KR102294874B1 - Ethylene/alpha-olefin copolymer - Google Patents

Abstract

_{The present invention provides an ethylene/alpha-olefin copolymer having excellent physical} properties, particularly high temperature stability, by having an ultra-low molecular weight, low unsaturated functional group content and R vd value.

Description

Ethylene/alpha-olefin copolymer {Ethylene/alpha-olefin copolymer}

The present invention relates to an ethylene/alpha-olefin copolymer having excellent _physical properties, particularly high temperature stability, by having an ultra-low molecular weight, a low content of unsaturated functional groups and a R vd value.

Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, and these two highly active catalyst systems have been developed according to their respective characteristics. Ziegler-Natta catalyst has been widely applied to existing commercial processes since its invention in the 1950s. There is a problem in that there is a limit in securing the desired physical properties because the composition distribution is not uniform.

On the other hand, the metallocene catalyst is composed of a combination of a main catalyst containing a transition metal compound as a main component and an organometallic compound containing aluminum as a main component. Such a catalyst is a homogeneous complex catalyst and is a single site catalyst. The molecular weight distribution is narrow according to the single active site characteristic, and a polymer with a uniform composition distribution of the comonomer is obtained. It has properties that can change crystallinity, etc.

U.S. Patent No. 5,914,289 discloses a method for controlling the molecular weight and molecular weight distribution of a polymer using a metallocene catalyst supported on each carrier, but the amount of solvent used in preparing the supported catalyst and preparation time are required. , the inconvenience of having to support each of the metallocene catalysts to be used on a carrier followed.

Korean Patent Laid-Open No. 2004-0076965 discloses a method of controlling molecular weight distribution by supporting a double-nuclear metallocene catalyst and a single-nuclear metallocene catalyst together with an activator on a carrier to change the combination of catalysts in the reactor and polymerization. have. However, this method has a limitation in simultaneously realizing the characteristics of each catalyst, and also the metallocene catalyst portion is released from the carrier component of the finished catalyst, thereby causing fouling in the reactor.

On the other hand, linear low-density polyethylene is produced by copolymerizing ethylene and alpha olefin at low pressure using a polymerization catalyst, and is a resin having a narrow molecular weight distribution, short-chain branches of a constant length, and no long-chain branches. The linear low-density polyethylene film has high breaking strength and elongation, along with the characteristics of general polyethylene, as well as excellent tear strength and falling impact strength. are doing

However, most of the linear low-density polyethylene using 1-butene or 1-hexene as a comonomer is produced in a single gas phase reactor or a single loop slurry reactor, and the productivity is high compared to the process using 1-octene comonomer, but these products are also used Due to limitations in catalyst technology and process technology, physical properties are significantly inferior to those in the case of using 1-octene comonomer, and the molecular weight distribution is narrow, resulting in poor processability.

In US Patent No. 4,935,474, two or more metallocene compounds are used to report a polyethylene production method having a broad molecular weight distribution. U.S. Patent No. 6,828,394 reports on a method for producing polyethylene having excellent processability and particularly suitable for films by using a mixture of those having good comonomer binding properties and those not having good comonomer binding properties. In addition, U.S. Patent Nos. 6,841,631 and 6,894,128 disclose that at least two metal compounds are used as metallocene catalysts to prepare polyethylene having a bicrystalline or polycrystalline molecular weight distribution, and to be used in films, blow molding, pipes, etc. reported to be applicable. However, these products have improved processability, but the dispersion state by molecular weight within the unit particles is not uniform, so the extrusion appearance is rough and the physical properties are not stable even under relatively good extrusion conditions.

Against this background, there is a constant demand for the production of better products with a balance between physical properties and processability, and in particular, the need for a polyethylene copolymer having excellent processability is further demanded.

U.S. Patent No. 5,914,289 Korean Patent Publication No. 2004-0076965 U.S. Patent No. 4,935,474 U.S. Patent No. 6,828,394 U.S. Patent No. 6,841,631 U.S. Patent No. 6,894,128

Accordingly, the present invention is to solve the problems of the prior art, and has an ultra-low molecular weight, low unsaturated functional group content and R _vd value to provide an ethylene/alpha-olefin copolymer having excellent physical properties, particularly high temperature stability. would like to provide

Another object of the present invention is to provide a hot melt adhesive composition including the ethylene/alpha olefin copolymer and exhibiting excellent processability and adhesive properties.

In order to solve the above problems, according to one embodiment of the present invention, there is provided an ethylene/alpha-olefin copolymer satisfying the conditions of i) to iv) below:

i) Density: 0.85 to 0.89 g/cc

ii) weight average molecular weight (Mw): 16,000 to 30,000 g/mol

iii) Number of unsaturated functional groups per 1000 carbon atoms: 0.6 or less

_{iv) R vd} value according to Equation 1 below: 0.5 or less

[Equation 1]

(Vinyl, vinylene, and vinylidene in Equation 1 refer to the number of functional groups per 1000 carbon atoms measured through nuclear magnetic spectroscopy)

According to another embodiment of the present invention, there is provided a hot melt adhesive composition comprising the above-described ethylene/alpha-olefin copolymer.

The ethylene/alpha-olefin copolymer according to the present invention has an ultra-low molecular weight, and has a low content of unsaturated functional groups and a _{low R vd} value, thereby exhibiting excellent physical properties, particularly stability at high temperature. Accordingly, it may be particularly useful for preparing a hot melt adhesive composition requiring excellent processability and adhesive properties.

1 to 3 are graphs showing nuclear magnetic resonance analysis results for the ethylene/1-octene copolymers prepared in Examples 1 to 3, respectively.
4 is a graph showing the results of nuclear magnetic resonance analysis of the ethylene/1-octene copolymer prepared in Comparative Example 1.

The terminology used herein is used to describe exemplary embodiments only, and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In this specification, terms such as "comprises", "comprises" or "have" are intended to designate the presence of an embodied feature, step, element, or a combination thereof, but one or more other features or steps; It should be understood that the possibility of the presence or addition of components, or combinations thereof, is not precluded in advance.

Since the present invention may have various changes and may have various forms, specific embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to the specific disclosed form, it should be understood to include all modifications, equivalents and substitutes included in the spirit and scope of the present invention.

Hereinafter, the ethylene/alpha-olefin copolymer of the present invention will be described in detail.

The ethylene/alpha-olefin copolymer according to an embodiment of the present invention satisfies the following conditions i) to iv):

Ethylene/alpha-olefin copolymers satisfying the following conditions i) to iv):

i) Density: 0.85 to 0.89 g/cc

ii) weight average molecular weight (Mw): 16,000 to 30,000 g/mol

iii) Number of unsaturated functional groups per 1000 carbon atoms: 0.6 or less

_{iv) R vd} value according to Equation 1 below: 0.5 or less

[Equation 1]

(In Equation 1, vinyl, vinylene, and vinylidene refer to the number of functional groups per 1000 carbon atoms measured through nuclear magnetic spectroscopy.

Crosslinking between the copolymers is caused by vinyl and vinylidene containing a double bond. The ethylene/alpha-olefin copolymer according to the embodiment is polymerized by adding an optimized amount of hydrogen together with a catalyst to be described later during polymerization, The content of unsaturated functional groups in the copolymer, particularly the ratio of vinylidene, can be reduced, and in particular, _{by satisfying the above-described content of unsaturated functional groups and the conditions of R vd} , it exhibits excellent high-temperature stability with small change in discoloration, molecular weight and viscosity even at high temperatures. can

Specifically, in the ethylene/alpha-olefin copolymer according to the embodiment, the number of unsaturated functional groups including vinyl, vinylene and vinylidene in the copolymer may be less than 0.6 per 1000 carbon atoms, and more specifically 0.5 or less, or 0.42 or less, or 0.35 or less, and may be 0.1 or more, or 0.2 or more, or 0.23 or more.

In addition, in the ethylene/alpha-olefin copolymer according to the embodiment, the R _vd value calculated according to Equation 1 may be 0.5 or less, and more specifically, 0.3 or less, or 0.25 or less, or 0.2 or less, and 0 greater than, or greater than or equal to 0.1, or greater than or equal to 0.15.

In the present invention, the content (or number) of vinyl, vinylene and vinylidene as unsaturated functional groups in the copolymer can be calculated from the results of nuclear magnetic resonance (NMR) analysis. Specifically, after dissolving the copolymer in chloroform-d (w/TMS) solution, using an Agilent 500 MHz NMR equipment, the acquisition time of 2 seconds at room temperature, and 16 measurements at a pulse angle of 45°, the TMS peak was measured in 1H NMR. Corrected to 0 ppm, checked the CH3-related peak (triplet) of 1-octene at 0.88 ppm, and the CH2-related peak (broad singlet) of ethylene at 1.26 ppm, respectively, and corrected the CH3 peak integral value to 3 to determine the content. It is possible to calculate each number based on the integral values of vinyl, vinylene, and vinylidene in the range of 4.5 to 6.0 ppm.

In addition, when two or more kinds of monomers are polymerized, molecular weight distribution (MWD) increases, and as a result, impact strength and mechanical properties decrease, and blocking phenomenon occurs. In contrast, in the present invention, by adding an optimal amount of hydrogen during the polymerization reaction, the molecular weight and molecular weight distribution of the prepared ethylene/alpha-olefin copolymer is reduced, and as a result, impact strength and mechanical properties can be improved.

Specifically, the ethylene/alpha-olefin copolymer according to the exemplary embodiment may be an ultra-low molecular weight polymer having a weight average molecular weight (Mw) of 16,000 to 30,000 g/mol. More specifically, the weight average molecular weight may be 18,000 g/mol or more, or 19,000 g/mol or more, or 20,000 g/mol or more, and 27,000 g/mol or less, or 25,000 g/mol or less.

In addition, the ethylene/alpha-olefin copolymer of the embodiment may have a narrow molecular weight distribution (MWD) of 2.05 or less. More specifically, the molecular weight distribution may be 1.8 or more, or 1.9 or more, or 1.94 or more, and may be 2.04 or less, or 2.0 or less.

In the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are polystyrene equivalent molecular weight analyzed by gel permeation chromatography (GPC), and the molecular weight distribution (MWD) is the ratio of Mw/Mn can be calculated from

In addition, the ethylene/alpha-olefin copolymer according to an embodiment of the present invention has a density of 0.85 to 0.89 g/cc days, additionally measured according to ASTM D-792, under conditions that meet the physical property requirements as described above. can Specifically, the density may be 0.865 or more, or 0.87 or more, and 0.89 or less, or 0.885 or less, or 0.880 or less.

In general, the density of the olefin-based polymer is affected by the type and content of the monomer used during polymerization, the degree of polymerization, and the like. In the present invention, it is possible to introduce a large amount of comonomer by using a catalyst including a transition metal compound having a specific structure. As a result, the ethylene/alpha-olefin copolymer according to an embodiment of the present invention may have a low density as described above, and as a result, excellent processability may be exhibited. More specifically, the ethylene/alpha-olefin copolymer according to the embodiment may have a density of 0.865 to 0.88 g/cc, and more specifically, 0.87 to 0.88 g/cc, and in this case, the mechanical density control according to the density control The effect of maintaining physical properties and improving impact strength is more remarkable.

In addition, the ethylene/alpha-olefin copolymer according to the exemplary embodiment may have a viscosity of 50,000 cP or less, measured at 180° C., under conditions satisfying the above physical properties. More specifically, the viscosity of the ethylene/alpha-olefin copolymer may be 45,000 cP or less, or 30,000 cP or less, or 20,000 cP or less, and 5,000 cP or more, or 8,000 cP or more, or 10,000 cP or more.

The viscosity affecting the mechanical properties, impact strength, and processability of the olefin-based polymer can be controlled by controlling the amount of catalyst used along with the type of catalyst used in the polymerization process. The ethylene/alpha-olefin copolymer according to an embodiment of the present invention may exhibit improved processability while maintaining excellent mechanical properties by satisfying the viscosity range along with the above conditions.

In addition, the ethylene/alpha-olefin copolymer according to the exemplary embodiment may have a crystallization temperature (Tc) of 45° C. or higher. More specifically, the crystallization temperature may be 50 °C or higher, or 51 °C or higher, 60 °C or lower, or 58 °C or lower, or 55 °C or lower. This high crystallization temperature is due to the uniform distribution of the comonomer in the ethylene/alpha-olefin copolymer, and by having the above temperature range, excellent structural stability may be exhibited.

In addition, the ethylene/alpha-olefin copolymer according to the exemplary embodiment may have a melting temperature (Tm) of 60 to 80°C. More specifically, the melting temperature may be 65 °C or higher, or 69 °C or higher, or 70 °C or higher, and 75 °C or lower, or 74.5 °C or lower, or 74 °C or lower. By having a melting temperature in such a temperature range, excellent thermal stability can be exhibited.

In the present invention, the crystallization temperature and melting temperature of the ethylene/alpha-olefin copolymer can be measured using a Differential Scanning Calorimeter (DSC). Specifically, the copolymer is heated to 150° C. and maintained for 5 minutes, then lowered to 20° C., and then the temperature is increased again. At this time, the rate of rise and fall of the temperature is controlled at 10 °C/min, respectively, and the maximum point of the endothermic peak in the section where the second temperature rises is the melting temperature, and the maximum point of the exothermic peak in the section where the temperature is decreased. is the crystallization temperature.

In addition, in the ethylene/alpha-olefin copolymer according to the embodiment, the alpha-olefin-based monomer as a comonomer may be an olefin-based monomer having 4 to 20 carbon atoms. Specific examples include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetra decene, 1-hexadecene, or 1-eicosene, and the like, and any one of them or a mixture of two or more thereof may be used. Among them, the alpha-olefin monomer may be 1-octene in consideration of the remarkable improvement effect when applied to the hot melt adhesive composition.

The content of the alpha-olefin, which is the comonomer, may be appropriately selected within a range that satisfies the above physical property requirements, and specifically, the alpha-olefin is greater than 0 and 99 mol% or less with respect to the total moles of the monomer for copolymer formation. , or may be included in an amount of 10 to 50 mol%.

On the other hand, the ethylene/alpha-olefin copolymer having the above physical properties is ethylene and alpha-olefin by adding hydrogen at 50 to 100 cc/min in the presence of a catalyst composition including a transition metal compound of Formula 1 below. It can be prepared by a manufacturing method comprising the step of polymerizing the system monomer. Accordingly, according to another embodiment of the present invention, there is provided a method for preparing the above-described ethylene/alpha-olefin copolymer:

[Formula 1]

In Formula 1,

M is a group 4 transition metal,

Q is Si or C;

R is hydrogen, alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons, alkoxy having 1 to 20 carbons, aryl having 6 to 20 carbons, arylalkoxy having 7 to 20 carbons, alkylaryl having 7 to 20 carbons, or It is an arylalkyl having 7 to 20 carbon atoms,

R ₁₁ to R ₁₆ are each independently hydrogen, alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons, aryl having 6 to 20 carbons, alkylaryl having 7 to 20 carbons, or arylalkyl having 7 to 20 carbons Or, two adjacent functional groups are linked to each other to form an aliphatic or aromatic ring,

R ₂₁ and R ₂₂ are each independently hydrogen, alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons, aryl having 6 to 20 carbons, alkylaryl having 6 to 20 carbons, arylalkyl having 7 to 20 carbons, arylalkyl having 7 to 20 carbons 1 to 20 alkylamino, 6 to 20 arylamino, or 1 to 20 carbon atoms alkylidene, or connected to each other to form an aliphatic or aromatic ring,

R ₃₁ and R ₃₂ are each independently hydrogen, halogen, alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons, aryl having 6 to 20 carbons, alkylaryl having 7 to 20 carbons, arylalkyl having 7 to 20 carbons , alkylamino having 1 to 20 carbon atoms, arylamino having 6 to 20 carbon atoms, or alkylidene having 1 to 20 carbon atoms.

The substituents in Formula 1 will be described in more detail as follows.

The alkyl having 1 to 20 carbon atoms includes straight or branched chain alkyl having 1 to 20 carbon atoms and cyclic alkyl having 3 to 20 carbon atoms. Specific examples include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclobutyl, or cyclohexyl.

The alkenyl having 2 to 20 carbon atoms includes linear or branched alkenyl having 1 to 20 carbon atoms. Specific examples include, but are not limited to, allyl, ethenyl, propenyl, butenyl or pentenyl.

The aryl having 6 to 20 carbon atoms includes monocyclic or condensed aryl. Specific examples include, but are not limited to, phenyl, biphenyl, naphthyl, phenanthrenyl or fluorenyl.

The alkoxy having 1 to 20 carbon atoms may be represented by a -ORa group, where Ra is as defined above as alkyl having 1 to 20 carbon atoms. Specific examples include, but are not limited to, methoxy, ethoxy, phenyloxy or cyclohexyloxy.

The halogen means fluorine (F), chlorine (Cl), bromine (Br), and iodine (I).

The transition metal compound of Formula 1 has a structure in which cyclopentadiene and an amino group to which benzothiophene is fused by a cyclic bond are stably crosslinked by Q, and a Group 4 transition metal (M) is coordinated. , When applied as a catalyst in the preparation of an olefin polymer, a polyolefin having a high molecular weight and high copolymerizability is prepared. However, in the present invention, an ethylene/alpha-olefin copolymer having a narrow molecular weight distribution and a uniform comonomer distribution along with an ultra-low molecular weight is prepared by using the transition metal compound as described above and adding hydrogen in an optimized content during the polymerization reaction. did.

More specifically, in the compound of Formula 1, the Group 4 transition metal (M) may be titanium, zirconium, or hafnium, and among them, titanium or zirconium.

Further, in the compound of Formula 1, R may be an alkyl having 1 to 10 carbon atoms, an aryl having 6 to 12 carbon atoms, an alkylaryl having 7 to 13 carbon atoms, or an arylalkyl having 7 to 13 carbon atoms, more specifically, iso branched alkyl having 3 to 6 carbon atoms such as propyl, t-butyl, iso-butyl and the like; phenyl; It may be an alkylphenyl having 7 to 13 carbon atoms, such as dimethylphenyl or diethylphenyl.

In addition, in the compound of Formula 1, R ₁₁ to R ₁₆ are each independently hydrogen, alkyl having 1 to 10 carbon atoms, aryl having 6 to 12 carbon atoms, alkylaryl having 7 to 13 carbon atoms, or aryl having 7 to 13 carbon atoms. It may be alkyl, and more specifically, R ₁₁ to R ₁₄ are each hydrogen, and R ₁₅ and R ₁₆ may be each independently an alkyl having 1 to 6 carbon atoms, such as methyl, ethyl, or propyl.

In addition, in Formula 1, Q may be Si, and R ₂₁ and R ₂₂ are each independently hydrogen, alkyl having 1 to 10 carbon atoms, or aryl having 6 to 12 carbon atoms, or connected to each other to have 6 to 12 carbon atoms. may form an aliphatic or aromatic ring of

In addition, in Formula 1, R ₃₁ and R ₃₂ may each independently be hydrogen, halogen, alkyl having 1 to 10 carbon atoms, or alkenyl having 2 to 10 carbon atoms, and more specifically, hydrogen, chloro, methyl, ethyl, vinyl, or may be allyl.

More specifically, specific examples of the compound of Formula 1 may include a compound represented by one of the following structural formulas, but the present invention is not limited thereto.

Meanwhile, in the preparation of the ethylene/alpha-olefin copolymer according to an embodiment of the present invention, the catalyst composition may further include a co-catalyst to activate the transition metal compound of Formula 1 above.

The cocatalyst is an organometallic compound including a Group 13 metal, and specifically, may include at least one of a compound of Formula 2 below, a compound of Formula 3 below, and a compound of Formula 4 below.

[Formula 2]

R ₄₁ -[Al(R ₄₂ )-O] _n -R ₄₃

In Formula 2,

R ₄₁ , R ₄₂ and R ₄₃ are each independently any one of hydrogen, halogen, a hydrocarbyl group having 1 to 20 carbon atoms, and a hydrocarbyl group having 1 to 20 carbon atoms substituted with a halogen;

n is an integer greater than or equal to 2,

[Formula 3]

D(R ₄₄ ) ₃

In Formula 3, D is aluminum or boron,

R ₄₄ is each independently any one of halogen, a hydrocarbyl group having 1 to 20 carbon atoms, and a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen,

[Formula 4]

[LH] ⁺ [Z(A) ₄ ] ^- or [L] ⁺ [Z(A) ₄ ] ^-

In Formula 4,

L is a neutral or cationic Lewis base, H is a hydrogen atom,

Z is a group 13 element, A is each independently a hydrocarbyl group having 1 to 20 carbon atoms; a hydrocarbyloxy group having 1 to 20 carbon atoms; and one or more of the substituents in which one or more hydrogen atoms of these substituents are substituted with one or more substituents among halogen, a C1-C20 hydrocarbyloxy group, and a C1-C20 hydrocarbylsilyl group.

More specifically, the compound of Formula 2 may be an alkylaluminoxane-based compound to which repeating units are bonded in a linear, circular or network form, and specific examples thereof include methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane, or tert-butyl aluminoxane etc. are mentioned.

In addition, specific examples of the compound of Formula 3 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclo Pentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide , trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron or tributyl boron, and in particular, may be selected from trimethyl aluminum, triethyl aluminum or triisobutyl aluminum.

In addition, specific examples of the compound of Formula 4 include borate-based compounds in the form of trisubstituted ammonium salts, dialkyl ammonium salts, and trisubstituted phosphonium salts, and more specific examples include trimetalammonium tetraphenylborate, methyl Dioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, methyltetradecyclooctadecylammonium tetraphenylborate, N,N-dimethylanyl nium tetraphenylborate, N,N-diethylanilium tetraphenylborate, N,N-dimethyl (2,4,6-trimethylanilium) tetraphenyl borate, trimethylammonium tetrakis (pentafluorophenyl) borate, methyl Ditetradecylammonium tetrakis(pentaphenyl)borate, methyldioctadecylammonium tetrakis(pentafluorophenyl)borate, triethylammonium, tetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentapruo) Rophenyl) borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylanilium tetrakis( Pentafluorophenyl) borate, N,N-diethylanilium tetrakis(pentafluorophenyl)borate, N,N-dimethyl(2,4,6-trimethylanilium)tetrakis(pentafluorophenyl)borate , trimethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tripropylammonium tetrakis (2, 3,4,6-Tetrafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(2,3,4,6-,tetrafluorophenyl)borate, dimethyl(t-butyl)ammonium tetrakis(2 ,3,4,6-tetrafluorophenyl)borate, N,N-dimethylaninium tetrakis(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylanilium tetrakis( 2,3,4,6-tetrafluorophenyl)borate or N,N-dimethyl-(2,4,6-trimethylaninium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate borate compounds in the form of trisubstituted ammonium salts such as; Borates in the form of dialkylammonium salts such as dioctadecylammonium tetrakis(pentafluorophenyl)borate, ditetradecylammonium tetrakis(pentafluorophenyl)borate, or dicyclohexylammonium tetrakis(pentafluorophenyl)borate compound; or triphenylphosphonium tetrakis(pentafluorophenyl)borate, methyldioctadecylphosphonium tetrakis(pentafluorophenyl)borate or tri(2,6-, dimethylphenyl)phosphonium tetrakis(pentafluorophenyl ) borate-based compounds in the form of trisubstituted phosphonium salts such as borate.

By using such a cocatalyst, the molecular weight distribution of the finally prepared ethylene/alpha-olefin copolymer becomes more uniform, and polymerization activity can be improved.

The cocatalyst may be used in an appropriate amount so that the activation of the transition metal compound of Formula 1 may be sufficiently progressed.

In addition, the catalyst composition may include the transition metal compound of Formula 1 supported on a carrier.

When the transition metal compound of Formula 1 is supported on the carrier, the weight ratio of the transition metal compound to the carrier may be 1:10 to 1:1,000, more specifically 1:10 to 1:500. When the carrier and the transition metal compound are included in a mid-ratio ratio within the above range, an optimal shape may be exhibited. In addition, when the promoter is supported on the carrier together, the weight ratio of the promoter to the carrier may be 1:1 to 1:100, more specifically 1:1 to 1:50. When the cocatalyst and the carrier are included in the above weight ratio, it is possible to improve the catalytic activity and optimize the microstructure of the polymer to be prepared.

On the other hand, as the carrier, silica, alumina, magnesia, or a mixture thereof may be used, or by drying these materials at a high temperature to remove moisture from the surface, a hydroxyl group or siloxane group having high reactivity on the surface is included. may be used. In addition, the high-temperature dried carriers may further include an oxide, carbonate, sulfate, or nitrate component such as _{Na 2} O, K ₂ CO ₃ , BaSO ₄ and Mg(NO ₃ ) _{2 .}

The drying temperature of the carrier is preferably 200 to 800°C, more preferably 300 to 600°C, and most preferably 300 to 400°C. When the drying temperature of the carrier is less than 200 ℃, there is too much moisture and the surface moisture and the cocatalyst react. It is undesirable because it disappears and only the siloxane remains, and the reaction site with the co-catalyst decreases.

In addition, the amount of hydroxyl groups on the surface of the carrier is preferably 0.1 to 10 mmol/g, more preferably 0.5 to 5 mmol/g. The amount of hydroxyl groups on the surface of the carrier can be controlled by the method and conditions or drying conditions of the carrier, such as temperature, time, vacuum or spray drying, and the like.

Meanwhile, the polymerization reaction of the ethylene/alpha-olefin copolymer may be performed by continuously polymerizing ethylene and an alpha-olefin monomer while continuously adding hydrogen in the presence of the catalyst composition.

In this case, the hydrogen gas serves to suppress the rapid reaction of the transition metal compound at the initial stage of polymerization and terminate the polymerization reaction. Accordingly, an ethylene/alpha-olefin copolymer having an ultra-low molecular weight and narrow molecular weight distribution can be effectively prepared by controlling the use and amount of hydrogen gas.

The hydrogen gas may be introduced at a rate of 50 to 100 cc/min, more specifically, 60 to 100 cc/min. When added under the above conditions, the ethylene/alpha-olefin polymer to be prepared may implement the physical properties in the present invention. If the content of hydrogen gas is added to less than 50 cc/min, the termination of the polymerization reaction does not occur uniformly, making it difficult to prepare an ethylene/alpha-olefin copolymer having desired physical properties, and exceeding 100 cc/min In this case, there is a risk that an ethylene/alpha-olefin copolymer having an excessively low molecular weight may be prepared because the termination reaction occurs too quickly.

In addition, the polymerization reaction may be performed at 80 to 200° C., but by controlling the polymerization temperature together with the hydrogen input amount, the vinyl content in the ethylene/alpha-olefin copolymer can be more easily controlled. Accordingly, specifically, the polymerization reaction may be 100 to 150 ℃, more specifically 100 to 140 ℃.

In addition, during the polymerization reaction, an organoaluminum compound for removing moisture in the reactor is further added, and the polymerization reaction may proceed in the presence of the compound. Specific examples of the organoaluminum compound include trialkylaluminum, dialkyl aluminum halide, alkyl aluminum dihalide, aluminum dialkyl hydride or alkyl aluminum sesqui halide, and more specific examples thereof include Al (C ₂ H ₅ ) ₃ , Al(C ₂ H ₅ ) ₂ H, Al(C ₃ H ₇ ) ₃ , Al(C ₃ H ₇ ) ₂ H, Al(iC ₄ H ₉ ) ₂ H, Al(C ₈ H _{17 )} ) ₃ , Al(C ₁₂ H ₂₅ ) ₃ , Al(C ₂ H ₅ )(C ₁₂ H ₂₅ ) ₂ , Al(iC ₄ H ₉ )(C ₁₂ H ₂₅ ) ₂ , Al(iC ₄ H ₉ ) ₂ H, Al (iC ₄ H ₉ ) ₃ , (C ₂ H ₅ ) ₂ AlCl, (iC ₃ H ₉ ) ₂ AlCl, or (C ₂ H ₅ ) ₃ Al ₂ Cl ₃ , and the like. Such an organoaluminum compound may be continuously added to the reactor, and may be added in a ratio of about 0.1 to 10 moles per 1 kg of the reaction medium fed into the reactor for proper moisture removal.

Also, the polymerization pressure may be from about 1 to about 100 Kgf/cm ² , preferably from about 1 to about 50 Kgf/cm ² , more preferably from about 5 to about 30 Kgf/cm ² .

In addition, when a transition metal compound is used in a supported form on a carrier, the transition metal compound is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, for example, pentane, hexane, heptane, nonane, decane, and isomers thereof and toluene, benzene. It may be dissolved in an aromatic hydrocarbon solvent such as, dichloromethane, or a hydrocarbon solvent substituted with a chlorine atom such as chlorobenzene, or added after dilution. The solvent used here is preferably used by treating a small amount of alkyl aluminum to remove a small amount of water or air that acts as a catalyst poison, and it is also possible to further use a cocatalyst.

The ethylene/alpha-olefin copolymer prepared by the above-described manufacturing method simultaneously satisfies the conditions i) to iv), thereby exhibiting excellent physical properties, in particular, greatly improved stability at high temperature. In addition, the copolymer may exhibit excellent processability and mechanical properties. Accordingly, when applied to the hot-melt adhesive composition, it is possible to significantly improve processability as well as adhesive properties.

Accordingly, according to another embodiment of the present invention, there is provided a hot melt adhesive composition comprising the above-described ethylene/alpha-olefin copolymer.

The hot-melt adhesive composition may be prepared and used according to a conventional method except for including the above-described ethylene/alpha-olefin copolymer as a main component.

Hereinafter, preferred examples are presented to help the understanding of the present invention. However, the following examples are only provided for easier understanding of the present invention, and the content of the present invention is not limited thereto.

Synthesis example

Step 1: Preparation of Ligand Compound (1a-1)

In a 100 ml Schlenk flask, add 330 mg (0.12 mmol) of 1-chloro-1-(2,3-dimethyl-1H-benzo[b]cyclopenta[d]thiophen-1-yl)-1,1-dimethyl-silaneamine After quantification, 20 ml of hexane was added. Here, t-BuNH ₂ (4eq, 0.47 ml) was added at room temperature, and reacted at room temperature for 3 days. After completion of the reaction, the resulting reactant was filtered and solvent dried to obtain an orange liquid ligand compound (N-tert-butyl-1-(2,3-dimethyl-1H-benzo[b]cyclopenta[d]thiophen-1-yl) -1,1-dimethylsilaneamine) (1a-1) was obtained (345 mg, yield 93%).

1H-NMR (in C ₆ D ₆ , 500 MHz): 7.82 (d, 1H), 7.69 (d, 1H), 7.27 (t, 1H), 7.03 (t, 1H), 3.39 (s, 1H), 2.03 (s, 3H), 1.99 (s, 3H), 1.04 (s, 9H), 0.07 (s, 3H), -0.11 (s, 3H).

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

In a 20 ml Schlenk flask, the ligand compound (1a-1) (260 mg, 0.80 mmol/1.0eq) and MTBE 6.0 ml (0.1M) prepared in step 1 were added and stirred. At -40°C, n-BuLi (0.65 ml, 2.03 eq, 2.5M in hexane) was further added thereto, followed by reaction at room temperature overnight. Thereafter, MeMgBr (0.6 ml, 2.5 eq, 3.0M in diethyl ether) was slowly added dropwise at -40°C, and after completion of the dropwise addition, TiCl ₄ (0.8 ml, 1.0 eq, 1.0M in toluene) was added, and overnight at room temperature. reacted. The resulting reactant was filtered through Celite using hexane, and then solvent-dried to obtain the transition metal compound (1a) as a brown solid (170 mg, yield 53%).

1H-NMR (in CDCl ₃ , 500 MHz): 7.99 (d, 1H), 7.47 (d, 1H), 7.10 (t, 1H), 6.97 (t, 1H), 2.12 (s, 3H), 1.89 (s) , 3H), 1.46 (s, 9H), 0.67 (s, 3H), 0.59 (s, 3H), 0.51 (s, 3H), 0.10 (s, 3H).

<Preparation of ethylene/alpha-olefin copolymer>

Example One

After the 1.5L autoclave continuous process reactor was charged with hexane solvent (5.0 kg/h) and 1-octene (0.86 kg/h), the temperature at the top of the reactor was preheated to 150°C. Triisobutylaluminum compound (0.05 mmol/min), transition metal compound (1a) (0.18 μmol/min) prepared in the above synthesis example as a catalyst, dimethylanilinium tetrakis (pentafluorophenyl) borate cocatalyst (0.54 μmol) /min) was simultaneously introduced into the reactor. Then, ethylene (0.87 kg/h) and hydrogen gas (88 cc/min) were introduced into the autoclave reactor, and the copolymerization reaction was continuously performed while maintaining a pressure of 89 bar and a polymerization temperature of 125.5° C. for at least 60 minutes. After completion of the reaction, the remaining ethylene gas was removed, and the resulting solution was dried in a vacuum oven for 12 hours or more to obtain a copolymer.

Examples 2 to 3, and Comparative Examples 1 and 2

A polymer was prepared in the same manner as in Example 1, except that the reactants were added in the amounts shown in Table 1 below.

catalyst
input
(μmol/min) Cocatalyst dosage
(μmol/min) C8 dose
(kg/h) TiBAl
(mmol/min) polymerization temperature
(℃) H ₂ dose
(cc/min) Comparative Example 1* 0.44 1.32 1.90 0.05 160.4 0 Comparative Example 2* 0.26 0.78 1.20 0.05 125.0 35 Example 1 0.18 0.54 0.86 0.05 125.5 88 Example 2 0.40 1.20 0.77 0.05 125.3 75 Example 3 0.75 2.25 1.30 0.05 139.7 67 C2: 0.87 kg/h, C6: 5.0 kg/h, C8: 78%
* In Comparative Examples 1 and 2, [Me ₂ Si(Me ₄ C ₅ )NtBu]Ti(CH ₃ ) ₂ was used as a catalyst

test example 1: Analysis of Olefin Polymer

The ethylene/alpha-olefin copolymers prepared in Examples 1 to 3 and Comparative Examples 1 and 2 were analyzed using a nuclear magnetic resonance spectrometer, and the results are shown in FIGS. 1 to 4 each is shown.

In addition, in order to evaluate the change in the physical properties of the polymer according to the difference in catalyst, the physical properties of each of the ethylene/alpha-olefin copolymers prepared in Examples 1 to 3 and Comparative Examples 1 and 2 were measured by the following method, The results are shown in Table 2.

1) Yield (yield, g/10min): The obtained polymer was vacuum-dried to measure the yield.

2) Density (g/cm ³ ): Measured according to ASTM D-792.

3) Viscosity (cP): It was measured according to the following method using a Brookfield RVDV3T viscometer. Specifically, the sample is placed in a 13ml sample chamber, heated to 180°C using a Brookfield Thermosel, and when the sample is completely melted, lower the viscometer to fix the spindle in the sample chamber, and the spindle (SC-29 hot-melt spindle) ) was read for at least 20 minutes or until the value was stabilized after fixing the rotation speed to 20 rpm, and the final value was recorded.

4) Crystallization temperature (Tc, ℃): The crystallization temperature of the polymer was measured using a Differential Scanning Calorimeter (DSC, device name: DSC 2920, manufacturer: TA instrument). Specifically, the polymer was heated to 150° C., maintained for 5 minutes, lowered to -100° C., and then increased again. At this time, the rate of rise and fall of the temperature was controlled at 10 °C/min, respectively. As for the crystallization temperature, the maximum point of the exothermic peak from the curve appearing while decreasing the temperature was taken as the crystallization temperature.

5) Melting temperature (Tm, °C): The crystallization temperature was measured using DSC in the same manner as in the measurement, and the maximum point of the endothermic peak in the section where the second temperature was increased was used as the melting temperature.

6) Weight average molecular weight (Mw) (g/mol) and molecular weight distribution (MWD): Number average molecular weight (Mn) and weight average molecular weight (Mw) were measured using gel permeation chromatography (GPC), respectively And, the molecular weight distribution was calculated by dividing the weight average molecular weight by the number average molecular weight.

7) Total number of unsaturated functional groups (units/1000 C): From the results of NMR analysis, the number of vinyl, vinylene, and vinylidene groups per 1000 carbons was measured.

Specifically, the polymer was prepared by re-precipitating before NMR analysis to remove residual 1-octene that may be present in the specimen. Specifically, 1 g of the polymer was completely dissolved in chloroform at 70° C., and the resulting polymer solution was slowly poured into 300 ml of methanol with stirring to re-precipitate the polymer, and then the re-precipitated polymer was vacuum-dried at room temperature. The above process was repeated once more to obtain a polymer from which residual 1-octene was removed.

30 mg of the polymer specimen obtained above was dissolved in 1 ml of chloroform-d (w/TMS) solution. Using an Agilent 500MHz NMR equipment, 16 measurements were taken at room temperature with an acquisition time of 2 seconds and a pulse angle of 45°. In 1H NMR, the TMS peak was corrected to 0 ppm, the CH3-related peak of 1-octene (triplet) at 0.88 ppm, and the CH2-related peak of ethylene at 1.26 ppm (broad singlet) were confirmed. The content was calculated by correcting the CH3 peak integral value to 3. The number of vinyl, vinylene and vinylidene was calculated based on the integral value of each functional group in the range of 4.5 to 6.0 ppm, respectively.

8) R _{vd : The R vd} value was calculated according to Equation 1 below from the number of vinyl, vinylene, and vinylidene measured through the NMR analysis.

[Equation 1]

(In Equation 1, vinyl, vinylene, and vinylidene refer to the number of functional groups per 1000 carbon atoms measured through nuclear magnetic spectroscopy)

transference number
(g/10min) density
(g/cc) Viscosity
(cP) Tc
(℃) Tm
(℃) Mw
(g/mol) MWD Total number of unsaturated functional groups ^* vinyl ^* vinylene ^* vinylidene ^* R _vd Comparative Example 1 180 0.875 15,800 57.4 75.9 23761 2.29 1.46 0.21 0.83 0.42 0.29 Comparative Example 2 182 0.876 13,900 56.3 75.4 22940 1.94 0.32 0.03 0.10 0.20 0.61 Example 1 105 0.875 13,750 56.6 72.5 20700 2.00 0.27 0.05 0.18 0.04 0.15 Example 2 158 0.875 14,200 54.2 72.6 21200 2.00 0.32 0.05 0.21 0.07 0.20 Example 3 165 0.874 14,300 55.3 71.6 21100 2.04 0.57 0.08 0.35 0.14 0.24

*pcs/1000C

As a result of the experiment, the polymers of Examples 1 to 3 prepared by using the catalyst composition according to the present invention showed equivalent results in terms of physical properties such as density and viscosity compared to Comparative Example 1, but Comparative Example 1 The ratio of the unsaturated functional groups and the R _vd value, and the R _vd value were significantly reduced compared to Comparative Example 2.

From the viewpoint of beta-hydride elimination, when octene is 1,2-inserted and polymerization is terminated, vinylidene is produced, and when polymerization is terminated after 2,1-insertion, vinylene is produced, When ethylene is inserted and terminated, vinyl is created. The catalyst (1a) used in Examples 1 to 3 has more superior copolymerizability than the catalysts used in Comparative Examples 1 and 2, and thus 2,1-insertion is also increased, so that the content of vinylene is increased and the content of vinylidene is increased. The content showed a tendency to decrease.

In addition, since crosslinking is caused by vinyl and vinylidene, it can be seen that the polymers of Examples 1 to 3 having _{low R vd values show better stability at high temperatures.}

Example 4 to 7, and comparative example 3 to 6

A polymer was prepared in the same manner as in Example 1, except that the reactants were added in the amounts shown in Table 3 below.

catalyst
input
(μmol/min) Cocatalyst dosage
(μmol/min) C8 dose
(kg/h) TiBAl
(mmol/min) polymerization temperature
(℃) H ₂ dose
(cc/min) Comparative Example 3 0.40 1.20 1.05 0.05 125.0 0 Comparative Example 4 0.40 1.20 1.05 0.05 124.9 6 Comparative Example 5 0.40 1.20 1.05 0.05 125.1 10 Comparative Example 6 0.40 1.20 1.15 0.05 125.0 120 Example 4 0.40 1.20 1.05 0.05 125.4 50 Example 5 0.40 1.20 1.15 0.05 125.3 60 Example 6 0.40 1.20 1.15 0.05 125.4 80 Example 7 0.40 1.20 1.15 0.05 125.4 100 C2: 0.87 kg/h, C6: 5.0 kg/h, C8: 78%

test example 2: Analysis of Olefin Polymer

In order to evaluate the change in physical properties due to hydrogen input during the preparation of the polymer, the physical properties of the ethylene/alpha-olefin copolymers prepared in Examples 4 to 7 and Comparative Examples 3 to 6 were measured by the method described below, and the The results are shown in Table 4.

1) Yield (yield, g/10min): The polymer obtained in the same manner as in Test Example 1 was vacuum-dried to measure the yield.

2) Density (g/cc): In the same manner as in Test Example 1, it was measured according to ASTM D-792.

3) Viscosity (cP): It was measured using a Brookfield RVDV3T viscometer in the same manner as in Test Example 1.

However, in the case of the copolymers of Comparative Examples 3 to 5, it is difficult to measure out of the measurement limit (50,000 cP) of the used viscometer. Index, MI) was measured.

4) Crystallization temperature (Tc, ℃) and melting temperature (Tm, ℃): The crystallization temperature and the melting temperature were measured using DSC in the same manner as in Test Example 1, respectively.

5) Weight average molecular weight (Mw) (g/mol) and molecular weight distribution (MWD): Using gel permeation chromatography (GPC) in the same manner as in Test Example 1, the weight average molecular weight (Mw) and The number average molecular weight (Mn) was measured, and molecular weight distribution was calculated from the result.

6) Total number of unsaturated functional groups (number/1000 C) and R _vd : NMR analysis was performed in the same manner as in Test Example 1, and vinyl, vinylene, and vinylidene per 1000 measured carbons From the number of (vinylidene) groups, the R _vd value was calculated according to Equation 1 above.

transference number
(g/10min) density
(g/cc) Viscosity
(cP) Tc
(℃) Tm
(℃) Mw
(g/mol) MWD Total number of unsaturated functional groups ^* vinyl ^* vinylene ^* vinylidene ^* R _vd Comparative Example 3 186 0.873 MI 17.5 48.3 68.4 57898 2.08 0.63 0.07 0.45 0.11 0.18 Comparative Example 4 176 0.874 MI 22.1 49.8 69.7 55339 2.05 0.56 0.06 0.42 0.08 0.14 Comparative Example 5 168 0.874 MI 27.7 50.2 71.1 51233 2.07 0.51 0.04 0.36 0.11 0.21 Comparative Example 6 - 0.870 4300 56.6 68.3 15500 1.97 0.35 - - - - Example 4 159 0.876 43000 53.0 74.5 29838 1.96 0.41 0.05 0.28 0.08 0.19 Example 5 175 0.872 22900 51.0 70.2 26303 1.94 0.41 0.05 0.28 0.08 0.19 Example 6 167 0.872 11800 51.9 70.2 22082 1.95 0.33 0.04 0.22 0.07 0.22 Example 7 167 0.871 8000 50.3 69.3 198010 1.97 0.31 0.04 0.21 0.06 0.20

*pcs/1000C

In Table 4, "-" means not measured.

As a result of the experiment, the ethylene/alpha-olefin copolymers of Examples 4 to 7 prepared by using the catalyst composition containing the transition metal compound according to the present invention and adding hydrogen during the polymerization reaction were compared with Comparative Examples 2 to 4, R _vd Although the values were similar, they had an ultra-low molecular weight, a narrow molecular weight distribution, and a significantly lower content of total unsaturated functional groups.

By having such a low molecular weight and narrow molecular weight distribution, it can be expected to have superior impact strength and mechanical properties compared to Comparative Examples, and from the low unsaturated functional group content, the ethylene/alpha-olefin copolymers of Examples 4 to 7 can be expected to have excellent high-temperature stability with small changes in discoloration, molecular weight and viscosity during long-term storage at high temperatures (heat aging). As a result, it can be seen that the ethylene/alpha-olefin copolymers of Examples 4 to 7 have improved reaction efficiency through a uniform reaction when applied to the hot melt adhesive composition, and as a result, adhesiveness and processability can be improved.

Test Example 3: Evaluation of Olefin Polymer

For the polymers prepared in Examples 1 to 3 and Comparative Examples 1 and 2, the viscosity change rate was evaluated in the following manner.

Viscosity change rate (%): It was measured according to the following method using a Brookfield RVDV3T viscometer. Specifically, the sample is placed in a 13ml sample chamber, heated to 180°C using a Brookfield Thermosel, and when the sample is completely melted, lower the viscometer device to fix the spindle in the sample chamber, and the spindle (SC-29 hot-melt spindle) ) was fixed at 20 rpm, and the values were recorded once per hour for 72 hours. The viscosity change rate was calculated by converting the difference between the initial viscosity and the viscosity after 72 hours into a percentage.

Total number of unsaturated functional groups ^* R _vd Viscosity change rate (%) Comparative Example 1 1.46 0.29 42 Comparative Example 2 0.32 0.61 21 Example 1 0.27 0.15 10 Example 2 0.32 0.20 15 Example 3 0.57 0.24 23

*pcs/1000C

When there are many unsaturated functional groups, the rate of change of viscosity increases significantly, and _{when the value of R vd} is low, the rate of change of viscosity decreases.

As a result of the experiment, in the case of the polymers of Examples 1 to 3, the viscosity change rate was significantly reduced due to the decrease in the number of unsaturated functional groups compared to Comparative Example 1. In addition, when comparing Example 2 and Comparative Example 2 containing the same level of unsaturated functional groups, Example 2 _{having a low R vd} value had a decrease in viscosity change rate compared to Comparative Example 2.

Claims (10)

Ethylene/alpha-olefin copolymers satisfying the following conditions i) to iv):
i) Density: 0.85 to 0.89 g/cc
ii) weight average molecular weight (Mw): 16,000 to 30,000 g/mol
iii) Number of unsaturated functional groups per 1000 carbon atoms: 0.35 or less
_{iv) R vd} value according to Equation 1 below: greater than 0 and less than or equal to 0.3
[Equation 1]

(Vinyl, vinylene, and vinylidene in Equation 1 refer to the number of functional groups per 1000 carbon atoms measured through nuclear magnetic spectroscopy)
According to claim 1,
wherein iii) the number of unsaturated functional groups per 1000 carbon atoms is 0.1 or more and 0.35 or less, an ethylene/alpha-olefin copolymer.
delete According to claim 1,
An ethylene/alpha-olefin copolymer having a viscosity of 50,000 cp or less.
According to claim 1,
An ethylene/alpha-olefin copolymer having a molecular weight distribution (MWD) of 2.05 or less.
According to claim 1,
An ethylene/alpha-olefin copolymer having a crystallization temperature (Tc) of 45°C or higher and a melting temperature (Tm) of 60 to 80°C.
According to claim 1,
The alpha-olefin is 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 containing at least one selected from the group consisting of, ethylene / alpha-olefin copolymer.
According to claim 1,
wherein the alpha-olefin is 1-octene.
According to claim 1,
The alpha-olefin is included in an amount of greater than 0 and 99 mol% or less based on the total weight of the copolymer, ethylene/alpha-olefin copolymer.
10. A hot melt adhesive composition comprising the ethylene/alpha-olefin copolymer according to any one of claims 1, 2, and 4 to 9.

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