Title of Invention: Ethylene/alpha-olefin copolymer with excellent electrical insulation
technology field
[One]
Cross-Citation with Related Applications
[2]
This application claims the benefit of priority based on Korean Patent Application No. 2020-0046025 dated April 16, 2020 and Korean Patent Application No. 2020-0103861 dated August 19, 2020, and all contents disclosed in the literature of the Korean patent applications are incorporated herein by reference. included as part of
[3]
[4]
technology field
[5]
The present invention relates to an ethylene/alpha-olefin copolymer having excellent volume resistance and light transmittance and a preparation method thereof.
[6]
background art
[7]
While global environmental problems and energy problems are becoming more and more serious, solar cells are attracting attention as a means of generating clean and non-depleting energy. It is common for solar cells to be used in the form of modules when used outdoors, such as on the roof of a building. In manufacturing solar cell modules, a protective sheet for solar cell modules (transparent protective member on the surface)/solar cell module is used to obtain crystalline solar cell modules. Cell encapsulant/crystalline solar cell element crystalline solar cell element/solar cell encapsulant/protective sheet for solar cell module (back side protection member) are laminated in this order to manufacture the product.
[8]
As solar cell encapsulants, ethylene/vinyl acetate copolymers or ethylene/alpha-olefin copolymers are generally used. In addition, since long-term weather resistance is required for the solar cell encapsulant, a light stabilizer is usually included as an additive, and a silane coupling agent or the like is generally used in consideration of the adhesion between the surface-side transparent protective member represented by glass or the back-side protective member. Included. However, when ethylene/vinyl acetate copolymer or the like is used as a constituent material of a solar cell encapsulant, there is concern about the possibility that components such as acetic acid gas generated by decomposition of the ethylene/vinyl acetate copolymer affect the solar cell element.
[9]
In addition, with the spread of photovoltaic power generation in recent years, the scale-up of power generation systems such as mega solar is progressing, and there is also a movement to increase the system voltage for the purpose of lowering transmission loss. As the system voltage rises, a 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 is 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, and the high voltage It will maintain power generation during the day under authorization. In addition, glass has a lower electrical resistance than that of the encapsulant, and a high voltage is generated between the glass and the cell through the frame. That is, under the condition of power generation during the day, the potential difference between cells and modules and between cells and the glass surface sequentially increases at the ground side of the modules connected in series, 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 power generation device in which output is greatly reduced and a potential induced degradation (PID) phenomenon in which characteristic deterioration occurs has also been reported. Therefore, in order to solve this problem, a higher specific volume resistivity is required for a solar cell encapsulant directly in contact with a solar cell element.
[10]
Volume resistance or resistivity (ρ), also known as electrical resistance, is defined as the electrical resistance between opposite sides of 1 cubic meter of material, which volume resistance is reproducible within a predetermined range in all of the above applications and is a permanent forming It is important to obtain the product. In the field of electrical insulation materials for high-voltage power cables, high-voltage 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 power loss that occurs during power transmission, and reduction of power loss can be achieved by enhancing high-voltage characteristics of insulating materials, particularly volume resistance. However, while the insulation material for power cables is heated up to a high temperature (about 90° C.) by heat generated by passing current in the vicinity of the inner conductor, the ambient temperature is maintained in the vicinity of the outer conductor. shows a significant drop in volume resistance.
[11]
As such, it is still necessary to develop an ethylene/alpha-olefin copolymer that has excellent volume resistance and can be widely used as a material requiring high insulation such as a solar cell encapsulant.
[12]
[13]
[Prior art literature]
[14]
[Patent Literature]
[15]
(Patent Document 1) Japanese Patent Laid-Open No. 2010-258439
[16]
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[17]
An object of the present invention is to provide an ethylene/alpha-olefin copolymer and a method for preparing the same, which can be usefully utilized as an insulating material because both volume resistance and light transmittance are excellent.
[18]
means of solving the problem
[19]
In order to solve the above problems, the present invention provides an ethylene/alpha-olefin copolymer that satisfies the following conditions (a) to (c).
[20]
(a) having a density of 0.85 to 0.89 g/cc;
[21]
(b) that the melting temperature (Tm) having the highest peak in the curve obtained by differential scanning calorimetry (DSC) is 40 to 90 ° C; and
[22]
(c) The melting temperature (Tm) and the elution temperature (Te) having the highest peak in the curve obtained by cross-fractionation chromatography (CFC) satisfy Equation 1 below.
[23]
[Equation 1]
[24]
35℃ < Tm - Te < 65℃
[25]
Effects of the Invention
[26]
Ethylene/alpha-olefin copolymers that satisfy all the conditions defined in the present invention have high volume resistance and excellent insulation properties, so they can be widely used for various purposes in the electric and electronic industry, and in particular, when used in solar cell modules, they delay the PID phenomenon as much as possible. and exhibits high light transmittance, thereby achieving excellent module efficiency.
[27]
Mode for Carrying Out the Invention
[28]
Hereinafter, the present invention will be described in more detail to aid understanding of the present invention.
[29]
The terms or words used in the description and claims of the present invention should not be construed as being limited to the ordinary or dictionary meaning, and the inventor appropriately defines the concept of the term in order to explain his/her invention in the best way. Based on the principle that it can be done, it should be interpreted as meaning and concept consistent with the technical spirit of the present invention.
[30]
[31]
The ethylene/alpha-olefin copolymer of the present invention is characterized by satisfying the following conditions (a) to (c).
[32]
(a) having a density of 0.85 to 0.89 g/cc;
[33]
(b) that the melting temperature (Tm) having the highest peak in the curve obtained by differential scanning calorimetry (DSC) is 40 to 90 ° C; and
[34]
(c) The melting temperature (Tm) and the elution temperature (Te) having the highest peak in the curve obtained by cross-fractionation chromatography (CFC) satisfy Equation 1 below.
[35]
[Equation 1]
[36]
35℃ < Tm - Te < 65℃
[37]
[38]
The present invention relates to an ethylene/alpha-olefin copolymer exhibiting excellent electrical insulation properties due to its high volume resistance. Since satisfies a specific range, the volume resistance is high and the light transmittance is excellent.
[39]
Specifically, the ethylene/alpha-olefin copolymer of the present invention is prepared by mixing transition metal compounds represented by Chemical Formulas 1 and 2 as described below and using them as catalysts. The transition metal compounds represented by Chemical Formula 1 are catalysts Due to structural characteristics, it is difficult to introduce alpha-olefin-based monomers, which tends to produce high-density copolymers, and since a large amount of alpha-olefins can be introduced into the transition metal compound represented by Formula 2, ultra-low-density polymers (elastomer) can also be produced, and when the two transition metal compounds are used alone, the copolymerizability of incorporating alpha-olefinic monomers is different.
[40]
The ethylene/alpha-olefin copolymer of the present invention prepared using these mixed compositions as a catalyst has both a low-density region in which a large amount of alpha-olefin monomer is incorporated and a high-density region in which a small amount of alpha-olefin monomer is incorporated. As a copolymer, the Tm - Te value appears above a certain value, which means that both the high crystalline region and the low crystalline region are contained, so the crystalline distribution is wide and the free volume is small, and therefore the charge of the polymer Since the mobility is low, the volume resistance is high. In addition, when the Tm-Te value is too high, the volume resistance is lowered due to the low crystalline region and the light transmittance is also lowered due to the high crystalline region. The Tm - Te value of was derived and an ethylene/alpha-olefin copolymer was developed that satisfies this value.
[41]
[42]
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, specifically, the density is 0.850 g/cc or more, 0.860 g/cc or more, or 0.870 g/cc or more. 0.890 g/cc or less, or 0.880 g/cc or less. In this case, the density may mean a density measured according to ASTM D-792.
[43]
In general, the density of ethylene/alpha-olefin copolymers is affected by the type and content of monomers used during polymerization, the degree of polymerization, and the like, and in the case of copolymers, it is greatly influenced by the content of comonomers. At this time, the higher the comonomer content, the lower density ethylene/alpha-olefin copolymer can be prepared, and the amount of the comonomer that can be introduced into the copolymer may depend on the inherent copolymerizability of the catalyst.
[44]
The copolymer of the present invention is a copolymer prepared using the compounds represented by Formulas 1 and 2 as a catalyst, and exhibits a low density as described above.As a result, excellent processability can be exhibited.
[45]
[46]
The ethylene/alpha-olefin copolymer of the present invention has a melting temperature (Tm) having the highest peak in a curve obtained by differential scanning calorimetry (DSC) and cross-fractionation chromatography (CFC) obtained by cross-fractionation chromatography (CFC). The elution temperature (Te) having the highest peak in the curve satisfies Equation 1 below.
[47]
[Equation 1]
[48]
35℃ < Tm - Te < 65℃
[49]
Here, the melting temperature refers to the peak temperature of the highest peak in the DSC curve expressed as heat flow versus temperature, and the elution temperature refers to the peak temperature of the highest peak in the CFC elution curve expressed as elution amount versus temperature (dC/dT). it means.
[50]
[51]
The cross-fractionation chromatography (CFC) is a method that combines Temperature Rising Elution Fractionation (TREF) and Gel Filtration Chromatography (GPC), through which ethylene/alpha-olefin The crystallinity distribution of the copolymer can be measured. Specifically, a high-temperature sample solution in which an ethylene/alpha-olefin copolymer is completely dissolved in a solvent is injected into a column filled with an inert carrier, and the temperature of the column is lowered to attach the sample to the surface of the filler, and then into the column The temperature of the column is slowly raised while flowing o-dichlorobenzene. Detect the concentration of the olefin-based copolymer eluted at each temperature, and at the same time send the components eluted at each temperature to GPC online for each fraction to obtain a chromatogram. The higher the crystallinity of the eluted component, the higher the elution temperature Therefore, the crystallinity distribution of the ethylene/alpha-olefin copolymer can be known by finding the relationship between the elution temperature and the elution amount (% by weight) of the ethylene/alpha-olefin copolymer.
[52]
When the Tm-Te value is 35°C or less, the volume resistance may decrease because the content of the highly crystalline region in the copolymer is low, and when the Tm-Te value is 65°C or more, the crystalline distribution of the copolymer A problem may occur in that the light transmittance is lowered due to the high crystalline region and the volume resistance is lowered due to the low crystalline region.
[53]
[54]
The ethylene/alpha-olefin copolymer of the present invention has a melting temperature (Tm) of 40 to 90° C. having the highest peak in a curve obtained by differential scanning calorimetry (DSC). Specifically, the melting temperature may be 40 ° C or higher, 50 ° C or higher, 55 ° C or higher, 60 ° C or higher, 61 ° C or higher, 90 ° C or lower, 80 ° C or lower, 75 ° C or lower, 70 ° C or lower, or 68 ° C or lower.
[55]
As described above, the ethylene / alpha-olefin copolymer of the present invention satisfies the Tm-Te value represented by the above formula 1, has a density of 0.85 to 0.89 g / cc and a melting temperature (Tm) of 40 to 90 ° C. It is characterized by being Even if Equation 1 is satisfied, if the density or melting temperature (Tm) value is too high out of the above range, a problem in that the light transmittance is lowered may occur. Therefore, all of the conditions (a) to (c) defined in the present invention When it is satisfied, excellent volume resistance and light transmittance are simultaneously implemented, and physical properties suitable for use in applications such as encapsulation films of solar cells are exhibited.
[56]
In addition, the elution temperature (Te) may be 10 to 50 ° C, specifically 10 ° C or more, 15 ° C or more, 20 ° C or more, 25 ° C or more, 50 ° C or less, 40 ° C or less, 35 ° C or less, or 30 ° C or less.
[57]
[58]
The ethylene/alpha-olefin copolymer of the present invention has a narrow molecular weight distribution (MWD) of 1.5 to 2.5. More specifically, the molecular weight distribution may be 1.5 or more, 1.7 or more, 1.8 or more, or 2.0 or more, and may be 2.5 or less, 2.4 or less, 2,3 or less, or 2.2 or less.
[59]
In general, when two or more monomers are polymerized, the molecular weight distribution increases, and as a result, impact strength and mechanical properties are reduced, and a blocking phenomenon may occur. In particular, since the polymerizability of the monomers is different for each catalyst, the molecular weight of the finally produced polymer is affected by the type of catalyst. There is a problem that the molecular weight distribution is also widened.
[60]
In order to narrow the molecular weight distribution in order to prevent deterioration of crosslinking properties, impact strength, mechanical properties, etc. of the copolymer, an appropriate amount of hydrogen is injected during polymerization to prevent β-hydride elimination from occurring at random in the polymer chain And it is possible to 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 addition of hydrogen, the effect of the catalyst structure on the weight average molecular weight and melt index It is necessary to determine an appropriate catalyst type and hydrogen input amount within a range that can take both the unique characteristics and the effect of reducing the molecular weight distribution according to the hydrogen input.
[61]
In view of the above, in the present invention, as will be described later, the transition metal compound represented by Formula 1 and the transition metal compound represented by Formula 2 were mixed and used as a catalyst while injecting an optimal amount of hydrogen. It has a narrow molecular weight distribution in the above-mentioned range to prevent deterioration of crosslinking properties, impact strength, mechanical properties, etc., while exhibiting high volume resistance and light transmittance.
[62]
The weight average molecular weight (Mw) and number average molecular weight (Mn) are molecular weights in terms of polystyrene analyzed by gel permeation chromatography (GPC), and the molecular weight distribution can be calculated from the ratio of Mw/Mn.
[63]
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 40,000 g / mol or more, 45,000 g / mol or more, 50,000 g / mol or more, 150,000 g / mol or less, 130,000 g / mol or less, 100,000 g / mol or less, 90,000 g / mol or less, 80,000 g/mol or less.
[64]
[65]
The ethylene/alpha-olefin copolymer of the present invention may have a melt index (Melt Index, MI, 190° C., under a load of 2.16 kg) of 1 to 100 dg/min. Specifically, the melt index may be 1 dg/min or more, 2 dg/min or more, 3 dg/min or more, or 4 dg/min or more, and 100 dg/min or less, 50 dg/min or less, or 20 dg/min Or less, it may be 15 dg/min or less.
[66]
If the melt index is less than 1 dg/min, the production rate may drop due to high load, and if the melt index is more than 100 dg/min, it is difficult to form a film, so that the ethylene/alpha-olefin copolymer is used as a solar cell encapsulant film. Unsuitable problems may occur when used as a composition for use.
[67]
[68]
The ethylene/alpha-olefin copolymer of the present invention is prepared by copolymerizing ethylene and an alpha-olefin monomer, wherein the alpha-olefin, which means the part derived from the alpha-olefin 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, 1-eicosene, and the like, and one of them may be used alone or in a mixture of two or more.
[69]
Among these, the alpha-olefin may be 1-butene, 1-hexene or 1-octene, preferably 1-butene, 1-hexene or a combination thereof.
[70]
In addition, the content of alpha-olefin in the ethylene / alpha-olefin copolymer may be appropriately selected within a range that satisfies the above physical property requirements, specifically, more than 0 and 99 mol% or less, or 10 to 50 mol% It may be, but is not limited thereto.
[71]
[72]
The above-described ethylene/alpha-olefin copolymer of the present invention is prepared by polymerizing ethylene and alpha-olefin monomers in the presence of a catalyst composition comprising a transition metal compound represented by Formula 1 and Formula 2 below can be produced in this way.
[73]
[Formula 1]
[74]

[75]
In Formula 1,
[76]
R 1 is hydrogen; Alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; alkenyl of 2 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; aryl of 6 to 20 carbon atoms; arylalkoxy having 7 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or an arylalkyl having 7 to 20 carbon atoms,
[77]
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 of 2 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; Alkylamido having 1 to 20 carbon atoms; or an arylamido having 6 to 20 carbon atoms;
[78]
R 4 and R 5 are each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; aryl of 6 to 20 carbon atoms; or alkenyl having 2 to 20 carbon atoms;
[79]
R 6 to R 9 are each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; aryl of 6 to 20 carbon atoms; or alkenyl having 2 to 20 carbon atoms;
[80]
Two or more of R 6 to R 9 adjacent to each other may be connected to each other to form a ring,
[81]
Q 1 is Si, C, N, P or S;
[82]
M 1 is Ti, Hf or Zr;
[83]
X 1 and X 2 are each independently hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; alkenyl of 2 to 20 carbon atoms; aryl of 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;
[84]
[Formula 2]
[85]

[86]
In Formula 2,
[87]
R 10 is hydrogen; Alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; alkenyl of 2 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; aryl of 6 to 20 carbon atoms; arylalkoxy having 7 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or an arylalkyl having 7 to 20 carbon atoms,
[88]
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 of 2 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; or an aryl having 6 to 20 carbon atoms;
[89]
R 12 is hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; alkenyl of 2 to 20 carbon atoms; aryl of 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 an arylamido having 6 to 20 carbon atoms;
[90]
R 13 and R 14 are each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; aryl of 6 to 20 carbon atoms; or alkenyl having 2 to 20 carbon atoms;
[91]
R 15 to R 18 are each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; aryl of 6 to 20 carbon atoms; or alkenyl having 2 to 20 carbon atoms;
[92]
Two or more of R 15 to R 18 adjacent to each other may be connected to each other to form a ring,
[93]
Q 2 is Si, C, N, P or S;
[94]
M 2 is Ti, Hf or Zr;
[95]
X 3 and X 4 are each independently hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; alkenyl of 2 to 20 carbon atoms; aryl of 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.
[96]
Specifically, in Formula 1, R 1 is hydrogen; Alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; alkenyl of 2 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; aryl of 6 to 20 carbon atoms; arylalkoxy having 7 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or an arylalkyl having 7 to 20 carbon atoms, more specifically, R 1 is methyl, ethyl, propyl, butyl, isobutyl, tbutyl, isopropyl, cyclohexyl, benzyl, phenyl, methoxyphenyl, ethoxyphenyl, fluoro phenyl, bromophenyl, chlorophenyl, dimethylphenyl or diethylphenyl.
[97]
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 of 2 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; Alkylamido having 1 to 20 carbon atoms; Or an arylamido having 6 to 20 carbon atoms, and more specifically, the R 2 and R 3 are each independently hydrogen; Alkyl having 1 to 20 carbon atoms; or arylalkyl having 7 to 20 carbon atoms.
[98]
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 of 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, the R 4 and R 5 may be methyl, ethyl or propyl.
[99]
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 of 6 to 20 carbon atoms; or alkenyl of 2 to 20 carbon atoms. More specifically, R 6 to R 9 are the same as or different from each other, and each independently may be hydrogen or methyl.
[100]
Two or more of R 6 to R 9 adjacent to each other 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, and the aliphatic ring or aromatic ring may be a halogen or a carbon atom having 1 to 20 carbon atoms. It may be substituted with an alkyl of 20 carbon atoms, an alkenyl of 2 to 20 carbon atoms or an aryl of 6 to 20 carbon atoms.
[101]
Specifically, in Chemical Formula 1, Q 1 may be Si, C, N, P, or S, and more specifically, Q 1 may be Si.
[102]
Specifically, in Chemical Formula 1, M 1 may be Ti, Hf, or Zr.
[103]
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 of 2 to 20 carbon atoms; aryl of 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.
[104]
[105]
In addition, the compound represented by Formula 1 may be a compound represented by any one of the following formulas.
[106]
[Formula 1-1]
[107]

[108]
[Formula 1-2]
[109]

[110]
[Formula 1-3]
[111]

[112]
[Formula 1-4]
[113]

[114]
[Formula 1-5]
[115]

[116]
[Formula 1-6]
[117]

[118]
In addition, it may be a compound having various structures within the range defined in Formula 1 above.
[119]
[120]
Also, in Formula 2, R 10 is hydrogen; Alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; alkenyl of 2 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; aryl of 6 to 20 carbon atoms; arylalkoxy having 7 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; or an 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 of 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.
[121]
Specifically, in Formula 2, 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 of 2 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; Or an aryl having 6 to 20 carbon atoms, 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.
[122]
Specifically, in Formula 2, R 12 is hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; alkenyl of 2 to 20 carbon atoms; aryl of 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 an arylamido having 6 to 20 carbon atoms, 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.
[123]
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 of 6 to 20 carbon atoms; or alkenyl having 2 to 20 carbon atoms, more specifically, hydrogen; or an alkyl having 1 to 12 carbon atoms.
[124]
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 of 6 to 20 carbon atoms; or alkenyl having 2 to 20 carbon atoms, more specifically, hydrogen; Alkyl having 1 to 12 carbon atoms; or cycloalkyl of 3 to 12 carbon atoms, or hydrogen; or methyl.
[125]
Specifically, in Formula 2, two or more of R 15 to R 18 adjacent to each other may be connected to each other to form a ring.
[126]
Specifically, in Chemical Formula 2, Q 2 is Si, C, N, P or S, and more specifically, Q may be Si.
[127]
Specifically, in Formula 2, X 3 and X 4 are each independently hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; alkenyl of 2 to 20 carbon atoms; aryl of 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 an alkyl having 1 to 12 carbon atoms.
[128]
[129]
In addition, the compound represented by Chemical Formula 2 may be any one of compounds represented by the following Chemical Formula.
[130]
[Formula 2-1]
[131]

[132]
[Formula 2-2]
[133]

[134]
[Formula 2-3]
[135]

[136]
[Formula 2-4]
[137]

[138]
[Formula 2-5]
[139]

[140]
[Formula 2-6]
[141]

[142]
[Formula 2-7]
[143]

[144]
[Formula 2-8]
[145]

[146]
[Formula 2-9]
[147]

[148]
[Formula 2-10]
[149]

[150] The molar ratio of the transition metal compound represented by Formula 1 and Formula 2 may be 1:0.5 to 1:8, 1:1 to 1:7, 1:1 to 1:5, 1:1 to 1:4, Not limited to this.
[151]
As described above, the transition metal compounds represented by Formulas 1 and 2 used in the present invention were used by mixing two types of transition metal compounds having different comonomer incorporation capabilities, and through this, all the conditions defined in the present invention By satisfying this, it shows excellent volume resistance and light transmittance.
[152]
The polymerization reaction may be carried out by continuously polymerizing ethylene and alpha-olefin monomers by continuously introducing hydrogen in the presence of the catalyst composition, and specifically, may be carried out while introducing hydrogen at 5 to 100 cc/min have.
[153]
The hydrogen gas suppresses a rapid reaction of the transition metal compound at the initial stage of polymerization and serves to terminate the polymerization reaction. Accordingly, an ethylene/alpha-olefin copolymer having a narrow molecular weight distribution can be effectively produced by using such hydrogen gas and adjusting the amount thereof.
[154]
For example, the hydrogen may be introduced at 5 cc/min or more, or 7 cc/min or more, or 10 cc/min or more, or 15 cc/min or more, or 19 cc/min or more, 100 cc/min or less, or 50 cc/min or less, or 45 cc/min or less, or 35 cc/min or less, or 29 cc/min or less. When added under the above conditions, the produced ethylene/alpha-olefin copolymer can realize the physical properties in the present invention.
[155]
When the hydrogen gas content is less than 5 cc/min, the polymerization reaction is not uniformly terminated, making it difficult to prepare an ethylene/alpha-olefin copolymer having desired physical properties. In this case, the termination reaction occurs too quickly, and there is a concern that an ethylene/alpha-olefin copolymer having a very low molecular weight may be produced.
[156]
In addition, the polymerization reaction may be carried out at 100 to 200 ° C., and the crystallinity distribution and molecular weight distribution in the ethylene/alpha-olefin copolymer may be more easily controlled by controlling the polymerization temperature together with the amount of hydrogen input. Specifically, the polymerization reaction may be performed at 100 to 200 °C, 120 to 180 °C, 130 to 170 °C, or 130 to 150 °C, but is not limited thereto.
[157]
[158]
In the present invention, a cocatalyst may be additionally used in the catalyst composition to activate the transition metal compound of Chemical Formula 1 and/or Chemical Formula 2. The cocatalyst is an organometallic compound containing a Group 13 metal, and may specifically include one or more selected from Chemical Formulas 3 to 5 below.
[159]
[Formula 3]
[160]
-[Al(R 19 )-O] a-
[161]
In Formula 3,
[162]
R 19 are each independently a halogen radical; a hydrocarbyl radical of 1 to 20 carbon atoms; or a hydrocarbyl radical of 1 to 20 carbon atoms substituted by halogen,
[163]
a is an integer greater than or equal to 2;
[164]
[Formula 4]
[165]
D(R 19) 3
[166]
In Formula 4,
[167]
D is aluminum or boron;
[168]
R 19 are each independently a halogen radical; a hydrocarbyl radical of 1 to 20 carbon atoms; or a hydrocarbyl radical of 1 to 20 carbon atoms substituted by halogen,
[169]
[Formula 5]
[170]
[L-H] +[Z(A) 4] - or [L] +[Z(A) 4] -
[171]
In Formula 5,
[172]
H is a hydrogen atom,
[173]
Z is a group 13 element,
[174]
A is independently aryl having 6 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a substituent; Or an alkyl having 1 to 20 carbon atoms,
[175]
The substituent is halogen; hydrocarbyl of 1 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; or aryloxy having 6 to 20 carbon atoms;
[176]
[L-H] + is trimethylammonium; triethylammonium; tripropylammonium; tributylammonium; diethylammonium; trimethylphosphonium; or triphenylphosphonium;
[177]
[L] + is N,N-diethylanilinium; or triphenylcarbonium.
[178]
[179]
More specifically, the compound of Formula 3 may be an alkylaluminoxane-based compound in which repeating units are bonded in a linear, circular, or network shape, and specific examples include methylaluminoxane (MAO), ethylaluminoxane, and isobutylaluminoxane. or tert-butylaluminoxane and the like.
[180]
In addition, the compound of Formula 4 is trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, triisopropyl aluminum, tri-s-butyl aluminum, tricyclopentyl aluminum, tri Pentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyldimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, and triethylboron, triisobutylboron, tripropylboron, or tributylboron, and the like, and may be particularly trimethylaluminum, triethylaluminum, or triisobutylaluminum, but is not limited thereto.
[181]
In addition, the compound of Formula 5 may include borate-based compounds in the form of trisubstituted ammonium salts, dialkyl ammonium salts, or trisubstituted phosphonium salts. More specific examples include trimethylammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, and methyltetradecylborate. Octadecylammonium tetraphenylborate, N,N-dimethylaninium tetraphenylborate, N,N-diethylaninium tetraphenylborate, N,N-dimethyl(2,4,6-trimethylaninium)tetraphenylborate, Trimethylammonium Tetrakis(pentafluorophenyl)borate, Methylditetradecylammonium Tetrakis(pentaphenyl)borate, Methyldioctadecylammonium Tetrakis(pentafluorophenyl)borate, Triethylammonium, Tetrakis(pentafluorophenyl)borate Phenyl) borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl) ) borate, N,N-dimethylaninium tetrakis(pentafluorophenyl)borate, N,N-diethylaniniumtetrakis(pentafluorophenyl)borate, N,N-dimethyl(2,4,6- Trimethylaninium) tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, triethylammonium tetrakis (2,3,4,6-tetrafluoro Rophenyl)borate, tripropylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(2,3,4,6-,tetrafluorophenyl) Borate, dimethyl(t-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylaninium tetrakis(2,3,4,6-tetrafluorophenyl) Borate, N,N-diethylaninium tetrakis(2,3,4,6-tetrafluorophenyl)borate or N,N-dimethyl-(2,4,6-trimethylaninium)tetrakis-(2 borate-based compounds in the form of trisubstituted ammonium salts such as ,3,4,6-tetrafluorophenyl)borate; A borate system in the form of a dialkylammonium salt such as dioctadecylammonium tetrakis(pentafluorophenyl)borate, ditetradecylammonium tetrakis(pentafluorophenyl)borate or dicyclohexylammonium tetrakis(pentafluorophenyl)borate. compound; Or triphenylphosphonium tetrakis (pentafluorophenyl) borate, methyldioctadecylphosphonium tetrakis (pentafluorophenyl) borate or tri (2,6-, dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) ) borate-based compounds in the form of trisubstituted phosphonium salts such as borates, but are not limited thereto.
[182]
By using such a cocatalyst, the molecular weight distribution of the finally prepared ethylene/alpha-olefin copolymer can be more uniform and polymerization activity can be improved.
[183]
The cocatalyst may be used in an appropriate amount so that the activation of the transition metal compound of Chemical Formula 1 and/or Chemical Formula 2 can sufficiently proceed.
[184]
[185]
In the present invention, the transition metal compound of Chemical Formula 1 and/or Chemical Formula 2 may be used in a supported form on a carrier.
[186]
When the transition metal compound of Chemical Formula 1 and/or Chemical Formula 2 is supported on a carrier, the weight ratio of the transition metal compound to the carrier may be 1:10 to 1:1,000, and more specifically, 1:10 to 1:500. When the carrier and the transition metal compound are included in the medium ratio in the above range, an optimal shape can be exhibited. In addition, when the cocatalyst is supported on a carrier, the weight ratio of the cocatalyst to the carrier may be 1:1 to 1:100, more specifically 1:1 to 1:50. When the cocatalyst and the carrier are included in the above weight ratio, the catalytic activity can be improved and the microstructure of the polymer produced can be optimized.
[187]
On the other hand, as the carrier, silica, alumina, magnesia, or a mixture thereof may be used, or by drying these materials at a high temperature to remove moisture from the surface, a state containing a highly reactive hydroxyl group or siloxane group on the surface may be used In addition, the high-temperature dried supports may further include oxides, carbonates, sulfates, or nitrates, such as Na 2 O, K 2 CO 3 , BaSO 4 and Mg(NO 3) 2 .
[188]
The drying temperature of the carrier is preferably 200 to 800 ° C, more preferably 300 to 600 ° C, and most preferably 300 to 400 ° C. When the drying temperature of the carrier is less than 200 ° C, the moisture on the surface is too high and the cocatalyst reacts with the moisture on the surface. This is undesirable because only siloxane remains and the reaction sites with the cocatalyst decrease.
[189]
In addition, the hydroxy group on the surface of the carrier The amount is preferably 0.1 to 10 mmol/g, more preferably 0.5 to 5 mmol/g. The amount of hydroxyl groups on the surface of the carrier can be controlled by the manufacturing method and conditions of the carrier or drying conditions, such as temperature, time, vacuum or spray drying.
[190]
[191]
In addition, during the polymerization reaction, an organic aluminum compound for removing moisture in the reactor may be further added, and the polymerization reaction may proceed in the presence of the organoaluminum compound. Specific examples of the organic aluminum compound include trialkyl aluminum, dialkyl aluminum halide, alkyl aluminum dihalide, aluminum dialkyl hydride, or alkyl aluminum sesqui halide. More specific examples thereof include Al(C 2 H 5) 3, Al(C 2H 5) 2H, Al(C 3H 7) 3, Al(C 3H 7) 2H, Al(i-C 4H 9) 2H, Al(C 8H 17) 3, Al(C 12H 25) 3, Al(C 2H 5)(C 12H 25) 2, Al(i-C 4H 9)(C 12H 25) 2, Al(i-C 4H 9) 2H, Al(i-C 4H 9) 3, (C 2H 5) 2AlCl , (i-C 3H 9) 2AlCl or (C 2H 5) 3A 12Cl 3 and the like. These organoaluminum compounds may be continuously charged to the reactor and may be added at a rate of about 0.1 to 10 moles per kilogram of reaction medium charged to the reactor for adequate moisture removal.
[192]
In addition, the polymerization pressure may be about 1 to about 100 Kgf/cm 2 , preferably about 1 to about 50 Kgf/cm 2 , and more preferably about 5 to about 30 Kgf/cm 2 .
[193]
In addition, when a transition metal compound is used in a supported form on a carrier, the transition metal compound is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, for example, pentane, hexane, heptane, nonane, decane, and isomers thereof and toluene, benzene It may be dissolved in an aromatic hydrocarbon solvent such as dichloromethane or a hydrocarbon solvent substituted with a chlorine atom such as chlorobenzene or added after dilution. The solvent used here is preferably used by removing a small amount of water or air that acts as a catalyst poison by treating a small amount of alkyl aluminum, and it is also possible to use a cocatalyst further.
[194]
[195]
The ethylene/alpha-olefin copolymer of the present invention may be processed into a resin composition including a crosslinking agent, a crosslinking aid, a silane coupling agent, a light stabilizer, a UV absorber, a heat stabilizer, etc. Accordingly, various additives known in the art may be appropriately additionally included.
[196]
In addition, it can be molded by a method such as extrusion and used as various molded articles, and can be specifically used as an encapsulant for encapsulating elements in various optoelectronic devices, such as solar cells, for example, at elevated temperatures. It can also be used as an industrial material applied to the lamination process, etc., but the use is not limited thereto.
[197]
[198]
Example
[199]
Hereinafter, the present invention will be described in more detail by examples. However, the following examples are for exemplifying the present invention, and the scope of the present invention is not limited only thereto.
[200]
[201]
[Preparation of transition metal compound]
[202]
Preparation Example 1
[203]
(1) Preparation of ligand compound
[204]

[205]
After quantifying and adding 4.65 g (15.88 mmol) of the compound of Formula 3 to a 100 ml Schlenk flask, 80 ml of THF was added thereto. After adding tBuNH 2 (4eq, 6.68ml) at room temperature, the mixture was reacted at room temperature for 3 days. After the reaction, after removing THF, the mixture was filtered with hexane. After solvent drying, a yellow liquid was obtained in a yield of 4.50 g (86%).
[206]
1H-NMR (in CDCl 3, 500 MHz): 7.99 (d, 1H), 7.83 (d, 1H), 7.35 (dd, 1H), 7.24 (dd, 1H), 3.49 (s, 1H), 2.37 (s , 3H), 2.17(s, 3H), 1.27(s, 9H), 0.19(s, 3H), -0.17(s, 3H).
[207]
(2) Preparation of transition metal compounds
[208]

[209]
The ligand compound (1.06g, 3.22mmol/1.0eq) and MTBE 16.0mL (0.2M) were put in a 50ml Schlenk flask and stirred first. At -40°C, n-BuLi (2.64ml, 6.60mmol/2.05eq, 2.5M in THF) was added and reacted overnight at room temperature. Then, after slowly adding MeMgBr (2.68ml, 8.05 mmol/2.5eq, 3.0M in diethyl ether) dropwise at -40℃, TiCl 4 (2.68ml, 3.22 mmol/1.0eq, 1.0M in toluene) was added in that order. It was reacted overnight at room temperature. The reaction mixture was then filtered through Celite using hexane. After solvent drying, a brown solid was obtained in a yield of 1.07 g (82%).
[210]
1H-NMR (in CDCl 3, 500 MHz): 7.99 (d, 1H), 7.68 (d, 1H), 7.40 (dd, 1H), 7.30 (dd, 1H), 3.22 (s, 1H), 2.67 (s , 3H), 2.05(s, 3H), 1.54(s, 9H), 0.58(s, 3H), 0.57(s, 3H), 0.40(s, 3H), -0.45(s, 3H).
[211]
[212]
Preparation Example 2-1
[213]
(1) Preparation of ligand compound
[214]

[215]
(i) Preparation of chloro-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophen-3-yl)-1,1-(methyl)(2-methylphenyl)silane
[216]
Into a 250 mL Schlenk flask, add 2.0 g (1.0 eq, 9.985 mmol) of 1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene and 50 mL of THF, and add 4.2 mL of n-BuLi (1.05 eq, 10.484 mmol, 2.5 M in hexane) was added dropwise at -30 °C and then stirred at room temperature overnight. The stirred Li-complex THF solution was cannulated in a Schlenk flask containing 2.46 g (1.2 eq, 11.982 mmol) of dichloro(O-tolylmethyl)silane and 30 mL of THF at -78°C, followed by stirring at room temperature overnight. After stirring, the mixture was vacuum dried and extracted with 100 mL of hexane.
[217]
(ii) N-tert-butyl-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophen-3-yl)-1,1-(methyl)(2-methylphenyl)silane Preparation of amines
[218]
4.0 g of extracted chloro-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophen-3-yl)-1,1-(methyl)(2-methylphenyl)silane 10.0 mmol) was stirred in 10 mL of hexane, and 4.2 mL (4.0 eq, 40.0 mmol) of t-BuNH 2 was added at room temperature, followed by stirring at room temperature overnight. After stirring and vacuum drying, the mixture was extracted with 150 mL of hexane. After solvent drying, 4.26 g (99%, dr = 1:0.83) of a sticky liquid was obtained.
[219]
1H-NMR (CDCl 3, 500 MHz): δ 7.95 (t, 2H), 7.70 (d, 1H), 7.52 (d, 1H), 7.47-7.44 (m, 2H), 7.24-7.02 (m, 9H) , 6.97(t, 1H), 3.59(s, 1H), 3.58(s, 1H), 2.50(s, 3H), 2.44(s, 3H), 2.25(s, 3H), 2.16(s, 3H), 2.06(s, 3H), 1.56(s, 3H), 1.02(s, 9H), 0.95(s, 9H), -0.03(s, 3H), -0.11(s, 3H)
[220]
(2) Preparation of transition metal compounds
[221]

[222]
The ligand compound (4.26 g, 10.501 mmol) of Formula 2-3 was added to 53 mL (0.2 M) of MTBE in a 250 mL round flask and stirred. After adding n-BuLi (8.6 mL, 21.52 mmol, 2.05 eq, 2.5 M in hexane) at -40°C, the mixture was stirred at room temperature overnight.
[223]
Thereafter, MeMgBr (8.8 mL, 26.25 mmol, 2.5 eq, 3.0 M in diethyl ether) was slowly added dropwise at -40°C, and then TiCl 4 (10.50 mL, 10.50 mmol) was sequentially added and stirred at room temperature overnight. Then the reaction mixture was filtered using hexane. DME (3.3 mL, 31.50 mmol) was added to the filtrate, and the solution was filtered over hexane and concentrated to obtain 3.42 g (68 %, dr=1:0.68) of a yellow solid.
[224]
1H NMR (CDCl 3, 500 MHz): δ 7.83 (d, 1H), 7.80 (d, 1H), 7.74 (d, 1H), 7.71 (d, 1H), 7.68 (d, 1H), 7.37 (d, 1H), 7.31-6.90(m, 9H), 6.84(t, 1H), 2.54(s, 3H), 2.47(s, 3H), 2.31(s, 3H), 2.20(s, 3H), 1.65(s) , 9H), 1.63(s, 9H), 1.34(s, 3H), 1.00(s, 3H), 0.98(s, 3H), 0.81(s, 3H), 0.79(s, 3H), 0.68(s, 3H), 0.14(s, 3H), -0.03(s, 3H)
[225]
[226]
Preparation Example 2-2
[227]
(1) Preparation of ligand compound
[228]

[229]
(i) Preparation of chloro-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophen-3-yl)-1,1-(methyl)(phenyl)silane
[230]
Into a 250 mL Schlenk flask, add 10 g (1.0 eq, 49.925 mmol) of 1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene and 100 mL of THF, and add 22 mL of n-BuLi (1.1 eq, 54.918 mmol, 2.5 M in hexane) was added dropwise at -30°C, and stirred at room temperature for 3 hours. The stirred Li-complex THF solution was cannulated into a Schlenk flask containing 8.1 mL (1.0 eq, 49.925 mmol) of dichloro(methyl)(phenyl)silane and 70 mL of THF at -78°C, followed by stirring at room temperature overnight. After stirring and vacuum drying, the mixture was extracted with 100 mL of hexane.
[231]
(ii) N-tert-butyl-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophen-3-yl)-1,1-(methyl)(phenyl)silanamine Produce
[232]
t-BuNH in 100 mL of the extracted chloro-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophen-3-yl)-1,1-(methyl)(phenyl)silane hexane solution After adding 42 mL (8 eq, 399.4 mmol) of 2 at room temperature, the mixture was stirred overnight at room temperature. After stirring and vacuum drying, the mixture was extracted with 150 mL of hexane. After solvent drying, 13.36 g (68%, dr = 1:1) of a yellow solid was obtained.
[233]
1H NMR (CDCl 3, 500 MHz): δ 7.93 (t, 2H), 7.79 (d, 1H), 7.71 (d, 1H), 7.60 (d, 2H), 7.48 (d, 2H), 7.40 to 7.10 ( m, 10H, aromatic), 3.62(s, 1H), 3.60(s, 1H), 2.28(s, 6H), 2.09(s, 3H), 1.76(s, 3H), 1.12(s, 18H), 0.23 (s, 3H), 0.13(s, 3H)
[234]
(2) Preparation of transition metal compounds
[235]

[236]
4.93 g (12.575 mmol, 1.0 eq) of the ligand compound of Formula 2-4 and 50 mL (0.2 M) of toluene were added to a 100 mL Schlenk flask, and 10.3 mL (25.779 mmol, 2.05 eq, 2.5 M in hexane) of n-BuLi was added. was added dropwise at -30 °C and then stirred overnight at room temperature. After stirring, 12.6 mL of MeMgBr (37.725 mmol, 3.0 eq, 3.0 M in diethyl ether) was added dropwise, followed by 13.2 mL of TiCl 4 (13.204 mmol, 1.05 eq, 1.0 M in toluene) sequentially, and the mixture was stirred overnight at room temperature. . After stirring, vacuum drying, extraction with 150 mL of hexane, and after removing the solvent to 50 mL, 4 mL of DME (37.725 mmol, 3.0eq) was added dropwise, followed by stirring at room temperature overnight. After vacuum drying again, the mixture was extracted with 150 mL of hexane. After solvent drying, 2.23 g (38%, dr = 1:0.5) of a brown solid was obtained.
[237]
1H NMR (CDCl 3, 500 MHz): δ 7.98 (d, 1H), 7.94 (d, 1H), 7.71 (t, 6H), 7.50 to 7.30 (10H), 2.66 (s, 3H), 2.61 (s, 3H), 2.15(s, 3H), 1.62(s, 9H), 1.56(s, 9H), 1.53(s, 3H), 0.93(s, 3H), 0.31(s, 3H), 0.58(s, 3H) ), 0.51(s, 3H), -0.26(s, 3H), -0.39(s, 3H)
[238]
[239]
Preparation Example 2-3
[240]
(1) Preparation of ligand compound
[241]

[242]
(i) Preparation of chloro-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophen-3-yl)-1,1-(2-ethylphenyl)(methyl)silane
[243]
In a 100 mL Schlenk flask, add 2 g (1 eq, 9.99 mmol) of 1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene and 50 mL of THF, and add 4 mL of n-BuLi (1 eq, 9.99 mmol, 2.5 M in hexane) was added dropwise at -30 °C and then stirred at room temperature overnight. The stirred Li-complex THF solution was cannulated in a Schlenk flask containing 2.19 mL (1.0 eq, 9.99 mmol) of dichloro(2-ethylphenyl)(methyl)silane and 50 mL of THF at -78 °C and stirred overnight at room temperature. did After stirring, the mixture was vacuum-dried, extracted with 60 mL of hexane, vacuum-dried again, and washed with hexane to obtain 3.83 g (99%, dr = 1:1) of an ivory solid.
[244]
(ii) N-tert-butyl-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophen-3-yl)-1,1-(2-ethylphenyl)(methyl) Preparation of Silanamines
[245]
Chloro-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophen-3-yl)-1,1-(2-ethylphenyl)(methyl)silane 3.87 in a 100 mL round flask After adding g (10.1 mmol) by quantification, 40 mL of hexane was added thereto. After adding t-BuNH 2 (10eq, 10.5 mL) at room temperature, the mixture was reacted at room temperature for 2 days. After the reaction, hexane was removed and filtered with hexane. After solvent drying, 3.58 g (84.4%, dr = 1:0.8) of a yellow solid was obtained.
[246]
1H-NMR (CDCl 3, 500 MHz): δ 7.98 (t, 2H), 7.71 (d, 1H), 7.55 (d, 1H), 7.52 (d, 1H), 7.48 (d, 1H), 7.30 (t , 1H), 7.26-7.22(m, 3H), 7.19(dd, 2H), 7.12-7.06(m, 3H), 7.00(t, 1H), 3.08-2.84(m, 4H) 3.05-2.84(m, 2H), 2.28(s, 3H), 2.20(s, 3H), 2.08(s, 3H), 1.62(s, 3H), 1.26-1.22(m, 6H), 1.06(s, 9H), 0.99(s) , 9H), 0.05(s, 3H), -0.02(s, 3H)
[247]
(2) Preparation of transition metal compounds
[248]

[249]
The ligand compound (1.74 g, 4.14 mmol/1.0eq) and 20.7 mL (0.2 M) of toluene were added to a 50 mL vial and stirred. At -40°C, n-BuLi (3.48 mL, 8.7 mmol/2.1eq, 2.5 M in hexane) was added, and the mixture was stirred at room temperature overnight. Thereafter, MeMgBr (4.14 mL, 12.42 mmol/3.0eq, 3.0 M in diethyl ether) was slowly added dropwise at -40°C, and then TiCl 4DME (1.1 g 4.14 mmol/1.0eq) was sequentially added and stirred overnight at room temperature. did After drying the solvent, the reaction mixture was filtered using hexane. Then, DME (1.29 mL, 12.42 mmol/3eq) was added to the filtrate and the mixture was stirred overnight at room temperature. After drying the solvent, it was filtered using hexane to obtain 335 mg (16.3%, dr=1:0.8) of a yellow solid.
[250]
1H NMR (CDCl 3, 500 MHz): δ 7.90 (d, 1H), 7.85 (d, 1H), 7.74 (d, 1H), 7.71 (d, 1H), 7.40 (d, 1H), 7.37 (d, 1H), 7.27(d, 1H), 7.23(t, 2H), 7.17(t, 2H), 7.13(t, 2H), 7.06(t, 1H), 7.01(t, 1H), 6.86(t, 1H) ), 2.97-2.91(m, 2H), 2.90-2.82(m, 2H), 2.33(s, 3H), 2.22(s, 3H), 1.96(s, 3H), 1.68(s, 9H), 1.66( s, 9H), 1.38(s, 3H), 1.32(t, 3H), 1.24(t, 3H), 1.07(s, 3H), 0.88(s, 3H), 0.85(s, 3H), 0.72(s , 3H), 0.19(s, 3H), 0.01(s, 3H)
[251]
[252]
Comparative Preparation Example 1
[253]

[254]
The compound was synthesized and used according to the method described in Korean Patent Publication No. 2015-0034653.
[255]
[256]
[Preparation of Ethylene/Alpha-Olefin Copolymer]
[257]
Example 1
[258]
A 1.5 L continuous process reactor was preheated at 130° C. while introducing 5.0 kg/h of hexane solvent and 0.95 kg/h of 1-butene. A triisobutylaluminum compound (0.050 mmol/min), a mixture of the transition metal compound obtained in Preparation Example 1 and Preparation Example 2-1 at a 3:7 molar ratio (0.120 μmol/min), dimethylanilinium tetrakis (pentane A fluorophenyl) borate cocatalyst (0.144 μmol/min) was simultaneously introduced into the reactor. Subsequently, ethylene (0.87 kg/h) and hydrogen gas (23 cc/min) were introduced into the reactor, and a copolymerization reaction was performed by maintaining the temperature at 130° C. for more than 60 minutes in a continuous process at a pressure of 89 bar to obtain a copolymer. Then, after drying in a vacuum oven for 12 hours or more, physical properties were measured.
[259]
[260]
Examples 2 to 4, Comparative Examples 1 to 6
[261]
An ethylene/alpha-olefin copolymer was prepared in the same manner as in Example 1, except that the polymerization conditions were changed as shown in Table 1 below.
[262]
[Table 1]
Catalyst Type Cat. Co-cat. Tibal C2 C6 alpha-olefin hydrogen temperature
μmol/min mmol/min kg/h Type kg/h cc/min ℃
Example 1 Preparation Example 1 + Preparation Example 2-1 0.120 0.144 0.050 0.87 5.0 1-C4 0.95 23 130
Example 2 Preparation Example 1 + Preparation Example 2-1 0.120 0.144 0.050 0.87 5.0 1-C4 0.90 27 130
Example 3 Preparation Example 1 + Preparation Example 2-1 0.120 0.144 0.050 0.87 5.0 1-C4 0.90 20 130
Example 4 Preparation Example 1 + Preparation Example 2-1 0.120 0.144 0.050 0.87 5.0 1-C4 0.85 24 130
Comparative Example 1 Comparative Preparation Example 1 0.700 2.100 0.030 0.87 5.1 1-C8 1.04 - 160
Comparative Example 2 Comparative Preparation Example 1 0.700 2.100 0.030 0.87 5.1 1-C8 1.04 - 160
Comparative Example 3 Production Example 2-1 0.120 0.144 0.040 0.87 5.0 1-C4 0.70 23 130
Comparative Example 4 Production Example 2-2 0.125 0.147 0.045 0.87 5.0 1-C4 0.76 26 130
Comparative Example 5 Production Example 2-3 0.125 0.147 0.045 0.87 5.0 1-C4 0.76 26 130
Comparative Example 6 Production Example 1 0.120 0.144 0.045 0.87 5.0 1-C8 0.45 6 130
[263]
[264]
[Ethylene/alpha-olefin air Analysis of coalescence]
[265]
Experimental Example 1
[266]
The physical properties of the ethylene/alpha-olefin copolymers prepared in Examples and Comparative Examples were measured by the following method and are shown in Table 2.
[267]
(1) Density
[268]
Measured according to ASTM D-792.
[269]
(2) Melt Index (MI2.16, Melt Index)
[270]
Measured according to ASTM D-1238 (Condition E, 190 ° C, 2.16 Kg load).
[271]
(3) Melting Temperature (Tm)
[272]
Using a Differential Scanning Calorimeter (DSC 6000) manufactured by PerkinElmer, the temperature of the copolymer was increased to 150 ° C under a nitrogen atmosphere, maintained for 5 minutes, cooled to -100 ° C, and the temperature was raised again. While increasing, the DSC curve was observed. At this time, the heating rate and cooling rate were each set to 10°C/min. In the measured DSC curve, the melting temperature was set as the maximum point of the endothermic peak at the second temperature increase.
[273]
(4) Elution temperature (Te)
[274]
Polymer Char's CFC (Cross-Fractionation Chromatography) equipment was used and measured in the range of -20 to 130 ° C using o-dichlorobenzene as a solvent. Specifically, a solution in which a copolymer sample was dissolved at a concentration of 5.0 mg/mL in an o-dichlorobenzene solvent at 130 °C was cooled to -20 °C at a rate of 0.50 °C/min, and then cooled from -20 °C to 130 °C. While heating and raising the temperature at a rate of 1 ° C./min, o-dichlorobenzene as a solvent was flowed through the column at a flow rate of 0.5 mL/min, and the amount (% by weight) of the polymer eluted at each temperature was measured. The elution temperature was defined as the temperature corresponding to the highest point in the peak existing after -20 ° C when the graph of temperature versus elution fraction was drawn.
[275]
(5) weight average molecular weight (Mw) and molecular weight distribution (MWD)
[276]
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resulting copolymer were measured under the following Gel Permeation Chromatography (GPC) analysis conditions, and the molecular weight distribution was calculated from the ratio of Mw/Mn.
[277]
- Column: Agilent Olexis
[278]
- Solvent: Trichlorobenzene
[279]
- Flow rate: 1.0ml/min
[280]
- Sample concentration: 1.0mg/ml
[281]
- Injection amount: 200μl
[282]
- Column temperature: 160 ℃
[283]
- Detector: Agilent High Temperature RI detector
[284]
- Standard: Polystyrene (corrected with cubic function)
[285]
- Data processing: Cirrus
[286]
[Table 2]
Density (g/cm3) MI (dg/min) Tm (℃) Te (℃) Tm-Te Mw (g/mol) MWD
Example 1 0.875 14.3 62.8 26.5 36.3 57,000 2.02
Example 2 0.876 20.0 64.2 27.2 37.0 51,000 2.05
Example 3 0.876 5.3 63.3 28.2 35.1 74,000 2.11
Example 4 0.877 14.1 66.2 28.6 37.6 58,000 2.05
Comparative Example 1 0.873 5.2 90.2 23.8 66.4 75,000 2.63
Comparative Example 2 0.872 5.0 86.1 20.6 65.5 76,000 2.51
Comparative Example 3 0.878 5.0 61.2 27.9 33.3 76,000 2.05
Comparative Example 4 0.877 5.8 60.7 27.0 33.7 78,000 2.06
Comparative Example 5 0.878 5.6 62.0 28.5 33.5 77,000 2.04
Comparative Example 6 0.900 6.4 97.8 59.8 38.0 67,000 2.18
[287]
As shown in Table 2, it was confirmed that the ethylene/alpha-olefin copolymers of Examples according to the present invention satisfy all of the density, Tm, and Tm-Te values ​​defined in the present invention. On the other hand, Comparative Examples 1 and 2 do not satisfy Equation 1 defined in the present invention because the Tm-Te value is larger than 65 ° C. and Comparative Examples 3 to 5 are smaller than 35 ° C., and Comparative Example 6 has the range of Equation 1 However, it was found that the density and Tm values ​​do not fall within the definition of the present invention.
[288]
[289]
[Manufacture of encapsulant film]
[290]
Example 1
[291]
To 500 g of the sample of Preparation Example 1, t-butyl 1-(2-ethylhexyl) monoperoxycarbonate (TBEC) 1 phr (parts per hundred rubber), triallyl isocyanurate (TAIC) 0.5 phr, methacrylic acid Oxypropyltrimethoxysilane (MEMO) 0.2 phr, a composition for an encapsulant film was prepared. Then, after soaking at 40°C for 1 hour, aging was performed for 15 hours.
[292]
Thereafter, an encapsulant film having an average thickness of 550 μm was prepared using a micro extruder at a low temperature (extruder barrel temperature of 100 ° C. or less) to the extent that high temperature crosslinking does not occur.
[293]
Examples 2 to 4, Comparative Examples 1 to 6
[294]
An encapsulant film was prepared in the same manner as in Example 1, except that the copolymers of Preparation Examples 2 to 4 and Comparative Preparation Examples 1 to 6 were used as samples.
[295]
[296]
[Analysis of encapsulant film]
[297]
Experimental Example 2
[298]
6 g of the ethylene/alpha-olefin copolymer was put into a 0.5T square strainer, and the front and back sides were covered with 3T steel plates, and then put into a hot press. 190 ℃, 25 N / cm 2 (240 seconds), reduced pressure / pressure degassing 6 times, 190 ℃ 151 N / cm 2 continuously treated for 240 seconds, then cooled to 30 ℃ while lowering 15 ℃ per minute, at this time The pressure was maintained at 151 N/cm 2 . 30 ℃, 151 N / cm 2 maintained for 300 seconds to complete the preparation of the specimen.
[299]
For the specimens prepared in this way, volume resistance and light transmittance were measured according to the following method, and are shown in Table 3.
[300]
(1) Volume resistance
[301]
Using an Agilent 4339B High-Resistance meter (manufactured by Agilent Technologies Co., Ltd.) under conditions of 23±1° C. temperature and 50±3% humidity, a voltage of 1000 V was applied for 60 seconds and measured.
[302]
(2) light transmittance
[303]
Light transmittance at 550 nm was measured using a Shimadzu UV-3600 spectrophotometer.
[304]
- Measurement mode: transmittance
[305]
- Wavelength interval: 1 nm
[306]
- Measurement speed: medium
[307]
[Table 3]
Volume resistance (Ω cm) Light transmittance (%)
Example 1 1.2 Х 1016 91.3
Example 2 1.0 Х 1016 91.5
Example 3 7.1 Х 1016 91.7
Example 4 4.7 Х 1016 91.6
Comparative Example 1 5.0 Х 1015 88.7
Comparative Example 2 5.5 Х 1015 89.1
Comparative Example 3 7.0 Х 1015 91.3
Comparative Example 4 7.5 Х 1015 91.4
Comparative Example 5 7.0 Х 1015 91.5
Comparative Example 6 9.0 Х 1015 88.3
[308]
As shown in the table above, it was confirmed that the ethylene/alpha-olefin copolymer of the present invention can realize both high volume resistance and light transmittance, unlike the ethylene/alpha-olefin copolymer of Comparative Example. In particular, Comparative Example 1 And 2 showed a lower volume resistance compared to the example due to the low crystalline region because the Tm-Te value was greater than 65 ° C., and the light transmittance was also low due to the high crystalline region. In Comparative Examples 3 to 5, the Tm-Te value It was confirmed that the volume resistance was particularly reduced due to the low crystalline region below 35°C. In addition, Comparative Example 6 satisfies the range of Equation 1, but the light transmittance was particularly low because the density and Te value were too large.
[309]
As described above, the ethylene/alpha-olefin copolymer that satisfies the density, Tm, and Tm-Te values ​​defined in the present invention could realize excellent volume resistance and light transmittance without using a separate additive.
claims
[Claim 1]
An ethylene/alpha-olefin copolymer that satisfies the following conditions (a) to (c): (a) has a density of 0.85 to 0.89 g/cc; (b) that the melting temperature (Tm) having the highest peak in the curve obtained by differential scanning calorimetry (DSC) is 40 to 90 ° C; and (c) the melting temperature (Tm) and the elution temperature (Te) having the highest peak in a curve obtained by cross-fractionation chromatography (CFC) satisfy Equation 1 below. [Equation 1] 35 ℃ < Tm - Te < 65 ℃
[Claim 2]
The ethylene/alpha-olefin copolymer of claim 1, wherein the molecular weight distribution is between 1.5 and 2.5.
[Claim 3]
The ethylene/alpha-olefin copolymer according to claim 1, wherein the elution temperature (Te) is 10 to 50 °C.
[Claim 4]
The ethylene/alpha-olefin copolymer of claim 1, wherein the melt index is from 1 to 100 dg/min.
[Claim 5]
The ethylene/alpha-olefin copolymer according to claim 1, wherein the weight average molecular weight is 40,000 to 150,000 g/mol.
[Claim 6]
The method of 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 -Ethylene/alpha-olefin copolymer containing at least one selected from the group consisting of dodecene, 1-tetradecene, 1-hexadecene and 1-eicosene.
[Claim 7]
The ethylene/alpha-olefin copolymer according to claim 1, wherein the alpha-olefin is contained in an amount greater than 0 and less than 99 mol% relative to the copolymer.