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    process for preparing ethylene copolymer in the presence of free radical polymerization initiator by ethylene copolymerization, ethylene copolymer obtained by such a process and its use, as well as process for extrusion coating of a substrate the present invention refers to a process for the preparation of ethylene copolymers in the presence of free radical polymerization initiator at pressures in the range of 160 mpa to 350 mpa and temperatures in the range of 100 ° c to 350 ° c in a tubular reactor by copolymerization of ethylene, a bi-comonomer or multifunctional and, optionally, additional comonomers, where the bi- or multifunctional comonomer has at least two different functional groups, of which at least one is an unsaturated group, which can be incorporated into the growing polymer chain, and at least one other group functional agent that acts as a chain transfer agent in the polymerization of ethylene by radicals, ethanol copolymers ilene obtained by this process, use of ethylene copolymers for extrusion coating and a process for extrusion coating of a substrate selected from the group consisting of paper, cardboard, polymeric film and metal with these ethylene copolymers.
    公开号:BR112013016031B1
    申请号:R112013016031
    申请日:2011-12-19
    公开日:2020-04-07
    发明作者:Gall Barbara；Lilge Dieter；Littmann Dieter；Mannebach Gerd；Vittorias Iakovos；Busch Markus；Herrmann Thomas
    申请人:Basell Polyolefine Gmbh；
    IPC主号:
    专利说明:

    Invention Patent Descriptive Report for PROCESS TO PREPARE ETHYLENE COPOLYMER IN THE PRESENCE OF POLYMERIZATION BEGINER BY FREE RADICALS BY ETHYLENE COPOLIMERIZATION, ETHYLENE COPOLYMER OBTAINED BY SUCH PROCESS AND ITS USE, AS WELL AS A PROCESS OF REPLACEMENT BY AN EXTRACTION FOR EXTRACTION.
    Description [0001] The present invention relates to a process for the preparation of ethylene copolymers in the presence of free radical polymerization initiator at pressures in the range of 160 MPa to 350 MPa and temperatures in the range of 100 ° C to 350 ° C in a tubular reactor by copolymerization of ethylene, a bi- or multifunctional comonomer and, optionally, additional comonomers and also refers to ethylene copolymers obtained by this process, the use of ethylene copolymers for extrusion coating and a process for extrusion coating of a substrate selected from the group consisting of paper, cardboard, polymeric film and metal with these ethylene copolymers.
    [0002] Polyethylene is the most widely used commercial polymer. It can be prepared by a few different processes. Polymerization in the presence of free radical initiators at high pressures was the first method discovered to obtain polyethylene and remains a valuable process, with great commercial relevance for the preparation of low density polyethylene (LDPE). LDPE is a versatile polymer, which can be used in various applications, such as film, coating, molding and insulation of wires and cables. Consequently, there is still a demand for the optimization of processes for their preparation.
    [0003] Common reactors for the preparation of LDPE polymers
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    2/20 at high pressure are tubular reactors or autoclave reactors with agitation. The advantages of polymerization in a tubular reactor are the greater rotations that can be achieved in the polymerization process, the process is easier to scale up and therefore it is possible to build world-scale facilities, and polymerization in general is more economical , because of less specific consumption of inputs, such as electricity and cooling water. However, LDPE polymers prepared in a high pressure tubular reactor have certain disadvantages for some applications. Compared to similar melt flow rate (MFR) and similar density LDPE polymers prepared in a high pressure autoclave LDPE reactor, LDPE polymers prepared in a tubular reactor generally have a narrower molecular weight distribution and a lesser amount of long chain branching (LCB).
    [0004] An example of an application in which the LDPE prepared in a tubular reactor is inferior to the LDPE prepared in an autoclave reactor is the extrusion coating. In this process, the melted LDPE is extruded through a slit matrix and cast into a film, which is then coated on a substrate such as paper, cardboard, a polymeric film, such as a polyethylene terephthalate (PET) film or a biaxially oriented polypropylene film (BOPP), or a metal such as aluminum foil. For good processability, LDPE must show a stable network, that is, the cast film of the matrix must not oscillate, and a low taper is required, that is, the ratio of the film width to the matrix width must not be too low. In addition, high processing temperatures of up to 350 ° C are required for the post-treatment of the polymeric film produced to increase its adhesion properties on substrates such as metal, paper or
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    3/20 cardboard. To meet these requirements, a certain level of LCB is advantageous.
    [0005] To provide an LDPE copolymer that increases the network stability during the extrusion coating process, WO 2006/094723 sets out a process for the preparation of an ethylene copolymer in a tubular reactor, in which ethylene is copolymerized with a difunctional (meth) acrylate or higher. WO 2007/110127 teaches how to copolymerize ethylene and a bifunctional α, ω-alkadiene for the same purpose. However, these bifunctional or higher comonomers can only be used in relatively small amounts, because otherwise too large a very high molecular component is produced, corresponding to a high risk of gel formation, particularly if these comonomers are not are perfectly homogenized in the reaction medium. In addition, the tendency for the formation of LCB is limited.
    [0006] Thus, the objective of the present invention was to overcome the disadvantages of LDPE polymers prepared by polymerization in a tubular reactor and to present the possibility of obtaining LDPE polymers with an increased amount of long chain branching in that reactor.
    [0007] We found that this goal is achieved by a process for the preparation of ethylene copolymers in the presence of free radical polymerization initiator at pressures in the range of 160 MPa to 350 MPa and temperatures in the range of 100 ° C to 350 ° C in a tubular reactor, by copolymerization of ethylene, a bi- or multifunctional comonomer and, optionally, additional comonomers, in which the bi- or multifunctional comonomer has at least two different functional groups, of which at least one is an unsaturated group, which can be incorporated into the polymer chain in
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    4/20 growth, and at least one other functional group that acts as a chain transfer agent in the polymerization of ethylene by radicals.
    [0008] Furthermore, we discovered ethylene copolymers obtained by this process, the use of ethylene copolymers for extrusion coating and a process for extrusion coating of a substrate selected from the group consisting of paper, cardboard, polymeric film and metal with those ethylene copolymers.
    [0009] The features and advantages of the present invention can be better understood with the following description and accompanying drawings, in which Figure 1 schematically shows the arrangement of a tubular polymerization reactor that can be used in the process of the present invention. Figure 2 represents the number of long chain branches of the LDPE contained in the reaction mixture throughout the tubular reactor for some polymerizations described in the examples, and Figure 3 shows the temperature profiles along the tubular reactor for these examples.
    [00010] The process of the present invention is suitable for the preparation of ethylene copolymers. For the purposes of the present invention, polymers are all substances that are composed of at least two monomer units. They are preferably LDPE polymers with an average molecular weight Mn of more than 20,000 g / mol. However, the method of the invention can also be advantageously employed in the preparation of oligomers, waxes and polymers with an Mn molecular weight of less than 20,000 g / mol.
    [00011] Possible initiators for starting free radical polymerization in the respective reaction zones are, for example, air, oxygen, azo compounds or peroxide polymerization initiators. Initiation using organic peroxides or azo compounds represents a particularly preferred embodiment of the process of the invention.
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    5/20
    Examples of suitable organic peroxides are peroxyesters, peroxycetals, peroxycetones and peroxycarbonates, for example, di (2-ethylhexyl) peroxydicarbonate, dicyclohexyl peroxydicarbonate, diacetyl peroxydicarbonate, tert-butyl peroxycarbonate, tert-butyl peroxide, di-tert-peroxide, tert-butyl peroxide. di-tert-amyl, dicumyl peroxide, 2,5-dimethyl-2,5-di-tert-butylperoxyethane, tert-butyl cumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hex -3 -ine, 1,3-diisopropyl monohydroperoxide or tert-butyl hydroperoxide, didecanoyl peroxide, 2,5-dimethyl-2,5-di (2-ethylexanoylperoxy) hexane, tert-amyl peroxy-2-ethylexanoate, peroxide dibenzoyl, tert-butyl peroxy-2 ethylexanoate, tert-butyl peroxyethylacetate, tert-butyl peroxydiethylisobutyrate, tert-butyl peroxy-3,5,5-trimethylexanoate, 1,1-di (tert-butylperoxy) -3 , 3,5-trimethylcyclohexane, 1,1-di (tertbutyl peroxy) cyclohexane, tert-butyl peroxyacetate, cumila peroxyenedecanoate, but tert-butyl xineodecanoate, tert-butyl peroxypivalate, tert-butyl peroxineodecanoate, tert-butyl permaleate, tert-butyl peroxypivalate, tert-butyl peroxyisononanoate, diisopropylbenzene hydroperoxide, butene peroxide, peroxybenzoate methyl isobutyl hydroperoxide ketone, 3,6,9-triethyl-3,6,9-trimethyl-triperoxycyclononane and 2,2-di (tert-butylperoxy) butane. Azoalkanes (diazenes), azodicarboxylic esters, azodicarboxylic dinitriles, such as azobisisobutyronitrile, and hydrocarbons that decompose to free radicals and are also called C-C initiators, for example, 1,2-diphenyl-1,2-dimethylethane derivatives
    1,1,2,2-tetramethylethane, are also suitable. It is possible to use individual primers or, preferably, mixtures of several primers. There is a wide range of initiators, in particular peroxides, commercially available, for example, Akzo Nobel products offered under the trade names Trigonox ® or
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    Perkadox®.
    [00012] In a preferred embodiment of the process of the invention, peroxide polymerization initiators with a relatively high decomposition temperature are used. Suitable peroxide polymerization initiators include, for example, 1,1di (tert-butylperoxy) cyclohexane, 2,2-di (tert-butylperoxy) butane, tert-butyl peroxy3,5,5-trimethylexanoate, tert-butyl peroxybenzoate, 2,5dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butyl cumyl peroxide, di-tert-butyl peroxide and 2,5-dimethyl-2,5-di (tert-butylperoxy) hex-3 -in, and preference is given in particular to the use of di-tert-butyl peroxide.
    [00013] The initiators can be used individually or as a mixture in concentrations of 0.1 to 50 moles / t of produced polyethylene, in particular from 0.2 to 20 moles / t, in each reaction zone. In a preferred embodiment of the present invention, the free radical polymerization initiator that is fed to a reaction zone is a mixture of at least two different azo compounds or organic peroxides. If these initiator mixtures are used, it is preferable that they are fed to all reaction zones. There is no limit to the number of different initiators in this mix; however, preferably, the mixtures are composed of two to six and, in particular, four or five different initiators. It gives particular preference to the use of mixtures of initiators that have different decomposition temperatures.
    [00014] It is often advantageous to use the initiators in the dissolved state. Examples of suitable solvents are aliphatic ketones and hydrocarbons, in particular octane, decane and isododecane, as well as other saturated C8-C25-hydrocarbons. The solutions comprise the initiators or mixtures of initiators in proportions of 2 to 65% by weight, preferably from 5 to 40% by weight and, particularly preferably, from 10 to 30% by weight.
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    7/20 [00015] The reaction mixture generally comprises polyethylene in an amount ranging from 0 to 45% by weight, based on the total monomer-polymer mixture, preferably from 0 to 35% by weight.
    [00016] The process of the invention is carried out at pressures from 160 MPa to 350 MPa, with pressures from 180 MPa to 340 MPa being preferred and pressures from 200 MPa to 330 MPa being particularly preferred. Temperatures are in the range of 100 ° C to 350 ° C, preferably from 120 ° C to 340 ° C and, most particularly preferably, from 150 ° C to 320 ° C.
    [00017] The process of the present invention can be carried out with all types of tubular reactors suitable for high pressure polymerization. Such reactors may have one or more reaction zones and preferably have 2 to 6 reaction zones and, particularly preferably, 3 to 5 reaction zones. The number of reaction zones is given by the number of injection points for the initiator. This means that, in each reaction zone, polymerization is initiated by the addition of initiators that decompose into free radicals. Typically, each reaction zone is followed by a zone of the tubular reactor in which the reaction mixture cools. Preferred tubular reactors have a length to diameter ratio greater than 1,000, preferably 10,000 to 40,000 and particularly 25,000 to 35,000. Figure 1 shows a typical arrangement for a suitable tubular polymerization reactor without, however, restricting the invention to the modalities described therein.
    [00018] Fresh ethylene, which is normally under a pressure of 1.7 MPa, is first compressed to a pressure of about 30 MPa by means of a primary compressor 1 and then compressed to a reaction pressure of about 300 MPa using a high pressure compressor 2. The molecular weight regulator is added to the primary compressor 1. The reaction mixture that comes out of the
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    8/20 high pressure 2 is fed to the preheater 3, where the reaction mixture is preheated to the reaction starting temperature of about 120 ° C to 220 ° C, and then transported to the tubular reactor 4.
    [00019] The tubular reactor 4 is basically a long, thick-walled pipe with cooling jackets to remove the reaction heat released from the reaction mixture via a refrigerant circuit (not shown). Usually, it is about 0.5 km to 4 km, preferably 1.5 km to 3 km and particularly from 2 km to 2.5 km in length. The internal diameter of the pipe is usually in the range of about 30 mm to 120 mm and preferably from 60 mm to 90 mm.
    [00020] The tubular reactor 4 shown in Figure 1 has four spatially separated primer injection points 5a to 5d for feeding primers or mixtures of primers I1 to I4 to the reactor and therefore also four reaction zones. With the supply of suitable free radical initiators, which decompose at the temperature of the reaction mixture, to the tubular reactor, the polymerization reaction begins. The reaction heat generated raises the temperature of the reaction mixture, as more heat is generated than can be removed from the walls of the tubular reactor. The rising temperature increases the rate of decomposition of free radical initiators and accelerates polymerization until all free radical initiators are consumed. After that, no more heat is generated, and the temperature decreases again, as the temperature of the reactor walls is lower than that of the reaction mixture. Therefore, the part of the tubular reactor downstream of an initiator injection point, in which the temperature rises, is the reaction zone, whereas the part afterwards, in which the temperature decreases again, is predominantly a cooling zone. .
    [00021] The quantity and nature of free radical initiators
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    9/20 added determines how much the temperature rises and, therefore, allows the adjustment of that value. Typically, the temperature rise in the first reaction zone is adjusted to be in the range of 70 ° C to 170 ° C and 50 ° C to 130 ° C for subsequent reaction zones, depending on product specifications and reactor configuration. The reaction mixture leaves the tubular reactor (4) through a high pressure relief valve 6 and passes through a post-reactor cooler 7. After that, the resulting polymer is separated from unreacted ethylene and other low molecular weight compounds (monomers , oligomers, polymers, additives, solvent and others) by means of a high pressure separator (8) and a low pressure separator (9), discharged and pelleted using an extruder and granulator 10.
    [00022] The ethylene that was separated in the high pressure separator 8 is fed back to the inlet end of the tube reactor 4 in the high pressure circuit 11 to 30 MPa. It is first rid of other constituents in at least one purification stage and then added to the monomer stream between primary compressor 1 and high pressure compressor 2. Figure 1 shows a purification stage consisting of a heat exchanger 12 and a separator 13. However, it is also possible to use a plurality of purification stages. The high pressure circuit 11 normally separates waxes. [00023] The ethylene that was separated in the low pressure separator 9, which also comprises, among others, most of the low molecular weight products of polymerization (oligomers) and the solvent, is worked in the low pressure circuit 14 at a pressure of about 0.1 to 0.4 MPa in a plurality of separators, with a heat exchanger being located between each of the separators. Figure 1 shows two purification stages consisting of heat exchangers 15 and 17 and separators 16 and 18. However, it is also possible to use only one purification stage or, preferably, more than
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    10/20 two stages of purification. The low pressure circuit 14 normally separates oil and waxes.
    [00024] Different configurations for a suitable tubular polymerization reactor are, of course, also possible. It may be advantageous to add the monomers not only at the inlet to the reactor tube, but to feed them, preferably cooled, at a plurality of different points in the reactor. This is done, in a particularly preferred way, at the beginning of additional reaction zones and particularly if oxygen or air is used as the initiator, which is normally added to the monomer feed in the primary compressor.
    [00025] In the process of the present invention, ethylene is copolymerized with a bi- or multifunctional comonomer with at least two different functional groups. At least one of the functional groups is an unsaturated group, which can be incorporated into the growing polymeric chain and qualifies the molecule as a comonomer that can be copolymerized with ethylene, and at least one other functional group that acts as a chain transfer agent in the polymerization of ethylene by radicals. If the multifunctional biou comonomer comprises two or more different unsaturated groups, which can be incorporated into the growing polymer chain, the chances of the groups being incorporated into the growing chain differ because they have different chemical structures. As according to the present invention at least one of the functional groups of the bi- or multifunctional comonomer can act as a chain transfer agent, the bi- or multifunctional comonomer comprises an additional functional group that can act as a chain transfer agent or one of the functional groups, preferably one that is not most likely to be incorporated into the growing chain, can act as
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    11/20 chain transfer.
    [00026] The bi- or multifunctional comonomer preferably has a high reactivity in polymerization by free radicals, which leads to an almost complete consumption of the bi- or multifunctional comonomer with the introduction of functional groups, which can act as transfer agents chain, in LDPE chains. After incorporating one of the bi- or multifunctional comonomers into the chain, the polymer chain obtained comprises at least one functional group that is more likely to react with free radicals from, for example, growing polymer chains and thereby act as chain transfer agent. As a consequence of this reaction, a free radical is generated at a position along the polymer chain, which can then either start an additional growing polymer chain or combine with another free radical, like another growing polymer chain. Consequently, an additional long chain branch is formed in a previously obtained polymer chain. Preferred bi- or multifunctional comonomers have a reactivity ratio in copolymerization with ethylene at 200 MPa and 180 ° C in the range of 0.1 to 500, preferably from 0.5 to 100 and most preferably from 0.9 to 50.
    [00027] The different reaction modes and the different reactivities of the functional groups of the bi- or multifunctional comonomer also reduce the risk of gel formation in the produced LDPE. Because of their different reaction behaviors, there is a high probability that the functional groups of the bi- or multifunctional comonomer will react at different times and therefore also in different places, and there is, consequently, a lesser risk that a rapid reaction of unevenly distributed comonomers results in crosslinking of polymer chains and an increase in the level of
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    12/20 gel. Therefore, it is possible to work with larger amounts of the bi- or multifunctional comonomer and obtain a reduced gel level compared to a copolymerization with a bifunctional diene comonomer or di- or multifunctional acrylate, which show a greater tendency to crosslink polymer chains.
    [00028] Preferably, the functional group of the bi- or multifunctional comonomer that is most likely to be incorporated into the growing chain is an acrylate group, a methacrylate group, an amide group or a double bond and, more preferably, a group acrylate or a methacrylate group. In addition, the bi- or multifunctional comonomer comprises at least one functional group that can act as a chain transfer agent in free radical polymerization. This functional group is preferably not most likely for the comonomer functional groups to be incorporated into the growing chain and is preferably an aldehyde group, a ketone group, an alcohol group, a thiol group or a double bond. The functional groups of the bi- or multifunctional comonomer are usually separated by a spacer group, which preferably separates the functional groups by at least one atom. Suitable spacer groups are, for example, composed of -CH2-, -Si (CH3) 2-, -CH2-O- and / or -Si (CH3) 2-O- units and comprise a chain from 1 to 32, of preferably from 1 to 22 and most preferably from 1 to 12 atoms.
    [00029] The bi- or multifunctional comonomers of the present invention are preferably bifunctional and comprise an unsaturated group, which can be incorporated into the growing polymer chain, and another functional group, which can act as a chain transfer agent in the polymerization of ethylene by radicals. Preferred examples of such bifunctional comonomers are compounds of general formula (I):
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    (I) where the substituents and indices have the following meanings:
    R 1 is methyl or hydrogen,
    X 1 is -O- or -NH-, preferably -O-,
    R 2 can be the same or different and are -Si (CH3) 2-, -CH2-Oor -Si (CH3) 2-O-, and preferably all R 2 are -CH2-, n is 1 to 32, from preferably from 1 to 22 and more preferably from 1 to 12,
    X 2 is -C (O) -, -CHOH- or -CHSH-, preferably -C (O) -, and
    R 3 is C1-C10-alkyl, preferably methyl, or hydrogen, and particularly preferably hydrogen, or the unit X 2 -R 3 represents -CH = CH2.
    [00030] Preferably, the bi- or multifunctional comonomer is first mixed with ethylene before being brought into contact with the free radical polymerization initiator. The bi- or multifunctional comonomer is therefore preferably added to the ethylene stream between the primary and the high pressure compressor. This mixture of ethylene and bi- or multifunctional comonomer can be fed only at the entrance to the tubular reactor. It is also possible to feed more than one stream of ethylene and bi- or multifunctional comonomer and therefore to feed one or more of these streams as collateral streams to the tubular reactor. However, it is also possible to feed the bi- or multifunctional comonomer of the present invention as a separate current to the reactor, at the reactor inlet and / or as a collateral current to one or more points along the reactor.
    [00031] The process of the present invention is not only suitable for the copolymerization of ethylene and the bi- or multifunctional comonomer, but also for the copolymerization of ethylene, the
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    14/20 bi- or multifunctional comonomer and one or more additional comonomers that are copolymerizable by free radicals with ethylene under high pressure. Examples of suitable additional comonomers are C3-C8-carboxylic acids α, β-unsaturated, in particular maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid and crotonic acid, derivatives of C3-C8-carboxylic acids α, β- unsaturated, for example, unsaturated C3-C15-carboxylic esters, in particular C1-C6-alkanols esters, or anhydrides, in particular methyl methacrylate, ethyl methacrylate, n-butyl methacrylate or tert-butyl methacrylate, methyl, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, tert-butyl acrylate, methacrylic anhydride, maleic anhydride or itaconic anhydride, and 1-olefins, such as propene, 1-butene, 1-pentene, 1 -hexene, 1-octene or 1-decene. In addition, vinyl carboxylates, particularly vinyl acetate, can be used as comonomers. N-butyl acrylate, acrylic acid or methacrylic acid are particularly advantageous for use as a comonomer. In the case of a copolymerization of ethylene, the bi- or multifunctional comonomer and additional comonomers, the proportion of the additional comonomer or additional comonomers in the reaction mixture is 1 to 45% by weight, preferably 3 to 30% by weight, based on the quantity of all monomers, that is, the sum of ethylene and all comonomers. Depending on the type of the additional comonomer, it may be preferable to feed the additional comonomers at a plurality of different points in the reactor.
    [00032] In the process of the present invention, the molecular weight obtained from ethylene copolymers is influenced by the addition of the bi- or multifunctional comonomer because it carries a functional group that can act as a chain transfer agent and, therefore, ends the additional growth of the polymer chains in
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    15/20 growth. However, preferably the molecular weight of the ethylene copolymers to be prepared is further changed by the addition of additional chain transfer agents which are common in high pressure polymerization. Examples of suitable additional chain transfer agents, sometimes also called modifiers, are hydrogen, aliphatic and olefin hydrocarbons, for example, pentane, hexane, cyclohexane, propene, 1-pentene or 1-hexene, ketones, such as acetone, methyl ethyl ketone (2-butanone), methyl isobutyl ketone, methyl isoamyl ketone, diethyl ketone or diamyl ketone, aldehydes, such as formaldehyde, acetaldehyde or propionaldehyde, and saturated aliphatic alcohols, such as methanol, ethanol, propanol, isopropanol or butanol. Particular preference is given to the use of saturated aliphatic aldehydes, in particular propionaldehyde or 1olefins, such as propene or 1-hexene.
    [00033] The present invention also relates to ethylene copolymers obtained by the process described above. These ethylene copolymers have a significantly increased content of long chain branching compared to LDPE normally obtained by polymerization by free radicals in tubular reactors. Because of their molecular structure, they are particularly suitable for use in extrusion coating processes. They have superior melt stability during processing, that is, high mesh stability and low taper, and the potential for superior adhesion to the substrate, such as paper, cardboard, polymeric film or metal. Consequently, the present invention also relates to the use of ethylene copolymers for extrusion coating and a process for extrusion coating of a substrate selected from the group consisting of paper, cardboard, polymeric film and metal with these ethylene copolymers.
    [00034] The invention is illustrated below with the aid of examples,
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    16/20 without being restricted to them.
    Examples
    Comparative Example A
    Homopolymerization of ethylene [00035] A simulation of a homopolymerization of ethylene in a high pressure tubular reactor was carried out using the commercial polymerization modeling software PREDICI by Dr. Michael Wulkow, Computing in Technology GmbH (CiT), Rastede, Germany . Kinetic data for ethylene homopolymerization were taken from M. Busch, Macromol. Theory Simul. 2001, 10, 408 - 429.
    [00036] The reactor was considered to have the design shown in Figure 1 with four points of primer injection, with a total length of 2,000 m and a diameter of 76 mm. The calculation was performed based on the following considerations:
    - ethylene production from the high pressure compressor: 117 metric tons / h;
    - supply of propionaldehyde as a chain transfer agent for the high pressure compressor: 1.5 kg per ton of LDPE produced;
    - temperature of the ethylene supply at the reactor inlet: 157 ° C;
    - pressure at the reactor inlet: 280 MPa
    - feed of 0.3754 g / s of tert-butyl peroxy-3,5,5-trimethylexanoate (TBPIN), 0.3610 g / s of di-tert-butyl peroxide (DTBP); 0.1506 g / s tert-butyl peroxineodecanoate (TBPND) and 0.3447 g / s tert-butyl peroxypivalate (TBPP) at the reactor inlet
    - feeding of 0.0476 g / s of tert-butyl peroxy-3,5,5-trimethylexanoate (TBPIN) and 0.3547 g / s of di-tert-butyl peroxide (DTBP) in a position at 640 m downstream of the reactor inlet
    - feeding of 0.0521 g / s of peroxy-3,5,5-trimethylexanoate
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    17/20 tert-butyl (TBPIN) and 0.2951 g / s of di-tert-butyl peroxide (DTBP) in a position 1,200 m downstream from the reactor inlet
    - feeding of 0.2797 g / s of di-tert-butyl peroxide (DTBP) in a position at 1,760 m downstream from the reactor inlet. [00037] The data resulting from long chain branching, expressed as number of long chain branches per 1,000 carbon atoms, and the molecular weight distribution of the LDPE obtained and the ethylene conversion are shown in Table 1. The calculated numbers of long chain branches in the LDPE contained in the reaction mixture along the tubular reactor are also shown in Figure 2 and also listed in Table 2 for positions at 500 m, 1,000 m, 1,500 m and 2,000 m downstream from the reactor inlet, ie , after the first, second, third and fourth reaction zones. The temperature profile calculated over the tubular reactor is also shown in Figure 3.
    Example 1 Copolymerization of ethylene with acrylic acid 4-oxo-butyl ester
    W γ q
    O [00038] The simulation of Comparative Example A has been repeated; however, with the additional supply of 4-oxo-butyl ester of acrylic acid in the amount indicated in Table 1 to the ethylene stream before entering the tubular reactor.
    [00039] For the kinetic characterization of the comonomer, it was considered that the reactivity of the functional groups can be taken independently. To describe the homopolymerization of the comonomer, the kinetic data of n-butyl acrylate were used. To describe the copolymerization of ethylene and the comonomer, data were taken for the copolymerization of methyl acrylate and ethylene.
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    18/20 [00040] The data resulting from long chain branching and the molecular weight distribution of the LDPE obtained and the ethylene conversion are shown in Table 1. The numbers of long chain branches in the LDPE contained in the reaction mixture over of the tubular reactor are shown in Figure 2 and Table 2, and the temperature profile is shown in Figure 3.
    Example 2 Copolymerization of ethylene with 2-oxo-propyl ester of acrylic acid
    O
    [00041] A simulation was carried out as in Example 1; however, with the supply of 2-oxo-propyl ester of acrylic acid in the amount indicated in Table 1 to the ethylene stream before entering the tubular reactor.
    [00042] The data resulting from long chain branching and the molecular weight distribution of the obtained LDPE and the ethylene conversion are shown in Table 1. The numbers of long chain branches in the LDPE contained in the reaction mixture throughout the tubular reactor are shown in Figure 2 and Table 2, and the temperature profile is shown in Figure 3.
    Example 3
    Copolymerization of ethylene with 2-hydroxy-propyl ester of acrylic acid
    OH
    [00043] A simulation was carried out as in Example 1; however, with the supply of 2-hydroxy-propyl ester of acrylic acid in the amount indicated in Table 1 to the ethylene stream before
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    19/20 inlet to the tubular reactor.
    [00044] The data resulting from long chain branching and the molecular weight distribution of the obtained LDPE and the ethylene conversion are shown in Table 1. The numbers of long chain branches in the LDPE contained in the reaction mixture throughout the tubular reactor are shown in Figure 2 and Table 2, and the temperature profile is shown in Figure 3.
    Comparative Examples B and C
    Copolymerization of ethylene with 1,4-butanedioldiacrylate
    O
    [00045] A simulation was carried out as in Example 1; however, with the feeding of 1,4-butanedioldiacrylate in the quantities indicated in Table 1 to the ethylene stream before entering the tubular reactor.
    [00046] The data resulting from long chain branching and the molecular weight distribution of the obtained LDPE and the ethylene conversion are shown in Table 1.
    [00047] The data resulting from long chain branching and molecular weight distribution of the obtained ethylene copolymers and the ethylene conversion are shown in Table 1.
    Table 1
    Example / Comparative Example Comonomer quantity [mol-%] LCB /1,000 C Mn[g / mol] Mw[g / mol] Mz[g / mol] Mw / Mz conversion [%] THE 0 2.1 14,305 79,980 185,071 5.6 29.9 1 0.23 2.8 12,907 70,123 161.752 5.4 30.4 2 0.23 2.5 13,951 75,345 170,892 5.4 31.1 3 0.24 2.4 14,082 75,345 170,892 5.4 31.4 B 0.0013 2.1 14,792 101,834 275,170 6.7 30.7 Ç 0.004 2.2 15,494 163,349 538,236 11.0 30.8
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    20/20
    Table 2
    Example/ExampleComparative LCB / 1,000 C a500 m LCB / 1,000 C a1,000 m LCB / 1,000 C a1,500 m LCB / 1,000 Cat 2,000 m THE 0.90 1.40 1.79 2.12 1 1.47 2.04 2.46 2.80 2 1.18 1.72 2.11 2.45 3 1.13 1.68 2.07 2.41 [00048] Comparison c the Examples 1, 2 and 3 with Example
    Comparative A shows that the addition of different bifunctional comonomers to the reaction mixture along the tubular reactor leads to increased branching of long chains and, therefore, to a better processing performance. All of these comonomers cause a significant increase in LCB. This can also be seen in Figure 1, which shows the amount of LCB / 1,000 C along the tube. On the other hand, there was no impact on the distribution of molecular weights.
    [00049] In contrast, as can be seen in Comparative Examples B and D, the addition of a diacrylate comonomer with similar reactivity to the functional groups has no impact on the amount of branching of long chains, only an extension of the distribution of molecular weights with increasing amount of diacrylate comonomer was observed. In addition, an increased amount of cross-links (0.031 / 1,000 C and 0.057 / 1,000 C) was found, i.e., a link to two polymer chains, indicating an increased gel level.
    权利要求:
    Claims (9)
    [1]
    1. Process for preparing ethylene copolymer in the presence of free radical polymerization initiator at pressures in the range of 200 MPa to 330 MPa and temperatures in the range of 100 ° C to 350 ° C in a tubular reactor having 2 to 6 reaction zones by copolymerization of ethylene, a bi- or multifunctional comonomer and optionally additional comonomers, in which the bi- or multifunctional comonomer has at least two different functional groups, characterized by the fact that at least one functional group is an unsaturated group, which can be incorporated into the growing polymer chain, and at least one other functional group can act as a chain transfer agent in ethylene polymerization by radicals, where the functional group of the bi- or multifunctional comonomer is most likely to be incorporated into the chain in growth is an acrylate group or a methacrylate group and at least one of the functional groups of the bi- or multifunctional comonomer that does not have The most likely to be incorporated into the growing chain is an aldehyde group or a ketone group.
    [2]
    Process for preparing ethylene copolymer according to claim 1, characterized by the fact that the functional groups of the bi- or multifunctional comonomer are separated by a spacer group composed of units -CH2-, Si (CH3) 2-, - CH2-O- and / or -Si (CH3) 2-O- e comprises a chain of 1 to 32 atoms.
    [3]
    Process for preparing ethylene copolymer according to claim 1 or 2, characterized in that the bi- or multifunctional comonomer is a bifunctional comonomer.
    [4]
    4. Process for preparing ethylene copolymer according to claim 3, characterized by the fact that the bifunctional comonomer has a structure represented by the general formula (I):
    Petition 870190117731, of 11/14/2019, p. 25/70
    2/3

    [5]
    Process according to claim 4, characterized in that the Process for preparing bifunctional ethylene copolymer is acrylic acid 4-oxo-butyl ester, methacrylic acid 4-oxo-butyl ester, 2-oxo-propyl ester of acrylic acid or 2oxo-propyl ester of methacrylic acid.
    [6]
    Process according to any one of claims 1 to 5, characterized Process for preparing ethylene copolymer in that the free radical polymerization initiator is added to a mixture comprising ethylene and the multifunctional biou comonomer.
    [7]
    7. Ethylene copolymer, characterized in that it is obtained by the process as defined in claim 5, wherein the bifunctional comonomer is acrylic acid 4-oxo-butyl ester, acrylic acid 2-oxo-propyl ester or 2-oxo ester -propyl methacrylic acid.
    [8]
    8. Use of an ethylene copolymer as defined in claim 7, characterized by the fact that it is for extrusion coating.
    [9]
    9. Extrusion coating process for a substrate selected from the group consisting of paper, cardboard,
    Petition 870190117731, of 11/14/2019, p. 26/70
    3/3 polymeric film and metal, characterized by the fact that it comprises the following steps: preparing an ethylene copolymer by a process defined in any one of claims 1 to 6; and coating the substrate with the obtained ethylene copolymer.
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    同族专利:
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    WO2012084787A1|2012-06-28|
    US9238700B2|2016-01-19|
    EP2655444A1|2013-10-30|
    CN103261244A|2013-08-21|
    CN103261244B|2016-01-06|
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    法律状态:
    2018-06-19| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-08-20| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-02-27| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-04-07| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 19/12/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP10015964|2010-12-22|
    PCT/EP2011/073196|WO2012084787A1|2010-12-22|2011-12-19|Process for the preparation of ethylene copolymers in the presence of free-radical polymerization initiator by copolymerizing ethylene, a bi- or multifunctional comonomer and optionally further comonomers|
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