Specification
Title of Invention: Ethylene/alpha-olefin copolymer with excellent electrical insulation properties
technical field
[One]
Cross-Citation with Related Applications
[2]
This application claims the benefit of priority based on the Korean Patent Application 2020-0046026 dated April 16, 2020, and all contents disclosed in the documents of the Korean patent applications are incorporated as a part of this specification.
[3]
[4]
technical field
[5]
The present invention relates to an ethylene/alpha-olefin copolymer having high volume resistance and light transmittance, and a method for preparing the same.
[6]
background
[7]
As global environmental problems and energy problems are becoming more and more serious, solar cells are attracting attention as a means of generating energy that is clean and not depleted. When solar cells are used outdoors, such as on the roof of a building, it is common to use them in the form of modules. Cell encapsulant/crystalline solar cell element crystalline solar cell element/solar cell sealing material/solar cell module protective sheet (rear side protective member) is laminated in this order and manufactured. On the other hand, in order to obtain a thin-film solar cell module, the thin-film solar cell element/solar cell sealing material/solar cell module protective sheet (rear side protective member) is laminated in order and manufactured.
[8]
As the above-mentioned solar cell sealing material, an ethylene/vinyl acetate copolymer, an ethylene/alpha-olefin copolymer, or the like is generally used. Moreover, since long-term weather resistance is calculated|required in a solar cell sealing material, the light stabilizer is normally contained as an additive. Moreover, in consideration of the adhesiveness of the front surface side transparent protective member thru|or the back surface side protective member represented by glass, a silane coupling agent is normally contained in a solar cell sealing material.
[9]
Specifically, an ethylene/vinyl acetate copolymer (EVA) sheet has been widely used because of its excellent transparency, flexibility, and adhesion. Ethylene/vinyl acetate copolymer (EVA) films are widely used because of their excellent transparency, flexibility, and adhesion. However, when the EVA composition is used as a constituent material of a solar cell sealing material, there is a concern that components such as acetic acid gas generated by decomposition of EVA may affect the solar cell element.
[10]
Moreover, with the recent spread of photovoltaic power generation, large-scale power generation systems, such as mega solar, are progressing, and there is also a movement to increase the system voltage for the purpose of lowering transmission loss or the like. As the system voltage rises, the potential difference between the frame and the cell increases in the solar cell module. That is, the frame of the solar cell module is generally grounded, and when the system voltage of the solar cell array becomes 600V to 1000V, in the module with the highest voltage, the potential difference between the frame and the cell becomes 600V to 1000V of the system voltage as it is, and the high voltage In this authorized state, power generation will be maintained during the day. In addition, compared to the sealing material, the glass has a low electrical resistance, and a high voltage is generated between the glass and the cell through the frame. That is, under the power generation situation during the day, in the series-connected modules, the potential difference between the cell and the module and between the cell and the glass surface increases sequentially on the ground side, and the potential difference of the high voltage of the system voltage is maintained at the largest place. Among the solar cell modules used in this state, an example of a module using a crystalline-based power generation device in which an output is greatly reduced and a PID (abbreviation for Potential Induced Degradation) phenomenon occurs is also reported. Therefore, in order to solve this problem, a higher volume resistivity is calculated|required for the solar cell sealing material which is in direct contact with a solar cell element.
[11]
Volume resistivity or resistivity (ρ), known as electrical resistance, is defined as the electrical resistance between opposite sides of 1 m3 of a material, this volume resistance being reproducible within a predetermined range in all of the above applications and being a permanent molded product It is important to obtain In the field of electrical insulation materials for high-voltage power cables, high-pressure processed low-density polyethylene, cross-linked polyethylene, and the like have been widely used due to their excellent electrical properties. One of the difficulties with high voltage power cables is the power loss that occurs during power transmission. Reduction of power loss is the most important requirement to be satisfied. Reduction of power loss can be achieved by enhancing the high voltage properties of the insulating material, in particular the volume resistance. However, the insulating material for a power cable is heated to a high temperature (about 90° C.) by heat generated by passing an electric current in the vicinity of the inner conductor, but is maintained at room temperature in the vicinity of the outer conductor. Conventional polyethylene shows a significant drop in volume resistance as the temperature rises. Therefore, polyethylene exhibits a significant drop in volume resistance near the inner conductor through current flow.
[12]
As such, it is still necessary to develop an ethylene/alpha-olefin copolymer that has excellent volume resistance and can be usefully used as a material requiring high insulation properties such as solar cell encapsulants.
[13]
[14]
[Prior art literature]
[15]
[Patent Literature]
[16]
Korean Patent Publication 2018-0063669
[17]
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[18]
An object of the present invention is to provide an ethylene/alpha-olefin copolymer that can be usefully used as an insulating material due to high volume resistance by showing a wide crystallinity distribution while maintaining a narrow molecular weight distribution, and a method for preparing the same.
[19]
means of solving the problem
[20]
In order to solve the above problems, the present invention provides an ethylene/alpha-olefin copolymer satisfying the following conditions (a) to (d).
[21]
(a) a density of 0.85 to 0.89 g/cc;
[22]
(b) the molecular weight distribution is 1.5 to 2.3;
[23]
(c) the melting temperature is 85° C. or less; and,
[24]
(d) the free volume proportional constant (C 2) derived from the following equations 1 and 2 is 600 or less;
[25]
[Equation 1]
[26]

[27]
In Equation 1 above,
[28]
η O(T) is the viscosity (Pa·s) of the copolymer measured by ARES-G2 (Advanced Rheometric Expansion System) at any temperature T(K),
[29]
η 0 (T r) is the viscosity (Pa s) of the copolymer measured by ARES-G2 at the reference temperature T r (K),
[30]
a T is a shift factor of an arbitrary temperature T(K) with respect to the reference temperature T r(K), and is obtained from Equation 1 above,
[31]
[Equation 2]
[32]

[33]
In Equation 2 above,
[34]
C 1 is an inverse constant of free volume,
[35]
C 2 is the free volume proportionality constant (K),
[36]
C 1 and C 2 are intrinsic constants of the ethylene/alpha-olefin copolymer, and are obtained from Equation 2 above.
[37]
Effects of the Invention
[38]
The ethylene/alpha-olefin copolymer of the present invention has a high crystallinity distribution and thus has a small free volume, and thus exhibits excellent volume resistance and light transmittance and excellent electrical insulation, so it is widely used in various applications in the field of electrical and electronic industries. It is possible.
[39]
Modes for carrying out the invention
[40]
Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.
[41]
The terms or words used in the description and claims of the present invention should not be construed as being limited to their ordinary or dictionary meanings, and the inventor appropriately defines the concept of the term in order to best describe his invention. Based on the principle that can be done, it should be interpreted as meaning and concept consistent with the technical idea of ​​the present invention.
[42]
[43]
[Ethylene/alpha-olefin copolymer]
[44]
The ethylene/alpha-olefin copolymer of the present invention is characterized in that the following conditions (a) to (d) are satisfied.
[45]
(a) a density of 0.85 to 0.89 g/cc;
[46]
(b) the molecular weight distribution is 1.5 to 2.3;
[47]
(c) the melting temperature is 85° C. or less; and,
[48]
(d) the free volume proportional constant (C 2) derived from the following equations 1 and 2 is 600 or less;
[49]
[Equation 1]
[50]

[51]
In Equation 1 above,
[52]
η O(T) is the viscosity (Pa·s) of the copolymer measured by ARES-G2 (Advanced Rheometric Expansion System) at any temperature T(K),
[53]
η 0 (T r) is the viscosity (Pa s) of the copolymer measured by ARES-G2 at the reference temperature T r (K),
[54]
a T is a shift factor of an arbitrary temperature T(K) with respect to the reference temperature T r(K), and is obtained from Equation 1 above,
[55]
[Equation 2]
[56]

[57]
In Equation 2 above,
[58]
C 1 is an inverse constant of free volume,
[59]
C 2 is the free volume proportionality constant (K),
[60]
C 1 and C 2 are intrinsic constants of the ethylene/alpha-olefin copolymer, and are obtained from Equation 2 above.
[61]
[62]
The present invention relates to an ethylene/alpha-olefin copolymer exhibiting excellent electrical insulation properties due to high volume resistance. Specifically, the ethylene/alpha-olefin copolymer of the present invention is used as a catalyst by mixing the transition metal compound represented by Chemical Formula 1 and Chemical Formula 2 during preparation. Since it is difficult to introduce an alpha-olefin-based monomer, there is a tendency to produce a high-density copolymer, and since a large amount of alpha-olefin can be introduced into the transition metal compound represented by Formula 2, the polymer (elastomer) in the ultra-low-density region is also can be prepared, the two transition metal compounds have different copolymerizability of incorporating an alpha-olefinic monomer when used alone, respectively.
[63]
The ethylene/alpha-olefin copolymer of the present invention prepared by using a mixed composition thereof as a catalyst has both a low-density region in which a large amount of alpha-olefinic monomer is mixed and a high-density region in which a small amount of alpha-olefin-based monomer is incorporated. As a copolymer, it has a wide crystallinity distribution and contains a small amount of free volume, and thus has excellent electrical insulation properties due to low charge mobility.
[64]
[65]
The ethylene/alpha-olefin copolymer of the present invention is a low density polymer having a density in the range of 0.85 to 0.89 g/cc, wherein the density is ASTM DIt can mean density according to -792. More specifically, the density may be 0.850 g/cc or more, 0.860 g/cc or more, 0.870 g/cc or more, 0.875 g/cc or more, and 0.890 g/cc or less, 0.880 g/cc or less.
[66]
If the density is out of the above range, there may be a problem in that the volume resistance or light transmittance of the ethylene/alpha-olefin copolymer is lowered.
[67]
In general, the density of the ethylene/alpha-olefin copolymer is affected by the type and content of the monomer used during polymerization, the degree of polymerization, and the like, and in the case of the copolymer, it is greatly affected by the content of the comonomer. In this case, as the content of the comonomer increases, a low-density ethylene/alpha-olefin copolymer can be prepared, and the content of the comonomer can be introduced into the copolymer may depend on the inherent copolymerizability of the catalyst.
[68]
The ethylene/alpha-olefin copolymer of the present invention is a copolymer prepared by using the compound represented by Chemical Formulas 1 and 2 as a catalyst, and exhibits a low density as described above, and, as a result, can exhibit excellent processability.
[69]
[70]
The ethylene/alpha-olefin copolymer of the present invention has a narrow molecular weight distribution (MWD) ranging from 1.5 to 2.3. More specifically, the molecular weight distribution may be 1.50 or more, 1.80 or more, or 1.90 or more, and may be 2.30 or less, 2.20 or less, 2.15 or less, or 2.00 or less.
[71]
In general, when two or more kinds of monomers are polymerized, the molecular weight distribution increases, and as a result, impact strength and mechanical properties are reduced, and there is a possibility that a blocking phenomenon may occur. In particular, since the polymerizability of the monomer is different for each catalyst, the molecular weight of the final polymer is affected depending on the type of catalyst. There is a problem that the molecular weight distribution also becomes wider.
[72]
In order to narrow the molecular weight distribution in order to prevent a decrease in the crosslinking characteristics, impact strength, mechanical properties, etc. of the copolymer, an appropriate amount of hydrogen is added during the polymerization reaction to arbitrarily cause a beta-hydride elimination reaction from the polymer chain. It is possible to prevent and induce a uniform termination reaction by adding hydrogen. In this case, since the weight average molecular weight and melt index of the copolymer tend to decrease according to the hydrogen input, the catalyst structure is dependent on the weight average molecular weight and melt index. It is necessary to determine the appropriate type of catalyst and the amount of hydrogen input within the range that can take both the unique properties of the catalyst and the effect of reducing the molecular weight distribution according to the hydrogen input.
[73]
In consideration of the above points, in the present invention, as described later, a transition metal compound represented by Formula 1 and a transition metal compound represented by Formula 2 were mixed and used as a catalyst, so that while having a narrow molecular weight distribution within the above-described range, other An excellent ethylene/alpha-olefin copolymer that satisfies all physical properties can be prepared.
[74]
In addition, the ethylene/alpha-olefin copolymer of the present invention may have a weight average molecular weight (Mw) of 40,000 to 150,000 g/mol. Specifically, the weight average molecular weight may be 45,000 g/mol or more, 49,000 g/mol or more, or 52,000 g/mol or more, and 130,000 g/mol or less, 90,000 g/mol or less, or 65,000 g/mol or less.
[75]
The weight average molecular weight (Mw) and the number average molecular weight (Mn) are polystyrene equivalent molecular weights analyzed by gel permeation chromatography (GPC), and the molecular weight distribution can be calculated from a ratio of Mw/Mn.
[76]
[77]
The ethylene/alpha-olefin copolymer of the present invention has a Melting Temperature (Tm) of 85° C. or less. Specifically, the melting temperature may be 50 °C or higher, 55 °C or higher, or 60 °C or higher, and 85 °C or lower, 70 °C or lower, 68 °C or lower, or 65 °C or lower.
[78]
In general, when the crystallinity distribution of the copolymer is high, the high crystal content increases, which may cause a decrease in light transmittance and crosslinking properties, whereas the copolymer of the present invention has a wide crystallinity distribution and thus has a high volume resistance and low There is an advantage that light transmittance and crosslinking properties are not lowered by having a melting temperature.
[79]
At the same time, the crystallization temperature (Crystallization Temperature, Tc) of the ethylene / alpha-olefin copolymer of the present invention may be 70 ℃ or less, 60 ℃ or less, 50 ℃ or less, or 49 ℃ or less, 30 ℃ or more, 35 ℃ or more, It may be 40 °C or higher, 45 °C or higher.
[80]
The melting temperature and crystallization temperature may be measured using a Differential Scanning Calorimeter (DSC). Specifically, the copolymer is heated to 150° C. and maintained for 5 minutes, then lowered to -100° 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. can do.
[81]
[82]
In the ethylene/alpha-olefin copolymer of the present invention, C 2, which is a free volume proportional constant derived from Equations 1 to 3, is 600 or less, where C 2 is an absolute temperature (K) in units. More specifically, the free volume proportionality constant (C 2) may be 600 or less, 550 or less, or 500 or less, and may be 300 or more.
[83]
Although the physical/chemical properties of polymers such as ethylene/alpha-olefin copolymers appear to be fixed, they are actually time- and temperature-dependent. When horizontally parallel shifted based on , all curves are superimposed and a single curve is derived, indicating time-temperature overlap.
[84]
At this time, with respect to the linear viscoelasticity data of the copolymer measured at various temperatures, the physical property data of an arbitrary temperature T (Kelvin, K) and a reference temperature T r (Kelvin, K) holds the relationship of Equation 1 below. In Equation 1, η O(T) is the viscosity (Pa s) of the copolymer measured by ARES-G2 at any temperature T(K), and η 0(T r) is the viscosity at a reference temperature T r(K). It is the viscosity (Pa·s) of the copolymer measured by ARES-G2. From this, according to Equation 1 below, the shift factor of an arbitrary temperature T(K) with respect to the reference temperature T r(K) The factor that shifts the phase of the graph) can be obtained, which shows the temperature dependence.
[85]
[Equation 1]
[86]

[87]
In addition, it has been found that the transfer factor (a T), which makes the physical property data at all temperatures overlap with one curve, has the following mathematical form, which is called the WLF equation (Williams-Landel-Ferry equation).
[88]
[Equation 2]
[89]

[90]
In Equation 2, C 1 is a free volume inverse proportional constant, C 2 is a free volume proportional constant (K), and C 1 and C 2 are intrinsic constants of the ethylene/alpha-olefin copolymer, which are obtained from Equation 2 above.
[91]
In the present invention, C 1 may be a value of 2 or more, 3 or more, 7 or less, and 5 or less, but is not limited thereto.
[92]
More specifically, in the present invention, the process of obtaining the C 2 value may be performed by using TA's ARES-G2 (Advanced Rheometric Expansion System) as a measuring device. Specifically, the sample of the ethylene/alpha-olefin copolymer was prepared as a disk-shaped disk specimen having a diameter of 25 mm and a thickness of 1 mm. For geometry, a parallel plate (flat shape) was used, and Equation 1 was calculated using the methods 1) and 2) below.
[93]
1) Frequency Sweep at 5 specific temperatures
[94]
Frequency sweep measurements were made at 5 specific temperatures selected at intervals of 10 °C, in a temperature range lower than the Tg + 200 °C of the ethylene/alpha-olefin copolymer. In the present invention, measured at 10°C intervals at a temperature of 110-150°C (Strain 0.5-3%, Frequency 0.1-500rad/s)
[95]
2) Derivation of Master Curve
[96]
A master curve is derived by setting the reference temperature T r (reference temperature) to 130°C, and shifting the measurement result of step 1) to 130°C
[97]
3) Derive the value of C 2
[98]
Obtain the shift factor (aT) value of the WLF equation and substitute it into equation 2 to derive the value of C 2
[99]
[Equation 3]
[100]

[101]
As in Equation 3, the C 2 value is proportional to the free volume (f 0), and a small C 2 means that the free volume in the copolymer is small, where α f is ethylene/alpha-olefin. It means the coefficient of thermal expansion of the copolymer.
[102]
[103]
In addition, the ethylene/alpha-olefin copolymer may have a melt index (Melt Index, MI, 190°C, 2.16 kg load condition) in the range of 0.1 to 50 dg/min. More specifically, the melt index may be 1 dg/min or more, 1.5 dg/min or more, 3 dg/min or more, or 4 dg/min or more, and 50 dg/min or less, 30 dg/min or less, 20 dg/min or more. min or less, or 10 dg/min or less.
[104]
In addition, the ethylene / alpha-olefin copolymer has a melt flow index (MFRR, Melt Flow) value that is a melt index (MI 10, 190 ° C, 10 kg load condition) for a melt index (MI 2.16, 190 ° C., 2.16 kg load condition) Rate Ratio, MI 10/MI 2.16) is less than 8.0, less than 7.0or 6.5 or less, or 6.3 or less, 5.0 or more, or 5.5 or more, or 6.0 or more.
[105]
The melt flow index is an indicator of the degree of long chain branching of the copolymer, and the ethylene/alpha-olefin copolymer of the present invention satisfies the melt flow index along with the above-described physical properties, so that it is suitable for a solar cell encapsulant composition, etc. can be applied.
[106]
[107]
The ethylene/alpha-olefin copolymer of the present invention is prepared by copolymerizing ethylene and an alpha-olefin-based monomer. In this case, the alpha-olefin, which means a portion derived from the alpha-olefin-based monomer in the copolymer, is C4 to C20. of alpha-olefins, specifically propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene , 1-tetradecene, 1-hexadecene, or 1-eicosene, and the like may be used alone or as a mixture of two or more thereof.
[108]
Among them, the alpha-olefin may be 1-butene, 1-hexene, or 1-octene, and preferably 1-butene, 1-hexene, or a combination thereof.
[109]
In addition, the content of the alpha-olefin in the ethylene/alpha-olefin copolymer may be appropriately selected within the range satisfying the above-described physical property requirements, and specifically, more than 0 to 99 mol% or less, or 10 to 50 mol% may be, but is not limited thereto.
[110]
[111]
[Method for producing ethylene/alpha-olefin copolymer]
[112]
The method for preparing an ethylene/alpha-olefin copolymer of the present invention comprises the steps of polymerizing ethylene and an alpha-olefinic monomer in the presence of a catalyst composition comprising a transition metal compound represented by the following Chemical Formulas 1 and 2; characterized in that
[113]
[Formula 1]
[114]

[115]
In Formula 1,
[116]
R 1 is hydrogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; arylalkoxy having 7 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; or arylalkyl having 7 to 20 carbon atoms,
[117]
R 2 and R 3 are each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; alkylamido having 1 to 20 carbon atoms; or arylamido having 6 to 20 carbon atoms,
[118]
R 4 and R 5 are each independently hydrogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; or alkenyl having 2 to 20 carbon atoms,
[119]
R 6 to R 9 are each independently hydrogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; or alkenyl having 2 to 20 carbon atoms,
[120]
Two or more adjacent to each other among R 6 to R 9 may be connected to each other to form a ring,
[121]
Q 1 is Si, C, N, P or S;
[122]
M 1 is Ti, Hf or Zr,
[123]
X 1 and X 2 are each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; alkylamino having 1 to 20 carbon atoms; or arylamino having 6 to 20 carbon atoms;
[124]
[Formula 2]
[125]

[126]
In Formula 2,
[127]
R 10 is hydrogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; arylalkoxy having 7 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; or arylalkyl having 7 to 20 carbon atoms,
[128]
R 11a to R 11e are each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; or aryl having 6 to 20 carbon atoms,
[129]
R 12 is hydrogen; halogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; alkylamido having 1 to 20 carbon atoms; or arylamido having 6 to 20 carbon atoms,
[130]
R 13 and R 14 are each independently hydrogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; or alkenyl having 2 to 20 carbon atoms,
[131]
R 15 to R 18 are each independently hydrogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; or alkenyl having 2 to 20 carbon atoms,
[132]
Two or more adjacent to each other among R 15 to R 18 may be connected to each other to form a ring,
[133]
Q 2 is Si, C, N, P or S;
[134]
M 2 is Ti, Hf or Zr,
[135]
X 3 and X 4 are each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; alkylamino having 1 to 20 carbon atoms; or arylamino having 6 to 20 carbon atoms.
[136]
[137]
Specifically, in Formula 1, R 1 is hydrogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; arylalkoxy having 7 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; or arylalkyl having 7 to 20 carbon atoms, more specifically, R 1 is methyl, ethyl, propyl, butyl, isobutyl, tibutyl, isopropyl, cyclohexyl, benzyl, phenyl, methoxyphenyl, ethoxyphenyl, fluorine phenyl, bromophenyl, chlorophenyl, dimethylphenyl or diethylphenyl.
[138]
Specifically, in Formula 1, R 2 and R 3 are each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; alkylamido having 1 to 20 carbon atoms; or arylamido having 6 to 20 carbon atoms, and more specifically, R 2 and R 3 are each independently hydrogen; alkyl having 1 to 20 carbon atoms; Or it may be an arylalkyl having 7 to 20 carbon atoms.
[139]
Specifically, in Formula 1, R 4 and R 5 are the same as or different from each other, and each independently hydrogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; or alkenyl having 2 to 20 carbon atoms, and more specifically, alkyl having 1 to 6 carbon atoms. More specifically, R 4 and R 5 may be methyl, ethyl or propyl.
[140]
Specifically, in Formula 1, R 6 To R 9 Are the same as or different from each other, and each independently, hydrogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; or alkenyl having 2 to 20 carbon atoms. More specifically, R 6 to R 9 may be the same as or different from each other, and each independently hydrogen or methyl.
[141]
At least two adjacent to each other of R 6 to R 9 may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms, wherein the aliphatic ring or aromatic ring is halogen, carbon number 1 to It may be substituted with alkyl having 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms.
[142]
Specifically, in Formula 1, Q 1 may be Si, C, N, P or S, and more specifically, Q 1 may be Si.
[143]
Specifically, in Formula 1, M 1 may be Ti, Hf, or Zr.
[144]
Specifically, in Formula 1, X 1 and X 2 are the same as or different from each other, and each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; alkylamino having 1 to 20 carbon atoms; Or it may be an arylamino having 6 to 20 carbon atoms.
[145]
[146]
In addition, the compound represented by Formula 1 may be a compound represented by any one of the following Formulas.
[147]
[Formula 1-1]
[148]

[149]
[Formula 1-2]
[150]

[151]
[Formula 1-3]
[152]

[153]
[Formula 1-4]
[154]

[155]
[Formula 1-5]
[156]

[157]
[Formula 1-6]
[158]

[159]
In addition, it may be a compound having various structures within the range defined in Formula 1 above.
[160]
[161]
In addition, in Formula 2, R 10 is hydrogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; arylalkoxy having 7 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; or arylalkyl having 7 to 20 carbon atoms, and more specifically, R 10 is hydrogen; alkyl having 1 to 20 carbon atoms or 1 to 12 carbon atoms; alkoxy having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; arylalkoxy having 7 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; Or it may be an arylalkyl having 7 to 20 carbon atoms.
[162]
Specifically, in Formula 2, R 11a to R 11e are each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; carbon number3 to 20 cycloalkyl; alkenyl having 2 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; or aryl having 6 to 20 carbon atoms, and more specifically, hydrogen; halogen; alkyl having 1 to 12 carbon atoms; cycloalkyl having 3 to 12 carbon atoms; alkenyl having 2 to 12 carbon atoms; alkoxy having 1 to 12 carbon atoms; or phenyl.
[163]
Specifically, in Formula 2, R 12 is hydrogen; halogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; alkylamido having 1 to 20 carbon atoms; or arylamido having 6 to 20 carbon atoms, and more specifically, hydrogen; halogen; alkyl having 1 to 12 carbon atoms; cycloalkyl having 3 to 12 carbon atoms; alkenyl having 2 to 12 carbon atoms; or phenyl.
[164]
Specifically, in Formula 2, R 13 and R 14 are each independently hydrogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; or alkenyl having 2 to 20 carbon atoms, and more specifically, hydrogen; Or it may be an alkyl having 1 to 12 carbon atoms.
[165]
Specifically, in Formula 2, R 15 to R 18 are each independently hydrogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; or alkenyl having 2 to 20 carbon atoms, and more specifically, hydrogen; alkyl having 1 to 12 carbon atoms; or cycloalkyl having 3 to 12 carbon atoms, or hydrogen; or methyl.
[166]
Specifically, in Formula 2, two or more of R 15 to R 18 that are adjacent to each other may be connected to each other to form a ring.
[167]
Specifically, in Formula 2, Q 2 may be Si, C, N, P or S, and more specifically, Q may be Si.
[168]
Specifically, in Formula 2, X 3 and X 4 are each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; alkylamino having 1 to 20 carbon atoms; or arylamino having 6 to 20 carbon atoms, specifically, hydrogen; halogen; alkyl having 1 to 12 carbon atoms; cycloalkyl having 3 to 12 carbon atoms; Or it may be an alkenyl having 2 to 12 carbon atoms, more specifically, hydrogen; Or it may be an alkyl having 1 to 12 carbon atoms.

Claims
[Claim 1]
An ethylene/alpha-olefin copolymer satisfying the following conditions (a) to (d): (a) having a density of 0.85 to 0.89 g/cc; (b) having a molecular weight distribution of 1.5 to 2.3; (c) the melting temperature is 85° C. or less; And, (d) the free volume proportional constant (C 2) derived from the following equations 1 and 2 is 600 or less; [Equation 1] In Equation 1, η O (T) is the viscosity (Pa s) of the copolymer measured by ARES-G2 (Advanced Rheometric Expansion System) at an arbitrary temperature T (K), η 0 (T r) is the viscosity (Pa s) of the copolymer measured by ARES-G2 at the reference temperature T r(K), and a T is the transfer factor of the arbitrary temperature T(K) with respect to the reference temperature T r(K). (Shift Factor) obtained from Equation 1, [Equation 2] In Equation 2, C 1 is a free volume inverse proportional constant, C 2 is a free volume proportional constant (K), and C 1 and C 2 are ethylene/ As an intrinsic constant of the alpha-olefin copolymer, it is obtained from Equation 2 above.
[Claim 2]
The method according to claim 1, The free volume proportional constant (C 2) will be 300 to 550, ethylene / alpha-olefin copolymer.
[Claim 3]
The ethylene/alpha-olefin copolymer of claim 1, wherein the molecular weight distribution is 1.8 to 2.2.
[Claim 4]
The method according to claim 1, Melt Flow Rate Ratio (MFRR, Melt Flow Rate Ratio, MI 10/) value of the melt index (MI 10, 190 °C, 10 kg load condition) to the melt index (MI 2.16, 190 °C, 2.16 kg load condition) MI 2.16) is less than or equal to 8.0.
[Claim 5]
The ethylene/alpha-olefin copolymer according to claim 1, wherein the crystallization temperature is 70° C. or less.
[Claim 6]
The ethylene/alpha-olefin copolymer according to claim 1, wherein the melt index (MI 2.16, 190°C, 2.16 kg load condition) is 0.1 to 50 dg/min.
[Claim 7]
The ethylene/alpha-olefin copolymer according to claim 1, wherein the weight average molecular weight is 40,000 to 150,000 g/mol.
[Claim 8]
The method according to claim 1, wherein the alpha-olefin is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1 -Dodecene, 1-tetradecene, 1-hexadecene, and 1-eicosene comprising at least one selected from the group consisting of, ethylene / alpha-olefin copolymer.
[Claim 9]
The ethylene/alpha-olefin copolymer according to claim 1, wherein the alpha-olefin is contained in an amount of greater than 0 and 99 mol% or less compared to the copolymer.