Ethylene-octene copolymers with improved performance characteristics

Abstract

The present invention provides an ethylene-1-octene copolymer, characterized in that the copolymer has a molecular weight of 850 kg / m 3 Up to 930kg / m 3 The density is in the range of 0.3 g / 10 min to 100 g / 10 min according to ISO 1133, the melt flow rate MFR2 (190°C, 2.16 kg) is in the range of 5.0 to 15.0 10 / MFR2, Mw / Mn in the range of 2.0 to 5.0, 1.0 to less than 20 ethylene unsaturated units / 100000 C atoms, more than 5.0 to 35 vinylidene unsaturated units / 100000 C atoms, more than 5.0 to 30 vinylidene unsaturated units / 100000 C atoms, more than 15.0 to 60 trisubstituted unsaturated units / 100000 C atoms, 26 to 150 total unsaturated units / 100000 C atoms, wherein the total unsaturated units / 100000 C atoms are vinyl unsaturated units. The sum of saturated units / 100000 C atoms, vinylidene unsaturated units / 100000 C atoms, vinylidene unsaturated units / 100000 C atoms, trisubstituted unsaturated units / 100000 C atoms, unsaturation of unsaturation types e) to h) according to formula (I), wherein the vinyl unsaturation is in the range of 5.0% to 15.0%, the vinylidene unsaturation is in the range of 20.0% to 30.0%, and wherein the sum of the vinyl unsaturation and the vinylidene unsaturation is at least 30.0% up to 50.0%

Description

Technical Field

[0001] The present invention relates to ethylene-1-octene copolymers having improved performance characteristics, such as unsaturation level, molecular weight distribution (MWD) and MFR 10 The invention further relates to a solution polymerization process for preparing these ethylene-1-octene copolymers using a specific catalyst system. The invention also relates to the use of these ethylene-1-octene copolymers for grafting and / or crosslinking. Background Art

[0002] Over the years, there have been many types of polyethylene polymers that have been polymerized, including those made using high pressure free radical chemistry (LDPE), the more traditional linear low density polyethylene (LLDPE) typically made using Ziegler-Natta catalysis and metallocenes, or constrained geometry catalyzed polyethylene—some linear, but others that are mostly linear with a small amount of long chain branching. While these polymers have different positive and negative aspects (depending on the application or end use), there is still a need for more control over the polymer structure.

[0003] Ethylene polymers are one of the most commonly used polymers for crosslinking. It is well known that certain properties of ethylene polymers, including those that may have an impact on 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 process, process conditions, and, particularly in the case of low pressure polymerization, the catalyst used in the process.

[0004] For example, polyethylene has a typical characteristic molecular weight distribution (MWD = Mw / Mn), comonomer distribution, so-called long chain branching (LCB) and / or unsaturation, depending on the type of catalyst used in the polymerization reaction, such as Ziegler Natta, Cr or single site catalyst. These variable properties, namely MWD and unsaturation (and its type) may have an impact on the crosslinking efficiency. In addition, a narrow MWD sacrifices the processing of the polymer.

[0005] Unsaturation in polyolefin polymers is important in many respects. During the past 50 years, a considerable number of authors have investigated the influence of different structural properties of various polyethylene types on the crosslinking reaction, partly leading to different conclusions.

[0006] These properties include the degree of unsaturation, the type of unsaturation, MFR, crystallinity and branching as well as the concentration of added peroxide, to name only the most important examples. The degree of unsaturation has a significant influence on the degree of crosslinking, although it is not the only influencing factor that must be considered. As a rule of thumb, the higher the number of double bonds in the uncrosslinked polyethylene, the better the crosslinking properties can be expected. However, the type of unsaturated bonds is also important, due to the different accessibility of the various unsaturated bonds and the different stability of the intermediate free radicals.

[0007] Crosslinking can be achieved by different methods. The three most important and widely used methods are crosslinking by a) peroxide treatment, b) silane treatment, and c) using high-energy radiation. All of 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 crystallinity, the concentration and type of peroxide. The type and amount of these structures produced 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.

[0008] EP 2580279 discloses ethylene polymers having less than 12 total unsaturated units / 100000 C, less than 2 vinylidene unsaturated units / 100000 C, less than 2 trisubstituted unsaturated units / 100000 C. These polymers are produced with post-metallocene catalysts which allow control of the unsaturation level in the polymer.

[0009] EP 885255 discloses the use of ethylene polymers having less than 0.30 ethylenically unsaturated units / 1000 carbon atoms for crosslinking. The MWD of the polymers of the inventive examples described is a maximum of 2.04.

[0010] EP 2256158 describes ethylene polymers produced with Ziegler-Natta catalysts having a carbon-carbon double bond count of more than 0.2 carbon-carbon double bonds / 1000 carbons (i.e. more than 20 / 100000C). The term "carbon-carbon double bond count" is defined as the sum of vinyl, vinylidene and trans-vinylene groups / 1000 carbon atoms.

[0011] The amount of vinyl unsaturation should be at least 0.19 vinyl / 1000C (at least 19 / 100000C).

[0012] Although several ethylene polymers having specific unsaturation levels which are also suitable for crosslinking have been described in the prior art, there is still a need in the polymer art to find improved polymer solutions having improved performance characteristics, such as unsaturation level, Mw / Mn and MFR. 10 Improved balance of / MFR2 ratio.

[0013] There remains a need for unsaturated polyalphaolefin materials, particularly as intermediate materials for making functionalized polyalphaolefins. Summary of the invention

[0014] It is therefore an object of the present invention to provide ethylene-1-octene copolymers having such improved property characteristics.

[0015] A specific object of the present invention is to provide a polyol having a high unsaturation level, a high Mw / Mn and a high MFR 10 Ethylene-1-octene copolymers having an improved balance of MFR / MFR2 ratio.

[0016] A further object is to provide ethylene-1-octene copolymers for crosslinking and / or grafting with comonomer units having hydrolyzable silane groups.

[0017] A further object is to provide a solution polymerization process for preparing such copolymers using a specific catalyst system.

[0018] Therefore, the present invention provides an ethylene-1-octene copolymer, characterized in that

[0019] a) Measured according to ISO 1183-187 at 850 kg / m 3 Up to 930kg / m 3 The density of the range,

[0020] 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 measured according to ISO 1133,

[0021] c) MFR of 5.0 to 15.0 10 / MFR2,

[0022] d) Mw / Mn of 2.0 to 5.0,

[0023] e) 1.0 to less than 20.0 ethylenically unsaturated units / 100,000 C atoms,

[0024] f) more than 5.0 to 35.0 units of vinylidene unsaturation per 100 000 C atoms,

[0025] g) more than 5.0 to 30.0 units of vinylene unsaturation / 100 000 C atoms,

[0026] h) more than 15.0 to 60.0 trisubstituted unsaturated units / 100 000 C atoms (all e) to h) measured by 1H NMR),

[0027] i) 26 to 150 total unsaturated units / 100,000 C atoms, wherein the total unsaturated units / 100,000 C atoms is the sum of vinyl unsaturated units / 100,000 C atoms, vinylidene unsaturated units / 100,000 C atoms, vinylene unsaturated units / 100,000 C atoms and trisubstituted unsaturated units / 100,000 C atoms, all measured by 1H NMR,

[0028] j) Unsaturation according to the following formula

[0029]

[0030] The vinyl unsaturation ranges from 5.0% to 15.0%,

[0031] The vinylidene unsaturation ranges from 20.0% to 30.0%, and

[0032] k) wherein the sum of vinyl unsaturation and vinylidene unsaturation is at least 30.0% up to 50.0%.

[0033] The ethylene-octene copolymers have several surprising advantages.

[0034] The ethylene 1-octene copolymers of the present invention not only show high unsaturation for different unsaturation types, but also show high unsaturation simultaneously over a range of average molecular weights Mw and / or a range of 1-octene comonomer contents.

[0035] In the present application, the different types of unsaturation are vinyl unsaturation, vinylidene unsaturation, vinylidene unsaturation and trisubstituted unsaturation. Vinylidene unsaturation here is the sum of trans-vinylene and cis-vinylene.

[0036] Without being bound by any theory, it is believed that higher unsaturation results in better resistance of the polymer to deformation at low temperatures.

[0037] Furthermore, due to the high unsaturation degree, improved cross-linking efficiency can be expected.

[0038] Preferably, the total unsaturated units / 100000C of the copolymer follows inequality (I):

[0039] y>-0.0002A+65.8(I)

[0040] Wherein, y is the total unsaturation / 100000 C atoms, A is the Mw of the copolymer in g / mol, and / or the total unsaturated units / 100000 C of the copolymer follows inequality (II):

[0041] y>0.12B+39.38(II)

[0042] Here, y is the total unsaturation / 100000 C atoms and B is the 1-octene content of the copolymer in wt.%.

[0043] More preferably, the total unsaturated units / 100,000 C follows inequality (I) and the total unsaturated units / 100,000 C follows inequality (II).

[0044] Preferably, the density measured according to ISO 1183-187 is 855 kg / m 3 Up to 920kg / m 3 The range is preferably 855kg / m 3 Up to 915kg / m 3 .

[0045] Preferably, the MFR 10 The ratio of MFR / MFR2 is in the range of 6.0 to 13.0, more preferably 7.0 to 11.0.

[0046] Preferably, the Mw / Mn is in the range of 2.4 to 4.0, more preferably 2.4 to 3.5.

[0047] 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.

[0048] Preferably, the ethylenic unsaturated units / 100,000 C atoms are in the range of 5.0 to 19.0, and / or the vinylidene unsaturated units / 100,000 C atoms are in the range of 13.0 to 32.0, and / or the vinylidene unsaturated units / 100,000 C atoms are in the range of 8.0 to 23.0, and / or the trisubstituted unsaturated units / 10,000 C atoms are in the range of 22.0 to 51.0.

[0049] The total unsaturated units / 100000 C atoms are preferably 35-135, more preferably 45-120.

[0050] Preferably, the vinyl unsaturation ranges from 7.0% to 17.0%.

[0051] 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%.

[0052] Preferably, the vinylidene unsaturation is in the range of 14.0% to 28.0%.

[0053] Preferably, the unsaturation degree of the tri-substitution is in the range of 35.0% to 50%, more preferably in the range of 36.0% to 45.5%.

[0054] Preferably, the sum of the vinyl unsaturation and the vinylidene unsaturation is at least 32.0% up to 46.0%.

[0055] 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.%, most preferably 15 wt.% to 41 wt.%.

[0056] The present invention further provides a process for producing the ethylene-1-octene copolymer according to the present invention.

[0057] Therefore, the present invention provides a method for preparing the ethylene-1-octene copolymer according to the present invention, which method is a continuous high temperature solution method at a temperature of 120°C to 250°C and a pressure of 50 bar to 300 bar, and the method comprises at least the following steps:

[0058] (A) polymerizing ethylene monomer and 1-octene comonomer in a first solvent in at least a first polymerization reactor in the presence of a first polymerization catalyst and optionally a chain transfer agent to produce a first solution comprising a first ethylene-1-octene copolymer and the first solvent;

[0059] wherein the first solvent, ethylene monomer and 1-octene comonomer are provided in a first feed stream; and

[0060] wherein the first polymerization reactor is operated under operating conditions that ensure that the contents of the reactor form a single homogeneous phase,

[0061] (B) extracting a first stream of the first solution from the first polymerization reactor,

[0062] (C) separating the first ethylene-1-octene copolymer from the first stream of step (B),

[0063] Wherein, the first polymerization catalyst comprises:

[0064] (i) at least one metallocene complex of formula (I)

[0065]

[0066] in

[0067] M is hafnium,

[0068] R are the same or different from each other, and can be saturated linear or branched C1 to C10 alkyl groups. Preferably, all R are the same and are linear or branched C1 to C3 alkyl groups. More preferably, all R are C1 alkyl groups. 1 is an unsubstituted C6 to C10 aryl group, preferably a phenyl group, and

[0069] R 2 is C4 to C20 cycloalkyl or C4 to C6 alkenyl,

[0070] X is C1 to C6 alkyl, preferably methyl, and

[0071] (ii) Boron-containing promoters.

[0072] Preferably, the method according to the present invention further comprises the following steps:

[0073] (D) polymerizing ethylene monomer and 1-octene comonomer in a second solvent in a second polymerization reactor in the presence of a second polymerization catalyst and optionally a chain transfer agent to produce a second solution comprising a second ethylene-1-octene copolymer and the second solvent;

[0074] wherein the second solvent, ethylene monomer and 1-octene comonomer are provided in a second feed stream; and

[0075] (E) extracting a second stream of the second solution from the second polymerization reactor,

[0076] (F) separating the second ethylene-1-octene copolymer from the second stream, and

[0077] (G) combining the first ethylene-1-octene copolymer of step (C) with the second ethylene-1-octene copolymer of step (F),

[0078] Wherein, the second polymerization catalyst comprises:

[0079] (i) at least one metallocene complex of formula (I)

[0080]

[0081] in

[0082] M is hafnium,

[0083] R are the same or different from each other, and can be saturated linear or branched C1 to C10 alkyl groups. Preferably, all R are the same and are linear or branched C1 to C3 alkyl groups. More preferably, all R are C1 alkyl groups. 1 is an unsubstituted C6 to C10 aryl group, preferably a phenyl group, and

[0084] R 2is C4 to C20 cycloalkyl or C4 to C6 alkenyl,

[0085] X is C1 to C6 alkyl, preferably methyl, and

[0086] (ii) a boron-containing promoter, and

[0087] The first polymerization catalyst and the second polymerization catalyst may be the same as or different from each other.

[0088] If a first polymerization reactor and a second polymerization reactor are used in the process according to the present invention, the first polymerization reactor and the second polymerization reactor are operated in a parallel configuration for the preparation of the copolymer according to the present invention.

[0089] The temperature within the one or more polymerization reactors (ie, 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.

[0090] The temperature is suitably greater than the melting temperature of the copolymer of the present invention. Therefore, the temperature is suitably 120°C to 220°C, such as 150°C to 200°C, depending on the content of comonomer units in the copolymer.

[0091] The pressure in the one or more polymerization reactors (i.e. the first polymerization reactor and the optional second polymerization reactor) depends on the temperature on the one hand and on the type and amount of hydrocarbons (i.e. comonomers, monomers and solvents) on the other hand. The pressure in the first polymerization reactor and the optional second polymerization reactor is suitably 50 bar to 300 bar, preferably 50 bar to 250 bar, more preferably 70 bar to 200 bar.

[0092] The first polymerization reactor and the optional second polymerization reactor are operated under operating conditions (e.g., temperature and pressure) to ensure that the contents of the reactor of each polymerization reactor form a single homogeneous phase, the contents of the reactor comprising the ethylene monomer, 1-octene comonomer, solvent, optional chain transfer agent and copolymer product.

[0093] The first polymerization reactor and the optional second polymerization reactor are preferably selected from the group of tubular reactors, stirred autoclaves, tank reactors, loop reactors or combinations thereof.

[0094] The residence time is short, usually less than 15 minutes.

[0095] The process is operated continuously. Thus, feed streams of monomer, comonomer, catalyst, solvent and optional chain transfer agent are all continuously delivered to the one or more polymerization reactors, ie to the first polymerization reactor and the optional second polymerization reactor.

[0096] A first solvent and preferably a second solvent are present in the polymerization process. The first solvent and the second solvent may be any suitable straight or branched alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms optionally having an alkyl substituent, or an aryl group having 6 to 20 carbon atoms optionally having an alkyl substituent, 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.

[0097] The first and second solvents must be inert to the one or more polymerization catalysts and the monomers. In addition, it should be stable under the polymerization conditions. It must also be able to dissolve the ethylene monomer, 1-octene comonomer, optional chain transfer agent and copolymer under the polymerization conditions.

[0098] As is known in the art, chain transfer agents can be used in one or both polymerization reactors to control the molecular weight of the copolymer. For example, a suitable chain transfer agent is hydrogen. By maintaining different concentrations of chain transfer agents in the two reactors, it is possible to produce a copolymer blend with an expanded molecular weight distribution.

[0099] Preferably, the first stream of the first solution in step (B) is conveyed from the first polymerization reactor to the first heating step (B1) before step (C), and / or the second stream of the second solution in step (E) is conveyed from the second polymerization reactor to the second heating step (E1) before step (F), more preferably, the first stream of the first solution in step (B) is conveyed from the first polymerization reactor to the first heating step (B1) before step (C), and the second stream of the second solution in step (E) is conveyed from the second polymerization reactor to the second heating step (E1) before 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 streams before they enter the first separation step (C) and / or the second separation step (F), respectively.

[0100] 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.

[0101] For example, a first flow of the first solution is distributed in some tubes of the first heat exchanger, and a heated fluid contacts the tubes, thereby heating the solution flowing therein, and / or a second flow of the second solution is distributed in some tubes of the second heat exchanger, and a heated fluid contacts the tubes, thereby heating the solution flowing therein.

[0102] The purpose of the first and second heating steps is to recover heat from the process stream, thereby improving the economics of the process.

[0103] The heated fluid may be any process fluid containing recoverable heat. Preferably, a steam stream recovered from the separation step (C) and / or (F) is used as the heated fluid. In the process, the heating fluid (e.g., the steam stream) is cooled. It is preferred to extract so much heat from the steam stream that at least a portion of the steam stream condenses in the heating step. Typically, the temperature of the first stream of the first solution and / or the second stream of the second solution is from 120°C to 240°C, preferably from 140°C to 220°C, and most preferably from 150°C to 200°C before entering the first and / or second heating step, respectively.

[0104] Preferably, the temperature of the stream immediately downstream of the first and / or second heating step is from 160° C. to 240° C., more preferably from 170° C. to 220° C., most preferably from 180° C. to 200° C. The temperature of the heated fluid (e.g., the steam stream) is preferably from 120° C. to 240° C. before entering the heating step.

[0105] 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, more preferably 70 bar to 200 bar.

[0106] The first stream of step (B) (or preferably the first stream of step (B1)) is transported 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 transported 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.

[0107] 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, the final portion of the unreacted comonomer and the final portion of the 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, more preferably in the range of 150°C to 200°C. The pressure in the separation step (C) and the separation step (F) is 1 bar to 15 bar, preferably 2 bar to 12 bar, more preferably 5 bar to 10 bar. The conditions in the separation step (C) and the separation step (F) should be such that no unwanted polymerization occurs downstream of the reactor, which would require deactivation of the polymerization catalyst, usually using polar substances.

[0108] In another aspect of the invention, which is however not preferred, a catalyst killer is added to the first or second stream before or during separation steps (C) and (F), respectively. The catalyst killer is typically a polar component, such as water, alcohols (such as methanol and ethanol), sodium stearate / calcium stearate, CO and combinations thereof. As mentioned 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 circulation of the reactants to the reactor can be kept as simple as possible.

[0109] The separation step (C) and the separation step (F) can be carried out according to any separation method known in the art in which a liquid phase and a gas phase coexist. Due to the ease of operation, it is preferred to carry out both the separation step (C) and the separation step (F) as flashing steps. As is well known in the art, the liquid feed is conveyed to a container operated under reduced pressure. Thus, a portion of the liquid phase evaporates and can be extracted from the flash as an overhead stream (or vapor stream). The remaining portion of the liquid phase is then extracted as a bottom stream (or liquid stream).

[0110] The advantage of the simultaneous presence of a gas phase and a liquid phase in the separation step is firstly that the equipment is simple and therefore the investment costs are low. In addition, the residues of polymer accompanying the vapor stream are minimal.

[0111] The flashing step is suitably carried out in a flash vessel, which is a vertical vessel, preferably having a generally cylindrical shape. Thus, the flash vessel has a portion of approximately circular cross-section. Preferably, the flash vessel has a cylindrical portion of cylindrical shape. In addition to the cylindrical portion, the flash vessel may have other portions, such as a bottom portion which may be conical and a top portion which may be hemispherical. Alternatively, the flash vessel may also have a generally conical shape.

[0112] The temperature in the flash vessel is typically between 120°C and 240°C. The temperature should be high enough to keep the viscosity of the solution at an appropriate level, but less than the temperature at which the polymer decomposes. The pressure in the flash vessel is typically between 15 bar and atmospheric pressure, or even below atmospheric pressure.

[0113] In an optional embodiment of the method of the present invention, a first stream of the first solution is extracted from the first polymerization reactor, and a second stream of the second solution is extracted from the second polymerization reactor, the first stream is combined with the second stream to form a combined stream, and the ethylene-1-octene copolymer is separated from the combined stream. All embodiments of the method of the present invention as described above are also preferred embodiments of the optional embodiments of the method of the present invention (if applicable).

[0114] Preferably, the reactivity of the comonomer is calculated according to formula (II):

[0115] Comonomer reactivity = (C8 / C2) 聚合物 / (C8 / C2) 进料 (II)

[0116] is greater than 0.28 up to 0.65, preferably 0.30 to 0.60, more preferably 0.32 to 0.58,

[0117] Wherein, in formula (II)

[0118] (C8 / C2) 聚合物 is the ratio of 1-octene wt.% / ethylene wt.% in the copolymer, and

[0119] (C8 / C2) 进料 It is the ratio of 1-octene wt.% / ethylene wt.% in the first feed stream, or the ratio of 1-octene wt.% / ethylene wt.% in the sum of the first feed stream and the second feed stream.

[0120] Polymerization catalyst

[0121] The process according to the invention comprises a first polymerisation catalyst and preferably a second polymerisation catalyst. The first polymerisation catalyst may be the same as or different from the second polymerisation catalyst.

[0122] The first polymerization catalyst and the second polymerization catalyst may be the same as or different from each other, and comprise

[0123] (i) at least one metallocene complex of formula (I), and

[0124] (ii) A boron-containing promoter (ii).

[0125] The at least one metallocene complex of formula (I) is

[0126]

[0127] in

[0128] M is hafnium,

[0129] R are the same or different from each other, and can be saturated linear or branched C1-C10 alkyl groups. Preferably, all R are the same and are linear or branched C1 to C3 alkyl groups. More preferably, all R are C1 alkyl groups. 1 is an unsubstituted C6 to C10 aryl group, preferably a phenyl group, and

[0130] R 2 is C4 to C20 cycloalkyl or C4 to C6 alkenyl,

[0131] X is a C1 to C6 alkyl group, preferably a methyl group.

[0132] Preferably, the at least one metallocene complex of formula (I) is a metallocene complex of formula (Ia)

[0133]

[0134] ((phenyl)(3-buten-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)hafnium dimethyl),

[0135] and / or a metallocene complex of formula (Ib)

[0136]

[0137] ((Phenyl)(cyclohexyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)hafnium dimethyl).

[0138] The preparation of these metallocene complexes of formula (I) is presented in WO2018 / 108918 and WO2018 / 178152, including the metallocene catalysts of formula (Ia) and formula (Ib).

[0139] Catalyst

[0140] In order to form the active catalytic component, it is usually necessary to use a cocatalyst well known in the art. According to the present invention, the process for preparing ethylene-1-octene copolymer uses a boron-containing cocatalyst (ii).

[0141] Boron-based co-catalysts include borate-containing + Ionic boron compounds, i.e. borate compounds. These compounds usually contain anions of formula (III):

[0142] (Z)4B-(III)

[0143] Wherein Z is an optionally substituted phenyl derivative, the substituent being a halogenated C 1-6 An alkyl or halogen group. Preferably, it is fluoro or trifluoromethyl. Most preferably, the phenyl group is perfluorinated.

[0144] Such ionic promoters preferably contain a non-coordinating anion, such as tetrakis(pentafluorophenyl)borate.

[0145] Suitable counterions are protonated amine or aniline derivatives, carbocations or phosphonium ions. These may have the general formula (IV), (V) or (VI):

[0146] NQ4 + (IV) or CQ3 + (V) or PQ4 + (VI)

[0147] Where Q is independent of H, C 1-6 Alkyl, C 3-8 Cycloalkyl, phenyl-C 1-6 The optional substituent may be C 1-6 Alkyl, halogen or nitro. There may be one or more such substituents. Therefore, preferred substituted Ph groups include para-substituted phenyl, preferably tolyl or dimethylphenyl.

[0148] If it is essential that in (IV) and (VI) at least one Q group is H, preferred compounds are therefore those of the formula:

[0149] NHQ3 + (VII) or PHQ3 + (VIII)

[0150] Preferred phenyl-C 1-6 The alkyl group includes benzyl.

[0151] 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.

[0152] As carbocation, in particular triphenylmethylcarbocation ("triphenyl") or tritolylcarbocation is used.

[0153] Relevant phosphonium ions include triphenylphosphine, triethylphosphine, diphenylphosphine, tri(methylphenyl)phosphine and tri(dimethylphenyl)phosphine.

[0154] A more preferred counterion is trityl (CPh3 + ) or its analogues, wherein the phenyl group is functionalized to carry one or more alkyl groups. Thus, highly preferred borates for use in the present invention comprise tetrakis(pentafluorophenyl)borate ions.

[0155] Preferred ionic compounds for use in accordance with the present invention include tributylammoniumtetra(pentafluorophenyl)borate, tributylammoniumtetra(trifluoromethylphenyl)borate, tributylammoniumtetra-(4-fluorophenyl)borate, N,N-dimethylcyclohexylammoniumtetrakis-(pentafluorophenyl)borate,

[0156] N,N-dimethylbenzylammoniumtetrakis(pentafluorophenyl)borate,

[0157] N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate,

[0158] N,N-di(propyl)ammoniumtetrakis(pentafluorophenyl)borate,

[0159] di(cyclohexyl)ammoniumtetrakis(pentafluorophenyl)borate and

[0160] Triphenylcarbeniumtetrakis(pentafluorophenyl)borate.

[0161] More preferred borates are triphenylcarbonium tetrakis(pentafluorophenyl)borate, N,N-dimethylcyclohexylammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylbenzylammonium tetrakis(pentafluorophenyl)borate, or N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate.

[0162] Even more preferred borates are triphenylcarbonium tetrakis(pentafluorophenyl)borate and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate.

[0163] N,N-Dimethylanilinium tetrakis(pentafluorophenyl)borate is most preferred.

[0164] Suitable levels of promoters are well known to those skilled in the art.

[0165] Preferably, the molar ratio of boron of 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, in particular 1:1 mol / mol to 5:1 mol / mol.

[0166] Even more preferred is a molar ratio of boron of the boron-containing cocatalyst (ii) to the metal ion (M) of the at least one metallocene complex of formula (I) of 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 from 1:1 mol / mol to 1.5:1 mol / mol.

[0167] The present invention further provides an ethylene-1-octene copolymer obtainable by the process of the present invention.

[0168] 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 silane group. By grafting the ethylene-1-octene according to the present invention with a comonomer unit containing a hydrolyzable silane group, a grafted ethylene-1-octene containing a hydrolyzable silane group is obtained.

[0169] The copolymers of the invention can be grafted with comonomer units comprising hydrolysable silane groups. Grafting is preferably effected by free radical reaction, for example in the presence of a free radical former, such as a peroxide.

[0170] The comonomer unit containing a hydrolyzable silane group is preferably an unsaturated silane compound of formula (A)

[0171] R 1 S i 2 q Y 3-q (A)

[0172] in

[0173] R 1 is an ethylenically unsaturated hydrocarbon group, a hydrocarbonoxy group or a (meth)acryloyloxy hydrocarbon group,

[0174] Each R 2 Each is an independent aliphatic saturated hydrocarbon group.

[0175] Y may be the same or different and is a hydrolyzable organic group, and q is 0, 1 or 2.

[0176] 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 alkyl or aromatic amino; R 2 (if present) is methyl, ethyl, propyl, decyl or phenyl.

[0177] Further suitable silane compounds or preferred comonomers are, for example, γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane and vinyltriacetoxysilane, or a combination of two or more thereof.

[0178] As a preferred subunit of formula (A), an unsaturated silane compound or, preferably, a comonomer of formula (B)

[0179] CH2=CHSi(OA)3(B)

[0180] wherein each A is independently a hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms.

[0181] Preferred comonomers / compounds of formula (B) are vinyltrimethoxysilane, vinylbismethoxyethoxysilane, vinyltriethoxysilane, with vinyltrimethoxysilane being most preferred.

[0182] Preferably, the grafted ethylene-1-octene comprising hydrolysable silane groups is cross-linked.

[0183] The hydrolyzable silane groups can be crosslinked in a manner known in the art by hydrolysis and subsequent condensation in the presence of a silanol condensation catalyst and H2O. Silane crosslinking technology is known and is described in US 4413066, US 4297310, US 4351876, US 4397981, US 4446283 and US 4456704.

[0184] For the crosslinking of polyolefins containing hydrolyzable silane groups, silanol condensation catalysts must be used. Conventional catalysts are organic compounds of, for example, tin, zinc, iron, lead or cobalt, such as dibutyltin dilaurate (DBTDL).

[0185] Preferably, the ethylene-1-octene according to the present invention is crosslinked. Preferably, the crosslinking is carried out by irradiation crosslinking or by peroxide crosslinking, more preferably by peroxide crosslinking. Both irradiation crosslinking and peroxide crosslinking of ethylene copolymers are known in the art. In irradiation crosslinking, the crosslinking occurs by subjecting the copolymer to 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

[0186] 1. Test Method

[0187] a) Melt flow rate (MFR) and flow rate ratio (FRR)

[0188] Melt flow rate (MFR) is determined according to ISO1133 - Determination of melt mass flow rate (MFR) and melt volume flow rate (MVR) of thermoplastics - Part 1: Standard method and is expressed in g / 10min. MFR is an indicator of polymer fluidity and processability. The higher the melt flow rate, the lower the viscosity of the polymer.

[0189] The MFR2 of polyethylene was measured at a temperature of 190°C and a load of 2.16 kg.

[0190] The MFR of polyethylene was measured at 190°C and 10 kg load. 10 .

[0191] Flow Rate Ratio (FRR) to MFR 10 / MFR2.

[0192] b) Density

[0193] The density of the polymers was measured according to ISO 1183-187.

[0194] c) Comonomer content

[0195] Quantitative nuclear magnetic resonance (NMR) spectroscopy was used to quantify the comonomer content of the polymers.

[0196] A Bruker Avance III 500 NMR spectrometer was used to analyze 1 H and 13 For C, the operation was performed at 500.13 MHz and 125.76 MHz, respectively, and quantitative data were recorded in the molten state.13 C{ 1 H} NMR spectroscopy. Nitrogen was used for all pneumatics and the temperature was 150 °C. 13 All spectra were recorded with a C-optimized 7 mm magic angle spinning (MAS) probe. Approximately 200 mg of material was packed into a 7 mm outer diameter zirconium oxide MAS rotor and spun 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 transient NOE and RS-HEPT decoupling schemes using a short recycle delay of 3 s. A total of 1024 (1k) transients were acquired for each spectrum.

[0197] Quantitation using custom spectral analysis automation routines 13 C{ 1 H} NMR spectra were processed, integrated and quantitatively determined. All chemical shifts were internally referenced to the bulk methylene group signal (d+) at 30.00 ppm.

[0198] A characteristic signal corresponding to 1-octene incorporation was observed and all comonomer contents were calculated relative to all other monomers present in the polymer.

[0199] The characteristic signal generated by isolated 1-octene incorporation, i.e., the EEOEE comonomer sequence, was observed. The isolated 1-octene incorporation was quantified using the signal integration at 38.3ppm. The integrations were attributed to the unresolved signals of the *B6 and *bB6B6 sites corresponding to the isolated (EEOEE) and isolated di-non-continuous (EEOEOEE) 1-octene sequences, respectively. The integration of the bbb6B6 site at 24.6ppm was used to compensate for the impact of the two *bB6B6 sites:

[0200] O=I *B6+*bB6B6 -2*I bbB6B6

[0201] A characteristic signal resulting from continuous 1-octene incorporation, namely the EEOOEE comonomer sequence, was also observed. This continuous 1-octene incorporation was quantified using the signal integral at 40.4 ppm attributed to the number of aaB6B6 sites per comonomer reporter site:

[0202] OO=2*I aaB6B6

[0203] A characteristic signal resulting from isolated non-continuous 1-octene incorporation, namely the EEOEOEE comonomer sequence, was also observed. This isolated non-continuous 1-octene incorporation was quantified using the integral of the signal at 24.6 ppm attributed to the number of bbB6B6 sites per comonomer reporter site:

[0204] OEO=2*I bbB6B6

[0205] A characteristic signal resulting from an isolated three-consecutive 1-octene incorporation, namely the EEOOOEE comonomer sequence, was also observed. This isolated three-consecutive 1-octene incorporation was quantified using the signal integral at 41.2 ppm attributed to the number of aagB6B6B6 sites per comonomer reporter site:

[0206] OOO=3 / 2*I aagB6B6B6

[0207] The total 1-octene comonomer content was calculated based solely on the amounts of isolated (EEOEE), isolated di-continuous (EEOOEE), isolated discontinuous (EEOEOEE), and isolated tri-continuous (EEOOOEE) 1-octene comonomer sequences, in the absence of observed signals representing other comonomer sequences:

[0208] O 总 =O+OO+OEO+OOO

[0209] Observe the characteristic signals generated by the saturated end groups. Use the average integral of the two resolved signals at 22.9ppm and 32.23ppm to quantify this saturated end group. The integral of 22.84ppm is attributed to the unresolved signals of 2B6 and 2S sites of 1-octene and saturated chain ends, respectively. The integral of 32.2ppm is attributed to the unresolved signals of 3B6 and 3S sites of 1-octene and saturated chain ends, respectively. Use the total 1-octene content to compensate for the influence of 2B6 and 3B6 1-octene sites:

[0210] S=(1 / 2)*(I 2s+2B6 +I 3S+3B6 -2*O 总 )

[0211] The ethylene comonomer content was quantified using the integration of the bulk methylene (bulk) signal at 30.00 ppm. This integral includes the g-site and 4B6-site from 1-octene as well as the d + The total ethylene copolymer content was calculated based on the bulk integral and compensation for the observed 1-octene sequences and end groups:

[0212] Total E=(1 / 2)*[I 主体 +2*O+1*OO+3*OEO+0*OOO+3*S]

[0213] It should be noted that no compensation for the presence of isolated tri-incorporated (EEOOOOEE) 1-octene sequences is required in the bulk integral, since the number of undercounted and overcounted ethylene units is equal.

[0214] The total mole fraction of 1-octene in the polymer is then calculated:

[0215] fO=O 总 / (E 总 +O 总 )

[0216] The total comonomer incorporation of 1-octene in weight percent was calculated from the mole fractions using standard methods:

[0217] O[wt%]=100*(fO*112.21) / ((fO*112.21)+((1-fO)*28.05))

[0218] More information can be found in the following references:

[0219] Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, HW, Wilhelm, M., Macromol. Chem. Phys. 2006; 207:382.

[0220] Parkinson, M., Klimke, K., Spiess, HW, Wilhelm, M., Macromol. Chem. Phys. 2007; 208:2128.

[0221] NMR Spectroscopy of Polymers:Innovative Strategies for ComplexMacromolecules,Chapter24,401(2011)

[0222] Pollard,M.,Klimke,K.,Graf,R.,Spiess,HW,Wilhelm,M.,Sperber,O.,Piel,C.,Kaminsky,W.,Macromolecules 2004;37:813.

[0223] Filip,X.,Tripon,C.,Filip,C.,J.Mag.Resn.2005,176,239

[0224] Griffin,JM,Tripon,C.,Samoson,A.,Filip,C.,and Brown,SP,Mag.Res.inChem.2007 45,S1,S198

[0225] Castignolles,P.,Graf,R.,Parkinson,M.,Wilhelm,M.,Gaborieau,M.,Polymer50(2009)2373

[0226] Zhou,Z.,Kuemmerle,R.,Qiu,X.,Redwine,D.,Cong,R.,Taha,A.,Baugh,D.Winniford,B.,J.Mag.Reson.187(2007)225

[0227] Busico,V.,Carbonniere,P.,Cipullo,R.,Pellecchia,R.,Severn,J.,Talarico,G.,Macromol.Rapid Commun.2007,28,1128

[0228] J. Randall, Macromol. Sci., Rev. Macromol. Chem. Phys. 1989, C29, 201.

[0229] Qiu,X.,Redwine,D.,Gobbi,G.,Nuamthanom,A.,Rinaldi,P.,Macromolecules2007,40,6879

[0230] Liu,W.,Rinaldi,P.,McIntosh,L.,Quirk,P.,Macromolecules 2001,34,4757

[0231] d) Unsaturation

[0232] Quantitative nuclear magnetic resonance (NMR) spectroscopy was used to quantify the amount of unsaturated groups in the polymer.

[0233] Quantitative measurements were recorded in solution using a Bruker Avance III 400 NMR spectrometer operating at 400.15 MHz. 1 H NMR spectroscopy. All pneumatic operations were performed using nitrogen gas at 125 °C. 13All spectra were recorded with a C optimized 10 mm selective excitation probe. Approximately 200 mg of material was dissolved in 1,2-tetrachloroethane-d2 (TCE-d2) using approximately 3 mg of Hostanox 03 (CAS 32509-66-3) as a stabilizer. Standard single pulse excitation with a 30 degree pulse, a relaxation delay of 10 s and a sample rotation of 10 Hz was employed. A total of 128 transients were acquired per spectrum using 4 virtual scans. This setup was chosen primarily for the high resolution and vinylidene stability required for unsaturation quantification. All chemical shifts were indirectly referenced to TMS at 0.00 ppm using the signal formed by the remaining protonated solvent at 5.95 ppm.

[0234] A characteristic signal corresponding to the presence of a terminal aliphatic vinyl group (R-CH=CH2) was observed and the amount was quantified using the integration of the number of two coupled unequal terminal CH2 protons (Va and Vb) occupying each functional group reporter site at 4.95 ppm, 4.98 ppm, 5.00 ppm and 5.05 ppm:

[0235] Nvinyl=IVab / 2

[0236] When a characteristic signal corresponding to the presence of an internal vinylidene group (RR'C=CH2) is observed, the amount is quantified using the integration of the number of two CH2 protons (D) occupying each functional group reporter site at 4.74 ppm:

[0237] N vinylidene = ID / 2

[0238] When a characteristic signal corresponding to the presence of an internal cis-vinylene (E-RCH=CHR') or related structure is observed, the amount is quantified using the integration of the number of two CH protons (C) occupying each functional group reporter site at 5.39 ppm:

[0239] Ncis=IC / 2

[0240] When a characteristic signal corresponding to the presence of an internal trans-vinylene (Z-RCH=CHR') is observed, the amount is quantified using the integration of the number of two CH protons (T) occupying each functional group reporter site at 5.45 ppm:

[0241] Ntrans=IT / 2

[0242] When a characteristic signal corresponding to the presence of an internal trisubstituted vinylene (RCH=CHR'R") or related structures is observed, the amount is quantified using the integration of the number of CH protons (Tris) occupying each functional group reporter site at 5.14 ppm:

[0243] Ntris=ITris

[0244] Hostanox 03 stabilizer was quantified using multiple integration of the number of reporting sites per molecule occupied by aromatic protons (A) at 6.92 ppm, 6.91 ppm, 6.69 ppm and 6.89 ppm:

[0245] H=IA / 4

[0246] Quantification of unsaturation in polyolefins Typically, the amount of unsaturation is determined based on total carbon atoms, even if 1 H NMR spectroscopy. This can be combined with other 13 C NMR spectra for direct comparison of microstructural quantities.

[0247] The total amount of carbon atoms was calculated from the integration of the bulk aliphatic signal between 2.85 ppm and -1.00 ppm, compensating for the methyl signal from the stabilizer and the carbon atoms associated with unsaturated functionality which were not included in this region:

[0248] NC total = (I host - 42*H) / 2 + 2*N vinyl + 2*N vinylidene + 2*Ncis + 2*Ntrans + 2*Ntris The content of unsaturated groups (U) is calculated as the number of unsaturated groups per thousand total carbons (kCHn) in the polymer:

[0249] U=1000*N / NC total

[0250] The total amount of unsaturated groups was calculated as the sum of each observed unsaturated group and is therefore also reported per thousand total carbons:

[0251] Utotal=Uvinyl+Uvinylidene+Ucis+Utrans+Utris

[0252] The relative content of a specific unsaturated group (U) is reported as the fraction or percentage of a given unsaturated group relative to the total number of unsaturated groups:

[0253] [U] = Ux / Utotal

[0254] More information can be found in the following references:

[0255] He,Y.,Qiu,X,and Zhou,Z.,Mag.Res.Chem.2010,48,537-542.

[0256] Busico,V.et.al.Macromolecules,2005,38(16),6988-6996

[0257] e) Determination of average molecular weight and molecular weight distribution

[0258] The average molecular weight (Mz, Mw and Mn), molecular weight distribution (MWD) and its breadth are determined by gel permeation chromatography (GPC) according to ISO 16014-1:2003, ISO 16014-2:2003, ISO 16014-4:2003 and ASTM D 6474-12 using the following formula, expressed as the polydispersity index, PDI = Mw / Mn (where Mn is the number average molecular weight and Mw is the weight average molecular weight):

[0259]

[0260]

[0261]

[0262] For a constant elution volume interval ΔVi, where A i and M i are respectively related to the elution volume V i The associated chromatographic peak slice area and the polyolefin molecular weight (MW), where N equals 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) and 3×Agilent-PLgel Olexis and 1×Agilent-PLgel Olexis guard columns was used. 1,2,4-Trichlorobenzene (TCB) stabilized with 250 mg / L 2,6-di-tert-butyl-4-methylphenol was used as solvent and mobile phase. The chromatographic system was operated at 160°C and a constant flow rate of 1 mL / min. 200 μL of sample solution was injected for each analysis. Data acquisition was performed using PolymerChar GPC-one software.

[0264] The column set was calibrated using a universal calibration method (according to ISO 16014-2:2003) of 19 narrow MWD polystyrene (PS) standards ranging from 0.5 kg / mol to 11500 kg / mol. The PS standards were dissolved at room temperature for several hours. The conversion of polystyrene peak molecular weight to 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 -3mL / g,α PE =0.725

[0267] A third-order polynomial was used to fit the calibration data.

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

[0269] 2. Polymerization catalyst

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

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

[0272] As a cocatalyst, N,N-dimethylanilinium tetrafluorophenyl borate (AB) (CAS 118612-00-3) was used, which is commercially available from Boulder.

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

[0274] The polymerization was carried out using Borceed TM The solution polymerization technology is carried out 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-butylfluorenyl-9-yl)dimethylhafnium (catalyst B) and N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate (AB) (CAS 118612-00-3) as a co-catalyst.

[0275] The polymerization conditions are chosen in such a way that the reaction system is in one 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 (commercially available from Dow Chemical), CE2 is Exact 9361 (commercially available from Exxon), CE3 is Engage 7467 (commercially available from Dow Chemical), and CE4 is LC170 (commercially available from LG Chemical).

[0279] 4. Results

[0280] The results are given below.

[0281] Table 1: Process conditions and reactivity

[0282]

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

[0284]

[0285] Table 3: Unsaturation Types of Inventive Examples IE1 to IE12 and CE1 to CE4

[0286]

[0287]

[0288] Table 4: Unsaturation levels of inventive examples IE1 to IE12 and CE1 to CE4

[0289]

[0290]

[0291] As can be seen from the above table, the copolymers of the present invention show improved unsaturation levels, Mw / Mn and MFR 10 / MFR2 ratio.

Claims

1. A method for producing ethylene-1-octene copolymers, the method being a continuous high temperature solution process at a temperature of 120°C to 250°C and a pressure of 50 bar to 300 bar, the method comprising at least the following steps: (A) polymerizing ethylene monomer and 1-octene comonomer in a first solvent in at least a first polymerization reactor in the presence of a first polymerization catalyst and optionally a chain transfer agent to produce a first solution comprising a first ethylene-1-octene copolymer and the first solvent; in, providing the first solvent, ethylene monomer, and 1-octene comonomer in a first feed stream; and wherein the first polymerization reactor is operated under operating conditions that ensure that the contents of the reactor form a single homogeneous phase, (B) extracting a first stream of the first solution from the first polymerization reactor, (C) separating the first ethylene-1-octene copolymer from the first stream of step (B), Wherein, the first polymerization catalyst comprises: (i) at least one metallocene complex of formula (I) and (ii) Boron-containing promoter wherein the at least one metallocene complex of formula (I) is a metallocene complex of formula (Ia) and / or a metallocene complex of formula (Ib) The ethylene-1-octene copolymer has a) Measured according to ISO 1183-187 at 850 kg / m 3 Up to 930kg / m 3 The density of the range, b) a melt flow rate MFR2 in the range of 0.8 g / 10 min to 100 g / 10 min measured according to ISO 1133 at 190° C. and 2.16 kg, c) MFR between 5.0 and 15.0 10 / MFR2, MFR measured according to ISO 1133 at a temperature of 190°C and a load of 10 kg 10 , MFR2 is measured according to ISO 1133 at a temperature of 190°C and a load of 2.16 kg, d) a Mw / Mn of 2.0 to 5.0 as determined by gel permeation chromatography, Its characteristics are e) 1.0 to less than 20.0 units of ethylenic unsaturation / 100 000 C atoms measured by 1H NMR, f) more than 5.0 to 35.0 units of vinylidene unsaturation / 100 000 C atoms measured by 1H NMR, g) more than 5.0 to 30.0 units of vinylene unsaturation / 100 000 C atoms as measured by 1H NMR, h) more than 15.0 to 60.0 trisubstituted unsaturated units / 100 000 C atoms measured by 1H NMR, i) 26 to 150 total unsaturated units / 100,000 C atoms, wherein the total unsaturated units / 100,000 C atoms is the sum of vinyl unsaturated units / 100,000 C atoms, vinylidene unsaturated units / 100,000 C atoms, vinylene unsaturated units / 100,000 C atoms and trisubstituted unsaturated units / 100,000 C atoms, all measured by 1H NMR, j) Unsaturation according to the following formula in The vinyl unsaturation ranges from 5.0% to 20%, The vinylidene unsaturation ranges from 12.0% to 30.0%, and The sum of the vinyl unsaturation and the vinylidene unsaturation is at least 30.0% up to 50.0%.

2. The method according to claim 1, wherein: The total unsaturated units / 100000 C of the copolymer follow the inequality (I) y>-0.0002A+65.8 (I) Wherein y is the total unsaturated units / 100000 C atoms, A is the Mw of the copolymer, in g / mol, and / or the total unsaturated units / 100000 C of the copolymer follow the inequality (II) y>0.12B+39.38 (II) Wherein y is the total unsaturated units / 100000 C atoms, and B is the 1-octene content of the copolymer, in wt.%.

3. The method according to claim 1 or 2, wherein: The MFR ratio of the ethylene-1-octene copolymer 10 / MFR2 is measured according to ISO 1133 in the range of 6.0 to 13.

0.

4. The method according to claim 1, wherein: The Mw / Mn of the ethylene-1-octene copolymer is in the range of 2.4 to 4.0 as measured by gel permeation chromatography.

5. The method according to claim 1, wherein: The melt flow rate MFR2 of the ethylene-1-octene copolymer is measured according to ISO 1133 at 190° C. and 2.16 kg and is in the range of 0.8 g / 10 min to 90 g / 10 min.

6. The method according to claim 1, wherein: The ethylene-1-octene copolymer has a vinylidene unsaturation in the range of 20.0% to 32.0% and / or a trisubstituted unsaturation in the range of 35.0% to 50.0%.

7. The method according to claim 1, wherein: The vinyl unsaturation is in the range of 7.0% to 17.0%, and / or wherein the vinylidene unsaturation is in the range of 22.0% to 28.0%, and / or wherein the vinylene unsaturation is in the range of 14.0% to 28.0%, and / or wherein the trisubstituted unsaturation is in the range of 36.0% to 45.5%.

8. The method according to claim 1, wherein: The 1-octene is present in an amount of 10 wt. % to 45 wt. %, based on the total weight of the copolymer.

9. The method according to claim 1, further comprising the steps of: (D) polymerizing ethylene monomer and 1-octene comonomer in a second solvent in a second polymerization reactor in the presence of a second polymerization catalyst and optionally a chain transfer agent to produce a second solution comprising a second ethylene-1-octene copolymer and the second solvent; wherein the second solvent, ethylene monomer and 1-octene comonomer are provided in a second feed stream; and wherein the second polymerization reactor is operated under operating conditions that ensure that the contents of the reactor form a single homogeneous phase, (E) extracting a second stream of the second solution from the second polymerization reactor, (F) separating the second ethylene-1-octene copolymer from the second stream of step (E), and (G) combining the first ethylene-1-octene copolymer of step (C) with the second ethylene-1-octene copolymer of step (F), Wherein, the second polymerization catalyst comprises: (i) at least one metallocene complex of formula (I) in M is hafnium, R are the same or different and can be saturated linear or branched C1 to C10 alkyl groups, R 1 is an unsubstituted C6 to C10 aryl group, and R 2 is C4 to C20 cycloalkyl or C4 to C6 alkenyl, X is a C1 to C6 alkyl group, and (ii) a boron-containing promoter, and The first polymerization catalyst and the second polymerization catalyst may be the same as or different from each other.

10. The method according to claim 9, wherein all R are the same and are linear or branched C1 to C3 alkyl groups.

11. The method according to claim 9, wherein all R are C1 alkyl groups.

12. The method according to claim 9, wherein R 1 It is phenyl.

13. The method according to claim 9, wherein X is methyl.

14. The method according to claim 1, wherein: Comonomer reactivity according to formula (II) Comonomer reactivity = (C8 / C2) 聚合物 / (C8 / C2) 进料 (II) Comonomer reactivity ranges from 0.28 to 0.65, Wherein, in formula (II) (C8 / C2) 聚合物 is the ratio of 1-octene wt.% / ethylene wt.% in the copolymer, and (C8 / C2) 进料 is the ratio of 1-octene wt.% / ethylene wt.% in the first feed stream, or the ratio of 1-octene wt.% / ethylene wt.% in the sum of the first feed stream and the second feed stream.

15. The method according to claim 1, wherein: The boron-containing co-catalyst comprises an anion of formula (III) (Z)4B - (III) Wherein Z is an optionally substituted phenyl derivative, the substituent is a halogenated C 1-6 an alkyl or halogen group.

16. The method according to claim 1, wherein: The boron-containing promoter is a borate selected from the group consisting of: Triphenylcarbonium tetrakis(pentafluorophenyl)borate, N,N-Dimethylcyclohexylammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylbenzylammonium tetrakis(pentafluorophenyl)borate, or N,N-Dimethylanilinium tetrakis(pentafluorophenyl)borate.

17. Ethylene-1-octene copolymer obtained by the process according to any one of claims 1 to 16.

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