Process for preparation of ethylene copolymers

Abstract

The present application provides a process for preparing an ethylene copolymer. The process comprises the steps of (i) feeding liquefied ethylene to at least one evaporator to evaporate at least a portion of the liquefied ethylene, (ii) combining the evaporated ethylene with at least one solvent and at least one comonomer in a receiver vessel to produce an educt stream comprising ethylene, at least one comonomer and at least one solvent, (iii) feeding the segregation stream to at least one reaction vessel wherein at least one polymerization reaction is carried out in the presence of at least one polymerization catalyst to produce an ethylene copolymer wherein the temperature of the segregation stream is reduced at least once before the segregation stream enters the reactor vessel and the temperature of the segregation stream is reduced at least once before the segregation stream enters the reactor vessel. And wherein the evaporation of liquefied ethylene is used to reduce the temperature of at least a portion of the segregation stream.

Description

Technical Field

[0001] The present disclosure relates to a process for producing ethylene copolymers using liquefied ethylene. Background Art

[0002] Many widely used synthetic rubbers are produced by solution polymerization or slurry polymerization using one or more polymerization catalysts. For optimal mixing of catalyst and reactants, the polymerization is usually carried out in a stirred tank reactor. The polymerization reaction is usually exothermic and the catalyst is deactivated above a certain temperature threshold. Therefore, the temperature in the reactor must be controlled and must be kept below the temperature at which the catalyst is deactivated. Cooling the reactor by external or internal cooling devices may lead to poor reaction control and reactor fouling, such as described in international patent application WO2010040732.

[0003] Alternatively, the polymerization heat can be controlled by the so-called evaporation method. In this case, the solution of the polymerization mixture or slurry is kept in a boiling state, and the components with lower boiling points (such as monomers and solvents) are evaporated continuously. Evaporation consumes heat and can therefore be used for cooling. A general description of this method can be found in WO2014 / 202715. In a continuous process, the evaporated monomer is usually condensed by a compressor and reintroduced into the polymerization vessel. However, the condensation process consumes a lot of energy and requires extensive equipment to condense the mixed vapor phase extracted from the reactor, i.e., a device for separating fluid and gas phase, a compressor for receiving the gas phase, and a cooler for refeeding it into the reactor.

[0004] Another way to remove heat is to carry out the polymerization adiabatically, wherein the educts are precooled before entering the reactor. In the adiabatic process, the polymerization solution or slurry is maintained in liquid form in a so-called "overflow" or "full" vessel. No external cooling is used, and the heat of polymerization is controlled by cooling the monomers to low temperatures before introducing them into the reaction. Cooling the monomers also consumes a lot of energy.

[0005] Typically, ethylene is produced by conversion of fossil raw materials in a cracker (so-called "naphtha cracker"). The final step after the cracker operation is the so-called C2 splitter, in which ethylene is separated from ethane, propylene and higher hydrocarbons by a distillation process. The operating pressure in the distillation column can be about 16 bar, while the temperature covers a wide range. As described in US2008141713, purified ethylene can leave the distillation at 25 bar and -20°C. The produced ethylene is usually fed to a local ethylene pipeline that serves ethylene consumers that contact the pipeline, usually in a pressurized form of about 60 bar and close to room temperature.

[0006] However, ethylene can also be provided in liquefied form. Typically, liquefied ethylene is stored or provided in cryogenic gas transport containers at ambient pressure and maintained at a temperature of about -104°C. Providing liquefied ethylene may become increasingly important for using ethylene produced from sustainable resources (such as plant-based materials, such as ethanol produced by hydrolysis of sugar cane or other plant-based materials). Such bio-based ethylene may have to be provided in liquefied form because producers of bio-based ethylene may not be connected to ethylene consumers by pipeline.

[0007] It would be desirable to provide energy efficient methods for producing ethylene polymers and copolymers using liquefied ethylene. Summary of the invention

[0008] Thus, in one aspect, there is provided a process for preparing an ethylene copolymer comprising the steps of:

[0009] (i) feeding liquefied ethylene into at least one evaporator to evaporate at least a portion of the liquefied ethylene,

[0010] (ii) combining the evaporated ethylene with at least one solvent and at least one comonomer in a receiver vessel to produce an educt stream comprising ethylene, at least one comonomer and at least one solvent,

[0011] (iii) feeding the educt stream into at least one reaction vessel, wherein at least one polymerization reaction is carried out in the presence of at least one polymerization catalyst to produce an ethylene copolymer,

[0012] wherein the temperature of the educt stream is reduced at least once prior to entering the reactor vessel, and wherein vaporization of liquefied ethylene is used to reduce the temperature of at least a portion of the educt stream. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 Schematic diagram of the reactor feed system before the reactor inlet for non-inventive examples 1 (with filler oil) (A) and 2 (without oil) (B).

[0014] Figure 2 . Schematic diagram of the reactor feed system before the reactor inlet for Inventive Examples 3 (with filler oil) (A) and 4 (without oil) (B). DETAILED DESCRIPTION

[0015] The method according to the present disclosure will now be described in more detail in the following description.

[0016] In the following description, the terms "comprising", "containing", "including", "having" are used in an open sense and do not exclude the presence of any additional components, steps or procedures, whether or not they are specifically disclosed. For example, the term "comprising a composition of components A and B" means that components other than A and B may also be present in the composition. The term "consisting of" is used in a restrictive sense to exclude the presence of any additional components, steps or procedures. For example, the term "composition consisting of components A and B" means that components other than A and B are not present in the composition.

[0017] In the following description, the specification may be used. If not otherwise specified, the specification in the version effective on March 1, 2020 is used. If no version is effective on that date, for example because the specification has expired, the version refers to the version effective on the date closest to March 1, 2020.

[0018] In the following description, the amount of a component of a composition or polymer may be represented by "weight percent", "wt. %" or "% by weight". Unless otherwise indicated, the terms "weight percent", "wt. %" or "% by weight" are used interchangeably and are based on the total weight of the composition or polymer, respectively (which is 100%).

[0019] The term "phr" means parts per hundred of rubber, ie, the percentage by weight based on the total amount of rubber set at 100%.

[0020] Unless otherwise stated, ranges identified in this disclosure are meant to include all values ​​between and including the endpoints of the disclosed ranges.

[0021] polymer:

[0022] Polymers with broad or narrow molecular weight distributions (Mw / Mn) can be produced. In one embodiment, polymers with molecular weight distributions (Mw / Mn) of 1.80-30 or 2-10 can be prepared.

[0023] Polymers with high or low Mooney viscosities can be produced. In one embodiment, the polymer produced by the method has a Mooney viscosity ML 1+4 of at least 40 at 125°C and a Mooney viscosity ML 1+8 of up to 100 at 150°C. In one embodiment of the present disclosure, the polymer has a Mooney viscosity ML 1+4 of about 40 to about 100 at 125°C. In another embodiment of the present disclosure, the polymer has a Mooney viscosity ML 1+8 of from about 50 to about 100 at 150°C.

[0024] Polymers of high or low weight average molecular weight (Mw) can be produced by the method according to the present disclosure, although an advantage of the present disclosure is that high molecular weight polymers can also be produced, such as polymers having a molecular weight (Mw) of at least 50 kg / mol, at least 90 kg / mol, at least 120 kg / mol, or even at least 200 kg / mol. In one embodiment of the present disclosure, polymers having a molecular weight (Mw) of 50 kg / mol to 150 kg / mol are produced. In another embodiment of the present disclosure, the polymer has a Mw of at least 200 kg / mol, such as about 200 kg / mol to about 600 kg / mol or about 200 kg / mol to about 500 kg / mol.

[0025] Polymers with high or low number average molecular weight (Mn) can be produced. In one embodiment, the polymer produced by the process according to the present disclosure has a Mn from 40 kg / mol to 250 kg / mol.

[0026] Branched or linear polymers can be produced with the method according to the present disclosure. The branching level of branched polymers can be high, medium or low. The polymer branching level can be characterized by the parameter Δδ. Δδ expressed in degrees is the difference between the phase angle at a frequency of 0.1rad / s and the phase angle at a frequency of 100rad / s, determined by dynamic mechanical spectroscopy (DMS) at 125°C and 10% strain. This is a measure of the amount of long-chain branched structures in the polymer, and has been introduced in HC Booij, Kautschuk+Gummi Kunststoffe, Vol. 44, No. 2, pp. 128-130, which is incorporated herein by reference. The lower Δδ is, the more branched structures there are in the polymer. In one embodiment of the present disclosure, a polymer with a Δδ of 2 to 50 is produced.

[0027] The polymers produced by the process according to the present disclosure may be unimodal, bimodal or multimodal, i.e. they may have a molecular weight distribution characterized by two peaks in the case of bimodal polymers or by more than two peaks in the case of multimodal polymers in a diagram obtained by gel permeation chromatography (GPC). Reactor blends may also be produced, meaning that the polymers are produced in at least two different reaction vessels and combined by blending, typically wet blending, i.e. by blending the reaction mixtures.

[0028] It is contemplated that the method according to the present disclosure may be applied to any polymerization process that produces a polymer using at least one polymerization catalyst and a solvent, and wherein the reaction is exothermic. This may include the production of thermoplastic or elastomeric polymers using ethylene as a monomer, and may include the production of rubbers such as polyethylene, thermoplastic polyethylene copolymers, vinyl acetate copolymers, EPM and EPDM. However, the method may be most useful for producing polymers selected from polyethylene or ethylene copolymers having at least 20% by weight of units derived from ethylene. In a preferred embodiment of the present disclosure, the polymer comprises an ethylene / α-olefin polymer.

[0029] Ethylene / α-olefin polymers:

[0030] In one embodiment, the polymer produced using the method according to the present disclosure is an ethylene / alpha-olefin polymer. Ethylene / alpha-olefin polymers are copolymers of ethylene and alpha-olefins and optionally one or more other comonomers. Ethylene / alpha-olefin polymers can be produced, comprising at least 20% by weight or at least 30% by weight (based on the gross weight of the polymer) of units derived from ethylene, and can comprise up to 80% (wt.%) of units derived from ethylene by weight. In one embodiment, the ethylene-alpha-olefin copolymer of the present disclosure comprises 40wt.% to 70wt.%, preferably 44wt.% to 65wt.% or 50wt.% to 60wt.% of units derived from ethylene. The weight percentage is based on the gross weight of the copolymer.

[0031] In addition to units derived from ethylene, the polymers according to the present disclosure also comprise units derived from one or more α-olefins.

[0032] α-Olefins:

[0033] Alpha-olefins are olefins with a single aliphatic carbon-carbon double bond. The double bond is located at the end (α-position) of the olefin. Alpha-olefins can be aromatic or aliphatic, linear, branched or cyclic. Typically, alpha-olefins have 3-20 carbon atoms.

[0034] α-olefins include those represented by the formula: H2C=X-CH3,

[0035] Wherein, X represents an aliphatic alkylene residue having 1 to 17 carbon atoms, which may be linear or branched. Preferably, the branches independently contain 1 to 3 carbon atoms.

[0036] In a preferred embodiment, the α-olefins include those represented by the formula: H2C=CH-(CH2) n-CH3, wherein n represents 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 and 17.

[0037] Preferred examples of α-olefins include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, and 12-ethyl-1-tetradecene.

[0038] One or more alpha-olefins can be used in combination. Preferably, the polymer comprises at least 5wt.% or at least 10wt.% of units derived from one or more alpha-olefins. It is possible to produce polymers comprising up to 57wt.%, more preferably up to 55wt.% of units derived from one or more alpha-olefins (weight percentage (wt.%) is based on the total weight of the polymer). Preferably, the ethylene-alpha-olefin copolymer comprises 17wt.% to 57wt.% of total units derived from one or more alpha-olefins. Preferably, the polymer comprises propylene.

[0039] Non-conjugated dienes:

[0040] Ethylene / α-olefin polymers may be produced which comprise, in addition to ethylene and α-olefins, units derived from one or more non-conjugated dienes as comonomers.

[0041] Non-conjugated dienes are polyenes containing at least two carbon-carbon double bonds, the double bonds being non-conjugated and being able to exist in chains, rings, ring systems or combinations thereof. The carbon-carbon double bonds are separated by at least two carbon atoms. The polyenes may have endocyclic and / or exocyclic double bonds and may have a variety of different substituents. Preferably, the non-conjugated diene is aliphatic, more preferably aliphatic and alicyclic. Suitable non-conjugated dienes include, for example, aromatic polyenes, aliphatic polyenes and alicyclic polyenes, preferably polyenes (C6-C 30 Polyene, more preferably C6-C 30Specific examples of non-conjugated dienes include, but are not limited to, 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4-ethyl-1,4-hexadiene, 3,3-dimethyl-1,4-hexadiene, 5-methyl-1,4-heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5-heptadiene, 1,6-octadiene, 4-methyl-1,4-octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene. , 5-ethyl-1,4-octadiene, 5-methyl-1,5-octadiene, 6-methyl-1,5-octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5-octadiene, 1,6-octadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene, 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 4-methyl-1,4-nonadiene, 5-methyl-1,4-nonadiene, 4-ethyl-1,4-nonadiene, 5-ethyl-1,4-nonadiene, 5-methyl-1,5-nonadiene , 6-methyl-1,5-nonadiene, 5-ethyl-1,5-nonadiene, 6-ethyl-1,5-nonadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 7-methyl-1,7-nonadiene, 8-methyl-1,7-nonadiene, 7-ethyl-1,7-nonadiene, 5-methyl-1,4-decadiene, 5-ethyl-1,4-decadiene, 5-methyl-1,5-decadiene, 6-methyl-1,5-decadiene, 5-ethyl-1,5-decadiene, 6-ethyl-1, 5-decadiene, 6-methyl-1,6-decadiene, 6-ethyl-1,6-decadiene, 7-methyl-1,6-decadiene, 7-ethyl-1,6-decadiene, 7-methyl-1,7-decadiene, 8-methyl-1,7-decadiene, 7-ethyl-1,7-decadiene, 8-ethyl-1,7-decadiene, 8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 8-ethyl-1,8-decadiene, 1,5,9-decatriene, 6-methyl-1,6-undecadiene, 9-methyl-1,8-undecadiene, dicyclopentadiene and mixtures thereof. Preferred non-conjugated dienes include alicyclic polyenes. The alicyclic diene has at least one ring unit. In a preferred embodiment, the non-conjugated diene is selected from a polyene having at least one endocyclic double bond and optionally at least one exocyclic double bond. Preferred examples include dicyclopentadiene, 5-methylene-2-norbornene and 5-ethylidene-2-norbornene (ENB), among which ENB is particularly preferred. In one embodiment, the copolymer of the present disclosure comprises only ENB as the non-conjugated diene.

[0042] Other examples of non-conjugated dienes include dipolymerizable dienes, including α-ω dienes, preferably linear α-ω-dienes, vinyl-substituted monocyclic and dicyclic non-conjugated dienes, which may be aromatic or aliphatic. Such dipolymerizable dienes may cause or contribute to the formation of polymer branches, because both double bonds of the diene may participate in the polymerization. Examples of aliphatic dipolymerizable dienes include, but are not limited to, 1,4-divinylcyclohexane, 1,3-divinylcyclohexane, 1,3-divinylcyclopentane, 1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane, 1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane, 1,5-diallylcyclooctane, 1-allyl-4-isopropenylcyclohexane, 1-isopropenyl-4-vinylcyclohexane and 1-isopropenyl-3-vinylcyclopentane, dicyclopentadiene (DCPD) and 1,4-cyclohexadiene. Preferred are non-conjugated vinyl norbornene and C8-C 12 α,ω linear diene (e.g., 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene). The dipolymerizable diene may be further substituted with at least one group comprising a heteroatom of Groups 13-17 (e.g., O, S, N, P, Cl, F, I, Br, or a combination thereof).

[0043] In a preferred embodiment of the present disclosure, the dual polymerizable diene is selected from dicyclopentadiene (DCPD), 5-vinyl-2-norbornene (VNB), 1,7-octadiene and 1,9-decadiene or a combination thereof, wherein 5-vinyl-2-norbornene (VNB) is most preferred.

[0044] Examples of the aromatic non-conjugated polyene include vinylbenzene (including isomers thereof) and vinyl-isopropenylbenzene (including isomers thereof).

[0045] In typical embodiments of the present disclosure, ethylene / α-olefin copolymers containing at least 3 wt. % and up to and including 15 wt. % of units derived from one or more non-conjugated dienes can be produced.

[0046] In another embodiment, a polymer containing a non-conjugated diene is produced, and the non-conjugated diene is selected from dicyclopentadiene (DCPD), 5-ethylidene-2-norbornene (ENB), 5-vinyl-2-norbornene (VNB), 1,7-octadiene or 1,9-decadiene or a combination thereof. Preferably, the copolymer of the present disclosure contains 0.05 wt.% to 5 wt.%, more preferably 0.10 wt.% to 3 wt.% or 0.15 wt.% to 1.2 wt.% of units derived from VNB (all weight percentages are based on the total weight of the ethylene-α-olefin copolymer). In another embodiment, an ethylene / α-olefin copolymer containing units derived from 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene can be produced, for example, the ethylene / α-olefin copolymer produced can contain 2 wt.% to 15 wt.% of units derived from ENB and 0.05 wt.% to 4 wt.% of units derived from VNB.

[0047] Ethylene / α-olefin copolymers can be produced by the process according to the present disclosure, which may or may not contain units derived from other comonomers. Based on the total weight of the ethylene / α-olefin polymer, the sum of units derived from ethylene, α-olefins and optionally non-conjugated dienes can be greater than 90 wt.%, greater than 99 wt.% and include 100 wt.%.

[0048] Suitable comonomers further include one or more α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and combinations thereof.

[0049] In one embodiment, the diene polymer according to the present disclosure comprises 0 to 20% by weight of units derived from ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and combinations thereof.

[0050] Suitable comonomers also include, but are not limited to, one or more other copolymerizable comonomers that introduce functional groups, including crosslinking sites, branching sites, branches, or functionalized groups. In one embodiment of the present disclosure, the diene polymer comprises 0% to 10% by weight or 0% to 5% by weight of units derived from one or more such other comonomers.

[0051] Combinations of one or more comonomers of the same chemical type as described above as well as combinations of one or more comonomers from different chemical types may be used.

[0052] Solvent:

[0053] The polymerization is preferably carried out in the presence of at least one solvent. Preferably, the polymerization is carried out as a solution polymerization. Preferred solvents include one or more inert hydrocarbon solvents. Suitable solvents include C 5-12 Hydrocarbons such as pentane, hexane, heptane, octane, cycloheptane, cyclohexane, methylcyclohexane, methylcycloheptane, pentamethylheptane, hydrogenated naphtha, isomers and mixtures thereof. In another embodiment, the polymerization is carried out as a slurry polymerization.

[0054] Chain transfer agent:

[0055] In a preferred embodiment, the polymerization includes the use of one or more chain transfer agents to control the molecular weight of the polymer. Preferred chain transfer agents include hydrogen (H2). Other chain transfer agents include, but are not limited to, ethane, diethyl zinc, and combinations thereof.

[0056] catalyst:

[0057] The polymers can be produced by using one or more than one conventional polymerization catalysts which are suitable for the polymerization of the corresponding polymer to be produced. Typical examples include Ziegler-Natta catalysts, organometallic catalysts or metallocene-type catalysts. Ziegler-Natta catalysts are polymerization catalysts based on halides of transition metals, in particular titanium or vanadium.

[0058] Metallocene catalysts are organometallic catalysts in which a metal (usually Ti, Hf or Zr) is bonded to at least one cyclic organic ligand, preferably at least one cyclopentadienyl ligand, fluorenyl ligand or indenyl ligand. The catalyst in which the metal is bonded to two anionic aromatic ligands is generally referred to as a "metallocene catalyst" in the art. The catalyst in which the second anionic aromatic ligand is replaced by another organic ligand is referred to as a "semi-metallocene catalyst". The metal catalyst in which two anionic ligands are replaced by organic residues is referred to as a "post-metallocene catalyst" in the art. Metallocene catalysts include metallocene catalysts, post-metallocene catalysts and semi-metallocene catalysts. Suitable metallocene polymerization catalysts are known in the art and are described in, for example, WO2005 / 090418A1, WO2016 / 114914A1, WO2017 / 048448, US2015 / 0025209A1, all of which are incorporated herein by reference.

[0059] Typically, one or more promoters are added to the reaction vessel. Typical promoters include, but are not limited to, boron-containing activators. In a preferred embodiment, the activator (b) is selected from borane (C1) or borate (C2 or C3).

[0060] Suitable boron activators (C1) can be represented by the general formula BQ1Q2Q3. Suitable borate activators according to (C2) can be represented by the general formula G(BQ1Q2Q3Q4). Suitable borate activators according to (C3) can be represented by the general formula (JH)(BQ1Q2Q3Q4).

[0061] In the activator according to (C1), B is boron, and Q1 to Q3 are substituted or unsubstituted aryl groups, preferably phenyl groups. Suitable substituents include, but are not limited to, halogen, preferably fluorine, and C1 to C 40 Hydrocarbyl, preferably C1 to C 20 Specific examples of the activator according to (C1) include tris(pentafluorophenyl)borane, tris(2,3,5,6-tetrafluorophenyl)borane, tris(2,3,4,5-tetrafluorophenyl)borane, tris(3,4,5-trifluorophenyl)borane, tris(2,3,4-trifluorophenyl)borane, phenyl-bis(pentafluorophenyl)borane, and the like.

[0062] In the activator according to (C2), G is an inorganic or organic cation, B is boron, and Q1 to Q3 are the same as in (C1), Q4 is also a substituted or unsubstituted aryl group, preferably a substituted or unsubstituted phenyl group. The substituents include, but are not limited to, halogen, preferably fluorine, and C1 to C 40 Hydrocarbyl, preferably C1 to C 20 Alkyl or aromatic groups. Specific examples of borate groups (BQ1Q2Q3Q4) include, but are not limited to, tetrakis(pentafluorophenyl)borate, tetrakis(2,3,5,6-tetrafluorophenyl)borate, tetrakis(2,3,4,5-tetrafluorophenyl)borate, tetrakis(3,4,5-trifluorophenyl)borate, tetrakis(2,3,4-trifluorophenyl)borate, phenyltris(pentafluorophenyl)borate, tetrakis(3,5-bistrifluoromethylphenyl)borate, etc. Specific examples of G include ferrocenium cations, alkyl-substituted ferrocenium cations, silver cations, etc. Specific examples of organic cations G include triphenylmethyl cations, etc. G is preferably a carbonium cation, and particularly preferably a triphenylmethyl cation.

[0063] In the activator according to (C3), J represents a neutral Lewis base, (JH) represents a Bronsted acid, B is boron, and Q1 to Q4 and the borate group (BQ1Q2Q3Q4) are the same as in (C2). Specific examples of the Bronsted acid (JH) include trialkyl-substituted ammonium, N,N-dialkylanilinium, dialkylammonium, triarylphosphonium, and the like. Specific examples of the activator according to (C3) include, but are not limited to, triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(3,5-bistrifluoromethylphenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, N,N-2,4,6-pentamethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, diisopropylammonium tetrakis(pentafluorophenyl)borate, dicyclohexylammonium tetrakis(pentafluorophenyl)borate, triphenylphosphonium tetrakis(pentafluorophenyl)borate, tri(methylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, tri(dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, and the like.

[0064] Other cocatalysts include, but are not limited to, alkylaluminum such as trialkylaluminum, trimethylaluminum, triethylaluminum, triisobutylaluminum or tri-n-octylaluminum. Other examples include, but are not limited to, alkylaluminum halides, such as diethylaluminum chloride, dimethylaluminum chloride and ethylaluminum sesquichloride and aluminoxanes, such as methylaluminoxane (MAO), tetraisobutylaluminoxane (TIBAO) or hexaisobutylaluminoxane (HIBAO). Cocatalysts are also referred to as "activators" in the art. The presence of cocatalysts usually increases the rate of catalyst polymerization of olefins. Cocatalysts can also affect the molecular weight, degree of branching, comonomer content or other properties of polymers. Cocatalysts are usually introduced into the reactor together with the catalyst.

[0065] Scavenger:

[0066] Impurities can damage the catalyst by reducing the activity of the catalyst. Compounds that react with these impurities and convert them into compounds that are harmless to the activity of the catalyst are referred to as scavengers by those skilled in the art of polymerization. The scavenger can be optionally fed into one or more reactors of the method disclosed herein. Non-limiting exemplary scavengers include alkyl aluminum compounds, such as trimethyl aluminum, triethyl aluminum, triisobutyl aluminum and trioctyl aluminum. The scavenger can be the same compound as the cocatalyst, and in that case, it is usually used in an amount exceeding the amount required for fully activating the catalyst. The scavenger can also be introduced into the reactor together with the monomer feed, or introduced separately from the monomer feed via any other feed stream.

[0067] The scavenger can be used in combination with a sterically hindered hydrocarbon (preferably a hindered phenol) containing heteroatoms of Group 15 or 16 (preferably O, N, P and S atoms, more preferably O and N heteroatoms). Specific examples of sterically hindered hydrocarbons include, but are not limited to, tert-butyl alcohol, isopropanol, triphenylmethanol, 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 2,6-di-tert-butylaniline, 4-methyl-2,6-di-tert-butylaniline, 4-ethyl-2,6-di-tert-butylaniline, diisopropylamine, di-tert-butylamine, diphenylamine, and the like.

[0068] method:

[0069] The polymerization process for producing ethylene copolymers can be carried out as known in the art. In the conventional production of ethylene copolymers, ethylene is provided in gaseous form through a pipeline connected to a naphtha cracker producing ethylene. The ethylene provided in the process according to the present disclosure is provided in liquefied form, preferably at 0.1-10 bar, preferably 0.5-2 bar, more preferably in liquefied form at ambient pressure. Preferably, the liquefied ethylene has a temperature of -130°C to -50°C or -115°C to -90°C.

[0070] Liquefied ethylene can be fossil-derived, or it can be obtained from sustainable sources, such as selected from plant-based sources or recycled materials, and recycled materials can be plant-based materials or not plant-based materials. In contrast to those products obtained from fossil sources, the use of products derived from natural sources as an effective means to reduce atmospheric carbon dioxide concentration increases, therefore helping to reduce the greenhouse effect has been increasingly concerned. The difference between the products obtained from natural raw materials and the products from fossil sources is only in their renewable carbon content. Renewable carbon content can be confirmed by the method described in technology ASTM D 6866-18 Norm, "Standard Test Methods for Determining the Biobased Content of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis" described. In other words, the carbonaceous product obtained from natural sources has C14 isotopes of different amounts obtained from fossil sources, but is chemically identical. Renewable carbon source can include one or more plant materials selected from the group consisting of sugar cane, beet, maple, date palm, sugar palm, sorghum, American agave, corn, wheat, barley, sorghum, rice, potato, cassava, sweet potato, algae and fruit. Renewable carbon source can also include materials comprising cellulose, including wood, straw, paper, wood or pulp and leaf. Bio-based ethylene can be obtained by, for example, fermenting renewable carbon source to produce ethanol, and ethanol can be subsequently dehydrated to produce ethylene. Higher alcohols can be formed as by-products during fermentation, and usually purify bio-based ethanol before dehydration. In addition, or as an alternative, bio-based ethylene can be purified, for example, distilled, to remove impurities. The ethanol of biological origin (referred to as bioethanol) can be obtained by the sugar derived from culture (such as culture of sugar cane and beet), or the fermentation of the sugar derived from the starch (which is then associated with other cultures (such as corn)) of hydrolysis. Bio-based ethylene can be obtained from hydrolysis-based products of cellulose and hemicellulose, which can be found in many agricultural byproducts such as straw and sugarcane husks. Fermentation can be carried out in the presence of different microorganisms (e.g., the yeast Saccharomyces cerevisiae). The resulting ethanol can be converted into ethylene, for example, by a catalytic reaction at a temperature above 300°C. A variety of catalysts can be used for this purpose. Examples of the production of bioethanol and its conversion into ethylene include U.S. Patents Nos. 9,181,143 and 4,396,789.

[0071] The liquefied ethylene is fed to at least one evaporator where it is evaporated. The evaporator may be any suitable vessel that applies energy to the liquefied ethylene to convert it into a gaseous state. Typically, the liquefied ethylene is converted into a gaseous state having a pressure of 10 to 50 bar and a temperature of 20 to 50° C. The heat required to evaporate the ethylene may be provided by steam or any other suitable source. Heat from an isolated stream may also be used.

[0072] Preferably, the evaporated ethylene is combined with other monomers and solvent to form an eluate stream, also referred to as a reactor feed stream. Preferably, the eluate stream is produced in at least one receiver vessel. The receiver vessel can be any suitable container known in the art, and the container has necessary components such as inlets and outlets and a mixing device for receiving and merging monomers and solvents in liquid and gaseous form. The receiver vessel can also be used as an evaporator for liquid ethylene, but this is less preferred. The eluate stream is fed into at least one polymerization vessel that carries out at least a portion of the polymerization reaction. Before arriving at the polymerization vessel, the eluate stream is preferably subjected to at least one cooling to reduce its temperature. The evaporation of liquefied ethylene is used to reduce the temperature of at least a portion of the eluate stream. This can be achieved by heat exchange, for example, by allowing the eluate stream to be subjected to heat exchange by an evaporator. Preferably, the eluate stream and the liquefied ethylene flow countercurrently to each other.

[0073] Before the eluate stream is fed to the reactor, at least one additional cooler may be used to reduce the temperature of the eluate stream. Any cooler known in the art may be used. The cooler may, for example, be cooled using cold water or a refrigerant. The number and type of coolers may be adjusted based on the amount of the eluate feed stream and the stream to be cooled and the temperature to which the stream must be reduced. The temperature to which the eluate stream will be reduced will depend on the reaction temperature generated in the polymerization reaction. Typically, higher solids will generate more heat in the polymerization. The heat of polymerization also depends on the monomer composition of the polymer, and higher ethylene content generates more heat. Products of lower molecular weight may be polymerized into higher solids with still acceptable viscosity, and more pre-cooling may be required. To maximize energy savings, the used cooler may be adjusted to the required cooling capacity or the volume of the eluate stream route may be adjusted to the capacity of the ethylene evaporator and the available cooler. Typically, further cooling at low temperatures is more expensive (consuming more energy) than cooling at higher temperatures. In one embodiment of the present disclosure, the feed stream eluate stream is divided into at least two eluate streams, such as a first eluate stream and a second eluate stream. The first stream may be cooled by heat exchange with an evaporator, and the second stream may be cooled by a cooler. The streams may be combined and optionally cooled by at least one other cooler before entering the reactor. In one embodiment, only the first eluate stream is cooled by heat exchange with an evaporator. The first stream and the second stream are combined and may be fed into the reactor without further cooling or, for example, by one or more coolers. The eluate stream may be divided equally or unequally, for example, one stream may carry more eluates than another stream or may be fed at a higher rate than another stream. The eluate stream may be cooled before it is divided into at least two streams, or it may be divided into two or more eluate streams before being cooled.

[0074] The eluate stream is fed to at least one polymerization vessel, in which at least a portion of the polymerization reaction can be carried out. A single reactor vessel or multiple reactor vessels can be used. In the case of using multiple reaction vessels, the vessels can be connected in series or in parallel or a combination thereof. The reaction vessel has at least one device for mixing the reactor contents or at least a portion of the reactor contents. Typical reaction vessels include stirred tank reactors, preferably continuous stirred tank reactors (CSTRs), which means that the reactor contents are continuously stirred during the polymerization reaction. Such reactors are known in the art. Typically, a stirred tank reactor is a pressure reactor vessel comprising one or more rotating agitators and / or one or more impellers (preferably on a central agitator shaft) for mixing the reactor contents. Examples of impellers include, but are not limited to, INTERMIG, VISCOPROP and VARIOBLADE from Ekato Systems GmbH. Typically, one or more baffles are often mounted on the wall of the reactor to improve the mixing quality. However, other types of reaction vessels with mixing elements suitable for solution or slurry polymerization other than stirred tank reactors can also be used. Typically, one or more eluate streams introduce reactants into at least one reaction vessel, and an outlet stream is used to remove the reactor effluent. Typically, chain transfer agents, solvents, catalysts and monomer feeds are introduced at one or more points in the reaction vessel using various types of feed injectors. Typically, one or more catalyst components are introduced in a similar manner via one or more catalyst injectors and separately from these monomers. Chain transfer agents and solvents can be introduced separately from the monomer stream, but are preferably pre-added to the monomer stream and introduced into the reactor as a component of the monomer stream. Scavengers are preferably introduced by the monomer stream. In the case of a connected reaction vessel, the reaction mixture from one reaction vessel can be fed to another reaction vessel instead of a freshly separated stream or in addition to a freshly separated stream. Instead of using the reaction vessel in series, the reaction vessel can also be arranged in parallel. Reactor effluents can be combined, for example, in a mixer or another reactor, before or during the removal and treatment of the solvent of the polymer. For example, such an arrangement allows the production of multimodal polymers or polymer blends, such as "reactor blends", i.e., polymer blends obtained by wet mixing. A mixer can be used downstream of each feed or catalyst injector to improve the mixing of these feed streams to the bulk fluid.

[0075] Preferably, the polymerization reaction is carried out as a continuous polymerization. Preferably, the polymerization is carried out adiabatically, wherein the reactor temperature is set primarily by the target polymer concentration and the temperature of the monomer / solvent mixture feed stream. Typically, the educt feed is cooled to a temperature below 0°C before the educt feed enters the reaction vessel, when the temperature in the reactor should be maintained at a fixed predetermined value in the range of about 60°C to 120°C, for example to allow the polymerization to proceed to form a high molecular weight polymer while avoiding deactivation of the catalyst. When the reactor is operated adiabatically, there is no removal or addition of heat by internal or external heating or cooling devices. Instead, the temperature in the reactor is controlled entirely or primarily by the exothermic reaction, the temperature and flow rate of the reactants and effluents, the temperature and flow rate of the reactant stream entering the reactor, the residence time in the reactor and the temperature and flow rate of the effluent leaving the reactor, or a combination thereof. Preferably, the reactor is operated to prevent the formation of condensable monomer gases, that is, the reactor is operated to keep the monomer dissolved in the solvent or in a liquid state. For example, the reactor may contain sufficient solvent and may be operated at a pressure sufficient to prevent the formation of monomer gases. For example, the reactor may be filled with at least 50%, or at least 75%, preferably at least 90% or even 95% of solvent or liquid based on the available reactor volume, typically including components like reactants, solvent and reaction products, such as in liquid, dissolved form, suspended form or dispersed form. Preferably, the polymerization is operated under sufficient pressure so that the (unused and fresh) monomers remain dissolved in the solvent or remain in liquid state or both.

[0076] In one embodiment of the present disclosure, the polymerization is carried out in at least one reaction vessel which is preferably operated as a stirred tank reactor. Typically, a temperature of about 50° C. to 160° C. or 60° C. to 120° C. can be reached in at least one reaction vessel of the polymerization unit during the polymerization. The temperature is adapted to the polymerization rate and the polymer to be produced and may depend on the reaction system used. However, the method is carried out so that the temperature in the reaction vessel in which the polymerization reaction is carried out is below the temperature at which the catalyst used for the polymerization is deactivated.

[0077] The residence time of the reactants in the reaction vessel is suitable for producing a reaction mixture containing a desired amount of the desired polymer. In addition to the polymer, the reaction mixture may contain a solvent and may also contain unreacted monomers and optionally chain transfer agents, catalysts and other components. The outlet stream generally removes the reactor effluent containing the reaction mixture. The reaction mixture can be fed to a subsequent reactor for further polymerization with or without fresh monomers (with or without fresh or different catalysts), or it can be sent to a post-processing section where the polymer is separated. The post-processing section may include a devolatilization unit, wherein solvent and / or unreacted monomers are removed by, for example, one or more strippers. The post-processing unit may include one or more containers, pumps and mixers for post-processing of the polymer or for mixing additional ingredients, such as extender oils or other additives. Solvents and unreacted monomers can be recycled and reused in the polymerization process. Before entering the post-processing unit, the catalyst contained in the outlet stream can be terminated by adding polar components such as water, alcohol, acid, ester, O2, CO, CO2 or any component known to react with the catalyst and stop polymerization. If an oil-extended polymer is to be produced as known in the art, one or more extender oils may be added to the reaction mixture before removing the solvent. Suitable extender oils include, but are not limited to, petroleum oils, such as aromatic and naphthenic oils; polyalkylbenzene oils; organic acid monoesters, such as alkyl and alkoxyalkyl oleates and stearates; organic acid diesters, such as dialkyl, dialkoxyalkyl and alkylaryl esters of phthalic, terephthalic, sebacic, adipic and glutaric acids; glycol diesters, such as tri-, tetra-, and polyethylene glycol dialkanoates; trialkyl trimellitates; trialkyl, trialkoxyalkyl, alkyl diaryl and triaryl phosphates; chlorinated paraffin oils; coumarone-indene resins; pine tar oil; vegetable oils, such as castor, tall, rapeseed and soybean oils, and their esters and epoxidized derivatives, and the like.

[0078] Example

[0079] The present disclosure will now be further illustrated by examples, but it is not intended that the present disclosure be limited to the specific examples given.

[0080] Test method:

[0081] Polymer composition:

[0082] Fourier transform infrared spectroscopy (FT-IR) can be used to determine the composition of the copolymer on the pressed polymer film, the C2 / C3 ratio according to ASTM D3900 (revised: 2017), and the diene content according to D6047 (revised: 2017).

[0083] Branching:

[0084] Δδ is a measure of the presence of long chain branches in the polymer structure. The lower the Δδ value, the more long chain branches are present in the polymer. The method is described in HC Booij, in Kautschuk+Gummi Kunststoffe, Vol. 44, No. 2, pp. 128-130, 1991, which is incorporated herein by reference.

[0085] Molecular Weight:

[0086] Molecular weight (weight average molecular weight (Mw), number average molecular weight (Mn) and Mz values) and molecular weight distribution (MWD) can be determined by gel permeation size exclusion chromatography (GPC) using a Polymer Char GPC-IR from Polymer Characterization S.A, Valencia, Spain. The size exclusion chromatograph was equipped with an online viscometer (Polymer Char V-400 viscometer), an online infrared detector (IR5 MCT), 3 AGILENT PL OLEXIS columns (7.5 x 300 mm) and a Polymer Char autosampler. Universal calibration of the system was performed with polyethylene (PE) standards.

[0087] The polymer samples were weighed (concentration range 0.3-1.3 mg / ml) into the vials of the PolymerChar autosampler. In the autosampler, the vials were automatically filled with solvent (1,2,4-trichlorobenzene stabilized with 1 g / l di-tert-butyl-p-cresol (DBPC)). The samples were kept in a high temperature oven (160°C) for 4 hours. After this dissolution time, the samples were automatically filtered through an in-line filter before injection onto the columns. The chromatography system was operated at 160°C. The flow rate of the 1,2,4-trichlorobenzene eluent was 1.0 mL / min.

[0088] Mooney viscosity:

[0089] The Mooney viscosity of the copolymer sample can be measured according to ISO 289 (revised 2015). The measurement condition is ML (1+4) @ 125°C.

[0090] Modeling

[0091] The energy consumption for two polymerizations for the preparation of two different EPDM polymers was calculated based on a thermodynamic model by using Aspen-Plus software. While the polymerization remained the same, the process setup was changed by cooling the reactor feed differently using evaporative cooling from the evaporation of liquefied C2.

[0092] The overall polymerization setup for calculation is as follows: monomers (ethylene, propylene, other monomers) are fed into a receiver container and combined with a solvent (mixture of hexane isomers) for polymerization to form an educt mixture. The educt mixture is fed and cooled to 10°C by a cooler (cooler 100). Cooler 100 is cooled using cold water. The educt stream is then passed into the reactor in different ways described in the following embodiments. In some embodiments, additional coolers (coolers 200 and coolers 300) are used, which use electricity and refrigerants for cooling. Liquefied ethylene is used as a monomer. In those embodiments of evaporating liquefied ethylene, the enthalpy of ethylene converted from liquid ethylene (-104°C, 1 bar) to gaseous ethylene (30°C, 13.5 or 16.5 bar) is used. The model assumes that the evaporation temperature for evaporating ethylene is -42.5°C or -35.5°C. The evaporator uses steam as an energy source, and the energy required for evaporation is calculated to be 106kWh / ton of polymer produced.

[0093] In the process setup for the thermodynamic model, the polymerization catalyst composition is fed separately into the polymerization vessel. The polymerization vessel is a continuous stirred tank reactor operated as a fully overflowed vessel and the polymerization is carried out adiabatically (i.e. there is no external or internal cooling of the polymerization reactor). The values ​​of catalyst concentration, retention time, amount and temperature of the feed stream are taken so that the temperature in the polymerization reactor as indicated in the examples is reached. The polymerization conditions used in Examples 1, 3 and 5 for the preparation of Polymer 1 are the same. The polymerization conditions used in Examples 2, 4, 6 and 7 for the preparation of Polymer 2 are the same. Polymer 1 is an EPDM polymer (65% ethylene, 6.4% ENB+VNB, 28.6% propylene) with a molecular weight (Mw) of 640 kg / mol. Polymer 1 is oil-extended after polymerization.

[0094] Polymer 2 is EPDM (66% ethylene, 5.3% ENB+VNB, 28.7% propylene, molecular weight (Mw) 250).

[0095] Example 1 (Comparative): Evaporatively Cooled Polymerization without Evaporative Stream 1

[0096] Liquid ethylene at a temperature of -104°C and ambient pressure is fed to an ethylene evaporator (C2-EVAP) where it is converted into gaseous form at a temperature of 30°C and a pressure of 30 bar. Steam is used for the energy of evaporation. The ethylene is then fed to a receiver vessel which also receives liquid propylene and other comonomers.

[0097] This mixture formed in the receiver vessel is fed as an educt stream through cooler 100 and cooled to 10° C. The educt stream is then fed through cooler 200 where it is cooled to -2° C. before being fed to the polymerization reactor. Cooler 300 is not used in this example. The reactor temperature is maintained at 70° C. The cooler and evaporator consume a total energy of 317 kWh / ton.

[0098] Example 2 (Comparative): Polymerization 2 without Evaporative Cooling of Feed Stream

[0099] The same process setup as in Example 1 was used, except that polymerization 2 was considered, in which the reactor temperature was maintained at 90°C and the temperature of the educt stream was -37°C before entering the reactor vessel. In this setup, the educt stream was cooled from 10°C to -20°C using cooler 200, requiring 198 kWh / ton of energy. The educt stream was then cooled to -37°C by an additional cooler 300 before being fed into the reactor. Cooler 300 consumed 87 kWh / ton. The total energy consumption for cooling was calculated to be 388 kWh / ton.

[0100] Example 3 (according to the invention): Polymerization 1 with evaporative cooling of the separate feed stream

[0101] Example 1 is repeated, except that after the eluate stream passes through cooler 100, it is divided into two eluate streams: one stream is cooled to -20°C with cooler 200, consuming 34 kWh / ton of energy. The other stream bypasses cooler 200 and is heat exchanged with an ethylene vaporizer to cool the stream to 0.1°C. The two eluate streams are then combined, which produces an eluate stream with a temperature of -2°C. The combined stream is then fed to a polymerization reactor. Cooler 300 is not used in this example. The total energy consumed is calculated to be 212 kWh / ton, compared to 317 kWh / ton for the process setting of Example 1.

[0102] Example 4 (according to the invention): Evaporatively cooled polymerization 2 with separate feed streams

[0103] The process set-up of Comparative Example 2 was used, except that the eluate stream leaving cooler 100 was split into two streams. The first eluate stream was fed into cooler 200 and cooled from 10°C to -20°C. This consumed energy in the amount of 92 kWh / ton. The second eluate stream was heat exchanged with an ethylene evaporator to cool the stream to -20°C, consuming 106 kWh / ton of energy. Before entering the reactor vessel, the streams were combined and fed through cooler 300 to cool to -37°C. The total energy consumed in this set-up was calculated to be 282 kWh / ton, compared to 388 kWh / ton calculated for Comparative Example 2.

[0104] Example 5 (according to the invention): Polymerization 2 with direct feeding of liquid ethylene into a receiver vessel.

[0105] The process set-up of Example 2 was used, except that the liquid ethylene was fed directly to the receiver vessel without evaporation, and the monomer-solvent mixture was cooled in the receiver vessel without causing freezing of the components. Calculations showed that less energy was saved compared to Examples 4 and 6. Although the need for water cooling of the receiver vessel was less, chillers 200 and 300, which require electrical energy, did not result in savings.

Claims

1. A method for preparing an ethylene copolymer comprising the following steps: (i) feeding liquefied ethylene into at least one evaporator to evaporate at least a portion of said liquefied ethylene, (ii) combining the evaporated ethylene with at least one solvent and at least one comonomer in a receiver vessel to produce an educt stream comprising ethylene, at least one comonomer and at least one solvent, (iii) feeding the educt stream into at least one reaction vessel, wherein at least one polymerization reaction is carried out in the presence of at least one polymerization catalyst to produce an ethylene copolymer, wherein the temperature of the educt stream is reduced at least once before the educt stream enters the reactor vessel, and wherein vaporization of the liquefied ethylene is used to reduce the temperature of at least a portion of the educt stream.

2. The method according to claim 1, wherein: The receiver vessel acts as an evaporator.

3. The method according to claim 1, wherein: The liquefied ethylene is evaporated in at least one evaporator, and the evaporated ethylene is fed to the receiver vessel.

4. The method according to claim 1, wherein: The liquefied ethylene is evaporated in at least one evaporator, and the evaporated ethylene is fed to the receiver vessel, wherein the receiver does not act as an evaporator.

5. The method according to claim 1, wherein: In addition to using the vaporization of the liquefied ethylene, at least one cooling operation is performed to cool the educt stream before feeding the educt stream to at least one reactor vessel.

6. The method according to claim 1, wherein: In addition to using the evaporation of the liquefied ethylene, at least one cooling operation is performed to cool the educt stream before feeding the educt stream into at least one reactor vessel, and a cooler is used, which uses water or a refrigerant for cooling in the at least one cooling operation.

7. The method according to claim 1, wherein: The method further comprises: (iv) separating the eluate stream into at least one first eluate stream and at least one second eluate stream, (v) feeding the at least one first eluate stream through at least one cooler to reduce the temperature of the first eluate stream, (vi) heat exchanging the at least one second educt stream with an ethylene vaporizer to reduce the temperature of the at least one second educt stream, (vii) Optionally, combining the first educt stream and the second educt stream prior to entering a reactor vessel, and optionally, feeding the combined educt stream to at least one additional cooler prior to entering the reactor vessel.

8. The method according to claim 1, wherein: The liquefied ethylene is maintained at a pressure of 0.1 to 10 bar, preferably 0.5 to 2 bar.

9. The method according to claim 1, wherein: The liquefied ethylene has a temperature of from -130°C to -50°C or from -115°C to -90°C.

10. The method according to claim 1, wherein: The polymerization was carried out adiabatically.

11. The method according to claim 1, wherein: The polymerization is a continuous polymerization.

12. The method according to claim 1, wherein: Said liquefied ethylene of fossil origin or said liquefied ethylene obtained from a sustainable source is selected from plant-based sources or recycled materials, which may be plant-based materials or non-plant-based materials.

13. The method according to claim 1, wherein: The ethylene copolymer is a copolymer comprising units derived from ethylene and propylene and optionally at least one copolymerizable non-conjugated diene or a combination of two or more copolymerizable non-conjugated dienes.

14. The method according to claim 1, wherein: The ethylene copolymer is a copolymer comprising units derived from ethylene, propylene and at least one copolymerizable non-conjugated diene or a combination of two or more copolymerizable non-conjugated dienes, wherein the copolymerizable non-conjugated diene is selected from ENB, VNB and DCPD.

15. The process for preparing an ethylene copolymer according to claim 1, comprising at least 30 wt.% of units derived from ethylene, based on the total weight of the polymer, and wherein the ethylene copolymer has a molecular weight Mw of at least 50 kg / mol.

16. The method according to claim 1, wherein: The reactor vessel is a continuously stirred tank.

17. The method according to claim 1, wherein: The polymerization reaction temperature reaches a temperature of 60°C to 120°C, and wherein the temperature of the educt stream is reduced to a temperature below 0°C before entering at least one reactor vessel.

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