Ethylene / alpha-olefin copolymer, method for preparing same, and adhesive composition comprising same

Abstract

The present invention relates to an ethylene / alpha-olefin copolymer exhibiting excellent thermal stability and adhesive properties, and an adhesive composition comprising same.

Description

Ethylene / alpha-olefin copolymer, method for producing the same, and adhesive composition comprising the same

[0001] Cross-citation with related applications

[0002] This application claims the benefit of priority to Korean Patent Application No. 2024-0113131, filed August 22, 2024, the entire disclosure of which is incorporated herein by reference.

[0003]

[0004] Technology field

[0005] The present invention relates to an ethylene / alpha-olefin copolymer exhibiting excellent thermal stability and adhesive properties and an adhesive composition comprising the same.

[0006]

[0007] Olefin polymerization catalysts can be categorized into Ziegler-Natta and metallocene catalysts, and these two highly active catalysts have been developed according to their respective characteristics. Since their invention in the 1950s, Ziegler-Natta catalysts have been widely applied in existing commercial processes. However, because they are multi-site catalysts with multiple active sites, they are characterized by a broad molecular weight distribution of the polymer, and the uneven distribution of the comonomer composition limits the achievement of desired physical properties.

[0008] Meanwhile, metallocene catalysts consist of a primary catalyst composed primarily of a transition metal compound and a secondary catalyst composed primarily of an organometallic compound composed primarily of aluminum. These catalysts are homogeneous complex catalysts, single-site catalysts. Due to their single-site nature, they produce polymers with narrow molecular weight distributions and uniform comonomer compositions. Furthermore, they possess the ability to alter the polymer's stereoregularity, copolymerization characteristics, molecular weight, and crystallinity by modifying the catalyst's ligand structure and changing polymerization conditions.

[0009] Meanwhile, linear low-density polyethylene is manufactured by copolymerizing ethylene and alpha olefin at low pressure using a polymerization catalyst, and is a resin with a narrow molecular weight distribution, short-chain branches of a constant length, and no long-chain branches. Linear low-density polyethylene film has the characteristics of general polyethylene, as well as high breaking strength and elongation, and excellent tear strength and impact strength, so it is increasingly being used in stretch films and overlap films, which were difficult to apply to conventional low-density polyethylene or high-density polyethylene.

[0010] However, linear low-density polyethylene using 1-butene or 1-hexene as a comonomer is mostly manufactured in a single gas phase reactor or a single loop slurry reactor, and although the productivity is higher than that of the process using 1-octene comonomer, these products also have problems such as poor processability due to the limitations of the catalyst technology and process technology, which are significantly inferior to those using 1-octene comonomer, and narrow molecular weight distribution. In addition, even if the processability is improved, the molecular weight distribution within a unit particle is not uniform, so there is a problem that the extrusion appearance is rough and the properties are not stable even under relatively good extrusion conditions.

[0011] Against this backdrop, there is a constant demand for the manufacture of superior products with a balance between physical properties and processability, and in particular, the need for polyethylene copolymers with excellent processability is growing.

[0012]

[0013] [Prior Art Literature]

[0014] [Patent Document]

[0015] (Patent Document 1) U.S. Patent No. 5,064,802

[0016]

[0017] The purpose of the present invention is to provide an ethylene / alpha-olefin copolymer containing a vinyl functional group and a vinylidene functional group in a certain ratio or more, which exhibits excellent thermal stability and adhesive properties, and an adhesive composition using the same.

[0018]

[0019] (1) The present invention provides an ethylene / alpha-olefin copolymer satisfying the following conditions (a) to (d).

[0020] (a) Density: 0.850 to 0.910 g / cc

[0021] (b) Melting index (190℃, 2.16 kg load condition): 1 to 1,500 dg / min

[0022] (c) Molecular weight distribution (MWD): 1.5 to 3.0

[0023] (d) The sum of the number of vinyl functional groups per 1,000 carbon atoms and the number of vinylidene functional groups per 1,000 carbon atoms measured through nuclear magnetic spectrometry analysis: 0.7 or more.

[0024] (2) The present invention provides an ethylene / alpha-olefin copolymer in which the number of vinyl functional groups per 1,000 carbon atoms is 0.4 to 0.9 in the above (1).

[0025] (3) The present invention provides an ethylene / alpha-olefin copolymer in which the number of vinylidene functional groups per 1,000 carbon atoms is 0.2 to 0.7 in (1) or (2).

[0026] (4) The present invention provides an ethylene / alpha-olefin copolymer in any one of the above (1) to (3), wherein the number of vinylene functional groups per 1,000 carbon atoms as measured through nuclear magnetic spectroscopic analysis is 0.3 to 0.8.

[0027] (5) The present invention provides an ethylene / alpha-olefin copolymer in any one of the above (1) to (4), wherein the number of trivinyl functional groups per 1,000 carbon atoms as measured through nuclear magnetic spectroscopic analysis is 0.03 to 0.4.

[0028] (6) The present invention provides an ethylene / alpha-olefin copolymer having a viscosity of 4,000 to 50,000 cP as measured by a Brookfield Viscometer at 177°C in any one of (1) to (5).

[0029] (7) The present invention provides an ethylene / alpha-olefin copolymer, wherein the alpha-olefin comprises at least one selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-eicosene, in any one of the above (1) to (6).

[0030] (8) The present invention provides an ethylene / alpha-olefin copolymer according to any one of the above (1) to (7), wherein the alpha-olefin is 1-butene.

[0031] (9) The present invention provides an adhesive composition comprising an ethylene / alpha-olefin copolymer according to any one of (1) to (8) above; and a tackifier.

[0032] (10) The present invention provides an adhesive composition in which, in the above (9), the tackifier is at least one selected from the group consisting of a modified C5 hydrocarbon resin, a styrenated tefrene resin, a fully or partially hydrogenated C9 hydrocarbon resin, a hydrogenated cycloaliphatic hydrocarbon resin, a hydrogenated aromatic modified cycloaliphatic hydrocarbon resin, and a mixture thereof.

[0033]

[0034] The ethylene / alpha-olefin copolymer of the present invention exhibits excellent thermal stability and adhesive properties by containing a vinyl functional group and a vinylidene functional group in a certain ratio or more.

[0035]

[0036] Hereinafter, the present invention will be described in more detail to help understand the present invention.

[0037]

[0038] The terms or words used in the description and claims of the present invention should not be interpreted as limited to their usual or dictionary meanings, and should be interpreted as meanings and concepts that conform to the technical idea of ​​the present invention, based on the principle that the inventor can appropriately define the concept of the term to explain his or her own invention in the best way.

[0039]

[0040] ethylene / alpha-olefin copolymer

[0041] The ethylene / alpha-olefin copolymer of the present invention satisfies the following conditions (a) to (d).

[0042] (a) Density: 0.850 to 0.910 g / cc

[0043] (b) Melting index (190℃, 2.16 kg load condition): 1 to 1,500 dg / min

[0044] (c) Molecular weight distribution (MWD): 1.5 to 3.0

[0045] (d) The sum of the number of vinyl functional groups per 1,000 carbon atoms and the number of vinylidene functional groups per 1,000 carbon atoms measured through nuclear magnetic spectrometry analysis: 0.7 or more.

[0046]

[0047] The present invention is characterized by improving the thermal stability and adhesive properties of an ethylene / alpha-olefin copolymer by thermally decomposing the conventional ethylene / alpha-olefin copolymer at an appropriate temperature range and time while stirring the copolymer at an appropriate rotation speed, as described below.

[0048] Specifically, the ethylene / alpha-olefin copolymer of the present invention is a low-density polymer having a density in the range of 0.850 to 0.910 g / cc as measured according to ASTM D-792. Specifically, the density may be at least 0.850 g / cc, at least 0.855 g / cc, at least 0.860 g / cc, at least 0.865 g / cc, at least 0.870 g / cc, or at least 0.873 g / cc, at most 0.910 g / cc, at most 0.900 g / cc, at most 0.890 g / cc, at most 0.885 g / cc, or at most 0.880 g / cc.

[0049] Typically, the density of an olefin polymer is affected by the type and content of monomers used during polymerization, the degree of polymerization, etc. In the case of a copolymer, the density is greatly affected by the content of the comonomer. The higher the content of the comonomer, the lower the density of the ethylene / alpha-olefin copolymer can be produced, and the content of the comonomer that can be introduced into the copolymer may depend on the copolymerizability of the catalyst, i.e., the characteristics of the catalyst.

[0050] The ethylene / alpha-olefin copolymer of the present invention may have a low density as described above, and as a result, may exhibit excellent processability. More specifically, the ethylene / alpha-olefin copolymer may have a density of 0.850 to 0.910 g / cc, in which case the effects of maintaining mechanical properties and improving impact strength according to density control are more remarkable.

[0051]

[0052] The ethylene / alpha-olefin copolymer of the present invention has a melt index (MI, 190° C., 2.16 kg load condition) in the range of 1 to 1,500 dg / min. As an example, the ethylene / alpha-olefin copolymer of the present invention may have a melt index (MI) of 1 dg / min or more, 10 dg / min or more, 50 dg / min or more, 100 dg / min or more, 150 dg / min or more, or 200 dg / min or less, 1,500 dg / min or less, 1,300 dg / min or less, 1,200 dg / min or less, or 1,100 dg / min or less, for example, 10 to 1,300 dg / min.

[0053] When the above numerical range is met, mechanical strength can be secured within the adhesive composition, and at the same time, an appropriate working temperature can be achieved when using the adhesive.

[0054]

[0055] The ethylene / alpha-olefin copolymer of the present invention has a narrow molecular weight distribution (MWD) in the range of 1.5 to 3.0. As an example, the molecular weight distribution may be 1.8 or greater, 2.0 or greater, 2.2 or greater, or 2.3 or greater, 2.8 or less, 2.7 or less, 2.6 or less, or 2.5 or less.

[0056] In the present invention, the ethylene / alpha-olefin copolymer may have a weight average molecular weight (Mw) of 10,000 to 150,000 g / mol. More specifically, the weight average molecular weight may be 15,000 g / mol or more, 17,000 g / mol or more, 19,000 g / mol or more, or 20,000 g / mol or more, 130,000 g / mol or less, 100,000 g / mol or less, 90,000 g / mol or less, 60,000 g / mol or less, 50,000 g / mol or less, or 30,000 g / mol or less.

[0057] When the weight average molecular weight satisfies the above range, a significant improvement in processability can be expected in conjunction with the viscosity of the adhesive composition containing it. That is, the mechanical properties, impact strength, and viscosity of the ethylene / alpha-olefin copolymer can be controlled by adjusting the type of catalyst used in the polymerization process and the amount of catalyst used, and together with the above conditions, it is possible to exhibit improved processability while maintaining excellent mechanical properties.

[0058] Meanwhile, the weight average molecular weight (Mw) and number average molecular weight (Mn) are polystyrene-converted molecular weights analyzed by gel permeation chromatography (GPC), and the molecular weight distribution can be calculated from the ratio of Mw / Mn.

[0059]

[0060] The ethylene / alpha-olefin copolymer of the present invention has a sum of the number of vinyl functional groups per 1,000 carbon atoms and the number of vinylidene functional groups per 1,000 carbon atoms, as measured by nuclear magnetic spectroscopy, of 0.7 or more. Specifically, the sum of the number of vinyl functional groups per 1,000 carbon atoms and the number of vinylidene functional groups per 1,000 carbon atoms, as measured by nuclear magnetic spectroscopy, may be 0.8 or more, 0.9 or more, or 1.0 or more, 3.0 or less, 2.5 or less, 2.0 or less, or 1.5 or less.

[0061] When the number of unsaturated functional groups satisfies the above numerical range, the vinylidene functional group suppresses radical reactions of the copolymer, thereby increasing stability, and the vinyl functional group imparts polarity to the copolymer, thereby increasing affinity with the adhesion interface, thereby improving adhesive strength. At the same time, by retaining an appropriate number of unsaturated functional groups, side reactions can be suppressed.

[0062] When the sum of the number of vinyl functional groups per 1,000 carbon atoms and the number of vinylidene functional groups per 1,000 carbon atoms measured by nuclear magnetic spectroscopy is less than 0.7, the thermal stability of the ethylene / alpha-olefin copolymer may be reduced and the adhesive properties may be poor.

[0063]

[0064] The ethylene / alpha-olefin copolymer of the present invention may have a number of vinyl functional groups per 1,000 carbon atoms of 0.4 to 0.9 as measured by nuclear magnetic spectroscopic analysis. More specifically, the number may be 0.41 or more, 0.42 or more, or 0.43 or more, 0.85 or less, 0.80 or less, or 0.78 or less.

[0065] Additionally, the ethylene / alpha-olefin copolymer of the present invention may have a number of vinylidene functional groups per 1,000 carbon atoms of 0.2 to 0.7. More specifically, the number may be 0.25 or more, 0.27 or more, 0.30 or more, 0.35 or more, or 0.36 or more, 0.65 or less, 0.62 or less, 0.60 or less, or 0.59 or less.

[0066] Additionally, the ethylene / alpha-olefin copolymer of the present invention may have a number of vinylene functional groups per 1,000 carbon atoms of 0.3 to 0.8 as measured by nuclear magnetic spectroscopic analysis. More specifically, the number may be 0.35 or more, 0.40 or more, 0.45 or more, or 0.48 or more, 0.75 or less, 0.70 or less, 0.68 or less, or 0.66 or less.

[0067] Additionally, the ethylene / alpha-olefin copolymer of the present invention may have a number of trivinyl functional groups per 1,000 carbon atoms of 0.03 to 0.4 as measured by nuclear magnetic spectroscopic analysis. More specifically, the number may be 0.04 or more, 0.05 or more, or 0.06 or more, 0.35 or less, 0.30 or less, 0.25 or less, 0.20 or less, or 0.15 or less.

[0068] Additionally, the ethylene / alpha-olefin copolymer of the present invention may have a total number of unsaturated functional groups per 1,000 carbon atoms of 0.6 to 2.5 as measured by nuclear magnetic spectroscopic analysis. More specifically, it may be 0.6 or more, 0.7 or more, 1.0 or more, 1.4 or more, 2.5 or less, 2.3 or less, 2.2 or less, or 2.1 or less.

[0069] The total number of unsaturated functional groups in the copolymer can be controlled by controlling the polymerization temperature and hydrogen input amount during manufacturing. The ethylene / alpha-olefin copolymer according to the present invention has the above number of unsaturated functional groups, and thus exhibits excellent long-term properties such as small discoloration, molecular weight, and viscosity changes when stored at high temperatures for a long time (heat aging).

[0070]

[0071] In the present invention, the vinyl group has a structure of R-CH=CH2, the trivinyl group has a structure of RCH=CR'R", the vinylene has a structure of RCH=CHR'(E-form) or Z-RCH=CHR'(Z-form), and the vinylidene means a structure of RR'C=CH2. Here, R, R', and R" may each independently be a polymer chain or a branched chain according to an alpha-olefin which is a comonomer.

[0072] In the present invention, the content of vinyl, vinylidene, vinylene, and trivinyl in the copolymer can be calculated from the NMR analysis results. Specifically, the copolymer can be dissolved in a 1,1,2,2-tetrachloroethane D2 (TCE-d2) solvent and then measured using a Bruker AVANCE III 500MHz NMR instrument at 393K. 1 In the H NMR spectrum, the TCE-d2 peak is corrected to 6.0 ppm, and the content ratio of comonomers is calculated using the integration values ​​in the 1.4 ppm and 0.96 ppm regions. The contents of vinyl, vinylidene, vinylene, and trivinylene groups observed at 4.7 ppm to 5.6 ppm are calculated (analytical method: AMT-3863). Peak assignments are referenced from the literature [Macromolecules 2014, 47, 3282-3790].

[0073]

[0074] In the present invention, the ethylene / alpha-olefin copolymer may have a viscosity of 4,000 to 50,000 cP as measured by a Brookfield Viscometer at 177°C. More specifically, the viscosity of the ethylene / alpha-olefin copolymer may be 4,000 cP or more, 5,000 cP or more, 6,000 cP or more, 7,000 cP or more, or 7,500 cP or more, 50,000 cP or less, 48,000 cP or less, 46,000 cP or less, 44,000 cP or less, or 42,000 cP or less.

[0075] When the above numerical range is met, mechanical strength can be secured within the adhesive composition, and at the same time, an appropriate working temperature can be achieved when using the adhesive.

[0076]

[0077] In the present invention, the comonomer alpha-olefin may be an olefin monomer having 4 to 20 carbon atoms. Specifically, examples thereof include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, or 1-eicosene, and one of these may be used alone or a mixture of two or more thereof may be used.

[0078] Among these, considering that the improvement effect is remarkable when applied to an adhesive composition, the alpha-olefin may be 1-butene, 1-hexene or 1-octene, and most preferably 1-butene.

[0079] In addition, the content of the alpha-olefin may be appropriately selected within a range that satisfies the above-mentioned physical property requirements, and specifically may be more than 0 and 99 mol% or less, or 10 to 50 mol%.

[0080]

[0081] The ethylene / alpha-olefin copolymer of the present invention can be produced by thermally decomposing a conventional ethylene / alpha-olefin copolymer at an appropriate temperature and time. Any conventional ethylene / alpha-olefin copolymer that can be easily obtained by a person skilled in the art, regardless of the route, such as a commercially available ethylene / alpha-olefin copolymer or an ethylene / alpha-olefin copolymer produced by a known method, can be used. More specifically, an ethylene / alpha-olefin copolymer having a melt index (MI, 190°C, 2.16 kg load condition) of 1.0 g / 10 min to 10.0 g / 10 min and a density of 0.850 g / cc to 0.890 g / cc can be used, but is not limited thereto.

[0082] Through the above thermal decomposition, the copolymer chain undergoes chain scission through a radical reaction, and after the reaction, unsaturated groups remain, generating vinylidene functional groups. By containing the vinylidene functional groups, crosslinking reactions are suppressed through disproportionation reactions and chain fragmentation reactions, so that the ethylene / alpha-olefin copolymer of the present invention can exhibit a low viscosity change rate. In addition, by imparting polarity to the copolymer through the vinyl functional groups, adhesive strength can also be improved.

[0083] The above thermal decomposition may be specifically heated at 350°C to 450°C, and may be 360°C or higher, 365°C or higher, or 370°C or higher, 445°C or lower, 440°C or lower, or 435°C or lower.

[0084] In addition, under the above temperature conditions, pyrolysis can be performed for 1 to 7 hours, and specifically, for 2 hours or more, 3 hours or more, 6 hours or less, or 5 hours or less, for example, for 2 to 6 hours, 2 to 5 hours, 3 to 6 hours, or 3 to 5 hours.

[0085] As described above, the present invention can produce an ethylene / alpha-olefin copolymer that satisfies the density, melting index, molecular weight distribution, number of vinyl functional groups per 1,000 carbon atoms measured through nuclear magnetic spectroscopic analysis, and the sum of the number of vinylidene functional groups per 1,000 carbon atoms through thermal decomposition.

[0086]

[0087] adhesive composition

[0088] The present invention provides an adhesive composition comprising the ethylene / alpha-olefin copolymer and a tackifier.

[0089] The tackifier may be an aliphatic hydrocarbon resin, for example, selected from modified C5 hydrocarbon resins (C5 / C9 resins), styrenated tefrene resins, fully or partially hydrogenated C9 hydrocarbon resins, hydrogenated cycloaliphatic hydrocarbon resins, hydrogenated aromatic modified cycloaliphatic hydrocarbon resins, and mixtures thereof.

[0090] The above tackifier is not particularly limited, but may be included in an amount of 5 to 70 parts by weight, and specifically 20 to 70 parts by weight, based on 100 parts by weight of the adhesive composition. If the tackifier is included in an amount of less than 5 parts by weight, the viscosity of the adhesive composition may increase, resulting in reduced processability, and if it is included in an amount exceeding 70 parts by weight, heat resistance may be reduced.

[0091] In the case of the above ethylene / alpha-olefin copolymer, it may be included in an amount of 10 to 50 parts by weight, and specifically, 15 to 30 parts by weight, based on 100 parts by weight of the adhesive composition. When the above numerical range is met, excellent adhesive properties can be maintained.

[0092]

[0093] In addition, the adhesive composition may further include a plasticizer. The plasticizer is not particularly limited, but may be, for example, a plasticized oil of paraffinic or naphthenic type. Specifically, the plasticizer may be a low molecular weight polymer such as an olefin oligomer, a liquid polybutene, a polyisoprene copolymer, a liquid styrene-isoprene copolymer, or a liquid hydrogenated styrene-conjugated diene copolymer, a vegetable oil and its derivatives, or a microcrystalline wax.

[0094] The plasticizer is not particularly limited, but may be included in an amount of 10 to 50 parts by weight, specifically 20 to 40 parts by weight, based on 100 parts by weight of the adhesive composition. If the plasticizer is included in an amount of less than 10 parts by weight, the adhesive composition may have high adhesion, thereby reducing processability, and if it is included in an amount of more than 50 parts by weight, the adhesive properties may be reduced.

[0095]

[0096] In addition, the adhesive composition may further include an antioxidant to improve heat resistance and color.

[0097] At this time, the antioxidant is not particularly limited and can be used as one commonly known in the art, and can be included in an amount of 0.01 to 5 parts by weight, or 0.01 to 1 part by weight, or 0.05 to 0.75 parts by weight relative to 100 parts by weight of the adhesive composition.

[0098] Additionally, the adhesive composition may further comprise one or more additives selected from the group consisting of UV stabilizers, colorants or pigments, fillers, flow aids, coupling agents, crosslinking agents, surfactants, solvents, and combinations thereof.

[0099] The filler may be selected from sand, talc, dolomite, calcium carbonate, clay, silica, mica, wollastonite, feldspar, aluminum silicate, alumina, hydrated alumina, glass beads, glass microspheres, ceramic microspheres, thermoplastic microspheres, barite, wood flour, or combinations thereof, and the filler may be present in an amount of up to 80 wt% of the total composition.

[0100]

[0101] One embodiment of the present invention provides an article comprising a substrate coated with the adhesive composition. The article may be selected from, but is not limited to, tapes, labels, transfer paper, boxes, cardboard, trays, medical devices, bandages, and sanitary products.

[0102]

[0103] Example

[0104] Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to illustrate the present invention and are not intended to limit the scope of the present invention solely to these examples.

[0105]

[0106] Example 1

[0107] 500 g of an ethylene / butene copolymer (MI 4.8 g / 10 min, density 0.877 g / cc, obtained according to the method described in KR 10-2348518 B1) was weighed and placed in a 2 L heat-resistant glass beaker, and vacuum was maintained to remove moisture and oxygen. After removal was complete, the beaker was filled with argon (Ar) gas to make it inert. A mechanical stirrer and an impeller were connected to the beaker containing the copolymer, and the mixture was stirred at a speed of 50 rpm. The copolymer was then pyrolyzed by heating at 430°C for 4 hours using a heating mantle. After the pyrolyzed copolymer was sufficiently cooled under argon (Ar), the beaker was opened to obtain a sample.

[0108]

[0109] Example 2

[0110] 500 g of an ethylene / butene copolymer (MI 4.8 g / 10 min, density 0.877 g / cc, obtained according to the method described in KR 10-2348518 B1) was weighed and placed in a 2 L heat-resistant glass beaker, and vacuum was maintained to remove moisture and oxygen. After removal was complete, the beaker was filled with argon (Ar) gas to make it inert. A mechanical stirrer and an impeller were connected to the beaker containing the copolymer, and the mixture was stirred at a speed of 50 rpm. The copolymer was then pyrolyzed by heating at 410°C for 3 hours using a heating mantle. After the pyrolyzed copolymer was sufficiently cooled under argon (Ar), the beaker was opened to obtain a sample.

[0111]

[0112] Example 3

[0113] 500 g of an ethylene / butene copolymer (MI 4.8 g / 10 min, density 0.877 g / cc, obtained according to the method described in KR 10-2348518 B1) was weighed and placed in a 2 L heat-resistant glass beaker, and a vacuum was maintained to remove moisture and oxygen. After removal was complete, the beaker was filled with argon (Ar) gas to make it inert. A mechanical stirrer and an impeller were connected to the beaker containing the copolymer, and the mixture was stirred at a speed of 50 rpm. The copolymer was then pyrolyzed by heating at 390°C for 5 hours using a heating mantle. After the pyrolyzed copolymer was sufficiently cooled under argon (Ar), the beaker was opened to obtain a sample.

[0114]

[0115] Example 4

[0116] 500 g of an ethylene / butene copolymer (MI 4.8 g / 10 min, density 0.877 g / cc, obtained according to the method described in KR 10-2348518 B1) was weighed and placed in a 2 L heat-resistant glass beaker, and vacuum was maintained to remove moisture and oxygen. After removal was complete, the beaker was filled with argon (Ar) gas to make it inert. A mechanical stirrer and an impeller were connected to the beaker containing the copolymer, and the mixture was stirred at a speed of 50 rpm. The copolymer was then pyrolyzed by heating at 380°C for 4 hours using a heating mantle. After the pyrolyzed copolymer was sufficiently cooled under argon (Ar), the beaker was opened to obtain a sample.

[0117]

[0118] Example 5

[0119] 500 g of an ethylene / octene copolymer (MI 5.2 g / 10 min, density 0.873 g / cc, obtained according to the method described in KR 10-2358450 B1) was weighed and placed in a 2 L heat-resistant glass beaker, and vacuum was maintained to remove moisture and oxygen. After removal was complete, the beaker was filled with argon (Ar) gas to make it inert. A mechanical stirrer and an impeller were connected to the beaker containing the copolymer, and the mixture was stirred at a speed of 50 rpm. The copolymer was then pyrolyzed by heating at 420°C for 3 hours using a heating mantle. After the pyrolyzed copolymer was sufficiently cooled under argon (Ar), the beaker was opened to obtain a sample.

[0120]

[0121] Synthetic example

[0122] [Synthesis Example: Preparation of Transition Metal Compounds]

[0123] Step 1: Preparation of ligand compound (1a-1)

[0124] A 250 mL Schlenk flask was charged with 10 g (1.0 eq, 49.925 mmol) of 1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene and 100 mL of THF, and 22 mL (1.1 eq, 54.918 mmol, 2.5 M in hexane) of n-BuLi was added dropwise at -30°C, and the mixture was stirred at room temperature for 3 h. The stirred Li-complex THF solution was cannulated into a Schlenk flask containing 8.1 mL (1.0 eq, 49.925 mmol) of dichloro(methyl)(phenyl)silane and 70 mL of THF at -78°C, and the mixture was stirred overnight at room temperature. After stirring, the mixture was vacuum-dried, and extracted with 100 mL of hexane.

[0125] To 100 mL of the extracted chloro-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophen-3-yl)-1,1-(methyl)(phenyl)silane hexane solution, 242 mL (8 eq, 399.4 mmol) of t-BuNH was added at room temperature, and the mixture was stirred overnight at room temperature. After stirring, the mixture was vacuum-dried and extracted with 150 mL of hexane. After drying the solvent, 13.36 g (68%, dr = 1:1) of a yellow solid was obtained.

[0126] (1a-1)

[0127]

[0128] 1 H NMR (CDCl3, 500 MHz): δ 7.93(t, 2H), 7.79(d,1H), 7.71(d,1H), 7.60(d, 2H), 7.48(d, 2H), 7.40~7.10(m, 10H, aromatic), 3.62(s, 1H), 3.60(s, 1H), 2.28(s, 6H), 2.09(s, 3H), 1.76(s, 3H), 1.12(s, 18H), 0.23(s, 3H), 0.13(s, 3H)

[0129]

[0130] Step 2: Preparation of transition metal compound (1a)

[0131] In a 100 mL Schlenk flask, 4.93 g (12.575 mmol, 1.0 eq) of the ligand compound of the above chemical formula 2-4 and 50 mL (0.2 M) of toluene were added, and 10.3 mL (25.779 mmol, 2.05 eq, 2.5 M in hexane) of n-BuLi was added dropwise at -30°C, and the mixture was stirred at room temperature overnight. After stirring, 12.6 mL (37.725 mmol, 3.0 eq, 3.0 M in diethyl ether) of MeMgBr was added dropwise, followed by 13.2 mL (13.204 mmol, 1.05 eq, 1.0 M in toluene) of TiCl4 was added in sequence, and the mixture was stirred at room temperature overnight. After stirring, vacuum drying was performed, extraction was performed with 150 mL of hexane, and the solvent was removed to 50 mL. 4 mL (37.725 mmol, 3.0 eq) of DME was added dropwise, followed by stirring at room temperature overnight. After vacuum drying again, extraction was performed with 150 mL of hexane. After drying the solvent, 2.23 g (38%, dr = 1:0.5) of a brown solid was obtained.

[0132] (1a)

[0133]

[0134] 1 H NMR (CDCl3, 500 MHz): δ 7.98 (d, 1H), 7.94 (d, 1H), 7.71 (t, 6H), 7.50-7.30 (10H), 2.66 (s, 3H), 2.61 (s, 3H), 2.15 (s, 3H), 1.62(s, 9H), 1.56(s, 9H), 1.53(s, 3H), 0.93(s, 3H), 0.31(s, 3H), 0.58(s, 3H), 0.51(s, 3H), -0.26(s, 3H), -0.39(s, 3H)

[0135]

[0136] Comparative Example 1

[0137] A 1.5 L autoclave continuous process reactor was filled with hexane solvent (5.0 kg / h) and 1-octene (1.00 kg / h), and the temperature at the top of the reactor was preheated to 125°C. Triisobutylaluminum compound (0.05 mmol / min), the transition metal compound prepared in the above synthesis example as a catalyst (0.40 μmol / min), and dimethylanilinium tetrakis(pentafluorophenyl) borate cocatalyst (1.20 μmol / min) were simultaneously fed into the reactor. Subsequently, ethylene (0.87 kg / h) and hydrogen gas (75 cc / min) were fed into the autoclave reactor, and the copolymerization reaction was continuously performed while maintaining the pressure of 89 bar and the polymerization temperature of 125°C for more than 60 minutes, thereby producing a copolymer.

[0138] Next, the remaining ethylene gas was removed, and the resulting copolymer-containing solution was dried in a vacuum oven for more than 12 hours, after which the physical properties of the obtained copolymer were measured.

[0139]

[0140] Comparative Example 2

[0141] A 1.5 L autoclave continuous process reactor was filled with hexane solvent (5.0 kg / h) and 1-octene (1.00 kg / h), and the temperature at the top of the reactor was preheated to 125°C. Triisobutylaluminum compound (0.05 mmol / min), the transition metal compound prepared in the above synthesis example as a catalyst (0.40 μmol / min), and dimethylanilinium tetrakis(pentafluorophenyl) borate cocatalyst (1.20 μmol / min) were simultaneously fed into the reactor. Subsequently, ethylene (0.87 kg / h) and hydrogen gas (95 cc / min) were fed into the autoclave reactor, and the copolymerization reaction was continuously performed while maintaining the pressure of 89 bar and the polymerization temperature of 125°C for more than 60 minutes, thereby producing a copolymer.

[0142] Next, the remaining ethylene gas was removed, and the resulting copolymer-containing solution was dried in a vacuum oven for more than 12 hours, after which the physical properties of the obtained copolymer were measured.

[0143]

[0144] Comparative Example 3

[0145] A 1.5 L autoclave continuous process reactor was charged with hexane solvent (5.0 kg / h) and 1-octene (1.20 kg / h), and the temperature at the top of the reactor was preheated to 125°C. Triisobutylaluminum compound (0.05 mmol / min), [Me2Si(Me4C5)NtBu]Ti(CH3)2 (0.26 μmol / min) as a catalyst, and dimethylanilinium tetrakis(pentafluorophenyl) borate cocatalyst (0.78 μmol / min) were simultaneously fed into the reactor. Subsequently, ethylene (0.87 kg / h) and hydrogen gas (35 cc / min) were fed into the autoclave reactor, and the copolymerization reaction was continuously performed at a pressure of 89 bar and a polymerization temperature of 125°C for more than 60 minutes, thereby producing a copolymer.

[0146] Next, the remaining ethylene gas was removed, and the resulting copolymer-containing solution was dried in a vacuum oven for more than 12 hours, after which the physical properties of the obtained copolymer were measured.

[0147]

[0148] Comparative Example 4

[0149] A 1.5 L autoclave continuous process reactor was filled with hexane solvent (5.0 kg / h) and 1-octene (1.00 kg / h), and the temperature at the top of the reactor was preheated to 125°C. Triisobutylaluminum compound (0.05 mmol / min), the transition metal compound prepared in the above synthesis example as a catalyst (0.40 μmol / min), and dimethylanilinium tetrakis(pentafluorophenyl) borate cocatalyst (1.20 μmol / min) were simultaneously fed into the reactor. Subsequently, ethylene (0.87 kg / h) and hydrogen gas (50 cc / min) were fed into the autoclave reactor, and the copolymerization reaction was continuously performed while maintaining the pressure of 89 bar and the polymerization temperature of 125°C for more than 60 minutes, thereby producing a copolymer.

[0150] Next, the remaining ethylene gas was removed, and the resulting copolymer-containing solution was dried in a vacuum oven for more than 12 hours, after which the physical properties of the obtained copolymer were measured.

[0151]

[0152] Comparative Example 5

[0153] A 1.5 L autoclave continuous process reactor was filled with hexane solvent (5.0 kg / h) and 1-octene (2.20 kg / h), and the temperature at the top of the reactor was preheated to 125°C. Triisobutylaluminum compound (0.05 mmol / min), [Me2Si(Me4C5)NtBu]Ti(CH3)2 (0.65 μmol / min) as a catalyst, and dimethylanilinium tetrakis(pentafluorophenyl) borate cocatalyst (1.95 μmol / min) were simultaneously fed into the reactor. Subsequently, ethylene (0.87 kg / h) was fed into the autoclave reactor, and the copolymerization reaction was continuously performed at a pressure of 89 bar and a polymerization temperature of 160°C for more than 60 minutes, thereby producing a copolymer.

[0154] Next, the remaining ethylene gas was removed, and the resulting copolymer-containing solution was dried in a vacuum oven for more than 12 hours, after which the physical properties of the obtained copolymer were measured.

[0155]

[0156] Comparative Example 6

[0157] 500 g of an ethylene / butene copolymer (MI 14.6 g / 10 min, density 0.878 g / cc, obtained according to the method described in KR 10-2348518 B1) was weighed and placed in a 2 L heat-resistant glass beaker, and vacuum was maintained to remove moisture and oxygen. After removal was complete, the beaker was filled with argon (Ar) gas to make it inert. A mechanical stirrer and an impeller were connected to the beaker containing the copolymer, and the mixture was stirred at a speed of 50 rpm. The copolymer was then pyrolyzed by heating at 340°C for 2 hours using a heating mantle. After the pyrolyzed copolymer was sufficiently cooled under argon (Ar), the beaker was opened to obtain a sample.

[0158]

[0159] Experimental Example 1

[0160] The physical properties of each copolymer manufactured in the above examples and comparative examples were compared and analyzed and are shown in Table 1. The measurement conditions and methods are as follows.

[0161]

[0162] (1) Density

[0163] According to ASTM D-792, the sample was made into a sheet with a thickness of 3 mm and a radius of 2 cm using a press mold at 180°C, cooled at 10°C / min, and measured on a Mettler balance.

[0164]

[0165] (2) Melt Index (MI)

[0166] MI according to ASTM D-1238 2.16 (Condition E, 190℃, 2.16Kg load) was measured.

[0167]

[0168] (3) Viscosity (cP)

[0169] The measurement was performed using a Brookfield RVDV3T viscometer according to the following method. Specifically, the sample was placed in a 13 ml sample chamber, heated to 177°C using a Brookfield Thermosel, and when the sample was completely melted, the viscometer device was lowered, the spindle was fixed to the sample chamber, and the rotation speed of the spindle (SC-29 high-temperature-melting spindle) was fixed to 10 rpm. Readings were taken for 20 minutes or more or until the values ​​stabilized, and the final values ​​were recorded.

[0170]

[0171] (4) Molecular weight distribution

[0172] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the produced copolymer were measured under the following gel permeation chromatography (GPC) analysis conditions.

[0173] - Column: Agilent Olexis

[0174] - Solvent: Trichlorobenzene (TCB)

[0175] - Flow rate: 1.0 ml / min

[0176] - Sample concentration: 1.0 mg / ml

[0177] - Injection volume: 200 ㎕

[0178] - Column temperature: 160 ℃

[0179] - Detector: Agilent High Temperature RI detector

[0180] - Standard: Polystyrene (corrected with a cubic function)

[0181] - Data processing: Cirrus

[0182] The molecular weight distribution was calculated from the ratio Mw / Mn.

[0183] Density (g / cc)MI 2.16 (dg / min) Viscosity (cP) Mw (g / mol) MWD Example 10.8771, 0218, 00020, 1002.45 Example 20.87755517, 80024, 7002.45 Example 30.87827235, 00028, 5002.38 Example 40.87823741, 00029, 4002.39 Example 50.87452117, 00025, 8002.40 Comparative Example 10.87656617, 10025, 7002.03 Comparative Example 20.8779678, 50019, 5001.77 Comparative Example Comparative Example 30.87662413,90022,8001.94 Comparative Example 40.87327235,00034,9001.98 Comparative Example 50.87555715,80026,7002.29 Comparative Example 60.87753-41,5002.10

[0184] Additionally, the number of vinylene, trivinyl, vinyl, and vinylidene functional groups per 1,000 carbon atoms in the copolymer was measured through nuclear magnetic spectroscopic analysis according to the following method.

[0185] The copolymer was dissolved in 1,1,2,2-tetrachloroethane D2 (TCE-d2) solvent and measured at 393 K using a Bruker AVANCE III 500 MHz NMR instrument.

[0186] In the 1H NMR spectrum, the TCE-d2 peak was corrected to 6.0 ppm, and the content ratio of comonomers was calculated using the integration values ​​in the 1.4 ppm and 0.96 ppm regions. The contents of vinyl, vinylidene, vinylene, and trivinyl groups observed at 4.7 ppm to 5.6 ppm were calculated (analytical method: AMT-3863). Peak assignments were referenced from the literature [Macromolecules 2014, 47, 3282-3790].

[0187] Vinylene (units / 1000C) Trivinyl (units / 1000C) Vinyl (units / 1000C) Vinylidene (units / 1000C) Total (units / 1000C) Vinyl + Vinylidene (units / 1000C) Example 10.65 0.07 0.77 0.58 2.07 1.35 Example 20.61 0.09 0.68 0.47 1.80 1.15 Example 30.64 0.09 0.64 0.41 1.78 1.05 Example 40.50 0.11 0.44 0.37 1.42 0.81 Example 50.57 0.12 0.68 0.54 1.90 1.22 Comparative Example 10.240.070.040.070.420.11Comparative Example 20.200.060.030.060.350.09Comparative Example 30.100.070.030.200.390.23Comparative Example 40.270.070.050.080.470.13Comparative Example 50.790.090.190.401.470.59Comparative Example 60.210.090.190.070.560.26

[0188] As shown in the above results, in Examples 1 to 5, which are ethylene / alpha-olefin copolymers manufactured by thermal decomposition according to the present invention, ethylene / alpha-olefin copolymers were manufactured in which the sum of vinyl and vinylidene functional groups was 0.7 or more.

[0189]

[0190] Experimental Example 2

[0191] Viscosity change rate (%) was measured using a Brookfield RVDV3T viscometer according to the following method.

[0192] Specifically, the sample was placed in a 13 ml sample chamber, heated to 177°C using a Brookfield Thermosel, and when the sample was completely melted, the viscometer device was lowered, the spindle was fixed to the sample chamber, and the rotation speed of the spindle (SC-29 high-temperature-melting spindle) was fixed to 10 rpm, and the value was recorded once per hour for 72 hours. The difference between the initial viscosity and the viscosity after 72 hours was converted into a percentage, and the viscosity change rate was calculated according to the following equation 1.

[0193] [Formula 1]

[0194] Viscosity change rate (%) = (second viscosity - first viscosity) / (first viscosity) X 100 (%)

[0195] In the above equation 1,

[0196] The first viscosity is the initial viscosity measured with a Brookfield viscometer at 177°C.

[0197] The second viscosity is the viscosity measured after leaving it in a Brookfield viscometer at 177°C at the same rotation speed as the measurement conditions of the first viscosity for 72 hours from the measurement time of the first viscosity.

[0198] Viscosity change rate (%) Example 113.7 Example 216.3 Example 319.5 Example 418.9 Example 514.8 Comparative Example 125.3 Comparative Example 223.6 Comparative Example 324.6 Comparative Example 423.2 Comparative Example 519.7 Comparative Example 625.5

[0199] It was confirmed that the ethylene / alpha-olefin copolymers of Examples 1 to 5 according to the present invention had excellent thermal stability with a sum of vinyl and vinylidene functional groups of 0.7 or more and a low viscosity change rate.

[0200]

[0201] Experimental Example 3

[0202] 1) Adhesive manufacturing

[0203] 200 g of the ethylene / alpha-olefin copolymer of the examples and comparative examples manufactured above, 200 g of Regaltac H100W from Eastman, 100 g of H1 from Sasol, and 2.5 g of an antioxidant were placed in a beaker, heated with a heating mantle to melt, and then mixed by sufficient stirring with an impeller.

[0204] 2) Measuring the viscosity of adhesive

[0205] The measurement was performed using a Brookfield RVDV3T viscometer according to the following method. Specifically, the sample was placed in an 8 mL sample chamber, heated to 177°C using a Brookfield Thermosel, and when the sample was completely melted, the viscometer device was lowered, the spindle was fixed to the sample chamber, and the rotation speed of the spindle (SC-21 high-temperature melting spindle) was fixed to 5 rpm. Readings were taken for 20 minutes or more or until the values ​​stabilized, and the final values ​​were recorded.

[0206] 3) Fiber Tear Measurement

[0207] The obtained adhesive was applied to a film of uniform thickness using a roll coater, transferred to kraft paper, and then bonded. The film was then stored in ovens at -30°C, 25°C, and 60°C. After storage for a certain period of time, the film was peeled off, and the ratio of the bonded area was calculated to determine fiber tear.

[0208] ViscosityFiber TearcP-30℃25℃60℃Example 1650839068Example 21,250829265Example 51,190829167Comparative Example 11,200718056Comparative Example 2660727956Comparative Example 31,020697854Comparative Example 51,110738157

[0209] As shown in the above results, the adhesives prepared using Examples 1, 2, and 5, which are ethylene / alpha-olefin copolymers that satisfy all the requirements of the present invention, were found to have high polarity and thus exhibited superior adhesive strength to polar substrates such as kraft paper at all temperatures compared to the comparative examples. This indicates that the ethylene / alpha-olefin copolymer of the present invention can be widely and usefully utilized as an adhesive.

Claims

1. An ethylene / alpha-olefin copolymer satisfying the following conditions (a) to (d): (a) Density: 0.850 to 0.910 g / cc (b) Melting index (190℃, 2.16 kg load condition): 1 to 1,500 dg / min (c) Molecular weight distribution (MWD): 1.5 to 3.0 (d) The sum of the number of vinyl functional groups per 1,000 carbon atoms and the number of vinylidene functional groups per 1,000 carbon atoms measured through nuclear magnetic spectrometry analysis: 0.7 or more.

2. In claim 1, An ethylene / alpha-olefin copolymer having a number of vinyl functional groups per 1,000 carbon atoms of 0.4 to 0.

9.

3. In claim 1, An ethylene / alpha-olefin copolymer having a number of vinylidene functional groups per 1,000 carbon atoms of 0.2 to 0.

7.

4. In claim 1, The above ethylene / alpha-olefin copolymer is an ethylene / alpha-olefin copolymer having a number of vinylene functional groups per 1,000 carbon atoms of 0.3 to 0.8 as measured by nuclear magnetic spectroscopic analysis.

5. In claim 1, The above ethylene / alpha-olefin copolymer is an ethylene / alpha-olefin copolymer having a number of trivinyl functional groups per 1,000 carbon atoms of 0.03 to 0.4 as measured by nuclear magnetic spectroscopic analysis.

6. In claim 1, The above ethylene / alpha-olefin copolymer is an ethylene / alpha-olefin copolymer having a viscosity of 4,000 to 50,000 cP as measured by a Brookfield Viscometer at 177°C.

7. In claim 1, An ethylene / alpha-olefin copolymer comprising at least one selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-eicosene.

8. In claim 1, The above alpha-olefin is an ethylene / alpha-olefin copolymer of 1-butene.

9. An adhesive composition comprising an ethylene / alpha-olefin copolymer according to any one of claims 1 to 8; and a tackifier.

10. In claim 9, An adhesive composition wherein the tackifier is at least one selected from the group consisting of a modified C5 hydrocarbon resin, a styrenated Tefrene resin, a fully or partially hydrogenated C9 hydrocarbon resin, a hydrogenated cycloaliphatic hydrocarbon resin, a hydrogenated aromatic modified cycloaliphatic hydrocarbon resin, and a mixture thereof.

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