non-elastomeric polyethylene (A) preferably has a weight-average molecular weight Mw(LS) of 35,000 g / mol to 100,000 g / mol, more preferably 40,000 g / mol to 90,000 g / mol, and most preferably 45,000 g / mol to 80,000 g / mol.

[0058] When polymerized in the presence of a single active site catalyst, the non-elastomeric polyethylene (A) preferably has a low weight-average molecular weight Mw (LS) of 35,000 g / mol to 85,000 g / mol, more preferably 40,000 g / mol to 75,000 g / mol, and most preferably 45,000 g / mol to 65,000 g / mol.

[0059] When polymerized in the presence of a Ziegler-Natta catalyst, the non-elastomeric polyethylene (A) preferably has a high weight-average molecular weight Mw (LS) of 45,000 g / mol to 100,000 g / mol, more preferably 55,000 g / mol to 90,000 g / mol, and most preferably 65,000 g / mol to 80,000 g / mol.

[0060] In addition, when measured by GPC-VISC-LS analysis, the non-elastomeric polyethylene (A) preferably has a z-average molecular weight Mz(LS) of 75,000 g / mol to 300,000 g / mol, more preferably 80,000 g / mol to 275,000 g / mol, and most preferably 85,000 g / mol to 260,000 g / mol.

[0061] When polymerized in the presence of a single active site catalyst, the non-elastomeric polyethylene (A) preferably has a low z-average molecular weight Mz (LS) of 75,000 g / mol to 200,000 g / mol, more preferably 80,000 g / mol to 175,000 g / mol, and most preferably 85,000 g / mol to 150,000 g / mol.

[0062] When polymerized in the presence of a Ziegler-Natta catalyst, the non-elastomeric polyethylene (A) preferably has a high z-average molecular weight Mz(LS) of 150,000 g / mol to 300,000 g / mol, more preferably 175,000 g / mol to 275,000 g / mol, and most preferably 200,000 g / mol to 260,000 g / mol.

[0063] Furthermore, the non-elastomeric polyethylene (A) preferably has a shear thinning index (SHI) of 0.1 to 10, more preferably 0.5 to 7.5, and most preferably 1.0 to 5.0. 1 / 100 .

[0064] Furthermore, the non-elastomeric polyethylene (A) preferably has a melt temperature Tm of 115°C to 140°C, more preferably 117°C to 135°C, and most preferably 120°C to 130°C.

[0065] Furthermore, the non-elastomeric polyethylene (A) preferably has a crystallization temperature Tc of 95°C to 125°C, more preferably 100°C to 120°C, and most preferably 105°C to 115°C.

[0066] Furthermore, the non-elastomeric polyethylene (A) preferably has a vinyl content of more than 0.6, such as 1.0 to 50.0, more preferably 2.5 to 45.0, and most preferably 5.0 to 40.0, as determined by quantitative nuclear magnetic resonance (NMR) spectroscopy in solution.

[0067] When polymerized in the presence of a single active site catalyst, the non-elastomeric polyethylene (A) preferably has a vinyl content of 1.0 to 20.0, more preferably 2.5 to 15.0, and most preferably 5.0 to 10.0 per 100,000 carbon atoms.

[0068] When polymerized in the presence of a Ziegler-Natta catalyst, the non-elastomeric polyethylene (A) preferably has a high vinyl content of 17.5 to 50.0, more preferably 20.0 to 45.0, and most preferably 25.0 to 40.0 per 100,000 carbon atoms.

[0069] Furthermore, the non-elastomeric polyethylene (A) preferably has an unsaturation degree of 10.0 to 75.0, more preferably 12.5 to 60.0, and most preferably 15.0 to 50.0 per 100,000 carbon atoms as determined by quantitative nuclear magnetic resonance (NMR) spectroscopy in solution.

[0070] The non-elastomeric polyethylene (A) of the adhesive polyethylene composition can be produced in a process comprising a single-active-center catalyst or a Ziegler-Natta catalyst.

[0071] Therefore, non-elastomeric polyethylene (A) can be produced in multiphase polymerization methods using, for example, slurry and / or gas-phase reactors, or in single-phase polymerization methods such as solution polymerization.

[0072] In one embodiment, non-elastomeric polyethylene (A) is polymerized in a multiphase polymerization process using a single-active-center catalyst.

[0073] Preferably, in the embodiment described, the non-elastomeric polyethylene (A) is produced in a method comprising a metallocene catalyst. More preferably, the catalyst comprises a metallocene component and an aluminoxane component on a porous support.

[0074] Preferred catalysts are those described in EP 0 678 103, WO 97 / 28170, WO 98 / 56831 and / or WO 00 / 34341.

[0075] Preferably, the non-elastomeric polyethylene (A) is produced by the method disclosed in EP 0 678 103, characterized in that the ethylene is subjected to slurry polymerization using a supported olefin polymerization catalyst, which is prepared as follows:

[0076] (1) A porous support is provided, which is an inorganic oxide selected from elements of Groups 2 to 4 and 13 to 14 of the periodic table, preferably alumina or silicon dioxide.

[0077] (2) Provide a solution comprising the substances described in (2.1) and (2.1).

[0078] The reaction product of the metallocene of formula (1) as described in (2.1)(2.1.1) and the aluminoxane of formula (2) as described in (2.1.2).

[0079] (2.1.1) Metallocene of Equation (1)

[0080] (Cp) m R n MR' o X p (1)

[0081] Where Cp is an unsubstituted or substituted and / or fused allotropic ring (or carbocyclic ring) or heterocyclic pentadienyl group, R is a group of 1 to 4 atoms connecting two Cp rings, M is a transition metal of group 4, 5 or 6 of the periodic table, preferably zirconium or hafnium, R' is a hydrocarbon group or hydroxyl group having 1 to 20 carbon atoms, X is a halogen atom, in which case m = 1 to 3, n = 0 or 1, o = 0 to 3, p = 0 to 3, and the sum m + n + p = has the same oxidation state as M, and

[0082] (2.1.2) Aluminoxane of formula (2)

[0083] R"-(AlO) x AIR"2(2)

[0084] Formula (II) describes linear compounds, and / or aluminum oxanes of formula (3).

[0085]

[0086] Formula (III) describes a cyclic compound, and in formulas (2) and (3), x is 1 to 40, preferably 10 to 20, y is 3 to 40, preferably 3 to 20, and R″ is an alkyl group having 1 to 20 carbon atoms.

[0087] (2.2) A solvent capable of dissolving the reaction products,

[0088] (3) Impregnate the porous support with a certain volume of solution, the volume of which does not exceed the total pore volume of the porous support.

[0089] (4) Recover the impregnated porous support, the pores of which are filled with the solution.

[0090] The preferred embodiment of the catalyst given in EP 0 678 103 is also preferably used in the production of non-elastomeric polyethylene (A).

[0091] Other preferred single-active-site catalysts are described in EP 688 794, EP 949 274, WO 95 / 12622, WO00 / 34341 and WO 00 / 40620. The most preferred are the catalysts described in WO 95 / 12622 and their preferred embodiments as described in that document.

[0092] In another embodiment, non-elastomeric polyethylene (A) is polymerized in a single-phase polymerization method using a single-active-center catalyst.

[0093] Preferably, in the embodiment, the non-elastomeric polyethylene (A) is produced in a method comprising a metallocene catalyst.

[0094] Therefore, the polymerization catalyst system can be metallocene catalysts disclosed in WO-A-1993025590, US-A-5001205, WO-A1987003604, and US-A-5001244, or combinations thereof. Other suitable catalysts, such as post-transition metal catalysts, can also be used.

[0095] Preferably, the polymerization catalyst system includes a metallocene catalyst.

[0096] According to one implementation scheme, the polymerization catalyst system includes

[0097] (i) at least one metallocene complex of formula (I)

[0098]

[0099] in

[0100] Mt1 is Hf,

[0101] X is a σ-donor ligand.

[0102] R1, R2, and R3 may be the same or different from each other, and may be hydrogen or saturated straight-chain or branched C1-C10 alkyl groups, wherein the alkyl group may optionally contain up to two heteroatoms belonging to groups 14 to 16 of the periodic table, or R1 and R2 or R2 and R3 may form a ring having 4 to 6 carbon atoms and 1 to 3 double bonds.

[0103] R4 and R5 may be the same as or different from each other, and may be saturated straight-chain or branched C1-C10 alkyl, C5-C10 aryl, C6-C20 alkylaryl, or C6-C20 aralkyl, which may optionally contain up to two heteroatoms belonging to groups 14 to 16 of the periodic table.

[0104] n can be 1 to 5.

[0105] Ar is a C6-C20 aryl or heteroaryl group, which may be unsubstituted or substituted with 1 to 5 straight-chain or branched C1-C10 alkyl groups.

[0106] and

[0107] (ii) Aluminoxane co-catalyst, and

[0108] (iii) Optional alkylaluminum compound Al(R7)3, wherein R7 is a straight-chain or branched C2-C8 alkyl group.

[0109] This catalyst is described in more detail in the literature WO 2018 / 178151 A1, the contents of which are incorporated herein by reference.

[0110] According to the implementation plan, the polymerization catalyst system includes

[0111] (i) at least one metallocene complex of formula (II)

[0112]

[0113] in

[0114] Mt1 is Hf,

[0115] x is a σ-donor ligand.

[0116] R1, R2, and R3 may be the same or different from each other, and may be hydrogen or saturated straight-chain or branched C1-C10 alkyl groups, wherein the alkyl group may optionally contain up to two heteroatoms belonging to groups 14 to 16 of the periodic table, or R1 and R2 or R2 and R3 may form a ring having 4 to 6 carbon atoms and 1 to 3 double bonds.

[0117] R4 and R5 may be the same as or different from each other, and may be saturated straight-chain or branched C1-C10 alkyl, C5-C10 aryl, C6-C20 alkylaryl, or C6-C20 aralkyl, which may optionally contain up to two heteroatoms belonging to groups 14 to 16 of the periodic table.

[0118] n can be 1 to 5.

[0119] Ar is a C6-C20 aryl or heteroaryl group, which may be unsubstituted or substituted with 1 to 5 straight-chain or branched C1-C10 alkyl groups.

[0120] and

[0121] (ii) Boron-containing cocatalysts.

[0122] This catalyst is described in more detail in the literature WO 2018 / 178152 A1, the contents of which are incorporated herein by reference.

[0123] According to the implementation plan, the polymerization catalyst system includes

[0124] (i) Metallocene complex of formula (III)

[0125]

[0126] in

[0127] M is Hf or a mixture with Zr, provided that more than 50 mol% of the complex of formula I has M = Hf.

[0128] X is a σ-ligand.

[0129] R may be the same as or different from each other, and may be a saturated straight-chain or branched C1-C10 alkyl, C5-C10 aryl, C6-C20 alkylaryl, or C6-C20 aralkyl, which may optionally contain up to two heteroatoms or silicon atoms.

[0130] R1 is a C6-C20 aryl group, which may be unsubstituted or substituted with one or up to five straight-chain or branched C1-C10 alkyl groups.

[0131] R2 is a saturated straight-chain or cyclic C3-C20 alkyl or branched CR3R4R5 group, wherein R3 is hydrogen or a C1-C20 alkyl group, and R4 and R5 may be the same or different, and may be C1-C20 alkyl groups.

[0132] and

[0133] (ii) Boron-containing cocatalysts.

[0134] This catalyst is described in more detail in the literature WO 2018 / 108917 A1, the contents of which are incorporated herein by reference.

[0135] According to the implementation plan, the polymerization catalyst system includes

[0136] (i) Metallocene complex of formula (IV)

[0137]

[0138] in

[0139] M is Hf or a mixture with Zr, provided that more than 50 mol% of the complex of formula I has M = Hf.

[0140] X is a σ-ligand.

[0141] R may be the same as or different from each other, and may be a saturated straight-chain or branched C1-C10 alkyl, C6-C10 aryl, C4-C10 heteroaryl, C6-C20 alkylaryl, or C6-C20 aralkyl, which may optionally contain up to two heteroatoms or silicon atoms.

[0142] R1 is optionally a C6-C10 aryl or C6-C20 alkylaryl or C4-C10 heteroaryl containing up to two heteroatoms or silicon atoms.

[0143] R2 is a C4-C20 cycloalkyl group of formula (V), which optionally carries an alkyl substituent at the β-position.

[0144]

[0145] Where R' can be the same as or different from each other, and can be hydrogen or defined as R, and n is 1 to 17.

[0146] and

[0147] (ii) Boron-containing co-catalysts

[0148] This catalyst is described in more detail in the literature WO 2018 / 108918 A1, the contents of which are incorporated herein by reference.

[0149] Other suitable metallocene catalysts are described in WO 2015 / 158790 A1 and WO 2015 / 158791 A1.

[0150] In yet another embodiment, non-elastomeric polyethylene (A) is polymerized in a multiphase polymerization process using a Ziegler-Natta catalyst.

[0151] In the embodiments described, a suitable Ziegler-Natta catalyst preferably comprises magnesium compounds, aluminum compounds, and titanium compounds supported on a particulate support.

[0152] The particulate support can be an inorganic oxide support, such as silicon dioxide, alumina, titanium dioxide, silicon dioxide-alumina, and silicon dioxide-titanium dioxide. Preferably, the support is silicon dioxide.

[0153] The average particle size of silica supports is typically 10 to 100 μm. However, it has been shown that particular advantages can be obtained if the support has an average particle size of 15 to 30 μm, preferably 18 to 25 μm. Alternatively, the support can have an average particle size of 30 to 80 μm, preferably 30 to 50 μm. Examples of suitable support materials are, for example, ES747JR manufactured and sold by IneosSilicas (formerly Crossfield) and SP9-491 manufactured and sold by Grace.

[0154] The magnesium compound is a reaction product of dialkyl magnesium and an alcohol. The alcohol is a straight-chain or branched aliphatic monohydric alcohol. Preferably, the alcohol has 6 to 16 carbon atoms. Branched alcohols are particularly preferred; 2-ethyl-1-hexanol is an example of a preferred alcohol. The dialkyl magnesium can be any compound of magnesium bonded to two alkyl groups, which can be the same or different. Butyl-octyl magnesium is an example of a preferred dialkyl magnesium.

[0155] The aluminum compound is a chloroalkyl aluminum. Particularly preferred compounds are alkyl aluminum dichloride and alkyl sesquichloride.

[0156] The titanium compound is a halogenated titanium compound, preferably a chlorinated titanium compound. A particularly preferred titanium compound is titanium tetrachloride.

[0157] As described in EP-A-688794 or WO-A-99 / 51646, the catalyst can be prepared by sequentially contacting the support with the aforementioned compounds. Alternatively, as described in WO-A-01 / 55230, the catalyst can be prepared by first preparing a solution from the components and then contacting the solution with the support.

[0158] Another particularly preferred group of suitable Ziegler-Natta catalysts contains titanium compounds and magnesium halide compounds without an inert support. Thus, the catalyst comprises a titanium compound on a magnesium dihalide (such as magnesium dichloride). Such catalysts are disclosed, for example, in WO-A-2005 / 118655 and EP-A-810235.

[0159] Ziegler-Natta catalysts are used in conjunction with activators. Suitable activators are metal alkyl compounds, especially alkylaluminum compounds. These compounds include alkylaluminum halides, such as ethylaluminum dichloride, diethylaluminum chloride, ethyl sesquichloride, dimethylaluminum chloride, etc. They also include trialkylaluminum compounds, such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, and tri-n-octylaluminum. In addition, they include alkylaluminum oxygen-containing compounds, such as methylaluminoxane, hexaisobutylaluminoxane, and tetraisobutylaluminoxane. Other alkylaluminum compounds, such as isoprene aluminum, can also be used. Particularly preferred activators are trialkylaluminum, with triethylaluminum, trimethylaluminum, and triisobutylaluminum being particularly used.

[0160] The amount of activator used depends on the specific catalyst and activator. Typically, triethylaluminum is used such that the molar ratio of aluminum to transition metal, such as Al / Ti, is 1 to 1000, preferably 3 to 100, and particularly about 5 to about 30 mol / mol.

[0161] In yet another embodiment, non-elastomeric polyethylene (A) is polymerized in a single-phase polymerization process using a Ziegler-Natta catalyst.

[0162] In the described embodiment, a suitable Ziegler-Natta polymerization catalyst may be selected from, for example, the Ziegler-Natta catalysts disclosed in EP 0 721474 A1 and EP 0 769 027A1.

[0163] When producing non-elastomeric polyethylene (A) in a multiphase process in the presence of a single-active-center catalyst or a Ziegler-Natta catalyst as described above, the non-elastomeric polyethylene (A) is preferably produced in a multi-stage process with a multi-step reaction sequence, such as that described in WO 92 / 12182. In this method, in the first step, ethylene is polymerized in a loop reactor in the liquid phase of an inert, low-boiling-point hydrocarbon medium. The polymerized reaction mixture is then discharged from the loop reactor, and at least most of the inert hydrocarbons are separated from the polymer. Then, in a second or further step, the polymer is transferred to one or more gas-phase reactors, where polymerization continues in the presence of gaseous ethylene. The polymer produced according to this method exhibits excellent uniformity in the distribution of different polymer fractions, which is not achievable, for example, by polymer mixing.

[0164] When a comonomer unit is copolymerized into the polymer chain of non-elastomeric polyethylene (A), the comonomer unit can be added to either or both of these reactors.

[0165] When two comonomer units are copolymerized into the polymer chain of non-elastomeric polyethylene (A), one comonomer unit can be added to a loop reactor, and the other comonomer unit can be added to one or more gas-phase reactors.

[0166] In another implementation, both comonomer units can be added to all reactors.

[0167] In yet another implementation, both comonomer units can be added to only one reactor.

[0168] When non-elastomeric polyethylene (A) is produced in a single-phase process in the presence of a single-active-center catalyst or a Ziegler-Natta catalyst as described above, the non-elastomeric polyethylene (A) is preferably produced in a solution process, for example, as disclosed in WO2017 / 108951A1 or WO 2017 / 108969 A1. Therefore, a solution comprising a catalyst component, ethylene monomer, comonomer, and hydrogen is typically introduced into a polymerization reactor, which is operated at a temperature ranging from 120°C to 250°C, such as 140°C to 220°C, most preferably 150°C to 200°C, and at a pressure ranging from 50 to 300 bar, preferably 60 to 250 bar, and more preferably 70 to 200 bar, depending on the comonomer unit content in the polymer.

[0169] Non-elastomeric polyethylene (A) can be unimodal polyethylene or multimodal polyethylene.

[0170] In one embodiment, the non-elastomeric polyethylene (A) may be multimodal polyethylene. More preferably, the multimodal polyethylene is bimodal polyethylene.

[0171] The term "polymer morphology" refers to the form of its molecular weight distribution (MWD) curve, that is, the appearance of a graph showing the polymer weight fraction as a function of its molecular weight. If the polymer is produced in a continuous-step process, for example by using reactors in series and different conditions in each reactor, the different polymer fractions produced in different reactors will each have their own molecular weight distribution, which may differ significantly from each other. The resulting final polymer MWD curve can be viewed as a superposition of the MWD curves of the polymer fractions, thus showing two or more distinct maxima, or at least significantly broadened compared to the curve of a single fraction. Polymers exhibiting such a MWD curve are referred to as "bimodal" or "multimodal." Multimodal polymers can be produced according to several methods described, for example, in WO 92 / 12182, WO 96 / 18662, WO 98 / 58001, WO 99 / 65949, and WO 2008 / 089978.

[0172] Multimodal polyethylene preferably comprises low molecular weight (LMW) ethylene homopolymer or copolymer fractions and high molecular weight (HMW) ethylene homopolymer or copolymer fractions.

[0173] Depending on whether the multimodal ethylene polymer is bimodal or has a higher morphology, the LMW and / or HMW fractions may each contain only one fraction, or two or more seed fractions.

[0174] Preferably, the ethylene polymer is a bimodal polymer composed of an LMW fraction and an HMW fraction.

[0175] At least one fraction of the ethylene polymer is preferably a copolymer polymerized with one or more comonomer units as defined above. Preferably, the amount of comonomer in the ethylene polymer is 0.02 to 5.0 mol%, more preferably 0.05 to 2.0 mol%.

[0176] Preferably, the HMW fraction is an ethylene copolymer, more preferably an ethylene copolymer copolymerized with one of the aforementioned comonomers. More preferably, the LMW fraction of polyethylene can be an ethylene homopolymer or an ethylene copolymer, preferably an ethylene copolymer copolymerized with one of the aforementioned comonomers.

[0177] Furthermore, preferably, if polyethylene (A) is produced according to the above-described multi-stage method, the LMW fraction is produced in a loop reactor, while the HMW fraction is produced in a gas-phase reactor.

[0178] The properties of multimodal polyethylene can be adjusted by the ratio of low molecular weight fractions to high molecular weight fractions in multimodal polyethylene.

[0179] In another embodiment, the non-elastomeric polyethylene (A) is unimodal polyethylene.

[0180] In this embodiment, unimodal polyethylene, such as a copolymer of ethylene and one or more comonomer units as described above, is typically polymerized in a polymerization reactor.

[0181] Single-peak polyethylene can also be polymerized in two or more polymerization reactors using polymerization conditions that allow for the fractional polymerization of polyethylene with substantially the same properties.

[0182] Vinyl elastomer (B)

[0183] Vinyl elastomer (B) is ethylene and C4-C 12 Copolymers of α-olefins.

[0184] Suitable C4-C 12 α-olefins include 1-butene, 1-hexene, and 1-octene, preferably 1-butene or 1-octene, and more preferably 1-octene.

[0185] A copolymer of ethylene and 1-octene is preferably used.

[0186] Vinyl elastomers (B) typically do not contain any polar comonomers.

[0187] Preferably, based on the total amount of the polymer composition, the vinyl elastomer (B) is present in the adhesive polyethylene composition in an amount of 9.0 to 38% by weight, more preferably 15 to 35% by weight, and most preferably 20 to 30% by weight.

[0188] Suitable vinyl elastomers (B) have a strength of 840 to 900 kg / m³. 3 Within the range, preferably between 845 and 890 kg / m 3 More preferably, it is within the range of 850 to 885 kg / m³. 3 Within the range, and more preferably within the range of 852 to 880 kg / m 3 Within the range, the most preferred value is between 855 and 875 kg / m³. 3 The density within the range.

[0189] Prior to grafting, the MFR2 (ISO 1133; 190°C; 2.16 kg) of the vinyl elastomer (B) is in the range of 0.5 to 10.0 g / 10 min, preferably in the range of 0.7 to 9.0 g / 10 min, more preferably in the range of 0.9 to 8.0 g / 10 min, and even more preferably in the range of 1.0 to 7.5 g / 10 min.

[0190] The suitable vinyl elastomer (B) has a temperature (measured by DSC according to ISO 11357-3) below 130°C, preferably below 120°C, more preferably below 110°C, and most preferably below 100°C.

[0191] In addition, the vinyl elastomer (B) has a glass transition temperature Tg (measured by DMTA according to ISO 6721-7) below -35°C, preferably below -40°C, more preferably below -45°C.

[0192] Based on the total amount of monomer units in the vinyl elastomer (B), the vinyl elastomer (B) preferably has a comonomer content of 15 to 45% by weight, more preferably 20 to 43% by weight, even more preferably 25 to 41% by weight, and most preferably 30 to 40% by weight.

[0193] When determined by GPC-VISC-LS analysis, the polydispersity (PDI-LS) of the vinyl elastomer (B), Mw / Mn, is most typically 1.0 to 4.5, more preferably 1.3 to 3.5, and most preferably 1.5 to 2.5.

[0194] Furthermore, when determined by GPC-VISC-LS analysis, the vinyl elastomer (B) preferably has a weight-average molecular weight Mw(LS) of 50,000 g / mol to 175,000 g / mol, more preferably 60,000 g / mol to 160,000 g / mol, and most preferably 65,000 g / mol to 150,000 g / mol.

[0195] Furthermore, when measured by GPC-VISC-LS analysis, the vinyl elastomer (B) preferably has a z-average molecular weight Mz(LS) of 75,000 g / mol to 250,000 g / mol, more preferably 85,000 g / mol to 230,000 g / mol, and most preferably 100,000 g / mol to 215,000 g / mol.

[0196] Furthermore, the vinyl elastomer (B) preferably has a vinyl content of 2.0 to 25.0, more preferably 3.5 to 20.0, and most preferably 5.0 to 15.0, as determined by quantitative nuclear magnetic resonance (NMR) spectroscopy in solution, per 100,000 carbon atoms.

[0197] Furthermore, the vinyl elastomer (B) preferably has an unsaturation of 5.0 to 75.0, such as 6.0 to 72.5, and most preferably 7.5 to 70.0 per 100,000 carbon atoms as determined by quantitative nuclear magnetic resonance (NMR) spectroscopy in solution.

[0198] Suitable vinyl elastomers can be ethylene and C4-C having the above properties. 12 Any copolymer of α-olefins, especially commercially available from Borealis under the trade name Queo, from DOW under the trade names Engage or Affinity, or from Mitsui under the trade name Tafmer.

[0199] Queo vinyl elastomers typically differ from Engage vinyl elastomers in that they have significantly higher vinyl content per 100,000 carbon atoms and a higher degree of unsaturation per 100,000 carbon atoms.

[0200] Alternatively, these vinyl elastomers can be prepared by known methods in a one- or two-step polymerization process, including solution polymerization, slurry polymerization, gas-phase polymerization, or combinations thereof, in the presence of a suitable catalyst, such as a vanadium oxide catalyst or a single-active-site catalyst, such as a metallocene or confined geometry catalyst known to those skilled in the art.

[0201] Preferably, these vinyl elastomers are prepared by one-step or two-step solution polymerization, especially by high-temperature solution polymerization at temperatures above 100°C.

[0202] This method is essentially based on polymerizing monomers and suitable comonomers in a liquid hydrocarbon solvent, the resulting polymer being soluble in the solvent. Polymerization is carried out at a temperature above the polymer's melting point, resulting in a polymer solution. This solution is then flash-evaporated to separate the polymer from unreacted monomers and solvent. The solvent is then recovered and recycled in this process.

[0203] Preferably, the solution polymerization method is a high-temperature solution polymerization method, using a polymerization temperature above 100°C. Preferably, the polymerization temperature is at least 110°C, more preferably at least 150°C. The polymerization temperature can be as high as 250°C.

[0204] The pressure in this solution polymerization method is preferably in the range of 10 to 100 bar, more preferably 15 to 100 bar, and even more preferably 20 to 100 bar.

[0205] The liquid hydrocarbon solvent used is preferably C 5-12 Hydrocarbons, which may be unsubstituted or C-substituted. 1-4 Alkyl-substituted compounds, such as pentane, methylpentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, and hydrogenated naphtha. More preferably, unsubstituted C6-C compounds are used. 10 - Hydrocarbon solvent.

[0206] The known solution technique suitable for the method according to the present invention is the COMPACT technique.

[0207] Acidic grafting agent (C)

[0208] As an acidic grafting agent, any such reagent known to be suitable for this purpose may be used by those skilled in the art.

[0209] Preferably, the acidic grafting agent is an unsaturated carboxylic acid or its derivatives, such as acid anhydrides, esters, and salts (metallic or nonmetallic). Preferably, the unsaturated group is conjugated with the carboxyl group.

[0210] Examples of such grafting agents include acrylic acid, methacrylic acid, fumaric acid, maleic acid, 4-norbornene-1,2-dicarboxylic acid, citraconic acid, itaconic acid, crotonic acid and its anhydrides, metal salts, esters, amides or imides.

[0211] Preferred grafting agents are maleic acid and its derivatives, such as maleic anhydride, especially maleic anhydride.

[0212] Preferably, based on the total amount of the adhesive polyethylene composition, the acid grafting agent (C) is present in the adhesive polyethylene composition in an amount of 0.01 to 3.0% by weight, more preferably 0.03 to 1.5% by weight, and most preferably 0.05 to 1.0% by weight.

[0213] Component (D)

[0214] Grafting can be carried out in the presence or absence of a free radical initiator (D), but is preferably carried out in the presence of a free radical initiator (D) such as an organic peroxide, organic perester, or organic hydroperoxide.

[0215] The preferred free radical initiator (D) is selected from organic peroxides.

[0216] Preferably, the free radical initiator (D), more preferably an organic peroxide, is dissolved in a solvent before being fed into the feed zone of the extruder.

[0217] Suitable organic peroxides can be selected from dialkyl peroxides, such as, for example, lauroyl peroxide, dicepanoyl peroxide, tert-butylcumyl peroxide, 2,5-bis(2-ethylhexanoyl peroxide)-2,5-dimethylhexane, 2,5-bis(tert-butyl peroxide)-2,5-dimethylhexane, tert-butylcumyl peroxide, tert-butyl peroxyneoplastate, di(tert-butyl peroxyisopropyl)benzene and mixtures thereof, preferably 2,5-bis(2-ethylhexanoyl peroxide)-2,5-dimethylhexane, 2,5-bis(tert-butyl peroxide)-2,5-dimethylhexane, di(tert-butyl peroxyisopropyl)benzene and mixtures thereof. The solid free radical initiator (D) can be dissolved in a solvent, such as isododecane.

[0218] Based on the total amount of the adhesive polyethylene composition, the amount of free radical initiator is preferably from 0% to 0.50% by weight, more preferably from 0.001% to 0.40% by weight, and most preferably from 0.01% to 0.25% by weight.

[0219] additive

[0220] The adhesive polyethylene composition may contain additional additives.

[0221] Suitable additives are those commonly used for polyolefins, such as stabilizers (e.g., antioxidants), metal scavengers and / or UV stabilizers, antistatic agents, and utilization agents (e.g., processing aids). The additives are preferably selected so that they do not react with the free radical initiator (D) under the conditions of the method for preparing the adhesive polyethylene compositions of the present invention as described above or below.

[0222] Based on the total amount of the adhesive polyethylene composition, the amount of additive is preferably from 0% to 1% by weight, more preferably from 0.001% to 0.8% by weight.

[0223] Grafting process

[0224] The adhesive polyethylene composition described above or below is prepared by grafting an acidic grafting agent (C) onto component (A) or both components (A) and (B).

[0225] Grafting can be performed by any method known in the art, such as in a solvent-free melt, in a solution or dispersion, or in a fluidized bed. Typically, grafting is performed in a heated extruder or mixer, as described, for example, in US3236917A, US 4639495A, US 4950541A, or US 5194509A. The contents of these documents are incorporated herein by reference. Grafting is typically performed in a twin-screw extruder, such as that described in US 4950541A.

[0226] Preferably, the adhesive polyethylene composition defined above or below can be obtained by the method for producing the adhesive polyethylene composition described above or below, the method comprising the following steps

[0227] - Feed components (A), (B) and (C) into the extruder;

[0228] - Components (A) and (B) are compounded in an extruder to form an adhesive polyethylene composition; and

[0229] - In the compounding step, component (C) is grafted onto component (A) or components (A) and (B).

[0230] The extruder preferably includes a feed section, a barrel section, and a die, wherein the extruder barrel section downstream of the feed section and upstream of the die is divided into multiple control zones, and a first control zone represents a first control zone within the barrel section downstream of the feed section, in which the fed component (A) and / or (B) begins to melt.

[0231] Components (A), (B) and (C) are preferably fed together into the feed section of the extruder.

[0232] Preferably, components (A), (B), and (C) are blended to form a blend of components (A), (B), and (C). The blend is the feed material entering the feed section of the extruder.

[0233] Preferably, the blend of components (A), (B) and (C), and more preferably components (A), (B) and (C) is fed into the feed section of the extruder through a hopper.

[0234] Alternatively, components (A) and (B) are preferably fed into the feed section of the extruder. Then, component (C) may also be fed into the feed section, but may also be fed into the barrel section, preferably into the control zone of the barrel section where the temperature is set to 180°C or lower.

[0235] Preferably, components (A) and (B) are fed into the feed section of the extruder, and component (C) is fed into the barrel section, preferably into the control zone of the barrel section where the temperature is set to 180°C or lower.

[0236] Optionally, additional additives as described above or below may be fed into the extruder. Preferably, the additional additives are fed into the barrel section of the extruder. These additional additives or other polymer components may also be fed together with component (C) into a control zone of the barrel section where the temperature is set to 180°C or lower. However, it is preferred that these additional additives or other polymer components be fed into one of the downstream control zones of the barrel section of the extruder, preferably into a control zone of the barrel section where the temperature is set to above 180°C.

[0237] The temperature of the feeding section is preferably below 100°C, such as 20°C to 70°C, more preferably 20°C to 60°C, even more preferably 25°C to 60°C, even more preferably 30°C to 60°C, and most preferably 35°C to 50°C.

[0238] Preferably, the grafting reaction is initiated by feeding a free radical initiator (D) into the extruder. The free radical initiator (D) can be separate from components (A), (B), and (C), such as by feeding it into the feed section of the extruder via a side feeder. The free radical initiator (D) can also be fed into the barrel section of the extruder, such as with component (C), such as into a control zone where the temperature is set to 180°C or lower.

[0239] The extruder is preferably a twin-screw extruder, and more preferably a co-rotating twin-screw extruder.

[0240] The extruder can be, for example, any conventionally used extruder. As an example of an extruder used in the compounding step of this application, it could be one supplied by Steelworks or Coperion of Japan, such as a ZSK co-rotating twin-screw extruder with a different screw diameter.

[0241] The extruder suitable for the method of the present invention can be a laboratory-scale extruder or a commercial-scale extruder.

[0242] In laboratory-scale extruders, the extrusion step is typically carried out using a feed rate of 1 kg / h to 100 kg / h, more preferably 5 kg / h to 50 kg / h. In commercial-scale extruders, the production rate is typically 1 to 50 tons / hour, more preferably 1.5 to 10 tons / hour.

[0243] The screw speed of the extruder is preferably 170 rpm to 550 rpm, more preferably 200 rpm to 500 rpm.

[0244] Preferably, in the extrusion step, the SEI (specific energy input) of the extruder can be from 150 kWh / ton to 350 kWh / ton, more preferably from 170 kWh / ton to 300 kWh / ton, wherein the SEI is calculated directly from the electrical input of the extruder, ignoring the inherently limited effectiveness.

[0245] The extruder temperature at the template is preferably in the range of 180°C to 250°C, more preferably in the range of 185°C to 230°C, and most preferably in the range of 195°C to 230°C.

[0246] The barrel section of the extruder preferably includes at least five control zones, each with independently controlled temperature. Suitably, the barrel section includes five to fifteen control zones, preferably six to twelve.

[0247] The temperature distribution of the barrel section can be adjusted in two different implementation schemes as needed, which typically results in different grafting patterns of the adhesive polyethylene composition.

[0248] In the first embodiment, the temperature of the second to last control zones in the barrel section remains constant across all these control zones, with a total deviation not exceeding 20°C, preferably not exceeding 15°C, and most preferably not exceeding 10°C (constant temperature distribution).

[0249] The temperature of the first control zone in the barrel section downstream of the feed zone can be lower than the temperature of the second to last control zones in the barrel section, or be within the same range as the temperature of the second to last control zones in the barrel section.

[0250] The temperature of the first control zone is preferably in the range of 165°C to 210°C, more preferably in the range of 170°C to 200°C, and most preferably in the range of 175°C to 190°C.

[0251] The temperature of the second to last control zone in the barrel section is preferably in the range of 180°C to 250°C, more preferably in the range of 185°C to 230°C, and most preferably in the range of 195°C to 230°C.

[0252] In the second embodiment, the temperature of the control zone of the barrel section, from the first control zone downstream of the feed section to the control zone in the middle of the barrel section, increases in two or more steps along the length of the barrel section (temperature rise distribution).

[0253] This means that for a barrel section that includes 5 or 6 control zones, the temperature in control zones 1 to 3 will increase.

[0254] For a barrel section that includes 7 or 8 control zones, the temperature in control zones 1 to 4 increases.

[0255] For a barrel section comprising 9 or 10 control zones, the temperature in control zones 1 to 5 increases.

[0256] For a barrel section comprising 11 or 12 control zones, the temperature in control zones 1 through 6 increases.

[0257] For a barrel section comprising 13 or 14 control zones, the temperature in control zones 1 through 7 increases.

[0258] For the barrel section, which includes 15 control zones, the temperature in control zones 1 to 8 increases.

[0259] Two or more steps of heating means that over the length of the barrel section from the first control zone downstream of the feed section to the control zone in the middle of the barrel section, the temperature of two or more barrels, such as two to five barrels, preferably two or three barrels, and most preferably two barrels, is set to be higher than the temperature of the barrel upstream of the two or more barrels.

[0260] From the first control zone of the barrel section downstream of the feed section to the control zone in the middle of the barrel section, the temperature of the control zone of the barrel section is typically increased in two to five steps, such as two, three, four, or five steps, preferably two to four steps, and more preferably two or three steps. In most extruder units, two-step heating is sufficient for the methods described above or below.

[0261] The temperature rise of each independent step in the two or more heating steps is preferably in the range of 5°C to 30°C, more preferably in the range of 7.5°C to 25°C, and most preferably in the range of 10°C to 20°C.

[0262] From the first control zone of the barrel section downstream of the feed section to the control zone in the middle of the barrel section, the temperature of the control zone of the barrel section increases in two or more steps, such that the temperature of the control zone in the middle of the barrel section is 105% to 145% of the temperature of the first control zone of the barrel section downstream of the feed section, more preferably 110% to 140%, and most preferably 110% to 135%.

[0263] The temperature of the first control zone of the barrel section downstream of the feed section is in the range of 85°C to 180°C, preferably in the range of 120°C to 180°C, more preferably in the range of 130°C to 175°C, and most preferably in the range of 140°C to 170°C.

[0264] The temperature of the control zone in the middle of the barrel section is preferably 15°C to 60°C higher than the temperature of the first control zone of the barrel section, and more preferably 20°C to 40°C higher.

[0265] Preferably, from the first control zone of the barrel section to the control zone in the middle of the barrel section, the temperature of the control zone increases in increments of 5 to 20°C from the control zone to the adjacent control zone.

[0266] From the control zone in the middle of the barrel section to the control zone of the barrel section directly upstream of the template, the temperature of the control zone of the barrel section is maintained at the same temperature, or is raised to no more than 120% of the temperature of the control zone in the middle of the barrel section, more preferably no more than 115%, and even more preferably no more than 110%.

[0267] This means that for a barrel section comprising 5 or 6 control zones, the temperature of control zones 3 to 5 or 6 is maintained at the same temperature, or raised to a temperature not exceeding 120% of the temperature of control zone 3.

[0268] For a barrel section comprising 7 or 8 control zones, the temperature of control zones 4 to 7 or 8 is maintained at the same temperature, or increased to a temperature not exceeding 120% of the temperature of control zone 4.

[0269] For a barrel section comprising 9 or 10 control zones, the temperature of control zones 5 through 9 or 10 is maintained at the same temperature, or increased to a temperature not exceeding 120% of the temperature of control zone 5.

[0270] For a barrel section comprising 11 or 12 control zones, the temperature of control zones 6 to 11 or 12 is maintained at the same temperature, or increased to a temperature not exceeding 120% of the temperature of control zone 5.

[0271] For a barrel section comprising 13 or 14 control zones, the temperature of control zones 7 to 13 or 14 is maintained at the same temperature, or increased to no more than 120% of the temperature of control zone 5.

[0272] For a barrel section comprising 15 control zones, the temperature of control zones 8 to 15 is maintained at the same temperature, or increased to no more than 120% of the temperature of control zone 5.

[0273] When the temperature rises, the temperature of the last control zone of the barrel section is preferably 5°C to 30°C higher than the temperature of the control zone in the middle of the barrel section, more preferably 10°C to 20°C higher.

[0274] When the temperature is maintained, the temperature of the last control zone of the barrel section is the same as the temperature of the control zone in the middle of the barrel section.

[0275] From the first to the last control zone of the barrel section, the temperature is preferably increased by 115% to 150% compared to the temperature of the first control zone of the barrel section, more preferably by 120% to 145%, and most preferably by 125% to 135%.

[0276] The temperature of the last control zone of the barrel section is preferably 30°C to 75°C higher than the temperature of the first control zone of the barrel section, more preferably 35°C to 70°C, and most preferably 40°C to 60°C higher.

[0277] The temperature of the last control zone in the barrel section can be the same as the temperature of the template.

[0278] In a particularly preferred embodiment, the barrel section has six control zones in which the temperature is independently controlled.

[0279] The feeding zone is preferably set at 35°C to 50°C.

[0280] The control zone 1 is preferably set to 140°C to 170°C.

[0281] The control zone 2 is preferably set to 170°C to 180°C.

[0282] The control zone 3 is preferably set to 180°C to 190°C.

[0283] The control zone 4 is preferably set to 190°C to 200°C.

[0284] The control zone 5 is preferably set to 190°C to 210°C.

[0285] The control zone 6 is preferably set at 190°C to 210°C.

[0286] The template is preferably set to 190°C to 210°C.

[0287] The measured temperature in the control zone of all the implementation schemes discussed above can differ from the set temperature by ±5°C, preferably ±4°C.

[0288] Adhesive polyethylene composition

[0289] The adhesive polyethylene composition comprises a non-elastomeric polyethylene (A) and a vinyl elastomer (B) grafted thereon with an acidic grafting agent (C) as described above or below. Components (A), (B), and (C) of the adhesive polyethylene composition are preferably as defined above or below.

[0290] The adhesive polyethylene composition may also contain additives as defined above or below.

[0291] In one embodiment, the adhesive polyethylene composition comprises a copolymer of ethylene grafted thereon with an acidic grafting agent (C) using a constant temperature distribution, a comonomer unit selected from α-olefins having 3 to 12 carbon atoms, and a vinyl elastomer (B).

[0292] In another embodiment, the adhesive polyethylene composition comprises a copolymer of ethylene to which an acidic grafting agent (C) has been grafted using a temperature distribution, a comonomer unit selected from α-olefins having 3 to 12 carbon atoms, and a vinyl elastomer (B).

[0293] In yet another embodiment, the adhesive polyethylene composition comprises a terpolymer of ethylene grafted thereon with an acidic grafting agent (C) using a temperature-controlled distribution, and two different comonomer units selected from α-olefins having 4 to 12 carbon atoms, and a vinyl elastomer (B).

[0294] In another embodiment, the adhesive polyethylene composition comprises a terpolymer of ethylene to which an acidic grafting agent (C) has been grafted using a temperature distribution, and two different comonomer units selected from α-olefins having 4 to 12 carbon atoms, and a vinyl elastomer (B).

[0295] The adhesive polyethylene composition preferably has an MFR2 value of 0.1 to 10.0 g / 10 min, more preferably 0.8 to 6.0 g / 10 min, and most preferably 1.0 to 5.0 g / 10 min for the final composition (after grafting).

[0296] The adhesive polyethylene composition preferably has a content of 900 to 950 kg / m³. 3 More preferably 905 to 940 kg / m 3 And most preferably 910 to 935 kg / m 3 The density.

[0297] Furthermore, the adhesive polyethylene composition preferably has a melt temperature Tm of 110 to 150°C, more preferably 115 to 135°C, and most preferably 120 to 130°C.

[0298] The heat of fusion Hf is preferably in the range of 90 to 125 J / g, more preferably 95 to 120 J / g, and most preferably in the range of 100 to 115 J / g.

[0299] Furthermore, the adhesive polyethylene composition preferably has a crystallization temperature Tc of 90 to 130°C, more preferably 95 to 120°C, and most preferably 100 to 115°C.

[0300] The heat of crystallization, Hc, is preferably in the range of 95 to 130 J / g, more preferably 100 to 125 J / g, and most preferably 105 to 120 J / g.

[0301] Furthermore, when measured using dynamic mechanical thermal analysis (DMTA), the adhesive polyethylene composition preferably has a glass transition temperature of -30.0°C to -65.0°C, more preferably -45.0°C to -60.0°C, and most preferably -47.5°C to -57.5°C.

[0302] Furthermore, when measured using dynamic mechanical thermal analysis (DMTA), the adhesive polyethylene composition preferably has a storage modulus of 125 to 250 MPa at 23°C, more preferably 140 to 225 MPa, and most preferably 160 to 210 MPa.

[0303] Furthermore, the adhesive polyethylene composition preferably has a rheological polydispersity index (PI) of no more than 2.25, such as in the range of 0.40 to 2.10, more preferably in the range of 0.50 to 2.00, and most preferably in the range of 0.60 to 1.90.

[0304] The adhesive polyethylene composition preferably has a shear thinning index (SHI) of not more than 22.0, such as 4.0 to 20.0, more preferably 5.5 to 18.5, and most preferably 7.5 to 17.5. 1 / 100 .

[0305] Furthermore, the elastic index EI (0.5kPa) of the adhesive polyethylene composition is preferably 75 to 320 Pa at a loss modulus G” = 0.5 kPa, more preferably 85 to 275 Pa, and most preferably 95 to 250 Pa.

[0306] Furthermore, the elastic index EI (2kPa) of the adhesive polyethylene composition is preferably 500 to 1500 Pa at a loss modulus G” = 2kPa, more preferably 650 to 1350 Pa, and most preferably 750 to 1200 Pa.

[0307] Furthermore, the elastic index EI (5kPa) of the adhesive polyethylene composition is preferably 1750 to 4000 Pa at a loss modulus G” = 5kPa, more preferably 2000 to 3500 Pa, and most preferably 2200 to 3250 Pa.

[0308] When determined by GPC-VISC-LS analysis, the adhesive polyethylene composition preferably has a z-average molecular weight Mz(LS) of 125,000 g / mol to 750,000 g / mol, more preferably 140,000 g / mol to 700,000 g / mol, even more preferably 150,000 g / mol to 650,000 g / mol, and most preferably 160,000 to 600,000 g / mol.

[0309] Furthermore, when determined by GPC-VISC-LS analysis, the adhesive polyethylene composition preferably has a weight-average molecular weight Mw(LS) of 50,000 to 175,000 g / mol, more preferably 60,000 to 150,000 g / mol, and most preferably 70,000 to 125,000 g / mol.

[0310] When determined by GPC-VISC-LS analysis, the polydispersity index (PDI-LS) of the adhesive polyethylene composition is preferably in the range of 1.5 to 4.5, more preferably 2.0 to 4.3, and most preferably in the range of 2.5 to 4.0, wherein the polydispersity index (PDI-LS) is the Mw / Mn ratio.

[0311] The adhesive polyethylene composition preferably exhibits only one distinct peak in the GPC curve. Therefore, in the measurement methods described below, the GPC curve is defined as the concentration-normalized LS 15 signal of the molecular weight along the conventional GPC obtained from GPC-VISC-LS analysis.

[0312] The adhesive polyethylene composition may have a cumulative fraction (CFLS-1M) of LS 15° angle light scattering signal greater than 1 million g / mol in the range of 0 to 17.5, preferably 0 to 15.0, and most preferably 0 to 12.5.

[0313] The adhesive polyethylene composition may have a cumulative fraction (CFLS-2M) of LS 15° angle light scattering signal greater than 2 million g / mol in the range of 0 to 10.0, preferably 0 to 8.5, and most preferably 0 to 7.5.

[0314] The adhesive polyethylene composition may have a cumulative fraction (CFLS-3M) of LS 15° angle light scattering signal greater than 3 million g / mol in the range of 0 to 8.0, preferably 0 to 6.5, and most preferably 0 to 5.0.

[0315] Preferably, the adhesive polyethylene composition has a vinyl content of 1.0 to 30.0, more preferably 2.0 to 27.5, even more preferably 2.5 to 25.0, and most preferably 3.0 to 22.5, as determined by quantitative nuclear magnetic resonance (NMR) spectroscopy in solution.

[0316] Furthermore, the adhesive polyethylene composition preferably has an unsaturation degree of 10.0 to 75.0, more preferably 12.5 to 60.0, and most preferably 15.0 to 50.0 per 1000 carbon atoms as determined by quantitative nuclear magnetic resonance (NMR) spectroscopy in solution.

[0317] The adhesive polyethylene compositions according to the invention, as described above or below, are particularly suitable for producing adhesive layers in multilayer structures, such as, for example, three-layer coatings of metal pipes (such as steel pipes).

[0318] Multi-layer structure

[0319] Furthermore, the present invention relates to a multilayer structure comprising a layer containing an adhesive polyethylene composition as defined above or below.

[0320] Preferably, the multilayer structure is a pipe coating, such as a three-layer coating on a metal pipe. The most preferred multilayer structure is a three-layer coating on a steel pipe.

[0321] The layer comprising the adhesive polyethylene composition as defined above or below is preferably an adhesive layer.

[0322] Preferably, the multilayer structure, more preferably a coated metal tube, and most preferably a coated steel tube, has a peel strength of at least 350 N / cm, more preferably at least 400 N / cm, and most preferably at least 420 N / cm at 23°C.

[0323] The upper limit of peel strength at 23°C is usually no higher than 850 N / cm.

[0324] Furthermore, the multi-layered structure, more preferably a coated metal tube, and most preferably a coated steel tube, has a peel strength of at least 60 N / cm, more preferably at least 63 N / cm, and most preferably at least 65 N / cm at 80°C.

[0325] The upper limit of peel strength at 80℃ is usually no higher than 350 N / cm.

[0326] In one embodiment, the adhesive polyethylene composition comprises a copolymer of ethylene grafted thereon with an acidic grafting agent (C) using a constant temperature distribution, a comonomer unit selected from α-olefins having 3 to 12 carbon atoms, and a vinyl elastomer (B).

[0327] In the embodiment described, the multilayer structure, more preferably a coated metal tube, and most preferably a coated steel tube, preferably has a peel strength of at least 375 N / cm, more preferably at least 425 N / cm, and most preferably at least 450 N / cm at 23°C.

[0328] The upper limit of peel strength at 23°C is usually no higher than 650 N / cm.

[0329] Furthermore, the multi-layered structure, more preferably a coated metal tube, and most preferably a coated steel tube, has a peel strength of at least 60 N / cm, more preferably at least 63 N / cm, and most preferably at least 65 N / cm at 80°C.

[0330] The upper limit of peel strength at 80℃ is usually no higher than 200 N / cm.

[0331] In another embodiment, the adhesive polyethylene composition comprises a copolymer of ethylene to which an acidic grafting agent (C) has been grafted using a temperature distribution, a comonomer unit selected from α-olefins having 3 to 12 carbon atoms, and a vinyl elastomer (B).

[0332] In the embodiment described, the multilayer structure, more preferably a coated metal tube, and most preferably a coated steel tube, preferably has a peel strength of at least 350 N / cm, more preferably at least 400 N / cm, and most preferably at least 420 N / cm at 23°C.

[0333] The upper limit of peel strength at 23°C is usually no higher than 550 N / cm.

[0334] Furthermore, the multi-layered structure, more preferably a coated metal tube, and most preferably a coated steel tube, has a peel strength of at least 100 N / cm, more preferably at least 125 N / cm, and most preferably at least 150 N / cm at 80°C.

[0335] The upper limit of peel strength at 80℃ is usually no higher than 350 N / cm.

[0336] In yet another embodiment, the adhesive polyethylene composition comprises a terpolymer of ethylene grafted thereon with an acidic grafting agent (C) using a temperature-controlled distribution, and two different comonomer units selected from α-olefins having 4 to 12 carbon atoms, and a vinyl elastomer (B).

[0337] In the embodiment described, the multilayer structure, more preferably a coated metal tube, and most preferably a coated steel tube, preferably has a peel strength of at least 400 N / cm, more preferably at least 450 N / cm, and most preferably at least 500 N / cm at 23°C.

[0338] The upper limit of peel strength at 23°C is usually no higher than 850 N / cm.

[0339] Furthermore, the multi-layered structure, more preferably a coated metal tube, and most preferably a coated steel tube, has a peel strength of at least 75 N / cm, more preferably at least 85 N / cm, and most preferably at least 95 N / cm at 80°C.

[0340] The upper limit of peel strength at 80℃ is usually no higher than 300 N / cm.

[0341] In another embodiment, the adhesive polyethylene composition comprises a terpolymer of ethylene to which an acidic grafting agent (C) has been grafted using a temperature distribution, and two different comonomer units selected from α-olefins having 4 to 12 carbon atoms, and a vinyl elastomer (B).

[0342] In the embodiment described, the multilayer structure, more preferably a coated metal tube, and most preferably a coated steel tube, preferably has a peel strength of at least 400 N / cm, more preferably at least 450 N / cm, and most preferably at least 500 N / cm at 23°C.

[0343] The upper limit of peel strength at 23°C is usually no higher than 850 N / cm.

[0344] Furthermore, the multi-layered structure, more preferably a coated metal tube, and most preferably a coated steel tube, has a peel strength of at least 100 N / cm, more preferably at least 125 N / cm, and most preferably at least 150 N / cm at 80°C.

[0345] The upper limit of peel strength at 80℃ is usually no higher than 350 N / cm.

[0346] Preferably, the cooling process of the multilayer structure or coated tube is independent of the cooling process of the tube, i.e., at conventional cooling rates and faster cooling rates, the multilayer structure, more preferably the coated metal tube, and most preferably the coated steel tube, has peel strength within the required protection range.

[0347] Pipes, preferably metal pipes, and most preferably steel pipes, are typically coated with three layers of coating according to the following procedure:

[0348] As is known in the art, the surface of the pipe is preferably properly prepared prior to coating. The pipe surface is typically inspected for any rust, dirt, cracks, discontinuities, and metallic defects. All excess material needs to be removed from the pipe surface to ensure proper adhesion of the coating. Suitable cleaning methods include high-pressure air and water cleaning, sandblasting or shot blasting, and mechanical brushing. Pickling and chromate pretreatment are sometimes also used.

[0349] Typically, the pipe is heated to approximately 200°C to 220°C via induction heating. The temperature can be adjusted depending on the linear velocity and the materials used in the anti-corrosion coating. When using the epoxy resin Teknos Infralit EP8054, the steel pipe is preferably heated to 190°C. The temperature may be slightly reduced during the coating process.

[0350] If epoxy powder is used (at 23°C), it is typically applied using an epoxy spray gun, with the rotating nozzle speed approximately 9 m / min. The thickness of the epoxy and other coating materials is determined based on the specific requirements of the end application. Normal epoxy layer thickness values ​​(for on-shore installations) range from 70 to 200 μm, such as 135 to 160 μm.

[0351] Materials that can be used in anti-corrosion coatings include, for example, epoxy resins and silicone compounds. Suitable examples of epoxy resins are phenolic epoxy resins and amino epoxy resins. These types of epoxy resins are sold under trade names such as (Teknos) Infralit EP8054, (3M) Scotchkote 6233P, and (BASF) PE50-7191. Suitable silicone compounds are disclosed in EP-A-1859926.

[0352] The extrusion of the adhesive layer and top coating can be carried out, for example, using two single-screw extruders. They can have diameters of, for example, 30 to 100 mm, such as 60 mm, and lengths of 15 to 50 L / D, such as 30 L / D. Temperatures are typically controlled in several zones, with the temperatures of the PE adhesive and coating after the die being 190 to 300°C, such as 210 to 250°C. The die width is 50 to 300 mm, such as 80 mm and 200 mm for the adhesive layer and coating, respectively. Both the adhesive layer and coating are typically pressed tightly onto the tube using silicone rollers. The thickness of the adhesive layer is typically 200 to 600 μm, such as 250 to 500 μm. The thickness of the coating is typically 1 to 6 mm, preferably 2 to 5 mm.

[0353] The adhesive layer preferably comprises a polymer composition, preferably an adhesive polymer composition according to the present invention.

[0354] The top coating preferably comprises a polyethylene resin, such as HDPE resin or cross-linked polyethylene resin, or polypropylene resin.

[0355] After coating, the coated pipe can be cooled, for example, by providing a flow of water to the surface of the coated pipe.

[0356] Example

[0357] 1. Measurement Method

[0358] a) melt flow rate

[0359] Melt flow rate (MFR) is determined according to ISO 1133-1, Method B, and expressed in g / 10 min. MFR indicates the flowability of a polymer and therefore its processability. A higher melt flow rate corresponds to a lower polymer viscosity. The MFR2 for polyethylene was measured at 190°C and a load of 2.16 kg.

[0360] b) density

[0361] The density of the polymer was measured according to ISO 1183-1:2004 Method A on compression-molded specimens prepared according to EN ISO 1872-2 (February 2007), and the unit is kg / m³. 3 .

[0362] c) Peel strength

[0363] Peel strength refers to the relative bond strength between the epoxy resin layer and the adhesive layer. The peel strength of the coated composition was measured using a Zwick Roell tensile testing machine at 23°C according to ISO 21809-1:2011, with the following modification: the peel strength was recorded for three minutes, and then the average of the peel strengths recorded over these three minutes was calculated. This average value corresponds to the reported peel strength of the composition.

[0364] d) Melting temperature Tm, crystallization temperature Tc

[0365] Melting temperature (Tm), crystallization temperature (Tc), and crystallinity were measured using a Mettler TA820 differential scanning calorimeter (DSC) according to ISO 11357 on samples ranging from 5 to 10 mg, typically 8 ± 0.5 mg. Crystallization and melting profiles were obtained during cooling and heating scans at 10 °C / min between 30 °C and 225 °C. Melting and crystallization temperatures were derived from the endothermic and exothermic peaks.

[0366] e) GPC Measurement

[0367] A PL 220 (Agilent) GPC was used, equipped with an infrared detector (IR4 (PolymerChar, Spain), an online four-capillary bridge viscometer (PL-BV 400-HT), and dual light scattering detectors with 15° and 90° angles (PL-LS15 / 90 light scattering detector). A 3x Olexis and 1x Olexis guard columns from Agilent were used as the stationary phase, and 1,2,4-trichlorobenzene (TCB, stabilized with 250 mg / L 2,6-di-tert-butyl-4-methylphenol) was used as the mobile phase at 160 °C and a constant flow rate of 1 mL / min. 200 μL of sample solution was injected for each analysis.

[0368] All samples were prepared in concentration ranges from 1.0 to 1.25 mg / ml and dissolved in 1,2,4-trichlorobenzene (TCB, stabilized with 250 mg / L of 2,6-di-tert-butyl-4-methylphenol) at 160 °C with continuous gentle shaking for 3 hours. Due to the volume expansion at 160 °C compared to 25 °C, the injection concentration (c) of the polymer solution at 160 °C was [not specified]. 160 (℃) Adjust as follows.

[0369]

[0370] Where: w 25 (polymer weight) and V 25 (Volume of TCB at 25°C).

[0371] Through GPC-Routine Analysis (GPC) 常规 Average molecular weight and polydispersity (Mn, Mw, Mz, MWD)

[0372] For GPC regular (GPC) 常规 The column assembly was calibrated using a universal calibration (according to ISO 16014-2:2003) with 19 narrow MWD polystyrene (PS) standards ranging from 0.5 kg / mol to 11,500 kg / mol. The PS standards were dissolved at 160 °C for 15 minutes, or at room temperature at concentrations of 0.2 mg / mL (for molecular weights greater than or equal to 899 kg / mol) and 1 mg / mL (for molecular weights less than 899 kg / mol). The conversion of the polystyrene peak molecular weight to the polyethylene molecular weight was accomplished using the Mark Houwink equation and the following Mark Houwink constants:

[0373] K PS =19x10 -3 ml / g, α PS =0.655

[0374] K PE =39x10 -3 ml / g, α PE =0.725

[0375] Third-order polynomial fitting was used to fit the calibration data.

[0376] The average molecular weight (Mz, Mw, and Mn), molecular weight distribution (MWD), and its width described by the polydispersity index are determined using the following formula: PD = Mw / Mn (where Mn is the number-average molecular weight and Mw is the weight-average molecular weight):

[0377]

[0378]

[0379]

[0380] GPC-VISC-LS analysis

[0381] For GPC light scattering method (GPC) LS The interdetector delay volume was determined using a narrow PS standard with a molar mass of 130,000 g / mol (MWD = 1.01). The corresponding detector constants for the light scattering detector and the online viscometer were determined using the wide standard NIST1475A (Mw = 52,000 g / mol and IV = 1.01 dl / g). For the PE standard used in the TCB, the corresponding dn / dc was 0.094 cm⁻¹. 3 / g. Calculations were performed using Cirrus Multi-Offline SEC software version 3.2 (Agilent).

[0382] The molar mass of each elution slice was calculated using a 15° light scattering angle. Data collection, processing, and calculations were performed using Cirrus Multi SEC software version 3.2. Molecular weight was calculated using the option "Use LS 15 angle" in the "Sample Calculation Options Sub-region Slice MW Data From" area of ​​the Cirrus software. A value of 0.094 was used as the dn / dc ratio for molecular weight determination.

[0383] The molecular weight of each slice was calculated at low angles in the manner described in C. Jackson and H. Gbarth (C. Jackson and H. Gbarth, Handbook of Size Exclusion Chromatography and related technology, C.-S. Wu, 2nd edition, Marcel Dekker, New York, 2004, page 103, "Molecular Weight Sensitive Detectors"). For low-molecular-weight and high-molecular-weight regions, which yielded less signal from the LS or RI detectors, respectively, linear fitting was used to correlate the elution volume with the corresponding molecular weight. The region of the linear fitting was adjusted according to the sample.

[0384] The mean molecular weight (Mz(LS), Mw(LS), and Mn(LS)), molecular weight distribution (MWD), and its width (described in terms of polydispersity, PD(LS) = Mw(LS) / Mn(LS)) (where Mn(LS) is the number-average molecular weight obtained from GPC-LS, and Mw(LS) is the weight-average molecular weight obtained from GPC-LS)) are calculated by gel permeation chromatography (GPC):

[0385]

[0386]

[0387]

[0388] For a constant elution volume interval ΔV i A i and M i(LS) These are the chromatographic peak slice area and the molecular weight (MW) of the polyolefin, determined by GPC-LS.

[0389] For average molecular weight Mz, M W And Mn, the molecular weight (Mw) of polyolefins is determined by GPC 常规 The values ​​were determined by GPC, where Mz(LS), Mw(LS), and Mn(LS) represent the average molecular weight. LS Obtained by the method.

[0390] CFLS value

[0391] The cumulative fraction (CFLS) of the light scattering signal at an LS 15° angle is defined as the relative area of ​​the total area of ​​the LS15 signal at 10^6 (g / mol) or above, or at 2*10^6 (2M) and 3*10^6 (3M) g / mol respectively, and is calculated from the normalized LS 15 signal as follows.

[0392]

[0393]

[0394]

[0395] Among them, LS(15) i It corresponds to the LS15 signal at the normal molecular weight.

[0396] f) Comonomer content

[0397] The content of 1-butene and 1-hexene comonomers in the ethylene-1-butene-1-hexene terpolymer was determined using quantitative nuclear magnetic resonance (NMR) spectroscopy.

[0398] Use for 1 H and 13 Quantitative recordings were performed in the molten state using a Bruker Avance III 500 NMR spectrometer operating at 500.13 and 125.76 MHz, respectively. 13 C{ 1 ¹H NMR spectroscopy. Nitrogen gas was used for all pneumatic devices at 150°C. 13 All spectra were recorded using a C-optimized 7mm magic angle rotation (MAS) probe. Approximately 200 mg of material was loaded into a 7mm outer diameter zirconia MAS rotor and rotated at 4 kHz. This setup was chosen primarily for the high sensitivity required for rapid identification and accurate quantification. Standard single-pulse excitation was employed with a short 3s cycle delay using NOE (pollard) and RS-HEPT decoupling schemes (fillip) and (griffin). A total of 1024 (1k) transient values ​​were acquired for each spectrum.

[0399] Quantitative 13 C{ 1 The H NMR spectra were processed, integrated, and the relevant quantitative properties were determined from the integration. All chemical shifts were internally referenced to the bulk methylene signal (δ+) at 30.00 ppm {randall89}.

[0400] The characteristic signal {randall89} corresponding to the incorporation of 1-butene was observed, and the comonomer fraction was calculated as the fraction of 1-butene in the polymer relative to all monomers in the polymer.

[0401] The amount of isolated 1-butene incorporated into the EEBEE sequence was quantified using the integral [I*B2] at the *B2 site at 39.8 ppm, taking into account the number of reporter sites for each comonomer:

[0402] B = I *B2

[0403] In the absence of observed signals indicating the incorporation of other comonomer sequences, i.e., consecutive comonomers, the total 1-butene comonomer content was calculated solely based on the amount of isolated 1-butene sequences:

[0404] B total = B

[0405] Therefore, the total mole fraction of 1-butene in the polymer is calculated as follows:

[0406] fB = B_total / (E_total + B_total + H_total)

[0407] The characteristic signal {randall89} corresponding to the incorporation of 1-hexene was observed, and the comonomer fraction was calculated as the fraction of 1-hexene in the polymer relative to all monomers in the polymer.

[0408] Using the integral at the *B4 site at 38.2 ppm [I *B4 The amount of isolated 1-hexene incorporated into the EEHEE sequence is quantified by considering the number of reporter sites for each comonomer.

[0409] H = I *B4

[0410] In the absence of observed signals indicating the incorporation of other comonomer sequences, i.e., consecutive comonomers, the total 1-hexene comonomer content was calculated solely based on the amount of isolated 1-hexene sequences:

[0411] H_total = H

[0412] Therefore, the total mole fraction of 1-hexene in the polymer is calculated as follows:

[0413] fH = H_total / (E_total + B_total + H_total)

[0414] The amount of ethylene was quantified using the integral of the bulk methylene (δ+) site at 30.00 ppm. This integral includes the γ site and the 3B4 site from 1-hexene. The total ethylene content was calculated based on the bulk integral and compensated for by the observed 1-butene and 1-hexene sequences and end groups.

[0415] E = I δ+ / 2

[0416] Characteristic signals generated by saturated end bases were observed. The integrals of the signals at 22.8, attributed to the 2s and 3s sites respectively, were used. 2S The integral of the signal at 32.2 ppm and [I] 3S The content of this saturated end group is quantified by the average value of [ ].

[0417] S=(1 / 2)*(I 2S +I 3S )

[0418] The presence of isolated comonomer units is corrected based on the number of existing comonomer units and saturated end groups:

[0419] Etotal = E + (3 / 2)*B + (2 / 2)*H + (3 / 2)*S

[0420] Calculate the molar percentage of the incorporated comonomer from the molar fraction:

[0421] B[moles%] = 100 * fB

[0422] H[molar%] = 100 * fH

[0423] Calculate the weight percentage of the incorporated comonomer from the mole fraction:

[0424] B[weight%] = 100*(fB*56.11) / ((fB*56.11)+(fH*84.16)+((1-(fB+fH))*28.05))

[0425] H[weight%] = 100 * (fH * 84.16) / ((fB * 56.11) + (fH * 84.16) + ((1 - (fB + fH)) * 28.05))

[0426] randall89

[0427] J. Randall, Macromol. Sci., Rev. Macromol. Chem. Phys. 1989, C29, 201.

[0428] klimke06

[0429] Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, HW, Wilhelm, M., Macromol. Chem. Phys. 2006; 207:382.

[0430] parkinson07

[0431] Parkinson, M., Klimke, K., Spiess, HW, Wilhelm, M., Macromol. Chem. Phys. 2007; 208:2128.

[0432] pollard04

[0433] Pollard,M.,Klimke,K.,Graf,R.,Spiess,HW,Wilhelm,M.,Sperber,O.,Piel,C.,Kaminsky,W.,Macromolecules 2004;37:813.

[0434] filip05

[0435] Filip,X.,Tripon,C.,Filip,C.,J.Mag.Resn.2005,176,239

[0436] griffin07

[0437] Griffin,JM,Tripon,C.,Samoson,A.,Filip,C.,and Brown,SP,Mag.Res.inChem.200745,S1,S198

[0438] castignolles09

[0439] Castignolles,P.,Graf,R.,Parkinson,M.,Wilhelm,M.,Gaborieau,M.,Polymer50(2009)2373

[0440] The 1-octene comonomer content of ethylene-1-octene copolymer and ethylene-1-octene elastomer was quantified using quantitative nuclear magnetic resonance (NMR) spectroscopy.

[0441] Use for 1 H and 13 Quantitative recordings were performed in the molten state using a Bruker Avance III 500 NMR spectrometer operating at 500.13 and 125.76 MHz, respectively. 13 C{ 1 ¹H NMR spectroscopy. Nitrogen gas was used for all pneumatic devices. 13A C-optimized 7mm magic angle rotation (MAS) probe was used to record all spectra at 150°C. Approximately 200 mg of material was loaded into a 7mm outer diameter zirconia MAS rotor and rotated at 4 kHz. This setup was chosen primarily for the high sensitivity required for rapid identification and accurate quantification. Standard single-pulse excitation was used with a short 3s cycle delay, utilizing transient NOE (pollard, klimke, 6) and RS-HEPT decoupling schemes. A total of 1024 (1k) transient values ​​were acquired for each spectrum.

[0442] Quantitative analysis was performed using a customized automated spectral analysis program. 13 C{ 1 The ¹H NMR spectra were processed, integrated, and quantitatively determined. All chemical shifts were internally referenced to the bulk methylene signal (δ+) at 30.00 ppm.

[0443] Characteristic signals corresponding to the incorporation of 1-octene were observed (randall89,liu01,qiu07), and the contents of all comonomers were calculated relative to all other monomers present in the polymer.

[0444] Characteristic signals generated by isolated 1-octene incorporation (i.e., the EEOEE comonomer sequence) were observed. Isolated 1-octene incorporation was quantified using the integral of the signal at 38.3 ppm. This integral was assigned to the unresolved signals corresponding to the *B6 and *βB6B6 sites of the isolated (EEOEE) and isolated bis-discontinuous (EEOEOEE) 1-octene sequences, respectively.

[0445] To compensate for the influence of the two *βB6B6 sites, the integral of the ββB6B6 site at 24.6 ppm is used:

[0446] O = I *B6+*βB6B6 -2*I ββB6B6

[0447] When a characteristic signal generated by continuous 1-octene incorporation (i.e., the EEOOEE comonomer sequence) is observed, this continuous 1-octene incorporation is quantified by using the signal integral assigned to the ααB6B6 site at 40.4 ppm, taking into account the number of reporter sites for each comonomer:

[0448] OO = 2 * I ααB6B6

[0449] When a characteristic signal is observed arising from isolated, discontinuous 1-octene incorporation (i.e., the EEOEOEE comonomer sequence), this isolated, discontinuous 1-octene incorporation is quantified by integrating the signal attributed to the ββB6B6 site at 24.6 ppm, taking into account the number of reporter sites for each comonomer:

[0450] OEO=2*I ββB6B6

[0451] When a characteristic signal is observed generated by isolated tricontinuous 1-octene incorporation (i.e., the EEEOOOEE comonomer sequence), this isolated tricontinuous 1-octene incorporation is quantified by integrating the signal attributed to the αγγB6B6B6 site at 41.2 ppm, taking into account the number of reporter sites for each comonomer:

[0452] OOO=3 / 2*I αγγB6B6B6

[0453] Since no other signals indicating other comonomer sequences were observed, the total 1-octene comonomer content was calculated solely based on the amounts of isolated (EEOEE), isolated bicontinuous (EEOOEE), isolated discontinuous (EEOEOEE), and isolated tricontinuous (EEOOOEE) 1-octene comonomer sequences:

[0454] O 总 =O+OO+OEO+OOO

[0455] Characteristic signals generated by saturated end groups were observed. These saturated end groups were quantified using the average integral of the two resolved signals at 22.9 and 32.23 ppm. The integral at 22.84 ppm was assigned to the unresolved signals corresponding to the 2B6 and 2S sites at the 1-octene and saturated chain ends, respectively. The integral at 32.2 ppm was assigned to the unresolved signals corresponding to the 3B6 and 3S sites at the 1-octene and saturated chain ends, respectively. The total 1-octene content was used to compensate for the influence of the 2B6 and 3B6 1-octene sites.

[0456] S=(1 / 2)*(I 2S+2B6 +I 3S+3B6 -2*O 总 )

[0457] The content of ethylene comonomers was quantified using the integral of the bulk methylene (bulk) signal at 30.00 ppm. This integral includes the γ and 4B6 sites from 1-octene and the δ + Site. Total ethylene comonomer content was calculated based on the ontological integral and by compensating for observed 1-octene sequences and end groups:

[0458] E 总=(1 / 2)*[I 本体 +2*O+1*OO+3*OEO+0*OOO+3*S]

[0459] It should be noted that since the number of unconsidered and overconsidered ethylene units is equal, there is no need to compensate for the presence of isolated tri-incorporated (EEOOOEE) 1-octene sequences in the bulk integral.

[0460] Therefore, the total molar fraction of 1-octene in the polymer is calculated as follows:

[0461] fO=(O 总 / (E 总 +O 总 )

[0462] The total monomer incorporation of 1-octene, calculated as a percentage by weight in the mole fraction using standard methods:

[0463] O[weight%]=100*(fO*112.21) / ((fO*112.21)+((1-fO)*28.05))

[0464] klimke06

[0465] Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, HW, Wilhelm, M., Macromol. Chem. Phys. 2006; 207:382.

[0466] parkinson07

[0467] Parkinson, M., Klimke, K., Spiess, HW, Wilhelm, M., Macromol. Chem. Phys. 2007; 208:2128.

[0468] parkinson11

[0469] NMR Spectroscopy of Polymers:Innovative Strategies for Complex

[0470] Macromolecules,Chapter 24,401(2011)

[0471] pollard04

[0472] Pollard,M.,Klimke,K.,Graf,R.,Spiess,HW,Wilhelm,M.,Sperber,O.,Piel,C.,Kaminsky,W.,Macromolecules 2004;37:813.

[0473] filip05

[0474] Filip,X.,Tripon,C.,Filip,C.,J.Mag.Resn.2005,176,239

[0475] griffin07

[0476] Griffin,JM,Tripon,C.,Samoson,A.,Filip,C.,and Brown,SP,Mag.Res.inChem.200745,S1,S198

[0477] castignolles09

[0478] Castignolles,P.,Graf,R.,Parkinson,M.,Wilhelm,M.,Gaborieau,M.,Polymer50(2009)2373

[0479] zhou07

[0480] Zhou,Z.,Kuemmerle,R.,Qiu,X.,Redwine,D.,Cong,R.,Taha,A.,Baugh,D.Winniford,B.,J.Mag.Reson.187(2007)225

[0481] busico07

[0482] Busico, V., Carbonniere, P., Cipullo, R., Pellecchia, R., Severn, J., Talarico, G., Macromol.Rapid Commun.2007,28,1128

[0483] randall89

[0484] J.Randall,Macromol.Sci.,Rev.Macromol.Chem.Phys.1989,C29,201.

[0485] here07

[0486] Qiu,X.,Redwine,D.,Gobbi,G.,Nuamthanom,A.,Rinaldi,P.,Macromolecules2007,40,6879

[0487] liu01

[0488] Liu,W.,Rinaldi,P.,McIntosh,L.,Quirk,P.,Macromolecules 2001,34,4757

[0489] The acrylate comonomer content of ethylene-butyl acrylate elastomer was quantified using quantitative nuclear magnetic resonance (NMR) spectroscopy.

[0490] Quantitative recordings were performed in the molten state using a Bruker Avance III 500 NMR spectrometer operating at 500.13 MHz. 1 HNMR spectroscopy. Nitrogen gas was used for all pneumatic devices at 150°C. 13 All spectra were recorded using a C-optimized 7mm magic angle rotation (MAS) probe. Approximately 200 mg of material was loaded into a 7mm outer diameter zirconia MAS rotor and rotated at 4 kHz. This setup was chosen primarily for the high sensitivity required for rapid identification and accurate quantification. A standard single-pulse excitation was used with a 2-second cycle delay. A total of 64 transient values ​​were acquired for each spectrum.

[0491] Quantitative analysis was performed using a customized automated spectral analysis program. 1 The 1H NMR spectra were processed, integrated, and quantitatively determined. All chemical shifts were referenced internally to the bulk ethylene methylene (or bulk ethylene-methyl) signal at 1.33 ppm.

[0492] The attribution of butyl acrylate (BA) inclusion is {brandolini01}:

[0493]

[0494] Considering the number of reporter nuclei for each comonomer, butyl acrylate (BA) incorporation was quantified using the integral of the signal at 4.06 ppm assigned to the 4BA site:

[0495] BA = I 4BA / 2

[0496] Use bulk aliphatic (I) fatty acids between 0.00 and 3.00 ppm. 本体 The ethylene content was quantified by integrating the signal. This integral included sites from isolated butyl acrylate-incorporated 1BA(3), 2BA(2), 3BA(2), *BA(1), and αBA(2) sites, as well as sites from the polyethylene sequence. The total ethylene content was calculated based on the ontological integral and compensation for the aforementioned BA sites.

[0497] E = (1 / 4) * [I] 本体 -10*BA]

[0498] The total mole fraction of butyl acrylate (BA) in the polymer is calculated as follows:

[0499] fBA = BA / (E + BA)

[0500] The total monomer incorporation of butyl acrylate (BA), expressed as a mole percentage, is calculated in the standard manner based on the mole fraction:

[0501] BA [moles %] = 100 * fBA

[0502] The total monomer incorporation of butyl acrylate (BA) in weight percentages is calculated using standard methods based on the mole fraction and molecular weight of the monomers:

[0503] BA [weight %] = 100 * (fBA * 128.17) / ((fBA * 128.17) + ((1 - fBA) * 28.05))

[0504] klimke06

[0505] Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, HW, Wilhelm, M., Macromol. Chem. Phys. 2006; 207:382.

[0506] parkinson07

[0507] Parkinson, M., Klimke, K., Spiess, HW, Wilhelm, M., Macromol. Chem. Phys. 2007; 208:2128.

[0508] pollard04

[0509] Pollard,M.,Klimke,K.,Graf,R.,Spiess,HW,Wilhelm,M.,Sperber,O.,Piel,C.,Kaminsky,W.,Macromolecules 2004;37:813.

[0510] castignolles09

[0511] Castignolles,P.,Graf,R.,Parkinson,M.,Wilhelm,M.,Gaborieau,M.,Polymer50(2009)2373

[0512] brandolini01

[0513] AJ Brandolini, DDHills, "NMR spectra of polymers and polymeradditives", Marcel Deker Inc., 2000

[0514] g) Quantitative analysis of unsaturation using NMR spectroscopy

[0515] The content of unsaturated groups in the polymer was quantified using quantitative nuclear magnetic resonance (NMR) spectroscopy.

[0516] Quantitative data were recorded in solution using a Bruker Avance III 400 NMR spectrometer operating at 400.15 MHz. 1 HNMR spectroscopy. Nitrogen gas was used for all pneumatic devices at 125°C. 13 All spectra were recorded using a C-optimized 10mm selective excitation probe. Approximately 200 mg of material was dissolved in 1,2-tetrachloroethane-d2 (TCE-d2) using approximately 3 mg of Hostanox O3 (CAS 32509-66-3) as a stabilizer. Standard single-pulse excitation was employed with a 30° pulse, a 10 s relaxation delay, and a 10 Hz sample rotation. Four virtual scans were performed, acquiring a total of 128 transient values ​​for each spectrum. This setup was chosen primarily for the high resolution {he10a, busico05a} required for the quantification and stability of vinylidene unsaturation. All chemical shifts were indirectly referenced to the TMS at 0.00 ppm using the signal generated by the residual protonated solvent at 5.95 ppm.

[0517] Characteristic signals corresponding to the presence of terminal aliphatic vinyl groups (R-CH=CH2) were observed, and the amount was quantified using integrals of two coupled, non-equivalent terminal CH2 protons (Va and Vb) at 4.95, 4.98, and 5.00 and 5.05 ppm, taking into account the number of reporter sites for each functional group:

[0518] N-vinyl = IVab / 2

[0519] When a characteristic signal corresponding to the presence of the internal vinylene (RR'C=CH2) is observed, the quantity is quantified by integrating the two CH2 protons (D) at 4.74 ppm, taking into account the number of reporter sites for each functional group:

[0520] N-vinylidene = ID / 2

[0521] When a characteristic signal corresponding to the presence of an internal cis-1,2-vinylidene (E-RCH=CHR') or related structure is observed, the quantity is quantified using the integral of two CH protons (C) at 5.39 ppm, taking into account the number of reporter sites for each functional group:

[0522] Ncis = IC / 2

[0523] When a characteristic signal corresponding to the presence of the internal trans-1,2-vinylidene (Z-RCH=CHR') is observed, the quantity is quantified by integrating the two CH protons (T) at 5.45 ppm, taking into account the number of reporter sites for each functional group:

[0524] Nconversion = IT / 2

[0525] When a characteristic signal corresponding to the presence of an internally trisubstituted -1,2-vinylidene (RCH=CHR'R”) or related structure is observed, the quantity is quantified using the integral of the CH protons (trisubstituted) at 5.14 ppm, taking into account the number of reporter sites for each functional group:

[0526] N-trisubstituted = I-trisubstituted

[0527] The Hostanox 03 stabilizer was quantified using the integrals of the multistates of aromatic protons (A) at 6.92, 6.91, 6.90, and 6.89 ppm, taking into account the number of reporter sites for each molecule.

[0528] H = IA / 4

[0529] Just as unsaturation is typically quantified in polyolefins, the amount of unsaturation is determined relative to the total number of carbon atoms, even through... 1 Quantification is achieved using 1H NMR spectroscopy. This allows for direct quantification from... 13The quantities of other microstructures obtained by C NMR spectroscopy were directly compared.

[0530] The total amount of carbon atoms was calculated by integrating the bulk aliphatic signal between 2.85 and -1.00 ppm, which compensated for the methyl signal from carbon atoms associated with stabilizers and unsaturated functional groups not included in this region:

[0531] NC total = (I bulk – 42*H) / 2 + 2*N vinyl + 2*N vinylene + 2*N cis + 2*N trans + 2*N trisubstituted

[0532] The content of unsaturated groups (U) is calculated as the number of unsaturated groups in the polymer per thousand total carbon atoms (kCHn):

[0533] U = 1000 * N / NC total

[0534] The total number of unsaturated groups is calculated as the sum of all observed unsaturated groups and is therefore reported relative to each thousand total carbons:

[0535] Utotal = Uvinyl + Uvinylidene + Ucis + Utrans + Utrisubstituted

[0536] The relative content (U) of a specific unsaturated group is reported as a fraction or percentage of a given unsaturated group relative to the total amount of unsaturated groups:

[0537] [U] = Ux / U total

[0538] he10a

[0539] He,Y.,Qiu,X,and Zhou,Z.,Mag.Res.Chem.2010,48,537-542.

[0540] busico05a

[0541] Busico,V.et.al.Macromolecules,2005,38(16),6988-6996

[0542] h) rheological parameters

[0543] Characterization of polymer melts by dynamic shear measurements conformed to ISO standards 6721-1 and 6721-10. Measurements were performed on an Anton Paar MCR501 stress-controlled rotational rheometer equipped with a 25 mm parallel plate geometry. Measurements were taken on a compression plate using a nitrogen atmosphere and with strain set within the linear viscoelastic range. Oscillatory shear tests were conducted at 190 °C with a frequency range between 0.01 and 600 rad / s and a gap of 1.3 mm.

[0544] In dynamic shear experiments, the probe undergoes uniform deformation under sinusoidally varying shear strain or shear stress (strain-controlled mode and stress-controlled mode, respectively). In controlled strain experiments, the probe is subjected to sinusoidal strain that can be expressed by the following equation:

[0545] γ(t)=γ0 sin(ωt) (1)

[0546] If the applied strain is within the linear viscoelastic range, the resulting sinusoidal stress response can be given by the following equation:

[0547] σ(t)=σ0 sin(ωt+δ) (2)

[0548] Where σ0 and γ0 are the stress and strain amplitudes, respectively; ω is the angular frequency; δ is the phase shift (the loss angle between the applied strain and the stress response); and t is time.

[0549] Dynamic test results are typically represented by several different rheological functions, namely shear storage modulus G', shear loss modulus G”, complex shear modulus G*, complex shear viscosity η*, dynamic shear viscosity η', heterogeneous component of complex shear viscosity η”, and loss tangent tanη, which can be expressed as follows:

[0550]

[0551]

[0552] G*=G'+iG“[Pa] (5)

[0553] η*=η'-iη"[Pa·s] (6)

[0554]

[0555]

[0556] The determination of the so-called shear thinning index, which is related to MWD but independent of Mw, is carried out as described in Equation 9.

[0557]

[0558] For example, SHI (2.7 / 210) The complex viscosity is defined by dividing the complex viscosity value (in Pa·s) determined by the G* value equal to 2.7 kPa by the complex viscosity value (in Pa·s) determined by the G* value equal to 210 kPa.

[0559] Accordingly, SHI (1 / 100)The viscosity is defined by dividing the complex viscosity value (in Pa·s) determined by the G* value equal to 1 kPa by the complex viscosity value (in Pa·s) determined by the G* value equal to 100 kPa.

[0560] As a function of frequency (ω), the values ​​of storage modulus (G'), loss modulus (G"), complex modulus (G*), and complex viscosity (η*) were obtained.

[0561] Therefore, for example, η* 300rad / s (eta* 300rad / s η* is used as an abbreviation for complex viscosity at a frequency of 300 rad / s. 0.05rad / s (eta* 0.05rad / s It is used as an abbreviation for complex viscosity at a frequency of 0.05 rad / s.

[0562] The loss tangent tan(δ) is defined as the ratio of the loss modulus (G") to the storage modulus (G') at a given frequency. Therefore, for example, tan... 0.05 Tandem is used as an abbreviation for the ratio of loss modulus (G') to storage modulus (G') at 0.05 rad / s. 300 It is used as an abbreviation for the ratio of loss modulus (G") to storage modulus (G') at 300 rad / s.

[0563] Elastic balance tan 0.05 / tan 300 Defined as the loss tangent tan 0.05 tan and loss angle 300 than.

[0564] In addition to the rheological functions mentioned above, other rheological parameters can be determined, such as the so-called elasticity index EI(x). The elasticity index Ei(x) is the value of the storage modulus (G') determined by the value of the loss modulus (G'') for x kPa, and can be described by Equation 10.

[0565] For (G″=x kPa), EI(x)=G′[Pa] (10)

[0566] For example, EI(5kPa) is defined by the value of the energy storage modulus (G') determined by the value of G” equal to 5kPa, EI(2kPa) is defined by the value of the energy storage modulus (G') determined by the value of G” equal to 2kPa, and EI(0.5kPa) is defined by the value of the energy storage modulus (G') determined by the value of G” equal to 0.5kPa.

[0567] The multidispersion index PI is defined by Equation 11.

[0568] For (G'=G''), ω COP =ω (11)

[0569] Where ω COP It is the cross angular frequency, which is determined to be the angular frequency when the energy storage modulus G' is equal to the loss modulus G".

[0570] These values ​​were determined using a single-point interpolation procedure defined by the Rheoplus software. In cases where the experiment did not reach a given G* value, the value was determined by extrapolation, using the same procedure as before. In both cases (interpolation or extrapolation), the options "Interpolate y-values ​​to x-values ​​from parameters" and "Logarithmic interpolation type" in Rheoplus were applied.

[0571] References:

[0572] [1]"Rheological characterization of polyethylene fractions",Heino,EL,Lehtinen,A.,Tanner J., J., Neste Oy, Porvoo, Finland, Theor.Appl.Rheol., Proc.Int.Congr.Rheol, 11th (1992), 1, 360-362.

[0573] [2] "The influence of molecular structure on some rheological properties of polyethylene", Heino, EL, Borealis Polymers Oy, Porvoo, Finland, Annual Transactions of the Nordic Rheology Society, 1995.

[0574] [3] "Definition of terms relating to the non-ultimate mechanicalproperties of polymers",Pure&Appl.Chem.,Vol.70,No.3,pp.701-754,1998.

[0575] i) Dynamic mechanical thermal analysis (DMTA)

[0576] Storage modulus G' and glass transition temperature T were measured by DMTA analysis. gDMTA evaluation and storage modulus G' measurement of compression-molded samples were performed in torsion mode at temperatures between -130°C and +150°C, according to ISO 6721-02 and ISO 6721-07, using a heating rate of 2°C / min and a frequency of 1Hz. Measurements were performed using an Anton Paar MCR 301 instrument. The compression-molded samples had the following dimensions: 40 × 10 × 1 mm, and were prepared according to ISO 1872-2:2007. The storage modulus G′23 was measured at 23°C.

[0577] 2. Components of the polymer composition

[0578] The following components are used to produce the polymer compositions of the examples:

[0579] PE1:

[0580] The terpolymer of ethylene, 1-butene, and 1-hexene was polymerized in a continuous multi-stage polymerization process using a single-active-center catalyst prepared as follows: after a loop reactor, the polymerization was carried out in a gas-phase reactor.

[0581] 130 g of the metallocene complex bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride (IV) (CAS No. 151840-68-5) and 9.67 kg of a 30% toluene solution of commercially available methylaluminoxane (MAO) were mixed, and 3.18 kg of dry, purified toluene was added. The resulting complex solution was then added to 17 kg of a silica support, Sylopol 55SJ (supplied by Grace), by very slow, uniform spraying over 2 hours. The temperature was maintained below 30 °C. After the complex was added at 30 °C, the mixture was allowed to react for 3 hours.

[0582] The loop reactor was operated at a temperature of 85°C and a pressure of 64 bar. Ethylene and 1-butene comonomers, hydrogen, and catalyst were introduced into the reactor together, such that the molar ratio of hydrogen to ethylene was 0.2 mol / kmol, and the molar ratio of 1-butene to ethylene was 98.4 mol / kmol.

[0583] Slurry was intermittently pumped from the loop reactor using a settling leg and directed to a flash evaporator operating at 50°C and 3 bar. From there, the polymer was directed to a gas-phase reactor (GPR) operating at 20 bar and 75°C. Ethylene comonomer and hydrogen were introduced into the reactor together, such that the molar ratio of hydrogen to ethylene was 0.4 mol / kmol and the ratio of 1-hexene to ethylene was 12.2 mol / kmol.

[0584] The polymerization conditions and polymer properties of PE1 are shown in Tables 2 and 3 below.

[0585] PE2: A copolymer of ethylene and 1-octene was polymerized in solution polymerization using the Ziegler-Natta catalyst described in Example III of WO 95 / 09191A. The average catalyst / donor feed in the reactor was BOMAG, SEAC, and TBT. The average catalyst / donor feed in the reactor was BOMAG, SEAC, TBT, 2-chlorobutane, and TEA as an activator. The resulting copolymer had a density of 935 kg / m³. 3 The MFR2 was 7.3 g / 10 min, and the melt temperature Tm was 124 °C. The polymerization conditions and polymer properties are shown in Tables 1 and 3 below.

[0586] Elastomer 1: Queo 6201LA-P, ethylene-1-octene elastomer, commercially available from Borealis AG.

[0587] Elastomer 2: Engage 8842, ethylene-1-octene elastomer, available from Dow Corporate.

[0588] EBA ethylene-butyl acrylate elastomer, which has a butyl acrylate content of 27% by weight and a strength of 927 kg / m³. 3 The density and MFR2 value at 4 g / 10min. The properties of elastomers 1, 2 and EBA are listed in Table 4 below.

[0589] MAH (maleic anhydride) is used as an acidic grafting agent.

[0590] POX was prepared by Akzo Nobel using Perkadox 14S-fl (10 wt% dissolved in isodecane) as a free radical initiator.

[0591] Table 1: Polymerization conditions of PE2

[0592] PE2 Aggregation conditions: C(8-1) / C2 ratio [kg / kg] 0.25 Reactor temperature [°C] 200.0 <![CDATA[H2 / C2 ratio [Nm 3 / t]]]> 0.75 C2 conversion rate [%) 95.00 Exit temperature deep cooling [°C] -30.0 Absorption rate C6 / C2 [kg / kg] 4.6 iPCl concentration in monomer stream [mg / l] 2.5

[0593] Table 2: Polymerization conditions and properties of PE1

[0594] PE1 Aggregation conditions: <![CDATA[ Loop reactor ]]> Temperature [°C] 85 Pressure [kPa] 5316 H2 / C2 ratio [mol / kmol] 0.2 C4 / C2 ratio [mol / kmol] 98.4 Split ratio [%] 41.6 <![CDATA[Density [kg / m 3 > 939 <![CDATA[MFR2[g / 10min]]]> 4.8 <![CDATA[ gas phase reactor ]]> Temperature [°C] 75 Pressure [kPa] 2000 H2 / C2 ratio [mol / kmol] 0.4 C6 / C2 ratio [mol / kmol] 12.2 Split ratio [%) 58.4 <![CDATA[Density [kg / m 3 > 932 <![CDATA[MFR2[g / 10min]]]> 5.2

[0595] Table 3: Performance of PE1, PE2 and EBA

[0596] Polymer properties: PE1 PE2 <![CDATA[Density (kg / m 3 )]]> 932 935 <![CDATA[MFR2[g / 10min]]]> 5.2 6.5 Tm[℃] / Hf[J / g] 123.1 / 148 125.4 / 155 Tc[℃] / Hc[J / g] 108.8 / 149 111.7 / 163 Mn(LS)[g / mol](GPC-VISC-LS) 26000 20000 Mw(LS)[g / mol](GPC-VISC-LS) 56800 69000 Mz(LS)[g / mol](GPC-VISC-LS) 94500 217000 PDI(Mw / Mn)(LS)(GPC-VISC-LS) 2.2 3.5 %C4 [weight%] 0.6 --- %C6 [weight%] 2.7 --- %C8 [weight%] --- 3.5 Vinyl / 1000C [wt%] 5.3 30.5 Vinylidene / 1000C [wt%] 3.8 3.8 Trisubstituted / 1000C [wt%] 6.3 0 cis-1,2-vinylidene / 1000C [wt%] 0 0 trans-1,2-vinylidene / 1000C [wt%] 2.0 0 Total unsaturation / 1000C [wt%] 17.3 32.8

[0597] nd = Undetermined

[0598] Table 4: Performance of Elastomers 1 and 2 and EBA

[0599]

[0600] The following feeds of the components listed in Table 5 are used to produce the adhesive polymer components of the embodiments:

[0601] Table 5: Feed of polymer compositions used in the production examples

[0602] CE1 IE1 IE2 CE2 IE3 IE4 IE5 CE3 IE6 PE1 [wt%] 73.8 73.8 73.8 --- --- --- --- --- --- PE2 [wt%] --- --- --- 73.8 73.8 73.8 73.8 73.8 73.8 Elastomer 1 [wt%] --- 26.0 --- --- 26.0 26.0 --- --- 26.0 Elastomer 2 [wt%] --- --- 26.0 --- --- --- 26.0 --- --- EBA [weight %] 26.0 --- --- 26.0 --- --- --- 26.0 --- MAH [weight %] 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 POX solution feed [g / min] 0.7 0.5 0.6 0.7 0.5 0.6 0.5 0.6 0.4

[0603] 3. Blending and grafting of the polymer compositions of the examples

[0604] The polymer composition of the grafting example was compounded in a Werner & Pfleiderer ZSK 30 co-rotating twin-screw extruder with an L / D of 38 and 6 temperature control sections.

[0605] In the embodiments of the present invention IE1 to IE5 and comparative examples CE1 and CE2, constant temperature distribution in the control zone was used for mixing, starting from a temperature of 180°C in the control zone, and the temperature in control zones 2 to 6 and the template was about 200°C.

[0606] In the control zone of the extruder, Example IE6 of the present invention and Comparative Example CE3 were compounded with a temperature distribution that began at a lower temperature of 160°C in control zone 1 and increased to 200°C in control zone 4. The temperature was then slightly increased to 210°C in subsequent control zones, specifically control zone 6 and the die.

[0607] Embodiment IE4 of the present invention is a repetition of Embodiment IE3 of the present invention. The only difference is that a lower screw speed of 200 rpm is used compared to 230 rpm, so as to better compare with IE6 and CE3, which also use a screw speed of 200 rpm for mixing.

[0608] The following mixing conditions were used in the examples, and the resulting adhesive polyethylene compositions obtained the following properties, as listed in Table 6 below.

[0609] The polymer compositions of Examples CE1-3 and IE1-6 prepared above were subjected to GPC measurement and GPC-VISC-LS analysis. Figure 1 The LS 15 signals obtained from GPC-VISC-LS analysis of embodiments CE1, IE1, and IE2 are shown. Figure 2 The LS 15 signals obtained from GPC-VISC-LS analysis of embodiments CE2, IE3, IE4 and IE5 are shown. Figure 3 The LS 15 signals obtained from GPC-VISC-LS analysis of Examples CE3, IE6, and IE4 are shown.

[0610] As can be observed from all the figures, the present invention embodiments that typically contain vinyl elastomers differ from the comparative examples that contain polar elastomers in that they exhibit only one distinct peak.

[0611] exist Figure 1 The diagram shows GPC data for Examples IE1, IE2, and CE1, all of which comprise the ethylene-1-octene non-elastomeric copolymer PE2. Examples IE1 and IE2 differ in their vinyl plastidity, but show comparable GPC curves with a single prominent peak, compared to the two distinct peaks of CE1.

[0612] exist Figure 2 The GPC data for Examples IE3, IE4, IE5, and CE2 are shown, all of which contain ethylene-1-butene-1-hexene non-elastomeric terpolymer PE1. Compared to the two distinct peaks in CE2, the examples of the present invention still show one distinct peak. IE3 and IE4 have the same composition and grafting process including plasmid 1, differing only in their screw speeds. Comparable GPC curves are shown for these examples. IE5 differs from IE3 and IE4 in that it contains plasmid 2 and exhibits a significant tailing at high molecular weights in its GPC curve, primarily understood as a higher Mz value.

[0613] exist Figure 3 In this study, the GPC data of the examples (IE6, CE3) prepared using a temperature-promoted distribution were compared with those of example IE4 of the present invention. The only difference between example IE4 and IE6 was that they were prepared using an isothermal distribution. As a key difference, a slight shoulder was observed at the high molecular weight in IE6, which is mainly understood to be a higher Mz value. Similarly, the present invention examples containing vinyl elastomers differed from comparative example CE3 in that they exhibited only one distinct peak.

[0614] Molecular weights Mw, Mn, Mz and PDI (Mw / Mn) are listed in Table 6 below.

[0615] Table 6: Mixing conditions and properties of the composition

[0616]

[0617]

[0618] nd = Undetermined

[0619] 4. Pipe coating

[0620] The polymer composition prepared as described above is used as the adhesive polymer composition in the adhesive layer of a three-layer pipe coating.

[0621] First, steel pipes with a diameter of 114.3 mm and a wall thickness of 5 mm are heated on a rotary steel pipe production line at a linear speed of 9 m / min and a temperature set at 200-220°C, and then coated with epoxy resin powder for corrosion protection. Subsequently, the polymer composition prepared above and conventional high-density polyethylene are co-extruded onto the epoxy resin layer as an adhesive layer and an outer protective layer. The co-extrusion is performed using a KM-45 single-screw extruder for the high-density polyethylene topcoat and an Extron 50 single-screw extruder for the polymer composition prepared above. The temperature at the extrusion die of the polymer composition is 215°C. The temperature at the extrusion die of the high-density polyethylene composition is 215°C.

[0622] The target layer thickness is as follows:

[0623] Epoxy resin layer: 150μm

[0624] Adhesive layer: 480μm

[0625] Protective outer layer: 4.2mm

[0626] Use a silicone roller to press both the adhesive layer and the protective outer layer firmly onto the coating surface.

[0627] As described in Table 7 below, two different cooling procedures are applied to the coated pipes.

[0628] Table 7: Cooling Procedure

[0629] Normal cooling Brief cooling Epoxy resin layer on hot steel pipe 190℃ 190℃ Adhesive layer on epoxy resin layer 225℃ 225℃ outer layer on adhesive layer 250℃ 250℃ Water cooling Up to 40℃ Up to 85℃ Cooling in ambient air Until 23℃ Until 23℃

[0630] In both cooling procedures, the coated pipes undergo a water cooling step, in which the pipes are cooled in a spray chamber until a target temperature of approximately 40°C is achieved for normal cooling and a target temperature of approximately 85°C for short-term cooling. In the short-term cooling procedure, the water cooling step is significantly shortened compared to the normal cooling procedure, reaching approximately 85°C until the pipes reach a temperature of approximately 40°C, instead of the approximately 40°C required in the normal cooling procedure, to simulate a faster linear velocity through the cooling bath. Instead, the coated pipes are removed from the spray chamber and cooled from approximately 80°C to approximately 23°C in ambient air, which takes approximately 90 to 120 minutes. In the normal cooling procedure, the pipes cooled to approximately 40°C in the water cooling step are also removed from the spray chamber and cooled from approximately 40°C to approximately 23°C in ambient air.

[0631] After cooling, the peel strength of the pipe coating was tested at 23℃ and 80℃. The results are shown in Table 8 below.

[0632] Table 8: Peel strength of pipe coating

[0633]

[0634] It can be seen that, compared with coatings containing adhesive layers made of comparative polymer compositions CE1 to CE3 using EBA instead of vinyl elastomers, coatings containing adhesive layers made of polymer compositions IE1 to IE6 according to the invention all exhibited higher peel strength at 23°C after a short cooling procedure.

[0635] Among them, compared with the present invention embodiments IE1 and IE2 which use ethylene-1-octene copolymer as non-elastomeric polyethylene, the present invention embodiments IE3 to IE6 which use ethylene-1-butene-1-hexene terpolymer as non-elastomeric polyethylene showed further improved peel strength properties at 23°C and 80°C under all conditions after normal cooling and short cooling procedures.

[0636] Among them, compared with the elastomer 1 used in embodiments IE1, IE3 and IE4 of the present invention, the elastomer 2 used in embodiments IE2 and IE5 of the present invention has a better effect on the peel strength at 23°C and 80°C, especially after short-term cooling.

[0637] Compared to the grafting process with constant temperature distribution in the barrel section of the extruder (IE4), the grafting process with heated distribution in the barrel section of the extruder (IE6) showed improved peel strength at 80°C after a short cooling process.

Claims

1. An adhesive polyethylene composition comprising... (A) 60 to 90% by weight of non-elastomeric polyethylene; (B) 9.0 to 38% by weight of a vinyl elastomer, wherein the vinyl elastomer is a copolymer of ethylene and 1-octene; The acidic grafting agent (C) has been grafted onto components (A) and (B) in amounts ranging from 0.01 to 3.0% by weight, all amounts being based on the total weight of the adhesive polyethylene composition.

2. The adhesive polyethylene composition according to claim 1, wherein the non-elastomeric polyethylene is a copolymer of ethylene and one or more comonomer units selected from α-olefins having 4 to 12 carbon atoms.

3. The adhesive polyethylene composition according to claim 1 or 2, wherein the vinyl elastomer has a content of 840 to 900 kg / m³. 3 The density.

4. The adhesive polyethylene composition according to claim 1 or 2, wherein the acidic grafting agent (C) is selected from unsaturated carboxylic acids or derivatives thereof.

5. The adhesive polyethylene composition according to claim 1 or 2, having a polydispersity index (PDI) of 1.5 to 4.5 as determined by GPC-VISC-LS analysis, i.e., a Mw / Mn ratio.

6. The adhesive polyethylene composition according to claim 1 or 2, wherein the elastic index EI at a loss modulus G'' = 0.5 kPa is 75 to 320 Pa.

7. The adhesive polyethylene composition according to claim 1 or 2, wherein it has only one peak in the GPC curve, the GPC curve being defined as the concentration-normalized LS 15 signal of molecular weight along conventional GPC obtained from GPC-VISC-LS analysis.

8. The adhesive polyethylene composition according to claim 1 or 2, wherein the non-elastomeric polyethylene is a copolymer of ethylene and a comonomer selected from α-olefins having 4 to 12 carbon atoms.

9. The adhesive polyethylene composition according to claim 1 or 2, wherein the non-elastomeric polyethylene is a terpolymer of ethylene and two comonomers selected from α-olefins having 4 to 12 carbon atoms.

10. The adhesive polyethylene composition according to claim 1 or 2, which can be obtained by a method comprising the following steps. - Components (A), (B) and (C) are fed into an extruder, into the feed section of the extruder, which includes a feed section, a barrel section and a die, wherein the barrel section of the extruder downstream of the feed section and upstream of the die is divided into multiple control zones, and a first control zone is defined as a first control zone within the barrel section downstream of the feed section, in which the fed components (A) and / or (B) begin to melt; - The components (A) and (B) are compounded in the extruder to form the adhesive polyethylene composition; and - During the mixing step, components (A) and (B) are grafted with component (C).

11. The adhesive polyethylene composition of claim 10, wherein the temperature of the second to last control zones in the barrel section remains constant in all of these control zones, with a total deviation not exceeding 20°C.

12. The adhesive polyethylene composition of claim 10, wherein the method further comprises the following steps: - Independently control the temperature of each of the plurality of control zones in the barrel section of the extruder, such that a) The temperature in the first control zone of the barrel section downstream of the feed section is in the range of 85°C to 180°C. b) The temperature of the control zone of the barrel section from the first control zone downstream of the feed section to the control zone in the middle of the barrel section increases in two or more steps along the length of the barrel section, such that the temperature of the control zone in the middle of the barrel section is 105% to 145% of the temperature of the first control zone of the barrel section downstream of the feed section; and c) The temperature of the control zone of the barrel section from the middle of the barrel section to the control zone of the barrel section directly upstream of the template is maintained at the same temperature, or increased to a temperature not exceeding 120% of the temperature of the control zone in the middle of the barrel section.

13. A multilayer structure comprising a layer containing an adhesive polyethylene composition according to any one of claims 1 to 12.

14. The multilayer structure according to claim 13 is a three-layer coating of a metal tube.

15. The multilayer structure according to claim 13 or 14, wherein the peel strength at 23°C is at least 350 N / cm and / or the peel strength at 80°C is at least 60 N / cm.

16. Use of the adhesive polyethylene composition according to any one of claims 1 to 12 for the production of multilayer structures.

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