KR102421535B1 - Ethylene/alpha-olefin Copolymer, Method For Preparing The Same - Google Patents

Abstract

상기 식 1에서, N_vd, N_tv, N_vl 및 N_v는 각각 핵자기 분광 분석을 통해 측정된 탄소원자 1000개당 비닐리덴(vinylidene), 트라이비닐(trivinyl), 비닐렌(vinylene) 및 비닐(vinyl) 작용기의 개수를 의미한다.The present invention provides an ethylene/alpha-olefin copolymer satisfying the following conditions (a) to (d):
(a) Density: 0.850 to 0.910 g/cc
(b) Melt Index (MI, 190 ℃, 2.16 kg load condition): 0.1 to 100 dg / min
(c) molecular weight distribution (MWD): 1.5 to 3.0
(d) R _v value according to the following formula 1 is 0.18 to 0.59.
[Equation 1]

In Equation 1, N _vd , N _tv , N _vl and N _v are vinylidene, trivinyl, vinylene and vinyl ( vinyl) means the number of functional groups.

Description

Ethylene/alpha-olefin copolymer, method for preparing same {Ethylene/alpha-olefin Copolymer, Method For Preparing The Same}

The present invention relates to an ethylene/alpha-olefin copolymer having a narrow molecular weight distribution and controlling the content of vinyl groups in a polymer within a certain range to exhibit excellent physical properties and a method for preparing the same.

Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, and these two high-activity 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 a cocatalyst containing 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 point 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 of 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 long, and , followed by the inconvenience of having to support each of the metallocene catalysts to be used on a carrier.

Korean Patent Application No. 10-2003-0012308 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 is starting. 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, and has excellent tear strength and drop 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, which has excellent processability and is 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, in U.S. Patent Nos. 6,841,631 and 6,894,128, polyethylene having a bicrystalline or polycrystalline molecular weight distribution is prepared with a metallocene-based catalyst using at least two metal compounds, and is 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 need to produce a better product with a balance between physical properties and processability, and in particular, there is a need for a polyethylene copolymer having excellent processability and excellent optical properties.

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 intended to solve the problems of the prior art, and the ethylene/alpha-olefin copolymer has a narrow molecular weight distribution, and the vinyl group content in the polymer is controlled within a certain range, and has excellent physical properties, particularly excellent crosslinking behavior. and to provide a method for manufacturing the same.

In addition, the present invention is to provide an ethylene/alpha olefin copolymer and a method for producing the same, which can be applied to a resin composition for an optical film by improving optical properties such as a yellow index (YI) and total light transmittance (Tt).

One embodiment of the present invention provides an ethylene/alpha-olefin copolymer satisfying the following conditions (a) to (d):

(a) Density: 0.850 to 0.910 g/cc

(b) Melt Index (MI, 190°C, 2.16 kg load condition): 0.1 to 100 dg/min

(c) molecular weight distribution (MWD): 1.5 to 3.0

(d) R _v value according to the following formula 1 is 0.18 to 0.59.

[Equation 1]

In Equation 1, N _vd , N _tv , N _vl and N _v are vinylidene, trivinyl, vinylene and vinyl ( vinyl) means the number of functional groups.

Another embodiment of the present invention comprises the step of polymerizing ethylene and alpha-olefinic monomers by adding hydrogen at 5 to 100 cc/min in the presence of a catalyst composition comprising a transition metal compound of Formula 1 below, A process for preparing an ethylene/alpha-olefin copolymer is provided:

[Formula 1]

In Formula 1,

R ₁ is hydrogen; C1~C20 alkyl; C3~C20 cycloalkyl; C2-20 alkenyl; C1~C20 alkoxy; C6-20 aryl; C7-20 aryl alkoxy; C7-20 alkylaryl; Or C7-20 arylalkyl,

R _2a to R _2e are each independently hydrogen; halogen; C1~C20 alkyl; C3~C20 cycloalkyl; C2-20 alkenyl; C1~C20 alkoxy; Or C6-20 aryl,

R ₃ is hydrogen; halogen; C1~C20 alkyl; C3~C20 cycloalkyl; C2-20 alkenyl; C6-20 aryl; C6~C20 alkylaryl; C7-20 arylalkyl; C1-20 alkyl amido; C6-20 aryl amido; C1~C20 alkylidene; Or halogen, C1-20 alkyl, C3-20 cycloalkyl, C2-20 alkenyl, C1-20 alkoxy, and C6-20 aryl substituted with one or more selected from the group consisting of phenyl,

R ₄ to R ₉ are each independently hydrogen; silyl; C1~C20 alkyl; C3~C20 cycloalkyl; C2-20 alkenyl; C6-20 aryl; C7-20 alkylaryl; C7-20 arylalkyl; or a metalloid radical of a Group 14 metal substituted with C1-20 hydrocarbyl; Two or more adjacent to each other among R ₆ to R ₉ may be connected to each other to form a ring,

Q is Si, C, N, P or S;

M is a Group 4 transition metal,

X ₁ and X ₂ are each independently hydrogen; halogen; C1~C20 alkyl; C3~C20 cycloalkyl; C2-20 alkenyl; C6-20 aryl; C7-20 alkylaryl; C7-20 arylalkyl; C1-20 alkylamino; C6~C20 arylamino; or C1-20 alkylidene.

The ethylene/alpha-olefin copolymer of the present invention has a narrow molecular weight distribution compared to the prior art, and the vinyl content in the polymer satisfies a specific ratio relative to the total unsaturated functional groups, thereby exhibiting excellent crosslinking properties.

In addition, when the ethylene/alpha-olefin copolymer of the present invention is applied as a resin composition for an optical film, optical properties such as yellow index (YI) and total light transmittance (Tt) are excellent. Therefore, the ethylene/alpha-olefin copolymer of the present invention can be usefully applied to the preparation of a resin composition for an optical film requiring excellent optical properties.

1 shows a molecular weight distribution diagram of Example 2 and Comparative Example 1 as an embodiment of the present invention.
2 shows crosslinking behavior characteristics of Example 1 and Comparative Example 1 according to a crosslinking recipe (a) as an embodiment of the present invention.
3 shows the crosslinking behavior characteristics of Example 2 and Comparative Example 1 according to a crosslinking recipe (b) as an embodiment of the present invention.

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 the present specification, terms such as "comprise", "comprising" or "having" are intended to designate the presence of an embodied feature, step, component, 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 modifications and 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.

The term "composition" as used herein includes reaction products and decomposition products formed from materials of the composition, as well as mixtures of materials comprising the composition.

The term "polymer," as used herein, refers to a polymer compound prepared by polymerizing monomers, whether of the same or a different type. The generic term polymer thus encompasses the term homopolymer, which is commonly used to refer to polymers prepared from only one monomer, and the term interpolymer, as defined below.

The term "interpolymer," as used herein, refers to a polymer prepared by the polymerization of at least two different monomers. As such, the generic term interpolymer includes copolymers, which are commonly used to refer to polymers prepared from two different monomers, and polymers prepared from two or more different monomers.

1. Ethylene/alpha-olefin copolymer

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 (a) to (d):

(a) Density: 0.850 to 0.910 g/cc

(b) Melt Index (MI, 190°C, 2.16 kg load condition): 0.1 to 100 dg/min

(c) molecular weight distribution (MWD): 1.5 to 3.0

(d) R _v value according to the following formula 1 is 0.18 to 0.59.

[Equation 1]

In Equation 1, N _vd , N _tv , N _vl and N _v are vinylidene, trivinyl, vinylene and vinyl ( vinyl) means the number of functional groups.

The present invention uses a catalyst as described below and adds an optimal amount of hydrogen during polymerization to satisfy the conditions (a) to (d) at the same time, so that the physical properties of the ethylene/alpha olefin copolymer, particularly the crosslinking properties can be greatly improved.

Specifically, the ethylene/alpha-olefin copolymer of the present invention is a low-density polymer having a density in the range of 0.850 to 0.910 g/cc as measured according to ASTM D-792. Specifically, the density may be 0.850 g/cc or more, or 0.855 g/cc or more, or 0.86 g/cc or more, or 0.865 or more, and 0.91 g/cc or less, or 0.90 g/cc or less, or 0.89 g/cc or less. may be below.

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, etc. In the case of a copolymer, the effect is large by the content of the comonomer. An olefin copolymer can be prepared, and the amount in which the comonomer can be introduced into the copolymer may depend on the copolymerizability of the catalyst, that is, the properties of the catalyst.

In the present invention, it is possible to introduce a large amount of comonomer by using a catalyst composition including a transition metal compound having a specific structure. As a result, the ethylene/alpha-olefin copolymer according to an exemplary embodiment of the present invention may have a low density as described above, and, as a result, may exhibit excellent processability. More specifically, the ethylene/alpha-olefin copolymer may have a density of 0.850 to 0.910 g/cc, and in this case, the effect of maintaining mechanical properties and improving impact strength according to the density control is more remarkable.

In addition, the ethylene/alpha-olefin copolymers of the present invention have a narrow molecular weight distribution (MWD) in the range of 1.5 to 3.0. As an example, the molecular weight distribution may be 1.6 or more, or 1.7 or more, or 1.8 or more, and may be 2.7 or less, or 2.4 or less, or 2.2 or less.

In general, 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, an optimal amount of hydrogen is added during the polymerization reaction, thereby reducing the molecular weight and molecular weight distribution of the prepared ethylene/alpha-olefin copolymer, and as a result, crosslinking properties, impact strength, mechanical properties, etc. are improved.

Meanwhile, 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 is from the ratio of Mw/Mn. can be calculated.

The ethylene/alpha-olefin copolymer according to an embodiment of the present invention may be a polymer having a weight average molecular weight (Mw) of 40,000 to 150,000 g/mol. More specifically, the weight average molecular weight may be 45,000 g/mol or more, or 49,000 g/mol or more, or 52,000 g/mol or more, and 130,000 g/mol or less, or 90,000 g/mol or less, or 65,000 g/mol or less. have.

In addition, the ethylene/alpha-olefin copolymer of the present invention has a melt index (Melt Index, MI, 190°C, 2.16 kg load condition) in the range of 0.1 to 100 dg/min. As an example, the ethylene/alpha-olefin copolymer of the present invention has a melt index (MI) of 1 dg/min or more, or 1.5 dg/min or more, or 3 dg/min or more, or 5 dg/min or more, or 12 It may be at least dg/min, or at least 16 dg/min, and at most 90 dg/min, or at most 70 dg/min, or at most 40 dg/min, or at most 37 dg/min, or at most 35 dg/min.

In addition, the ethylene/alpha-olefin copolymer may have a melt index (Melt Index, MI, measured under a load of 10 kg at 190°C according to ASTM D1238) in the range of 5 to 230 dg/min.

In addition, the ethylene / alpha-olefin copolymer has a MFR ₁₀ / MFR _2.16 value, which is the ratio of the melt index measured at 10 kg load, 190 ° C. and 2.16 kg load, and melt index measured at 190 ° C., of 8.5 or less, or 7.9 or less, or 7.5 or less, 5.0 or more, or 5.5 or more, or 6.0 or more. MFR ₁₀ /MFR _2.16 is an index of the degree of long chain branching of the copolymer, and when the MFR ₁₀ /MFR _2.16 value is 8.5 or less, it means that there is little long chain branching.

When the weight average molecular weight and melt index satisfy the above ranges, it may be suitable for application to the resin composition for an optical film.

That is, the mechanical properties and impact strength of the ethylene/alpha-olefin copolymer can be controlled by adjusting the amount of catalyst used together with the type of catalyst used in the polymerization process, and by satisfying the above conditions, excellent mechanical properties are maintained while improving It can show processed machinability.

In addition, the ethylene/alpha-olefin copolymer of the present invention is characterized in that the content of vinyl groups per 1000 carbon atoms in the copolymer is controlled within a certain range. Specifically, the ethylene/alpha-olefin copolymer of the present invention has an R _v value of 0.18 or more and 0.59 or less according to Formula 1 below.

[Equation 1]

In Equation 1, R _v is the ratio of the number of vinyl groups to the number of functional groups per 1000 carbon atoms measured through nuclear magnetic spectroscopy.

Optionally, the ethylene/alpha-olefin copolymer of the present invention may have an R _vd value of 0.25 or less according to Equation 2 below.

[Equation 2]

In Equation 2, R _vd is the ratio of the number of vinylidene groups to the number of functional groups per 1000 carbon atoms measured through nuclear magnetic spectroscopy.

In Equations 1 and 2, N _vd , N _tv , N _vl and N _v are vinylidene, trivinyl, vinylene and per 1000 carbon atoms measured through nuclear magnetic spectroscopy, respectively. It means the number of vinyl (vinyl) functional groups.

As an example, the R _v value may be 0.55 or less, or 0.50 or less, or 0.46 or less, or 0.40 or less, or 0.39 or less, or 0.35 or less, or 0.32 or less, or 0.30 or less, or 0.29 or less, 0.19 or more, or 0.22 or greater, or 0.24 or greater.

The content of the vinyl group in the copolymer is possible through control of the polymerization temperature and the amount of hydrogen input during manufacturing. When applied to, it can exhibit excellent crosslinking degree and/or optical properties.

As an example, the R _vd value may be 0.25 or less, or 0.22 or less, or 0.20 or less, or 0.15 or less, or 0.10 or less, or 0.09 or less, or 0.08 or less, or 0.07 or less, or 0.06 or less, 0.02 or more, or 0.03 or greater, or 0.04 or greater. When the vinylidene group content satisfies the numerical range, it may exhibit a narrow molecular weight distribution, excellent crosslinking properties, and optical properties accordingly.

In addition, the ethylene / alpha-olefin copolymer of the present invention satisfies the above R _v value and at the same time, the number of unsaturated functional groups including vinyl, trivinyl, vinylene and vinylidene in the copolymer is 0.65 or less per 1000 carbon atoms. it is preferable Specifically, it may be 0.6 or less, or 0.5 or less, or 0.45 or less, or 0.4 or less, and may be 0.1 or more, or 0.15 or more, or 0.2 or more, or 0.23 or more. When the number of the unsaturated functional groups satisfies the numerical range, a narrow molecular weight distribution, excellent crosslinking properties, and optical properties accordingly may be exhibited.

In addition, the number of vinyl functional groups in the copolymer may be 0.3 or less per 1000 carbon atoms. Specifically, 0.29 or less, or 0.25 or less, or 0.2 or less, or 0.15 or less, or 0.1 or less, 0.01 or more, or 0.02 or more, or 0.04 or more, or 0.06 or more. When the number of the unsaturated functional groups satisfies the numerical range, a narrow molecular weight distribution, excellent crosslinking properties, and optical properties accordingly may be exhibited.

In addition, the number of trivinyl functional groups in the copolymer is 0.15 or less, or 0.1 or less, or 0.08 or less, and may be 0.01 or more, or 0.02 or more per 1000 carbon atoms. When the number of the unsaturated functional groups satisfies the numerical range, a narrow molecular weight distribution, excellent crosslinking properties, and optical properties accordingly may be exhibited.

Further, the number of vinylene functional groups in the copolymer is 0.3 or less, or 0.29 or less, or 0.25 or less, or 0.2 or less, or 0.15 or less, or 0.1 or less, and 0.01 or more, or 0.02 or more, or 0.04 or more, or 0.06 or more. When the number of the unsaturated functional groups satisfies the numerical range, a narrow molecular weight distribution, excellent crosslinking properties, and optical properties accordingly may be exhibited.

In addition, the number of vinylidene functional groups in the copolymer is 0.07 or less, or 0.05 or less, and may be 0.01 or more, or 0.02 or more per 1000 carbon atoms. When the number of the unsaturated functional groups satisfies the numerical range, a narrow molecular weight distribution, excellent crosslinking properties, and optical properties accordingly may be exhibited.

In the present invention, the vinyl group has a structure of R-CH=CH ₂ , the trivinyl group has a structure of RCH=CR'R", and the vinylene is RCH=CHR' (E form) or RCH=CHR' (Z form) structure, and the vinylidene means RR'C=CH ₂ structure. Here, R, R' and R" may each independently be a polymer chain or a branched chain according to an alpha-olefin that is a comonomer.

In the present invention, the contents of each of vinyl, vinylidene, vinylene and trivinyl in the copolymer may be calculated from the results of NMR analysis. Specifically, after dissolving the copolymer in 1,1,2,2-tetrachloroethane D2 (TCE-d2) solvent, it can be measured at 393K using a Bruker AVANCE III 500 MHz NMR instrument. The TCE-d2 peak in the 1H NMR spectrum is corrected to 6.0 ppm, and the comonomer content ratio is calculated using the integral values of the 1.4 ppm and 0.96 ppm regions. Calculate the contents of each of the vinyl group, vinylidene group, vinylene group and trivinylene group observed at 4.7 ppm ~ 5.6 ppm (analysis method: AMT-3863). For peak assignment, see Macromolecules 2014, 47, 3282-3790 .

In addition, the ethylene/alpha-olefin copolymer according to an embodiment of the present invention may have a crystallization temperature (Tc) of 35°C to 80°C. More specifically, the crystallization temperature may be 40 °C or higher, or 45 °C or higher, and 75 °C or lower, or 70 °C or lower, or 65 °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 an embodiment of the present invention may have a melting temperature (Tm) of 50 to 110°C. More specifically, the melting temperature may be 55 °C or higher, or 60 °C or higher, or 70 °C or higher, and 110 °C or lower, or 105 °C or lower, or 95 °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 result measured in the section where the second temperature rises is the melting temperature, and the result measured in the section where the temperature is decreased is the crystallization temperature.

In addition, in the ethylene/alpha-olefin copolymer according to an embodiment of the present invention, the alpha-olefinic monomer as a comonomer is C4-20 It may be an olefinic monomer. 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 one type alone or a mixture of two or more types thereof may be used.

Among them, in consideration of the remarkable improvement effect when applied to the resin composition for an optical film, the alpha-olefin monomer may be 1-butene, 1-hexene, or 1-octene, and most preferably 1-butene. .

In addition, in the ethylene/alpha-olefin copolymer, the content of alpha-olefin, which is the comonomer, may be appropriately selected within the range satisfying the above-described physical property requirements, and specifically, more than 0 and 99 mol% or less, or It may be 10 to 50 mol%.

2. Resin composition for optical film

A resin composition for an optical film comprising the ethylene/alpha-olefin copolymer of the present invention can be prepared. It may be extruded into a shape such as a sheet or film, but is not particularly limited thereto.

The resin composition including the ethylene/alpha olefin copolymer may exhibit an excellent degree of crosslinking. For example, the crosslinking degree of the resin composition for an optical film may be 55% or more, or 58% or more, or 63% or more, or 67% or more, or 69% or more.

The resin composition for the optical film may have a glass transition temperature of -55 °C to -45 °C, or -53 °C to -42 °C, or -50 °C to -40 °C.

In addition, The resin composition comprising the ethylene / alpha olefin copolymer is a result of measuring the yellow index (YI) and the total light transmittance (Tt) before and after crosslinking of the ethylene / alpha olefin copolymer, respectively, after crosslinking, the yellow index (YI) and The value of the total light transmittance (Tt) may satisfy a range suitable for use in the optical film.

Specifically, the yellow index (Yellowness Index, hereinafter, YI) value of the resin composition for an optical film may be 0.5 or more, or 1.0 or more, or 1.25 or more, or 1.30 or more, 5.5 or less, or 4.9 or less, or 4.5 or less, or 3.9 or less, or 2.9 or less, or 1.5 or less, or 1.2 or less. As the YI value is smaller, the quality stability of the optical film is corrected.

In particular, when the yellow index is measured after crosslinking is performed on the resin composition including the ethylene/alpha-olefin copolymer, better values may be obtained. For example, the yellow index after performing the crosslinking may be 0.5 or more, or 0.7 or more, or 0.9 or more, or 1.0 or more, and may be 1.5 or less, or 1.48 or less, or 1.3 or less, or 1.2 or less.

The yellow index is a value obtained by quantifying the yellowing phenomenon of the resin composition when exposed to ultraviolet light, and may be measured using a UV/Vis spectrometer according to ASTM D1925. For example, by using the UV/Vis spectrometer, the reflectance of the resin composition in a wavelength region of 400 nm to 700 nm may be measured, and a yellow index value may be calculated by Equation 3 below using this.

[Equation 3]

YI = [100(1.28XCIE - 1.06ZCIE)] / YCIE

In Equation 3, YI is a value calculated using a color difference analysis program in a UV/VIS/NIR spectrometer, and XCIE, YCIE, and ZCIE are relative values indicated by red, green, and blue color coordinates, respectively.

In addition, the resin composition for an optical film may have excellent light transmittance. As an example, the total light transmittance (Tt) measured with a haze meter after crosslinking the sheet-shaped resin composition at a temperature of 150° C. may satisfy Equation 4 below.

[Equation 4]

Tt ≥ 90.0%

The total light transmittance may be a value measured with a haze meter with respect to a wavelength of light having a wavelength of 200 nm or more, for example, 300 nm, 350 nm, 400 nm, 450 nm, 500 nm, 550 nm or 600 nm, and , preferably with respect to light having a wavelength of 550 nm, may be a value measured with a haze meter. The total light transmittance of the resin composition measured above represents the total light transmittance after the sheet-shaped resin composition is crosslinked, and the sheet-shaped resin composition may be laminated through a vacuum laminator.

The total light transmittance of the resin composition has a value measured after crosslinking the sheet-shaped resin composition at a temperature of 150° C. of 90% or more, or 90.2% or more, or 90.5% or more, or 90.9% or more, or 91% or more, or 92% or more. In addition, in consideration of the photoelectric efficiency of the optical device, it may be adjusted to have a total light transmittance within the above-described range.

In addition, a modified resin composition, for example, a silane-modified resin composition or an amino silane-modified resin composition may be prepared by using the resin composition for an optical film.

For example, the resin composition for an optical film may further include a known unsaturated silane compound, an amino silane compound, a crosslinking agent, and a crosslinking aid in addition to the ethylene/alpha-olefin copolymer of the present invention.

The unsaturated silane compound is grafted onto the main chain including the polymerization unit of the monomer of the copolymer of the present invention in the presence of a radical initiator and the like, and may be included in a polymerized form in a silane-modified resin composition or an amino silane-modified resin composition.

As an example, the unsaturated silane compound is vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, vinyltripentoxysilane, vinyltriphenoxy. It may be silane or vinyltriacetoxysilane, and as an example, vinyltrimethoxysilane or vinyltriethoxysilane may be used, but is not limited thereto.

In addition, the amino silane compound is an unsaturated silane compound grafted to the main chain of the copolymer of the present invention in the grafting modification step of the ethylene/alpha-olefin copolymer, for example, a reactive functional group such as an alkoxy group of vinyltriethoxysilane as a hydroxyl group. By acting as a catalyst for accelerating the conversion hydrolysis reaction, the adhesive strength with the upper and lower glass substrates or the back sheet composed of a fluororesin or the like can be further improved. In addition, at the same time, the amino silane compound may also be directly involved as a reactant in the copolymerization reaction, thereby providing a moiety having an amine functional group to the amino silane-modified resin composition.

The amino silane compound is not particularly limited as long as it is a silane compound containing an amine group, and is a primary amine or a secondary amine. For example, as the amino silane compound, aminotrialkoxysilane, aminodialkoxysilane, etc. may be used. Examples include 3-aminopropyltrimethoxysilane (APTMS), 3-aminopropyltriethoxysilane. (3-aminopropyltriethoxysilane; APTES), bis[(3-triethoxysilyl)propyl]amine, bis[(3-trimethoxysilyl)propyl]amine, 3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyl Dimethoxysilane, N-[3-(trimethoxysilyl)propyl]ethylenediamine (N-[3-(Trimethoxysilyl)propyl]ethylenediamine; DAS), aminoethylaminopropyltriethoxysilane, aminoethylaminopropylmethyldime Toxysilane, aminoethylaminopropylmethyldiethoxysilane, aminoethylaminomethyltriethoxysilane, aminoethylaminomethylmethyldiethoxysilane, diethylenetriaminopropyltrimethoxysilane, diethylenetriaminopropyltriethoxysilane, Diethylenetriaminopropylmethyldimethoxysilane, diethyleneaminomethylmethyldiethoxysilane, (N-phenylamino)methyltrimethoxysilane, (N-phenylamino)methyltriethoxysilane, (N-phenylamino)methyl Methyldimethoxysilane, (N-phenylamino)methylmethyldiethoxysilane, 3-(N-phenylamino)propyltrimethoxysilane, 3-(N-phenylamino)propyltriethoxysilane, 3-(N- at least one selected from the group consisting of phenylamino)propylmethyldimethoxysilane, 3-(N-phenylamino)propylmethyldiethoxysilane, and N-(N-butyl)-3-aminopropyltrimethoxysilane can be heard The amino silane compounds may be used alone or in combination.

In the resin composition, the content of the unsaturated silane compound and/or the amino silane compound is not particularly limited.

The crosslinking agent is a radical initiator in the manufacturing step of the silane-modified resin composition, and may serve to initiate a reaction in which the unsaturated silane compound is grafted to the resin composition. In addition, by forming a cross-linkage between the silane-modified resin composition or between the silane-modified resin composition and the unmodified resin composition in the lamination step in the manufacture of an optoelectronic device, the heat resistance durability of the final product, such as an encapsulant sheet, can be improved. have.

If the crosslinking agent is a crosslinking compound capable of initiating radical polymerization of a vinyl group or forming a crosslinking bond, various crosslinking agents known in the art may be variously used, for example, organic peroxides, hydroperoxides And one or two or more selected from the group consisting of azo compounds may be used.

Specifically, t-bufilcumyl peroxide, di-t-butyl peroxide, di-cumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl dialkyl peroxides such as -2,5-di(t-butylperoxy)-3-hexyne; hydroperoxides such as cumene hydroperoxide, diisopropyl benzene hydroperoxide, 2,5-dimethyl-2,5-di(hydroperoxy)hexane and t-butyl hydroperoxide; diacyl peroxides such as bis-3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, benzoyl peroxide, o-methylbenzoyl peroxide, and 2,4-dichlorobenzoyl peroxide; t-butylperoxy isobutylate, t-butylperoxy acetate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy fivalate, t-butylperoxy octoate, t-butylperoxy Isopropyl carbonate, t-butylperoxybenzoate, di-t-butylperoxyphthalate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, 2,5-dimethyl-2,5-di peroxy esters such as (benzoyl peroxy)-3-hexyne; and ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, lauryl peroxide, azobisisobutyronitrile, and azo compounds such as azobis(2,4-dimethylvaleronitrile). It may include one or more selected from, but is not limited thereto.

The organic peroxide may be an organic peroxide having a 1-hour half-life temperature of 120°C to 135°C, for example, 120°C to 130°C, 120°C to 125°C, and preferably 121°C. As used herein, the term "one-hour half-life temperature" means a temperature at which the half-life of the cross-linking agent becomes one hour. According to the one-hour half-life temperature, the temperature at which the radical initiation reaction efficiently occurs is different, and therefore, when an organic peroxide having a one-hour half-life temperature in the above-described range is used as a crosslinking agent, the lamination process temperature for manufacturing an optoelectronic device In the radical initiation reaction, that is, the crosslinking reaction can proceed effectively.

The crosslinking agent is included in an amount of 0.01 to 1 parts by weight, for example, 0.05 to 0.55, 0.1 to 0.5, or 0.15 to 0.45 parts by weight, based on 100 parts by weight of the resin composition, and when the crosslinking agent is included in an amount of less than 0.01 parts by weight, The effect of improving the heat resistance is insignificant, and when it contains more than 1 part by weight, the formability of the encapsulant sheet is reduced, which may cause a problem in that a process restriction occurs, and may affect the physical properties of the encapsulant.

In addition, the resin composition may include a crosslinking aid in addition to the crosslinking agent. When the crosslinking aid is included in the resin composition, the degree of crosslinking between the resin compositions by the crosslinking agent can be increased, thereby further improving the heat resistance durability of the final product, for example, an encapsulant sheet.

The crosslinking aid is included in an amount of 0.01 to 0.5 parts by weight, for example, 0.01 to 0.3, 0.015 to 0.2, or 0.016 to 0.16 parts by weight, based on 100 parts by weight of the resin composition, and when the crosslinking aid is included in an amount of less than 0.01 parts by weight , the effect of improving the heat resistance property is insignificant, and when it is included in excess of 0.5 parts by weight, a problem affecting the physical properties of the final product, such as an encapsulant sheet, may occur and the production cost may increase.

As the crosslinking aid, various crosslinking aids known in the art may be used. For example, as the crosslinking aid, a compound containing at least one unsaturated group such as an allyl group or a (meth)acryloxy group may be used.

The compound containing the allyl group may be, for example, a polyallyl compound such as triallyl isocyanurate, triallyl cyanurate, diallyl phthalate, diallyl fumarate or diallyl maleate, The compound containing a meth)acryloxy group is, for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, t-butyl 1-(2-ethylhexyl) monoperoxycarbonate ( TBEC), methacryloxypropyltrimethoxysilane (MEMO), and the like may be exemplified, but are not particularly limited thereto.

In addition, the resin composition may further include at least one additive selected from a light stabilizer, a UV absorber, and a heat stabilizer, if necessary.

The light stabilizer may serve to prevent photooxidation by catching active species that initiate photodegradation of the resin depending on the application to which the composition is applied. The type of light stabilizer that can be used is not particularly limited, and, for example, a known compound such as a hindered amine-based compound or a hindered piperidine-based compound may be used.

The UV absorber, depending on the use of the composition, absorbs ultraviolet rays from sunlight or the like, converts it into harmless thermal energy in the molecule, and prevents the active species of photodegradation initiation in the resin composition from being excited. . Specific types of UV absorbers that can be used are not particularly limited, and for example, inorganic UV absorbers such as benzophenone-based, benzotriazole-based, acrylnitrile-based, metal complex salt-based, hindered amine-based, ultrafine particle titanium oxide or ultrafine particle zinc oxide. One type or a mixture of two or more types, such as an absorbent, can be used.

In addition, examples of the thermal stabilizer include tris(2,4-di-tert-butylphenyl)phosphite, bis[2,4-bis(1,1-dimethylethyl)-6-methylphenyl]ethyl ester phosphorous acid, tetra kiss(2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4'-diylbisphosphonate and bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, etc. Phosphorus-based thermal stabilizer; and a lactone-based thermal stabilizer such as a reaction product of 8-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene, and one or two or more of the above may be used. have.

In the resin composition, the content of the light stabilizer, the UV absorber and/or the heat stabilizer is not particularly limited. That is, the content of the additive may be appropriately selected in consideration of the use of the resin composition, the shape or density of the additive, and the like, and is usually appropriately selected within the range of 0.01 parts by weight to 5 parts by weight based on 100 parts by weight of the total solid content of the resin composition. can be adjusted.

In addition, the resin composition, in addition to the above components, according to the use to which the resin component is applied, may further include various additives known in the art as appropriate.

In addition, the resin composition for an optical film may be used as an encapsulant for encapsulating devices in various optoelectronic devices, but is not limited thereto, and for example, as an industrial material applied to a temperature rise lamination process, etc. can be used

3. Method for preparing ethylene/alpha-olefin copolymer

Another embodiment of the present invention includes the step of polymerizing ethylene and alpha-olefinic monomers by adding hydrogen at 5 to 100 cc/min in the presence of a catalyst composition comprising a transition metal compound of Formula 1 below, ethylene /Provides a method for preparing an alpha-olefin copolymer:

[Formula 1]

In Formula 1,

R ₁ is hydrogen; C1~C20 alkyl; C3~C20 cycloalkyl; C2-20 alkenyl; C1~C20 alkoxy; C6-20 aryl; C7-20 aryl alkoxy; C7-20 alkylaryl; Or C7-20 arylalkyl,

R _2a to R _2e are each independently hydrogen; halogen; C1~C20 alkyl; C3~C20 cycloalkyl; C2-20 alkenyl; C1~C20 alkoxy; Or C6-20 aryl,

R ₃ is hydrogen; halogen; C1~C20 alkyl; C3~C20 cycloalkyl; C2-20 alkenyl; C6-20 aryl; C6~C20 alkylaryl; C7-20 arylalkyl; C1-20 alkyl amido; C6-20 aryl amido; C1~C20 alkylidene; Or halogen, C1-20 alkyl, C3-20 cycloalkyl, C2-20 alkenyl, C1-20 alkoxy, and C6-20 aryl substituted with one or more selected from the group consisting of phenyl,

R ₄ to R ₉ are each independently hydrogen; silyl; C1~C20 alkyl; C3~C20 cycloalkyl; C2-20 alkenyl; C6-20 aryl; C7-20 alkylaryl; C7-20 arylalkyl; or a metalloid radical of a Group 14 metal substituted with C1-20 hydrocarbyl; Two or more adjacent to each other among R ₆ to R ₉ may be connected to each other to form a ring,

Q is Si, C, N, P or S;

M is a Group 4 transition metal,

X ₁ and X ₂ are each independently hydrogen; halogen; C1~C20 alkyl; C3~C20 cycloalkyl; C2-20 alkenyl; C6-20 aryl; C7-20 alkylaryl; C7-20 arylalkyl; C1-20 alkylamino; C6~C20 arylamino; or C1-20 alkylidene.

In the transition metal compound of Formula 1 according to an example of the present invention,

wherein R ₁ is hydrogen; C1~C20 alkyl; C3~C20 cycloalkyl; C1~C20 alkoxy; C6-20 aryl; C7-20 aryl alkoxy; C7-20 alkylaryl; Or it may be a C7-20 arylalkyl,

The R _2a to R _2e are each independently hydrogen; halogen; C1-12 alkyl; C3-12 cycloalkyl; C2-12 alkenyl; C1-12 alkoxy; or phenyl,

wherein R ₃ is hydrogen; halogen; C1-12 alkyl; C3-12 cycloalkyl; C2-12 alkenyl; C6-20 aryl; C7-13 alkylaryl; C7-13 arylalkyl; or halogen, C1-12 alkyl, C3-12 cycloalkyl, C2-12 alkenyl, C1-12 alkoxy, and phenyl may be substituted with one or more selected from the group consisting of phenyl,

The R ₄ to R ₉ are each independently hydrogen; C1~C20 alkyl; C3~C20 cycloalkyl; C6-20 aryl; C7-20 alkylaryl; Or it may be a C7-20 arylalkyl,

two or more adjacent to each other among R ₆ to R ₉ may be connected to each other to form a C5-20 aliphatic ring or a C6-20 aromatic ring; The aliphatic ring or aromatic ring may be substituted with halogen, C1-20 alkyl, C2-12 alkenyl, or C6-12 aryl,

Q may be Si,

M may be Ti,

The X ₁ and X ₂ are each independently hydrogen; halogen; C1-12 alkyl; C3-12 cycloalkyl; C2-12 alkenyl; C6-12 aryl; C7-13 alkylaryl; C7-13 arylalkyl; C1-13 alkylamino; C6-12 arylamino; Or it may be a C1-12 alkylidene.

In addition, in the transition metal compound of Formula 1 according to another example of the present invention,

wherein R ₁ is hydrogen; C1-12 alkyl; C3-12 cycloalkyl; C1-12 alkoxy; C6-12 aryl; C7-13 arylalkoxy; C7-13 alkylaryl; Or it may be a C7-13 arylalkyl,

The R _2a to R _2e are each independently hydrogen; halogen; C1-12 alkyl; C3-12 cycloalkyl; C2-12 alkenyl; C1-12 alkoxy; or phenyl,

wherein R ₃ is hydrogen; halogen; C1-12 alkyl; C3-12 cycloalkyl; C2-12 alkenyl; C7-13 alkylaryl; C7-13 arylalkyl; phenyl; or halogen, C1-12 alkyl, C3-12 cycloalkyl, C2-12 alkenyl, C1-12 alkoxy, and phenyl may be substituted with one or more selected from the group consisting of phenyl,

The R ₄ to R ₉ are each independently hydrogen; C1-12 alkyl; C3-12 cycloalkyl; C6-12 aryl; C7-13 alkylaryl; Or it may be a C7-13 arylalkyl,

two or more adjacent to each other among R ₆ to R ₉ may be connected to each other to form a C5-12 aliphatic ring or a C6-12 aromatic ring;

The aliphatic ring or aromatic ring may be substituted with halogen, C1-12 alkyl, C2-12 alkenyl, or C6-12 aryl,

Q may be Si,

M may be Ti,

The X ₁ and X ₂ are each independently hydrogen; halogen; C1~C12 alkyl group; Or it may be a C2-12 alkenyl.

In addition, in the transition metal compound of Formula 1 according to another example of the present invention,

Wherein R ₁ may be hydrogen or C1-12 alkyl,

The R _2a to R _2e are each independently hydrogen; C1-12 alkyl; Or it may be a C1-12 alkoxy,

wherein R ₃ is hydrogen; C1-12 alkyl; or phenyl,

The R ₄ and R ₅ are each independently hydrogen; Or it may be a C1-12 alkyl,

The R ₆ to R ₉ may each independently be hydrogen or methyl,

Q may be Si,

M may be Ti,

The X ₁ and X ₂ may each independently be hydrogen or C1-12 alkyl.

In the transition metal compound of Formula 1, cyclopentadiene to which benzothiophene is fused by a cyclic bond, and an amido group (NR ₁ ) are stably cross-linked by Q (Si, C, N or P), Group 4 transition metals form a coordinated structure. When the catalyst composition is applied to oliphene polymerization using the catalyst composition, it is possible to produce polyolefins having characteristics such as high activity, high molecular weight, and high copolymerizability even at a high polymerization temperature.

Furthermore, the transition metal compound of Formula 1 has a structure in which an amido group (NR ₁ ) is crosslinked by Q (Si, C, N, P) and a substituted or unsubstituted phenyl group is bonded to Q, It can be cross-linked more stably, and can have excellent electronic stability when coordinated with a transition metal.

In addition, since the phenyl group, which is a bulky substituent, is located around the central metal, β-hydrogen transfer is inhibited, so that an olefin polymer having a higher molecular weight can be prepared and have excellent copolymerizability.

That is, in the present invention, an ethylene/alpha-olefin copolymer having a narrow molecular weight distribution and excellent crosslinking properties can be provided by using the transition metal compound as described above, but by adding hydrogen in an optimized content during the polymerization reaction. Due to the electronic/structural stability of the metal compound, the incorporation of hydrogen is advantageous. In addition, since the initial molecular weight of the polymer formed by the injection of the catalyst before hydrogen injection is high, it is also possible to manufacture a product having a high molecular weight while having a narrow molecular weight distribution after hydrogen injection.

The compound represented by Formula 1 may be any one of compounds represented by the following Formula.

[Formula 1-1] [Formula 1-2] [Formula 1-3] [Formula 1-4]

[Formula 1-5] [Formula 1-6] [Formula 1-7] [Formula 1-8]

[Formula 1-9] [Formula 1-10]

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 cocatalyst 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 include methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane, or tert-butylaluminoxane 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 , trimethylboron, triethylboron, triisobutylboron, tripropylboron, or tributylboron, and in particular, may be selected from trimethylaluminum, triethylaluminum, or triisobutylaluminum.

In addition, the compound of Formula 4 may include a borate-based compound in the form of a trisubstituted ammonium salt, a dialkyl ammonium salt, or a trisubstituted phosphonium salt. More specific examples include trimetalammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, methyltetradecyclo Octadecylammonium tetraphenylborate, N,N-dimethylaninium tetraphenylborate, N,N-diethylaninium tetraphenylborate, N,N-dimethyl(2,4,6-trimethylanilium)tetraphenylborate, Trimethylammonium tetrakis(pentafluorophenyl)borate, methylditetradecylammonium tetrakis(pentaphenyl)borate, methyldioctadecylammonium tetrakis(pentafluorophenyl)borate, triethylammonium, tetrakis(pentafluoro Phenyl) borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl) ) borate, N,N-dimethylanilium tetrakis(pentafluorophenyl)borate, N,N-diethylaniniumtetrakis(pentafluorophenyl)borate, N,N-dimethyl (2,4,6- Trimethylaninium)tetrakis(pentafluorophenyl)borate, trimethylammoniumtetrakis(2,3,4,6-tetrafluorophenyl)borate, triethylammonium tetrakis(2,3,4,6-tetrafluoro Rophenyl) 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-diethylaninium tetrakis(2,3,4,6-tetrafluorophenyl)borate or N,N-dimethyl-(2,4,6-trimethylaninium)tetrakis-(2 borate compounds in the form of trisubstituted ammonium salts such as ,3,4,6-tetrafluorophenyl)borate; 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)phosphoniumtetrakis(pentafluorophenyl ) borate 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 in a supported form 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 a siloxane group having high reactivity on the surface. 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, reducing the reaction site with the promoter.

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 adding hydrogen in the presence of the catalyst composition and continuously polymerizing ethylene and an alpha-olefin-based monomer.

At this time, the hydrogen gas serves to suppress the rapid reaction of the transition metal compound in the initial stage of polymerization and terminate the polymerization reaction. Accordingly, by controlling the use and amount of hydrogen gas, an ethylene/alpha-olefin copolymer having a narrow molecular weight distribution and having a vinyl group content controlled within a certain range in the copolymer can be effectively prepared.

For example, the hydrogen gas may be at least 5 cc/min, or at least 7 cc/min, or at least 10 cc/min, or at least 15 cc/min, or at least 19 cc/min, or at least 22 cc/min, and , 100 cc/min or less, or 50 cc/min or less, or 45 cc/min or less, or 35 cc/min or less, or 29 cc/min or less. 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 5 cc/min, the polymerization reaction is not uniformly terminated, making it difficult to prepare an ethylene/alpha-olefin copolymer having desired physical properties, and also 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 carried out at 80 to 200° C., but by controlling the polymerization temperature together with the hydrogen input amount, the content of vinyl groups in the ethylene/alpha-olefin copolymer can be more easily controlled. Accordingly, specifically, the polymerization reaction temperature may be 100 °C or higher, or 120 °C or higher, or 140 °C or higher, 190 °C or lower, or 180 °C or lower, or 170 °C or lower, or 160 °C or lower.

In addition, during the polymerization reaction, an organoaluminum compound for removing moisture in the reactor may be further added, and the polymerization reaction may proceed in the presence thereof. 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 adequate moisture removal.

Further, the polymerization pressure may be from about 1 to about 100 Kgf/cm ² , preferably from about 70 to about 96 Kgf/cm ² , more preferably from about 80 to about 93 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 or diluted in an aromatic hydrocarbon solvent, such as dichloromethane, or a hydrocarbon solvent substituted with a chlorine atom, such as chlorobenzene. 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.

Example

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 1: Preparation of transition metal compound]

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

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

t-BuNH in 100 mL of extracted chloro-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophen-3-yl)-1,1-(methyl)(phenyl)silane hexane solution ₂ 42 mL (8 eq, 399.4 mmol) was added at room temperature, followed by stirring at room temperature overnight. After stirring, the mixture was dried in vacuo, and extracted with 150 mL of hexane. After solvent drying, 13.36 g (68 %, dr = 1:1) of a yellow solid was obtained.

(1a-1)

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

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

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

(1a)

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

[Synthesis Example 2: Preparation of transition metal compound]

Step 1: Preparation of Ligand Compound (2a-1)

(i) Preparation of lithium carbamate

1,2,3,4-tetrahydroquinoline (13.08 g, 98.24 mmol) and diethyl ether (150 mL) were placed in a shlenk flask. The Schlenk flask was immersed in a -78 °C low temperature bath made of dry ice and acetone and stirred for 30 minutes. Then, n-BuLi (39.3 mL, 2.5 M, 98.24 mmol) was injected into a syringe under a nitrogen atmosphere, and a pale yellow slurry was formed. Then, after stirring the flask for 2 hours, the temperature of the flask was raised to room temperature while removing the butane gas produced. The flask was again immersed in a low temperature bath at -78° C. to lower the temperature, and then CO ₂ gas was introduced. As the carbon dioxide gas was added, the slurry disappeared and became a transparent solution. The flask was connected to a bubbler and the temperature was raised to room temperature while removing carbon dioxide gas. After that, excess CO ₂ gas and solvent were removed under vacuum. After moving the flask to a dry box, pentane was added, stirred vigorously, and filtered to obtain lithium carbamate, a white solid compound. The white solid compound is coordinated with diethyl ether. In this case, the yield is 100%.

¹ H NMR(C ₆ D ₆ , C ₅ D ₅ N): δ 1.90 (t, J = 7.2 Hz, 6H, ether), 1.50 (br s, 2H, quin-CH ₂ ), 2.34 (br s, 2H) , quin-CH ₂ ), 3.25 (q, J = 7.2 Hz, 4H, ether), 3.87 (br, s, 2H, quin-CH ₂ ), 6.76 (br d, J = 5.6 Hz, 1H, quin-CH ) ppm

¹³ C NMR (C ₆ D ₆ ): δ 24.24, 28.54, 45.37, 65.95, 121.17, 125.34, 125.57, 142.04, 163.09 (C=O) ppm

(ii) 8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline (8-(2,3,4,5- Preparation of tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline)

The lithium carbamate compound (8.47 g, 42.60 mmol) prepared in step (i) was placed in a Schlenk flask. Then, tetrahydrofuran (4.6 g, 63.9 mmol) and 45 mL of diethyl ether were sequentially added. The Schlenk flask was immersed in a low temperature bath at -20°C made with acetone and a small amount of dry ice and stirred for 30 minutes, and then t-BuLi (25.1 mL, 1.7 M, 42.60 mmol) was added. At this time, the color of the reaction mixture changed to red. Stirring was continued for 6 hours while maintaining -20°C. A solution of CeCl ₃ ·2LiCl dissolved in tetrahydrofuran (129 mL, 0.33 M, 42.60 mmol) and tetramethylcyclopentinone (5.89 g, 42.60 mmol) were mixed in a syringe, and then put into a flask under a nitrogen atmosphere. The temperature of the flask was slowly raised to room temperature, and after 1 hour, the thermostat was removed and the temperature was maintained at room temperature. Then, after adding water (15 mL) to the flask, ethyl acetate was added and filtered to obtain a filtrate. After transferring the filtrate to a separatory funnel, hydrochloric acid (2 N, 80 mL) was added thereto, and the mixture was shaken for 12 minutes. Then, after neutralization by adding a saturated aqueous sodium hydrogen carbonate solution (160 mL), the organic layer was extracted. Anhydrous magnesium sulfate was added to the organic layer to remove moisture, filtered, and the filtrate was taken to remove the solvent. The obtained filtrate was purified by column chromatography using a solvent of hexane and ethyl acetate (v/v, 10: 1) to obtain a yellow oil. The yield was 40%.

(2a-1)

¹ H NMR(C ₆ D ₆ ): δ 1.00 (br d, 3H, Cp-CH ₃ ), 1.63 - 1.73 (m, 2H, quin-CH ₂ ), 1.80 (s, 3H, Cp-CH ₃ ), 1.81 (s, 3H, Cp-CH ₃ ), 1.85 (s, 3H, Cp-CH ₃ ), 2.64 (t, J = 6.0 Hz, 2H, quin-CH ₂ ), 2.84 - 2.90 (br, 2H, quin -CH ₂ ), 3.06 (br s, 1H, Cp-H), 3.76 (br s, 1H, NH), 6.77 (t, J = 7.2 Hz, 1H, quin-CH), 6.92 (d, J = 2.4) Hz, 1H, quin-CH), 6.94 (d, J = 2.4 Hz, 1H, quin-CH) ppm

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

(i) Preparation of [(1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl- η ⁵ , κ -N]dilithium compound

8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline (8.07 g) prepared through step (1) in a dry box , 32.0 mmol) and 140 mL of diethyl ether were placed in a round flask, the temperature was lowered to -30°C, and n-BuLi (17.7 g, 2.5 M, 64.0 mmol) was slowly added with stirring. The reaction was carried out for 6 hours while raising the temperature to room temperature. After that, it was filtered while washing with diethyl ether several times to obtain a solid. A vacuum was applied to remove the remaining solvent to obtain a dilithium compound (9.83 g) as a yellow solid. The yield was 95%.

¹ H NMR(C ₆ D ₆ , C ₅ D ₅ N): δ 2.38 (br s, 2H, quin-CH ₂ ), 2.53 (br s, 12H, Cp-CH ₃ ), 3.48 (br s, 2H, quin-CH ₂ ), 4.19 (br s, 2H, quin-CH ₂ ), 6.77 (t, J = 6.8 Hz, 2H, quin-CH), 7.28 (br s, 1H, quin-CH), 7.75 (brs) , 1H, quin-CH) ppm

(ii) (1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl- η ⁵ , κ -N]titanium dimethyl ([(1,2,3,4-Tetrahydroquinolin-8 Preparation of -yl)tetramethylcyclopentadienyl-eta5,kapa-N]titanium dimethyl)

In a dry box, TiCl ₄ ·DME (4.41 g, 15.76 mmol) and diethyl ether (150 mL) were placed in a round flask, and while stirring at -30°C, MeLi (21.7 mL, 31.52 mmol, 1.4 M) was slowly added thereto. After stirring for 15 minutes, the [(1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl- η ⁵ , κ -N]dilithium compound prepared in step (i) ( 5.30 g, 15.76 mmol) was placed in a flask. While raising the temperature to room temperature, the mixture was stirred for 3 hours. After the reaction was completed, vacuum was applied to remove the solvent, dissolved in pentane, and filtered to obtain a filtrate. When the pentane was removed by vacuum, a dark brown compound (3.70 g) was obtained. The yield was 71.3%.

(2a)

¹ H NMR(C ₆ D ₆ ): δ 0.59 (s, 6H, Ti-CH ₃ ), 1.66 (s, 6H, Cp-CH ₃ ), 1.69 (br t, J = 6.4 Hz, 2H, quin-CH ₂ ), 2.05 (s, 6H, Cp-CH ₃ ), 2.47 (t, J = 6.0 Hz, 2H, quin-CH ₂ ), 4.53 (m, 2H, quin-CH ₂ ), 6.84 (t, J = 7.2 Hz, 1H, quin-CH), 6.93 (d, J =7.6 Hz, quin-CH), 7.01 (d, J =6.8 Hz, quin-CH) ppm

¹³ C NMR (C ₆ D ₆ ): δ 12.12, 23.08, 27.30, 48.84, 51.01, 119.70, 119.96, 120.95, 126.99, 128.73, 131.67, 136.21 ppm.

[Preparation of ethylene/alpha-olefin copolymer]

Example 1

After the 1.5L autoclave continuous process reactor was charged with hexane solvent (5.5 kg/h) and 1-butene (0.8 kg/h), the temperature at the top of the reactor was preheated to 155°C. Triisobutylaluminum compound (0.05 mmol/min), transition metal compound (1a) (0.15 μmol/min) prepared in Synthesis Example 1 as a catalyst, dimethylanilinium tetrakis(pentafluorophenyl) borate cocatalyst (0.15) μmol/min) was simultaneously introduced into the reactor. Then, ethylene (0.87 kg/h) and hydrogen gas (25 cc/min) were introduced into the autoclave reactor, maintained at a pressure of 89 bar and a polymerization temperature of 140° C. for at least 60 minutes, and the copolymerization reaction was continued to proceed. was prepared.

Next, the remaining ethylene gas was drained, and the resulting copolymer-containing solution was dried in a vacuum oven for at least 12 hours, and then physical properties of the obtained copolymer in the form of a bale were measured.

Examples 2 to 14 and Comparative Examples 1 to 6

Polymers of Examples 2 to 14 were prepared in the same manner as in Example 1, except that the reactants were added in the amounts shown in Table 1 below.

In addition, the polymers of Comparative Examples 4 to 6 were used in the same manner as in Example 1, except that the transition metal compound (2a) prepared in Synthesis Example 2 was used, but the reactants were added in the amounts shown in Table 1 below. was prepared.

On the other hand, as Comparative Example 1, LG Chem's LC885X product was purchased, as Comparative Example 2, Mitsui's DF8200 product was purchased, and as Comparative Example 3, Mitsui's DF610 product was purchased and used.

C2 C6 1-C4 H ₂ Cat. Co-cat. polymerization temperature kg/h sccm μmol/min ℃ Example 1 0.87 5.5 0.8 25 0.15 0.15 140 Example 2 0.87 5.5 0.8 26 0.25 0.375 144 Example 3 0.87 5.5 0.9 15 0.3 0.45 160 Example 4 0.87 5.5 0.8 20 0.075 One 140 Example 5 0.87 5.5 0.8 20 0.25 0.04 140 Example 6 0.87 5.5 0.7 22 0.075 0.5 140 Example 7 0.87 5.5 0.7 22 0.25 0.04 140 Example 8 0.87 5.5 0.85 24 0.25 0.375 155 Example 9 0.87 5.5 0.8 10 0.25 0.375 148 Example 10 0.87 5.5 0.8 10 0.25 0.375 146 Example 11 0.87 5.5 0.85 24 0.25 0.375 152 Example 12 0.87 5.5 0.85 24 0.25 0.375 161 Example 13 0.87 5.5 0.85 24 0.25 0.375 172 Example 14 0.87 7.0 0.83 16 0.17 0.34 140 Comparative Example 4 0.87 5.5 0.45 6 0.30 0.90 160 Comparative Example 5 0.87 5.5 0.43 6 0.24 0.72 160 Comparative Example 6 0.87 5.0 0.62 0 0.32 0.96 145

In addition, Examples 1 to 14 and Comparative Examples 1 to 6 The number of each functional group of vinylene, trivinyl, vinyl and vinylidene per 1000 carbon atoms in the copolymer was measured through nuclear magnetic spectroscopy according to the following method, and is shown in Table 2.

① After dissolving the copolymer in 1,1,2,2-tetrachloroethane D2 (TCE-d2) solvent, it was measured at 393K using Bruker AVANCE III 500MHz NMR equipment.

② The TCE-d2 peak in the 1H NMR spectrum was corrected to 6.0 ppm, and the comonomer content ratio was calculated using the integral values of 1.4 ppm and 0.96 ppm regions. The contents of each of the vinyl group, vinylidene group, vinylene group and trivinylene group observed at 4.7 ppm to 5.6 ppm were calculated (analysis method: AMT-3863). For peak assignment, reference was made to the literature [ Macromolecules 2014, 47, 3282-3790 ].

Relative content (number/1000C) Vinyl/Total Vylidene/Total vinylene tri vinyl vinyl vinylidene Total Example 1 0.1 0.04 0.05 0.02 0.2 0.25 0.1 Example 2 0.16 0.02 0.06 0.02 0.26 0.23 0.08 Example 3 0.19 0.04 0.1 0.03 0.36 0.28 0.08 Example 4 0.1 0.02 0.07 0.06 0.25 0.28 0.24 Example 5 0.08 0.02 0.05 0.04 0.2 0.25 0.2 Example 6 0.07 0.03 0.05 0.04 0.19 0.26 0.21 Example 7 0.06 0.02 0.05 0.04 0.17 0.29 0.24 Example 8 0.12 0.07 0.07 0.01 0.27 0.26 0.04 Example 9 0.11 0.07 0.07 0.01 0.25 0.28 0.04 Example 10 0.11 0.06 0.08 0.01 0.25 0.32 0.04 Example 11 0.15 0.13 0.14 0.01 0.43 0.33 0.02 Example 12 0.13 0.08 0.09 0.02 0.31 0.29 0.06 Example 13 0.1 0.05 0.05 0.02 0.22 0.23 0.09 Example 14 0.09 0.03 0.03 0 0.15 0.20 0.00 Comparative Example 1 0.46 0.05 0.1 0.08 0.69 0.14 0.12 Comparative Example 2 0.01 0 0.03 0.01 0.05 0.60 0.20 Comparative Example 3 0.06 0.02 0.02 0.03 0.12 0.17 0.25 Comparative Example 4 0.10 0.02 0.03 0.05 0.21 0.14 0.24 Comparative Example 5 0.08 0.02 0.03 0.04 0.18 0.17 0.22 Comparative Example 6 0.4 0.09 0.09 0.07 0.65 0.14 0.11

In addition, the melt index, density, weight average molecular weight (Mw) and molecular weight distribution (MWD) of Examples 1 to 14 and Comparative Examples 1 to 6 were measured and shown in Table 3 below.

① Density (Density, g/cm ³ ): It was measured according to ASTM D-792.

② Melt Index (MI): Measured by ASTM D-1238 (Condition E, 190°C, 2.16 kg load).

③ Melt Index (MI10): Measured by ASTM D-1238 (Condition E, 190 ℃, 10 kg load).

④ The weight average molecular weight (Mw) and number average molecular weight (Mn) were measured for the resulting copolymer under the following gel permeation chromatography (GPC) analysis conditions:

- Column: Agilent Olexis

- Solvent: Trichlorobenzene (TCB)

- Flow rate: 1.0 ml/min

- Sample concentration: 1.0 mg/ml

- Injection volume: 200 μl

- Column temperature: 160 ℃

- Detector : Agilent High Temperature RI detector

- Standard : Polystyrene (corrected by cubic function)

- Data processing: Cirrus

⑤ The molecular weight distribution was calculated from the ratio of Mw/Mn.

density MI _2.16 MI ₁₀ MI ₁₀ /MI _2.16 Mw MWD g/cm ³ dg/min dg/min - Da - Example 1 0.876 18 102.5 5.69 55,000 1.94 Example 2 0.879 20 113.8 5.69 55,000 2.1 Example 3 0.877 14 103.2 7.37 55,000 1.9 Example 4 0.870 14.5 93.3 6.43 - - Example 5 0.871 13.5 84.1 6.23 - - Example 6 0.876 12.8 82.4 6.44 54,000 1.9 Example 7 0.876 14 85.2 6.08 52,000 1.9 Example 8 0.879 18.4 119.7 6.50 55,000 2.14 Example 9 0.879 2.24 16.3 7.29 89,000 2.04 Example 10 0.879 0.95 7.3 7.67 112,000 2.1 Example 11 0.874 33.7 217.8 6.46 47,000 2.06 Example 12 0.883 25.3 160.8 6.36 50,000 2.01 Example 13 0.893 11.9 83.3 7.00 58,000 2.12 Example 14 0.880 16.3 103.0 6.32 50,000 2.14 Comparative Example 1 0.881 22 151.8 6.9 54,000 2.4 Comparative Example 2 0.884 17 108.2 6.36 55,000 1.9 Comparative Example 3 0.863 1.32 8.6 6.52 107,000 1.98 Comparative Example 4 0.897 5.86 41.7 7.12 68,000 1.92 Comparative Example 5 0.900 2.80 20.4 7.30 77,000 2.02 Comparative Example 6 0.862 1.20 9.3 7.72 91,000 2.18

From the results in Table 3, it can be seen that the ethylene/alpha-olefin copolymers of Examples 1 to 14 of the present invention have a narrower molecular weight distribution than Comparative Examples 1 and 6.

In addition, the molecular weight distribution diagrams of Example 2 and Comparative Example 1 are shown in FIG. 1 . From this, it can also be confirmed that Example 2 has a narrower molecular weight distribution than Comparative Example 1.

Experimental Example 1 - Crosslinking behavior properties and degree of crosslinking

[Production of Film]

(1) A crosslinking aid composition was added to 500 g of the sample of Example 1 according to the following recipe (a), then soaked at 40° C. for 1 hour, and then aged for 15 hours.

In addition, as shown in Table 4 below, to each sample of Examples 2, 8, 14, and Comparative Examples 1, 2, 4, 5, except that different recipes (a) to (f) were applied, except that A resin composition was prepared and applied in the same manner as described above.

(a) t-butyl 1-(2-ethylhexyl) monoperoxycarbonate (TBEC) 1 phr (parts per hundred rubber), triallyl isocyanurate (TAIC) 0.5 phr, methacryloxypropyltrimethoxysilane (MEMO) 0.2 phr

(b) TBEC 0.6 phr, TAIC 0.8 phr, MEMO 0.2 phr / toluene

(c) TBEC 0.6 phr, TAIC 0.93 phr, MEMO 0.21 phr / toluene

(d) The same as in (c) above, except that the soaking time was 1.5 hours instead of 1 hour.

(e) TBEC 0.6 phr, TAIC 0.93 phr, MEMO 0.21 phr/xylene

(f) TBEC 0.6 phr, TAIC 0.8 phr, MEMO 0.3 phr/xylene

(2) Using a micro-extruder with the soaked sample, a film having an average thickness of 450 μm was prepared at a low temperature (extruder barrel temperature of 90° C. or lower) to the extent that high-temperature cross-linking would not occur.

In order to understand the crosslinking behavior characteristics, the film containing the crosslinking aid composition in (2) was prepared in the form of a disk with a diameter of 5 g of 4 cm, and the maximum torque MH until scorched at 150° C. for 1 hour The resulting values, including the values, are shown in Table 4.

These crosslinking behavior characteristics were measured using a Moving Die Rheometer called Premier MDR of Alpha Technologies.

[Production of cross-linked sheets]

After covering the top/bottom of the film sample prepared in the [Production of Film] process (2) with a Teflon sheet, put it in a vacuum laminator, and lamination at 150° C. for 15 minutes to prepare a cross-linked sheet. The crosslinked sheet is for measuring the degree of crosslinking and optical properties after crosslinking, and is not attached to any substrate such as a glass substrate.

0.5 g of the cross-linked sheet was put into toluene (non-cross-linked polymer extraction solvent) and aged at 60° C. for 15 hours. After washing with toluene, it was dried at 80° C. for 6 hours. After drying, the weight of the sample was measured, and the degree of crosslinking was measured according to the following formula and shown in Table 4.

* Crosslinking degree = (weight after drying / weight before toluene treatment)*100

degree of crosslinking ML MH Final Torque T10 T50 T90 T95 Max Rate % dNm min dNm/min ^(a) Example 1 67 0.02 2.77 2.75 1.64 4.49 13.26 18.48 0.45 ^(a) Comparative Example 1 57 0.04 2.54 2.53 2.14 5.87 16.17 20.26 0.30 ^(b) Example 2 58 0.01 2.54 2.51 2.94 6.26 15.63 20.07 0.34 ^(b) Comparative Example 1 44 0.03 1.88 1.87 2.08 6.11 17.03 23.32 0.20 ^(c) Example 8 56 0.02 2.79 2.78 3.03 6.78 17.00 22.90 0.33 ^(d) Example 8 60.2 0.02 2.97 2.96 2.95 6.52 16.58 20.58 0.37 ^(c) Comparative Example 2 49 0.01 2.80 2.79 3.09 6.07 15.07 18.95 0.41 ^(e) Example 14 55 0.02 2.41 2.40 3.26 7.12 17.17 22.66 0.27 ^(e) Comparative Example 2 51 0.02 2.10 2.09 3.19 6.59 15.93 19.53 0.27 ^(f) Example 14 56 0.01 2.51 2.49 3.08 6.62 16.82 21.45 0.30 ^(f) Comparative Example 4 41 0.02 1.62 1.60 3.87 7.42 18.44 26.12 0.18 ^(f) Comparative Example 5 39 0.01 1.59 1.56 3.94 7.57 18.62 26.35 0.17

(a) TBEC 1 phr, TAIC 0.5 phr, MEMO 0.2 phr / toluene (non-crosslinked polymer extraction solvent)

(b) TBEC 0.6 phr, TAIC 0.8 phr, MEMO 0.2 phr / toluene (non-crosslinked polymer extraction solvent)

(c) TBEC 0.6 phr, TAIC 0.93 phr, MEMO 0.21 phr / toluene (non-crosslinked polymer extraction solvent)

(d) The same as in (c) above, except that the soaking time was 1.5 hours instead of 1 hour.

(e) TBEC 0.6 phr, TAIC 0.93 phr, MEMO 0.21 phr / xylene (non-crosslinked polymer extraction solvent)

(f) TBEC 0.6 phr, TAIC 0.8 phr, MEMO 0.3 phr / xylene (non-crosslinked polymer extraction solvent)

In the crosslinking behavior characteristic results of Table 4, the MH value and the Final Torque value mean that the higher the value, the higher the crosslinking degree. In addition, the T value is a factor related to the crosslinking speed. For example, T90 represents the time it takes until the torque value is 90% saturated, and it can be said that the smaller the value, the faster the crosslinking speed.

FIG. 2 shows the crosslinking behavior characteristics of Example 1 and Comparative Example 1 according to the crosslinking recipe (a), and FIG. 3 shows the crosslinking behavior characteristics of Example 2 and Comparative Example 1 according to the crosslinking recipe (b), respectively. .

In addition, from the results of Table 4, when comparing Examples and Comparative Examples to which the same crosslinking recipe is applied, it can be confirmed that the resin composition using the polymer of the Example has a higher degree of crosslinking compared to the Comparative Example. In particular, the degree of crosslinking of the resin compositions of Examples 1 and 2 is higher by 10% or more compared to Comparative Example 1 to which the same crosslinking recipe is applied. In addition, Example 14 showed a much higher degree of crosslinking compared to Comparative Examples 4 and 5 to which the same crosslinking recipe (f) was applied.

In addition, it was confirmed that when the soaking time was increased for Example 8 (ie, recipe (d)), the degree of crosslinking was further improved.

Experimental Example 2 - Optical Properties

The yellow index (YI) and total light transmittance (Tt) of the crosslinked sheet were measured according to the following method, and are shown in Table 5 below.

In addition, the yellow index (YI) and total light transmittance (Tt) were measured after the [production of the film] process and before the cross-linking sheet was manufactured, as 'before cross-linking' data was shown in Table 5 below.

① Yellow index (YI): Based on ASTM 1925, the reflectance in the 400 nm to 700 nm region was measured using Colorflex (Hunter lab), and using this, a YI value was obtained according to Equation 3 below.

[Equation 3]

YI = [100(1.28XCIE-1.06ZCIE)]/YCIE

The YI is a value calculated using a color difference analysis program in a UV/VIS/NIR spectrometer (ASTM, D1925), and XCIE, YCIE, and ZCIE are relative values indicated by red, green, and blue color coordinates, respectively.

② Total light transmittance (Tt): Using a hazemeter (Hazemeter), the total light transmittance for light of a wavelength of 550 nm was measured. Transmittance was measured three times after putting the specimen in the specimen holder, and the average value thereof was obtained, and was measured under the standard conditions of JIS K 7105.

after crosslinking before bridging Tt@550nm YI Tt@550nm YI ^(a) Example 1 91 0.82 89.4 3.5 ^(b) Example 2 90.9 1.34 88.7 3.9 ^(c) Example 8 90.9 0.86 88.2 3.4 ^(e) Example 14 91.2 0.83 89.1 3.7 ^(f) Example 14 91.5 0.9 90.0 3.4 ^(a) Comparative Example 1 89.4 1.63 86 6.1 ^(c) Comparative Example 2 89.3 1.74 85.3 5.9 ^(f) Comparative Example 4 89.1 3.1 88.5 7.4 ^(f) Comparative Example 5 88.8 3.7 88.1 8.1

In Table 5, in the case of the film formed including the ethylene/alpha-olefin copolymer of the present invention, it can be seen that the total light transmittance and the yellow index are very excellent compared to the comparative example.

Specifically, in the case of the example of the present invention, the yellow index value after crosslinking is in the range of 0.82 to 1.34, which is very excellent compared to 1.63 to 3.7 of the comparative example. In addition, it can be seen that the embodiment of the present invention has a total light transmittance of 90.9 or more after crosslinking, which is greatly improved compared to the comparative example showing a maximum value of 89.4. Therefore, it is expected that the ethylene/alpha-olefin copolymer of the present invention can be applied to the production of an optical film having excellent optical properties.

Claims (15)

Ethylene/alpha-olefin copolymers satisfying the following conditions (a) to (e):
(a) Density: 0.850 to 0.910 g/cc
(b) Melt Index (MI, 190 ℃, 2.16 kg load condition): 0.1 to 100 dg / min
(c) molecular weight distribution (MWD): 1.5 to 3.0
(d) R _v value according to the following formula 1 is 0.18 to 0.59
(e) R _vd value according to the following formula 2 is 0.02 to 0.10
[Equation 1]

[Equation 2]

In Equation 1 and Equation 2 above,
N _vd , N _tv , N _vl and N _v are the number of vinylidene, trivinyl, vinylene and vinyl functional groups per 1000 carbon atoms, respectively, measured through nuclear magnetic spectroscopy. means
delete According to claim 1,
wherein the R _v value is 0.19 to 0.46.
delete According to claim 1,
An ethylene/alpha-olefin copolymer having a density of 0.855 to 0.90 g/cc.
According to claim 1,
An ethylene/alpha-olefin copolymer having a melt index (190°C, 2.16 kg load condition) of 1.5 to 37 dg/min.
According to claim 1,
the number of vinyl functional groups per 1000 carbon atoms measured by nuclear magnetic spectroscopy is 0.01 to 0.3;
An ethylene/alpha-olefin copolymer having an MFR ₁₀ /MFR _2.16 of 8.5 or less, which is the ratio of the melt index measured at a load of 10 kg and 190°C to a melt index measured at a load of 2.16 kg and 190°C.
According to claim 1,
An ethylene/alpha-olefin copolymer having a weight average molecular weight (Mw) of 40,000 to 150,000 g/mol.
According to claim 1,
An ethylene/alpha-olefin copolymer having a molecular weight distribution of 1.5 to 2.2.
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 - An ethylene/alpha-olefin copolymer comprising at least one selected from the group consisting of tetradecene, 1-hexadecene and 1-eicosene.
According to claim 1,
The alpha-olefin is an ethylene/alpha-olefin copolymer in an amount of greater than 0 and 99 mol% or less based on the total weight of the copolymer.
In the presence of a catalyst composition comprising a transition metal compound of Formula 1, the ethylene/alpha-olefin of claim 1, comprising the step of polymerizing ethylene and alpha-olefinic monomers by introducing hydrogen at 5 to 100 cc/min Method for preparing the copolymer:
[Formula 1]

In Formula 1,
R ₁ is hydrogen; C1~C20 alkyl; C3~C20 cycloalkyl; C2-20 alkenyl; C1~C20 alkoxy; C6-20 aryl; C7-20 aryl alkoxy; C7-20 alkylaryl; Or C7-20 arylalkyl,
R _2a to R _2e are each independently hydrogen; halogen; C1~C20 alkyl; C3~C20 cycloalkyl; C2-20 alkenyl; C1~C20 alkoxy; Or C6-20 aryl,
R ₃ is hydrogen; halogen; C1~C20 alkyl; C3~C20 cycloalkyl; C2-20 alkenyl; C6-20 aryl; C6~C20 alkylaryl; C7-20 arylalkyl; C1-20 alkyl amido; C6-20 aryl amido; C1~C20 alkylidene; or halogen, C1-20 alkyl, C3-20 cycloalkyl, C2-20 alkenyl, C1-20 alkoxy, and C6-20 aryl substituted with one or more selected from the group consisting of phenyl,
R ₄ to R ₉ are each independently hydrogen; silyl; C1~C20 alkyl; C3~C20 cycloalkyl; C2-20 alkenyl; C6-20 aryl; C7-20 alkylaryl; C7-20 arylalkyl; or a metalloid radical of a Group 14 metal substituted with C1-20 hydrocarbyl; Two or more adjacent to each other among R ₆ to R ₉ may be connected to each other to form a ring,
Q is Si, C or S;
M is a Group 4 transition metal,
X ₁ and X ₂ are each independently hydrogen; halogen; C1~C20 alkyl; C3~C20 cycloalkyl; C2-20 alkenyl; C6-20 aryl; C7-20 alkylaryl; C7-20 arylalkyl; C1-20 alkylamino; C6~C20 arylamino; or C1-20 alkylidene.
13. The method of claim 12,
wherein R ₁ is hydrogen; C1-12 alkyl; C3-12 cycloalkyl; C1-12 alkoxy; C6-12 aryl; C7-13 arylalkoxy; C7-13 alkylaryl; Or it may be a C7-13 arylalkyl,
The R _2a to R _2e are each independently hydrogen; halogen; C1-12 alkyl; C3-12 cycloalkyl; C2-12 alkenyl; C1-12 alkoxy; or phenyl,
wherein R ₃ is hydrogen; halogen; C1-12 alkyl; C3-12 cycloalkyl; C2-12 alkenyl; C7-13 alkylaryl; C7-13 arylalkyl; phenyl; or halogen, C1-12 alkyl, C3-12 cycloalkyl, C2-12 alkenyl, C1-12 alkoxy, and phenyl may be substituted with one or more selected from the group consisting of phenyl,
The R ₄ to R ₉ are each independently hydrogen; C1-12 alkyl; C3-12 cycloalkyl; C6-12 aryl; C7-13 alkylaryl; Or it may be a C7-13 arylalkyl,
two or more adjacent to each other among R ₆ to R ₉ may be connected to each other to form a C5-12 aliphatic ring or a C6-12 aromatic ring;
The aliphatic ring or aromatic ring may be substituted with halogen, C1-12 alkyl, C2-12 alkenyl, or C6-12 aryl,
Q may be Si,
M may be Ti,
The X ₁ and X ₂ are each independently hydrogen; halogen; C1~C12 alkyl group; Or C2-12 alkenyl, ethylene / alpha- olefin copolymer production method.
13. The method of claim 12,
The transition metal compound is selected from the group consisting of compounds represented by the following Chemical Formulas 1-1 to 1-10. Method for preparing an ethylene/alpha-olefin copolymer:
[Formula 1-1] [Formula 1-2] [Formula 1-3] [Formula 1-4]

[Formula 1-5] [Formula 1-6] [Formula 1-7] [Formula 1-8]

[Formula 1-9] [Formula 1-10]

13. The method of claim 12,
The polymerization is carried out at 100 to 180 ℃ ethylene / alpha- method for producing an olefin copolymer.

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