Ethylene-octene copolymers with improved performance characteristics

Abstract

The present invention provides an ethylene-octene copolymer with improved performance characteristics having an improved balance of unsaturation levels, Mw / Mn, and MFR10 / MFR2 ratios.

Description

[0001] This application is a divisional application of the invention patent application with the application date of September 27, 2021, the application number of 202180065233.8, and the invention name of "Ethylene-octene copolymer with improved performance characteristics". Technical Field

[0002] The present invention relates to ethylene-1-octene copolymers having improved performance characteristics, such as an improved balance of unsaturation level, molecular weight distribution (MWD), and MFR / MFR2 ratio. The present invention further relates to a solution polymerization process for preparing these ethylene-1-octene copolymers using a specific catalyst system. The present invention also relates to the use of these ethylene-1-octene copolymers for grafting and / or crosslinking. 10 / MFR2 ratio improvement balance. The present invention further relates to a solution polymerization process for preparing these ethylene-1-octene copolymers using a specific catalyst system. The present invention also relates to the use of these ethylene-1-octene copolymers for grafting and / or crosslinking. Background Art

[0003] For many years, there have been many types of polyethylene polymers obtained by polymerization, including those obtained using high-pressure free radical chemical reactions (LDPE), more traditional linear low-density polyethylene (LLDPE) typically made using Ziegler-Natta catalysis and metallocenes, or polyethylene made using constrained geometry catalysis - some linear polyethylenes, but also some polyethylenes that are substantially linear with a small amount of long-chain branching. Although these polymers have different pros and cons (depending on the application or end use), there is still a need for more control over the polymer structure.

[0004] Ethylene polymers are one of the polymers commonly used for crosslinking. It is well known that certain properties of ethylene polymers, including those that can affect crosslinking efficiency (i.e., crosslinking rate and degree), may vary depending on the type of polymerization process, such as high-pressure polymerization or low-pressure polymerization processes, process conditions, and especially when using low-pressure polymerization, the catalyst used in the process.

[0005] For example, polyethylene has typical characteristic molecular weight distribution (MWD = Mw / Mn), comonomer distribution, so-called long-chain branching (LCB), and / or unsaturation, which depend on the type of catalyst used in the polymerization reaction, such as Ziegler-Natta, Cr, or single-site catalysts. These variable properties, namely MWD and unsaturation (and its type), may have an impact on crosslinking efficiency. In addition, a narrow MWD sacrifices the processing of the polymer.

[0006] Unsaturated structures in polyolefin polymers are important in many aspects. In the past 50 years, a considerable number of authors have studied the effects of different structural properties of various polyethylene types on crosslinking reactions, which have partly led to different conclusions.

[0007] These properties include the degree of unsaturation, type of unsaturation, MFR, crystallinity and degree of branching, as well as the concentration of added peroxide, to name only the most important examples. The degree of unsaturation has a significant effect on the degree of crosslinking, although it is not the only factor that has to be considered. Empirically, it can be expected that the higher the number of double bonds in the uncrosslinked polyethylene, the better the crosslinking properties. However, the type of unsaturated bond is also important, due to the different accessibility of the various unsaturated bonds and the different stability of the intermediate free radicals.

[0008] Crosslinking can be achieved by different methods. The three most important and widely used methods are crosslinking by a) peroxide treatment, b) silane treatment, c) using high energy radiation. All these processes are more or less affected by the different structures and functional groups of the polymer. These include the degree and type of unsaturation, the degree and type of branching, the degree of crystallization, the concentration and type of peroxide. The type and amount of these structures generated in pure polyethylene resins are controlled by the production process and its conditions, the catalyst, and the type and amount of comonomer and hydrogen introduced.

[0009] EP 2580279 discloses ethylene polymers having less than 12 total unsaturated units / 100,000C, less than 2 vinylidene unsaturated units / 100,000C, and less than 2 trisubstituted unsaturated units / 100,000C. These polymers are produced with a post-metallocene catalyst, which allows control of the unsaturation level in the polymer.

[0010] EP 885255 discloses crosslinking using an ethylene polymer having less than 0.30 vinylidene unsaturated units / 1000 carbon atoms. The MWD of the polymers of the invention examples is at most 2.04.

[0011] EP 2256158 describes ethylene polymers produced with a Ziegler-Natta catalyst, which have a number of carbon-carbon double bonds greater than 0.2 carbon-carbon double bonds / 1000 carbons (i.e., greater than 20 / 100,000C). The term "number of carbon-carbon double bonds" is defined as the sum of vinyl, vinylidene, and trans vinylidene / 1000 carbon atoms.

[0012] The amount of vinyl unsaturation should be at least 0.19 vinyl / 1000C (at least 19 / 100,000C).

[0013] Although several ethylene polymers with specific unsaturation levels have been described in the prior art and are also suitable for crosslinking, there is still a need in the polymer art to find improved polymer solutions with improved performance characteristics, such as an improved balance of unsaturation level, Mw / Mn, and MFR 10 / MFR2 ratio.

[0014] There is still a need for unsaturated poly-α-olefin materials, especially as intermediate materials for the production of functionalized poly-α-olefins. SUMMARY OF THE INVENTION

[0015] Accordingly, an object of the present invention is to provide ethylene-1-octene copolymers having such improved performance characteristics.

[0016] A specific object of the present invention is to provide ethylene-1-octene copolymers having an improved balance of unsaturation level, Mw / Mn, and MFR 10 / MFR2 ratio.

[0017] A further object is to provide ethylene-1-octene copolymers for crosslinking and / or grafting with comonomer units having hydrolyzable silyl groups.

[0018] A further object is to provide a solution polymerization process for preparing such copolymers using a specific catalyst system.

[0019] Accordingly, the present invention provides an ethylene-1-octene copolymer, characterized in that

[0020] a) a density in the range of 850 kg / m 3 to 930 kg / m 3 as measured according to ISO 1183-187,

[0021] b) a melt flow rate MFR2 (190 °C, 2.16 kg) in the range of 0.3 g / 10 min to 100 g / 10 min as measured according to ISO 1133,

[0022] c) an MFR 10 / MFR2 of 5.0 to 15.0,

[0023] d) an Mw / Mn of 2.0 to 5.0,

[0024] e) from 1.0 to less than 20.0 vinyl unsaturated units per 100,000 C atoms,

[0025] f) more than 5.0 to 35.0 vinylidene unsaturated units per 100,000 C atoms,

[0026] g) more than 5.0 to 30.0 tri-substituted unsaturated units per 100,000 C atoms,

[0027] h) more than 15.0 to 60.0 trisubstituted unsaturated units per 100,000 C atoms (all of e) to h) are measured by 1H NMR),

[0028] i) 26 to 150 total unsaturated units per 100,000 C atoms, where the total unsaturated units per 100,000 C atoms is the sum of vinyl unsaturated units per 100,000 C atoms, vinylidene unsaturated units per 100,000 C atoms, vinylene unsaturated units per 100,000 C atoms, and trisubstituted unsaturated units per 100,000 C atoms, all measured by 1H NMR,

[0029] j) The degree of unsaturation obtained according to the following formula

[0030]

[0031] The vinyl unsaturation is in the range of 5.0% to 15.0%,

[0032] The vinylene unsaturation is in the range of 20.0% to 30.0%, and

[0033] k) where the sum of the vinyl unsaturation and the vinylidene unsaturation is at least 30.0% up to 50.0%.

[0034] The ethylene-octene copolymer has several amazing advantages.

[0035] The ethylene 1-octene copolymer of the present invention shows high degrees of unsaturation not only for different unsaturated types but also simultaneously in the range of the average molecular weight Mw and / or the range of the 1-octene comonomer content.

[0036] In current applications, the different unsaturated types are vinyl unsaturation, vinylidene unsaturation, vinylene unsaturation, and trisubstituted unsaturation. Here, the vinylene unsaturation is the sum of trans-vinylene and cis-vinylene.

[0037] Without being bound by any theory, it is believed that at low temperatures, higher degrees of unsaturation lead to better anti-deformation properties of the polymer.

[0038] In addition, improved crosslinking efficiency can be expected due to the high degree of unsaturation.

[0039] Preferably, the total unsaturated units per 100,000 C of the copolymer follow inequality (I)

[0040] y > -0.0002A + 65.8 (I)

[0041] where y is the total degree of unsaturation per 100,000 C atoms and A is the Mw of the copolymer in g / mol,

[0042] and / or the total unsaturated units per 100,000 C of the copolymer follow inequality (II)

[0043] y > 0.12B + 39.38 (II)

[0044] Wherein, y is the total degree of unsaturation per 100,000 C atoms, and B is the 1-octene content of the copolymer in wt.%.

[0045] More preferably, the total unsaturated units per 100,000 C follow Inequality (I) and the total unsaturated units per 100,000 C follow Inequality (II).

[0046] Preferably, the density measured according to ISO 1183-187 is in the range of 855 kg / m 3 to 920 kg / m 3 range, more preferably 855 kg / m 3 to 915 kg / m 3 .

[0047] Preferably, the ratio of MFR 10 / MFR2 is in the range of 6.0 to 13.0, more preferably 7.0 to 11.0.

[0048] Preferably, the Mw / Mn is in the range of 2.4 to 4.0, more preferably 2.4 to 3.5.

[0049] Preferably, the melt flow rate MFR2 (190 °C, 2.16 kg) is in the range of 0.8 g / 10 min to 90 g / 10 min, more preferably 0.9 g / 10 min to 50 g / 10 min.

[0050] Preferably, the vinyl unsaturated units per 100,000 C atoms are in the range of 5.0 to 19.0, and / or the vinylidene unsaturated units per 100,000 C atoms are in the range of 13.0 to 32.0, and / or the vinylene unsaturated units per 100,000 C atoms are in the range of 8.0 to 23.0, and / or the trisubstituted unsaturated units per 10,000 C atoms are in the range of 22.0 to 51.0.

[0051] The total unsaturated units per 100,000 C atoms are preferably 35 to 135, more preferably 45 to 120.

[0052] Preferably, the vinyl unsaturation is in the range of 7.0% to 17.0%.

[0053] Preferably, the vinylidene unsaturation is in the range of 20.0% to 32.0%, more preferably in the range of 22.0% to 28.0%.

[0054] Preferably, the vinylene unsaturation is in the range of 14.0% to 28.0%.

[0055] Preferably, the trisubstituted unsaturation is in the range of 35.0% to 50%, more preferably in the range of 36.0% to 45.5%.

[0056] Preferably, the sum of the vinyl unsaturation and the vinylene unsaturation is at least 32.0% up to 46.0%.

[0057] The copolymer of the present invention is a copolymer with ethylene and 1-octene as comonomers. Preferably, based on the weight of the total copolymer, the 1-octene is present in an amount of 10 wt.% to 45 wt.%, more preferably 12 wt.% to 43 wt.%, and most preferably 15 wt.% to 41 wt.%.

[0058] The present invention further provides a method for producing the ethylene-1-octene copolymer according to the present invention.

[0059] Therefore, the present invention provides a method for preparing the ethylene-1-octene copolymer according to the present invention, which is a continuous high-temperature solution method with a temperature of 120 °C to 250 °C and a pressure of 50 bar to 300 bar, and the method includes at least the following steps:

[0060] (A) In the presence of a first polymerization catalyst and an optional chain transfer agent, in at least a first polymerization reactor, polymerize an ethylene monomer and a 1-octene comonomer in a first solvent to produce a first solution containing a first ethylene-1-octene copolymer and the first solvent;

[0061] wherein the first solvent, the ethylene monomer, and the 1-octene comonomer are provided in a first feed stream; and

[0062] wherein the first polymerization reactor operates under operating conditions that ensure the contents of the reactor form a single homogeneous phase,

[0063] (B) Extract a first stream of the first solution from the first polymerization reactor,

[0064] (C) Separate the first ethylene-1-octene copolymer from the first stream of step (B),

[0065] wherein the first polymerization catalyst comprises:

[0066] (i) at least one metallocene complex of formula (I)

[0067]

[0068] wherein

[0069] M is hafnium,

[0070] R's are the same or different and can be saturated straight-chain or branched C1-C10 alkyl groups, preferably all R's are the same and are straight-chain or branched C1-C3 alkyl groups, more preferably all R's are C1 alkyl groups, R 1 is an unsubstituted C6-C10 aryl group, preferably phenyl, and

[0071] R 2 is a C4-C20 cycloalkyl group or a C4-C6 alkenyl group,

[0072] X is a C1-C6 alkyl group, preferably methyl, and

[0073] (ii) a boron-containing cocatalyst.

[0074] Preferably, the method according to the present invention further comprises the following steps:

[0075] (D) Polymerizing an ethylene monomer and a 1-octene comonomer in a second polymerization reactor in the presence of a second polymerization catalyst and an optional chain transfer agent in a second solvent to produce a second solution comprising a second ethylene-1-octene copolymer and the second solvent;

[0076] wherein the second solvent, the ethylene monomer and the 1-octene comonomer are provided in a second feed stream; and

[0077] (E) Extracting a second stream of the second solution from the second polymerization reactor,

[0078] (F) Separating the second ethylene-1-octene copolymer from the second stream, and

[0079] (G) Combining the first ethylene-1-octene copolymer of step (C) with the second ethylene-1-octene copolymer of step (F),

[0080] wherein the second polymerization catalyst comprises:

[0081] (i) at least one metallocene complex of formula (I)

[0082]

[0083] wherein

[0084] M is hafnium,

[0085] R's are the same or different and can be saturated straight-chain or branched C1-C10 alkyl groups, preferably all R's are the same and are straight-chain or branched C1-C3 alkyl groups, more preferably all R's are C1 alkyl groups, R 1 is an unsubstituted C6-C10 aryl group, preferably phenyl, and

[0086] R 2 is a C4 to C20 cycloalkyl or a C4 to C6 alkenyl,

[0087] X is a C1 to C6 alkyl, preferably methyl, and

[0088] (ii) a boron-containing cocatalyst, and

[0089] wherein, the first polymerization catalyst and the second polymerization catalyst may be the same as or different from each other.

[0090] If a first polymerization reactor and a second polymerization reactor are used in the method according to the invention, the first polymerization reactor and the second polymerization reactor operate in a parallel configuration for preparing the copolymer according to the invention.

[0091] The temperature in the one or more polymerization reactors (i.e., the first polymerization reactor and the second polymerization reactor) is such that the copolymer formed in the polymerization reaction is completely dissolved in the reaction mixture comprising the solvent, comonomer, optional chain transfer agent, and copolymer.

[0092] The temperature is suitably higher than the melting temperature of the copolymer according to the invention. Thus, the temperature is suitably from 120 °C to 220 °C, such as from 150 °C to 200 °C, depending on the content of comonomer units in the copolymer.

[0093] The pressure in the one or more polymerization reactors (i.e., the first polymerization reactor and the optional second polymerization reactor) depends, on the one hand, on the temperature and, on the other hand, on the type and amount of hydrocarbons (i.e., comonomer, monomer, and solvent). The pressure in the first polymerization reactor and the optional second polymerization reactor is suitably from 50 bar to 300 bar, preferably from 50 bar to 250 bar, more preferably from 70 bar to 200 bar.

[0094] The first polymerization reactor and the optional second polymerization reactor operate under operating conditions (such as temperature and pressure) to ensure that the contents of the reactor in each polymerization reactor form a single homogeneous phase, and the contents of the reactor comprise the ethylene monomer, 1-octene comonomer, solvent, optional chain transfer agent, and copolymer product.

[0095] The first polymerization reactor and the optional second polymerization reactor are preferably selected from the group consisting of tubular reactors, stirred autoclaves, tank reactors, loop reactors, or a combination thereof.

[0096] The residence time is short, usually less than 15 minutes.

[0097] The method is run continuously. Thus, the feed streams of monomer, comonomer, catalyst, solvent and optionally chain transfer agent are all fed continuously to the one or more polymerization reactors, i.e., to the first polymerization reactor and the optional second polymerization reactor.

[0098] There is a first solvent and preferably a second solvent in the polymerization process. The first solvent and the second solvent can be any suitable straight-chain or branched-chain alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms optionally having alkyl substituents, or an aryl group having 6 to 20 carbon atoms optionally having alkyl substituents, or a mixture of two or more of the above compounds. Preferably, the first solvent and the second solvent comprise or consist of n-hexane.

[0099] The first and second solvents must be inert to the one or more polymerization catalysts and the monomer. In addition, it should be stable under the polymerization conditions. It must also be capable of dissolving the ethylene monomer, 1-octene comonomer, optionally chain transfer agent and copolymer under the polymerization conditions.

[0100] As is known in the art, a chain transfer agent can be used in one or two polymerization reactors to control the molecular weight of the copolymer. For example, a suitable chain transfer agent is hydrogen. By maintaining different concentrations of the chain transfer agent in the two reactors, it is possible to produce a copolymer blend having an expanded molecular weight distribution.

[0101] Preferably, the first stream of the first solution in step (B) is fed from the first polymerization reactor to a first heating step (B1) before performing step (C), and / or the second stream of the second solution in step (E) is fed from the second polymerization reactor to a second heating step (E1) before performing step (F), more preferably, the first stream of the first solution in step (B) is fed from the first polymerization reactor to a first heating step (B1) before performing step (C), and the second stream of the second solution in step (E) is fed from the second polymerization reactor to a second heating step (E1) before performing step (F). The purpose of the first heating step (B1) and / or the second heating step (E1) is to preheat the first and / or second stream respectively before the first and / or second stream enters the first separation step (C) and / or the second separation step (F).

[0102] The first heating step (B1) is suitably carried out in a first heat exchanger, and the second heating step (E1) is suitably carried out in a second heat exchanger.

[0103] For example, the first stream of the first solution is distributed in some tubes of the first heat exchanger, and the heated fluid contacts the tubes, thereby heating the solution flowing therein, and / or the second stream of the second solution is distributed in some tubes of the second heat exchanger, and the heated fluid contacts the tubes, thereby heating the solution flowing therein.

[0104] The purpose of the first and second heating steps is to recover heat from the process stream, thereby improving the economy of the process.

[0105] The heated fluid can be any process fluid containing recoverable heat. Preferably, the steam stream recovered from the separation step (C) and / or (F) is used as the heated fluid. In this process, the heated fluid (such as the steam stream) is cooled. It is preferred to extract so much heat from the steam stream that at least a part of the steam stream condenses in the heating step. Generally, before entering the first and / or second heating steps respectively, the temperature of the first stream of the first solution and / or the second stream of the second solution is 120 °C to 240 °C, preferably 140 °C to 220 °C, and most preferably 150 °C to 200 °C.

[0106] Preferably, the temperature of the stream immediately downstream of the first and / or second heating step is 160 °C to 240 °C, more preferably 170 °C to 220 °C, and most preferably 180 °C to 200 °C. Before entering the heating step, the temperature of the heated fluid (such as the steam stream) is preferably 120 °C to 240 °C.

[0107] Preferably, the pressure of the first stream of the first solution and / or the second stream of the second solution is not substantially affected by the first and / or second heating steps respectively. The pressure is suitably 50 bar to 300 bar, preferably 60 bar to 250 bar, and more preferably 70 bar to 200 bar.

[0108] The first stream of step (B) (or preferably the first stream of step (B1)) is conveyed to the separation step (C), and the temperature and pressure in the separation step (C) are adjusted to obtain a liquid phase and a gas phase. Similarly, the second stream of step (E) (or preferably the second stream of step (E1)) is conveyed to the separation step (F), and the temperature and pressure in the separation step (F) are adjusted to obtain a liquid phase and a gas phase.

[0109] The ethylene-1-octene copolymer is dissolved in the liquid phase, which contains a portion of the final solvent and a portion of the final unreacted comonomer, while the majority of the unreacted monomer, the final unreacted chain transfer agent, a portion of the final unreacted comonomer, and a portion of the final solvent form the gas phase. The temperature in the separation step (C) and the separation step (F) is suitably in the range of 120 °C to 240 °C, preferably in the range of 140 °C to 220 °C, and more preferably in the range of 150 °C to 200 °C. The pressure in the separation step (C) and the separation step (F) is from 1 bar to 15 bar, preferably from 2 bar to 12 bar, and more preferably from 5 bar to 10 bar. The conditions of the separation step (C) and the separation step (F) should be such that no unnecessary polymerization occurs downstream of the reactor, which would require the inactivation of the polymerization catalyst typically using polar substances.

[0110] In another aspect of the present invention, however, which is not preferred, the catalyst inactivator is added to the first stream or the second stream, respectively, before or during the separation steps (C) and (F). The catalyst inactivator is typically a polar component, such as water, alcohols (e.g., methanol and ethanol), sodium stearate / calcium stearate, CO, and combinations thereof. As described above, the conditions in the separation steps (C) and (F) need to be such that the gas phase and the liquid phase are formed. Thus, the recycle of the reactants to the reactor can be kept as simple as possible.

[0111] The separation step (C) and the separation step (F) can be carried out according to any separation method known in the art for the coexistence of a liquid phase and a gas phase. Due to the simplicity of operation, it is preferred that both the separation step (C) and the separation step (F) are carried out as flashing steps. As is well known in the art, the liquid feed is fed into a vessel operating under reduced pressure. Thus, a portion of the liquid phase evaporates and can be withdrawn from the flash as an overhead stream (or vapor stream). The remaining liquid phase portion is then withdrawn as a bottom stream (or liquid stream).

[0112] The advantage of the simultaneous presence of a gas phase and a liquid phase in the separation step is firstly the simplicity of the equipment and thus the low investment cost. In addition, the residue of the polymer accompanying the vapor stream is minimal.

[0113] The flashing step is suitably carried out in a flash vessel, which is a vertical vessel, preferably having a common cylindrical shape. Thus, the flash vessel has a portion with an approximately circular cross-section. Preferably, the flash vessel has a cylindrical portion in the shape of a cylinder. In addition to the cylindrical portion, the flash vessel may have other portions, such as a bottom portion that may be conical and a top portion that may be hemispherical. Alternatively, the flash vessel may also have a general conical shape.

[0114] The temperature in the flash vessel is typically from 120 °C to 240 °C. The temperature should be high enough to keep the viscosity of the solution at a suitable level, but less than the temperature at which the polymer decomposes. The pressure in the flash vessel is typically from 15 bar to atmospheric pressure, or even below atmospheric pressure.

[0115] In an alternative embodiment of the process of the present invention, a first stream of the first solution is withdrawn from the first polymerization reactor and a second stream of the second solution is withdrawn from the second polymerization reactor, the first stream and the second stream are combined to form a combined stream, and the ethylene-1-octene copolymer is separated from the combined stream. All embodiments of the process of the present invention as described above are also preferred embodiments (where applicable) of the alternative embodiments of the process of the present invention.

[0116] Preferably, the reactivity of the comonomer is calculated according to formula (II)

[0117] Comonomer reactivity = (C8 / C2) 聚合物 / (C8 / C2) 进料 (II)

[0118] is greater than 0.28 up to 0.65, preferably from 0.30 to 0.60, more preferably from 0.32 to 0.58,

[0119] wherein, in formula (II)

[0120] (C8 / C2) 聚合物 is the ratio of wt.% of 1-octene / wt.% of ethylene in the copolymer, and

[0121] (C8 / C2) 进料 is the ratio of wt.% of 1-octene / wt.% of ethylene in the first feed stream, or the ratio of wt.% of 1-octene / wt.% of ethylene in the sum of the first feed stream and the second feed stream.

[0122] Polymerization catalyst

[0123] The process according to the present invention comprises a first polymerization catalyst and preferably a second polymerization catalyst. The first polymerization catalyst may be the same as or different from the second polymerization catalyst.

[0124] The first polymerization catalyst and the second polymerization catalyst may be the same as or different from each other and comprise

[0125] (i) at least one metallocene complex of formula (I), and

[0126] (ii) a boron-containing cocatalyst (ii).

[0127] The at least one metallocene complex of formula (I) is

[0128]

[0129] wherein

[0130] M is hafnium,

[0131] R are the same as or different from each other and can be a saturated straight-chain or branched C1-C10 alkyl group, preferably all R are the same and are straight-chain or branched C1 to C3 alkyl groups, more preferably all R are C1 alkyl groups, R 1 is an unsubstituted C6 to C10 aryl group, preferably phenyl, and

[0132] R 2 is a C4 to C20 cycloalkyl group or a C4 to C6 alkenyl group,

[0133] X is a C1 to C6 alkyl group, preferably methyl.

[0134] Preferably, the at least one metallocene complex of formula (I) is a metallocene complex of formula (Ia)

[0135]

[0136] ((phenyl)(3-buten-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)dimethylhafnium),

[0137] and / or a metallocene complex of formula (Ib)

[0138]

[0139] ((phenyl)(cyclohexyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)dimethylhafnium).

[0140] The preparation of these metallocene complexes of formula (I), including the metallocene catalysts of formula (Ia) and formula (Ib), is described in WO2018 / 108918 and WO2018 / 178152.

[0141] Cocatalyst

[0142] To form the active catalytic component, cocatalysts well known in the art are generally required. According to the present invention, a boron-containing cocatalyst (ii) is used in the method for preparing an ethylene-1-octene copolymer.

[0143] The boron-based cocatalyst includes a boron compound containing a borate 3 + ionic boron compound, i.e., a borate compound. These compounds generally contain an anion of formula (III):

[0144] (Z)4B-(III)

[0145] where Z is an optionally substituted phenyl derivative, and the substituent is a halo C 1-6 alkyl or a halogen group. Preferably it is fluorine or trifluoromethyl. Most preferably, the phenyl is perfluorinated.

[0146] Such an ionic cocatalyst preferably contains a non-coordinating anion such as tetrakis(pentafluorophenyl)borate.

[0147] Suitable counterions are protonated amines or aniline derivatives, carbocations or phosphonium ions. These may have the general formula (IV), (V) or (VI):

[0148] NQ4 + (IV) or CQ3 + (V) or PQ4 + (VI)

[0149] where Q is independently H, C 1-6 alkyl, C 3-8 cycloalkyl, phenyl-C 1-6 alkylene or an optionally substituted phenyl (Ph). The optional substituent may be C 1-6 alkyl, halogen or nitro. There may be one or more such substituents. Thus, preferred substituted Ph groups include para-substituted phenyl, preferably tolyl or dimethylphenyl.

[0150] If it is necessary that at least one Q group in (IV) and (VI) is H, thus preferred compounds are those of the following formula:

[0151] NHQ3 + (VII) or PHQ3 + (VIII)

[0152] Preferred phenyl-C 1-6 alkyl includes benzyl.

[0153] Thus, suitable counterions include: methylammonium, anilinium, dimethylammonium, diethylammonium, N-methylanilinium, diphenylammonium, N,N-dimethylaniline, trimethylammonium, triethylammonium, tri-n-butylammonium, methyldiphenylammonium, p-bromo-N,N-dimethylaniline or p-nitro-N,N-dimethylaniline, especially dimethylammonium or N,N-dimethylaniline. Using pyridinium salts as ions is a further option.

[0154] As carbocations, especially triphenylmethyl carbon (“triphenyl”) or mesityl carbon are used.

[0155] Related phosphonium ions include triphenylphosphine, triethylphosphine, diphenylphosphine, tris(methylphenyl)phosphine and tris(dimethylphenyl)phosphine.

[0156] More preferred counterions are trityl (CPh3 + ) or analogs thereof, where the phenyl groups are functionalized to carry one or more alkyl groups. Thus, highly preferred borates used in the present invention include tetra(pentafluorophenyl)borate ions.

[0157] Preferred ionic compounds used according to the present invention include tributylammonium tetra(pentafluorophenyl)borate, tributylammonium tetra(trifluoromethylphenyl)borate, tributylammonium tetra(4-fluorophenyl)borate, N,N-dimethylcyclohexylammonium tetrakis-(pentafluorophenyl)borate,

[0158] N,N-dimethylbenzylammonium tetrakis(pentafluorophenyl)borate,

[0159] N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,

[0160] N,N-di(propyl)ammonium tetrakis(pentafluorophenyl)borate,

[0161] di(cyclohexyl)ammonium tetrakis(pentafluorophenyl)borate and

[0162] triphenylcarbenium tetrakis(pentafluorophenyl)borate.

[0163] More preferred borates are triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylcyclohexylammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylbenzylammonium tetrakis(pentafluorophenyl)borate, or N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate.

[0164] Even more preferred borates are triphenylcarbenium tetrakis(pentafluorophenyl)borate and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate.

[0165] N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate is most preferred.

[0166] An appropriate content of cocatalyst is well known to those skilled in the art.

[0167] Preferably, the molar ratio of boron in the boron-containing cocatalyst (ii) to the metal ion (M) in the at least one metallocene complex of formula (I) is in the range of 0.5:1 mol / mol to 10:1 mol / mol, preferably 1:1 mol / mol to 10:1 mol / mol, particularly 1:1 mol / mol to 5:1 mol / mol.

[0168] Even more preferably, the molar ratio of boron in the boron-containing cocatalyst (ii) to the metal ion (M) of the at least one metallocene complex of formula (I) is from 1:1 mol / mol to less than 2:1 mol / mol, for example from 1:1 mol / mol to 1.8:1 mol / mol or 1:1 mol / mol to 1.5:1 mol / mol.

[0169] The present invention further provides an ethylene-1-octene copolymer obtained by the method according to the present invention.

[0170] The present invention further provides the use of the ethylene-1-octene according to the present invention for grafting with a comonomer unit containing a hydrolyzable silyl group. By grafting the ethylene-1-octene according to the present invention with a comonomer unit containing a hydrolyzable silyl group, a grafted ethylene-1-octene containing a hydrolyzable silyl group is obtained.

[0171] The copolymer of the present invention can be grafted with a comonomer unit containing a hydrolyzable silyl group. The grafting is preferably achieved by a radical reaction, for example in the presence of a radical former, such as a peroxide.

[0172] The comonomer unit containing a hydrolyzable silyl group is preferably an unsaturated silane compound of formula (A)

[0173] R 1 SiR 2 q Y 3-q (A)

[0174] wherein

[0175] R 1 is an ethylenically unsaturated hydrocarbon group, a hydrocarbyloxy group or a (meth)acryloyloxyhydrocarbyl group,

[0176] each R 2 is an independent aliphatic saturated hydrocarbon group,

[0177] Y may be the same or different and is a hydrolysable organic group, and q is 0, 1 or 2.

[0178] Specific examples of the unsaturated silane compounds are those in which R 1 is vinyl, allyl, isopropenyl, butenyl, cyclohexyl or γ-(meth)acryloyloxypropyl; Y is methoxy, ethoxy, formyloxy, acetoxy, propionyloxy or an alkyl or aromatic amino group; and R 2 (if present) is methyl, ethyl, propyl, decyl or phenyl.

[0179] Further suitable silane compounds or preferred comonomers are, for example, γ-(meth)acryloyloxypropyltrimethoxysilane, γ-(meth)acryloyloxypropyltriethoxysilane and vinyltriacetoxysilane, or a composition of two or more of them.

[0180] As a preferred subunit of formula (A), an unsaturated silane compound, or preferably, a comonomer of formula (B)

[0181] CH2=CHSi(OA)3(B)

[0182] where each A is independently a hydrocarbyl group having 1 - 8 carbon atoms, preferably 1 - 4 carbon atoms.

[0183] Preferred comonomers / compounds of formula (B) are vinyltrimethoxysilane, vinylbis(methoxyethoxy)silane, vinyltriethoxysilane, with vinyltrimethoxysilane being most preferred.

[0184] Preferably, the grafted ethylene-1-octene comprising hydrolysable silyl groups is crosslinked.

[0185] The hydrolysable silyl groups can be crosslinked in the presence of a silanol condensation catalyst and H2O by hydrolysis and subsequent condensation in a manner known in the art. Silane crosslinking techniques are known and are described in US 4413066, US 4297310, US 4351876, US 4397981, US 4446283 and US 4456704.

[0186] For the crosslinking of polyolefins containing hydrolyzable silyl groups, a silanol condensation catalyst must be used. Conventional catalysts are organic compounds of, for example, tin, zinc, iron, lead or cobalt, such as dibutyltin dilaurate (DBTDL).

[0187] Preferably, the ethylene-1-octene according to the present invention is crosslinked. Preferably, the crosslinking is carried out by radiation crosslinking or by peroxide crosslinking, more preferably by peroxide crosslinking. Both radiation crosslinking and peroxide crosslinking of ethylene copolymers are known in the art. In radiation crosslinking, the crosslinking occurs by irradiating the copolymer with high-energy radiation (such as electron radiation), while in peroxide crosslinking, the crosslinking occurs by adding a peroxide compound, such as dicumyl peroxide or di(tert-butyl) peroxide, which forms free radicals. Detailed Description

[0188] 1. Test Methods

[0189] a) Melt Flow Rate (MFR) and Flow Rate Ratio (FRR)

[0190] The melt flow rate (MFR) is determined according to ISO 1133 - Determination of the melt mass-flow rate (MFR) and melt volume-flow rate (MVR) of thermoplastics - Part 1: Standard method and is expressed in g / 10 min. MFR is an indicator of the polymer's fluidity and processability. The higher the melt flow rate, the lower the viscosity of the polymer.

[0191] The MFR2 of polyethylene was determined at a temperature of 190 °C and a load of 2.16 kg.

[0192] The MFR of polyethylene was determined at a temperature of 190 °C and a load of 10 kg 10 .

[0193] The flow rate ratio (FRR) is MFR 10 / MFR2.

[0194] b) Density

[0195] The density of the polymer was measured according to ISO 1183-187.

[0196] c) Comonomer Content

[0197] Quantitative nuclear magnetic resonance (NMR) spectroscopy was used to quantify the comonomer content of the polymer.

[0198] Using a Bruker Avance III 500 NMR spectrometer, for 1 H and 13 C, the operations were carried out at 500.13 MHz and 125.76 MHz respectively, and the quantitative was recorded in the molten state13 C{ 1 H} NMR spectra. Nitrogen was used for all pneumatics and all spectra were recorded using a 13 C optimized 7 mm magic angle spinning (MAS) probe. Approximately 200 mg of material was loaded into a zirconia MAS rotor with an outer diameter of 7 mm and spun at 4 kHz. This setting was chosen mainly for the high sensitivity required for rapid identification and accurate quantification. Standard single pulse excitation was employed with a short recycle delay of 3 s and a transient NOE and RS-HEPT decoupling scheme. A total of 1024 (1k) transients were acquired for each spectrum.

[0199] Quantitative 13 C{ 1 H} NMR spectra were processed, integrated, and determined for quantitative properties using a custom spectral analysis automation program. All chemical shifts were internally referenced to the signal of the bulk methylene group (δ+) located at 30.00 ppm.

[0200] Characteristic signals corresponding to 1-octene incorporation were observed and all comonomer contents were calculated relative to all other monomers present in the polymer.

[0201] Characteristic signals resulting from isolated 1-octene incorporation, i.e., the EEOEE comonomer sequence, were observed. The isolated 1-octene incorporation was quantified using the signal integration at 38.3 ppm. The integration was attributed to the unresolved signals at the *B6 and *bB6B6 sites corresponding to the isolated (EEOEE) and isolated double non-consecutive (EEOEOEE) 1-octene sequences, respectively.

[0202] The influence of the two *bB6B6 sites was compensated using the integration at the bbB6B6 site at 24.6 ppm:

[0203] O = I *B6+*bB6B6 -2*I bbB6B6

[0204] Characteristic signals resulting from consecutive 1-octene incorporation, i.e., the EEOOEE comonomer sequence, were also observed. This consecutive 1-octene incorporation was quantified using the signal integration at 40.4 ppm attributed to the aaB6B6 site as the number of each comonomer reporting site:

[0205] OO = 2*I aaB6B6

[0206] Characteristic signals resulting from isolated non-consecutive 1-octene incorporation, i.e., the EEOEOEE comonomer sequence, were also observed. This isolated non-consecutive 1-octene incorporation was quantified using the signal integration at 24.6 ppm attributed to the bbB6B6 site as the number of each comonomer reporting site:

[0207] OEO = 2*I bbB6B6

[0208] The characteristic signals generated by the incorporation of isolated three consecutive 1-octene are also observed, namely the EEOOOEE comonomer sequence. The signal integration at 41.2 ppm attributed to the aagB6B6B6 site per comonomer reporting site is used to quantify this isolated three consecutive 1-octene incorporation:

[0209] OOO = 3 / 2*I aagB6B6B6

[0210] In the case where signals representing other comonomer sequences are not observed, the total 1-octene comonomer content is calculated based only on the amounts of isolated (EEOEE), isolated double consecutive (EEOOEE), isolated non-consecutive (EEOEOEE), and isolated triple consecutive (EEOOOEE) 1-octene comonomer sequences:

[0211] O 总 = O + OO + OEO + OOO

[0212] The characteristic signals generated by the saturated end groups are observed. The average integration of two resolved signals at 22.9 ppm and 32.23 ppm is used to quantify this saturated end group. The integration at 22.84 ppm is attributed to the unresolved signals of the 2B6 and 2S sites of 1-octene and the saturated chain end respectively. The integration at 32.2 ppm is attributed to the unresolved signals of the 3B6 and 3S sites of 1-octene and the saturated chain end respectively. The effects of the 2B6 and 3B6 1-octene sites are compensated using the total 1-octene content:

[0213] S = (1 / 2)*(I 2s+2B6 + I 3S+3B6 - 2*O 总 )

[0214] The content of ethylene comonomer is quantified using the integration of the backbone methylene (backbone) signal at 30.00 ppm. This integration includes the g site and 4B6 site from 1-octene and the d + site. Based on the backbone integration and the compensation for the observed 1-octene sequences and end groups, the total ethylene copolymer content is calculated:

[0215] E total = (1 / 2)*[I 主体 + 2*O + 1*OO + 3*OEO + 0*OOO + 3*S]

[0216] It should be noted that no compensation for the backbone integration is required for the presence of the isolated triple incorporation (EEOOOEE) 1-octene sequence, because the number of undercounted and overcounted ethylene units is equal.

[0217] Then calculate the total mole fraction of 1-octene in the polymer:

[0218] fO = O 总 / (E 总 +O 总 )

[0219] Calculate the total comonomer incorporation of 1-octene in weight percentage from the mole fraction using standard methods:

[0220] O[wt%] = 100*(fO*112.21) / ((fO*112.21)+((1 - fO)*28.05))

[0221] More information can be found in the following references:

[0222] Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, H.W., Wilhelm, M., Macromol. Chem. Phys. 2006; 207:382.

[0223] Parkinson, M., Klimke, K., Spiess, H.W., Wilhelm, M., Macromol. Chem. Phys. 2007; 208:2128.

[0224] NMR Spectroscopy of Polymers: Innovative Strategies for Complex Macromolecules, Chapter 24, 401(2011)

[0225] Pollard, M., Klimke, K., Graf, R., Spiess, H.W., Wilhelm, M., Sperber, O., Piel, C., Kaminsky, W., Macromolecules 2004; 37:813.

[0226] Filip, X., Tripon, C., Filip, C., J. Mag. Resn. 2005, 176, 239

[0227] Griffin, J.M., Tripon, C., Samoson, A., Filip, C., and Brown, S.P., Mag. Res. in Chem. 2007 45, S1, S198

[0228] Castignolles, P., Graf, R., Parkinson, M., Wilhelm, M., Gaborieau, M., Polymer 50 (2009) 2373 Zhou, Z., Kuemmerle, R., Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh, D. Winniford, B., J. Mag. Reson. 187 (2007) 225

[0229] Busico, V., Carbonniere, P., Cipullo, R., Pellecchia, R., Severn, J., Talarico, G., Macromol. Rapid Commun. 2007, 28, 1128

[0230] J. Randall, Macromol. Sci., Rev. Macromol. Chem. Phys. 1989, C29, 201.

[0231] Qiu, X., Redwine, D., Gobbi, G., Nuamthanom, A., Rinaldi, P., Macromolecules 2007, 40, 6879

[0232] Liu, W., Rinaldi, P., McIntosh, L., Quirk, P., Macromolecules 2001, 34, 4757

[0233] d) Degree of unsaturation

[0234] The content of unsaturated groups in the polymer was quantified using quantitative nuclear magnetic resonance (NMR) spectroscopy.

[0235] In the solution state, a Bruker Avance III 400 NMR spectrometer, operating at 400.15 MHz, was used to record the quantitative 1 1H NMR spectrum. All pneumatics were carried out using nitrogen, and at 125 °C using 13A C-optimized 10 mm selective excitation probe records all spectra. Approximately 200 mg of material is dissolved in 1,2-tetrachloroethane-d2 (TCE-d2), and approximately 3 mg of Hostanox 03 (CAS 32509-66-3) is used as a stabilizer. Standard single pulse excitation with a 30-degree pulse, a 10 s relaxation delay, and 10 Hz sample rotation is employed. Four dummy scans are used, and a total of 128 transients are acquired for each spectrum. This setting is chosen mainly for the high resolution and vinylidene stability required for quantification without saturation. Using the signal formed by the remaining protonated solvent located at 5.95 ppm, all chemical shifts are indirectly referenced to TMS located at 0.00 ppm.

[0236] Characteristic signals corresponding to the presence of terminal aliphatic vinyls (R-CH=CH2) are observed, and the quantity is quantified by integrating the two coupled unequal terminal CH2 protons (Va and Vb) at 4.95 ppm, 4.98 ppm, 5.00 ppm, and 5.05 ppm that account for the number of reporting sites per functional group:

[0237] Nvinyl = IVab / 2

[0238] When characteristic signals corresponding to the presence of internal vinylidene (RR'C=CH2) are observed, the quantity is quantified by integrating the two CH2 protons (D) at 4.74 ppm that account for the number of reporting sites per functional group:

[0239] Nvinylidene = ID / 2

[0240] When characteristic signals corresponding to the presence of internal cis-vinyldene (E-RCH=CHR') or related structures are observed, the quantity is quantified by integrating the two CH protons (C) at 5.39 ppm that account for the number of reporting sites per functional group:

[0241] Ncis = IC / 2

[0242] When characteristic signals corresponding to the presence of internal trans-vinyldene (Z-RCH=CHR') are observed, the quantity is quantified by integrating the two CH protons (T) at 5.45 ppm that account for the number of reporting sites per functional group:

[0243] Ntrans = IT / 2

[0244] When characteristic signals corresponding to the presence of internal trisubstituted vinyldene (RCH=CHR'R”) or related structures are observed, the quantity is quantified by integrating the CH proton (Tris) at 5.14 ppm that account for the number of reporting sites per functional group:

[0245] Ntris = ITris

[0246] Quantify the Hostanox 03 stabilizer using the multiple integral of the number of aromatic protons (A) at 6.92 ppm, 6.91 ppm, 6.69 ppm, and 6.89 ppm per molecule at the reported sites:

[0247] H = IA / 4

[0248] In the quantification of unsaturation in polyolefins, typically, the amount of unsaturation is determined based on the total carbon atoms, even when using 1 1H NMR spectroscopy for quantification. This can be directly compared with other microstructural quantities directly derived from 13 13C NMR spectroscopy.

[0249] Calculate the total amount of carbon atoms by integrating the main aliphatic signals between 2.85 ppm and -1.00 ppm, compensating for the methyl signals from the stabilizer and the carbon atoms related to unsaturated functionalities not included in this region:

[0250] NC total = (I main - 42*H) / 2 + 2*N vinyl + 2*N vinylidene + 2*N cis + 2*N trans + 2*N tris The content of unsaturated groups (U) is calculated as the number of unsaturated groups per thousand total carbon (kCHn) in the polymer:

[0251] U = 1000*N / NC total

[0252] The total amount of unsaturated groups is calculated as the sum of each observed unsaturated group and is thus also reported per thousand total carbon:

[0253] U total = U vinyl + U vinylidene + U cis + U trans + U tris

[0254] 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 number of unsaturated groups:

[0255] [U] = Ux / U total

[0256] More information can be found in the following references:

[0257] He, Y., Qiu, X, and Zhou, Z., Mag. Res. Chem. 2010, 48, 537 - 542.

[0258] Busico, V. et al. Macromolecules, 2005, 38(16), 6988 - 6996

[0259] e) Determine the average molecular weight and molecular weight distribution

[0260] The average molecular weights (Mz, Mw, and Mn), molecular weight distribution (MWD), and its breadth, expressed as the polydispersity index, PDI = Mw / Mn (where Mn is the number-average molecular weight and Mw is the weight-average molecular weight), were determined by gel permeation chromatography (GPC) using the following equations in accordance with ISO 16014-1:2003, ISO 16014-2:2003, ISO 16014-4:2003, and ASTM D 6474-12:

[0261]

[0262] For a constant elution volume interval ΔVi, where A i and M i are the chromatographic peak slice area and the polyolefin molecular weight (MW) related to the elution volume V i respectively, and where N is equal to the number of data points obtained from the chromatogram between the integration limits.

[0263] A high-temperature GPC instrument equipped with an IR5 multi-band infrared detector (PolymerChar, Valencia, Spain), 3 × Agilent-PLgel Olexis columns, and 1 × Agilent-PLgel Olexis guard column was used. 1,2,4-Trichlorobenzene (TCB) stabilized with 250 mg / L of 2,6-di-tert-butyl-4-methylphenol was used as the solvent and mobile phase. The chromatographic system was operated at 160 °C with a constant flow rate of 1 mL / min. 200 μL of the sample solution was injected for each analysis. PolymerChar GPC-one software was used for data acquisition.

[0264] The column set was calibrated using the universal calibration method (in accordance with 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 for several hours at room temperature. 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:

[0265] K PS = 19 × 10 -3 mL / g, α PS = 0.655

[0266] K PE = 39 × 10 -3 mL / g, α PE = 0.725

[0267] The calibration data were fitted using a third-order polynomial.

[0268] All samples were prepared in the concentration range of 0.5 mg / mL to 1 mg / mL and dissolved for 3 hours with gentle shaking at 160 °C.

[0269] 2. Polymerization catalyst

[0270] Catalyst A is (phenyl)(cyclohexyl)methylene(cyclopentadienyl)(2,7 - di - tert - butylfluoren - 9 - yl)dimethylhafnium produced according to WO2018 / 108918,

[0271] Catalyst B is (phenyl)(3 - buten - 1 - yl)methylene(cyclopentadienyl)(2,7 - di - tert - butylfluoren - 9 - yl)dimethylhafnium produced according to WO2018 / 178152.

[0272] N,N - dimethylanilinium tetrakis(pentafluorophenyl)borate (AB) (CAS 118612 - 00 - 3) was used as a cocatalyst, which can be purchased from Boulder.

[0273] 3. Polymerization of ethylene - 1 - octene copolymer

[0274] The polymerization was carried out using the solution polymerization technology of Borceed from Borealis TM in the presence of a metallocene catalyst (phenyl)(cyclohexyl)methylene(cyclopentadienyl)(2,7 - di - tert - butylfluorenyl)dimethylhafnium (Catalyst A) or (phenyl)(3 - buten - 1 - yl)methylene(cyclopentadienyl)(2,7 - di - tert - butylfluoren - 9 - yl)dimethylhafnium (Catalyst B), and N,N - dimethylanilinium tetrakis(pentafluorophenyl)borate (AB) (CAS 118612 - 00 - 3) as a cocatalyst.

[0275] The polymerization conditions were selected in such a way that the reaction system was a liquid phase (temperature T between 120 and 220 °C; pressure between 50 bar and 300 bar).

[0276] Inventive examples IE1 to IE9 were produced using Catalyst A.

[0277] Inventive examples IE10 to IE12 were produced using Catalyst B.

[0278] Comparative example CE1 is Engage 8540 (purchased from Dow Chemical), CE2 is Exact 9361 (purchased from Exxon), CE3 is Engage 7467 (purchased from Dow Chemical), and CE4 is LC170 (purchased from LG Chemical).

[0279] 4. Results

[0280] The results are given as follows.

[0281] Table 1: Process Conditions and Reactivity

[0282]

[0283] Table 2: Properties of Invention Examples IE1 to IE12 and Comparative Examples CE1 to CE4

[0284]

[0285]

[0286] Table 3: Unsaturation Types of Invention Examples IE1 to IE12 and Comparative Examples CE1 to CE4

[0287]

[0288]

[0289] Table 4: Unsaturation Levels of Invention Examples IE1 to IE12 and Comparative Examples CE1 to CE4

[0290]

[0291]

[0292] As can be seen from the above table, the copolymers of the present invention exhibit improved unsaturation levels, Mw / Mn, and MFR 10 / MFR2 ratio.

Claims

1. An ethylene-1-octene copolymer having a) Measure the density in the range of 850 kg / m 3 to 930 kg / m 3 in accordance with ISO 1183-187. b) a melt flow rate MFR2 (190 °C, 2.16 kg) measured according to ISO 1133 in the range from 0.8 g / 10 min to 100 g / 10 min, c) Measure the MFR according to ISO 1133 at 5.0 to 15.0 10 / MFR2, d) an Mw / Mn determined by gel permeation chromatography in the range from 2.0 to 5.0, characterized by e) from 1.0 to less than 20.0 vinyl unsaturated units per 100,000 C atoms measured by 1H NMR, f) more than 5.0 to 35.0 vinylidene unsaturated units per 100,000 C atoms measured by 1H NMR, g) more than 5.0 to 30.0 vinylene unsaturated units per 100,000 C atoms measured by 1H NMR, h) more than 22.0 to 51.0 trisubstituted unsaturated units per 100,000 C atoms measured by 1H NMR, i) from 26 to 150 total unsaturation units per 100,000 C atoms, wherein, wherein the total unsaturated units per 100,000 C atoms is the sum of vinyl unsaturated units per 100,000 C atoms, vinylidene unsaturated units per 100,000 C atoms, vinylene unsaturated units per 100,000 C atoms and trisubstituted unsaturated units per 100,000 C atoms, all measured by 1H NMR, j) an unsaturation degree obtained according to the following formula where the vinyl unsaturation degree is in the range from 5.0% to 20%, the vinylene unsaturation degree is in the range from 12.0% to 30.0%, and k) wherein the sum of the vinyl unsaturation degree and the vinylidene unsaturation degree is at least 30.0% up to 50.0%.

2. The ethylene-1-octene copolymer according to claim 1, wherein The total unsaturated units per 100,000 C of the copolymer follows the inequality (I) y > -0.0002A + 65.8 (I) where y is the total unsaturated units per 100,000 C atoms and A is the Mw of the copolymer in g / mol, and / or the total unsaturated units per 100,000 C of the copolymer follows the inequality (II) y > 0.12B + 39.38 (II) where y is the total unsaturated units per 100,000 C atoms and B is the 1-octene content of the copolymer in wt.%.

3. The ethylene-1-octene copolymer according to claim 1 or 2, wherein, Ratio MFR 10 / MFR2 is in the range from 6.0 to 13.0 measured according to ISO 1133.

4. The ethylene-1-octene copolymer according to any one of the above claims, wherein, The Mw / Mn is in the range from 2.4 to 4.0 as determined by gel permeation chromatography.

5. The ethylene-1-octene copolymer according to any one of the above claims, wherein The melt flow rate MFR2 (190 °C, 2.16 kg) is measured according to ISO 1133 in the range from 0.8 g / 10 min to 90 g / 10 min.

6. The ethylene-1-octene copolymer according to any one of the above claims, wherein, The vinylidene unsaturation degree is in the range from 20.0% to 32.0% and / or the trisubstituted unsaturation degree is in the range from 35.0% to 50.0%.

7. The ethylene-1-octene copolymer according to any one of the above claims, wherein The vinyl unsaturation degree is in the range from 7.0% to 17.0%, and / or wherein the vinylidene unsaturation degree is in the range from 22.0% to 28.0%, and / or wherein the vinylene unsaturation degree is in the range from 14.0% to 28.0%, and / or wherein the trisubstituted unsaturation degree is in the range from 36.0% to 45.5%.

8. The ethylene-1-octene copolymer according to any one of the above claims, wherein, Based on the weight of the total copolymer, the 1-octene is present in an amount of 10 wt.% to 45 wt.%.

9. Use of the ethylene-1-octene according to any one of claims 1-8 for grafting with a comonomer unit containing a hydrolyzable silyl group to obtain a grafted ethylene-1-octene containing a hydrolyzable silyl group.

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