This application claims the benefit of priority based on Korean Patent Application No. 10-2019-0126480 on October 11, 2019 and Korean Patent Application No. 10-2020-0125237 on September 25, 2020, All content disclosed in the literature is incorporated as a part of this specification.
[3]
The present invention relates to polyethylene exhibiting improved low-temperature sealing properties by increasing the content and molecular weight of a low-crystalline polymer and a method for preparing the same.
background
[4]
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.
[5]
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.
[6]
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.
[7]
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 has a disadvantage in that the metallocene catalyst portion is released from the carrier component of the finished catalyst, thereby causing fouling in the reactor.
[8]
On the other hand, linear low-density polyethylene is prepared by copolymerizing ethylene and α-olefin at low pressure using a metallocene-based polymerization catalyst, has a narrow molecular weight distribution, has a short-chain branch (SCB) of a constant length, and has no long-chain branch (LCB). Linear low-density polyethylene film has excellent mechanical properties such as breaking strength, elongation, tear strength, and falling impact strength in addition to the characteristics of general polyethylene. usage is increasing.
[9]
In the case of a film for high-speed packaging, it is required to increase hot-tack strength in order to increase productivity. However, in the case of the conventional linear low-density polyethylene, the melting temperature (Tm) is high, there is a disadvantage that the low-temperature sealing strength is low. Accordingly, there is a problem in that the sealing property is deteriorated during high-speed processing and the packaging material flows out.
[10]
[Prior art literature]
[11]
[Patent Literature]
[12]
(Patent Document 1) US Patent No. 5,914,289
[13]
(Patent Document 2) Korean Patent Publication No. 2004-0076965
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[14]
Accordingly, the present invention is to solve the problems of the prior art, and to provide a polyethylene exhibiting improved low-temperature sealing properties by increasing the content and molecular weight of a low-crystalline polymer and a method for manufacturing the same.
[15]
In addition, the present invention, including the polyethylene, exhibits excellent hot-tack strength characteristics, and as a result, it is intended to provide a film useful for high-speed packaging.
means of solving the problem
[16]
In order to solve the above problems, according to an embodiment of the present invention,
[17]
An ethylene repeating unit and an α-olefinic repeating unit,
[18]
a density of 0.916 g/cm 3 or greater, as measured in accordance with ASTM D1505 ;
[19]
When analyzed by Temperature Rising Elution Fractionation (TREF), three elution temperatures of Te1, Te2, and Te3 respectively corresponding to the elution temperatures of the first to third semi-crystalline polymers in the temperature range of 20 to 120° C. were obtained. , wherein Te2 has a lower temperature than Te3 and a higher temperature than Te1,
[20]
The Te1 is 25 to 30 ℃,
[21]
The first semicrystalline polymer has a weight average molecular weight (Mw) of 200,000 g/mol or more, and provides polyethylene, which is contained in an amount of 5 wt% or more based on the total weight of the polyethylene.
[22]
In addition, according to another embodiment of the present invention, in the presence of a catalyst composition comprising a first transition metal compound represented by the following Chemical Formula 1 and a second transition metal compound represented by the following Chemical Formula 2, hydrogen gas is introduced into the reactor and polymerizing an ethylene monomer and an α-olefin-based monomer having 3 or more carbon atoms, wherein the hydrogen gas is 10 ppm or more 200 ppm based on the total weight of the monomer including the ethylene monomer and an α-olefin-based monomer having 3 or more carbon atoms The method for producing polyethylene as described above, in which it is added in an amount less than, and in the polymerization reaction, the molar ratio of the α-olefin monomer to the ethylene monomer present in the reactor (molar ratio of the α-olefin monomer/ethylene monomer) is 0.25 or more to provide:
[23]
[Formula 1]
[24]

[25]
In Formula 1,
[26]
R 1 and R 2 are each independently hydrogen, halogen, C 1-20 alkyl, C 2-20 alkenyl, C 1-20 alkoxy, C 2-20 alkoxyalkyl, C 6-20 aryl, C 7-20 alkyl aryl, or C 7-20 arylalkyl;
[27]
X 1 and X 2 are each independently halogen or C 1-20 alkyl,
[28]
[Formula 2]
[29]

[30]
In Formula 2,
[31]
R 3 and R 4 are each independently hydrogen, halogen, C 1-20 alkyl, C 2-20 alkenyl, C 1-20 alkoxy, C 2-20 alkoxyalkyl, C 6-20 aryl, C 7-20 alkyl aryl, or C 7-20 arylalkyl;
[32]
X 3 and X 4 are each independently halogen or C 1-20 alkyl.
[33]
According to another embodiment of the present invention, there is provided a film comprising the above-described polyethylene, in particular, a film for high-speed packaging.
Effects of the Invention
[34]
The polyethylene according to the present invention can exhibit improved low-temperature sealing properties by increasing the polymer content and molecular weight of low crystallinity. Accordingly, when applied to the production of packaging films, particularly high-speed packaging films, excellent hot-tack properties can be exhibited, thereby increasing productivity.
Brief description of the drawing
[35]
1 to 4 are graphs showing analysis results according to TREF (Temperature Rising Elution Fractionation) for polyethylene prepared in Example 1 and Comparative Examples 5 to 7, respectively.
[36]
5 to 7 are graphs showing the results of Gel Permeation Chromatography (GPC) analysis of the first quasi-crystalline polymer in the polyethylene prepared in Example 1 and Comparative Examples 5 and 6, respectively.
[37]
8 to 11 show the SCB content according to the polyethylene molecular weight obtained as a result of GPC-FTIR (Gel Permeation Chromatography-Fourier-transform infrared spectroscopy) analysis of the polyethylene prepared in Example 1 and Comparative Examples 5 to 7, respectively. It is a graph representing
[38]
12 is a graph showing the results of measuring the low-temperature sealing strength of the polyethylene prepared in Example 1 and Comparative Examples 5 to 7.
Modes for carrying out the invention
[39]
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", "comprising" 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.
[40]
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.
[41]
In the present invention, the term "short chain branching (SCB)" in polyethylene refers to a chain branched in a branched form with respect to the longest main chain in each of the polymer chains, specifically, the number of carbon atoms. 2 to 7 chains. The number of such short chain branches may be calculated by FT-IR analysis of the polymer, and may be proportional to the content of the α-olefinic monomer included in the polymer chains.
[42]
Hereinafter, the polyethylene of the present invention, a method for producing the same, and a film using the same will be described in detail.
[43]
[44]
Specifically, polyethylene according to an embodiment of the present invention is an ethylene/α-olefin-based copolymer comprising an ethylene repeating unit and an α-olefin-based repeating unit,
[45]
a density of 0.916 g/cm 3 or greater, as measured in accordance with ASTM D1505 ;
[46]
Three elution temperatures of Te1, Te2 and Te3, respectively, corresponding to the elution temperatures of the first to third quasi-crystalline polymers in the temperature range of 20 to 120° C., as analyzed by temperature rising elution fractionation (TREF), wherein Te2 is Lower temperature than Te3 and higher temperature than Te1,
[47]
The Te1 is 25 to 30 ℃,
[48]
The first semi-crystalline polymer has a weight average molecular weight (Mw) of 200,000 g/mol or more, and is included in an amount of 5 wt% or more based on the total weight of polyethylene.
[49]
The present inventors used a specific catalyst composition to be described later in the production of polyethylene, and as a result of controlling the mixing ratio of the ethylene monomer and the comonomer and the amount of hydrogen input, the produced polyethylene has a controlled density of at least a certain level, and is different from the conventional one. It was confirmed that the crystal properties were exhibited, and the present invention was completed.
[50]
The crystalline properties of the polyethylene were confirmed through TREF analysis. According to the analysis results, the polyethylene is distinguished from showing generally only one peak in the first to the same analysis results in three different specific temperature ranges.
[51]
More specifically, the first to third peaks are fractions of polymer chains exhibiting different crystallinity in the polyethylene of one embodiment, more specifically, the first fraction showing the lowest crystallinity, and the third peak showing the highest crystallinity. fraction, and a second fraction exhibiting crystallinity between the first and third fractions are included. As the first to third fractions of polymer chains having different crystallinities are simultaneously included as described above, the polyethylene according to an embodiment has all physical properties required for various uses, for example, compatibility with other resins, processability. , it is possible to simultaneously improve the strength and impact strength when compounded with other resins or alone. This is presumed because the polyethylene contains polymer chains exhibiting various crystallinities at the same time.
[52]
In particular, it was confirmed that the polyethylene according to an embodiment of the present invention includes the first fraction showing low crystallinity at a high fractionation ratio (fraction), and the polymer chains included in the first fraction have a high molecular weight. As a result, polyethylene according to an embodiment of the present invention can not only excellently express various physical properties at the same time, but also significantly improve sealing strength characteristics at low temperatures. Accordingly, it can be particularly usefully used for manufacturing a high-speed packaging film requiring excellent hot-tack properties.
[53]
Meanwhile, in the present invention, TREF analysis for polyethylene may be performed using a TREF equipment manufactured by Polymer Char. Specifically, the polyethylene is dissolved in a solvent such as 1,2,4-trichlorobenzene to prepare a solution sample, and after introducing the prepared sample to the TREF column, the initial temperature is lowered to 20° C., and then a constant temperature increase rate 1 While raising the temperature to 120 °C at °C/min, the concentration of the eluted polymer is measured while flowing 1,2,4-trichlorobenzene as a solvent through the column at a flow rate of 0.5 mL/min. A more specific measurement method will be described in detail in Test Examples below.
[54]
As a result of the above-described TREF analysis, a TREF elution curve expressed as the elution amount (dW/dT) versus temperature can be obtained, and the first to third peaks corresponding to the first to third fractions in the above-described temperature range can be confirmed. can The identified first and third peaks mean that the polyethylene comprises a semi-crystalline polymer corresponding to each peak.
[55]
As used herein, “quasicrystal” refers to a first-order transition temperature, crystal melting temperature (Tm) or elution temperature, etc. measured by temperature rising elution fractionation (TREF), differential scanning calorimetry (DSC) or equivalent techniques. refers to polymers. For mesocrystalline, the density, Tm, elution temperature, etc., vary depending on the crystallinity. On the other hand, the term "amorphous" refers to a polymer that lacks a crystalline melting temperature as measured by elevated elution fractionation (TREF), differential scanning calorimetry (DSC) or equivalent techniques.
[56]
In addition, the temperature of the highest point of each peak in the TREF elution curve is the elution temperature (Te), and is expressed by Te1, Te2, and Te3, respectively. Te2 is present at a temperature lower than Te3 and higher than Te1, specifically, Te1 is 25 to 30°C, Te2 is 40 to 65°C, and Te3 is 80 to 100°C.
[57]
Polyethylene according to an embodiment of the present invention includes first to third semi-crystalline polymers corresponding to the first to third peaks and having different crystallinities.
[58]
Specifically, Te1 represents the elution temperature of the first quasi-crystalline polymer exhibiting low crystallinity, and is 25°C or higher, or 27°C or higher, or 28°C or higher, or 28.1°C or higher, 30°C or lower, or 29°C or lower, or 28.5°C or less. In addition, Te2 represents the elution temperature of the second quasi-crystalline polymer having higher crystallinity than the first polymer, and is 40°C or higher, or 50°C or higher, or 60°C or higher, or 62°C or higher, and 65°C or lower. , or 63° C. or less, or 62.5° C. or less. As such, since the elution temperature, Te2, of the polymer chains exhibiting an intermediate level of crystallinity is as low as 65° C. or less, the low-crystal content is relatively high and can be rapidly melted even at low temperatures, and as a result, the effect of improving the low-temperature sealing properties can be exhibited. have. In addition, Te3 represents the elution temperature of the third polymer having higher crystallinity compared to the second semi-crystalline polymer, and is 80°C or higher, or 90°C or higher, or 93°C or higher, 100°C or lower, or 95°C or lower, or 94°C or less.
[59]
In addition, the fractional ratio (or content) of the first to third fractions of polymer chains exhibiting different crystallinities in the total polyethylene can be determined by the integrated areas of the first to third peaks and their ratios, Each of these integral areas may be derived by dividing the first to third peaks for each peak area according to, for example, a constant temperature area, and then obtaining the lower area thereof, and the integral of each peak relative to the total area of ​​each peak A fraction ratio of each fraction corresponding to each peak may be determined as a ratio of an area.
[60]
When analyzed in this way, the polyethylene of one embodiment has a fraction ratio of the first fraction defined from the integral area of ​​the first peak of 5% or more, more specifically 10% or more, or 11% or more, or 12% or more, and may be 20% or less, or 15% or less, or 13% or less. When converted based on the total weight of polyethylene, the content of the first quasi-crystalline polymer corresponding to the first fraction may be 5 wt% or more, and more specifically, 10 wt% or more, 11 wt% or more, or 12 wt% or more and 20 wt% or less, 15 wt% or less, or 13 wt% or less. As such, since the content of the first quasi-crystalline polymer having the lowest crystallinity in polyethylene is high, it can be rapidly melted at a low temperature, thereby improving the low-temperature sealing properties.
[61]
In addition, in the polyethylene, the weight average molecular weight (Mw) of the first quasi-crystalline polymer exhibiting the lowest crystallinity may be 200,000 g/mol or more, and more specifically, 200,000 g/mol or more, or more than 200,000 g/mol, or 202,000 g/mol or more, or 205,000 g/mol or more, and 500,000 g/mol or less, or 300,000 g/mol or less, or 250,000 g/mol or less, or 210,000 g/mol or less, or 206,000 g/mol or less . As it has such a high molecular weight, sealing strength can be improved even at low temperatures due to entanglement between polymer chains.
[62]
In addition, the number average molecular weight (Mn) of the first quasi-crystalline polymer is also high as 50,000 g/mol or more, and more specifically, 50,000 g/mol or more, or 60,000 g/mol or more, or 70,000 g/mol or more, and 100,000 g/mol or more. g/mol or less, or 80,000 g/mol or less, or 75,000 g/mol or less, or 73,000 g/mol or less. Further, the first quasi-crystalline polymer has a high molecular weight distribution (Mw/Mn ratio) of 2 or more, or 2.3 or more, or 2.5 or more, or 2.8 or more, or 2.82 or more, and 3 or less, or 2.95 or less, or 2.93 or less. can indicate
[63]
Meanwhile, in the present invention, the weight average molecular weight, number average molecular weight, and molecular weight distribution of the first quasi-crystalline polymer can be measured through gel permeation chromatography (GPC) analysis, and the specific measurement method thereof is described in Test Examples below. It will be described in detail.
[64]
In addition, the polyethylene exhibits a density of 0.916 g/cm 3 or more when measured according to ASTM D1505 standard along with the above-described crystal properties .
[65]
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 composition including a transition metal compound having a specific structure. As a result, polyethylene according to an embodiment of the present invention exhibits a density of 0.916 g/cm 3 or more, and as a result, it can exhibit processability with excellent mechanical properties. More specifically, the polyethylene may have a density of 0.916 g/cm 3 or more, 0.920 g/cm 3 or less, or 0.918 g/cm 3 or less, and maintain mechanical properties and impact strength through optimization of such a density range. The improvement effect can be further enhanced.
[66]
Furthermore, the polyethylene has an average number of short chain branches (SCB) per 1000 carbons in the polymer in the polymer region having a log Mw of 5.5 or more when analyzed by gel permeation chromatography (GPC-FTIR) combined with Fourier transform infrared spectroscopy, 35 or more, or more specifically, 35 or more, or 35.5 or more, or 36 or more, or 36.5 or more, and 40 or less, or 39 or less, or 38.5 or less, or 38 or less. As such, the high number of SCBs in the polymer region reflects that the polymers in the polymer region contain a higher content of α-olefin-based repeating units, and as a result, the polymers in the polymer region form low crystals to improve low-temperature sealing strength. It can have an effect that can be improved.
[67]
Further, the polyethylene may have an average number of short chain branches (SCB) per 1000 carbons in the entire polymer of 18 or more, or 19 or more, or 20 or more, and 22 or less, or 21.5 or less. Such a high number of SCBs means that the content of comonomers is high, and as a result, excellent low-temperature sealing strength improvement effect can be exhibited even when the density is lowered.
[68]
In the present invention, the number of short chain branches (SCB) and the number of SCBs in polyethylene in the polymer region having log Mw of 5.5 or more are expressed as average values ​​after calculating each value from the GPC-FTIR analysis result, and a specific method will be described in detail in the following test examples.
[69]
In addition, the polyethylene exhibits a narrow molecular weight distribution (MWD) of 3 or less, and more specifically, 2.75 or less, or 2.70 or less, and 2 or more, or 2.5 or more, or 2.65 or more.
[70]
In general, having two or more Te in the measurement of TREF means that two or more types of polymers having different branched chain contents are mixed. In addition, when two or more types of polymers are mixed and present, molecular weight distribution increases, and as a result, impact strength and mechanical properties decrease, and blocking phenomenon occurs. However, the polyethylene in the present invention exhibits three Tes and has a narrow molecular weight distribution as described above, thereby exhibiting excellent impact strength and mechanical properties.
[71]
In addition, under the conditions satisfying the above molecular weight distribution range, the polyethylene has a number average molecular weight (Mn) of 35,000 g/mol or more, or 40,000 g/mol or more, or 42,000 g/mol or more, or 43,000 g/mol or more, and , 50,000 g/mol or less, or 45,000 g/mol or less, or 44,000 g/mol or less, and a weight average molecular weight (Mw) of 100,000 g/mol or more, or 110,000 g/mol or more, or 112,000 g/mol or more, 130,000 g/mol or less, or 120,000 g/mol or less, or 115,000 g/mol or less, or 114,000 g/mol or less.
[72]
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 (MWD) is Mw / Mn can be calculated from the ratio of The specific measurement method will be described in detail in the following experimental examples.
[73]
In addition, the polyethylene may satisfy any one or more, or two or more, or three or more, or four or more, or all five of the following conditions (i) to (v):
[74]
(i) Melt index measured at 190° C. and a load of 2.16 kg according to ASTM D-1238: 0.8 to 2 g/10 min;
[75]
(ii) melting temperature: 120 to 125 °C;
[76]
(iii) crystallization temperature: 100 to 110 °C;
[77]
(iv) heat of fusion in the temperature range of 0 to 130° C.: 99.5 to 120 J/g, and
[78]
(v) According to ASTM F1921 measurement method, the sealing initiation temperature under 2N conditions is 95°C or less, and the hot tack strength at 100°C is 3.0N or more.
[79]
Specifically, the polyethylene has a melt index (MI) of 0.8 g/10min or more, or 0.9 g/10min or more, or 1 g/10min or more, measured according to ASTM D-1238 (Condition E, 190°C, 2.16kg load), and , 2 g/10 min or less, or 1.8 g/10 min or less, or 1.5 g/10 min or less. By having a melt index in the optimum range with a density in the above range, the polyethylene can exhibit improved processability while maintaining excellent mechanical properties.
[80]
In addition, the polyethylene has a high melting temperature of 120 to 125 ℃ can exhibit excellent heat resistance. Specifically, the polyethylene may have a melting temperature (Tm) measured by DSC of 120°C or higher, 125°C or lower, or 122°C or lower.
[81]
In addition, the polyethylene may have a crystallization temperature (Tc) of 100°C or higher, 110°C or lower, or 105°C or lower, or 103°C or lower. This high crystallization temperature is due to the uniform distribution of comonomers in polyethylene, and excellent structural stability can be exhibited by having the above temperature range.
[82]
In addition, the polyethylene is subjected to DSC in a temperature range of -50 to 190°C, and in the resulting graph, heat of fusion (heat of fusion; heat of fusion; ΔH) is 99.5 J/g or more, or 100.0 J/g or more, or 105 J/g or more, and 120 J/g or less, or 115 J/g or less. Accordingly, excellent heat resistance can be exhibited.
[83]
In the present invention, the melting temperature (Tm), crystallization temperature (Tc), and heat of fusion (ΔH) of polyethylene can be measured using a Differential Scanning Calorimeter (DSC), and the specific method is the test below. Examples will be described in detail.
[84]
Meanwhile, the aforementioned polyethylene may be a copolymer including an ethylene-based repeating unit and an α-olefin-based repeating unit, wherein the α-olefin-based repeating unit is 1-butene, 1-pentene, and 4-methyl-1- Derived from α-olefins having 3 to 20 carbon atoms, such as pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, or 1-hexadecene It may be a single repeating unit, and may appropriately be a repeating unit derived from 1-hexene in consideration of the excellent impact strength of polyethylene and the like.
[85]
The polyethylene of the above-described embodiment may exhibit excellent low-temperature sealing strength properties. Specifically, the polyethylene has a low sealing initiation temperature (SIT) of 95° C. or less, or 93° C. or less, or 90° C. or less under 2N conditions measured according to ASTM F1921 measurement method, and hot-tack strength at 100° C. (N/25mm)) is as high as 3.0N or more, or 3.2N or more.
[86]
Accordingly, it is used for blow molding, extrusion molding or injection molding in various fields and uses such as materials for automobiles, shoes, electric wires, toys, textiles, medical products, etc. It can be usefully used, and is particularly useful as a film for high-speed packaging.
[87]
On the other hand, it was confirmed that the above-mentioned polyethylene can be prepared by a manufacturing method using a specific catalyst system to be described later. Accordingly, according to another embodiment of the present invention, in the presence of a catalyst composition comprising a first transition metal compound represented by the following Chemical Formula 1 and a second transition metal compound represented by the following Chemical Formula 2, an ethylene monomer, and 3 carbon atoms in a reactor a polymerization reaction of the α-olefin-based monomers, wherein the hydrogen gas is input in an amount of 10 ppm or more and less than 200 ppm based on the total weight of the monomer including the ethylene monomer and the α-olefin-based monomer having 3 or more carbon atoms, There is provided a method for producing polyethylene as described above, wherein the molar ratio of the α-olefin monomer to the ethylene monomer in the reactor (the molar ratio of the α-olefin monomer/ethylene monomer) is 0.25 or more:
[88]
[Formula 1]
[89]

[90]
In Formula 1,
[91]
R 1 and R 2 are each independently hydrogen, halogen, C 1-20 alkyl, C 2-20 alkenyl, C 1-20 alkoxy, C 2-20 alkoxyalkyl, C 6-20 aryl, C 7-20 alkyl aryl, or C 7-20 arylalkyl;
[92]
X 1 and X 2 are each independently halogen or C 1-20 alkyl,
[93]
[Formula 2]
[94]

[95]
In Formula 2,
[96]
R 3 and R 4 are each independently hydrogen, halogen, C 1-20 alkyl, C 2-20 alkenyl, C 1-20 alkoxy, C 2-20 alkoxyalkyl, C 6-20 aryl, C 7-20 alkyl aryl, or C 7-20 arylalkyl;
[97]
X 3 and X 4 are each independently halogen or C 1-20 alkyl.
[98]
In the transition metal compound included in the catalyst composition according to the embodiment, the substituents in Chemical Formulas 1 and 2 will be described in more detail as follows.
[99]
The halogen may be fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).
[100]
C 1-20 alkyl may be straight chain, branched chain or cyclic alkyl. Specifically, C 1-20 alkyl is C 1-20 straight chain alkyl; C 1-10 straight chain alkyl; C 1-5 straight chain alkyl; C 3-20 branched or cyclic alkyl; C 3-15 branched or cyclic alkyl; or C 3-10 branched chain or cyclic alkyl. More specifically, C 1-20 alkyl may be methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl or cyclohexyl.
[101]
C 2-20 alkenyl may be straight chain, branched chain or cyclic alkenyl. Specifically, C 2-20 alkenyl is C 2-20 straight chain alkenyl, C 2-10 straight chain alkenyl, C 2-5 straight chain alkenyl, C 3-20 branched chain alkenyl, C 3-15 branched chain alkenyl kenyl, C 3-10 branched chain alkenyl, C 5-20 cyclic alkenyl or C 5-10 cyclic alkenyl. More specifically, C 2-20 alkenyl may be ethenyl, propenyl, butenyl, pentenyl or cyclohexenyl, and the like.
[102]
C 6-20 aryl may mean a monocyclic, bicyclic or tricyclic aromatic hydrocarbon. Specifically, C 6-20 aryl may be phenyl, naphthyl or anthracenyl, and the like.
[103]
C 7-20 alkylaryl may mean a substituent in which one or more hydrogens of aryl are substituted with alkyl. Specifically, C 7-20 alkylaryl may be methylphenyl, ethylphenyl, n-propylphenyl, iso-propylphenyl, n-butylphenyl, iso-butylphenyl, tert-butylphenyl or cyclohexylphenyl.
[104]
C 7-20 arylalkyl may mean a substituent in which one or more hydrogens of the alkyl are substituted by aryl. Specifically, C 7-20 arylalkyl may be benzyl, phenylpropyl, or phenylhexyl.
[105]
C 1-20 alkoxy may be straight chain, branched chain or cyclic alkoxy. Specifically, the C 1-20 alkoxy may include, but is not limited to, methoxy, ethoxy, n-butoxy, tert-butoxy, phenyloxy, cyclohexyloxy, and the like.
[106]
C 2-20 alkoxyalkyl may mean a substituent in which one or more hydrogens of alkyl are substituted by alkoxy. Specifically, as C 2-20 alkoxyalkyl, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, butoxymethyl, butoxyethyl, butoxypropyl, butoxybutyl, butoxyheptyl, butoxy hexyl, and the like, but is not limited thereto.
[107]
In the catalyst composition according to the embodiment, in Formula 1, R 1 and R 2 are the same as or different from each other, and each independently C 4-20 or C 4-12 straight-chain alkyl; Or it may be C 5-12 or C 6-10 straight-chain alkyl substituted with tert-butoxy, and X 1 and X 2 are the same as or different from each other, and each independently halogen such as chloro; or C 1-4 straight chain alkyl such as methyl ;
[108]
More preferably, in Formula 1, R 1 and R 2 are both C 6-10 straight-chain alkyl substituted with tert-butoxy, or both are n-hexyl substituted with tert-butoxy, and X 1 and X 2 may all be C 1-4 straight chain alkyl or methyl.
[109]
Specifically, the first transition metal compound represented by Formula 1 may be a compound represented by Formula 1a or Formula 1b, but is not limited thereto.
[110]
[Formula 1a]
[111]

[112]
[Formula 1b]
[113]

[114]
The first transition metal compound represented by the above structural formulas may be synthesized by applying known reactions, and for more detailed synthesis methods, refer to Examples.
[115]
In the catalyst composition according to the embodiment, in Formula 1, R 3 and R 4 are the same as or different from each other, and each independently C 3- such as n-propyl, n-butyl, n-pentyl, or n-hexyl 12 straight-chain alkyl, and X 3 and X 4 are the same as or different from each other, and each independently may be a C 1-4 straight-chain alkyl such as methyl or ethyl .
[116]
More preferably, in Formula 2, R 3 and R 4 may be both or C 4-6 straight-chain alkyl, and X 3 and X 4 may both be C 1-4 straight-chain alkyl or methyl.
[117]
Specifically, the second transition metal compound represented by Formula 2 may be a compound represented by Formula 2a or Formula 2b, but is not limited thereto.
[118]
[Formula 2a]
[119]

[120]
[Formula 2b]
[121]

[122]
The second transition metal compound represented by the above structural formulas may be synthesized by applying known reactions, and for more detailed synthesis methods, refer to Examples.
[123]
In the catalyst composition according to the embodiment, the first transition metal compound represented by Formula 1 contributes to making a low molecular weight linear copolymer, and the second transition metal compound represented by Formula 2 is a high molecular weight linear copolymer. It can contribute to the creation of a synthesis. The catalyst composition may exhibit excellent supporting performance, catalytic activity, and high copolymerizability by using a low-copolymerizable first transition metal compound and a high-copolymerizable second transition metal compound together as a hybrid catalyst. In particular, when ultra-low-density polyethylene is manufactured in a slurry process under such a catalyst composition, process stability is improved, thereby preventing a fouling problem that has occurred in the past. In addition, it is possible to provide polyethylene having excellent physical properties by using the catalyst composition.
[124]
In addition, in the catalyst composition, by controlling the mixing molar ratio of the first transition metal compound and the second transition metal compound, catalyst activity and copolymerizability can be improved, and the molecular structure and physical properties of polyethylene can be more easily implemented. . Specifically, the mixing molar ratio (A:B) of the first transition metal compound (A) and the second transition metal compound (B) may be 1:0.3 to 1:3.5, and when included in the above molar ratio, a high catalyst It can exhibit activity and copolymerizability, and as a result, the structure and physical properties of polyethylene as described above can be more easily implemented. In particular, when ultra-low-density polyethylene is produced in a slurry process under such a catalyst composition, problems in which conventional ultra-low-density polyethylene melts or swells, lowering productivity and generating fouling, are solved, and excellent process stability can be exhibited. .
[125]
If the molar ratio (A:B) of the first transition metal compound and the second transition metal compound is less than 1:0.3, it may be difficult to manufacture ultra-low density polyethylene as copolymerization is lowered, and if it exceeds 1:3.5, the desired polymer molecule Implementation of the structure can be difficult. More specifically, the molar ratio (A:B) of the first transition metal compound to the second transition metal compound in the catalyst composition may be 1:0.5 to 1:2, or 1:1 to 1:1.5.
[126]
Meanwhile, the catalyst composition may further include at least one of a carrier and a cocatalyst.
[127]
Specifically, the catalyst composition may further include a carrier supporting the first transition metal compound and the second transition metal compound. When the catalyst composition is used in the form of a supported catalyst, the morphology and physical properties of the polyethylene to be produced can be further improved, and it can be suitably used for slurry polymerization, bulk polymerization, and gas phase polymerization.
[128]
Specifically, as the carrier, a carrier having a hydroxyl group, a silanol group or a siloxane group having high reactivity on the surface is preferably used instead of removing moisture that prevents the loading of the transition metal compound on the surface of the carrier. The surface may be modified by calcination, or a drying process may be performed. For example, silica prepared by calcining silica gel, silica dried at high temperature, silica-alumina, and silica-magnesia may be used, and these are typically Na 2 O, K 2 CO 3 , BaSO 4 , and Mg(NO 3 ). 2 and the like oxide, carbonate, sulfate, and nitrate components.
[129]
When calcining or drying the carrier, the temperature may be 200 to 600 °C, and 250 to 600 °C. When the calcination or drying temperature of the carrier is low below 200° C., there is too much moisture remaining in the carrier, and there is a risk that the surface moisture and the co-catalyst may react, and the co-catalyst is loaded due to the excess hydroxyl groups. Although the fertility rate may be relatively high, a large amount of co-catalyst is required. In addition, when the drying or calcination temperature is excessively high, exceeding 600° C., the pores on the surface of the carrier coalesce and the surface area decreases, a lot of hydroxyl groups or silanol groups disappear on the surface, and only siloxane groups remain, so that the reaction site with the promoter is likely to decrease.
[130]
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. If the amount of the hydroxyl group is too low, there are few reaction sites with the cocatalyst, and if it is too large, it may be due to moisture other than the hydroxyl group present on the surface of the carrier particle. For example, the amount of hydroxyl groups on the surface of the carrier may be 0.1 to 10 mmol/g or 0.5 to 5 mmol/g.
[131]
Among the above-mentioned carriers, in the case of silica, since the transition metal compound is chemically bonded to the silica carrier and supported, there is almost no catalyst released from the surface of the carrier in the copolymerization process. As a result, when polyethylene is produced by slurry polymerization or gas phase polymerization, it is preferable because it is possible to minimize fouling of the reactor wall or polymer particles agglomerated with each other.
[132]
In addition, when the catalyst composition is used in the form of a supported catalyst, the first and second transition metal compounds are, for example, 10 μmol or more, or 30 μmol or more, and 500 μmol or less, based on 1 g of silica, by weight of the carrier; Or it may be supported in a content range of 100 μmol or less. When supported in the above content range, it may exhibit an appropriate supported catalyst activity, which may be advantageous in terms of maintaining the activity of the catalyst and economic feasibility.
[133]
In addition, the catalyst composition may further include a co-catalyst to activate the transition metal compound, which is a catalyst precursor. The cocatalyst is not particularly limited as long as it is an organometallic compound containing a Group 13 metal, and can be used when polymerizing olefins under a general metallocene catalyst. Specifically, the cocatalyst may be at least one compound selected from the group consisting of compounds represented by the following Chemical Formulas 3 to 5.
[134]
[Formula 3]
[135]
-[Al(R 11 )-O] m -
[136]
In Formula 3,
[137]
R 11 may be the same as or different from each other, and each independently halogen; C 1-20 hydrocarbons; or a C 1-20 hydrocarbon substituted with halogen ;
[138]
m is an integer greater than or equal to 2;
[139]
[Formula 4]
[140]
J(R 12 ) 3
[141]
In Formula 4,
[142]
R 12 may be the same as or different from each other, and each independently halogen; C 1-20 hydrocarbons; or a C 1-20 hydrocarbon substituted with halogen ;
[143]
J is aluminum or boron;
[144]
[Formula 5]
[145]
[EH] + [ZQ 4 ] - or [E] + [ZQ 4 ] -
[146]
In Formula 5,
[147]
E is a neutral or cationic Lewis base;
[148]
H is a hydrogen atom;
[149]
Z is a group 13 element;
[150]
Q are the same or be different, each independently represent at least one hydrogen atom is halogen, C to each other 1 to 20 substituted by a city of the hydrocarbon, alkoxy or phenoxy or unsubstituted, C 6-20 aryl group or C 1-20 of is an alkyl group.
[151]
Examples of the compound represented by Formula 3 include C 1-20 alkylaluminoxane-based compounds such as methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, or butylaluminoxane , any one or two of them A mixture of the above may be used.
[152]
In addition, examples of the compound represented by Formula 4 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, tributyl boron, and the like, and more specifically, may be selected from trimethyl aluminum, triethyl aluminum, and triisobutyl aluminum.
[153]
In addition, examples of the compound represented by Formula 5 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, and trimethylammonium tetra (p- Tolyl) boron, trimethylammonium tetra(o,p-dimethylphenyl) boron, tributylammonium tetra(p-trifluoromethylphenyl) boron, trimethylammonium tetra(p-trifluoromethylphenyl) boron, tributylammonium Umtetrapentafluorophenylboron, N,N-diethylaniliniumtetraphenylboron, N,N-diethylaniliniumtetrapentafluorophenylboron, diethylammoniumtetrapentafluorophenylboron, triphenyl Phosphonium tetraphenyl boron, trimethyl phosphonium tetraphenyl boron, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium tetraphenyl aluminum, tripropyl ammonium tetraphenyl aluminum, trimethyl ammonium tetra (p -Tolyl)aluminum, tripropylammonium tetra(p-tolyl)aluminum, triethylammoniumtetra(o,p-dimethylphenyl)aluminum, tributylammonium tetra(p-trifluoromethylphenyl)aluminum, trimethylammonium Tetra(p-trifluoromethylphenyl)aluminum, tributylammonium tetrapentafluorophenylaluminum, N,N-diethylaniliniumtetraphenylaluminum, N,N-diethylaniliniumtetrapentafluorophenylaluminum , diethyl ammonium tetrapentafluorophenyl aluminum, triphenyl phosphonium tetraphenyl aluminum, trimethyl phosphonium tetraphenyl aluminum, tripropyl ammonium tetra (p-tolyl) boron, triethyl ammonium tetra (o, p-dimethyl phenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, triphenyl carbonium tetra (p-trifluoromethylphenyl) boron, or triphenyl carbonium tetrapentafluorophenyl boron. and any one or a mixture of two or more thereof may be used.
[154]
Among the cocatalysts, in consideration of the fact that they can exhibit superior catalytic activity when used with the transition metal compound, the cocatalyst is a compound represented by Formula 3, more specifically C 1 such as methylaluminoxane It may be an alkylaluminoxane-based compound of -20 . The alkylaluminoxane-based compound acts as a scavenger of hydroxyl groups present on the surface of the carrier to improve catalytic activity, and converts the halogen group of the catalyst precursor to a methyl group to promote chain growth during polymerization of polypropylene make it
[155]
The promoter may be supported in an amount of, for example, 0.1 g or more, or 0.5 g or more, and 20 g or less, or 10 g or less, based on 1 g of silica per weight of the carrier. When included in the above content range, it is possible to sufficiently obtain the effect of reducing the generation of fine powder together with the effect of improving the catalytic activity according to the use of the cocatalyst.
[156]
In addition, when the catalyst composition includes both the carrier and the co-catalyst, the catalyst composition may include: supporting a co-catalyst compound on a carrier; and supporting the transition metal compound on the carrier. At this time, the supporting of the transition metal compound is performed by supporting the first transition metal compound and then supporting the second transition metal compound. may be, or vice versa. A supported catalyst having a structure determined according to such a supporting order may exhibit superior process stability with higher catalytic activity in the polyethylene manufacturing process.
[157]
In addition, the catalyst composition may be used in a slurry state in a solvent, may be used in a diluted state, or may be used in the form of a mud catalyst mixed with a mixture of oil and grease according to a polymerization method.
[158]
When used in a slurry state or diluted in a solvent, the solvent includes an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for the polymerization process of propylene monomer, for example, pentane, hexane, heptane, nonane, decane, and these and an aromatic hydrocarbon solvent such as toluene and benzene, or a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane and chlorobenzene, and any one or a mixture of two or more thereof may be used. In this case, the catalyst composition may further include the above solvent, and a small amount of water or air that may act as a catalyst poison may be removed by treating the solvent with a small amount of alkylaluminum before use.
[159]
On the other hand, the polymerization process may be carried out as a continuous polymerization process, for example, a continuous solution polymerization process, a bulk polymerization process, a suspension polymerization process, a slurry polymerization process or an emulsion polymerization process, such as various polymerizations known as polymerization of olefinic monomers. process may be employed.
[160]
Specifically, the polymerization reaction for the production of polyethylene may be performed using one continuous slurry polymerization reactor, a loop slurry reactor, or the like to copolymerize an ethylene monomer and an α-olefin-based monomer as a comonomer. However, according to the method of one embodiment, in order to more effectively control the molecular weight distribution, it is more appropriate to polymerize the olefinic monomer by continuous bulk-slurry polymerization or gas phase polymerization. In particular, the polymerization reaction may proceed as slurry polymerization in a hydrocarbon-based solvent (eg, an aliphatic hydrocarbon-based solvent such as hexane, butane, or pentane). As the first and second transition metal compounds according to the present invention exhibit excellent solubility even in an aliphatic hydrocarbon-based solvent, they are stably dissolved and supplied to the reaction system, so that the polymerization reaction can proceed effectively.
[161]
Specifically, the α-olefin monomer includes 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, 1-aitocene, etc. may be used, and among them, 1-hexene may be used. Accordingly, in the slurry polymerization, ultra-low density polyethylene may be prepared by polymerizing the ethylene and 1-hexene.
[162]
Meanwhile, during the polymerization reaction, the molar ratio of the α-olefin monomer/ethylene monomer in the reactor is 0.25 or more.
[163]
The molar ratio of the monomers introduced into the reactor before the polymerization reaction and the molar ratio of the monomers present in the reactor during the polymerization reaction may vary depending on catalyst reactivity. In the present invention, by controlling the molar ratio of the ethylene monomer and the α-olefin monomer present in the reactor (or remaining) in the polymerization reaction within the above range, the prepared copolymer has the above crystal structure and physical properties, particularly 0.916 g/cm A density of 3 or higher may indicate sufficient stiffness. However, when the molar ratio of the α-olefin monomer/ethylene monomer is less than 0.25, it is difficult to prepare and implement polyethylene having the above-described crystal structure and physical properties. More specifically, the molar ratio of the α-olefin monomer/ethylene monomer in the reactor may be 0.25 or more, or 0.26 or more, and 0.3 or less, or 0.28 or less, or 0.27 or less, in which case the density of the copolymer is 0.916 to 0.920 g/ By maintaining the cm 3 level, better stiffness can be exhibited.
[164]
On the other hand, the molar ratio of the ethylene monomer and the α-olefin monomer in the reactor can be calculated using the gas chromatograph after measuring each concentration. The specific measurement method will be described in detail in the following test examples.
[165]
In addition, the polymerization reaction temperature may be 70 to 200 ℃. If the polymerization reaction temperature is less than 70 °C, there is a fear that the polymerization rate and productivity may decrease, and if it exceeds 200 °C, there is a possibility that a fouling phenomenon in the reactor may occur. Considering the ease and fairness of realizing the physical properties of polyethylene according to the polymerization temperature control, the polymerization reaction may be performed at a temperature of 80°C or higher and 150°C or lower.
[166]
In addition, the pressure during the polymerization reaction may be 20 to 50 bar to secure optimal productivity. Polyethylene can be produced with better efficiency within the above range. More specifically, it may be carried out at a pressure of 20 bar or more and 40 bar or less.
[167]
In addition, during the polymerization reaction, hydrogen gas may be introduced for the purpose of controlling the molecular weight and molecular weight distribution of polyethylene. In this case, 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, polyethylene having the above-described molecular structure and physical properties can be effectively produced.
[168]
The hydrogen gas may be added in an amount of 10 ppm or more, and less than 200 ppm, based on the total weight of the monomer including ethylene and α-olefin.
[169]
When added under the above conditions, the ethylene/α-olefin polymer to be prepared may implement the physical properties in the present invention. If the content of hydrogen gas is less than 10 ppm, the polymerization reaction is not uniformly terminated, making it difficult to produce polyethylene having desired properties, and if it is 200 ppm or more, the termination reaction occurs too quickly, resulting in polyethylene having an excessively low molecular weight. there is a risk of becoming More specifically, the hydrogen gas may be added in an amount of 10 ppm or more, or 15 ppm or more, 180 ppm or less, or 150 ppm or less, or 100 ppm or less, or 50 ppm or less, or 30 ppm or less based on the total weight of the monomer.
[170]
In addition, during the polymerization reaction, trialkylaluminum such as triethylaluminum may be optionally further added.
[171]
When moisture or impurities exist in the polymerization reactor, a part of the catalyst is decomposed. Since the trialkylaluminum acts as a scavenger to catch moisture, impurities or moisture contained in the monomer in advance in the reactor, It is possible to maximize the activity of the catalyst used for production, and as a result, it is possible to more efficiently produce homopolyethylene having excellent physical properties, particularly, a narrow molecular weight distribution. Specifically, in the trialkylaluminum, alkyl is as defined above, specifically C 1-20 alkyl, more specifically C 1-6 straight or branched chain alkylyl such as methyl, ethyl, isobutyl, etc. can The trialkylaluminum (based on 1M) may be added in an amount of 300 ppm or more, or 400 ppm or more, and 600 ppm or less, or 500 ppm or less, based on the total weight of the monomer including ethylene and α-olefin, and the tree in this content range Upon polymerization in the presence of alkylaluminum, homopolyethylene having excellent strength properties can be more easily prepared.
[172]
In addition, an organic solvent may be further used as a reaction medium or a diluent in the polymerization reaction. Such an organic solvent may be used in an amount such that slurry-phase polymerization can be appropriately performed in consideration of the content of the olefinic monomer.
[173]
Polyethylene produced by the manufacturing method as described above may exhibit improved low-temperature sealing properties by increasing the content and molecular weight of the low-crystalline polymer, and may exhibit increased hot-tack sealing properties when used as a packaging film.
[174]
Accordingly, according to another embodiment of the present invention, a film including the above-described polyethylene, more specifically, a film for high-speed packaging is provided.
[175]
The film may be prepared and used according to a conventional method except for containing the above-mentioned polyethylene as a main component.
[176]
[177]
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 thus the content of the present invention is not limited thereto.
[178]

[179]
Synthesis Example 1
[180]
Silica (SP952 manufactured by Grace Davison) was dehydrated and dried under vacuum at a temperature of 200° C. for 12 hours.
[181]
3.0 kg of toluene solution was put into a 20L sus high-pressure reactor, 1000 g of the dried silica (SP952 manufactured by Grace Davison) was added, and then the temperature of the reactor was raised to 40° C. and stirred. After the silica was sufficiently dispersed for 60 minutes, 8 kg of a 10 wt% methylaluminoxane (MAO)/toluene solution was added and stirred at 200 rpm for 12 hours. After raising the reactor temperature to 60°C, 0.01 mmol of the compound represented by Formula 1b was dissolved in a solution state, and after 2 hours of reaction, 0.01 mmol of the compound represented by Formula 2a was dissolved in a solution state, added, and reacted for 2 hours was added Stop stirring and settling for 30 minutes, then decantation the reaction solution. 3.0 kg of hexane was put into the reactor, the hexane slurry was transferred to filter dry, and the hexane solution was filtered. A supported catalyst was prepared by drying at 50° C. under reduced pressure for 4 hours.
[182]
(1b)
[183]
(2a)
[184]
[185]
Synthesis Example 2
[186]
0.14 mol of a Grignard reagent tBu-O-(CH 2 )6MgCl solution was obtained from the reaction between the tBu-O-(CH 2 ) 6 Cl compound and Mg(0) in diethyl ether (Et 2 O) solvent . . MeSiCl 3 compound (24.7 mL, 0.21 mol) was added thereto at -100° C. , stirred at room temperature for 3 hours or more, and the filtered solution was vacuum dried (tBu-O-(CH 2 ) 6 SiMeCl 2 of A compound was obtained (yield: 84%) In a solution of tBu-O-(CH 2 ) 6 SiMeCl 2 (7.7 g, 0.028 mol) dissolved in hexane (50 mL) at -78 ° C. (fluorenyllithium, 4.82 g) ; O-(CH 2) 6 ) A compound of SiMe (9-C 13 H 10 ) was obtained (yield 99%).
[187]
A THF solvent (50 ml) was added thereto, and after reacting with a C 5 H 5 Li (2.0 g, 0.028 mol)/THF (50 ml) solution for 3 hours or more at room temperature , all volatile substances were vacuum dried and extracted with hexane. Thus, the final ligand, (tBu-O-(CH 2 ) 6 )(CH 3 )Si(C 5 H 5 )(9-C 13 H 10 ) in the form of orange oil, was obtained (yield 95%). The structure of the ligand was confirmed through 1H NMR.
[188]
In addition, in (tBu-O-(CH 2 ) 6 )(CH 3 )Si(C 5 H 5 )(9-C 13 H 10 ) (12 g, 0.028 mol)/THF (100 mol) solution at -78 ° C. 2 equivalents of n-BuLi was added and reacted for at least 4 hours while raising to room temperature to form (tBu-O-(CH 2 ) 6 )(CH 3 )Si(C 5 H 5 Li)(9-C 13 H 10 Li) was obtained (yield 81%). In addition, ZrCl 4 at -78 ℃ (1.05 g, 4.50 mmol)/ether (30 mL) of dilithium salt (2.0 g, 4.5 mmol)/ether (30 mL) solution was slowly added to a suspension solution of ether (30 mL) and stirred at room temperature for 3 hours. more reacted. All volatiles were dried in vacuo, and dichloromethane solvent was added to the obtained oily liquid material and filtered off. After vacuum drying the filtered solution, hexane was added to induce a precipitate. The resulting precipitate was washed several times with hexane to form a red solid racemic-(tBu-O-(CH 2 ) 6 )(CH 3 )Si(C 5 H 4 )(9-C 13 H 9 )ZrCl 2 compound ( 3) was obtained (yield 54%).
[189]
Then, in Synthesis Example 1, in the same manner as in Synthesis Example 1, except that the compound (3) synthesized above was used instead of the compound of Formula 2a, compound (1b) and compound (3) were A hybrid supported supported catalyst was prepared.
[190]
[191]

[192]
Example 1
[193]
In the presence of the hybrid supported catalyst prepared above, ethylene-1-hexene was slurry-polymerized under the conditions shown in Table 1 below.
[194]
In this case, the polymerization reactor was a continuous polymerization reactor of an isobutane slurry loop process, the reactor volume was 140L, and the reaction flow rate was about 7 m/s. Gases (ethylene, hydrogen) required for polymerization and 1-hexene as a comonomer were constantly and continuously input, and the individual flow rates were adjusted to suit the target product. The concentrations of all gases and comonomer 1-hexene were confirmed by on-line gas chromatograph. The supported catalyst was introduced into the isobutane slurry, the reactor pressure was maintained at about 40 bar, and the polymerization temperature was carried out at about 85°C.
[195]
[196]
Examples 2 to 4, and Comparative Examples 1 to 4
[197]
An ethylene/1-hexene copolymer was prepared in the same manner as in Example 1, except that the conditions described in Table 1 were changed.
[198]
[199]
Comparative Example 5
[200]
A commercially available ethylene/1-hexene copolymer (Exxon XP8318™, gas phase polymerization) was used.
[201]
[202]
Comparative Example 6
[203]
A commercially available ethylene/1-hexene copolymer (Exxon XP8656ML™, gas phase polymerization) was used.
[204]
[205]
Comparative Example 7
[206]
A commercially obtained ethylene/1-hexene copolymer (Daelim BO1801EN™, gas phase polymerization) was used.
[207]
[Table 1]
Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4
catalyst Synthesis Example 1 Synthesis Example 1 Synthesis Example 1 Synthesis Example 1 Synthesis Example 1 Synthesis Example 1 Synthesis Example 1 Synthesis Example 2
Catalytic Activity*
(kgPE/gCat) 6.0 6.2 6.2 6.4 6.0 6.5 5.8 6.7
polymerization process slurry polymerization slurry polymerization slurry polymerization slurry polymerization slurry polymerization slurry polymerization slurry polymerization slurry polymerization
Polymerization temperature (℃) 85 85 85 85 85 85 85 85
H 2 Dosage (ppm) 15 15 20 50 5 200 15 20
Ethylene input
(kg/h) 25 25 25 25 25 25 25 25
comonomer 1-hexene 1-hexene 1-hexene 1-hexene 1-hexene 1-hexene 1-hexene 1-hexene
Comonomer input (kg/h) 3.0 3.5 3.0 3.0 2.8 3.5 2.5 4.5
Comonomer/ethylene molar ratio** 0.25 0.27 0.25 0.26 0.24 0.26 0.20 0.32
[208]
* Catalytic activity (kgPE/gCat): After measuring the weight of the catalyst (Cat) used in the polymerization reaction of the above Examples or Comparative Examples and the weight of the polymer (PE) prepared from the polymerization reaction, respectively, prepared relative to the weight of the catalyst used The catalyst activity was calculated as the weight ratio of the polymer.
[209]
** Molar ratio of comonomer/ethylene: In the above table, the molar ratio of comonomer/ethylene is the molar ratio of comonomer (1-hexene) to ethylene present in the slurry reactor during the polymerization reaction. Using a gas chromatograph, ethylene and 1-hexene The concentration of each was measured, and the molar ratio was calculated from the result.
[210]
In addition, the concentration of each monomer using the gas chromatograph was measured using gas chromatography (7890B GC) equipped with an Al 2 O 3 KCl column of Agilent Co., which has a length of 50 m and an inner diameter of 0.53 mm, and the carrier gas was 12 mL. High-purity helium flowing at a rate of /min, the inlet temperature was 200 °C, and the injection was performed using the separation mode (10:1).
[211]
[212]
Test Example 1
[213]
The elution temperature (Te) and the content of the low crystalline polymer, i.e., the first quasi-crystalline polymer at 25-30 ° C. of Te, were measured through temperature rising elution fractionation (TREF) analysis, and also through gel permeation chromatography analysis. A number average molecular weight (Mn) and a weight average molecular weight (Mw) were measured, respectively.
[214]
(1) TREF analysis
[215]
PolymerChar's TREF equipment was used, and 1,2,4-trichlorobenzene was used as a solvent in the range of 20°C to 120°C. Specifically, each sample was prepared by dissolving 30 mg of polyethylene of the above Examples or Comparative Examples at 135° C. for 30 minutes in 20 ml of 1,2,4-trichlorobenzene solvent and then stabilizing at 95° C. for 30 minutes. After the prepared sample was introduced into the TREF column, it was cooled to 20° C. at a cooling rate of 0.5° C./min, and maintained for 2 minutes. Then, while heating at a constant temperature increase rate of 1°C/min from 20°C to 120°C, the solvent, 1,2,4-trichlorobenzene, was flowed through the column at a flow rate of 0.5 mL/min to measure the concentration of eluted polyethylene.
[216]
From the TREF elution curve obtained as a result, the elution temperature (Te) of the polyethylene was confirmed, and the content of the first quasi-crystalline polymer at Te 25-30°C was calculated based on the total weight of the polyethylene (weight %).
[217]
(2) GPC analysis
[218]
Gel permeation chromatography (GPC) was used to measure the number average molecular weight (Mn) and weight average molecular weight (Mw) of the low crystalline polymer, that is, the semicrystalline polymer at 25 to 30° C. of Te.
[219]
Measurements were made using a Polymer Laboratories PLgel MIX-B 300 mm long column and a Waters PL-GPC220 instrument. At this time, the evaluation temperature was 160 ℃, 1,2,4-trichlorobenzene was used as a solvent, and the flow rate was measured at a rate of 1 mL/min. Samples were prepared at a concentration of 10 mg/10 mL and then supplied in an amount of 200 μL. Using a calibration curve formed using polystyrene standards, the values ​​of Mw and Mn were derived. The molecular weight (g/mol) of the polystyrene standard was 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000.
[220]
The above analysis results are shown in Table 2 and FIGS. 1 to 7 below.
[221]
1 to 4 are graphs showing analysis results according to TREF for polyethylene prepared in Example 1 and Comparative Examples 5 to 7, respectively, and FIGS. 5 to 7 are each in Example 1 and Comparative Examples 5 and 6 It is a graph showing the results of GPC analysis of the first semi-crystalline polymer in the prepared polyethylene.
[222]
[Table 2]
Example comparative example
One 2 3 4 One 2 3 4 5 6 7
Te1 (℃) 28.5 28.1 28.0 28.1 28.0 28.0 28.1 28.1 28.1 28.1 25.1
Te2 (℃) 62.5 62.0 62.6 62.2 63.5 60.2 62.3 - 68.1 67.5 73.9
Te3 (℃) 93.8 93.0 93.7 93.5 94.0 92.8 93.0 87.4 95.8 95.7 85.0
Te4 (℃) - - - - - - - - - - 95.8
Te first quasi-crystalline polymer at 25-30 °C content
(wt%) 12.0 13.0 12.2 12.5 8.0 9.5 6.5 1.2 3.9 4.9 2.1
Mn (g/mol) 70,000 73,000 70,000 70,000 300 305 300 300 302 315 295
Mw (g/mol) 205,000 206,000 204,000 202,000 320 310 310 310 325 329 309
Mw/Mn 2.93 2.95 2.92 2.90 1.07 1.02 1.03 1.03 1.08 1.04 1.05
[223]
Test Example 2
[224]
The physical properties of the ethylene/α-olefin copolymers prepared in Examples and Comparative Examples were measured by the following method, and the results are shown in Table 3 and FIGS. 8 and 11 below.
[225]
(1) Melt index (MI) (g/10min): Melt index (MI2.16) was measured at 190°C under a load of 2.16 kg according to ASTM D 1238, and the weight of the polymer melted for 10 minutes (g) ) is shown.
[226]
(2) Density (g/cm 3 ): Measured according to ASTM D1505.
[227]
(3) Melting temperature (Tm), crystallization temperature (Tc), and ΔH (0 to 130° C.): Tm, Tc and ΔH were measured using a Differential Scanning Calorimeter (DSC), respectively.
[228]
Specifically, as a differential scanning calorimeter (DSC), it was measured using a DSC 2920 (TA instrument). The copolymer in Examples or Comparative Examples was heated to 190° C. and maintained for 5 minutes, and then lowered to -50° C. and then the temperature was increased again. At this time, the rate of rise and fall of the temperature was controlled at 10 °C/min, respectively. The melting temperature (Tm) was taken as the maximum point of the endothermic peak measured in the section where the second temperature was increased.
[229]
In addition, the crystallization temperature (Tc) was performed in the same manner as in the measurement of the melting temperature, and the maximum point of the exothermic peak was defined as the crystallization temperature from the curve appearing while decreasing the temperature.
[230]
In addition, ΔH is an integral value for a peak observed in a temperature range of 0 to 130°C in the graph obtained by performing DSC in a temperature range of -50 to 190°C in the same manner as in the measurement of the melting temperature. , the heat of fusion value was confirmed (unit: J/g).
[231]
(4) number average molecular weight (Mn), weight average molecular weight (Mw), molecular weight distribution (MWD): using gel permeation chromatography (GPC) to measure number average molecular weight (Mn) and weight average molecular weight (Mw), respectively , the weight average molecular weight was divided by the number average molecular weight to calculate the molecular weight distribution (Mw/Mn).
[232]
Specifically, it was measured using a Polymer Laboratories PLgel MIX-B 300 mm long column and a Waters PL-GPC220 instrument. At this time, the evaluation temperature was 160° C., 1,2,4-trichlorobenzene was used as a solvent, and the flow rate was 1 mL/min. Polymer samples were prepared at a concentration of 10 mg/10 mL and then fed in an amount of 200 μL. The values ​​of Mw and Mn were derived using a calibration curve formed using polystyrene standards. The molecular weight (g/mol) of the polystyrene standard was 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000.
[233]
(5) Average number of SCBs: Through gel permeation chromatography (GPC-FTIR) analysis combined with Fourier transform infrared spectroscopy, the number of SCBs in the copolymer and the number of SCBs in the polymer region having log Mw of 5.5 or more were calculated and averaged, respectively It is expressed as a value.
[234]
Specifically, each copolymer prepared in Examples and Comparative Examples was analyzed by gel permeation chromatography (GPC) in the same manner as in 4) above, and the log value (log Mw) of the weight average molecular weight (Mw) was x A molecular weight distribution curve of the polymer chains constituting the copolymer was derived with the axis as the axis and the molecular weight distribution (dw_dlogM) with respect to the log value as the y axis.
[235]
Then, each copolymer was analyzed by FT-IR to derive a distribution curve of the number of SCBs per 1000 carbons (right y-axis; SCB per 1000TC) according to the weight average molecular weight (x-axis) of the polymer chains.
[236]
From these derivation results, the number of SCBs per 1000 carbons in the polymer and the number of SCBs per 1000 carbons in the copolymer in the polymer region having a log Mw of 5.5 or more were respectively calculated and expressed as average values.
[237]
[Table 3]
Example comparative example
One 2 3 4 One 2 3 4 5 6 7
Density (g/cm 3 ) 0.918 0.916 0.918 0.918 0.918 0.918 0.921 0.918 0.918 0.916 0.918
MI (g/10min) 1.0 1.0 1.5 2.0 0.4 10.5 1.0 1.0 1.0 0.5 1.0
Tm (℃) 121.5 120.0 120.5 120.2 122.5 119.5 122.0 118.0 122.1 122.7 122.3
Tc (℃) 102.1 101.5 102.0 101.7 105.1 100.0 102.0 105.0 107.4 105.8 63.2/106.4
ΔH(0~130℃)(J/g) 115.0 105.0 112.0 110.0 118.5 114.0 119.5 114.0 111.9 99.2 141.2
Mn
(g/mol) 43,000 44,000 40,000 38,000 52,000 16,000 41,000 42,000 32,000 34,000 29,000
Mw
(g/mol) 112,000 114,000 110,000 107,000 152,000 48,000 111,000 100,000 110,000 131,000 99,000
MWD 2.65 2.70 2.65 2.60 2.70 2.80 2.75 2.52 3.41 3.82 3.41
Average number of SCBs (#1000C) 20.0 21.5 20.5 20.7 18.5 19.0 16.5 17.0 20.4 21.7 17.5
Average number of SCBs in the polymer region of log Mw 5.5 or higher (#1000C) 36.5 38.0 36.7 37.0 32.5 34.0 32.5 11.5 27.4 32.5 26.1
[238]
8 to 11 are graphs showing the SCB content according to the polyethylene molecular weight obtained as a result of GPC-FTIR analysis of the polyethylene prepared in Example 1 and Comparative Examples 5 to 7, respectively.
[239]
8 to 11, in the case of Example 1, it can be confirmed that the SCB content in the ultra-high molecular weight region is high, and as a result, the low crystal content is high, and the low crystal has a high molecular weight.
[240]
From the above experimental results, in the case of Examples 1 and 2, it can be confirmed that the SCB content is high in the ultra-high molecular weight region compared to the copolymers of Comparative Examples 4, 5 and 7 having the same level of MI and density, From this, it can be expected to exhibit excellent low-temperature sealing strength properties.
[241]
[242]
Test Example 3
[243]
For the ethylene/1-hexene copolymer prepared in Examples and Comparative Examples, according to ASTM F1921 measurement using J & B hot tack tester (Hot tacker 4000), sealing initiation temperature (SIT) and low temperature sealing Hot-tack strength (N/25mm) was measured as the strength, and the results are shown in Table 4 and FIG. 12 .
[244]

[245]
Pressure: 0.275 N/mm 2
[246]
Sealing time: 0.5 sec
[247]
Cooling time: 0.1 sec
[248]
Peeling speed: 200 mm/s
[249]
Width: 25mm
[250]
Thickness: 50~60㎛
[251]
[Table 4]
Example comparative example
One 2 3 4 One 2 3 4 5 6 7
SIT(℃), 2N 90.0 87.0 89.0 87.0 97.0 95.0 100.1 115.0 107.5 98.0 120.0
Hot-tack Strength (N/25mm) 90℃ 2.0 2.5 2.1 2.5 - - - - - - -
95℃ 3.0 3.2 3.0 3.0 1.5 2.0 - - - 1.5 -
100℃ 3.2 3.8 3.1 3.3 2.3 2.3 2.0 - 1.1 2.6 -
[252]
In Table 4, "-" means not measured.
[253]
12 is a graph showing the results of measuring the low-temperature sealing strength of the polyethylene prepared in Example 1 and Comparative Examples 5 to 7.
[254]
As a result of the experiment, in the case of Examples 1 and 2, the sealing initiation temperature (SIT) in the 2N condition was as low as 90° C. or less, and high sealing strength was exhibited at a wide melting temperature, as compared with Comparative Examples.
Claims
[Claim 1]
It contains an ethylene repeat unit and an α-olefin repeat unit, and has a density of 0.916 g/cm 3 or more measured according to ASTM D1505, and, when analyzed by temperature rise elution fractionation, the first to three elution temperatures of Te1, Te2, and Te3 respectively corresponding to the elution temperatures of the third quasi-crystalline polymer, wherein Te2 has a lower temperature than Te3 and a higher temperature than Te1, wherein Te1 is 25 to 30°C, and the first The monocrystalline polymer has a weight average molecular weight of 200,000 g/mol or more, and is contained in an amount of 5% by weight or more based on the total weight of polyethylene.
[Claim 2]
The polyethylene according to claim 1, wherein the first semi-crystalline polymer has a weight average molecular weight of 200,000 to 500,000 g/mol, and is included in an amount of 10 to 20% by weight based on the total weight of the polyethylene.
[Claim 3]
According to claim 1, wherein Te2 is 40 to 65 ℃, Te3 is 80 to 100 ℃, polyethylene.
[Claim 4]
According to claim 1, wherein the polyethylene, when analyzed by gel permeation chromatography combined with Fourier transform infrared spectroscopy, the average number of short-chain branches per 1000 carbons in the polymer in the polymer region having a log Mw of 5.5 or more is 35 or more, polyethylene .
[Claim 5]
The polyethylene according to claim 1, wherein the average number of short chain branches per 1000 carbons in the polyethylene is from 18 to 22.
[Claim 6]
The polyethylene according to claim 1, wherein the polyethylene has a molecular weight distribution of 3 or less.
[Claim 7]
The polyethylene according to claim 1, wherein the polyethylene has a number average molecular weight of 35,000 to 50,000 g/mol, and a weight average molecular weight of 100,000 to 130,000 g/mol.
[Claim 8]
The polyethylene according to claim 1, wherein the polyethylene satisfies at least one of the following conditions (i) to (v): (i) Melting measured at 190° C. and a load of 2.16 kg according to ASTM D-1238 Index: 0.8 to 2 g/10min, (ii) Melting temperature: 120 to 125°C, (iii) Crystallization temperature: 100 to 110°C, (iv) Heat of fusion in the temperature range from 0 to 130°C: 99.5 to 120 J/g , and (v) according to ASTM F1921 measurement method, the sealing initiation temperature under the 2N condition is 95° C. or less, and the hot tack strength at 100° C. is 3.0 N or more.
[Claim 9]
The method of claim 1, wherein the α-olefin is 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, Polyethylene comprising 1-hexadecene or mixtures thereof.
[Claim 10]
10. Polyethylene according to claim 9, wherein the α-olefin is 1-hexene.
[Claim 11]
In the presence of a catalyst composition comprising a first transition metal compound represented by the following Chemical Formula 1 and a second transition metal compound represented by the following Chemical Formula 2, hydrogen gas is introduced into the reactor, and an ethylene monomer and an α-olefinic monomer having 3 or more carbon atoms a polymerization reaction, wherein the hydrogen gas is introduced in an amount of 10 ppm or more and less than 200 ppm based on the total weight of the monomer including the ethylene monomer and the α-olefinic monomer having 3 or more carbon atoms, and during the polymerization reaction, the reactor The method for producing polyethylene according to claim 1, wherein the molar ratio of the α-olefin monomer to the ethylene monomer present therein is 0.25 or more: [Formula 1] In Formula 1, R 1 and R 2 are each independently hydrogen, halogen, C 1-20 alkyl, C 2-20 alkenyl, C 1-20 alkoxy, C 2-20 alkoxyalkyl, C 6-20 aryl, C 7-20 alkylaryl, or C 7-20 arylalkyl, X 1 and X 2are each independently halogen or C 1-20 alkyl, [Formula 2] In Formula 2, R 3 and R 4 are each independently hydrogen, halogen, C 1-20 alkyl, C 2-20 alkenyl, C 1 -20 alkoxy, C 2-20 alkoxyalkyl, C 6-20 aryl, C 7-20 alkylaryl, or C 7-20 arylalkyl, and X 3 and X 4 are each independently halogen or C 1-20 alkyl .
[Claim 12]
12. The method of claim 11, wherein R 1 and R 2 are each independently C 4-12 straight-chain alkyl; or C 5-9 straight chain alkyl substituted with tert-butoxy .
[Claim 13]
The method of claim 11, wherein R 3 and R 4 are each independently C 3-12 straight-chain alkyl, and X 3 and X 4 are each independently C 1-4 straight-chain alkyl.
[Claim 14]
The method according to claim 11, wherein the first transition metal compound is a compound represented by the following Chemical Formula 1a or Chemical Formula 1b: [Formula 1a] [Formula 1b] .
[Claim 15]
The method according to claim 11, wherein the second transition metal compound is a compound represented by the following Chemical Formula 2a or Chemical Formula 2b: [Formula 2a] [Formula 2b] .
[Claim 16]
The method of claim 11 , wherein the first transition metal compound and the second transition metal compound are included in a molar ratio of 1:0.3 to 1:3.5.
[Claim 17]
The method according to claim 11, wherein the catalyst composition further comprises at least one of a carrier and a cocatalyst.
[Claim 18]
A film comprising the polyethylene according to any one of claims 1 to 10.