Ethylene-butene copolymers and adhesive compositions comprising the same

Abstract

This invention relates to an ethylene-butene copolymer exhibiting excellent processability and adhesive properties, and adhesive compositions comprising the same.

Description

[0001] Cross-references to related applications This application claims priority based on Korean Patent Application No. 10-2024-0195268, filed on December 24, 2024, the entire contents of which are incorporated herein by reference. Technical Field

[0002] This invention relates to an ethylene-butene copolymer exhibiting excellent processability and adhesive properties, and adhesive compositions comprising the same. Background Technology

[0003] Olefin polymerization catalyst systems can be divided into Ziegler-Natta catalyst systems and metallocene catalyst systems. These two types of highly active catalyst systems have been developed based on their respective characteristics. Since its invention in the 1950s, the Ziegler-Natta catalyst has been widely used in existing commercial processes. However, as a multi-site catalyst with multiple active sites, it is characterized by a wide molecular weight distribution of the polymer and an uneven distribution of comonomer composition, making it difficult to obtain the desired physical properties.

[0004] On the other hand, metallocene catalysts consist of a main catalyst primarily composed of transition metal compounds and a cocatalyst primarily composed of aluminum organometallic compounds. Such catalysts, as homogeneous complex catalysts, are single-site catalysts. Due to the characteristics of a single active site, the resulting polymer has a narrow molecular weight distribution and a uniform composition of comonomers. Furthermore, by changing the ligand structure and polymerization conditions, the stereoregularity, copolymerization properties, molecular weight, and crystallinity of the polymer can be altered.

[0005] On the other hand, linear low-density polyethylene (LLDPE) is manufactured by copolymerizing ethylene with α-olefins under low pressure using a polymerization catalyst. It is a resin with a narrow molecular weight distribution and short branches of a certain length, without long branches. In addition to the properties of general polyethylene, LLDPE films also exhibit high tensile strength and elongation, as well as excellent tear strength and drop hammer impact strength. Therefore, its use is increasingly increasing in fields where traditional LLDPE or HLDPE stretch films and overlap films are difficult to apply.

[0006] However, when using 1-butene or 1-hexene as comonomers to produce linear low-density polyethylene, the productivity is higher compared to the process using 1-octene comonomers. However, due to limitations in the catalyst and process technologies used, the physical properties of this product are still significantly inferior to those of copolymers using 1-octene, and it also suffers from poor processability due to a narrower molecular weight distribution.

[0007] Furthermore, even with improved processability, the uneven dispersion of different molecular weights within a unit particle results in a rough extruded appearance and unstable physical properties, even under relatively good extrusion conditions.

[0008] Against this backdrop, there is a continued need to manufacture superior products that balance physical properties and processability, particularly with the increasing demand for polyethylene copolymers that offer excellent processability.

[0009] Existing technical documents Patent documents (Patent Document 1) U.S. Patent No. 5,064,802 Summary of the Invention

[0010] Technical issues The object of the present invention is to provide an ethylene-butene copolymer that exhibits excellent processability and adhesive properties by controlling density, viscosity and melt index, as well as an adhesive composition utilizing the thereof.

[0011] Technical solution (1) The present invention provides an ethylene-butene copolymer that satisfies the following conditions (a) to (c): (a) Density: 0.867 g / cc to 0.889 g / cc; (b) Viscosity: 4,500 cP to 16,000 cP at 177°C; (c) Melt index (190°C, 2.16 kg load): 500 dg / min to 1,600 dg / min.

[0012] (2) The present invention provides an ethylene-butene copolymer as described in (1) above, wherein the density is from 0.868 g / cc to 0.888 g / cc.

[0013] (3) The present invention provides an ethylene-butene copolymer as described in (1) or (2) above, wherein the viscosity is 4,600 cP to 15,900 cP at 177°C.

[0014] (4) The present invention provides an ethylene-butene copolymer as described in any one of (1) to (3) above, wherein the melt index (190°C, 2.16 kg load conditions) is from 520 dg / min to 1,580 dg / min.

[0015] (5) The present invention provides an ethylene-butene copolymer as described in any one of (1) to (4) above, wherein the number of vinyl functional groups in each 1,000 carbon atoms of the ethylene-butene copolymer, as measured by nuclear magnetic resonance analysis, is 0.01 to 2.0.

[0016] (6) The present invention provides an ethylene-butene copolymer as described in any one of (1) to (5) above, wherein the number of ethylene-butene functional groups per 1,000 carbon atoms in the ethylene-butene copolymer, as measured by nuclear magnetic resonance analysis, is 0.01 to 0.9.

[0017] (7) The present invention provides an ethylene-butene copolymer as described in any one of (1) to (6) above, wherein the number of vinylene functional groups per 1,000 carbon atoms in the ethylene-butene copolymer, as measured by nuclear magnetic resonance analysis, is 0.1 to 1.9.

[0018] (8) The present invention provides an ethylene-butene copolymer as described in any one of (1) to (7) above, wherein the number of trisubstituted vinyl functional groups per 1,000 carbon atoms in the ethylene-butene copolymer is from 0.01 to 0.8 as measured by nuclear magnetic resonance analysis.

[0019] (9) The present invention provides an ethylene-butene copolymer as described in any one of (1) to (8) above, wherein the melting temperature of the ethylene-butene copolymer is 50°C to 90°C.

[0020] (10) The present invention provides an ethylene-butene copolymer as described in any one of (1) to (9) above, wherein the crystallization temperature of the ethylene-butene copolymer is 30°C to 70°C.

[0021] (11) The present invention provides an adhesive composition comprising an ethylene-butene copolymer as described in any one of (1) to (10) above and a tackifier.

[0022] (12) The present invention provides an adhesive composition as described in (11) above, wherein the tackifier is selected from one or more of modified C5 hydrocarbon resins, styrene-modified terpene resins, fully hydrogenated or partially hydrogenated C9 hydrocarbon resins, hydrogenated alicyclic hydrocarbon resins, hydrogenated aromatic modified alicyclic hydrocarbon resins, and mixtures thereof.

[0023] (13) The present invention provides an adhesive composition as described in (11) or (12) above, wherein the adhesive composition has a viscosity of 350 cP to 1,250 cP at 177°C.

[0024] Invention Effects The ethylene-butene copolymer of the present invention exhibits excellent processability and adhesion properties. Detailed Implementation

[0025] The present invention will now be described in more detail to aid in understanding it.

[0026] The terms or words used in this specification and claims should not be construed as limited to their ordinary or dictionary meanings, but should be interpreted as meanings and concepts consistent with the technical concept of this invention. The principle is that the inventor is able to properly define the concepts of the terms to best interpret his invention.

[0027] ethylene-butene copolymer The ethylene-butene copolymer of the present invention satisfies the following conditions (a) to (c): (a) Density: 0.867 g / cc to 0.889 g / cc; (b) Viscosity: 4,500 cP to 16,000 cP at 177°C; (c) Melt index (190°C, 2.16 kg load): 500 dg / min to 1,600 dg / min.

[0028] The inventors completed this invention by controlling the density, viscosity, and melt index of the ethylene-butene copolymer within a specific range, confirming that it exhibits excellent processability and adhesive properties during adhesive manufacturing. In particular, by using butene as the α-olefin, copolymers using other α-olefins such as ethylene-octene and ethylene-hexene demonstrate superior adhesive strength at low temperatures and reduce the production cost of copolymer manufacturing.

[0029] The ethylene-butene copolymer of the present invention has a density of 0.867 g / cc to 0.889 g / cc as measured according to ASTM D-792. The density can be above 0.868 g / cc, above 0.869 g / cc, or above 0.870 g / cc, or below 0.888 g / cc, below 0.886 g / cc, or below 0.885 g / cc; for example, it can be from 0.868 g / cc to 0.888 g / cc.

[0030] Ethylene-butene copolymers have densities within the aforementioned range, thus exhibiting excellent processability and low-temperature adhesion.

[0031] The ethylene-butene copolymer of the present invention has a viscosity of 4,500 cP to 16,000 cP at 177°C. Specifically, the viscosity can be 4,600 cP or more, 4,700 cP or more, 4,900 cP or more, or 5,000 cP or more, and can be 15,900 cP or less, 15,800 cP or less, 15,700 cP or less, 15,600 cP or less, 15,500 cP or less, or 15,400 cP or less, for example, 4,600 cP to 15,900 cP at 177°C.

[0032] Ethylene-butene copolymers have viscosity ranges as described above, thus exhibiting excellent processability and adhesion at room temperature and low temperature.

[0033] The melt index (190°C, 2.16 kg load) of the ethylene-butene copolymer of the present invention is 500 dg / min to 1,600 dg / min.

[0034] Specifically, the melt flow index can be above 520 dg / min, above 550 dg / min, or above 570 dg / min, and can be below 1,580 dg / min, below 1,560 dg / min, or below 1,550 dg / min, for example, it can be from 520 dg / min to 1,580 dg / min.

[0035] The ethylene-butene copolymer has a melt index within the range described above, thereby ensuring mechanical rigidity in the adhesive composition, while achieving an appropriate operating temperature when using the adhesive, and exhibiting excellent adhesion at both room temperature and low temperature.

[0036] In this invention, the melting temperature (Tm) of the ethylene-butene copolymer is... m The temperature can range from 50°C to 90°C. Specifically, it can be above 51°C, above 53°C, or above 55°C, and below 88°C, below 85°C, or below 82°C.

[0037] In this invention, the crystallization temperature (T) of the ethylene-butene copolymer is... c The temperature can range from 30°C to 70°C. Specifically, it can be above 32°C, above 34°C, or above 36°C, and below 68°C, below 65°C, or below 62°C.

[0038] When the melting and crystallization temperatures meet the above ranges, the low-temperature adhesion is excellent and the processability is improved.

[0039] The melting and crystallization temperatures can be measured using a differential scanning calorimeter (DSC). Specifically, the copolymer is heated to 150°C and held for 5 minutes, then cooled to 20°C, and then heated again. The heating and cooling rates are controlled at 10°C / min, and the result measured during the second heating phase is taken as the melting temperature, while the result measured during the cooling phase is taken as the crystallization temperature.

[0040] In this invention, the number of vinyl functional groups per 1,000 carbon atoms in the ethylene-butene copolymer, as measured by nuclear magnetic resonance analysis, can be from 0.01 to 2.0. Specifically, it can be more than 0.02, more than 0.03, or more than 0.04, and less than 1.8, less than 1.5, or less than 1.2.

[0041] Furthermore, the number of vinylidene functional groups per 1,000 carbon atoms in the ethylene-butene copolymer of the present invention can be from 0.01 to 0.9. Specifically, it can be more than 0.02, and can be less than 0.8, less than 0.7, or less than 0.6.

[0042] Furthermore, the number of vinylene functional groups per 1,000 carbon atoms in the ethylene-butene copolymer of the present invention, as measured by nuclear magnetic resonance analysis, can be from 0.1 to 1.9. Specifically, it can be more than 0.11, more than 0.12, and less than 1.8, less than 1.7, or less than 1.6.

[0043] Furthermore, the number of trisubstituted vinyl functional groups per 1,000 carbon atoms in the ethylene-butene copolymer of the present invention can be from 0.01 to 0.8. Specifically, it can be more than 0.02, and can be less than 0.7, less than 0.6, or less than 0.5.

[0044] The ethylene-butene copolymer of the present invention has the number of trisubstituted vinyl functional groups within the above-mentioned range, thereby improving the adhesion at low and room temperatures, exhibiting excellent processability, and demonstrating excellent long-term physical properties.

[0045] Furthermore, the total number of unsaturated functional groups per 1,000 carbon atoms in the ethylene-butene copolymer of the present invention, as measured by nuclear magnetic resonance analysis, can be from 0.2 to 5.5. More specifically, it can be more than 0.21, more than 0.22, and less than 5.0, less than 4.5, or less than 4.0.

[0046] The ethylene-butene copolymer of the present invention has the number of unsaturated functional groups within the above-mentioned range, thereby improving the adhesion at low and room temperatures, exhibiting excellent processability, and demonstrating excellent long-term physical properties.

[0047] The vinyl group has an R-CH=CH2 structure, the trisubstituted vinyl group has an RCH=CR'R" structure, the ethylene propylene (also known as "1,2-vinylene") has an RCH=CHR'(E-form) or Z-RCH=CHR'(Z-form) structure, and the ethylene propylene (also known as "1,1-vinylene") has an RR'C=CH2 structure. R, R', and R" can each independently be a polymer chain or a branch formed from α-olefin comonomers.

[0048] In this invention, the contents of vinyl groups, ethylene derivatives, ethylene propylene, and trisubstituted vinyl groups in the copolymer can be calculated from NMR analysis results. Specifically, the copolymer is dissolved in 1,1,2,2-deuterated tetrachloroethane (TCE-d2) solvent, and the measurements are performed at 393 K using a Bruker AVANCE III 500MHz NMR instrument. 1 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 integral values ​​in the 1.4 ppm and 0.96 ppm regions. The contents of vinyl, ethylene ide, ethylene ethylene, and trisubstituted vinyl groups observed in the range of 4.7 ppm to 5.6 ppm were calculated (analytical method: AMT-3863). Peak assignment is referenced in [Macromolecules 2014, 47, 3282-3790].

[0049] Furthermore, the molecular weight distribution (MWD) of the ethylene-butene copolymer of the present invention can be from 1.5 to 3.5. Specifically, it can be 1.6 or more, 1.7 or more, or 1.8 or more, and can be 3.4 or less, 3.3 or less, or 3.2 or less.

[0050] The weight-average molecular weight (Mw) of the ethylene-butene copolymer described in one embodiment of the present invention can be from 16,000 g / mol to 29,000 g / mol. Specifically, it can be 17,000 g / mol or more, 18,000 g / mol or more, or 19,000 g / mol or more, and can be 28,000 g / mol or less, 27,000 g / mol or less, or 26,000 g / mol or less.

[0051] When the weight-average molecular weight meets the above-mentioned range, it is associated with the viscosity of the binder composition containing it, thereby expecting a significant improvement in processability. That is, the mechanical properties, impact strength, and viscosity of the ethylene-butene copolymer can be controlled by adjusting the type and amount of catalyst used in the polymerization process, and while meeting the above conditions, it can maintain excellent mechanical properties and exhibit improved processability.

[0052] On the other hand, in this invention, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are the equivalent molecular weights of polystyrene analyzed by gel permeation chromatography (GPC), and the molecular weight distribution can be calculated by the ratio of Mw / Mn.

[0053] Furthermore, in the ethylene-butene copolymer, the content of butene as a comonomer can be appropriately selected within the range that meets the above-mentioned physical property requirements. Specifically, it can be greater than 0 and less than 99 mol%, or 10 to 50 mol%.

[0054] The ethylene-butene copolymer of the present invention can be manufactured by thermally decomposing an existing ethylene-butene copolymer at an appropriate temperature and time. The existing ethylene-butene copolymer is independent of commercially available ethylene-butene copolymers or ethylene-butene copolymers manufactured by known methods, as long as they are readily available to those skilled in the art. More specifically, ethylene-butene copolymers with a melt index (MI; 190°C, 2.16 kg load) of 5.0 g / 10 min to 15.0 g / 10 min and a density of 0.850 g / cc to 0.890 g / cc can be used, but are not limited thereto.

[0055] The thermal decomposition can specifically be heating at 350°C to 450°C, or above 360°C, 370°C, 380°C, or 390°C, and can be below 440°C, 430°C, 420°C, or 410°C, for example, 390°C to 410°C.

[0056] Furthermore, under the temperature conditions described above, thermal decomposition can be carried out for 1 to 7 hours. Specifically, it can be carried out for more than 1 hour, and can be carried out for less than 6 hours, less than 5 hours, less than 4 hours, or less than 3 hours. More specifically, it can be carried out for 1 to 3 hours, but is not limited to these.

[0057] Furthermore, the ethylene-butene copolymer of the present invention can be manufactured by a manufacturing method that involves adding hydrogen to a catalyst composition containing metallocene compounds while simultaneously polymerizing ethylene and butene.

[0058] The amount of hydrogen added can be from 100cc / min to 700cc / min, and can be above 150cc / min, above 170cc / min, above 200cc / min or above 250cc / min, and can be below 600cc / min, below 500cc / min, below 400cc / min or below 350cc / min, but is not limited thereto.

[0059] Adhesive composition The present invention provides an adhesive composition comprising the ethylene-butene copolymer and a tackifier.

[0060] In this invention, the viscosity of the adhesive composition at 177°C can be from 350 cP to 1,250 cP. Specifically, the viscosity can be 360 ​​cP or more, 370 cP or more, 380 cP or more, 390 cP or more, or 400 cP or more, and can be 1,230 cP or less, 1,200 cP or less, 1,180 cP or less, 1,150 cP or less, or 1,120 cP or less.

[0061] The tackifier may be an aliphatic hydrocarbon resin, for example selected from modified C5 hydrocarbon resins (C5 / C9 resins), styrene-modified terpene resins, fully hydrogenated or partially hydrogenated C9 hydrocarbon resins, hydrogenated alicyclic hydrocarbon resins, hydrogenated aromatic modified alicyclic hydrocarbon resins, and mixtures thereof.

[0062] The tackifier is not particularly limited, and its content can be from 5 to 70 parts by weight, specifically 20 to 70 parts by weight, relative to 100 parts by weight of the adhesive composition. If the tackifier content is less than 5 parts by weight, the viscosity of the adhesive composition may increase, resulting in decreased processability; if the content is greater than 70 parts by weight, it may lead to decreased heat resistance.

[0063] The content of the ethylene-butene copolymer can be 10 to 50 parts by weight, specifically 15 to 30 parts by weight, relative to 100 parts by weight of the adhesive composition. Excellent adhesive properties are maintained when the above numerical range is met.

[0064] In addition, the adhesive composition may also contain a plasticizer. The plasticizer is not particularly limited and may be, for example, a paraffinic or naphthenic plasticizing oil. Specifically, it may be a low molecular weight polymer such as olefin oligomers, liquid polybutene, polyisoprene copolymers, liquid styrene-isoprene copolymers, or liquid hydrogenated styrene-conjugated diene copolymers, vegetable oils and their derivatives, or microcrystalline waxes.

[0065] The plasticizer is not particularly limited, and its content may be from 10 to 50 parts by weight, specifically from 20 to 40 parts by weight, relative to 100 parts by weight of the adhesive composition. If the plasticizer content is less than 10 parts by weight, the viscosity of the adhesive composition may increase, resulting in decreased processability; if the content is greater than 50 parts by weight, it may lead to decreased adhesive properties.

[0066] In addition, the adhesive composition may also contain antioxidants to improve heat resistance and color, etc.

[0067] At this point, the antioxidant is not particularly limited and can be any commonly known in the art, and its content relative to 100 parts by weight of the adhesive composition can be 0.01 to 5 parts by weight, or 0.01 to 1 part by weight, or 0.05 to 0.75 parts by weight.

[0068] In addition, the adhesive composition may also contain one or more additives selected from UV stabilizers, colorants or pigments, fillers, flow aids, coupling agents, crosslinking agents, surfactants, solvents, and combinations thereof.

[0069] 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 less than 80% by weight of the total composition.

[0070] In this invention, the adhesive composition may be a hot melt adhesive composition.

[0071] 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 hygiene products.

[0072] Example The present invention will be further described in detail below through embodiments. However, the following embodiments are only for illustrating the present invention and do not limit the scope of the present invention.

[0073] Example 1 1 kg of ethylene-butene copolymer (LG Chem LUCENE LC675, MI: 14 g / 10 min, density: 0.877 g / cc) was weighed and placed in a 5 L batch reactor. Vacuum was maintained to remove moisture and oxygen. After removal, argon (Ar) gas was introduced into the beaker to create an inert environment. The beaker containing the ethylene-butene copolymer was connected to a mechanical stirrer and impeller, stirred at 100 rpm, and heated at 390 °C for 2 hours for thermal decomposition. After the thermally decomposed copolymer was fully cooled under an argon (Ar) atmosphere, the beaker was opened to obtain the product.

[0074] Example 2 1 kg of ethylene-butene copolymer (LG Chem LUCENE LC675, MI: 14 g / 10 min, density: 0.877 g / cc) was weighed and placed in a 5 L batch reactor. Vacuum was maintained to remove moisture and oxygen. After removal, argon (Ar) gas was introduced into the beaker to create an inert environment. The beaker containing the ethylene-butene copolymer was connected to a mechanical stirrer and impeller, stirred at 100 rpm, and heated at 400 °C for 2 hours for thermal decomposition. After fully cooling the thermally decomposed copolymer under an argon (Ar) atmosphere, the beaker was opened to obtain the product.

[0075] Example 3 1 kg of ethylene-butene copolymer (LG Chem LUCENE LC675, MI: 14 g / 10 min, density: 0.877 g / cc) was weighed and placed in a 5 L batch reactor. Vacuum was maintained to remove moisture and oxygen. After removal, argon (Ar) gas was introduced into the beaker to create an inert environment. The beaker containing the ethylene-butene copolymer was connected to a mechanical stirrer and impeller, stirred at 200 rpm, and heated at 410 °C for 3 hours for thermal decomposition. After fully cooling the thermally decomposed copolymer under an argon (Ar) atmosphere, the beaker was opened to obtain the product.

[0076] Example 4 In a 1.5L continuous process reactor, hexane solvent was added at a rate of 5.0 kg / h, and 1-butene was added at a rate of 0.8 kg / h, with preheating at 150 °C. Simultaneously, triisobutylaluminum compound (0.045 mmol / min), a metallocene catalyst (obtained according to KR 10-2236921 B1) (0.240 μmol / min), and dimethylphenylammonium tetra(pentafluorophenyl)borate co-catalyst (2.288 μmol / min) were added to the reactor. Subsequently, ethylene (0.87 kg / h) and hydrogen (350 cc / min) were added to the reactor, and the copolymerization reaction was carried out at 150.1 °C for at least 60 minutes in a continuous process at a pressure of 89 bar to obtain an ethylene-butene copolymer. The copolymer was then dried in a vacuum oven for at least 12 hours before its physical properties were measured.

[0077] Example 5 1 kg of ethylene-butene copolymer (LG Chem LUCENE LF686, MI: 14 g / 10 min, density: 0.881 g / cc) was weighed and placed in a 5 L batch reactor. Vacuum was maintained to remove moisture and oxygen. After removal, argon (Ar) gas was introduced into the beaker to create an inert environment. The beaker containing the ethylene-butene copolymer was connected to a mechanical stirrer and impeller, stirred at 100 rpm, and heated at 400 °C for 1 hour for thermal decomposition. After the thermally decomposed copolymer was fully cooled under an argon (Ar) atmosphere, the beaker was opened to obtain the product.

[0078] Example 6 In a 1.5L continuous process reactor, hexane solvent was added at a rate of 5.0 kg / h, and 1-butene was added at a rate of 0.9 kg / h, with preheating at 140 °C. Simultaneously, triisobutylaluminum compound (0.045 mmol / min), a metallocene catalyst (obtained according to KR 10-2236921 B1) (0.180 μmol / min), and dimethylphenylammonium tetra(pentafluorophenyl)borate co-catalyst (1.716 μmol / min) were added to the reactor. Subsequently, ethylene (0.87 kg / h) and hydrogen (250 cc / min) were added to the reactor, and the copolymerization reaction was carried out at 140.1 °C for at least 60 minutes in a continuous process at a pressure of 89 bar to obtain an ethylene-butene copolymer. The copolymer was then dried in a vacuum oven for at least 12 hours before its physical properties were measured.

[0079] Comparative Example 1 1 kg of ethylene-butene copolymer (LG Chem LUCENE LC675, MI: 14 g / 10 min, density: 0.877 g / cc) was weighed and placed in a 5 L batch reactor. Vacuum was maintained to remove moisture and oxygen. After removal, argon (Ar) gas was introduced into the beaker to create an inert environment. The beaker containing the ethylene-butene copolymer was connected to a mechanical stirrer and impeller, stirred at 100 rpm, and heated at 380 °C for 3 hours for thermal decomposition. After sufficient cooling of the thermally decomposed copolymer under an argon (Ar) atmosphere, the beaker was opened to obtain the product.

[0080] Comparative Example 2 1 kg of ethylene-butene copolymer (LG Chem LUCENE LC675, MI: 14 g / 10 min, density: 0.877 g / cc) was weighed and placed in a 5 L batch reactor. Vacuum was maintained to remove moisture and oxygen. After removal, argon (Ar) gas was introduced into the beaker to create an inert environment. The beaker containing the ethylene-butene copolymer was connected to a mechanical stirrer and impeller, stirred at 200 rpm, and heated at 420 °C for 2 hours for thermal decomposition. After sufficient cooling of the thermally decomposed copolymer under an argon (Ar) atmosphere, the beaker was opened to obtain the product.

[0081] Comparative Example 3 In a 1.5L continuous process reactor, hexane solvent was added at a rate of 5.0 kg / h, and 1-butene was added at a rate of 0.6 kg / h, with preheating at 140 °C. Simultaneously, triisobutylaluminum compound (0.045 mmol / min), a metallocene catalyst (obtained according to KR 10-2236921 B1) (0.180 μmol / min), and dimethylphenylammonium tetra(pentafluorophenyl)borate co-catalyst (1.716 μmol / min) were added to the reactor. Subsequently, ethylene (0.87 kg / h) and hydrogen (300 cc / min) were added to the reactor, and the copolymerization reaction was carried out at 140.1 °C for at least 60 minutes in a continuous process at a pressure of 89 bar to obtain an ethylene-butene copolymer. The copolymer was then dried in a vacuum oven for at least 12 hours before its physical properties were measured.

[0082] Comparative Example 4 In a 1.5L continuous process reactor, hexane solvent was added at a rate of 5.0 kg / h, and 1-butene was added at a rate of 0.95 kg / h, with preheating at 140 °C. Simultaneously, triisobutylaluminum compound (0.045 mmol / min), a metallocene catalyst (obtained according to KR 10-2236921 B1) (0.180 μmol / min), and dimethylphenylammonium tetra(pentafluorophenyl)borate co-catalyst (1.716 μmol / min) were added to the reactor. Subsequently, ethylene (0.87 kg / h) and hydrogen (200 cc / min) were added to the reactor, and the copolymerization reaction was carried out at 140.1 °C for at least 60 minutes in a continuous process at a pressure of 89 bar to obtain an ethylene-butene copolymer. The copolymer was then dried in a vacuum oven for at least 12 hours before its physical properties were measured.

[0083] Comparative Example 5 In a 1.5L continuous process reactor, hexane solvent was added at a rate of 5.0 kg / h, and 1-octene was added at a rate of 1.4 kg / h, with preheating at 140 °C. Simultaneously, triisobutylaluminum compound (0.045 mmol / min), a metallocene catalyst (obtained according to KR 10-2236921 B1) (0.180 μmol / min), and dimethylphenylammonium tetra(pentafluorophenyl)borate co-catalyst (1.716 μmol / min) were added to the reactor. Subsequently, ethylene (0.87 kg / h) and hydrogen (250 cc / min) were added to the reactor, and the copolymerization reaction was carried out at 140.1 °C for at least 60 minutes in a continuous process at a pressure of 89 bar to obtain an ethylene-octene copolymer. The copolymer was then dried in a vacuum oven for at least 12 hours before its physical properties were measured.

[0084] Comparative Example 6 In a 1.5L continuous process reactor, hexane solvent was added at a rate of 5.0 kg / h, and 1-octene was added at a rate of 1.4 kg / h, with preheating at 150 °C. Simultaneously, triisobutylaluminum compound (0.045 mmol / min), a metallocene catalyst (obtained according to KR 10-2236921 B1) (0.240 μmol / min), and dimethylphenylammonium tetra(pentafluorophenyl)borate co-catalyst (2.288 μmol / min) were added to the reactor. Subsequently, ethylene (0.87 kg / h) and hydrogen (350 cc / min) were added to the reactor, and the copolymerization reaction was carried out at 150.1 °C for at least 60 minutes in a continuous process at a pressure of 89 bar to obtain an ethylene-octene copolymer. The copolymer was then dried in a vacuum oven for at least 12 hours before its physical properties were measured.

[0085] Experimental Example 1 The physical properties of the copolymers manufactured in the above examples and comparative examples were compared and analyzed. The measurement conditions and methods are as follows: density According to ASTM D-792, the sample was pressed into a sheet with a thickness of 3 mm and a radius of 2 cm at 180°C, cooled at 10°C / min, and then measured using a Mettler balance.

[0086] Viscosity (cP) The following method was used to measure the viscosity using a Brookfield RVDV3T viscometer. Specifically, the sample was placed in a 13 mL sample chamber and heated to 177°C using a Brookfield Thermosel. After the sample was completely melted, the viscometer was lowered, and the rotor was fixed in the sample chamber. The rotation speed of the rotor (SC-29 high-temperature melting rotor) was fixed at 10 rpm. The readings were then taken for at least 20 minutes or until the values ​​stabilized, and the final values ​​were recorded.

[0087] Melt Index (MI) MI was measured according to ASTM D-1238. 2.16 (Condition E, 190℃, 2.16kg load).

[0088] Molecular weight distribution Under the following gel permeation chromatography (GPC) analytical conditions, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the generated copolymer were measured: -Column: Agilent Olexis Solvent: Trichlorobenzene (TCB) - Flow rate: 1.0 mL / min - Sample concentration: 1.0 mg / mL -Injection volume: 200μL - Column temperature: 160℃ - Detector: Agilent High Temperature RI detector -Standard: Polystyrene (corrected using a cubic function) Data processing: Cirrus software The molecular weight distribution is calculated from the Mw / Mn ratio.

[0089] Melting temperature and crystallization temperature Melting temperature (T) m ) and crystallization temperature (T) c The results were obtained using a Differential Scanning Calorimeter (DSC 6000) manufactured by PerkinElmer. Specifically, the copolymer was heated to 200°C and held for 5 minutes under a nitrogen atmosphere using DSC, then cooled to 30°C, and then heated again while observing the DSC curve. The heating and cooling rates were 10°C / min.

[0090] In the measured DSC curve, the melting temperature is the maximum point of the endothermic peak during the second heating, and the crystallization temperature is the maximum point of the exothermic peak during cooling.

[0091] Table 1 Referring to Table 1, the ethylene-butene copolymers of Examples 1 to 6 of the present invention have densities ranging from 0.867 g / cc to 0.889 g / cc, viscosities ranging from 4,500 cP to 16,000 cP at 177°C, and melt flow indexes ranging from 500 dg / min to 1,600 dg / min at 190°C and 2.16 kg load conditions.

[0092] On the other hand, the ethylene-butene copolymers of Comparative Examples 1 to 4 did not meet the range in at least one of density, viscosity, and melt index, while ethylene-octene copolymers were produced in Comparative Examples 5 and 6.

[0093] Number of unsaturated functional groups Furthermore, the number of ethylene, trisubstituted vinyl, vinyl, and vinylidene functional groups per 1,000 carbon atoms in the copolymer was measured by nuclear magnetic resonance analysis, as follows: The copolymer was dissolved in 1,1,2,2-deuterated tetrachloroethane (TCE-d2) solvent and measured at 393 K using a Bruker AVANCE III 500MHz NMR instrument.

[0094] exist 1 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 integral values ​​in the 1.4 ppm and 0.96 ppm regions. The contents of vinyl, ethylene ide, ethylene ethylene, and trisubstituted vinyl groups observed in the range of 4.7 ppm to 5.6 ppm were calculated (analytical method: AMT-3863). Peak assignments are referenced in [Macromolecules 2014, 47, 3282-3790].

[0095] Table 2 Experiment Example 2 200g of ethylene-α-olefin copolymer, 200g of Eastman's Regaltac H100W, 100g of Sasol's H1, and 2.5g of antioxidant, prepared in the above examples and comparative examples, were placed in a beaker, heated and melted using a heating mantle, and then thoroughly stirred and mixed with an impeller to produce an adhesive.

[0096] Viscosity measurement The following method was used to measure the viscosity using a Brookfield RVDV3T viscometer. Specifically, the sample was placed in an 8 mL sample chamber and heated to 150°C using a Brookfield Thermosel. After the sample was completely melted, the viscometer was lowered, and the rotor was fixed in the sample chamber. The rotation speed of the rotor (SC-21 high-temperature melting rotor) was fixed at 5 rpm. The readings were taken for at least 20 minutes or until the values ​​stabilized, and the final value was recorded.

[0097] Using the same method, the viscosity was measured when the heating temperature was set to 177°C.

[0098] Measurement of fiber tear The obtained adhesive was used to form a film of uniform thickness using a roller coater, which was then transferred onto kraft paper and bonded together. The film was stored in ovens at -30°C and 25°C. After a certain period of storage, the film was peeled off, and the proportion of the bonded area was calculated to determine the fiber tearing.

[0099] The results of the evaluation, based on the following criteria, are shown in Table 3.

[0100] ◎: Fiber tear rate greater than 75% ○: Fiber tearing greater than 50% △: Fiber tearing greater than 25% ×: Fiber tearing less than 25% Measurement of set time After the adhesive is fully melted in an oven at 180°C, it is applied to kraft paper to a certain thickness. The kraft paper is then quickly attached. The kraft paper is peeled off every second, and the time required for the bonded area to reach more than 50% is measured. A shorter curing time indicates less time for the adhesive to cure and gain adhesion, thus indicating excellent productivity.

[0101] The results of the evaluation, based on the following criteria, are shown in Table 3.

[0102] ◎: Curing time less than 5 seconds ○: Curing time less than 10 seconds △: Curing time less than 15 seconds ×: Curing time 15 seconds or more Table 3 If the viscosity of the adhesive is too high, the adhesion at room temperature is improved, but the flowability is low, leading to a decrease in processability; conversely, if the viscosity is too low, the processability is good, but the adhesion is reduced, resulting in a deterioration in the performance of the adhesive. On the other hand, low density results in excellent low-temperature adhesion, but prolonged curing time, leading to a decrease in productivity; high density increases productivity, but low-temperature adhesion decreases.

[0103] From this perspective, the ethylene-butene copolymer of the present invention can simultaneously exhibit excellent performance and processability, producing an adhesive with optimal physical properties. On the other hand, in Comparative Examples 1 to 4, which used ethylene-butene copolymers that did not meet the density, viscosity, and melt index requirements of the present invention, and in Comparative Examples 5 and 6, which used ethylene / octene copolymers, the physical properties of the adhesives decreased compared to the examples.

Claims

1. An ethylene-butene copolymer that satisfies the following conditions (a) to (c): (a) Density: 0.867 g / cc to 0.889 g / cc; (b) Viscosity: 4,500 cP to 16,000 cP at 177°C; (c) Melt flow index: 500 dg / min to 1,600 dg / min at 190 °C and 2.16 kg load.

2. The ethylene-butene copolymer according to claim 1, wherein, The density is between 0.868 g / cc and 0.888 g / cc.

3. The ethylene-butene copolymer according to claim 1, wherein, The viscosity is 4,600 cP to 15,900 cP at 177°C.

4. The ethylene-butene copolymer according to claim 1, wherein, The melt flow index ranges from 520 dg / min to 1,580 dg / min at 190°C and a load of 2.16 kg.

5. The ethylene-butene copolymer of claim 1, wherein, The number of vinyl functional groups per 1,000 carbon atoms in the ethylene-butene copolymer, as measured by nuclear magnetic resonance analysis, ranges from 0.01 to 2.

0.

6. The ethylene-butene copolymer of claim 1, wherein, The number of ethylene-butene functional groups per 1,000 carbon atoms in the ethylene-butene copolymer, as measured by nuclear magnetic resonance analysis, ranges from 0.01 to 0.

9.

7. The ethylene-butene copolymer according to claim 1, wherein, The number of ethylene-butene functional groups per 1,000 carbon atoms in the ethylene-butene copolymer, as measured by nuclear magnetic resonance analysis, ranges from 0.1 to 1.

9.

8. The ethylene-butene copolymer of claim 1, wherein, The number of trisubstituted vinyl functional groups per 1,000 carbon atoms in the ethylene-butene copolymer, as measured by nuclear magnetic resonance analysis, is between 0.01 and 0.

8.

9. The ethylene-butene copolymer of claim 1, wherein, The melting temperature of the ethylene-butene copolymer is 50°C to 90°C.

10. The ethylene-butene copolymer according to claim 1, wherein, The crystallization temperature of the ethylene-butene copolymer is 30°C to 70°C.

11. An adhesive composition comprising: an ethylene-butene copolymer as described in any one of claims 1 to 10; and a tackifier.

12. The adhesive composition according to claim 11, wherein, The tackifier is selected from one or more of the following: modified C5 hydrocarbon resin, styrene-modified terpene resin, fully hydrogenated or partially hydrogenated C9 hydrocarbon resin, hydrogenated alicyclic hydrocarbon resin, hydrogenated aromatic modified alicyclic hydrocarbon resin, and mixtures thereof.

13. The adhesive composition of claim 11, wherein, The adhesive composition has a viscosity of 350 cP to 1,250 cP at 177°C.

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